CN105967295B - Synchronous dephosphorization fluorine removal built-up flocculant of a kind of electroplating wastewater and preparation method thereof - Google Patents
Synchronous dephosphorization fluorine removal built-up flocculant of a kind of electroplating wastewater and preparation method thereof Download PDFInfo
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- CN105967295B CN105967295B CN201610496127.6A CN201610496127A CN105967295B CN 105967295 B CN105967295 B CN 105967295B CN 201610496127 A CN201610496127 A CN 201610496127A CN 105967295 B CN105967295 B CN 105967295B
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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
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F2101/105—Phosphorus compounds
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses synchronous dephosphorization fluorine removal built-up flocculants of a kind of electroplating wastewater and preparation method thereof, are compounded in molar ratio by hydrogen peroxide, aluminium polychloride, inorganic aluminate and inorganic cerium salt.Aluminium polychloride, inorganic aluminate and inorganic cerium salt are sufficiently mixed according to the ratio, water is added, mixed solution is made, hydrogen peroxide is then added, be uniformly mixed, sufficiently react.Built-up flocculant of the present invention overcomes the defect that phosphorus in traditional electroplating wastewater is difficult to synchronous advanced treating with fluorine, have the characteristics that at low cost, effect is good, it solves and leads to not the problems such as being effectively treated because of the morphology issues of phosphorus, phosphate radical and fluorine ion in removal water body can be synchronized, settling velocity is fast, the sludge quantity of high treating effect, generation is small, meets the minimizing principle of solid waste.
Description
Technical field
The present invention relates to sewage treatment field, the synchronous dephosphorization fluorine removal built-up flocculant of specifically a kind of electroplating wastewater and its system
Preparation Method.
Background technique
Phosphorus index is one of the most important index of water eutrophication control.Total phosphorus in water content is more than 0.02mg/L
When, it is possible to cause water eutrophication.Water eutrophication can seriously destroy the ecological balance, influence human health, therefore need
Strict control is wanted to be discharged into the phosphorus concentration in water body.Fluorine one of the important indicator that also sewage discharge controls, this is because mistake
Polyfluoro intake can also have a adverse impact to nervous system, endocrine and immune function, cause brain damage, senile dementia
Etc. diseases, for children, or even will affect the normal development of intelligence.
Electroplating industry average annual waste water yield in China's is up to 4,000,000,000 tons, accounts for the 1/6 of total discharged volume of industrial waste water.Meanwhile by
In the complexity of electroplating technology, cause the waste component generated complicated and changeable, pollutant concentration is high, it is difficult to reach increasingly stringent
Discharge standard.It is handled currently, electroplating wastewater generallys use " materialization+biochemistry " mode, but due to being used in electroplating wastewater
Hypophosphite is as reducing agent, it is difficult to which effectively precipitating causes in biochemical tail water total phosphorus concentration usually in 2-5mg/L, and uses
After calcium precipitation, usually also containing the fluorine ion of high concentration, concentration range 10-20mg/L.With electroplating wastewater discharge standard
It is further stringent with reclamation rate requirement, therefore, it is necessary to carry out advanced treating to waste water, it is made to meet reuse water quality requirement.
Tradition is phosphorous and fluoride waste minimizing technology is calcium salt precipitation method, Coagulation Method, absorption method etc..Wherein calcium salt is heavy
Shallow lake method is suitable for the processing of high-density phosphorus and fluoride waste, is not suitable for the processing of low concentration biochemical tail water；Absorption method is to just
Phosphate has certain effect, but does not have effect to hypophosphite；Traditional coagulant is for the phosphorous and fluorine-containing of low concentration
Waste water removal effect is unobvious, it is difficult to reach the requirement of recycle-water.Phosphorus and fluorine belong to inorganic anion pollutant, if by it
Separately processing, is easy to cause sewage treatment process excessively complicated, and process flow is longer, and cost of investment is high, and it is useless to be unfavorable for big yield
The processing of water.
