CN109399832A - The processing method of acid heavy metal wastewater - Google Patents

The processing method of acid heavy metal wastewater Download PDF

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Publication number
CN109399832A
CN109399832A CN201811426950.5A CN201811426950A CN109399832A CN 109399832 A CN109399832 A CN 109399832A CN 201811426950 A CN201811426950 A CN 201811426950A CN 109399832 A CN109399832 A CN 109399832A
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China
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processing
heavy metal
ion
mercury
treatment fluid
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郭红兵
孙文亮
李想
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China ENFI Engineering Corp
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China ENFI Engineering Corp
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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
    • C02F9/00—Multistage treatment of water, waste water, or sewage
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The present invention provides a kind of processing methods of acid heavy metal wastewater.The processing method includes: S1, and oxidation reaction is occurred for acid heavy metal wastewater and oxidant and obtains the first treatment fluid so that the mercury metal in acid heavy metal wastewater is changed into mercury ion from atomic state；The pH of first treatment fluid is adjusted to 2.5~5 using alkaline pH adjusting agent, obtains second processing liquid by S2；Second processing liquid is reacted with sulfiding reagent, obtains mercuric sulphide sediment and third treatment fluid by S3；S4 makes heavy metal ion and precipitating reagent in third treatment fluid carry out precipitation reaction, obtains sediment and fourth process liquid；The pH of fourth process liquid is adjusted to 6~9 using pH adjusting agent, obtains sediment and scavenging solution by S5.On the one hand the processing method can remove mercury metal, improve the environmentally friendly degree of outlet purified water, on the other hand also have process flow short, can reduce cost for wastewater treatment, be easy to implement industrialization promotion, economic value with higher.

Description

The processing method of acid heavy metal wastewater
Technical field
The present invention relates to field of sewage treatment, in particular to a kind of processing method of acid heavy metal wastewater.
Background technique
With the propulsion of industrialization and urbanization, the annual production such as plating, printing and dyeing, mining, metallurgy and chemical industry largely contains The waste water of heavy metal ion and mercury metal, the pollution so as to cause heavy metal and mercury metal are got worse.Heavy metal is difficult to degrade simultaneously It can constitute and biology and human health are seriously threatened by food chain biological concentration.And mercury metal is volatile, human body sucking After the symptoms such as be also easy to produce insanity, gingivitis, tremble.
In recent years, heavy metal wastewater thereby Treatment process is quickly grown, new technology, new method are continuously emerged, but in practice It was found that the methods of traditional neutralization precipitation, vulcanization, ion exchange, reverse osmosis, ferrite and absorption are in processing heavy metal wastewater thereby Middle Shortcomings, such as treatment process are longer, treatment conditions are harsh, higher cost, waste residue is more, introduce secondary pollution, processing The problems such as limited is measured, needs to continuously improve and develop new processing technique；Simultaneously when in solution there are when atomic state mercury, with top Method can not remove it up to standard.
Summary of the invention
It is existing to containing to solve the main purpose of the present invention is to provide a kind of processing method of acid heavy metal wastewater Not the problem of method of heavy metal containing wastewater treatment not can be removed mercury metal.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of processing of acid heavy metal wastewater Method, acid heavy metal wastewater include mercury metal and heavy metal ion, which includes: S1, by acid heavy metal wastewater Oxidation reaction occurs with oxidant, so that the mercury metal in acid heavy metal wastewater is changed into mercury ion from atomic state, obtains the One treatment fluid；The pH of first treatment fluid is adjusted to 2.5~5 using alkaline pH adjusting agent, obtains second processing liquid by S2；S3, by Two treatment fluids are reacted with sulfiding reagent, obtain mercuric sulphide sediment and third treatment fluid；S4 makes the heavy metal in third treatment fluid Ion and precipitating reagent carry out precipitation reaction, obtain sediment and fourth process liquid；S5, using acidic ph modifier by fourth process The pH of liquid is adjusted to 6~9, obtains sediment and scavenging solution.
Further, acid heavy metal wastewater includes one of mercury metal and following ion or a variety of: lead ion, zinc from Son, cadmium ion, chromium ion, arsenic ion and fluorine ion.
