CN101492192B - Coagulating agent for treating wastewater containing fluorine and use process thereof - Google Patents
Coagulating agent for treating wastewater containing fluorine and use process thereof Download PDFInfo
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- CN101492192B CN101492192B CN2009100959794A CN200910095979A CN101492192B CN 101492192 B CN101492192 B CN 101492192B CN 2009100959794 A CN2009100959794 A CN 2009100959794A CN 200910095979 A CN200910095979 A CN 200910095979A CN 101492192 B CN101492192 B CN 101492192B
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- coagulating agent
- fluoride waste
- containing fluorine
- wastewater containing
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- 239000000701 coagulant Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 13
- 239000011737 fluorine Substances 0.000 title abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 23
- 239000002351 wastewater Substances 0.000 title abstract description 21
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 10
- 238000005345 coagulation Methods 0.000 claims abstract description 13
- 230000015271 coagulation Effects 0.000 claims abstract description 13
- 239000006259 organic additive Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 6
- 238000005576 amination reaction Methods 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 39
- 239000002699 waste material Substances 0.000 claims description 36
- 238000012545 processing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 238000011282 treatment Methods 0.000 abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004411 aluminium Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 2
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000004571 lime Substances 0.000 abstract description 2
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 159000000007 calcium salts Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 4
- 238000006115 defluorination reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- -1 Tai-Ace S 150 Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002894 chemical waste Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 208000035719 Maculopathy Diseases 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 206010033892 Paraplegia Diseases 0.000 description 1
- 206010061363 Skeletal injury Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 208000002780 macular degeneration Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a coagulating agent for use in the treatment of wastewater containing fluorine and an application process thereof. The coagulating agent for use in the treatment of water containing fluorine is a composite coagulating agent prepared by adding a polymer organic additive during the synthesis of aluminium polychlorid; the polymer organic additive is a cationic polyacrylamide having a 10 to 30 percent amination degree and a 5 to 8 million molecular weight; and the mass of the added polymer organic additive is 1 to 10 percent of that of AlCl3.H20. The application process comprises: adding a modifier of lime milk into the wastewater containing fluorine to adjust the pH value of the wastewater containing fluorine to between 6 and 9; and adding the coagulating agent for use in the treatment of wastewater containing fluorine into the wastewater containing fluorine for coagulation in an amount of 900 to 1,500 milligrams of coagulating agent for use in the treatment of wastewater containing fluorine per liter of wastewater containing fluorine. The coagulating agent for use in the treatment of wastewater containing fluorine is low in raw material price and production cost, and the application process is simple, high in removal efficiency and low in investment cost and has the advantages of high efficiency and economy.
Description
(1) technical field
The invention belongs to water-treatment technology field, relate to a kind of fluoride waste and handle with coagulating agent and application art thereof.
(2) background technology:
Fluorochemical (F
-) be one of trace element of needed by human, fluorine content is too high or too low all unfavorable to HUMAN HEALTH, and the fluorine content suitable concentration of tap water is 0.5～1.0mg/L.When tap water lacks fluorine, then easily suffer from dental caries, but, gently then can cause illnesss such as maculopathy, renal tubal dysfunction when if the long-term drinking fluorine content is higher than the water of 1.0mg/L, heavy then cause skeletal injury and even paraplegia, promptly so-called osteofluorosis.In environment, fluorochemical can also be accumulated in vivo and shifts by food chain, and the whole ecological environment is impacted.Many industry all may be discharged fluoride waste as fluorine-containing ore extraction, Metal smelting, aluminum profile extrusion, coke, glass etc., cause environmental fluoride pollution.So the technical study that fluorine falls in defluorination has just become the important directions of domestic and international chemical industry, environmental protection and health field.