Chinese patent " a kind of compound oxidant and wastewater treatment method of advanced treating plating phosphorus-containing wastewater ", patent application
Number: 201410334337.6, phosphorus in electroplating wastewater is handled using " oxidation+absorption ", although treatment effect is preferable,
Its processing technological flow is complicated, while cannot be effectively treated to fluorine, therefore be not suitable for for synchronizing phosphorous fluoride waste.And
For the fluoride pollution in electroplating wastewater, Chinese Papers " improvement of Fluorine Containing Electroplating Wastewater Treatment Process " (" being electroplated and environmental protection ",
2007) it is mentioned in using conditions and environment, the increase precipitating by adjusting processing sequence, change reaction to Pollutants in Wastewater
Sludge reflux in the process etc. improves fluoride wastewater treatment effect, but after treatment process processing, Funing tablet is still greater than
6mg/L is unable to satisfy into film water quality requirement, while effective to non-ortho-phosphoric removal ability.
In conclusion the advanced treating that phosphorous fluoride waste is electroplated needs to meet increasingly strict wastewater discharge standard
For waste water quality, new treatment process is developed, rapidly and efficiently can be switched to hypophosphite in water body to be easily handled
Orthophosphates, while but also with by Phosphorus From Wastewater it is synchronous with fluorine removal, reduce process flow, reduce investment and operating cost,
Meet reuse water quality requirement.But this kind of technology still extremely lacks at present.
Summary of the invention
The purpose of the present invention is to provide a kind of electroplating wastewaters to synchronize dephosphorization fluorine removal built-up flocculant and preparation method thereof, with
Solve the problems mentioned above in the background art.
To achieve the above object, the invention provides the following technical scheme:
The synchronous dephosphorization fluorine removal built-up flocculant of a kind of electroplating wastewater, by hydrogen peroxide, aluminium polychloride, inorganic aluminate and inorganic
Cerium salt is by 1:(5~10): (2~5): the molar ratio of (1~2) compounds.
As a further solution of the present invention: the inorganic aluminate be one of aluminum sulfate, aluminium chloride, aluminum nitrate or
It is several.
As further scheme of the invention: the inorganic cerium salt is cerous nitrate, cerous sulfate, cerium chloride, oxychlorination
One of cerium.
The preparation method of the synchronous dephosphorization fluorine removal built-up flocculant of a kind of electroplating wastewater, by aluminium polychloride, inorganic
Aluminium salt and inorganic cerium salt are sufficiently mixed according to the ratio, and water is added, and prepare the mixed solution that mass fraction is 5~20%, then
Hydrogen peroxide is added, is uniformly mixed, sufficiently reacts.
It is worth noting that using inorganic aluminate and aluminium polychloride as precipitating reagent, it can be with the phosphate in water body
Al is formed with fluorine ion2PO4F3Co-precipitation, achievees the purpose that synchronize dephosphorization and fluorine.If inorganic aluminate, shape is used alone
At wadding body it is smaller, settling property is poor, if be used alone aluminium polychloride led since aluminium ion cannot sufficiently discharge
Cause treatment effect bad.It not only can use inorganic aluminate using inorganic aluminate and aluminium polychloride to be adequately ionized, release big
The aluminium ion of amount, while effect is caught using aluminium polychloride as high molecular net, the wadding body generated is effectively sunk
It forms sediment.
Inorganic cerium salt ionization generates cerium ion, belongs to variable valency metal, Ce (IV) and Ce (II) can be formed, when itself and dioxygen
Water is used cooperatively, and is capable of forming class Fenton's reaction, increases the rate of release of OH, to substantially increase the oxidation speed of hydrogen peroxide
Rate increases the efficiency of hypophosphite；Cerium salt and the affinity of fluorine ion are strong simultaneously, so that fluorine ion is adsorbed
To cerium salt surface, to be removed by precipitating.
The dosing method of flocculant of the present invention adds for wet type, and dosage is 30~200ppm.
