CN100537798C - A kind of method of dearsenification from trioxygen-containingization two arsenic flue dust - Google Patents
A kind of method of dearsenification from trioxygen-containingization two arsenic flue dust Download PDFInfo
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- CN100537798C CN100537798C CNB2006101368656A CN200610136865A CN100537798C CN 100537798 C CN100537798 C CN 100537798C CN B2006101368656 A CNB2006101368656 A CN B2006101368656A CN 200610136865 A CN200610136865 A CN 200610136865A CN 100537798 C CN100537798 C CN 100537798C
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- arsenic
- hydrogen peroxide
- flue dust
- liquid
- leach
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
A kind of method of dearsenification from trioxygen-containingization two arsenic flue dust is applicable to it mainly is with As
2O
3The arsenic removal of the materials such as flue dust that exist of form handle.Be that the pH value of regulating leach liquor with sodium hydroxide, yellow soda ash or ammoniacal liquor is 5～12, solvent and solute weight ratio is 2～10: 1, adding hydrogen peroxide under agitation condition leaches, the addition of hydrogen peroxide is 100～300% of chemical reaction metering, extraction temperature is 20～100 ℃, and extraction time is 1～10 hour, makes the arsenic dissolving enter solution, arsenic-removing rate can reach more than 80% and the valuable element concentration in the solution is very low, and major part is retained in the slag.
Description
Technical field
The present invention relates to the method for the non-roasting method of a kind of usefulness dearsenification from flue dust.
Background technology
In the industrial production that zinc extracts, contain zinc, lead, germanium, arsenic etc. in the flue dust that fuming furnace produces, wherein arsenic mainly is with As
2O
3Form exist, in order to reclaim zinc, lead and germanium, normally flue dust is turned back to the sintering circuit batching, thereby causes arsenic constantly enrichment in system, therefore how arsenic removal evil is a problem demanding prompt solution in producing.
At present more existing arsenic removing methods to arsenic-containing material.Introduced the method for using sodium hydroxide reagent to handle high-arsenic material as Chinese patent CN96112949.2 disclosed " dearsenicating technology of high-arsenic material ", be the NaOH aqueous solution to be mixed with high-arsenic material mix thoroughly, the solid weight of mixture is than being high-arsenic material: NaOH=1: 0.3-1; After the oven dry of said mixture 300-650 ℃ of following medium temperature roasts 2-10 hours; The gained calcining leaches 2-3 times with 50-95 ℃ of hot water, each 1-2 hours time; Then with containing Ca
2+Compound or contain NH
4++ Mg
2+Compound precipitation gained arsenic containing solution in arsenic, till not having precipitation and separating out.Because this method comprises the pyrogenic process process, its complex process, the treatment time is long, the cost height.
Chinese patent CN02110552.9 " a kind of copper zinc cobalt material removes the method for arsenic " in addition, be with sodium hydroxide solution dipping copper zinc cobalt material particles, concentration of sodium hydroxide solution is at 80-160 grams per liters, sodium hydroxide solution and solid materials quality proportioning are 3-7: 1, extraction time was at 0.5-2 hours, and extraction temperature is at 80-95 ℃.The decreasing ratio of this method arsenic and sulphur is high, and it is few that the leached mud product that obtains contains harmful impurity.But the solution that this method obtains contain arsenic still for strong toxicity+arsenic of 3 valencys, technology is more complicated also, also needs further oxide treatment in the heavy arsenic of follow-up lime is handled.
Summary of the invention
Purpose of the present invention is under little prerequisite is tried one's best in the loss of valuable element, adopts non-roasting method to remove effectively in the material+3 valency arsenic.
The solution of the present invention, regulate the pH value of leach liquor in 5～12 scopes with sodium hydroxide, yellow soda ash or ammoniacal liquor, leach liquor and solid materials weight ratio are 2～10:1, adding hydrogen peroxide under agitation condition leaches, the addition of hydrogen peroxide is 100～300% of chemical reaction metering, extraction temperature: 20～100 ℃, extraction time: 1～10 hour.
Further way is, the arsenic that adopts circulation to be leached in the leach liquor is enriched near saturation value.
Contain arsenic and leach back liquid employing known method, add lime and make the arsenic precipitation, 20～100 ℃ of the heavy arsenic temperature of control, in 3～10 hours reaction times, the Ca/As mol ratio is 1～5:1.
Method of the present invention makes arsenic be converted into the dissolving of 5 valency arsenic and enters solution, and arsenic-removing rate generally can reach more than 80%; Valuable element is retained in the slag, and when returning sintered material, the arsenic of having been eliminated effectively in producing because most of arsenic has sloughed is harmful; Valuable element concentration in the solution is very low, can be used as leach liquor behind the heavy arsenic of liquid after leaching and returns use, does not have discharge of wastewater basically, greatly reduces the pollution to environment.The present invention adopts the weak caustic solution oxidation to leach, technical process is simple, can heat the arsenic that can make leaching quickly exists with the big sodium arseniate form of solubleness in solution, help its further processing, add the milk of lime causticization as employing, make sodium arseniate be converted into the Tricalcium arsenate precipitation, become the pentavalent arsenic hydrochlorate form more stable, that toxicity is lower, after liquid-solid separation, remove.
Embodiment
Table 1, table 2, table 3 are material conditions of certain spelter works's flue dust (secondary zinc oxide).
The content of different shape arsenic in table 1 material
Table 2 material Chemical Composition (mean value)
Table 3 raw meal particle size is formed
Annotate: the material mean particle size is 1.72 μ m (laser particle size analyzer).
In the embodiment of the inventive method, according to containing As in the 100 gram secondary zinc oxide materials
2O
3Mean value calculation, make 3 valency arsenic wherein be converted into 5 valency arsenic, the theoretical consumption of hydrogen peroxide is 7.5ml.In order to improve leaching efficiency and to remedy the loss that produces because of decomposition, the addition of hydrogen peroxide is preferably 120～200% of chemical reaction metering, and leaching efficiency increases limited and consumption is excessive when higher.
During leaching, though can carry out, cross that material concentration is too high when low is unfavorable for that reaction system is even in bigger liquid-solid ratio scope, the treatment capacity that leaches back liquid when too high is too big, and general leach liquor and solid materials weight ratio L/S are advisable with 3～5:1.
Because arsenic content is generally lower in the flue dust, for reducing the treatment capacity that leaches back liquid, adopt repeatedly circulation to leach, cycle index is generally 2～5 times, to improve the enrichment value of arsenic in the leach liquor, till approaching or the value of reaching capacity, add the heavy arsenic of precipitation agent again, liquid returns use as leach liquor after the leaching after the liquid-solid separation.
In order to contrast, under same material condition, made not add the Comparative Examples of hydrogen peroxide.
Comparative Examples: 100 gram secondary zinc oxide materials, hydrogen peroxide addition 0ml; Extraction temperature: room temperature (30 ℃); Extraction time: 3h; The pH value of adjusting solution with NaOH is 11; L/S is 5:1.
Arsenic-removing rate is 13.4%, leaches [Pb]＜0.01g/L in the liquid of back; [Zn]＜0.01g/L; [Ge]＜0.005g/L; But 91.7% As is with As
3+Form exist.
Below be example of the present invention:
Embodiment 1:100 gram secondary zinc oxide material, hydrogen peroxide addition 10ml; Extraction temperature: 23 ℃; Extraction time: 3h; The pH value of adjusting solution with NaOH is 11; L/S is 3:1.
Arsenic-removing rate reaches 83.6%, leaches [Pb]＜0.08g/L in the liquid of back; [Zn]＜0.1g/L; [Ge]＜0.005g/L; 98.8% As is with As
5+Form exist.
