CN105967294B - Defluorination flocculation reaction method for fluorine-containing wastewater - Google Patents
Defluorination flocculation reaction method for fluorine-containing wastewater Download PDFInfo
- Publication number
- CN105967294B CN105967294B CN201610492278.4A CN201610492278A CN105967294B CN 105967294 B CN105967294 B CN 105967294B CN 201610492278 A CN201610492278 A CN 201610492278A CN 105967294 B CN105967294 B CN 105967294B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- water
- waste
- reaction
- precipitation reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 123
- 239000002351 wastewater Substances 0.000 title claims abstract description 86
- 238000005189 flocculation Methods 0.000 title claims abstract description 65
- 230000016615 flocculation Effects 0.000 title claims abstract description 65
- 239000011737 fluorine Substances 0.000 title claims abstract description 54
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 54
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006115 defluorination reaction Methods 0.000 title abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 136
- 238000001556 precipitation Methods 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002699 waste material Substances 0.000 claims description 99
- 238000004062 sedimentation Methods 0.000 claims description 25
- 229910001424 calcium ion Inorganic materials 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 20
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 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 17
- 239000001110 calcium chloride Substances 0.000 claims description 17
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 15
- 229920002401 polyacrylamide Polymers 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- DKFCNIGGENJIJN-UHFFFAOYSA-L aluminum;iron(2+);sulfate Chemical compound [Al+3].[Fe+2].[O-]S([O-])(=O)=O DKFCNIGGENJIJN-UHFFFAOYSA-L 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
- 229920001661 Chitosan Polymers 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 230000002308 calcification Effects 0.000 claims 1
- 229910052635 ferrosilite Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 19
- 238000001704 evaporation Methods 0.000 abstract 6
- 230000008020 evaporation Effects 0.000 abstract 6
- 239000010409 thin film Substances 0.000 abstract 3
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 8
- 239000000701 coagulant Substances 0.000 description 7
- 230000007812 deficiency Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000247 postprecipitation Methods 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NQMZNYDGOJUGRE-UHFFFAOYSA-J [OH-].[OH-].[OH-].[OH-].[Ca++].[Ca++] Chemical compound [OH-].[OH-].[OH-].[OH-].[Ca++].[Ca++] NQMZNYDGOJUGRE-UHFFFAOYSA-J 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- VNWKDIUSXQCPGN-UHFFFAOYSA-J dicalcium tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ca+2].[Ca+2] VNWKDIUSXQCPGN-UHFFFAOYSA-J 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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 of fluorine-containing wastewater, which comprises the steps of carrying out precipitation reaction on the fluorine-containing wastewater by adopting a three-stage precipitation reaction tank, adjusting the pH value of the wastewater in each stage of precipitation reaction, adding a precipitant into the wastewater, carrying out thin film evaporation on the fluorine-containing wastewater in unit volume in the first stage reaction by means of evaporation at the energy density of 10-20W/m, carrying out thin film evaporation on the fluorine-containing wastewater in the second stage reaction by means of evaporation at the energy density of 7-17W/m, carrying out thin film evaporation on the fluorine-containing wastewater in the third stage reaction by means of evaporation at the energy density of 4-14W/m, adding the precipitant and a flocculant into the wastewater for flocculation treatment after the third stage precipitation reaction, and finally precipitating the wastewater after. The method fully considers the influence of hydraulic conditions on the flocculation precipitation reaction, is suitable for treating the fluorine-containing wastewater with high fluorine ion content and large water amount, has low fluorine content in the treated effluent, and obtains good fluorine removal effect.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to a kind of fluorine removal flocculation reaction method of fluoride waste.
Background technique
With industrialized propulsion, a large amount of fluorine ions are contained in many industry productions, thus in the industrial wastewater of its generation
Also contain fluorine element, the fluoride that contains in the waste water that some production of electronic components industries give off severely exceeds, it is last this
A little exceeded fluoride waste water flow into nature water body, cause serious water environment pollution, while also giving people's lives band
Carry out certain insecurity factor.