Over nearly two, 30 years, number of research projects has been carried out in the processing of fluorinated water both at home and abroad, lowering fluorine and removing fluorine technology and relevant fundamental research have also been had some progress.At present, the defluorination reducing fluoride method of fluorinated water mainly contains absorption method, electrocoagulation, reverse osmosis method, ion exchange method, chemical precipitation method and coagulation sedimentation etc.In these methods, ion exchange method expense height, and strict to waste water quality; Electrocoagulation and reverse osmosis method device complexity, current consumption is big, thereby all seldom adopts.What often adopt in the reality is absorption method, chemical precipitation method and coagulation sedimentation.The water yield that absorption method is handled is very limited, only is suitable for handling the less occasion of the water yield, and as the lowering fluorine and removing fluorine processing of tap water etc., Industrial Wastewater Treatment feasibility very big for the water yield or that fluorine content is higher is little.Chemical precipitation method is suitable for the processing of high-concentration industrial fluoride waste, generally adopts calcium salt precipitation method, promptly adds soluble calcium salt in waste water, makes F
-And Ca
2+Generate CaF
2The precipitation and remove.The calcium salt that adds mainly contains lime, calcium sulfate and calcium chloride.Because Ca
2+And F
-Generate CaF
2This speed of response is slower, and reaching balance needs long time, the fine CaF of Sheng Chenging simultaneously
2Crystal grain is colloidal attitude, is difficult for from liquid phase, separating out, and the new CaF that forms
2Fine-grain itself has certain solubleness, thereby when adopting calcium salt precipitation method purely, required calcium salt dosage can be very high, the calcium salt that generally adds is more than two times of chemical requirement, and the treatment time is long, and the fluorinion concentration of water outlet generally between 20～50mg/L, still is higher than country and allows emission standard 10mg/L, and the suspension content in the water is higher, still needs and further handles.Compare with calcium salt precipitation method, coagulation sedimentation is handled industrial fluoride waste, and it is few to have an added amount of chemical, the processing water yield is big, and cost is low, and water outlet can reach country's permission emission standard after the primary treatment, and can remove advantages such as other pollutent simultaneously, day by day extensive in industrial application.
According to our practical work experience, be the trade effluent of 20～50mg/L to fluorine content, in the two big class inorganic coagulant molysite and aluminium salt commonly used, the fluoride removing rate of iron salt coagulant is relatively poor, and between 10～30%, and the aluminum salt fluoride removing rate can reach 50～80%.Molysite will reach the higher fluorine effect of going, and needs to cooperate Ca (OH)
2Under alkaline environment, use, with acid pH is transferred to neutrality again at last and could discharge complex process.Aluminium salt then can be under near the neutral condition defluorination, be the first-selected kind of defluorination coagulating agent.Aluminum salt such as Tai-Ace S 150, polymeric aluminum all has coagulation removal effect preferably to fluorion.After aluminium salt is added in the water, can pass through Al
3+With F
-The intermediate product and the last unformed Al (OH) that generates of complexing, aluminium salt hydrolysis
3(am) alumen ustum is to F
-Ligand exchange, absorption charge neutrality, the volume effect of sweeping etc. remove the fluorion in the water.When using Tai-Ace S 150, the best pH scope of coagulation is 6.4～7.2, but dosage is bigger, need add 150～1000g according to different situations water per ton, this can make contain in the water outlet a certain amount of to the deleterious dissolved aluminum of HUMAN HEALTH.When using polymeric aluminum, consumption can reduce about half, and the best pH range extension of coagulation is 5～8.
The poly-main form of aluminium in water is the hydroxyl aluminium cations of respectively birdsing of the same feather flock together with high electric charge, they have very strong absorption charge neutrality and compression double electric layer ability, can make that suspended particle effectively takes off surely in the water, but its hydrolytic polymerization long-chain is because of being subjected to the restriction of the inorganic polymer polymerization degree, removal to molecule lacks strong adsorption bridging effect, for organic polymer coargulator, this is the general weakness of inorganic coagulant.So we carry out modification to poly-aluminium product, introduce organic polymer coargulator in the polymerization engineering of poly-aluminium, discover the intervention of macromolecule organic flocculating agent by experiment, have strengthened the adsorption bridging ability of poly-aluminium to a certain extent, have improved the water treatment effect.