Embodiment 2:100 gram secondary zinc oxide material, hydrogen peroxide addition 20ml; Extraction temperature: 29 ℃; Extraction time: 3h; Use Na
2CO
3The pH value of adjusting solution is 9; L/S is 5:1.
Arsenic-removing rate reaches 83.3%, leaches [Pb]＜0.1g/L in the liquid of back; [Zn]＜0.2g/L; [Ge]＜0.005g/L; 100% As is with As
5+Form exist.
Embodiment 3:100 gram secondary zinc oxide material, hydrogen peroxide addition 15ml; Extraction temperature: 75 ℃; Extraction time: 1h; The pH value of adjusting solution with ammoniacal liquor is 5.0; L/S is 4:1.
Arsenic-removing rate reaches 84.1%, leaches [Pb]＜0.1g/L in the liquid of back; [Zn]＜0.2g/L; [Ge]＜0.005g/L; 100% As is with As
5+Form exist.
Embodiment 4:100 gram secondary zinc oxide material, hydrogen peroxide addition 15ml; Extraction temperature: 75 ℃; Extraction time: 10h; The pH value of adjusting solution with NaOH is 8.2; L/S is 4:1.
Arsenic-removing rate reaches 84.4%, leaches [Pb]＜0.1g/L in the liquid of back; [Zn]＜0.3g/L; [Ge]＜0.005g/L; 100% As is with As
5+Form exist.
Arsenic leaching solution in above-mentioned each example is added lime make the arsenic precipitation, the heavy arsenic temperature of control is 60～90 ℃, and in 5～7 hours reaction times, the Ca/As mol ratio is 2～4:1, and heavy arsenic rate reaches 86.2～89.3%.
Example 5: adopt three circulations to leach, each leach liquor adds next batch material and hydrogen peroxide again and adjusts the pH value after isolating solid slag.Each 100 gram secondary zinc oxide materials, the addition that at every turn leaches hydrogen peroxide is 10ml; Extraction temperature: room temperature (30 ℃); Extraction time: 3h; The pH value of adjusting solution with NaOH is 10～11.5; L/S is 5:1, and the result is as shown in table 4.
Table 4 leach liquor circulation dearsenification effect
As shown in table 2, each arsenic-removing rate all is stabilized in more than 80%, leaches [Pb]＜0.1g/L in the liquid of back; [Zn]＜0.1g/L; 100% As is with As
5+Form exist.
Contain arsenic 32.1g/L through 3 round-robin leach liquors in the example 5, add lime and make the arsenic precipitation, the heavy arsenic temperature of control is 90 ℃, and in 5 hours reaction times, the Ca/As mol ratio is 3:1, and heavy arsenic rate reaches 92.3%.
Claims (2)
1. the method for a dearsenification from trioxygen-containingization two arsenic flue dust, comprise the 5 valency arsenic that leach in the liquid of back are removed with lime precipitation, it is characterized by, the pH value of regulating leach liquor with sodium hydroxide, yellow soda ash or ammoniacal liquor is 5～12, solvent and solute weight ratio is 2～10:1, adds hydrogen peroxide and leach under agitation condition, and the addition of hydrogen peroxide is 100～300% of chemical reaction metering, extraction temperature is 20～100 ℃, and extraction time is 1～10 hour; Liquid is isolated and is added next batch material and hydrogen peroxide again behind the solid slag and adjust the leaching that circulates of pH value after each leaching, and cycle index is 2～5 times, returns as leach liquor after will leaching the heavy arsenic of back liquid.
2. arsenic removing method according to claim 1 is characterized by, and described solvent and solute weight ratio is 3～5:1, and the addition of hydrogen peroxide is 120～200% of chemical reaction metering.
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| CNB2006101368656A CN100537798C (en) | 2006-12-14 | 2006-12-14 | A kind of method of dearsenification from trioxygen-containingization two arsenic flue dust |
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