The processing method of fluoride waste mainly has both at home and abroad at present: coagulant sedimentation, ion-exchange, absorption method, electric osmose
Analysis, reverse osmosis, membrane separation process etc..Wherein, coagulant sedimentation is most effective, simplest method, has operating cost low, removal
It is high-efficient, can handle the advantages that high-concentration fluorine-containing waste water.But coagulant sedimentation processing after ultimate density can only achieve 20mg/L ~
30mg/L, and defluorination effect is unstable, it is poor that this is primarily due to post precipitation effect, leads to a large amount of tiny fluorine-containing colloidal suspension
Yu Shuizhong.Due to coagulant sedimentation deficiency also occur it is some follow-on using coagulating sedimentation as the technique of principle and reaction
Device.Such as: a kind of " method of FLUORIDE REMOVAL IN WASTEWATER " of Publication No. CN104496063A, but that there is precipitation reaction is not thorough for this method
The deficiencies of bottom, dosage of PAC is larger, and processing fluorinion concentration is up to 500mg/L；For another example Authorization Notice No. is
" defluorinating method of photovoltaic wastewater " of CN102001766B, the treatment process combined using chemistry, flocculation sedimentation and air-float filtration
Fluoride waste is handled, but this method is only applicable to the water quality situation of smaller, the low fluorinion concentration of water, while there is also processed
Journey is complicated, the higher disadvantage of processing cost；For another example Publication No. CN104843818A " defluorination method of fluoride waste and its is removed
Fluorine device " is carried out using the chelating resin with absorption fluorine ion to fluorine ion Adsorption, but there is adsorbents for this method
Adsorbance is limited, the larger problem of adsorbent reactivation cost, and it is 50 ~ 150mg/L's that this method, which is only applicable to fluorinion concentration,
Desulfurization wastewater processing, thus there is also certain deficiencies.Other than above-mentioned deficiency, it is often more important that the above defluorinating process and equipment are equal
It does not account for after precipitating reagent and coagulant is added, influence of the hydraulics of coagulation to fluorine removal, therefore treatment effect is obviously not
It is high.
As it can be seen that the processing method of prior art fluoride waste, due to a series of influences on fluorine removal flocculation precipitation reaction because
Element and hydraulics do not have enough understandings or are not given to enough attention, blindness by some method for treating water simple superposition
Or set is used for fluoride wastewater treatment, it is expensive to result in not only processing cost, but also influence subsequent flocculation precipitation reaction effect
A series of problems.
Summary of the invention
In view of the above shortcomings of the prior art, the technical problem to be solved by the present invention is for containing in the prior art
The processing method of fluorine waste water there are complex disposal process, higher cost, do not account for the water project situation of coagulation to defluorination effect
It influences
, the bad technical problem of defluorination effect, and one kind is provided and is simple and efficient, invests and operating cost is lower, sufficiently examines
A kind of fluorine removal flocculation reaction method of the water project situation of the worry coagulation fluoride waste excellent on defluorination effect influence, defluorination effect.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme: a kind of fluorine removal flocculation of fluoride waste is anti-
Induction method includes the following steps:
1) content of fluoride ion in fluoride waste is measured, fluoride waste is introduced into first order precipitation reaction pond, is adjusted useless
Water-soluble calcium containing compound is added into the waste water after adjusting pH, makes the energy of unit volume fluoride waste by the pH to 5 ~ 12 of water
Density is 10 ~ 20 W/m3, starts to carry out first order precipitation reaction；Wherein, in the water-soluble calcium containing compound calcium ion with contain
The molar ratio of fluorine fluorinion in waste water is 1:2 ~ 10；Content of fluoride ion measurement in fluoride waste can be selected using standard fluorine ion
Electrode method is selected to be measured；
2) fluoride waste of the step 1) after first order precipitation reaction is introduced into the precipitation reaction pond of the second level, is adjusted useless
Water-soluble calcium containing compound is added into the waste water after adjusting pH, makes the energy of unit volume fluoride waste by the pH to 5 ~ 12 of water
Density is 7 ~ 17 W/m3, starts to carry out second level precipitation reaction；Wherein, in the water-soluble calcium containing compound calcium ion with contain
The molar ratio of fluorine fluorinion in waste water is 1:2 ~ 10；
3) fluoride waste of the step 2 after the precipitation reaction of the second level is introduced into third level precipitation reaction pond, is adjusted useless
Water-soluble calcium containing compound is added into the waste water after adjusting pH, makes the energy of unit volume fluoride waste by the pH to 5 ~ 12 of water
Density is 4 ~ 14 W/m3, starts to carry out third level precipitation reaction；Wherein, in the water-soluble calcium containing compound calcium ion with contain
The molar ratio of fluorine fluorinion in waste water is 1:2 ~ 10；
4) fluoride waste after step 3) third level precipitation reaction is introduced into flocculation basin, adjusts the pH to 5 ~ 10 of waste water,
Water-soluble calcium containing compound, inorganic flocculating agent and organic flocculant are added into the waste water after adjusting pH and carries out flocculation reaction, makes
Fluoride waste energy per volume density in the front half section hydraulic detention time of flocculation basin is 8 ~ 10W/m3, and second half section waterpower is stopped
Staying energy per volume density in the time is 1 ~ 4W/m3；Wherein, calcium ion and fluoride waste in the water-soluble calcium containing compound
The molar ratio of middle fluorine ion is 1:2 ~ 10；The mass volume ratio of the inorganic flocculating agent, organic flocculant and fluoride waste be 5 ~
The mg:1L of 50 mg:1 ~ 20；
5) waste water after step 4) flocculation reaction is introduced into sedimentation basin, removes the suspension colloid formed in coagulating sedimentation in water removal
Clear liquid is collected and be discharged to body particle, completes the fluorine removal processing of fluoride waste.
