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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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.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN1266822A (en) * | 1999-03-12 | 2000-09-20 | 中国科学院生态环境研究中心 | Polyaluminium chloride and polyacrylamide compounded efficient flocculant and its preparing process |
| WO2003100169A1 (en) * | 2002-05-27 | 2003-12-04 | Green Technology Inc. | Process for preparing a dispersion polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1266822A (en) * | 1999-03-12 | 2000-09-20 | 中国科学院生态环境研究中心 | Polyaluminium chloride and polyacrylamide compounded efficient flocculant and its preparing process |
| WO2003100169A1 (en) * | 2002-05-27 | 2003-12-04 | Green Technology Inc. | Process for preparing a dispersion polymer |
| CN1850647A (en) * | 2005-04-22 | 2006-10-25 | 中国科学院生态环境研究中心 | Method for preparing composite coagulating agent for water supply reinforcing coagulating treatment |
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