Further, precipitating reagent is selected from one of group of calcium hydroxide, sodium hydroxide and quick lime composition or a variety of.
Further, the pH of the first treatment fluid is adjusted to 3~4 using alkaline pH adjusting agent, obtains second processing liquid.
Further, oxidant is selected from one of group of potassium permanganate, perchloric acid, HClO and NaClO composition or a variety of.
Further, the reaction time of oxidation reaction is 30~50min.
Further, alkaline pH adjusting agent is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, quick lime, sodium bicarbonate and carbon One of group of sour sodium composition is a variety of.
Further, acidic ph modifier is selected from one of group of sulfuric acid, hydrochloric acid and nitric acid composition or a variety of.
Further, sulfiding reagent is selected from one of group of vulcanized sodium, sodium bisulfide and magnesium sulfide composition or a variety of.
Further, during precipitation reaction, the pH of reaction system is 11.5~12, and the reaction time is 30~60min.
It applies the technical scheme of the present invention, first passes through oxidation reaction for mercury metal and be converted into mercury ion, use alkaline pH tune It saves agent and reaction system is adjusted to specific pH range, be then deposited mercury ion using vulcanizing agent, to realize removal metal The purpose of mercury.Then the heavy metal ion etc. in third treatment fluid is removed in the form of precipitating precipitation reaction, thus real The further clean-up effect to waste water is showed.The waste water containing mercury metal and heavy metal ion is carried out using above-mentioned processing method Processing, on the one hand can remove mercury metal, the environmentally friendly degree of the purified water of outlet be improved, on the other hand compared to existing waste water Processing method, it is short with process flow, it can reduce cost for wastewater treatment, and be easy to implement industrialization promotion, have higher Economic value.In conclusion above-mentioned processing method has many advantages, such as that the feature of environmental protection is high, at low cost and convenient for large-scale application.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the structural schematic diagram for the processing system that a kind of typical embodiment according to the present invention provides；
Fig. 2 shows the structural schematic diagrams of the processing system provided according to a preferred embodiment of the present invention.
Wherein, the above drawings include the following reference numerals:
A, oxidant；B, acid heavy metal wastewater；C, alkaline pH adjusting agent；D, vulcanizing agent；E, precipitating reagent；G, acid pH tune Save agent；
10, oxidation unit；11, oxidant feeding mechanism；12, acid heavy metal wastewater feeding mechanism；20, first dress is neutralized It sets；21, alkaline pH adjusting agent feeding mechanism；30, vulcanize removal of mercury unit；31, vulcanize mercury removal device；32, filter-pressing device；33, sulphur Agent feeding mechanism；40, precipitation unit；41, settler；42, dense device；43, second device is neutralized；44, precipitating reagent supplies Answer device；45, acidic ph modifier feeding mechanism；50, recycle-water storage device.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, the existing method to heavy metal-containing wastewater treatment, which exists, not can be removed mercury metal The problem of.In order to solve the above-mentioned technical problem, this application provides a kind of processing method of acid heavy metal wastewater, above-mentioned acidity Heavy metal wastewater thereby includes mercury metal and heavy metal ion, which includes: S1, and acid heavy metal wastewater and oxidant are sent out Raw oxidation reaction obtains the first treatment fluid so that the mercury metal in acid heavy metal wastewater is changed into mercury ion from atomic state； The pH of first treatment fluid is adjusted to 2.5~5 using alkaline pH adjusting agent, obtains second processing liquid by S2；S3 makes second processing Liquid and sulfiding reagent carry out vulcanization reaction, obtain mercuric sulphide and third treatment fluid；S4, by the heavy metal ion in third treatment fluid Precipitation reaction is carried out with precipitating reagent, obtains sediment and fourth process liquid；S5, using acidic ph modifier by the fourth process The pH of liquid is adjusted to 6~9, is purified liquid.