Fluoride waste is handled using such method, when handling fluoride waste, waste water is introduced first first
Order reaction area, pH adjusting agent and precipitating reagent are added into waste water, and the energy density of setting unit volume fluoride waste is 10 ~ 20
W/m3 enables waste water to mix well in first area's reaction tank, and initial flocculation reaction occurs, after the processing of first order reaction zone
Water flow into second level reaction zone in, since flocculation reaction can reduce the basicity of water body and make under the precipitating agent content in water body
Drop, in order to guarantee that flocculation precipitation reaction is complete, pH adjusting agent and precipitating reagent are continuously added into waste water, are being suitble to the pH of waste water
In the range of fluorine ion flocculation sedimentation, and the precipitating reagent for being sufficient to fluorine ions in water body content flocculation sedimentation is added, setting is single
The energy density of position volume fluoride waste is 7 ~ 17 W/m3, extends waste water hydraulic detention time in the reaction zone of the second level, fills
Distribute raw flocculation precipitation reaction, treated for the second level, and waste water flows into third level reaction zone, pH adjusting agent and precipitating reagent are added,
It is 4 ~ 14 W/m3 that energy density of the fluoride waste in third level reaction tank, which is arranged, on the one hand makes waste water in third level reaction tank
In the water conservancy residence time more extend, be further ensured that the flocculation time of fluorinion in waste water is sufficient, can be as much as possible
Flocculate precipitating is formed, on the other hand since preceding two-stage reaction has generated partial flocculation object, setting waste water is anti-in the third level
It answers the motive force in area small, can be more advantageous to post precipitation to avoid the flocculation sedimentation Particle Breakage formed and remove flocculate；
Flocculation zone is flowed by the waste water of third order reaction, addition pH adjusting agent, precipitating reagent and flocculant, the flocculant of addition can be more
Fluorine ion flocculation sedimentation is further assisted, fluoride waste unit volume energy in the front half section hydraulic detention time of flocculation basin is set
Metric density is 8 ~ 10W/m3, and energy per volume density is 1 ~ 4W/m3 in second half section hydraulic detention time, and fluoride waste is made to wad a quilt with cotton
It can sufficiently be reacted with precipitating reagent and flocculant in the front half section hydraulic detention time in solidifying pond, keep the fluorine ion in waste water further
Removal, and the decrease of power density in second half section hydraulic detention time, the flocculate that effective protection is formed, which is not vortexed, to be crushed,
And then flocculate is easy to precipitate in later period precipitation process, the substance without will become tiny remains in water outlet, passes through
Water after flocculation is passed through in sedimentation basin, is precipitated coagulated particles in sedimentation basin and is removed, the clear liquid after exit discharge precipitating,
Complete fluorine removal flocculation precipitation reaction.
Further, the first order precipitation reaction, second level precipitation reaction, third level precipitation reaction of the fluoride waste are controlled
Total hrt with flocculation reaction is 1 ~ 10h.The third-order reaction and flocculation time for controlling fluoride waste are in this way, can make
Fluoride waste mixing is more uniform, more abundant with reacting for precipitating reagent, and then is more applicable for high fluorinion concentration waste water
Processing, the fluorinion in waste water concentration that makes that treated obtain excellent defluorination effect down to 7 mg/L.
Further, first order precipitation reaction pond, second level precipitation reaction pond and third level precipitation reaction pond are reciprocal
Baffled reflection chamber.Using such reciprocating partition plate reaction tank, the mixing of waste water can be made more uniform, make the fluorine in water body
Ion can more sufficiently react generation flocculate with precipitating reagent, keep coagulation effect more preferable.
Further, the flocculation basin is folded plate type reaction tank.Flocculation zone reacts pool structure using folded plate, increases flow-disturbing list
Member reaches turbulent condition required for flocculation, can effectively be sufficiently mixed to fluoride waste, improve the removal of fluorine ion
Effect.
Further, the water-soluble calcium containing compound includes at least one of calcium hydroxide, calcium oxide and calcium chloride.It adopts
It uses such calcium containing compound as precipitating reagent, will not will not be brought to great variety is brought to the pH value etc. of waste water to be processed
Negative effect, and be easier to generate infusible precipitate compound calcirm-fluoride with calcium ion, it is more advantageous to the removal of fluorine ion.