(3) summary of the invention:
The primary technical problem that the present invention will solve provides that a kind of cost of material is cheap, production cost is low, the fluoride waste of efficient economy is handled and used coagulating agent.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of fluoride waste is handled and use coagulating agent, and it is adding polymer organic additive and the compounding coagulation agent that makes in the building-up process of polymerize aluminum chloride that described fluoride waste is handled with coagulating agent; Polymer organic additive of the present invention is a cationic polyacrylamide, amination degree 10～30%, molecular weight 500～8,000,000.
Fluoride waste of the present invention is handled and specifically is prepared as follows with coagulating agent:
(1) with an amount of AlCl
3.6H
2O is dissolved in the hydrochloric acid soln of 0.03～0.05mol/L, is made into the AlCl of 70～300g/L
3Solution;
(2) under 70～80 ℃ of temperature of reaction and agitation condition, the AlCl that past step (1) obtains
3Add the polymer organic additive in the solution, the dosage of described polymer organic additive is AlCl
3.6H
21～10% of O quality stirs, and the dropping mass concentration is 5～10% Ca (OH)
2Emulsion makes Ca (OH)
2Add-on be AlCl
3.6H
21～5% of O quality makes the Al (H of generation
2O)
6 3+Hydrolytic polymerization gets described fluoride waste processing coagulating agent.
Further, in above-mentioned preparation technology, recommend control Ca (OH) in the described step (2)
2The dropping time of emulsion is at 0.5～2h.
Ca of the present invention (OH)
2Emulsion is Ca (OH)
2Emulsion with water formation.
Stirring velocity is recommended as 200～320r/min in the described step (2).
Second technical problem that the present invention will solve provided a kind of technology simple, remove the efficient height, above-mentioned fluoride waste that cost of investment is low is handled the application art with coagulating agent, concrete application art is as follows: add conditioning agent milk of lime earlier in fluoride waste, the pH that makes fluoride waste is between 6～9; Add described fluoride waste then and handle and use coagulating agent, make in the fluoride waste fluoride waste processing count 900～1500mg/L with its solid content, stirred 15～30 minutes, precipitate 1～2 hour with the final concentration of coagulating agent.
In the application art of the present invention, add conditioning agent milk of lime earlier in fluoride waste, this is owing to coming the unsettled reason of water water quality (particularly to come the F in the water
-), in order to improve the coagulating treatment benefit, before adding this compounding coagulation agent, add milk of lime, one can regulate water pH value to improve poly-aluminium processing power, two can with fluorion microcrystallite CaF
2, the volume that is beneficial to the coagulation flco is swept, net is caught.
Adopt above-mentioned application art, the main detection index in the pond water outlet of coagulating treatment stage precipitation all can qualified discharge.
The invention has the beneficial effects as follows:
A) fluoride waste for preparing of the present invention is handled and is used the compounding coagulation agent, the advantage of having gathered strong absorption charge neutrality, compression double electric layer and adsorption bridging through modification later on, cost of material is cheap simultaneously, production cost is low, can significantly reduce the medicament investment cost, be that a kind of efficient, economic fluoride waste is handled medicament.
B) application art of coagulating agent of the present invention, different with the composite treatment process of coagulation in the past, adding of different coagulated agents was not synchronous generally in the technology in the past, and coagulating agent of the present invention only need once add processing, and treatment time of water is short, technological operation is easy, removal efficient height, and, conditioning agent milk of lime in fluoride waste, added before the dosing coagulant, strengthen the effect that the flco volume is swept, net is caught again, improved the water treatment effect of coagulating agent to a greater extent.Adopt application art of the present invention simultaneously, treatment facility is little, thereby can reduce the facility investment expense.So the application art of coagulating agent of the present invention is a kind of efficient, economic waste water treatment process.
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
Embodiment 1: the preparation of coagulating agent
(1) with 20 gram AlCl
3.6H
20 (Zhejiang Jiande Jianye Organic Chemical Co.ltd's production) is dissolved in the hydrochloric acid soln of 0.05mol/L, is made into the AlCl of 130g/L
3Solution;
(2) under 70～80 ℃ of temperature of reaction and speed stirring with 250r/min, the AlCl that past step (1) obtains
3Add 1 gram cationic polyacrylamide (Renqiu City sky profit chemical industry company limited, effective constituent＞88%) in the solution, stir, in 1.5h, drip 10%Ca (OH)
28 milliliters of emulsions make Al (H
2O)
6 3+Hydrolytic polymerization gets described fluoride waste processing coagulating agent.