In above-mentioned processing method, oxidation reaction is first passed through by mercury metal and is converted into mercury ion, it will using alkaline pH adjusting agent Reaction system is adjusted to specific pH range, is then deposited mercury ion using vulcanizing agent, to realize the mesh of removal mercury metal 's.Then it is removed by way of precipitation reaction is by the heavy metal ion precipitating in third treatment fluid, while by fourth process liquid PH be adjusted to 6~9, liquid is purified, to realize the further clean-up effect to waste water.
The waste water containing mercury metal and heavy metal ion is handled using above-mentioned processing method, on the one hand can be removed Mercury metal improves the environmentally friendly degree of the purified water of outlet, on the other hand compared to existing wastewater treatment method, has processing Process is short, can reduce cost for wastewater treatment, and be easy to implement industrialization promotion, economic value with higher.In conclusion Above-mentioned processing method has many advantages, such as that the feature of environmental protection is high, at low cost and convenient for large-scale application.
And specifically, it is preferable to which above-mentioned acid heavy metal wastewater includes one of mercury metal and following ion or a variety of: lead from Son, zinc ion, cadmium ion, chromium ion, arsenic ion and fluorine ion.
The purified water obtained when being handled using above-mentioned processing method the waste water containing mercury metal and heavy metal ion Mercury metal can not only be removed, additionally it is possible to meet all other environmental protection indexs of national regulation.It, can be in wastewater treatment process It is carried out using the method commonly used in the art precipitated to heavy metal ion etc..In a preferred embodiment, it precipitates Reaction includes: that heavy metal ion and precipitating reagent are carried out precipitation reaction, obtains fourth process liquid and sediment；And use acid pH The pH of fourth process liquid is adjusted to 6~9 by regulator, is purified water.After heavy metal ion is precipitated, by fourth process liquid PH be adjusted to above range purified water can be made to be in neutral or alkalescent, can be directly outer without subsequent other processing Row.
During above-mentioned precipitation reaction, precipitating reagent can select precipitating reagent commonly used in the art.In a kind of preferred implementation In mode, precipitating reagent includes but is not limited to one of group of calcium hydroxide, sodium hydroxide and quick lime composition or a variety of.It is above-mentioned several Kind precipitating reagent has the advantages that source is wide, price is low etc., thus above-mentioned several precipitating reagents is selected to advantageously reduce process costs, improves The efficiency of precipitating, while new impurity will not be introduced after precipitating.
In a preferred embodiment, the pH of the first treatment fluid is adjusted to 3~4 using alkaline pH adjusting agent, obtained Second processing liquid.When carrying out vulcanization reaction, the pH range of the first treatment fluid includes but unlimited above range that can guarantee that vulcanization is anti- Mercury ion is by High-rate sedimentation during answering, so that this can make vulcanization reaction have more specific aim.
In a preferred embodiment, oxidant includes but is not limited to potassium permanganate, perchloric acid, HClO and NaClO One of group of composition is a variety of.Oxidant includes but is not limited to above-mentioned several oxidants, and selects above-mentioned several oxidants Be conducive to improve the oxidation efficiency of mercury metal, and then improve the removal rate of mercury metal.
In actual use, when oxidant is directly added into, using device shown in FIG. 1 to acid heavy metal wastewater It is handled.
In actual use, when needing to adjust the concentration of oxidant, using device shown in Fig. 2 to an acid huge sum of money Belong to waste water to be handled.
In a preferred embodiment, the reaction time of oxidation reaction is 30~50min.Above-mentioned oxidation processes In, the time of oxidation processes includes but is not limited to above range, and limits and be conducive to guaranteeing mercury ion within the above range Under the precursor of conversion ratio, shorten the process time as far as possible, so as to improve treatment effeciency.
In above-mentioned processing method, alkaline pH adjusting agent commonly used in the art can be selected.Preferably, above-mentioned alkaline pH is adjusted Agent includes but is not limited to one in the group of sodium hydroxide, potassium hydroxide, calcium hydroxide, quick lime, sodium bicarbonate and sodium carbonate composition Kind is a variety of.
In above-mentioned processing method, acidic ph modifier commonly used in the art can be selected.Preferably, above-mentioned acid pH is adjusted Agent includes but is not limited to one of group of sulfuric acid, hydrochloric acid and nitric acid composition or a variety of.