Further, the inorganic flocculating agent includes aluminium polychloride, poly-ferric chloride, bodied ferric sulfate, polyaluminum sulfate
At least one of aluminium, polymeric aluminum sulfate iron, polymeric aluminium ferrum silicate, polyferric silicate sulfate, polyaluminum ferric chloride and polyphosphate iron sulfate.
Such inorganic coagulant is selected, dosage is few compared with other inorganic coagulants, and SO is not introduced in processed waste water4 2-And Cl-
Plasma will not introduce the new pollutant such as iron and aluminium in residue, and treatment effect is more preferable, and the feature of environmental protection is good.
As optimization, the organic flocculant include non-ionic polyacrylamide, anion-polyacrylamide, sun from
At least one of sub- polyacrylamide, amphoteric polyacrylamide and chitosan flocculant.Such organic flocculant is selected,
It is small compared to other flocculant dosages, form that wadding body is fast, wadding body volume is big, and precipitate rapidly, therefore required sedimentation basin is small, investment
It saves, operating cost is low.
As optimization, the fluoride waste is the fluorine-containing pickling waste waters of height that photovoltaic enterprise produces that solar panel generates.
The defluorination method of the prior art can not be suitable for fluorinated volume height, and the biggish photovoltaic enterprise production solar panel of water generates
High fluorine-containing pickling wastewater treatment, and the method that defluorination method of the present invention is combined by three-level precipitation reaction and flocculation reaction, more
Add and be suitable for such fluoride wastewater treatment, overcomes art methods to the fluorine-containing pickling water treatment effect of such height not
Good technological deficiency.
As optimization, the concentration of fluorine ion is 1500 ~ 34000 mg/L, pH value≤4 in the fluoride waste.The present invention couple
The fluoride wastewater treatment better effect of levels and pH content in this way, the fluorinated volume being discharged after processing are obtained down to 7 mg/L
Unexpected technical effect.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention uses three-level precipitation reaction process, plays mixing and buffer function to fluoride waste, different anti-
It answers and all adjusts pH and addition precipitating reagent in area, so that fluoride waste and flocculant mixture can obtain most preferably in each reaction zone
Flocculation precipitation reaction condition, and then so that fluorine ion is more flocculated and precipitate, the present invention is also comprehensive
Influence of the hydraulics to flocculation reaction is considered, adjusts different energy densities in each precipitation reaction area, in leading portion processing
Middle increase energy density keeps fluoride waste mixing more uniform, and the flow-disturbing of generation enables fluorine ion can be more with precipitating reagent
Haptoreaction, on the one hand the decrease of power density step by step in back segment treatment process extends hydraulic detention time, makes flocculation sedimentation
The time of reaction and reaction are more abundant, and another invention declines flow rate of water flow, can be broken to avoid the flocculate generated,
Facilitate it is subsequent carry out precipitating removal flocculate processing, without containing tiny colloid flocculate, fluorine removal effect in the water outlet that makes that treated
Fruit is more excellent.
2, third-order reaction pond is set reciprocating baffled reflection chamber by the present invention, has fully ensured that fluoride waste and precipitating
Agent is sufficiently mixed, and increases flow-disturbing unit, promotes reaction more abundant, so that subsequent operation program is stablized effectively, is used
Folded plate type reaction tank has reached turbulent condition required for flocculation as flocculation basin, effectively carries out to fluoride waste sufficiently mixed
It closes, while coagulated particles generate disrepair phenomenon during flow-disturbing in order to prevent, and flocculant is also added in flocculation basin, to add
By force to the flocculation sedimentation of crushed particles, make to be substantially free of tiny colloidal solid in subsequent water outlet, treatment effect is more excellent.
3, drug used in the method for the present invention be it is conventional be easy to get, cheap test article, and in treatment process
Parameter is easy to be controlled, and operates simpler convenience, has good market promotion prospect.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.The implementation case is being with the technology of the present invention
Under the premise of implemented, now provide detailed embodiment and specific operating process illustrate the present invention it is creative, but
Protection scope of the present invention embodiment not limited to the following.
