CN107285421A - A kind of segment processing method for the acidic fluorine-containing waste water for being conducive to recycling sludge - Google Patents
A kind of segment processing method for the acidic fluorine-containing waste water for being conducive to recycling sludge Download PDFInfo
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- CN107285421A CN107285421A CN201710529185.9A CN201710529185A CN107285421A CN 107285421 A CN107285421 A CN 107285421A CN 201710529185 A CN201710529185 A CN 201710529185A CN 107285421 A CN107285421 A CN 107285421A
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- Prior art keywords
- water
- waste water
- sludge
- fluoride
- containing waste
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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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- 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
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
Abstract
A kind of segment processing method for the acidic fluorine-containing waste water for being conducive to recycling sludge, belongs to water-treatment technology field.Methods described step is as follows：（1）Precipitation：Acidic fluorine-containing waste water is passed through into tank to be stored, 5m is being hoarded3Afterwards, fluoride waste is got into neutralization precipitation pond using water pump, calcium oxide is added into neutralization precipitation pond, open mechanical agitation oar stirring 40min, rotating speed is 300r/min；（2）Absorption：The reacted precipitation of step one and waste water are passed through plate and frame filter press and carry out mud-water separation, obtained sludge outward transport, supernatant is pumped into regulating reservoir, is adjusted the pH of supernatant to neutrality using hydrochloric acid or sodium hydroxide in regulating reservoir, into adsorption tower, adsorption tower water removal is qualified discharge water.It is an advantage of the invention that：Cost is low, calcium salt utilization rate high, operation is simple, realizes the recycling of sludge reduction and sludge.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to a kind of acidic fluorine-containing waste water for being conducive to recycling sludge
Segment processing method.
Background technology
High purity graphite is modern science and technology and the important source material of industrial development, and the acidic fluorine-containing waste water that graphite purification is produced has
Environmental risk, fluoride wastewater treatment is the important guarantee of graphite industry healthy development.The fluoride waste water quality that graphite purification is produced
Complexity, fluorinion concentration is very high, is the mixed liquor of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, simultaneously containing calcium ion, magnesium ion, iron
The compositions such as ion, fluosilicic acid radical ion.The main methods of fluoride waste include chemical precipitation, coagulating sedimentation, absorption, ion
Exchange, counter-infiltration and electrodialysis etc..
Chemical precipitation method refers to add precipitating reagent in waste water so that with precipitating reagent precipitation reaction occurs for the fluorine in waste water,
The fluoride precipitation or fluoride that generation is insoluble in water are adsorbed in the sediment co-precipitation to be formed, and pass through natural subsidence or mistake
The methods such as filter carry out separation of solid and liquid, so as to realize fluorine removal, the Oil repellent in reduction waste water, and conventional precipitating reagent has quick lime, ripe
Lime, calcium salt etc..Chemical precipitation method is in the processing of fluoride waste using universal, the especially processing of high-concentration fluorine-containing waste water.
Coagulant sedimentation is the dosing coagulant in waste water, forms colloid in the solution, so that a part of fluorine ion is adsorbed,
Elimination of colloid stability is made by the effect stirred with coagulant simultaneously, then by flocculation process, forms the flco of supernatant and deposition, will
Fluorine in water is transferred in flco, while promoting the sedimentation of sludge.Coagulant sedimentation is economical and practical, and equipment is simple, and operation is also compared
It is easier to, but has that sludge quantity is larger, pharmaceutical quantities is larger, water outlet the problems such as containing inorganic ion.Such as use aluminum salt
Water outlet containing solubilised state in a large amount of dissolving aluminium, and water often containing also fluoro complex is contained, and fluorine removal is not thorough, there is safety hidden
Suffer from.
Absorption method is that, by adsorbent equipment, fluorine ion occurs ion with the group or ion on adsorbent and handed over by fluoride waste
Change, so as to remove the fluorine ion in waste water.Absorption method is a kind of surface process based on contact method, is generally used for handling fluorine ion
The relatively low waste water of concentration, it is adaptable to drinking water defluorination, or by the advanced treating of the water pre-processed.
The method such as ion exchange, counter-infiltration and electrodialysis treatment effeciency is high, and effect is good, stable effluent quality, but needs pair
Raw water is pre-processed, and is built and operating cost height, and technology is more complicated, using less.
The content of the invention
The invention aims to solve present in prior art that cost of sewage disposal is high, treatment effect is undesirable,
There is provided a kind of segment processing method for the acidic fluorine-containing waste water for being conducive to recycling sludge for the problems such as technology is more complicated.
