CN105967294A - Defluorination flocculation reaction method for fluorine-containing wastewater - Google Patents
Defluorination flocculation reaction method for fluorine-containing wastewater Download PDFInfo
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- CN105967294A CN105967294A CN201610492278.4A CN201610492278A CN105967294A CN 105967294 A CN105967294 A CN 105967294A CN 201610492278 A CN201610492278 A CN 201610492278A CN 105967294 A CN105967294 A CN 105967294A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 238000005189 flocculation Methods 0.000 title claims abstract description 73
- 230000016615 flocculation Effects 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 48
- 239000011737 fluorine Substances 0.000 title claims abstract description 48
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000006115 defluorination reaction Methods 0.000 title abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 124
- 238000001556 precipitation Methods 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000008394 flocculating agent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims description 113
- 230000033228 biological regulation Effects 0.000 claims description 40
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910001424 calcium ion Inorganic materials 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 18
- 239000001110 calcium chloride Substances 0.000 claims description 18
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 18
- 238000004062 sedimentation Methods 0.000 claims description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 abstract 1
- 239000000701 coagulant Substances 0.000 description 7
- 230000007812 deficiency Effects 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- AHLWZBVXSWOPPL-RGYGYFBISA-N 20-deoxy-20-oxophorbol 12-myristate 13-acetate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(C=O)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C AHLWZBVXSWOPPL-RGYGYFBISA-N 0.000 description 2
- 241001602688 Pama Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000247 postprecipitation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000013475 authorization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/66—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a defluorination flocculation reaction method for fluorine-containing wastewater. The defluorination flocculation reaction method includes carrying out precipitation reaction on the fluorine-containing wastewater by the aid of three-level precipitation reaction tanks; regulating the pH (potential of hydrogen) of the fluorine-containing wastewater in each level of precipitation reaction and adding precipitants into the fluorine-containing wastewater in each level of precipitation reaction so that the energy density of each unit volume of the fluorine-containing wastewater during the first-level reaction is 10-20 W/m<3>, the energy density of each unit volume of the fluorine-containing wastewater during the second-level reaction is 7-17 W/m<3> and the energy density of each unit volume of the fluorine-containing wastewater during the third-level reaction is 4-14 W/m<3>; adding precipitants and flocculants into the fluorine-containing wastewater after the three-level precipitation reaction is carried out on the fluorine-containing wastewater and carrying out flocculation treatment on the fluorine-containing wastewater; precipitating the fluorine-containing wastewater after flocculation reaction is carried out on the fluorine-containing wastewater; draining liquid supernatants. The defluorination flocculation reaction method has the advantages that influence of hydraulic conditions on the flocculation reaction and the precipitation reaction is sufficiently considered, the defluorination flocculation reaction method is applicable to treating a large quantity of fluorine-containing wastewater with a high fluorine ion content, treated drained water is low in fluorine content, and excellent defluorination effects can be realized.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of fluorine removal flocculation reaction method of fluoride waste.
Background technology
Along with industrialized propelling, containing a large amount of fluorions in a lot of industry production, thus its industrial wastewater produced also contains fluorine element, the fluoride severe overweight contained in the waste water that some production of electronic components industry gives off, the last fluoride waste water that these exceed standard flows in nature water body, cause serious water environment pollution, bring certain unsafe factor the most also to the life of people.