Embodiment 1
The concentration that certain photovoltaic enterprise produces the fluorine-containing pickling fluorinion in waste water of height that solar panel generates is 1500mg/
L, pH value 1.Fluoride waste is introduced into first order precipitation reaction pond, the pH to 9 of waste water is adjusted, into the waste water after adjusting pH
Calcium chloride is added, makes 10 W/m3 of energy density of unit volume fluoride waste, starts to carry out first order precipitation reaction；Wherein,
The molar ratio of calcium ion and fluorine ion in fluoride waste is 1:2 in calcium chloride；Fluoride waste after first order precipitation reaction
It is introduced into the precipitation reaction pond of the second level, adjusts the pH to 5 of waste water, calcium hydroxide is added into the waste water after adjusting pH, makes unit
The energy density of volume fluoride waste is 7 W/m3, starts to carry out second level precipitation reaction；Wherein, in calcium hydroxide calcium ion with
The molar ratio of fluorine ion is 1:2 in fluoride waste；It is anti-that fluoride waste after the precipitation reaction of the second level introduces third level precipitating
Ying Chizhong adjusts the pH to 10 of waste water, and calcium chloride is added into the waste water after adjusting pH, makes the energy of unit volume fluoride waste
Density is 4 W/m3, starts to carry out third level precipitation reaction；Wherein, calcium ion rubs with fluorine ion in fluoride waste in calcium chloride
You are than being 1:2；Fluoride waste after third level precipitation reaction is introduced into flocculation basin, adjusts the pH to 5 of waste water, to after adjusting pH
Calcium chloride, poly-ferric chloride and chitosan flocculant are added in waste water and carries out flocculation reaction, makes fluoride waste before flocculation basin
Energy per volume density is 8W/m3 in half section of hydraulic detention time, and energy per volume is close in second half section hydraulic detention time
Degree is 1W/m3；Wherein, the molar ratio of calcium ion and fluorine ion in fluoride waste is 1:2 in calcium chloride；Poly-ferric chloride, shell are poly-
The mass volume ratio of sugared flocculant and fluoride waste is 5 mg:1 mg:1L；Waste water after flocculation reaction is introduced into sedimentation basin, is gone
The suspension colloid particle formed in coagulating sedimentation in water removal, collects and is discharged clear liquid, completes the fluorine removal processing of fluoride waste, water outlet
Fluorinion concentration is 7mg/L.
Embodiment 2
The concentration for the fluorine-containing pickling fluorinion in waste water of height that certain photovoltaic enterprise production solar panel generates is
34000mg/L, pH value 2.Fluoride waste is introduced into first order precipitation reaction pond, the pH to 10 of waste water is adjusted, to adjusting pH
Calcium chloride is added in waste water afterwards, makes 20 W/m3 of energy density of unit volume fluoride waste, starts to carry out first order precipitating
Reaction；Wherein, the molar ratio of calcium ion and fluorine ion in fluoride waste is 1:10 in calcium chloride；By first order precipitation reaction
Fluoride waste afterwards is introduced into the precipitation reaction pond of the second level, adjusts the pH to 12 of waste water, and hydrogen is added into the waste water after adjusting pH
Calcium oxide makes 17 W/m3 of energy density of unit volume fluoride waste, starts to carry out second level precipitation reaction；Wherein, hydrogen-oxygen
Changing the molar ratio of calcium ion and fluorine ion in fluoride waste in calcium is 1:10；Fluoride waste after the precipitation reaction of the second level
It is introduced into third level precipitation reaction pond, adjusts the pH to 12 of waste water, calcium hydroxide is added into the waste water after adjusting pH, makes unit
The energy density of volume fluoride waste is 14 W/m3, starts to carry out third level precipitation reaction；Wherein, in calcium chloride calcium ion with
The molar ratio of fluorine ion is 1:10 in fluoride waste；Fluoride waste after third level precipitation reaction is introduced into flocculation basin, is adjusted useless
The pH to 10 of water is added calcium chloride, bodied ferric sulfate and cationic polyacrylamide into the waste water after adjusting pH and flocculates
Reaction, makes fluoride waste energy per volume density 10W/m3, second half section in the front half section hydraulic detention time of flocculation basin
Energy per volume density is 4W/m3 in hydraulic detention time；Wherein, calcium ion and fluorine ion in fluoride waste in calcium chloride
Molar ratio is 1:10；The mass volume ratio of bodied ferric sulfate, cationic polyacrylamide and fluoride waste is 50 mg:20
Mg:1L；Waste water after flocculation reaction is introduced into sedimentation basin, removes the suspension colloid particle formed in coagulating sedimentation in water removal, is collected
And clear liquid is discharged, the fluorine removal processing of fluoride waste is completed, water outlet fluorinion concentration is 8mg/L.
