CN105060431A - Treatment method for high arsenic contaminated acid wastewater - Google Patents
Treatment method for high arsenic contaminated acid wastewater Download PDFInfo
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- CN105060431A CN105060431A CN201510461192.0A CN201510461192A CN105060431A CN 105060431 A CN105060431 A CN 105060431A CN 201510461192 A CN201510461192 A CN 201510461192A CN 105060431 A CN105060431 A CN 105060431A
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Abstract
The invention discloses a treatment method for high arsenic contaminated acid wastewater. The method utilizes an iron salt as the precipitating agent to regulate the formation of minerals in high arsenic contaminated acid wastewater so as to reach the purpose of direct removal of trivalent arsenic without oxidation. Specifically, the initial As(III) concentration of the high arsenic contaminated acid wastewater is 1.5-7.5g/L, the mole ratio of iron to arsenic is controlled at 1-2, the pH value is 2.8-4.5, the temperature is at a room temperature of 15-30DEG C, the stirring speed is 400-500rpm, the reaction time is greater than 10h, the obtained minerals have a good crystal form, and the arsenic removal efficiency is greater than 90%. The method has the advantages of simple operation, low agent dosage, low cost, no need of oxidation, small amount of slag and stability, etc.
Description
Technical field
The invention belongs to field of environment engineering, be specifically related to a kind of method processing high arsenic acid water.
Background technology
The SO being mingled with the heavy metal such as arsenic, mercury flue dust in a large number of the smelting process generation of non-ferrous metal
2flue gas, mainly for the preparation of sulfuric acid.The high-concentration acidic wastewater heavy metal wastewater thereby that before flue gas acid preparing, scrubbing dust collection produces, is nonferrous heavy metal flue gas during smelting washes (being called for short " dirty acid "), the features such as acidity is large, arsenic content is high, complicated component that it has.In dirty acid, the concentration of sulfuric acid is between 4-11%, containing negatively charged ion such as other heavy metal ion such as arsenic and lead, cadmium, zinc, copper, iron, mercury and high density fluorine, chlorine, sulfate radicals, wherein the concentration of arsenic pollutent is up to 0.72-9g/L, far above the emission standard 0.5ppm of arsenic in trade effluent, serious threat environmental safety and residents ' health.
Acidic arsenic-containing method of wastewater treatment conventional is at present mainly limestone vegetation method, molysite deposition method and sulfurization-precipitation method etc., but all has deficiency.Limestone vegetation method need the acid that adds in a large amount of calcium hydroxide neutralized wastewater and produce a large amount of in and slag, because the solubleness of calcium arsenite is comparatively large, so unsatisfactory to arsenious removal effect; The key of iron salt method arsenic removal is expose to the sun oxygen (air) or add hydrogen peroxide to be oxidized trivalent arsenic, also increases operation easier while adding cost; Although sulfurization-precipitation method effectively can remove trivalent arsenic, cost is high and can produce hydrogen sulfide in acid condition, and Working environment is had a strong impact on; Although development in recent years faster absorption method, ion exchange method and membrane separation process achieves good effect of removing arsenic, these class methods are only applicable to process lower concentration, arsenic-containing waste water that composition is single, and cost is higher.
The present invention intends regulation and control and form mineral in high arsenic acid water, to realize directly removing arsenious object in waste water without the need to being oxidized, has good application prospect.
Summary of the invention
The present invention is directed to acid water arsenic concentration and the high feature of sulfuric acid concentration, provide a kind of method processing high arsenic acid water, the method has simple to operate, and it is few, with low cost to add pharmaceutical quantities, without the need to oxidation, and the little and advantage such as comparatively stable of the quantity of slag.
The object of the invention is to realize in the following manner:
Process the method for high arsenic acid water: in high arsenic acid water, add a ferron, adjusted to ph, after stirring reaction, solid-liquid separation arsenic removal.
In aforesaid method height arsenic acid water, the concentration of trivalent arsenic As (III) is 1.5-7.5g/L.
Aforesaid method ferron comprises ferric sulfate, iron(ic) chloride, iron nitrate, preferably sulfuric acid iron.
It is 0.8-2 that aforesaid method ferron dosage controls at Fe (III) and As (III) mol ratio; Preferably 1.5.
The pH value of aforesaid method reaction system is adjusted to 2.8-4.5.Adopt sulfuric acid or sodium hydroxide solution as pH value adjusting agent.
Aforesaid method magnetic agitation speed is 400-500rpm, and the sustained reaction time is greater than 10h.
Aforesaid method reaction process temperature controls as 15-30 DEG C.
What the smelting process of non-ferrous metal produced is mingled with the SO comprising arsenic, mercury heavy metal flue dust in a large number
2flue gas, mainly for the preparation of sulfuric acid; The high-concentration acidic wastewater heavy metal wastewater thereby that before flue gas acid preparing, scrubbing dust collection produces, is dirty acid; In dirty acid, the concentration of sulfuric acid is between 4-11%, and containing arsenic and lead, cadmium, zinc, copper, iron, mercury heavy metal ion and high density fluorine, chlorine, sulfate anion, wherein the concentration of arsenic pollutent is up to 0.72-9g/L.
The present invention utilizes molysite in high arsenic acid water, to form mineral as precipitation agent regulation and control and directly removes arsenious object to reach without the need to being oxidized.The method has simple to operate, and it is few, with low cost to add pharmaceutical quantities, without the need to oxidation, and the little and advantage such as comparatively stable of the quantity of slag.
Accompanying drawing explanation
Fig. 1: the removal effect figure of arsenic under different pH condition;
Fig. 2: the XRD figure of arsenic slag under different pH condition;
Fig. 3: the arsenious removal effect figure of different concns in waste water;
Fig. 4: the XRD figure of different concns trivalent arsenic gained arsenic slag in process waste water;
Fig. 5: the removal effect figure of arsenic under differential responses time conditions;
Fig. 6: the XRD figure of arsenic slag under differential responses time conditions;
Fig. 7: the XRD figure of copper dirty acid treatment gained arsenic slag.
Embodiment
Following examples are intended to further illustrate the present invention, instead of limitation of the invention.
Embodiment 1
Be the sulphuric acid soln of 1.8 with vitriol oil secure ph, the precipitation agent storage liquid that acidic arsenic-containing waste water that As (III) concentration is 0.2mol/L and Fe (III) concentration are 0.4mol/L is prepared respectively with this sulphuric acid soln, also added a small amount of Cu (II), Zn (II) in the arsenic-containing waste water simultaneously prepared, concentration is respectively 0.01mol/L and 0.005mol/L.Get the acidic arsenic-containing waste water that 10 glasss of 50mL prepare, add appropriate isopyknic precipitation agent storage liquid wherein, sodium hydroxide is adopted to regulate pH to be respectively 1.8,2.05,2.3,2.55,2.8,3.05,3.3,3.55,4.0,4.5 after abundant mixing, with the magnetic agitation speed of 480rpm stirring reaction under room temperature (25 ± 1 DEG C), the rotating speed centrifugation of having reacted rear employing 5000rpm obtains supernatant liquor and arsenic slag, by arsenic slag in 60 DEG C of vacuum dryings.
Fig. 1 is the effect of removing arsenic under different pH condition.As seen from Figure 1, along with the rising of pH value, the removal efficiency of arsenic significantly promotes.When pH is 1.8, the removal efficiency of arsenic only has 33%, pH, and between 2.8 to 4.5, arsenic removal efficiency is all higher than 95%, and when pH is 4, arsenic removal efficiency reaches 99%, also removes the iron of more than 95% simultaneously.
The XRD figure of Fig. 2 is pH value when being 1.8-4.5 gained arsenic slag.As seen from Figure 2, under different pH condition, although the intensity slightly difference at each peak of XRD, the position of main diffraction peak is basically identical, illustrates all to define the good mineral of crystal formation in this pH value range.
Embodiment 2
Be the sulphuric acid soln of 1.8 with vitriol oil secure ph, preparing As (III) concentration respectively with this sulphuric acid soln is 6, 4.5, 3, 1.5, the acidic arsenic-containing waste water of 0.5g/L (also added a small amount of Cu (II) in the arsenic-containing waste water simultaneously prepared, Zn (II), concentration is respectively 0.01mol/L and 0.005mol/L), get the acidic arsenic-containing waste water that 50ml prepares respectively, respectively add isopyknic ferric sulphate precipitate agent storage liquid wherein, adjustment iron, arsenic mol ratio is 2, sodium hydroxide adjust ph is adopted to be 4 after abundant mixing, with the speed of 480rpm stirring reaction under room temperature (25 ± 1 DEG C), the rotating speed centrifugation of having reacted rear employing 5000rpm obtains supernatant liquor and arsenic slag, by arsenic slag in 60 DEG C of vacuum dryings.
Fig. 3 is the effect of removing arsenic under different trivalent arsenic concentration conditions.As seen from Figure 3, along with the rising of initial trivalent arsenic concentration, the removal efficiency of arsenic significantly promotes.When initial trivalent arsenic concentration be 1.5g/L and above time, the removal efficiency of arsenic all can reach more than 90%, and most iron is also simultaneously removed.
Fig. 4 is the XRD figure of gained arsenic slag under different trivalent arsenic concentration.As seen from Figure 4, under the initial trivalent arsenic concentration of difference, although the intensity slightly difference at each peak of XRD, the position of main diffraction peak is basically identical, illustrates that arsenious starting point concentration all defines the good mineral of crystal formation within the scope of 1.5-7.5g/L.
Embodiment 3
The sulphuric acid soln that pH value is 1.8 is joined with the vitriol oil, the precipitation agent storage liquid that High-arsenic wastewater (also added a small amount of Cu (II), Zn (II) ion in the arsenic-containing waste water simultaneously prepared, concentration is respectively 0.01mol/L and 0.005mol/L) that As (III) concentration is 0.2mol/L and Fe (III) concentration are 0.4mol/L is prepared respectively with this sulphuric acid soln.Get the High-arsenic wastewater that 10 glasss of 50mL prepare, respectively add isopyknic precipitation agent storage liquid wherein, sodium hydroxide is adopted to regulate pH to be 4.0 after abundant mixing, with the speed of 480rpm Keep agitation under room temperature (25 ± 1 DEG C), and sample in the different reaction times, the rotating speed centrifugation of 5000rpm is adopted to obtain supernatant liquor and arsenic slag, by arsenic slag in 60 DEG C of vacuum dryings.
Fig. 5 is the effect of removing arsenic of differential responses time.As seen from Figure 5, along with the prolongation of time, the removal efficiency of arsenic progressively promotes, and reacts the clearance of arsenic after 24 hours up to 99%.
Fig. 6 is the XRD figure of differential responses time gained arsenic slag.As seen from Figure 6, react in the arsenic slag of 10 hours and occurred characteristic diffraction peak.And along with the continuous prolongation of time, the intensity of this characteristic peak raises gradually.Composition graphs 5 illustrates that this reaction is carried out just defining mineral in 10 hours and time longer crystal formation is better, and arsenic removal efficiency all can reach more than 90%, and most iron is simultaneously removed.
Embodiment 4
In the acid water that certain copper smelting plant produces, arsenious concentration is 7.66g/L, simultaneously also as shown in table 1 containing sulfate radical, sodium, silicon, copper, zinc, iron etc.Get this acid water of 100mL in 200mL beaker, add 4.8g ferric sulfate solid, hydro-oxidation sodium adjust ph is 4, and employing rotating speed is that the magnetic stirring apparatus of 480rpm at room temperature stirs, and reaction terminates rear centrifugation and obtains supernatant liquor and arsenic slag respectively.Supernatant liquor adopts inductively coupled plasma spectrum generator (ICP) to detect wherein remaining arsenic concentration, and the removal efficiency calculating total arsenic is 90.3%; The concentration of iron before and after Simultaneously test reaction, calculating the clearance tapped a blast furnace is 98%; Arsenic slag is dried under 60 DEG C of vacuum, adopts X-ray diffraction (XRD) to be parsed into ore deposit situation.
Certain copper smelting plant acid water component list (grams per liter) of table 1
| Material | As | As(III) | S | Na | Si | Ca | Zn | Bi | Cu | Fe | Mg | pH |
| Concentration | 9.01 | 7.66 | 26.4 | 7.04 | 0.67 | 0.54 | 0.37 | 0.26 | 0.18 | 0.12 | 0.11 | 1.21 |
Fig. 7 is the XRD figure of acid water process gained arsenic slag, as can be seen from the figure really there is the characteristic diffraction peak of mineral, but peak position slightly offsets compared with above-described embodiment, has occurred Fe simultaneously
4(AsO
4)
3(SO
4) OH15H
2the characteristic peak of O, this is because in initial waste containing have an appointment 1/3 pentavalent arsenic.In addition, owing to containing a large amount of sulfate radicals and sodium ion in former dirty acid, so have also appeared the diffraction peak of obvious sodium sulfate in arsenic slag.Cu a small amount of in solution
2+with S
2-define Cu
9s
5, there is its characteristic peak in precipitation.More than analyze and show that the method also can form the good mineral of crystal formation and reach preliminary effect of removing arsenic preferably in the actual acid water of process, arsenic removal efficiency can reach more than 90%, eliminates the iron of 98% and a small amount of copper simultaneously.
Claims (10)
1. process a method for high arsenic acid water, it is characterized in that: in high arsenic acid water, add ferron, adjusted to ph, after stirring reaction, solid-liquid separation arsenic removal.
2. method according to claim 1, is characterized in that, in high arsenic acid water, the concentration of trivalent arsenic As (III) is 1.5-7.5g/L.
3. method according to claim 1, is characterized in that, ferron comprises ferric sulfate, iron(ic) chloride, iron nitrate, preferably sulfuric acid iron.