The processing method of fluoride waste mainly has the most both at home and abroad: coagulant sedimentation, ion exchange, absorption method, electrodialysis, reverse osmosis, membrane separation process etc..Wherein, coagulant sedimentation is method most effective, simplest, has operating cost low, and removal efficiency is high, can process the advantages such as high-concentration fluorine-containing waste water.But after coagulant sedimentation processes, ultimate density can only achieve 20mg/L ~ 30mg/L, and defluorination effect is unstable, and this is primarily due to post precipitation weak effect, causes substantial amounts of tiny fluorine-containing colloidal suspension in water.Owing to the deficiency of coagulant sedimentation also occurs in that some follow-on technique with coagulating sedimentation as principle and reactors.As: " a kind of method of FLUORIDE REMOVAL IN WASTEWATER " of Publication No. CN104496063A, but the method also exists precipitation thoroughly, and dosage of PAC is relatively big, and process fluorinion concentration is up to the deficiencies such as 500mg/L；And for example Authorization Notice No. is " defluorinating method of photovoltaic wastewater " of CN102001766B, use the process PROCESS FOR TREATMENT fluoride waste that chemistry, flocculation sediment and air-float filtration combine, but the method is only applicable to, and the water yield is less, the water quality situation of low fluorinion concentration, there is also complex disposal process, the shortcoming that processing cost is higher simultaneously；For another example " defluorination method of fluoride waste and the fluorine removal device thereof " of Publication No. CN104843818A, the chelating resin with absorption fluorion is used to carry out fluorion Adsorption, but it is limited that the method also exists adsorbent amount, the problem that adsorbent reactivation cost is bigger, and the method is only applicable to the desulfurization wastewater that fluorinion concentration is 50 ~ 150mg/L and processes, thus there is also certain deficiency.In addition to above-mentioned deficiency, it is often more important that above defluorinating process and equipment all do not account for after adding precipitant and coagulant, the impact on fluorine removal of the hydraulics of coagulation, and therefore treatment effect is the highest.
Visible, the processing method of prior art fluoride waste, owing to the series of influence factors of fluorine removal flocculation precipitation reaction and hydraulics be there is no enough understanding or be not given to enough attention, blindly some method for treating water simple superposition or set are used for fluoride wastewater treatment, result in not only processing cost expensive, and affect the series of problems of follow-up flocculation precipitation reaction effect.
Summary of the invention
For deficiencies of the prior art, the technical problem to be solved in the present invention is: for the processing method of fluoride waste in prior art exist complex disposal process, relatively costly, do not account for the water project situation impact on defluorination effect of coagulation
, the best technical problem of defluorination effect, and provide a kind of simple efficiently, investment and the fluorine removal flocculation reaction method of operating cost is relatively low, to take into full account the water project situation of coagulation excellent on defluorination effect impact, defluorination effect a kind of fluoride waste.
In order to solve above-mentioned technical problem, the present invention adopts the following technical scheme that a kind of fluorine removal flocculation reaction method of fluoride waste, comprises the steps:
1) content of fluoride ion in fluoride waste is measured, fluoride waste is introduced in first order precipitation pond, the pH to 5 ~ 12 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, the energy density making unit volume fluoride waste is 10 ~ 20 W/m, proceeds by first order precipitation；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；Content of fluoride ion in fluoride waste measures and standard fluorine ion selective electrode method can be used to be measured；
2) step 1) fluoride waste after first order precipitation is introduced in precipitation pond, the second level, the pH to 5 ~ 12 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, the energy density making unit volume fluoride waste is 7 ~ 17 W/m, proceeds by second level precipitation；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；
3) by step 2) fluoride waste after the precipitation of the second level introduces in third level precipitation pond, the pH to 5 ~ 12 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, the energy density making unit volume fluoride waste is 4 ~ 14 W/m, proceeds by third level precipitation；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；
4) fluoride waste after step 3) third level precipitation is introduced in flocculation basin, the pH to 5 ~ 10 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, inorganic flocculating agent and organic flocculant and carries out flocculation reaction, making fluoride waste energy per volume density in the first half section hydraulic detention time of flocculation basin is 8 ~ 10W/m, and in second half section hydraulic detention time, energy per volume density is 1 ~ 4W/m；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；Described inorganic flocculating agent, organic flocculant are 5 ~ 50 mg:1 ~ 20 mg:1L with the mass volume ratio of fluoride waste；
5) introducing in sedimentation tank by the waste water after step 4) flocculation reaction, remove the suspension colloid granule formed in coagulating sedimentation in water, collect and discharge clear liquid, the fluorine removal completing fluoride waste processes.