Embodiment 3
The concentration for the fluorine-containing pickling fluorinion in waste water of height that certain photovoltaic enterprise production solar panel generates is
24000mg/L, pH value 3.Fluoride waste is introduced into first order precipitation reaction pond, the pH to 10 of waste water is adjusted, to adjusting pH
Calcium chloride is added in waste water afterwards, makes 15 W/m3 of energy density of unit volume fluoride waste, starts to carry out first order precipitating
Reaction；Wherein, the molar ratio of calcium ion and fluorine ion in fluoride waste is 1:8 in calcium chloride；After first order precipitation reaction
Fluoride waste be introduced into the precipitation reaction pond of the second level, adjust the pH to 11 of waste water, to adjust pH after waste water in hydrogen-oxygen is added
Change calcium, make 15 W/m3 of energy density of unit volume fluoride waste, starts to carry out second level precipitation reaction；Wherein, calcium chloride
The molar ratio of fluorine ion is 1:6 in middle calcium ion and fluoride waste；Fluoride waste after the precipitation reaction of the second level introduces the
In three-level precipitation reaction pond, the pH to 12 of waste water is adjusted, calcium hydroxide is added into the waste water after adjusting pH, contains unit volume
The energy density of fluorine waste water is 6 W/m3, starts to carry out third level precipitation reaction；Wherein, calcium ion gives up with fluorine-containing in calcium hydroxide
The molar ratio of fluorine ion is 1:7 in water；Fluoride waste after third level precipitation reaction is introduced into flocculation basin, adjust the pH of waste water to
7, calcium chloride, polymeric aluminum sulfate iron and anionic polyacrylamide is added into the waste water after adjusting pH and carries out flocculation reaction, makes
Fluoride waste energy per volume density in the front half section hydraulic detention time of flocculation basin is 9 W/m3, second half section hydraulic retention
Energy per volume density is 2 W/m3 in time；Wherein, in calcium chloride in calcium ion and fluoride waste fluorine ion molar ratio
For 1:2 ~ 10；The mass volume ratio of polymeric aluminum sulfate iron, anionic polyacrylamide and fluoride waste is 5 ~ 50 mg:1 ~ 20
Mg:1L；Waste water after flocculation reaction is introduced into sedimentation basin, removes the suspension colloid particle formed in coagulating sedimentation in water removal, is collected
And clear liquid is discharged, the fluorine removal processing of fluoride waste is completed, water outlet fluorinion concentration is 7 mg/L.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (6)
1. a kind of fluorine removal flocculation reaction method of fluoride waste, which comprises the steps of:
1) content of fluoride ion in fluoride waste is measured, fluoride waste is introduced into first order precipitation reaction pond, waste water is adjusted
Water-soluble calcium containing compound is added into the waste water after adjusting pH, makes the energy density of unit volume fluoride waste by pH to 5 ~ 12
For 10 ~ 20 W/m3, start to carry out first order precipitation reaction；Wherein, calcium ion gives up with fluorine-containing in the water-soluble calcium containing compound
The molar ratio of fluorine ion is 1:2 ~ 10 in water；
2) fluoride waste of the step 1) after first order precipitation reaction is introduced into the precipitation reaction pond of the second level, adjusts waste water
Water-soluble calcium containing compound is added into the waste water after adjusting pH, makes the energy density of unit volume fluoride waste by pH to 5 ~ 12
For 7 ~ 17 W/m3, start to carry out second level precipitation reaction；Wherein, calcium ion gives up with fluorine-containing in the water-soluble calcium containing compound
The molar ratio of fluorine ion is 1:2 ~ 10 in water；
3) fluoride waste of the step 2 after the precipitation reaction of the second level is introduced into third level precipitation reaction pond, adjusts waste water
Water-soluble calcium containing compound is added into the waste water after adjusting pH, makes the energy density of unit volume fluoride waste by pH to 5 ~ 12
For 4 ~ 14 W/m3, start to carry out third level precipitation reaction；Wherein, calcium ion gives up with fluorine-containing in the water-soluble calcium containing compound
The molar ratio of fluorine ion is 1:2 ~ 10 in water；
4) fluoride waste after step 3) third level precipitation reaction is introduced into flocculation basin, the pH to 5 ~ 10 of waste water is adjusted, to tune
Water-soluble calcium containing compound, inorganic flocculating agent and organic flocculant are added in waste water after saving pH and carries out flocculation reaction, makes fluorine-containing
Waste water energy per volume density in the front half section hydraulic detention time of flocculation basin is 8 ~ 10W/m3, when second half section hydraulic retention
Interior energy per volume density is 1 ~ 4W/m3；Wherein, calcium ion and fluorine in fluoride waste in the water-soluble calcium containing compound
The molar ratio of ion is 1:2 ~ 10；The mass volume ratio of the inorganic flocculating agent, organic flocculant and fluoride waste is 5 ~ 50
The mg:1L of mg:1 ~ 20；
5) waste water after step 4) flocculation reaction is introduced into sedimentation basin, removes the suspension colloid formed in coagulating sedimentation in water removal
Grain, collects and is discharged clear liquid, completes the fluorine removal processing of fluoride waste；
First order precipitation reaction pond, second level precipitation reaction pond and third level precipitation reaction pond are the reaction of reciprocal iris type
Pond；The flocculation basin is folded plate type reaction tank；Control the first order precipitation reaction of the fluoride waste, second level precipitation reaction,
The total hrt of third level precipitation reaction and flocculation reaction is 1 ~ 10h.