In above-mentioned processing method, sulfiding reagent commonly used in the art can be selected.Preferably, above-mentioned sulfiding reagent include but It is not limited to one of group of vulcanized sodium, sodium bisulfide and magnesium sulfide composition or a variety of.
In above-mentioned processing method, it is preferable that during precipitation reaction, the pH of reaction system is 11.5~12, the reaction time For 30~60min.This is conducive to the rate of deposition for improving heavy metal ion, to improve the water outlet quality of purified water.
On the other hand above-mentioned process in order to better understand, the application additionally provide a kind of acid heavy metal wastewater Processing system, as shown in Figure 1, the processing system includes that oxidation unit 10, first neutralizes device 20, vulcanization removal of mercury unit 30 and sinks Shallow lake unit 40.Oxidation unit 10 is provided with feed opening and the outlet of the first treatment fluid, and feed opening is for being added acid heavy metal wastewater And oxidant；Neutralization device is provided with alkaline pH adjusting agent entrance, the first treatment fluid entrance and second processing liquid and exports, at first Reason liquid entrance is exported with the first treatment fluid to be connected by the first treatment fluid transfer pipeline, and vulcanization removal of mercury unit 30 is provided with vulcanization Agent entrance, second processing liquid entrance and the outlet of third treatment fluid, second processing liquid entrance and the outlet of second processing liquid pass through second Treatment fluid transfer pipeline is connected；Precipitation unit 40 is provided with third treatment fluid entrance, precipitant inlet and treated water outlet, the Three treatment fluid entrances are exported with third treatment fluid to be connected by third treatment fluid transfer pipeline, and precipitation unit 40 is for making a huge sum of money Belong to ion and forms precipitating.
During being handled using above-mentioned processing system acid heavy metal wastewater, acid heavy metal wastewater is in oxidation unit Oxidation reaction occurs with oxidant in 10, converts mercury ion for mercury metal, obtains the first treatment fluid.First treatment fluid is defeated It send to first and neutralizes in device 20, the pH of the first treatment fluid is adjusted using alkaline pH adjusting agent, obtains second processing liquid.Then will Second processing liquid is delivered in vulcanization removal of mercury unit 30, so that the mercury ion in second processing liquid is converted into mercuric sulphide using vulcanizing agent Precipitating, to realize the purpose of removal mercury metal.After the processing of over cure removal of mercury unit 30, third treatment fluid is obtained.By Three treatment fluids are delivered to precipitation unit 40, in precipitation unit 40, by precipitation reaction by third processing also in heavy metal from The form removal to precipitate such as son, to realize the further clean-up effect to waste water.
When being handled using above-mentioned processing system the waste water containing mercury metal and heavy metal ion, on the one hand it can go Except mercury metal, the environmentally friendly degree of the purified water of outlet is improved, on the other hand compared to existing wastewater treatment equipment, is arranged Process flow is short, can reduce cost for wastewater treatment, and be easy to implement industrialization promotion, economic value with higher.To sum up Described, above-mentioned processing system has many advantages, such as that the feature of environmental protection is high, at low cost and convenient for large-scale application.
Preferably, as shown in Fig. 2, above-mentioned processing system further includes alkaline pH adjusting agent feeding mechanism 21, alkaline pH is adjusted Agent feeding mechanism 21 is connected with the first neutralization device 20 by alkaline pH adjusting agent transfer pipeline.
In above-mentioned processing system, the main function of vulcanization removal of mercury unit 30 is that mercury ion is made to be converted into mercuric sulphide precipitating, because And any vulcanization removal of mercury unit 30 with the above function is suitable for the application.In a preferred embodiment, such as Fig. 1 Shown, vulcanization removal of mercury unit 30 includes vulcanization mercury removal device 31 and filter-pressing device 32.Vulcanization mercury removal device 31 is provided with vulcanizing agent Entrance, second processing liquid entrance and the first slurry outlet；Filter-pressing device 32 is provided with the first slurry inlet and third treatment fluid goes out Mouthful, the first slurry inlet is connected with the first slurry outlet by the first fluid-conveying pipe road.
