CN101475250A - Method for removing fluorine in wastewater - Google Patents
Method for removing fluorine in wastewater Download PDFInfo
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- CN101475250A CN101475250A CNA2008100430127A CN200810043012A CN101475250A CN 101475250 A CN101475250 A CN 101475250A CN A2008100430127 A CNA2008100430127 A CN A2008100430127A CN 200810043012 A CN200810043012 A CN 200810043012A CN 101475250 A CN101475250 A CN 101475250A
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- slag
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- packings
- fluorine
- water
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Abstract
The invention provides a method for removing fluorine in wastewater. The method comprises the following steps: (1) sifting of steel slag; (2) filling of the sifted steel slag into a filling bed according to the combination of size of particle diameter; and (3) introduction of fluorine-containing wastewater to the bottom of the filling bed. The method removes the fluorine in the wastewater, reduces cost for wastewater treatment and achieves the aim of resource utilization of the steel slag.
Description
Technical field
The invention belongs to environment protection and resource utilization field, be specifically related to the second stage employ of wastewater treatment and slag, particularly the processing of fluoride waste.
Background technology
Fluorine is one of necessary trace element of human body, and the intake of adult's fluorochemical every day is generally 1.0-1.5mg.Some investigator thinks in the water fluoridize to reducing decayed tooth effectively, has advocated for many years fluoridize prevention children decayed tooth in the water in the U.S., but nearest enquiry data shows, the city of fluoridize in drinking-water, cancer mortality all more not the city of fluoridize be height.More data shows that the excessive absorption meeting of fluorine is unhealthful, even causes poisoning.Endemic fluorine poisoning is a kind of systemic disease, not only influence bone and tooth, form dental fluorosis, skeletal fluorosis, but also involve a plurality of systems such as comprising cardiovascular, nervus centralis, digestion, internal secretion, the visual organ, skin, China mainly with drinking water type fluorosis lesion distribute the widest, number of patients is maximum.The fundamental measure of prevention endemic fluorine poisoning is to reduce the intake of fluorine.It is principle that the drinking water type fluorosis is fallen fluorine with modify-water, uses the low fluorine water source instead, as quotes the surface water of river, river, reservoir, beats the deep-well of low fluorine and collection, deposit natural rainfall etc.; Prevent the fluorine health education simultaneously, change bad life habits, improve nutrition, build up health etc.In order to control the harm of excessive fluoride to HUMAN HEALTH, many countries fix on the fluorine content of drinking-water in the scope of 0.5-1.0mg/L.The current standards of China is: tap water is no more than 1.0mg/L; Maximum permissible concentration 0.02mg/m of atmosphere
3, per day maximum permissible concentration 0.007mg/m
3The emission concentration of fluorine is below the 10mg/L in the waste water.
Though the fluorine in the waste water can directly not impact HUMAN HEALTH, along with sewage emissions, the fluorine in the waste water can enter surface water and shallow ground water polluted drinking water source along with the flowing of water, infiltration and circulation, thus the health of indirect hazard human body.Along with the progress of expanding economy and society, citizen's sense of legal system and rights and interests consciousness constantly strengthen, and the Health hazard that fluoride pollution causes more and more is subjected to the extensive concern of society and the great attention of governmental environmental protection department.
The processing of fluorine can be adopted multiple technologies in the waste water, concludes method commonly used both at home and abroad and mainly is divided into two big classes: the heavy and shallow lake method of absorption method.Absorption method is to utilize fluorine to select sorbing material to remove by filter fluorochemical.Its mechanism is a kind of ion-exchange or absorption reaction, and the material of employing mainly comprises activated alumina, phosphorus containg substances, active zeolite sex change material, activated magnesia, ion exchange resin, granular activated charcoal and reverse osmosis membrane etc.It only is applicable to that usually fluorine content is low or through the advanced treatment of pre-treatment fluorine content at the fluorinated water of 15-30mg/L.The precipitator method mainly are to reach the purpose of removing fluorine by adding medicament in fluorinated water, form the fluorochemical precipitation or use various medicines to obtain flocculation sediment, fluorochemical co-precipitation on the throw out that generates, separating by solid.The medicament that the precipitator method adopt has lime, carbide slag, rhombspar, alum etc.The effective constituent of lime, carbide slag, rhombspar medicament is calcium, is used for precipitating into Calcium Fluoride (Fluorspan) with fluorine; The effective constituent of alum is aluminium, and effect is a flocculation sediment.