2. the fluorine removal flocculation reaction method of fluoride waste according to claim 1, which is characterized in that described water-soluble containing calcification
Closing object includes at least one of calcium hydroxide, calcium oxide and calcium chloride.
3. the fluorine removal flocculation reaction method of fluoride waste according to claim 1, which is characterized in that the inorganic flocculating agent packet
Include aluminium polychloride, poly-ferric chloride, bodied ferric sulfate, polyaluminium sulfate, polymeric aluminum sulfate iron, polymeric aluminium ferrum silicate, polymerization
At least one of ferrosilite, polyaluminum ferric chloride and polyphosphate iron sulfate.
4. the fluorine removal flocculation reaction method of fluoride waste according to claim 1, which is characterized in that the organic flocculant packet
Include non-ionic polyacrylamide, anion-polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide and shell
At least one of chitosan flocculant.
5. the fluorine removal flocculation reaction method of fluoride waste according to claim 1, which is characterized in that the fluoride waste is light
Lie prostrate the fluorine-containing pickling waste waters of height that enterprise's production solar panel generates.
6. the fluorine removal flocculation reaction method of fluoride waste according to claim 1, which is characterized in that fluorine in the fluoride waste
The concentration of ion is 1500 ~ 34000 mg/L, pH value≤4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610492278.4A CN105967294B (en) | 2016-06-29 | 2016-06-29 | Defluorination flocculation reaction method for fluorine-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610492278.4A CN105967294B (en) | 2016-06-29 | 2016-06-29 | Defluorination flocculation reaction method for fluorine-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105967294A CN105967294A (en) | 2016-09-28 |
| CN105967294B true CN105967294B (en) | 2019-05-28 |
Family
ID=57019493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610492278.4A Active CN105967294B (en) | 2016-06-29 | 2016-06-29 | Defluorination flocculation reaction method for fluorine-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105967294B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106746088A (en) * | 2016-12-23 | 2017-05-31 | 程艳青 | A kind of processing system and handling process of fluorine-containing trade effluent |
| CN108217894A (en) * | 2017-12-13 | 2018-06-29 | 赛恩斯环保股份有限公司 | A kind of preparation method and application of efficient defluorinate ferro-aluminum complex reagent |
| CN108911091A (en) * | 2018-07-24 | 2018-11-30 | 湖北蓝钴环保科技有限公司 | A kind of compound defluorinating agent and preparation method thereof |
| CN109160631A (en) * | 2018-09-12 | 2019-01-08 | 苏州依斯倍环保装备科技有限公司 | A kind of system and technique of advanced treating fluoride ion waste water |
| CN109502813A (en) * | 2018-12-09 | 2019-03-22 | 湖南涌鑫源环保有限公司 | A kind of processing of cathode carbon pieces waste water and recyclable device |
| CN109879550B (en) * | 2019-04-08 | 2023-11-21 | 重庆港力环保股份有限公司 | Photovoltaic cell production wastewater purification system |
| CN110040878B (en) * | 2019-05-14 | 2021-10-26 | 山东环瑞生态科技有限公司 | Advanced treatment method for fluorine-containing wastewater |
| CN110240253B (en) * | 2019-07-23 | 2021-11-02 | 大连民族大学 | Method for treating refined cotton black liquor by using residual alkali waste heat |
| CN110304765A (en) * | 2019-07-25 | 2019-10-08 | 鞍钢贝克吉利尼水处理有限公司 | Rapid subsidence defluorinating agent and the preparation, application method of fluorine-containing turbid circulating water are made steel in processing |
| CN110697928A (en) * | 2019-09-11 | 2020-01-17 | 山西晋城无烟煤矿业集团有限责任公司 | Fluorine removal system and method for high-fluorine wastewater |
| CN112897668B (en) * | 2019-12-03 | 2023-04-14 | 苏州天瑞环境科技有限公司 | Defluorination medicament and preparation method and application thereof |
| CN111533318A (en) * | 2020-05-19 | 2020-08-14 | 苏州钢特威钢管有限公司 | Method for treating fluoride-containing pickling passivation wastewater in stainless steel production |
| CN113087040B (en) * | 2021-04-20 | 2022-10-14 | 山西国际电力技术咨询有限公司 | Novel defluorinating agent and fluorine-containing waste liquid treatment process |
| CN114644414A (en) * | 2022-03-23 | 2022-06-21 | 山东兖矿国际焦化有限公司 | First-stage defluorination agent regulation and control method |
| CN115626698A (en) * | 2022-11-16 | 2023-01-20 | 中科润蓝环保技术(北京)股份有限公司 | Drinking water defluorinating agent and preparation and application methods thereof |