nullUse such method that fluoride waste is processed，When processing fluoride waste，First waste water is introduced first order reaction zone，PH adjusting agent and precipitant is added in waste water，The energy density of setting unit volume fluoride waste is 10 ~ 20 W/m，Waste water is enable fully to mix at first district's reaction tank，And occur initial flocculation to react，Water after first order reaction zone processes flows in reaction zone, the second level，Owing to flocculation reaction can reduce the basicity of water body and makes the precipitant content in water body decline，In order to ensure that flocculation precipitation reaction is complete，PH adjusting agent and precipitant is continuously added in waste water，The pH making waste water is being suitable in the range of fluorion flocculation sediment，And add the precipitant being sufficient to fluorine ions in water body content flocculation sediment，The energy density of setting unit volume fluoride waste is 7 ~ 17 W/m，Waste water hydraulic detention time in reaction zone, the second level is made to extend，Fully there is flocculation precipitation reaction，Waste water after the second level processes flows in third level reaction zone，Add pH adjusting agent and precipitant，Arranging fluoride waste energy density in third level reaction tank is 4 ~ 14 W/m，On the one hand the waste water water conservancy time of staying in third level reaction tank is made more to extend，It is further ensured that the flocculation time of fluorinion in waste water is sufficient，Can formation flocculate as much as possible precipitation，On the other hand partial flocculation thing has been generated due to front two-stage reaction，It is little that the waste water motive force in third level reaction zone is set，The flocculation sediment grain breakage formed can be avoided，It is more beneficial for post precipitation and removes flocculate；nullWaste water through third level reaction flows into flocculation zone，Add pH adjusting agent、Precipitant and flocculant，The flocculant added can further assist fluorion flocculation sediment，Arranging fluoride waste energy per volume density in the first half section hydraulic detention time of flocculation basin is 8 ~ 10W/m，In second half section hydraulic detention time, energy per volume density is 1 ~ 4W/m，Make fluoride waste fully can react with precipitant and flocculant in the first half section hydraulic detention time of flocculation basin，The fluorion in waste water is made to remove further，And in second half section hydraulic detention time the decrease of power density，The flocculate that effectively protection is formed is not crushed by eddy current，And then flocculate easily precipitates in later stage precipitation process，Remain in water outlet without becoming tiny material，Water after flocculation is passed through in sedimentation tank，Coagulated particles precipitation is removed by sedimentation tank，Clear liquid after precipitation is discharged in exit，Complete fluorine removal flocculation precipitation reaction.
Further, the total hrt controlling the first order precipitation of described fluoride waste, second level precipitation, third level precipitation and flocculation reaction is 1 ~ 10h.The third-order reaction and the flocculation time that control fluoride waste are such, fluoride waste mixing can be made more uniform, and the reaction with precipitant is more abundant, and then is more applicable for the process of high fluorinion concentration waste water, make the fluorinion in waste water concentration after process as little as 7 mg/L, obtain excellent defluorination effect.
Further, described first order precipitation pond, precipitation pond, the second level and third level precipitation pond are reciprocal baffled reflection chamber.Using such reciprocating partition plate reaction tank, the mixing that can make waste water is more uniform, enables the fluorion in water body more fully to react generation flocculate with precipitant, makes coagulation effect more preferable.
Further, described flocculation basin is folded plate type reaction tank.Flocculation zone uses flap reaction tank structure, adds flow-disturbing unit, reaches required turbulent condition of flocculating, effectively can be sufficiently mixed fluoride waste, improves the removal effect of fluorion.
Further, described water solublity calcium containing compound includes at least one in calcium hydroxide, calcium oxide and calcium chloride.Use such calcium containing compound as precipitant, bring great variety will not to the pH value etc. to pending waste water, will not be negatively affected, and be easier to generate infusible precipitate compound calcium fluoride with calcium ion, be more beneficial for the removal of fluorion.
Further, at least one during described inorganic flocculating agent includes aluminium polychlorid, poly-ferric chloride, bodied ferric sulfate, polyaluminium sulfate, PAFS, polymeric aluminium ferrum silicate, polyferric silicate sulfate, PAFC and PPFS.Selecting such inorganic coagulant, consumption is few compared with other inorganic coagulants, does not introduce SO in processed waste water4 2-And Cl-Plasma, also will not introduce the pollutant that ferrum and aluminum etc. are new in residue, treatment effect is more preferable, and the feature of environmental protection is good.
As optimization, described organic flocculant includes at least one in non-ionic polyacrylamide, anion-polyacrylamide, PAMC, amphoteric polyacrylamide and chitosan flocculant.Select such organic flocculant, little compared to other flocculant dosages, form that flco is fast, flco volume big, and precipitation is rapidly, therefore required sedimentation tank is little, investment is saved, and operating cost is low.