F can with many metals, as Ca
2+, Mg
2+, Pb
2+, Ba
2+Deng, generating the compound that is insoluble in water, the solubility product SP of several indissoluble fluorochemicals is as follows:
CaF
2：3.4×10
-11；MgF
2：7.7×10
-9
PbF
2：2.7×10
-6；BaF
2：1.05×10
-6
CaF wherein
2It is the compound that is insoluble in water most.Therefore, technology of Fluoride Removal mainly adopts calcium precipitation method and flocculation sediment synergy method at present.This class methods effect is obvious, but need add a large amount of medicaments, and the precipitation capacity of generation is big, no matter is that the cost or the sedimentary processing cost of medicament is all higher, has difficulties on the advanced treatment of fluoride waste in enormous quantities.
In iron and steel enterprise, the slag quantum of output is the second largest solid by-product that is only second to blast furnace slag.The crude steel output of China in 2006 is about 4.18 hundred million tons, and the slag quantity discharged accounts for 12%～15% of crude steel output, and in prediction on such basis, the year quantum of output of slag is at least 5,000 ten thousand tons.Up to the present, the best approach of slag second stage employ is as blast furnace, converter raw material, recycle voluntarily in Steel Plant, but utilization is limited; In addition, slag also can be used for road engineering, building materials raw material and fills out the hole and make ground etc.However, also have a large amount of bessemer furnace slags to fail in time to be handled and utilize.Along with finishing and the end of large-scale construction project of city fundamental construction, the problem of slag surplus will highlight, and slag if can be applied in the sewage disposal, both can realize the processing cost of the treatment of wastes with processes of wastes against one another, reduction sewage, can open up the new Application Areas of slag again, reduce the stacking amount of slag.
The main chemical compositions of slag has CaO, MgO, SiO
2, Al
2O
3And TFe (composition sees Table 1), water-soluble back alkalescence is very strong.And the fluorine in the processing waste water exactly needs effective constituents such as Ca, Mg, Al, Fe.The a large amount of calcium oxide that exist in the slag are the best medicaments that remove fluorine in the waste water, can react rapidly with fluorine to generate the Calcium Fluoride (Fluorspan) precipitation; In addition, magnesium in the slag, aluminium and iron is also constantly stripping in water, magnesium ion is easy to generate the magnesium fluoride precipitation with the fluorion reaction, aluminum ion is easy to the fluorion reacting generating complex, and iron ion is highly effective water treatment flocculant, can play the effect that Calcium Fluoride (Fluorspan), magnesium fluoride precipitation adsorption bridging and volume are swept, promote fluorion from waste water, to separate.Therefore, if slag is used for administering the fluorine of waste water, the effect of calcium oxide and magnesium, aluminium and ferrous components in the slag will be given full play to, both can reduce the processing cost of fluorine in the waste water, also can open up the frontier that the bessemer furnace slag resource utilization is used, can also solve the big problem of precipitation generation that causes greatly owing to added amount of chemical in traditional precipitator method simultaneously.
The chemical ingredients of table 1 slag (%)
Annotate: data are that the converter slag with Baosteel is an example.
Therefore, the object of the present invention is to provide a kind of novel method of utilizing slag to remove fluorine in the waste water.
Summary of the invention
The method of fluorine in the removal waste water provided by the invention, may further comprise the steps: sieve slag (1); (2) slag after will sieving is filled in the bed of packings by the size combination; And introduce fluoride waste (3) from the bed of packings bottom.
The step that slag is sieved comprises sieves into several groups of granular fillers that particle diameter is 1-2mm, 2-5mm and 5-10mm, 10-15mm and 15-20mm with slag.
Described screening can adopt sieve apparatus to carry out.
The filling system of slag is filled in the bed of packings by the size combination, can adopt two or more mechanical fraction, and the slag particle diameter is loaded in bed of packings from the bottom to top by big and little.
Size combination decide according to the concentration of fluorion in the waste water is different, the filling order from the bottom to top, particle diameter is little by reaching greatly.When fluorine concentration is high in the waste water, can also adopt two-stage or multistage slag bed of packings to carry out continuous defluorinate.
Fluoride waste pumps into from the bottom of slag defluoroing filling bed, and the fluoride waste slag bed of packings of flowing through is from bottom to up flowed out by the top behind defluorination.
Stop up the slag bed of packings for the tiny Calcium Fluoride (Fluorspan) precipitation that prevents to generate, influence the stripping of calcium, can carry out irregular back flushing the slag bed of packings.
When bed of packings is carried out that fluorinion concentration still is higher than 10mg/L in the bed of packings water outlet after the irregular back flushing, the slag bed of packings that need more renew.
Fluoride waste is flowed through and effects such as precipitation, flocculation has been taken place in the process of slag bed of packings, removal to fluorine in the waste water is remarkable, analyze after testing and know: after fluoride waste was handled through the slag bed of packings, the concentration of fluorine reached the discharging standards (discharging standards of fluorion is 10mg/L) of industrial sewage fluorion in the water outlet.
Beneficial effect
Precipitator method FLUORIDE REMOVAL IN WASTEWATER Technology Need at present commonly used adds a large amount of medicaments, and the precipitation generation is big, and cost is higher, has difficulties for the advanced treatment of fluoride waste in enormous quantities; Absorption method FLUORIDE REMOVAL IN WASTEWATER technology only is applicable to that usually fluorine content is low or through the advanced treatment of pre-treatment fluorine content at the fluorinated water of 15-30mg/L.
The method that the present invention adopts slag to remove fluorine in the waste water has then overcome the shortcoming and defect of above method.Only slag need be filled to packed bed, not need to add a large amount of medicaments, avoid adding the high processing cost of a large amount of mud that a large amount of medicaments produce and the mud that thereupon causes; Also overcome the limitation that absorption method only is applicable to the waste water that fluorine content is low simultaneously.Adopting the slag bed of packings to handle fluorine can be according to the progression that how much determines the slag bed of packings of fluorine content, and flexible operation is convenient, removes the efficient height, effective.The slag raw material is abundant, and cost is low, is suitable for the processing of extensive fluoride waste.
The present invention has not only removed the fluorine in the waste water with the method that slag is removed fluorine in the waste water, subdued the hidden danger of fluoride pollution to human health damage, but also make the main solid by-product-slag of steel industry in wastewater treatment, bring into play vital role, in the cost that reduces wastewater treatment, reached the purpose of steel slag resource utilization.Thereby the environmental benefit of the technology of the present invention, social benefit and economic benefit are huge.
Specific implementation method
Below for a more detailed description to the present invention with embodiment and accompanying drawing.These embodiment only are the descriptions to best mode for carrying out the invention, scope of the present invention are not had any restriction.
Embodiment 1
Fluorinion concentration is 15-30mg/L in the waste water.Slag is loaded into the one-level bed of packings, and the mechanical fraction of slag is in the bed of packings: 5-20mm particle diameter slag compares 1:5 with 2-5mm particle diameter slag; The fluoride waste slag bed of packings of flowing through from the bottom to top, the residence time of control fluoride waste is 1 hour.Through the processing of slag bed of packings, the concentration of fluorine is reduced to about 5mg/L in the water outlet.The clearance of fluorion is 66.7%-88.3% in the waste water.
Embodiment 2
Fluorinion concentration is 50-70mg/L in the waste water.Slag is loaded into the secondary bed of packings.The mechanical fraction of slag is in the first step bed of packings: 10-20mm particle diameter slag, 5-10mm particle diameter slag and 2-5mm particle diameter slag are than being 1:2:2; In the packed bed of the second stage slag mechanical fraction be: 5-20m particle diameter slag and 2-5mm particle diameter slag are than being 1:6.The fluoride waste slag bed of packings of flowing through from the bottom to top, the residence time of control fluoride waste is 40 minutes, the concentration of fluorine is reduced to 5-8mg/L in the water outlet.The clearance of fluorion is 84%-93% in the waste water.
Embodiment 3
Fluorinion concentration is 100-150mg/L in the waste water.Slag is loaded into three grades of bed of packings.In the first step bed of packings slag mechanical fraction be: 15-20mm particle diameter slag, 10-15mm particle diameter slag and 5-10mm particle diameter slag are than being 1:1:3; The mechanical fraction of slag is in the packed bed of the second stage: 10-15m particle diameter slag, 5-10mm particle diameter slag and 2-5mm particle diameter slag are than being 1:2:5, and the mechanical fraction of slag is in the third stage packed bed: 10-15mm particle diameter slag, 2-5mm particle diameter slag and 1-2mm particle diameter slag are than being 1:3:3.The fluoride waste slag bed of packings of flowing through from the bottom to top, the residence time of control fluoride waste is 30 minutes, the concentration of fluorine is reduced to 5-8mg/L in the water outlet.The clearance of fluorion is 92%-95% in the waste water.
Embodiment 4
The environment sensitive metallic element Cr that contains in the slag, Cu, Ni, Pb etc. have been carried out the dissolution test in water.The results are shown in Table 2.
The concentration of table 2 slag stripping in time in water (mg/L of unit)
| 7d | 14d | 21d | 28d | 35d | 42d | 48d | |
| Ca | 792 | 987 | 800 | 660 | 739 | 774 | 784 |
| Mg | 4.99 | 9.68 | 3.44 | 2.68 | 3.72 | 3.79 | 4.86 |
| Fe | 3.84 | 5.14 | 7.17 | 5.89 | 5.02 | 1.96 | 3.64 |
| Al | 0.22 | 0.26 | 0.18 | 0.11 | 0.16 | <0.05 | 0.11 |
| Cd | <0.005 | 0.006 | <0.005 | <0.005 | <0.005 | <0.005 | <0.005 |
| Cr | <0.02 | <0.02 | <0.02 | <0.02 | <0.02 | <0.02 | <0.02 |
| Cu | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 |
| Mn | 1.01 | 1.70 | 0.96 | 0.61 | 0.51 | 0.25 | 0.46 |
| Ni | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 | <0.01 |
| Pb | <0.02 | <0.02 | <0.02 | <0.02 | <0.02 | <0.02 | <0.02 |
| Zn | 0.063 | 0.193 | 0.095 | 0.094 | 0.027 | 0.019 | 0.017 |
As shown in Table 2: the stripping concentration in water such as the environment sensitive metallic element Cr that contains in the slag, Cu, Ni, Pb all do not surpass the national standard of metal ion discharging, the stripping of these metals does not pollute water surrounding, can use safely in water treatment.Wherein the stripping of Ca, Mg, Fe, Al can be made full use of by the defluorination process just, reaches the purpose of valuable element recycling.
Claims (8)
1. method of removing fluorine in the waste water, it is characterized in that may further comprise the steps: sieve slag (1); (2) slag after will sieving is filled in the bed of packings by the size combination; And (3) introduce the bed of packings bottom with fluoride waste.
2. the method for claim 1, the wherein said step that slag is sieved comprises sieves into several groups of granular fillers that particle diameter is 1-2mm, 2-5mm and 5-10mm, 10-15mm and 15-20mm with slag.
3. the method for claim 1, wherein said screening adopt sieve apparatus to carry out.
4. the method for claim 1, wherein said slag is loaded system by the size combination and is adopted two or more mechanical fraction, filling be in proper order bed of packings from the bottom to top, the slag particle diameter of filling is little by reaching greatly.
5. the method for claim 1, wherein said fluoride waste pumps into from the bed of packings bottom, and flow out at the top.
6. the method for claim 1, described method adopt two-stage or multistage bed of packings to carry out continuous defluorination.
7. the method for claim 1, described method also comprises carries out irregular back flushing to bed of packings.
8. when the method for claim 1, described method also are included in bed of packings are carried out that fluorinion concentration still is higher than 10mg/L in the bed of packings water outlet after the irregular back flushing, the slag bed of packings that more renews.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100430127A CN101475250A (en) | 2008-01-04 | 2008-01-04 | Method for removing fluorine in wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100430127A CN101475250A (en) | 2008-01-04 | 2008-01-04 | Method for removing fluorine in wastewater |
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| CN101475250A true CN101475250A (en) | 2009-07-08 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086019A (en) * | 2014-06-17 | 2014-10-08 | 湖北富邦科技股份有限公司 | Industrial high-concentration phosphorus-containing wastewater treatment method |
| CN109621892A (en) * | 2019-01-23 | 2019-04-16 | 云南天朗再生资源有限责任公司 | A kind of AMD fast purification inorganic agent and the preparation method and application thereof |
-
2008
- 2008-01-04 CN CNA2008100430127A patent/CN101475250A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086019A (en) * | 2014-06-17 | 2014-10-08 | 湖北富邦科技股份有限公司 | Industrial high-concentration phosphorus-containing wastewater treatment method |
| CN109621892A (en) * | 2019-01-23 | 2019-04-16 | 云南天朗再生资源有限责任公司 | A kind of AMD fast purification inorganic agent and the preparation method and application thereof |
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Open date: 20090708 |