The present invention adds calcium oxide by wastewater treatment to neutrality using the calcium salt precipitation method in depositing technology, while calcium ion
Calcium fluoride precipitate is generated with fluorine ion, by the fluoride ion removing in solution.During the present invention is for hydrogen fluoride purification graphite
The two kinds of waste water produced are handled respectively, and the first waste water fluorinion concentration is very high in more than 10000mg/L, and second useless
Water fluorinion concentration is only 285mg/L, and other compositions such as chlorion, sulfate ion etc. are also that one section of water is much higher.Illustrate
Two kinds of waste water are more pure water compared with the first waste water, and impurity content is few, and content of fluoride ion is low, corresponding acid relatively low.This
Invention is by precipitation+absorption two stage treatment technique by wastewater treatment to neutrality, and fluorinion concentration is in below 10mg/L.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of segment processing method for the acidic fluorine-containing waste water for being conducive to recycling sludge, methods described is comprised the following steps that：
Step one：Precipitation：High-fluoride-acid-containing is passed through into tank one to be stored, 5m is being hoarded3Afterwards, water pump is utilized
High-concentration fluorine-containing waste water is got into neutralization precipitation pond one, calcium oxide 120g/L is added into neutralization precipitation pond one, machinery is opened and stirs
Mix oar and stir 30 ~ 40min, rotating speed is 250 ~ 300r/min；Low concentration acidic fluorine-containing waste water is passed through tank two, hoarded
5m3Afterwards, low concentration fluoride waste is got into neutralization precipitation pond two using water pump, calcium oxide 15g/ is added into neutralization precipitation pond two
L, opens mechanical agitation oar and stirs 30 ~ 40min, rotating speed is 250 ~ 300r/min；
Step 2：Absorption：The reacted sediment of step one and waste water are passed through plate and frame filter press and carry out mud-water separation, is obtained
Sludge is transported outward, and supernatant is pumped into regulating reservoir, is adjusted the pH of supernatant into using hydrochloric acid or sodium hydroxide in regulating reservoir
Property after, into adsorption tower, adsorption tower water removal is qualified discharge water.
The present invention is relative to the beneficial effect of prior art：
（1）Selective oxidation calcium is lower than calcium hydroxide cost as precipitating reagent, stronger than carbonic acid Calcium treatment regulation pH abilities, sludge quantity
It is few.After calcium salt precipitation method processing, water outlet pH is neutrality, and fluorinion concentration is in 20mg/L or so.
（2）By by waste water segment processing, improving the utilization rate of calcium oxide, compared with waste water mixed processing, at segmentation
Manage wastewater oxidation calcium consumption per ton and reduce 21kg, save cost.
（3）Sludge volume reduces 20%, and the calcirm-fluoride purity of the first sludge is 80% or so, the calcirm-fluoride of second of sludge
Purity is 20% or so, and the sludge calcirm-fluoride purity of composite waste is 50% or so.The raising of sludge purity is conducive to its recycling
Using such as firing fluoroaluminate cement, ceramic post sintering, bake bricks, or calcirm-fluoride etc. is extracted in flotation, segment processing realizes sludge
Minimizing, and it is easy to recycling.
（4）Adsorption treatment effectively can further remove fluorinion concentration, it is ensured that water outlet fluorinion concentration is in 10mg/L
Below.Using sodium hydroxide and aluminum sulfate can effective regenerative adsorption saturation activated alumina, adsorbance declines little.
（5）Integrated artistic floor space is small, simple to operate, convenient and easy, and effect is reliable.
Brief description of the drawings
Fig. 1 is the process chart of processing method of the present invention.
Embodiment
Technical scheme is described further with reference to the accompanying drawings and examples, but is not limited thereto, it is all
It is technical solution of the present invention to be modified or equivalent substitution, without departing from the scope of technical solution of the present invention, all should contains
Cover among protection scope of the present invention.
Embodiment one：What present embodiment was recorded is a kind of acidic fluorine-containing waste water for being conducive to recycling sludge
Segment processing method, methods described is comprised the following steps that：
Step one：Precipitation：High-fluoride-acid-containing is passed through into tank 1 to be stored, 5m is being hoarded3Afterwards, water is utilized
High-concentration fluorine-containing waste water is got to neutralization precipitation pond 1 by pump, and calcium oxide 120g/L is added into neutralization precipitation pond 1, opens machine
Tool agitating paddle stirs 30 ~ 40min, and rotating speed is 250 ~ 300r/min；Low concentration acidic fluorine-containing waste water is passed through tank 22,
Hoard 5m3Afterwards, low concentration fluoride waste is got into neutralization precipitation pond 24 using water pump, oxidation is added into neutralization precipitation pond 24
Calcium 15g/L, opens mechanical agitation oar and stirs 30 ~ 40min, rotating speed is 250 ~ 300r/min；
Step 2：Absorption：The reacted sediment of step one and waste water are passed through plate and frame filter press 5 and carry out mud-water separation, is obtained
Sludge outward transport, supernatant is pumped into regulating reservoir 6, is adjusted the pH of supernatant using hydrochloric acid or sodium hydroxide in regulating reservoir 6
To after neutral, into adsorption tower 7, the water removal of adsorption tower 7 is qualified discharge water, and adsorption tower water outlet detects fluorinion concentration in real time,
When fluorinion concentration is more than 10mg/L, adsorbent is regenerated, regenerated liquid uses sodium hydroxide solution, activator uses sulphur
Sour aluminum solutions.
Embodiment two：A kind of described in embodiment one is conducive to the acidic fluorine-containing waste water of recycling sludge
Segment processing method, in step one, Fu Li Nong Du≤10000mg/L, low dense in the high-fluoride-acid-containing one
It is 285mg/L to spend fluorinion concentration in acidic fluorine-containing waste water two.