As optimization, described fluoride waste is the fluorine-containing pickling waste waters of height that photovoltaic enterprise produces that solar panel produces.It is high that the defluorination method of prior art cannot be applicable to fluorinated volume, the photovoltaic enterprise that the water yield is bigger produces the height fluorine-containing pickling waste waters process that solar panel produces, and the method that defluorination method of the present invention is combined by three grades of precipitation and flocculation reaction, it is more applicable for such fluoride wastewater treatment, overcomes the technological deficiency that art methods pickling fluorine-containing to such height water treatment effect is the best.
As optimization, in described fluoride waste, the concentration of fluorion is 1500 ~ 34000 mg/L, pH value≤4.The present invention is better to the fluoride wastewater treatment of such levels and pH content, and after process, the fluorinated volume of water outlet as little as 7 mg/L, achieves beyond thought technique effect.
Compared to existing technology, there is advantages that
null1、The present invention uses three grades of precipitation reaction process，Fluoride waste is served mixing and cushioning effect，In differential responses district, all regulate pH and add precipitant，So that fluoride waste and flocculant mixture can obtain optimal flocculation precipitation reaction condition in each reaction zone，And then make fluorion in fluoride waste to be flocculated more to precipitate，The present invention has also considered the hydraulics impact on flocculation reaction，Different energy density is regulated in each precipitation district，Increase energy density in leading portion processes，Make fluoride waste mixing more uniform，The flow-disturbing produced enables fluorion and the precipitant can more haptoreaction，The decrease of power density step by step in back segment processing procedure，On the one hand hydraulic detention time is extended，The time and the reaction that make flocculation precipitation reaction are more abundant，Another invention makes flow rate of water flow decline，The flocculate generated can be avoided to crush，The follow-up precipitation that carries out is facilitated to remove flocculate process，Make the water outlet after process does not contains tiny colloid flocculate，Defluorination effect is more excellent.
2, third-order reaction pond is set to reciprocating baffled reflection chamber by the present invention, fully ensure that fluoride waste is sufficiently mixed with precipitant, add flow-disturbing unit, promote to react more abundant, follow-up operation program is enable to stablize effectively, use folded plate type reaction tank as flocculation basin, reach the turbulent condition required for flocculation, effectively fluoride waste is sufficiently mixed, simultaneously in order to prevent coagulated particles from producing disrepair phenomenon during flow-disturbing, in flocculation basin, also add flocculant, to strengthen the flocculation sediment to crushed particles, make follow-up water outlet is substantially free of tiny colloidal solid, treatment effect is more excellent.
3, the medicine used in the inventive method be routine be easy to get, cheap test articles for use, and in processing procedure, parameter is easily controlled, and operates simpler convenience, has good marketing prospect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.The implementation case is implemented under premised on the technology of the present invention, now provides detailed embodiment and concrete operating process to illustrate that the present invention is creative, but protection scope of the present invention is not limited to below example.
Embodiment
1
It is 1500mg/L that certain photovoltaic enterprise produces the concentration of the height fluorine-containing pickling fluorinion in waste water that solar panel produces, and pH value is 1.Fluoride waste is introduced in first order precipitation pond, the pH to 9 of regulation waste water, the waste water after regulation pH adds calcium chloride, the energy density making unit volume fluoride waste is 10 W/m, proceeds by first order precipitation；Wherein, in calcium chloride, calcium ion is 1:2 with the mol ratio of fluorion in fluoride waste；Fluoride waste after first order precipitation introduces in precipitation pond, the second level, the pH to 5 of regulation waste water, adds calcium hydroxide in the waste water after regulation pH, and the energy density making unit volume fluoride waste is 7 W/m, proceeds by second level precipitation；Wherein, in calcium hydroxide, calcium ion is 1:2 with the mol ratio of fluorion in fluoride waste；Fluoride waste after the precipitation of the second level introduces in third level precipitation pond, the pH to 10 of regulation waste water, adds calcium chloride in the waste water after regulation pH, and the energy density making unit volume fluoride waste is 4 W/m, proceeds by third level precipitation；Wherein, in calcium chloride, calcium ion is 1:2 with the mol ratio of fluorion in fluoride waste；Fluoride waste after third level precipitation introduces in flocculation basin, the pH to 5 of regulation waste water, waste water after regulation pH adds calcium chloride, poly-ferric chloride and chitosan flocculant and carries out flocculation reaction, making fluoride waste energy per volume density in the first half section hydraulic detention time of flocculation basin is 8W/m, and in second half section hydraulic detention time, energy per volume density is 1W/m；Wherein, in calcium chloride, calcium ion is 1:2 with the mol ratio of fluorion in fluoride waste；Poly-ferric chloride, chitosan flocculant are 5 mg:1 mg:1L with the mass volume ratio of fluoride waste；Waste water after flocculation reaction introduces in sedimentation tank, removes the suspension colloid granule formed in coagulating sedimentation in water, collects and discharge clear liquid, and the fluorine removal completing fluoride waste processes, and water outlet fluorinion concentration is 7mg/L.