It can be after forming mercuric sulphide precipitating using the vulcanization removal of mercury unit 30 with above structure, then pass through filter-pressing device 32, realize the purpose that the mercuric sulphide precipitating of solid phase is separated with the liquid product in reaction system, this can be subsequent progress Preamble preparation is made in precipitation reaction, and is conducive to that mercuric sulphide is inhibited to precipitate the influence for reacting post precipitation, to be conducive to improve The rate of deposition of heavy metal ion etc. in precipitation reaction improves the outer feature of environmental protection drained.
Preferably, as shown in Fig. 2, above-mentioned processing system further includes vulcanizing agent feeding mechanism 33, the vulcanizing agent feeding mechanism 33 are connected with vulcanization mercury removal device 31 by vulcanizing agent transfer pipeline.
In above-mentioned processing system, the main function of precipitation unit 40 is to make heavy metal ion to be precipitated in the form precipitated, because And any precipitation unit with the above function 40 is suitable for the application.In a preferred embodiment, such as Fig. 1 institute Show, precipitation unit 40 includes settler 41 and dense device 42.Settler 41 is provided with precipitant inlet, third treatment fluid Entrance and the second slurry outlet；Dense device 42 is provided with the second slurry inlet and the outlet of fourth process liquid, the second slurry inlet It is connected with the second slurry outlet by the second fluid-conveying pipe road.
After precipitation reaction occurs in precipitation unit 40, the second slurries are obtained, then by dense device 42, by the second slurry Solid phase and liquid phase in liquid are separated, and liquid phase (fourth process liquid) is flowed out in a manner of overflow, and solid phase is in the form of underflow It is delivered to the processing of filter-pressing device 32.Be conducive to improve the solid phase in outlet purified water using the precipitation unit 40 with above structure Particulate matter, to be conducive to further increase its feature of environmental protection.
In a preferred embodiment, as shown in Figure 1, precipitation unit 40 further includes the second neutralization device 43, second It neutralizes device 43 and is provided with acidic ph modifier entrance and fourth process liquid entrance, fourth process liquid entrance goes out with fourth process liquid Mouth is connected.
The pH that can externally drain in setting second with device 43 in precipitation unit 40 is adjusted, to further mention The high outer feature of environmental protection and utility value drained.
Preferably, as shown in Fig. 2, above-mentioned processing system further includes precipitating reagent feeding mechanism 44, the precipitating reagent feeding mechanism 44 are connected with settler 41 by precipitating reagent transfer pipeline.
Preferably, as shown in Fig. 2, above-mentioned processing system further includes acidic ph modifier feeding mechanism 45, the acid pH tune Section agent feeding mechanism 45 is connected with the second neutralization device 43 by acidic ph modifier transfer pipeline.
In a preferred embodiment, as shown in Fig. 2, above-mentioned oxidation unit 10 includes 11 He of oxidant feeding mechanism Acid heavy metal wastewater feeding mechanism 12.Oxidant feeding mechanism 11 is provided with oxidant supply opening, and acid heavy metal wastewater supplies Answer device 12 to be provided with waste water supply opening, oxidation unit 13 is provided with feed opening and the outlet of the first treatment fluid, feed opening respectively with Oxidant supply opening and waste water supply opening are connected.
Oxidation unit 10 with above structure is conducive to improve the degree of automation of entire processing system, to reduce behaviour The labor intensity of author.
Preferably, as shown in Fig. 2, above-mentioned processing system further includes recycle-water storage device 50, recycle-water storage device 50 It is provided with purification water inlet, purification water inlet is connected with treated water outlet by purifying water input.Recycle-water storage device The purified water of discharge can be recycled and be stored by 50 setting, in order to be used for other process, to improve entire processing The feature of environmental protection and economy of technique.
Preferably, above-mentioned processing system further includes pH on-Line Monitor Device, and pH on-Line Monitor Device is for monitoring in first With the pH in device 20.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally Apply for range claimed.
Embodiment 1
Acid heavy metal wastewater is handled using processing system shown in Fig. 2, the ingredient of acid heavy metal wastewater and Concentration value is shown in Table 1.
Table 1
Element PH Zn2+ Pb2+ Hg2+ Cd2+ Cl- As3+ F-
Content, mg/L 1 60 11 80 2 600 45 400
Processing method is as follows:
Acid heavy metal wastewater (material B) is stored in acid heavy metal wastewater feeding mechanism 12, and is pumped (Q by S1 =5m3/ h) into oxidation unit 13 (oxidation trough).By solid-state KMnO4It is mixed to prepare in oxidant feeding mechanism 11 with production water The KMnO of 5wt%4Then above-mentioned oxidant mixed liquor is inputted 13 (oxygen of oxidation unit with the speed of 500L/h by solution (material A) Change slot) in.By oxidation reaction, the atomic state mercury in acid heavy metal wastewater is made to be converted into mercury ion, the reaction time is 40min obtains the first treatment fluid, and the first treatment fluid overflow to first is neutralized device 20.
S2, alkaline pH adjusting agent feeding mechanism 21 supplies alkaline pH adjusting agent (NaOH aqueous solution), and alkaline pH is adjusted Agent (NaOH aqueous solution, material C) is delivered in the first neutralization device 20, and the pH of the first treatment fluid is adjusted to 3, obtains second processing Then liquid is transported to vulcanization mercury removal device 31 in a manner of overflow (except mercury tank).
S3, the vulcanizing agent that vulcanizing agent feeding mechanism 33 provides, and by the vulcanizing agent (Na of 5wt%2S solution, dosage are 400L/h, material D) it is continuously added in vulcanization mercury removal device 31 (waste acid removes mercury tank).Make the mercury in vulcanizing agent and second processing liquid Ion carries out vulcanization reaction, and reaction time 40min obtains the mixed serum of mercuric sulphide precipitating and third treatment fluid.By overflowing Above-mentioned conjunction slurries are delivered to intermediate storage tank by the mode of stream, and mixed serum is delivered to 32 (filters pressing of filter-pressing device with elevator pump Machine) filters pressing is carried out, obtain filtrate (third treatment fluid) and filter residue (mercuric sulphide).It is (dirty that filtrate is back to vulcanization mercury removal device 31 Acid removes mercury tank), filter residue (mercuric sulphide) is transported to solid dangerous waste slag library.
S4, the filtrate (third treatment fluid) after the removal of mercury enter settler 41 (removing heavy metals and fluorine reaction by delivery pump Slot).
S5, precipitating reagent feeding mechanism 44 provide precipitating reagent (lime milk solution of 20wt%, material E), and by precipitating reagent (lime milk solution of 20wt%) is continuously added in settler 41 (removing heavy metals and fluorine reactive tank).Make above-mentioned third filtrate with Precipitating reagent carries out precipitation reaction, while the pH of reaction system being controlled to 11.8, and reaction time 60min obtains slurries.Then Slurries are delivered in dense device 42 (concentrator) and carry out solid-liquor separation, supernatant overflow to supernatant tank, and conveyed by pump Neutralize device 43 to second (pH adjusts back slot).
S6, acidic ph modifier feeding mechanism 45 are continuously added to 98wt% to above-mentioned second neutralization device 43 (pH adjusts back slot) The concentrated sulfuric acid (material E), after so that the pH of above-mentioned supernatant is pulled back to 7.5 overflow to recycle-water storage device 50 (reuse pool) return With or outlet." lead, Zn Cr coating pollutant emission standard " (GB25466-2010) row is fully achieved in waste acid after the process Put standard.
Embodiment 2
With the difference of embodiment 1 are as follows: the pH of the first treatment fluid is adjusted to 5 using alkaline pH adjusting agent, obtains second processing Liquid.
Embodiment 3
With the difference of embodiment 1 are as follows: oxidant uses the sodium hypochlorite of 60wt%.
Embodiment 4
With the difference of embodiment 1 are as follows: the reaction time of oxidation reaction is 20min.
Comparative example 1
With the difference of embodiment 1 are as follows: the pH of the first treatment fluid is adjusted to 6 using alkaline pH adjusting agent, obtains second processing Liquid.