Embodiment 1
The present embodiment is handled using two sections of fluoride wastes of Jixi City Ao Yu graphite group as water sample using segmentation calcium salt precipitation method
Fluoride waste, is adsorbed, concrete scheme is as follows with activated alumina absorption method afterwards：
One section of water enters tank 1, is hoarding 5m3Afterwards, neutralization precipitation pond is got to using water pump, adds calcium oxide 120g/L, open
Mechanical agitation oar stirring 40min is opened, rotating speed is 300r/min.
One section of water enters tank 2, is hoarding 5m3Afterwards, neutralization precipitation pond is got to using water pump, adds calcium oxide 15g/L,
Mechanical agitation oar stirring 40min is opened, rotating speed is 300r/min.
Plate type pressure filter is squeezed into by sludge pump after two sections of water neutralization reactions, mud-water separation is carried out, sludge outward transport processing goes out
Water is discharged into regulating reservoir.
It is 7 that hydrochloric acid and sodium hydroxide regulation pH are added in regulating reservoir.The water in regulating reservoir is squeezed into activity using filter pump
Alumina adsorption tower.
Adsorption tower water outlet carries out fluorinion concentration detection, and when more than 10mg/L, adsorbent is regenerated, regenerated liquid choosing
0.6mol/L sodium hydroxide solution is selected, the recovery time is 5 hours.It is neutral to be rinsed after regeneration with running water to water outlet, then is used
1% aluminum sulfate solution activation 3h, is rinsed with running water afterwards.
After precipitation+adsorption treatment, water outlet pH is neutrality, and fluorinion concentration is in below 10mg/L.
Claims (2)
1. a kind of segment processing method for the acidic fluorine-containing waste water for being conducive to recycling sludge, it is characterised in that：Methods described has
Body step is as follows：
Step one：Precipitation：High-fluoride-acid-containing is passed through tank one（1）Stored, hoarding 5m3Afterwards, water is utilized
High-concentration fluorine-containing waste water is got to neutralization precipitation pond one by pump（3）, to neutralization precipitation pond one（3）Interior addition calcium oxide 120g/L, is opened
Open mechanical agitation oar and stir 30 ~ 40min, rotating speed is 250 ~ 300r/min；Low concentration acidic fluorine-containing waste water is passed through tank two
（2）, hoarding 5m3Afterwards, low concentration fluoride waste is got into neutralization precipitation pond two using water pump（4）, to neutralization precipitation pond two（4）
Interior addition calcium oxide 15g/L, opens mechanical agitation oar and stirs 30 ~ 40min, rotating speed is 250 ~ 300r/min；
Step 2：Absorption：The reacted sediment of step one and waste water are passed through plate and frame filter press（5）Mud-water separation is carried out, is obtained
The sludge outward transport arrived, supernatant is pumped into regulating reservoir（6）, in regulating reservoir（6）Interior use hydrochloric acid or sodium hydroxide are by supernatant
PH is adjusted to neutrality, into adsorption tower（7）, adsorption tower（7）Water removal is qualified discharge water.
2. a kind of segment processing method of acidic fluorine-containing waste water for being conducive to recycling sludge according to claim 1, its
It is characterised by：In step one, Fu Li Nong Du≤10000mg/L in the high-fluoride-acid-containing one, low concentration is acid
Fluorinion concentration is 285mg/L in fluoride waste two.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710529185.9A CN107285421B (en) | 2017-07-01 | 2017-07-01 | Sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling |
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| CN201710529185.9A CN107285421B (en) | 2017-07-01 | 2017-07-01 | Sectional treatment method of acidic fluorine-containing wastewater beneficial to sludge recycling |
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| CN107285421A true CN107285421A (en) | 2017-10-24 |
| CN107285421B CN107285421B (en) | 2020-11-24 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823799A (en) * | 2009-03-06 | 2010-09-08 | 昆山工研院华科生物高分子材料研究所有限公司 | Method for treating acidic fluorine-containing waste water |
| CN105347574A (en) * | 2015-12-10 | 2016-02-24 | 浙江奇彩环境科技有限公司 | Fluoride removal method of graphite purification waste water and processing system |
| CN105905933A (en) * | 2016-06-23 | 2016-08-31 | 昆山阳澄蓝谷环境研究所有限公司 | Process for preparing high-purity artificial fluorite by recovering fluoride-containing wastewater |
-
2017
- 2017-07-01 CN CN201710529185.9A patent/CN107285421B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823799A (en) * | 2009-03-06 | 2010-09-08 | 昆山工研院华科生物高分子材料研究所有限公司 | Method for treating acidic fluorine-containing waste water |
| CN105347574A (en) * | 2015-12-10 | 2016-02-24 | 浙江奇彩环境科技有限公司 | Fluoride removal method of graphite purification waste water and processing system |
| CN105905933A (en) * | 2016-06-23 | 2016-08-31 | 昆山阳澄蓝谷环境研究所有限公司 | Process for preparing high-purity artificial fluorite by recovering fluoride-containing wastewater |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| CN107285421B (en) | 2020-11-24 |
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