Embodiment
2
It is 34000mg/L that certain photovoltaic enterprise produces the concentration of the height fluorine-containing pickling fluorinion in waste water that solar panel produces, and pH value is 2.Fluoride waste is introduced in first order precipitation pond, the pH to 10 of regulation waste water, the waste water after regulation pH adds calcium chloride, the energy density making unit volume fluoride waste is 20 W/m, proceeds by first order precipitation；Wherein, in calcium chloride, calcium ion is 1:10 with the mol ratio of fluorion in fluoride waste；Fluoride waste after first order precipitation introduces in precipitation pond, the second level, the pH to 12 of regulation waste water, adding calcium hydroxide in waste water after regulation pH, the energy density making unit volume fluoride waste is 17 W/m, proceeds by second level precipitation；Wherein, in calcium hydroxide, calcium ion is 1:10 with the mol ratio of fluorion in fluoride waste；Fluoride waste after the precipitation of the second level introduces in third level precipitation pond, the pH to 12 of regulation waste water, adding calcium hydroxide in waste water after regulation pH, the energy density making unit volume fluoride waste is 14 W/m, proceeds by third level precipitation；Wherein, in calcium chloride, calcium ion is 1:10 with the mol ratio of fluorion in fluoride waste；Fluoride waste after third level precipitation introduces in flocculation basin, the pH to 10 of regulation waste water, waste water after regulation pH adds calcium chloride, bodied ferric sulfate and PAMC and carries out flocculation reaction, making fluoride waste energy per volume density in the first half section hydraulic detention time of flocculation basin is 10W/m, and in second half section hydraulic detention time, energy per volume density is 4W/m；Wherein, in calcium chloride, calcium ion is 1:10 with the mol ratio of fluorion in fluoride waste；Bodied ferric sulfate, PAMC are 50 mg:20 mg:1L with the mass volume ratio of fluoride waste；Waste water after flocculation reaction introduces in sedimentation tank, removes the suspension colloid granule formed in coagulating sedimentation in water, collects and discharge clear liquid, and the fluorine removal completing fluoride waste processes, and water outlet fluorinion concentration is 8mg/L.
Embodiment
3
It is 24000mg/L that certain photovoltaic enterprise produces the concentration of the height fluorine-containing pickling fluorinion in waste water that solar panel produces, and pH value is 3.Fluoride waste is introduced in first order precipitation pond, the pH to 10 of regulation waste water, the waste water after regulation pH adds calcium chloride, the energy density making unit volume fluoride waste is 15 W/m, proceeds by first order precipitation；Wherein, in calcium chloride, calcium ion is 1:8 with the mol ratio of fluorion in fluoride waste；Fluoride waste after first order precipitation introduces in precipitation pond, the second level, the pH to 11 of regulation waste water, adding calcium hydroxide in waste water after regulation pH, the energy density making unit volume fluoride waste is 15 W/m, proceeds by second level precipitation；Wherein, in calcium chloride, calcium ion is 1:6 with the mol ratio of fluorion in fluoride waste；Fluoride waste after the precipitation of the second level introduces in third level precipitation pond, the pH to 12 of regulation waste water, adding calcium hydroxide in waste water after regulation pH, the energy density making unit volume fluoride waste is 6 W/m, proceeds by third level precipitation；Wherein, in calcium hydroxide, calcium ion is 1:7 with the mol ratio of fluorion in fluoride waste；Fluoride waste after third level precipitation introduces in flocculation basin, the pH to 7 of regulation waste water, waste water after regulation pH adds calcium chloride, PAFS and PAMA and carries out flocculation reaction, making fluoride waste energy per volume density in the first half section hydraulic detention time of flocculation basin is 9 W/m, and in second half section hydraulic detention time, energy per volume density is 2 W/m；Wherein, in calcium chloride, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；PAFS, PAMA are 5 ~ 50 mg:1 ~ 20 mg:1L with the mass volume ratio of fluoride waste；Waste water after flocculation reaction introduces in sedimentation tank, removes the suspension colloid granule formed in coagulating sedimentation in water, collects and discharge clear liquid, and the fluorine removal completing fluoride waste processes, and water outlet fluorinion concentration is 7 mg/L.
Finally illustrate is, above example is only in order to illustrate technical scheme and unrestricted, although the present invention being described in detail with reference to preferred embodiment, it will be understood by those within the art that, technical scheme can be modified or equivalent, without deviating from objective and the scope of technical solution of the present invention, it all should be contained in the middle of scope of the presently claimed invention.
Claims (9)
1. the fluorine removal flocculation reaction method of a fluoride waste, it is characterised in that comprise the steps:
1) content of fluoride ion in fluoride waste is measured, fluoride waste is introduced in first order precipitation pond, the pH to 5 ~ 12 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, the energy density making unit volume fluoride waste is 10 ~ 20 W/m, proceeds by first order precipitation；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；
2) step 1) fluoride waste after first order precipitation is introduced in precipitation pond, the second level, the pH to 5 ~ 12 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, the energy density making unit volume fluoride waste is 7 ~ 17 W/m, proceeds by second level precipitation；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；
3) by step 2) fluoride waste after the precipitation of the second level introduces in third level precipitation pond, the pH to 5 ~ 12 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, the energy density making unit volume fluoride waste is 4 ~ 14 W/m, proceeds by third level precipitation；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；
4) fluoride waste after step 3) third level precipitation is introduced in flocculation basin, the pH to 5 ~ 10 of regulation waste water, waste water after regulation pH adds water solublity calcium containing compound, inorganic flocculating agent and organic flocculant and carries out flocculation reaction, making fluoride waste energy per volume density in the first half section hydraulic detention time of flocculation basin is 8 ~ 10W/m, and in second half section hydraulic detention time, energy per volume density is 1 ~ 4W/m；Wherein, in described water solublity calcium containing compound, calcium ion is 1:2 ~ 10 with the mol ratio of fluorion in fluoride waste；Described inorganic flocculating agent, organic flocculant are 5 ~ 50 mg:1 ~ 20 mg:1L with the mass volume ratio of fluoride waste；
5) introducing in sedimentation tank by the waste water after step 4) flocculation reaction, remove the suspension colloid granule formed in coagulating sedimentation in water, collect and discharge clear liquid, the fluorine removal completing fluoride waste processes.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterised in that the total hrt controlling the first order precipitation of described fluoride waste, second level precipitation, third level precipitation and flocculation reaction is 1 ~ 10h.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterised in that described first order precipitation pond, precipitation pond, the second level and third level precipitation pond are reciprocal baffled reflection chamber.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterised in that described flocculation basin is folded plate type reaction tank.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterised in that described water solublity calcium containing compound includes at least one in calcium hydroxide, calcium oxide and calcium chloride.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterized in that, described inorganic flocculating agent includes at least one in aluminium polychlorid, poly-ferric chloride, bodied ferric sulfate, polyaluminium sulfate, PAFS, polymeric aluminium ferrum silicate, polyferric silicate sulfate, PAFC and PPFS.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterized in that, described organic flocculant includes at least one in non-ionic polyacrylamide, anion-polyacrylamide, PAMC, amphoteric polyacrylamide and chitosan flocculant.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterised in that described fluoride waste is the fluorine-containing pickling waste waters of height that photovoltaic enterprise produces that solar panel produces.
The fluorine removal flocculation reaction method of fluoride waste the most according to claim 1, it is characterised in that in described fluoride waste, the concentration of fluorion is 1500 ~ 34000 mg/L, pH value≤4.
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