Comparative example 2
With the difference of embodiment 1 are as follows: using activated carbon adsorption and coagulant sedimentation, (precipitating reagent is quick lime, molysite, aluminium Salt) handle the acid heavy metal wastewater.After processing, the mercury of 90~95wt% can be removed, at the same remove other heavy metals from Son, but it is not able to satisfy the discharge standard to mercury.
Ion concentration contained in draining outside after processing in embodiment 1 to 4 and comparative example 1 to 2 is shown in Table 1.
Table 1
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Comparing embodiment 1 to 4 and comparative example 2 are it is found that can effectively remove metal using processing method provided by the present application Mercury, while treated that purified water can directly carry out outlet.
The pH of first treatment fluid is limited to this it is found that when carrying out vulcanization reaction by comparing embodiment 1 and 2 and comparative example 1 Apply for the removal rate for being conducive to further increase mercury metal in preferred range.
Comparing embodiment 1 and 3 is it is recognized that while the two mercury metal removal rate is suitable, but is preferably aoxidized using the application When agent, the dosage of oxidant is substantially reduced.
Comparing embodiment 1 and 4 is conducive to it is found that the time of oxidation reaction is limited in the preferred range of the application into one Step improves the oxidation efficiency of mercury ion, and then is conducive to further increase the removal rate of mercury metal.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of processing method of acid heavy metal wastewater, which is characterized in that the acid heavy metal wastewater include mercury metal and Heavy metal ion the treating method comprises:
Oxidation reaction is occurred for the acid heavy metal wastewater and oxidant, so that the gold in the acid heavy metal wastewater by S1 Belong to mercury and be changed into mercury ion from atomic state, obtains the first treatment fluid；
The pH of first treatment fluid is adjusted to 2.5~5 using alkaline pH adjusting agent, obtains second processing liquid by S2；
The second processing liquid is reacted with sulfiding reagent, obtains mercuric sulphide sediment and third treatment fluid by S3；
S4 makes heavy metal ion in the third treatment fluid and precipitating reagent carry out precipitation reaction, obtains sediment and the everywhere Manage liquid；
The pH of the fourth process liquid is adjusted to 6~9 using acidic ph modifier, obtains sediment and scavenging solution by S5.
2. processing method according to claim 1, which is characterized in that the acid heavy metal wastewater includes the mercury metal With one of following ion or a variety of: lead ion, zinc ion, cadmium ion, chromium ion, arsenic ion and fluorine ion.
3. processing method according to claim 1 or 2, which is characterized in that the precipitating reagent is selected from calcium hydroxide, sodium hydroxide With one of the group of quick lime composition or a variety of.
4. processing method according to any one of claim 1 to 3, which is characterized in that use alkaline pH adjusting agent by institute The pH for stating the first treatment fluid is adjusted to 3~4, obtains the second processing liquid.
5. processing method according to claim 1, which is characterized in that the oxidant be selected from potassium permanganate, perchloric acid, One of group of HClO and NaClO composition is a variety of.
6. processing method according to claim 1, which is characterized in that the reaction time of the oxidation reaction be 30~ 50min。
7. processing method according to any one of claim 1 to 6, which is characterized in that the alkaline pH adjusting agent is selected from One of group of sodium hydroxide, potassium hydroxide, calcium hydroxide, quick lime, sodium bicarbonate and sodium carbonate composition is a variety of.
8. processing method according to claim 2, which is characterized in that the acidic ph modifier be selected from sulfuric acid, hydrochloric acid and One of group of nitric acid composition is a variety of.
9. processing method according to claim 1, which is characterized in that the sulfiding reagent is selected from vulcanized sodium, sodium bisulfide With one of the group of magnesium sulfide composition or a variety of.
10. processing method according to claim 1, which is characterized in that during the precipitation reaction, the pH of reaction system It is 11.5~12, the reaction time is 30~60min.
CN201811426950.5A 2018-11-27 2018-11-27 The processing method of acid heavy metal wastewater Pending CN109399832A (en)

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