Compared with prior art, the beneficial effects of the present invention are:
(1) built-up flocculant of the present invention overcomes the defect that phosphorus in traditional electroplating wastewater is difficult to synchronous advanced treating with fluorine,
Have the characteristics that at low cost, effect is good；
(2) flocculant of the present invention passes through the catalysis oxidation class Fenton's reaction of hydrogen peroxide and cerium salt, so that in waste water first
Hypophosphite is converted into orthophosphates so that the phosphorus in water body is easy to be removed by coagulating sedimentation, solve because
The morphology issues of phosphorus and lead to not the problems such as being effectively treated；Simultaneously as cerium salt and fluorine ion affinity are stronger, so that part
Fluorine ion adsorbs to be removed by cerium salt；
(3) flocculant of the present invention is used cooperatively using inorganic aluminate and aluminium polychloride, solves exclusive use inorganic aluminum
The defects of wadding body existing for during salt or aluminium polychloride is smaller or treatment effect is bad can synchronize phosphorus in removal water body
Acid group and fluorine ion, settling velocity is fast, high treating effect, and the sludge quantity of generation is small, meets the minimizing principle of solid waste.
(4) flocculant of the present invention carries out advanced treating to phosphorous fluoride waste is electroplated, and in processed waste water, total phosphorus concentration is small
In 0.2mg/L, fluoride is less than 2mg/L, can satisfy membrane technology water inlet and requires.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1
Built-up flocculant by hydrogen peroxide, aluminium polychloride, aluminum sulfate and cerous sulfate by 1:5:2:1 molar ratio compounding and
At the solution that mass fraction is 5% is made in addition water.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 2.5mg/L, and fluorine contains
Amount is 15.2mg/L, and the flocculant usage of addition is 50mg/L, is mixed slowly after quickly stirring 1min with 160rpm using 50rpm
20min measures phosphorus and Funing tablet in supernatant after staticly settling 30min, the results showed that, using built-up flocculant processed waste water
In total phosphorus concentration be 0.19mg/L, fluoride concentration 1.8mg/L, meet into reverse osmosis membrane requirement.
Embodiment 2
Built-up flocculant by hydrogen peroxide, aluminium polychloride, aluminum nitrate and cerous nitrate by 1:10:5:2 molar ratio compounding and
At, add water be made mass fraction be 20% solution.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 5.0mg/L, and fluorine contains
Amount is 18.9mg/L, and the flocculant usage of addition is 150mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.15mg/L, fluoride concentration 1.6mg/L, full
Foot is required into reverse osmosis membrane.
Embodiment 3
Built-up flocculant by hydrogen peroxide, aluminium polychloride, aluminium chloride and cerium chloride by 1:8:4:1 molar ratio compounding and
At, add water be made mass fraction be 16% solution.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 4.2mg/L, and fluorine contains
Amount is 20.0mg/L, and the flocculant usage of addition is 300mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.30mg/L, fluoride concentration 1.2mg/L, full
Foot is required into reverse osmosis membrane.
Embodiment 4
Built-up flocculant is compounded by hydrogen peroxide, aluminium polychloride, aluminium chloride and oxychlorination cerium by the molar ratio of 1:7:3:1.5
It forms, adds water that the solution that mass fraction is 12% is made.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 3.8mg/L, and fluorine contains
Amount is 17.9mg/L, and the flocculant usage of addition is 200mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.17mg/L, fluoride concentration 1.4mg/L, full
Foot is required into reverse osmosis membrane.
Embodiment 5
Built-up flocculant by hydrogen peroxide, aluminium polychloride, inorganic aluminate and cerium chloride by 1:6:4:1 molar ratio compounding and
At, add water be made mass fraction be 15% solution, wherein inorganic aluminate is made of aluminum sulfate and aluminium chloride, ratio 2:2.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 3.9mg/L, and fluorine contains
Amount is 11.0mg/L, and the flocculant usage of addition is 80mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.17mg/L, fluoride concentration 2.0mg/L, full
Foot is required into reverse osmosis membrane.