| CN116282435B (en) * | 2023-04-10 | 2024-06-28 | 济南大学 | Coagulation cooperative adsorption precipitation method for synchronously reducing turbidity and middle-low concentration fluorine by inorganic fluorine removal and turbidity removal agent |
| CN117023750B (en) * | 2023-10-09 | 2024-01-23 | 杭州尚善若水环保科技有限公司 | Treatment method of fluorine-containing wastewater |
| CN117069226A (en) * | 2023-10-18 | 2023-11-17 | 山东九龙清江净水科技有限公司 | Preparation method of pH-controllable fluorine removal agent and application of pH-controllable fluorine removal agent in fluorine-containing sewage treatment |
| CN117509810B (en) * | 2024-01-05 | 2024-03-22 | 深圳市盘古环保科技有限公司 | Efficient reaction industrial wastewater defluorination treatment method and equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062817A (en) * | 2006-04-30 | 2007-10-31 | 深圳市金达莱环保股份有限公司 | Method for removing fluorinion in waste water |
| CN103991984A (en) * | 2014-05-28 | 2014-08-20 | 合肥海润光伏科技有限公司 | Fluoride-contained wastewater treatment method and device |
| CN104496063A (en) * | 2014-11-17 | 2015-04-08 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for removing fluorine in wastewater |
-
2016
- 2016-06-29 CN CN201610492278.4A patent/CN105967294B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062817A (en) * | 2006-04-30 | 2007-10-31 | 深圳市金达莱环保股份有限公司 | Method for removing fluorinion in waste water |
| CN103991984A (en) * | 2014-05-28 | 2014-08-20 | 合肥海润光伏科技有限公司 | Fluoride-contained wastewater treatment method and device |
| CN104496063A (en) * | 2014-11-17 | 2015-04-08 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method for removing fluorine in wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105967294A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105967294B (en) | Defluorination flocculation reaction method for fluorine-containing wastewater | |
| CN105800820B (en) | A kind of method and apparatus of silicon-containing wastewater processing | |
| CN105060545B (en) | A kind of system and method for sofening treatment Desulphurization for Coal-fired Power Plant waste water | |
| CN106145451A (en) | A kind of processing method of waste water containing thallium | |
| CN111892142A (en) | Silicon removal agent, silicon removal and hardness removal sewage treatment system and method | |
| CN212450783U (en) | Sewage treatment system for removing silicon and hardness | |
| CN107162253A (en) | A kind of processing method of fluoride waste | |
| CN104150639A (en) | Treatment method of limestone-gypsum wet flue gas desulfurization waste water of steel sintering machine | |
| CN105502765A (en) | System and method for treating desulfurization wastewater and recycling resources cooperatively | |
| CN110342740A (en) | The purification method and purification system of salt-containing organic wastewater | |
| CN207361950U (en) | The special purpose device of coal chemical industry strong brine silicon removing process | |
| CN108383269A (en) | A kind of combination treatment method of HEDP copper plating wastewaters | |
| CN103723813B (en) | A kind of MAP precipitates the method for the recycle system and Ammonia-Containing Wastewater Treatment | |
| CN106746088A (en) | A kind of processing system and handling process of fluorine-containing trade effluent | |
| CN114275961A (en) | Concentrated decrement system of strong brine | |
| CN102976537A (en) | Comprehensive physical and chemical treatment device and method of organic silicon wastewater | |
| CN207121501U (en) | A kind of hardness removing device suitable for the hard waste water of high magnesium | |
| CN101708927B (en) | Method for deeply processing waste water from paper making | |
| CN108017196B (en) | A kind of wastewater deep treatment process of acid out oxidizing, flocculating precipitating | |
| CN215975294U (en) | Processing apparatus of concentrated water and sodium chloride evaporation mother liquor receive filtering | |
| CN115716689A (en) | Wastewater recycling method combining ultrafiltration system and bipolar membrane electrodialysis system | |
| CN212403800U (en) | Coal fired power plant desulfurization waste water integrated processing system | |
| CN211871618U (en) | Device for treating desulfurization wastewater by composite method | |
| CN113003800A (en) | Wastewater quality-based treatment process | |
| CN109879379A (en) | A kind of three-stage electricity Fenton reduces the system and method for waste water COD |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |