CN107285421B - Sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling - Google Patents
Sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling Download PDFInfo
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- CN107285421B CN107285421B CN201710529185.9A CN201710529185A CN107285421B CN 107285421 B CN107285421 B CN 107285421B CN 201710529185 A CN201710529185 A CN 201710529185A CN 107285421 B CN107285421 B CN 107285421B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
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Abstract
A sectional treatment method of acid fluorine-containing wastewater beneficial to sludge recycling, belonging to the technical field of water treatment. The method comprises the following steps: (1) and (3) precipitation: introducing the acid fluorine-containing wastewater into a water storage tank for storage, and storing the wastewater for 5m3Then, pumping the fluorine-containing wastewater into a neutralization sedimentation tank by using a water pump, adding calcium oxide into the neutralization sedimentation tank, starting a mechanical stirring paddle to stir for 40min, wherein the rotating speed is 300 r/min; (2) adsorption: and (3) introducing the precipitate and the wastewater after the reaction in the step one into a plate-and-frame filter press for mud-water separation, transporting the obtained sludge to the outside, pumping the supernatant into an adjusting tank, adjusting the pH of the supernatant in the adjusting tank to be neutral by using hydrochloric acid or sodium hydroxide, and introducing the supernatant into an adsorption tower, wherein the adsorption tower is used for removing water to obtain the discharge water reaching the standard. The invention has the advantages that: low cost, high utilization rate of calcium salt, simple and easy operation, and realizes sludge reduction and sludge resource utilization.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling.
Background
High-purity graphite is an important raw material for modern science and technology and industrial development, acidic fluorine-containing wastewater generated by graphite purification has environmental risk, and fluorine-containing wastewater treatment is an important guarantee for the healthy development of the graphite industry. The fluorine-containing wastewater generated by graphite purification has complex water quality and high fluorine ion concentration, is a mixed solution of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid, and simultaneously contains calcium ions, magnesium ions, iron ions, fluosilicic acid radical ions and other components. The main treatment methods of the fluorine-containing wastewater comprise chemical precipitation, coagulating precipitation, adsorption, ion exchange, reverse osmosis, electrodialysis and the like.
The chemical precipitation method is characterized in that a precipitator is added into the wastewater, so that fluorine in the wastewater and the precipitator are subjected to precipitation reaction to generate fluoride precipitate which is insoluble in water or fluoride is adsorbed to the formed precipitate for co-precipitation, solid-liquid separation is carried out by methods such as natural precipitation or filtration, and therefore, fluorine removal is achieved, and the fluorine content in the wastewater is reduced. The chemical precipitation method is generally applied to the treatment of the fluorine-containing wastewater, in particular to the treatment of the high-concentration fluorine-containing wastewater.
The coagulating sedimentation method is that coagulant is added into waste water to form colloid in the solution, so that part of fluorine ions are adsorbed, meanwhile, the colloid is destabilized through the action of stirring and the coagulant, and then, supernatant and deposited floc are formed through the flocculation process, fluorine in the water is transferred into the floc, and meanwhile, the sedimentation of sludge is promoted. The coagulating sedimentation method is economical and practical, simple in equipment and easy to operate, but has the problems of large sludge amount, large medicament amount, inorganic salt ion contained in effluent and the like. If the aluminum salt coagulant is adopted, the effluent water often contains a large amount of dissolved aluminum, and the water also contains a dissolved fluorine-containing complex, so that the fluorine removal is incomplete, and the potential safety hazard exists.
The adsorption method is that fluorine-containing wastewater passes through an adsorption device, and fluorine ions are subjected to ion exchange with groups or ions on an adsorbent, so that the fluorine ions in the wastewater are removed. The adsorption method is a surface process based on a contact method, is usually used for treating wastewater with low fluoride ion concentration, and is suitable for removing fluorine from drinking water or deeply treating pretreated water.
The ion exchange, reverse osmosis, electrodialysis and other methods have high treatment efficiency, good effect and stable effluent quality, but need to pretreat raw water, and have high construction and operation cost, complex technology and less application.
Disclosure of Invention
The invention aims to solve the problems of high sewage treatment cost, unsatisfactory treatment effect, complex technology and the like in the prior art, and provides a sectional treatment method of acidic fluorine-containing wastewater, which is beneficial to sludge recycling.
The method adopts a calcium salt precipitation method in a precipitation process to add calcium oxide to treat the wastewater to be neutral, and simultaneously calcium ions and fluoride ions generate calcium fluoride precipitate to remove the fluoride ions in the solution. The invention respectively treats two kinds of waste water generated in the process of purifying graphite by a hydrofluoric acid method, wherein the concentration of fluorine ions in the first waste water is higher than 10000mg/L, the concentration of fluorine ions in the second waste water is only 285mg/L, and other components such as chloride ions, sulfate ions and the like are much higher in one section of water. The second wastewater is purer than the first wastewater, and has less impurity content, low fluorine ion content and lower acidity. The wastewater is treated to be neutral through a two-stage treatment process of precipitation and adsorption, and the concentration of fluorine ions is below 10 mg/L.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling comprises the following specific steps:
the method comprises the following steps: and (3) precipitation: introducing the high-concentration acidic fluorine-containing wastewater into a first water storage tank for storage, and storing the wastewater for 5m3Then, pumping the high-concentration fluorine-containing wastewater into a neutralization sedimentation tank I by using a water pump, adding 120g/L of calcium oxide into the neutralization sedimentation tank I, starting a mechanical stirring paddle to stir for 30-40 min, and controlling the rotating speed to be 250-300 r/min; introducing the low-concentration acidic fluorine-containing wastewater into a second water storage tank, and storing for 5m3Then, pumping the low-concentration fluorine-containing wastewater into a second neutralization sedimentation tank by using a water pump, adding 15g/L of calcium oxide into the second neutralization sedimentation tank, starting a mechanical stirring paddle to stir for 30-40 min, and controlling the rotating speed to be 250-300 r/min;
step two: adsorption: and (3) introducing the precipitate and the wastewater after the reaction in the step one into a plate-and-frame filter press for mud-water separation, transporting the obtained sludge to the outside, pumping the supernatant into an adjusting tank, adjusting the pH of the supernatant to be neutral by using hydrochloric acid or sodium hydroxide in the adjusting tank, and then introducing the supernatant into an adsorption tower, wherein the adsorption tower is used for removing water to obtain the discharge water reaching the standard.
Compared with the prior art, the invention has the beneficial effects that:
(1) the calcium oxide is selected as the precipitator, the cost is lower than that of calcium hydroxide, the pH adjusting capability is stronger than that of calcium carbonate treatment, and the sludge amount is less. After the calcium salt precipitation treatment, the pH of the effluent is neutral, and the concentration of fluorine ions is about 20 mg/L.
(2) Through the sectional treatment of the wastewater, the utilization rate of calcium oxide is improved, and compared with the mixed treatment of wastewater, the consumption of calcium oxide in each ton of wastewater subjected to sectional treatment is reduced by 21kg, so that the cost is saved.
(3) The volume of the sludge is reduced by 20 percent, the purity of calcium fluoride of the first sludge is about 80 percent, the purity of calcium fluoride of the second sludge is about 20 percent, and the purity of calcium fluoride of the sludge of the mixed wastewater is about 50 percent. The improvement of the purity of the sludge is beneficial to resource utilization of the sludge, such as baking fluoroaluminate cement, ceramic sintering and brick baking, or flotation extraction of calcium fluoride and the like, the sludge reduction is realized by sectional treatment, and the resource utilization is facilitated.
(4) The adsorption treatment can effectively remove the concentration of the fluorinion, and the concentration of the fluorinion in the effluent is ensured to be below 10 mg/L. The saturated active alumina can be effectively regenerated and adsorbed by using the sodium hydroxide and the aluminum sulfate, and the adsorption quantity is not greatly reduced.
(5) The whole process has the advantages of small occupied area, simple operation, convenience, easiness and feasibility and reliable effect.
Drawings
FIG. 1 is a process flow diagram of the treatment method of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention.
The first embodiment is as follows: the embodiment describes a sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling, which comprises the following specific steps:
the method comprises the following steps: and (3) precipitation: introducing the high-concentration acidic fluorine-containing wastewater into a first water storage tank 1 for storage, and storing the wastewater for 5m3Then, pumping the high-concentration fluorine-containing wastewater into a neutralization sedimentation tank I3 by using a water pump, adding 120g/L of calcium oxide into the neutralization sedimentation tank I3, starting a mechanical stirring paddle to stir for 30-40 min, wherein the rotating speed is 250-300 r/min; introducing the low-concentration acidic fluorine-containing wastewater into a second water storage tank 2, and storing for 5m3Then, the low concentration is pumped by a water pumpThe fluorine wastewater is delivered to a neutralization sedimentation tank II 4, 15g/L of calcium oxide is added into the neutralization sedimentation tank II 4, a mechanical stirring paddle is started to stir for 30-40 min, and the rotating speed is 250-300 r/min;
step two: adsorption: and (2) introducing the precipitate and the wastewater after the reaction in the step one into a plate-and-frame filter press 5 for mud-water separation, transporting the obtained sludge to the outside, pumping the supernatant into an adjusting tank 6, adjusting the pH of the supernatant to be neutral by using hydrochloric acid or sodium hydroxide in the adjusting tank 6, then introducing the supernatant into an adsorption tower 7, removing water in the adsorption tower 7 to obtain standard-reaching discharge water, detecting the concentration of fluorine ions in the effluent of the adsorption tower in real time, regenerating the adsorbent when the concentration of the fluorine ions exceeds 10mg/L, wherein the regenerated liquid uses a sodium hydroxide solution, and the activating agent uses an aluminum sulfate solution.
The second embodiment is as follows: in a sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling according to a first specific embodiment, in the first step, the concentration of fluorine ions in the high-concentration acidic fluorine-containing wastewater is not less than 10000mg/L, and the concentration of fluorine ions in the low-concentration acidic fluorine-containing wastewater is 285 mg/L.
Example 1
In the embodiment, two sections of fluorine-containing wastewater of an Auyu graphite group in the Western chicken city are taken as water samples, the fluorine-containing wastewater is treated by a sectional calcium salt precipitation method, and then is adsorbed by an activated alumina adsorption method, and the specific scheme is as follows:
a section of water enters a water storage tank 1 and is stored for 5m3Then pumping the mixture into a neutralization sedimentation tank by using a water pump, adding 120g/L of calcium oxide, starting a mechanical stirring paddle to stir for 40min, wherein the rotating speed is 300 r/min.
A section of water enters a water storage tank 2 and is stored for 5m3Then pumping the mixture into a neutralization sedimentation tank by using a water pump, adding 15g/L of calcium oxide, starting a mechanical stirring paddle to stir for 40min, wherein the rotating speed is 300 r/min.
And pumping the two sections of water into a plate filter press through a sludge pump after the two sections of water react, separating mud from water, transporting the sludge outwards, and discharging the effluent into a regulating tank.
Hydrochloric acid and sodium hydroxide are added into the adjusting tank to adjust the pH value to 7. And pumping the water in the regulating tank into an activated alumina adsorption tower by using a filter pump.
And (3) detecting the concentration of fluorine ions in the effluent of the adsorption tower, and regenerating the adsorbent when the concentration of the fluorine ions exceeds 10mg/L, wherein 0.6mol/L sodium hydroxide solution is selected as a regeneration solution, and the regeneration time is 5 hours. After regeneration, the mixture is washed by tap water until the effluent is neutral, activated by 1 percent of aluminum sulfate solution for 3 hours and then washed by tap water.
After precipitation and adsorption treatment, the pH of the effluent is neutral, and the concentration of fluorine ions is below 10 mg/L.
Claims (1)
1. A sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: and (3) precipitation: introducing the high-concentration acidic fluorine-containing wastewater into a first water storage tank (1) for storage, and storing the wastewater in a stockpile of 5m3Then, pumping the high-concentration fluorine-containing wastewater into a neutralization sedimentation tank I (3) by using a water pump, adding 120g/L of calcium oxide into the neutralization sedimentation tank I (3), starting a mechanical stirring paddle to stir for 30-40 min, and controlling the rotating speed to be 250-300 r/min; introducing the low-concentration acidic fluorine-containing wastewater into a second water storage pool (2) and storing for 5m3Then, pumping the low-concentration fluorine-containing wastewater into a second neutralization sedimentation tank (4) by using a water pump, adding 15g/L of calcium oxide into the second neutralization sedimentation tank (4), starting a mechanical stirring paddle to stir for 30-40 min, and controlling the rotating speed to be 250-300 r/min; the concentration of fluorine ions in the high-concentration acidic fluorine-containing wastewater is not less than 10000mg/L, and the concentration of fluorine ions in the low-concentration acidic fluorine-containing wastewater is 285 mg/L;
step two: adsorption: and (3) introducing the precipitate and the wastewater after the reaction in the step one into a plate-and-frame filter press (5) for mud-water separation, transporting the obtained sludge to the outside, pumping the supernatant into an adjusting tank (6), adjusting the pH of the supernatant to be neutral by using hydrochloric acid or sodium hydroxide in the adjusting tank (6), and then introducing the supernatant into an adsorption tower (7), wherein the adsorption tower (7) is used for removing water to obtain the standard-reaching discharge water.
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| CN109437443A (en) * | 2018-12-27 | 2019-03-08 | 王平 | A kind of efficient process system applied to acidic fluorine-containing waste water |
| CN110282778A (en) * | 2019-06-28 | 2019-09-27 | 沈阳铝镁设计研究院有限公司 | A kind of technique for electrolytic aluminium factory fluoride wastewater treatment |
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| CN105347574B (en) * | 2015-12-10 | 2018-03-16 | 浙江奇彩环境科技股份有限公司 | A kind of defluorination method and processing system of graphite purification waste water |
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