Embodiment 2: the preparation of coagulating agent
(1) with 10 kilograms of AlCl
3.6H
2O (Zhejiang Jiande Jianye Organic Chemical Co.ltd's production) is dissolved in the hydrochloric acid soln of 0.03mol/L, is made into the AlCl of 150g/L
3Solution;
(2) under 70～80 ℃ of temperature of reaction and speed stirring with 250r/min, the AlCl that past step (1) obtains
3Add 400 gram cationic polyacrylamides (Renqiu City sky profit chemical industry company limited, effective constituent＞88%) in the solution, stir, in 2h, drip 6%Ca (OH)
23 liters of emulsions make Al (H
2O)
6 3+Hydrolytic polymerization gets described fluoride waste processing coagulating agent.
Embodiment 3: the preparation of coagulating agent
(1) with 200 kilograms of AlCl
3.6H
2O (Zhejiang Jiande Jianye Organic Chemical Co.ltd's production) is dissolved in the hydrochloric acid soln of 0.04mol/L, is made into the AlCl of 200g/L
3Solution;
(2) under 70～80 ℃ of temperature of reaction and speed stirring with 250r/min, the AlCl that past step (1) obtains
3Add 2.5 kilograms of cationic polyacrylamides (Renqiu City sky profit chemical industry company limited, effective constituent＞88%) in the solution, stir, in 2h, drip 8%Ca (OH)
230 liters of emulsions make Al (H
2O)
6 3+Hydrolytic polymerization gets described fluoride waste processing coagulating agent.
The coking chemical waste water of getting the coke-oven plant, Shanghai experimentizes, and the coking chemical waste water that enters this segment process contains COD
CrBe about 200～400mg/l, colourity 200-300 doubly about, F
-At 20～30mg/l, at present, according to " integrated wastewater discharge standard (GB8978-1996) ", these several leading indicators all can not qualified discharge.
Embodiment 4: the application of coagulating agent
(1) gets and contain COD
CrBe 205mg/l, colourity is 300, F
-Waste water for 23mg/l;
(2) in waste water, add synthetic milk of lime, make its pH about 6;
(3) add the coagulating agent that embodiment 1 makes, making its final concentration is 1000mg/L, and starting the agitator churning time is 20 minutes, precipitates 1.5 hours.
Detection method is to adopt " integrated wastewater discharge standard (GB8978-1996) "; COD measures and adopts potassium dichromate process; Determination of colority adopts platinum cobalt colorimetry; F
-Mensuration adopt the ion specific electrode method.
Water sample treatment effect such as following table to this coke-oven plant:
Embodiment 5: the application of coagulating agent
(1) gets and contain COD
CrBe 185mg/l, colourity is 230, F
-Waste water for 30mg/l;
(2) in waste water, add synthetic milk of lime, make its pH about 6;
(3) add the coagulating agent that embodiment 2 makes, making its ultimate density is 900mg/L, and starting the agitator churning time is 25 minutes, precipitates 1.5 hours.
Detection method is to adopt " integrated wastewater discharge standard (GB8978-1996) "; COD measures and adopts potassium dichromate process; Determination of colority adopts platinum cobalt colorimetry; F
-Mensuration adopt the ion specific electrode method.
Water sample treatment effect such as following table to this coke-oven plant:
Embodiment 6: the application of coagulating agent
(1) gets and contain COD
CrBe 247mg/l, colourity is 180, F
-Waste water for 25mg/l;
(2) in waste water, add synthetic milk of lime, make its pH about 8;
(3) add the coagulating agent that embodiment 3 makes, making its ultimate density is 1200mg/L, and starting the agitator churning time is 20 minutes, precipitates 1.5 hours.
Detection method is to adopt " integrated wastewater discharge standard (GB8978-1996) "; COD measures and adopts potassium dichromate process; Determination of colority adopts platinum cobalt colorimetry; F
-Mensuration adopt the ion specific electrode method.
Water sample treatment effect such as following table to this coke-oven plant:
From embodiment as seen, remove to handle fluoride waste with the prepared coagulating agent of the present invention, under normal operation, the main detection index in the pond water outlet of coagulating treatment stage precipitation all can qualified discharge.
Claims (4)
1. a fluoride waste is handled and use coagulating agent, it is characterized in that it is adding polymer organic additive and the compounding coagulation agent that makes in the building-up process of polymerize aluminum chloride that described fluoride waste is handled with coagulating agent; Described polymer organic additive is a cationic polyacrylamide, amination degree 10～30%, molecular weight 500～8,000,000; Described fluoride waste is handled and specifically is prepared as follows with coagulating agent:
(1) with AlCl
3.6H
2O is dissolved in the hydrochloric acid soln of 0.03～0.05mol/L, is made into the AlCl of 70～300g/L
3Solution;
(2) under 70～80 ℃ of temperature of reaction and agitation condition, the AlCl that past step (1) obtains
3Add the polymer organic additive in the solution, the dosage of described polymer organic additive is AlCl
3.6H
21～10% of O quality continues to stir, and the dropping mass concentration is 5～10% Ca (OH)
2Emulsion makes Ca (OH)
2Add-on be AlCl
3.6H
21～5% of O quality makes the Al (H of generation
2O)
6 3+Hydrolytic polymerization gets described fluoride waste processing coagulating agent.
2. fluoride waste as claimed in claim 1 is handled and is used coagulating agent, it is characterized in that the middle controlling quality concentration of described step (2) is 5～10% Ca (OH)
2The dropping time of emulsion is at 0.5～2h.
3. fluoride waste as claimed in claim 1 is handled and is used coagulating agent, it is characterized in that described step (2) stirring velocity is 200～320 rev/mins.
4. a fluoride waste as claimed in claim 1 is handled the application art of using coagulating agent, it is characterized in that described application art is: add conditioning agent milk of lime earlier in fluoride waste, the pH that makes fluoride waste is between 6～9; Add described fluoride waste then and handle and use coagulating agent, make in the fluoride waste fluoride waste processing count 900～1500mg/L with its solid content, stirred 15～30 minutes, precipitate 1～2 hour with the final concentration of coagulating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100959794A CN101492192B (en) | 2009-02-26 | 2009-02-26 | Coagulating agent for treating wastewater containing fluorine and use process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100959794A CN101492192B (en) | 2009-02-26 | 2009-02-26 | Coagulating agent for treating wastewater containing fluorine and use process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101492192A CN101492192A (en) | 2009-07-29 |
| CN101492192B true CN101492192B (en) | 2011-08-10 |
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ID=40923008
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|---|---|---|---|
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| CN101898233A (en) * | 2010-08-20 | 2010-12-01 | 秦皇岛首秦金属材料有限公司 | Method for reducing fluorine content of continuous casting secondary cooling water |
| CN102258985B (en) * | 2011-06-15 | 2012-11-28 | 郭家延 | Material for treating fluorine-containing drinking water, and preparation method thereof |
| CN107487826B (en) * | 2017-09-20 | 2020-10-20 | 北京美斯顿科技开发有限公司 | Composite coagulant for treating flue gas desulfurization waste liquid and preparation method and application thereof |
| CN110205442B (en) * | 2019-05-29 | 2021-06-29 | 广德林峰科技有限公司 | Preparation method of artificial fluorite ball |
| CN110526366A (en) * | 2019-07-27 | 2019-12-03 | 江苏长江水务股份有限公司 | The preparation method of the coagulant of fluoride in a kind of removal water body |
| CN111573806A (en) * | 2020-05-25 | 2020-08-25 | 神美科技有限公司 | Deep fluorine removal agent and preparation method and application thereof |
| CN112408652A (en) * | 2020-12-02 | 2021-02-26 | 辽宁博创环保技术有限公司 | A high-efficient reaction unit for fluoride waste water handles |
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