4. the method according to claim 1 or 2 or 3, is characterized in that, it is 0.8-2 that ferron dosage controls at Fe (III) and As (III) mol ratio.
5. method according to claim 4, is characterized in that, it is 1.5 that ferron dosage controls at Fe (III) and As (III) mol ratio.
6. method according to claim 1, is characterized in that, the pH value of reaction system is adjusted to 2.8-4.5.
7. method according to claim 6, is characterized in that, adopts sulfuric acid and sodium hydroxide solution as pH value adjusting agent.
8. method according to claim 1, is characterized in that, magnetic agitation speed is 400-500rpm, and the sustained reaction time is greater than 10h.
9. the method according to claim 1 or 6 or 7 or 8, is characterized in that, reaction process temperature controls as 15-30 DEG C.
10. method according to claim 1, is characterized in that, what the smelting process of non-ferrous metal produced is mingled with the SO comprising arsenic, mercury heavy metal flue dust in a large number
2flue gas, mainly for the preparation of sulfuric acid; The high-concentration acidic wastewater heavy metal wastewater thereby that before flue gas acid preparing, scrubbing dust collection produces, is dirty acid; In dirty acid, the concentration of sulfuric acid is between 4-11%, and containing arsenic and lead, cadmium, zinc, copper, iron, mercury heavy metal ion and high density fluorine, chlorine, sulfate anion, wherein the concentration of arsenic pollutent is up to 0.72-9g/L.
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Cited By (8)
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| CN106242008A (en) * | 2016-07-29 | 2016-12-21 | 中南大学 | A kind of method removing arsenic in waste acid system |
| CN106396029A (en) * | 2016-11-16 | 2017-02-15 | 昆明冶金研究院 | Arsenic removal method of SCR catalyst |
| CN107500362A (en) * | 2017-09-15 | 2017-12-22 | 中南大学 | A kind of new figure water hydroxyl sarmientite and its preparation method and application |
| CN107794372A (en) * | 2017-10-25 | 2018-03-13 | 湖南水口山有色金属集团有限公司 | A kind of dearsenification selective from lead anode slurry and the method for zero emission of wastewater treatment |
| CN108178127A (en) * | 2018-02-27 | 2018-06-19 | 宣城亨旺新材料有限公司 | The minimizing technology of arsenic in hydrofluoric acid |
| CN110451598A (en) * | 2019-08-20 | 2019-11-15 | 中南大学 | A kind of method that humic peracid strengthening removes trivalent arsenic in acid waste water |
| CN110981026A (en) * | 2019-12-25 | 2020-04-10 | 昆明理工大学 | Method for harmlessly treating arsenic-containing waste acid in nonferrous smelting |
| CN113000027A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Method for removing arsenic in non-ferrous metal smelting wastewater through FeOOH @ COFs |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242008A (en) * | 2016-07-29 | 2016-12-21 | 中南大学 | A kind of method removing arsenic in waste acid system |
| CN106242008B (en) * | 2016-07-29 | 2019-01-25 | 中南大学 | The method of arsenic is removed in a kind of waste acid system |
| CN106396029A (en) * | 2016-11-16 | 2017-02-15 | 昆明冶金研究院 | Arsenic removal method of SCR catalyst |
| CN107500362A (en) * | 2017-09-15 | 2017-12-22 | 中南大学 | A kind of new figure water hydroxyl sarmientite and its preparation method and application |
| CN107500362B (en) * | 2017-09-15 | 2019-05-10 | 中南大学 | A kind of figure water hydroxyl sarmientite and its preparation method and application |
| CN107794372A (en) * | 2017-10-25 | 2018-03-13 | 湖南水口山有色金属集团有限公司 | A kind of dearsenification selective from lead anode slurry and the method for zero emission of wastewater treatment |
| CN108178127A (en) * | 2018-02-27 | 2018-06-19 | 宣城亨旺新材料有限公司 | The minimizing technology of arsenic in hydrofluoric acid |
| CN110451598A (en) * | 2019-08-20 | 2019-11-15 | 中南大学 | A kind of method that humic peracid strengthening removes trivalent arsenic in acid waste water |
| CN110451598B (en) * | 2019-08-20 | 2020-10-27 | 中南大学 | Method for removing trivalent arsenic in acidic wastewater by enhancing humic acid |
| CN110981026A (en) * | 2019-12-25 | 2020-04-10 | 昆明理工大学 | Method for harmlessly treating arsenic-containing waste acid in nonferrous smelting |
| CN113000027A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Method for removing arsenic in non-ferrous metal smelting wastewater through FeOOH @ COFs |
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