Embodiment 6
Built-up flocculant by hydrogen peroxide, aluminium polychloride, aluminium chloride and cerium chloride by 1:7:3:1 molar ratio compounding and
At, be made mass fraction be 11% solution.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 3.2mg/L, and fluorine contains
Amount is 14.0mg/L, and the flocculant usage of addition is 200mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.13mg/L, fluoride concentration 1.1mg/L, full
Foot is required into reverse osmosis membrane.
Embodiment 7
Built-up flocculant by hydrogen peroxide, aluminium polychloride, aluminium chloride and cerous nitrate by 1:6.5:3:1 molar ratio compounding and
At, add water be made mass fraction be 17% solution.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 3.9mg/L, and fluorine contains
Amount is 14.4mg/L, and the flocculant usage of addition is 180mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.11mg/L, fluoride concentration 1.5mg/L, full
Foot is required into reverse osmosis membrane.
Embodiment 8
Built-up flocculant by hydrogen peroxide, aluminium polychloride, aluminium chloride and cerous nitrate by 1:8:4:1 molar ratio compounding and
At, add water be made mass fraction be 14% solution.
By flocculant concentration made of compounding to being electroplated in phosphorous fluoride waste, wherein total phosphorus content is 4.1mg/L, and fluorine contains
Amount is 12.4mg/L, and the flocculant usage of addition is 110mg/L, after stirring precipitates, measures the concentration of phosphorus and fluorine in supernatant, knot
Fruit shows to use the total phosphorus concentration in built-up flocculant processed waste water for 0.16mg/L, fluoride concentration 1.3mg/L, full
Foot is required into reverse osmosis membrane.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
Claims (3)
1. a kind of synchronous dephosphorization fluorine removal built-up flocculant of electroplating wastewater, which is characterized in that by hydrogen peroxide, aluminium polychloride, inorganic
Aluminium salt and inorganic cerium salt are by 1:(5~10): (2~5): the molar ratio of (1~2) compounds, and the inorganic aluminate is sulfuric acid
One or more of aluminium, aluminium chloride, aluminum nitrate.
2. the synchronous dephosphorization fluorine removal built-up flocculant of electroplating wastewater according to claim 1, which is characterized in that described is inorganic
Cerium salt is one of cerous nitrate, cerous sulfate, cerium chloride, oxychlorination cerium.
3. a kind of preparation side for synchronizing dephosphorization fluorine removal built-up flocculant such as electroplating wastewater according to any one of claims 1 to 2
Method, which is characterized in that aluminium polychloride, inorganic aluminate and inorganic cerium salt are sufficiently mixed according to the ratio, water is added, prepares matter
The mixed solution that score is 5~20% is measured, hydrogen peroxide is then added, is uniformly mixed, is sufficiently reacted.
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| CN107555661B (en) * | 2017-10-13 | 2020-08-25 | 贵州大学 | Deep purification method for phosphorus and fluorine coexisting wastewater |
| CN108862520A (en) * | 2018-07-12 | 2018-11-23 | 浙江正洁环境科技有限公司 | Time phosphorous medicament and its preparation and application in a kind of removal electroplating wastewater |
| WO2020102542A1 (en) * | 2018-11-14 | 2020-05-22 | Chemtreat, Inc. | Waste water fluoride and cyanide removal |
| CN117566981B (en) * | 2024-01-17 | 2024-04-09 | 惠州金茂源环保科技有限公司 | Method and system for removing phosphorus from electroplating wastewater |
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Address after: 10 / F, academician building, northeast corner of Xiyou road and Yulan Avenue, high tech Zone, Hefei City, Anhui Province Patentee after: ANHUI GLOBAL GREEN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: 230000 room 404, zone B, business incubation center, Hefei National University Science Park, 602 Huangshan Road, Shushan District, Hefei City, Anhui Province Patentee before: ANHUI GLOBAL GREEN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |