CN102330108B - Method for treating sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue - Google Patents
Method for treating sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue Download PDFInfo
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- CN102330108B CN102330108B CN201110248846.3A CN201110248846A CN102330108B CN 102330108 B CN102330108 B CN 102330108B CN 201110248846 A CN201110248846 A CN 201110248846A CN 102330108 B CN102330108 B CN 102330108B
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Abstract
The invention provides a method for treating a sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue. The method comprises the following steps of: (1) adding a sodium hydroxide solution with concentration of 1-30g/L to a cathode chamber of an ion exchange membrane electrolytic cell; taking the sodium arsenate composite salt solution with the same volume and adding the sodium arsenate composite salt solution to an anode chamber of an ion exchange membrane electrolytic cell, wherein the temperature of the anode solution is 30-60 DEG C; respectively connecting an anode and a cathode of the ion exchange membrane electrolytic cell with an anode and a cathode of an external direct current stabilized voltage supply; controlling the voltage at 1-12 V; detecting the pH value of the anode solution by using a pH meter; and finishing the electrolysis while the pH value is less than 1; (2) moving out the solution in the anode chamber; slowly adding ammonia water to the solution until no precipitate is generated; filtering the precipitate; and drying the precipitate below 35 DEG C to obtain arsenic acid; and moving out the solution in the cathode chamber; and concentrating and drying the solution to obtain the sodium hydroxide. The method provided by the invention is used for treating the sodium arsenate composite salt solution formed by leaching the antimony smelting arsenic alkaline residue and has the advantages of short process flow, less equipment investment and obvious economic benefits and environment friendly benefits.
Description
Technical field
The present invention relates to the environmental protection technology of non-ferrous metal metallurgy, particularly process the method for sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue.
Background technology
Arsenic alkali slag is the scum silica frost producing while adding alkali arsenic removal in antimony refining process, and its main component has stibnate and antimonite, arsenate and arsenite, selenite and antimony etc., and wherein, 99% arsenic is to exist with the form of sodium arseniate.Conventionally adopt hot water leaching, de-antimony agent leaching-out technique substantially can reach the object of the separation of As, Sb to arsenic alkali slag.The antimony slag forming returns to antimony smelting system and processes, and a large amount of sodium arseniates and a small amount of soluble sodium salt such as sodium carbonate, sodium hydroxide dissolved salt enter leach liquor.Be the key problem in technology of processing arsenic alkali slag if realize separation and the comprehensive utilization of soluble sodium salt in leach liquor, also can produce reasonable economic benefit and significant environmental benefit.
Traditional antimony smelting arsenic alkali alkaline residue leach liquor treatment process has chemical precipitation method, sodium arseniate composite salt method, CAM etc.As the treatment process of the arsenic alkali slag of calcium hydroxide arsenic precipitation for the propositions such as Jin Zhenan [refer to Jin Zhenan etc., process the novel process of antimony regulus arsenic alkali slag, non-ferrous metal (Smelting Part), 1999,11(5): 11-14]; Adopt Na when Xu Li etc.
2s makes vulcanizing agent Sulphuration Dearsenication of Leaching Liquor from Arsenic Containing Alkaline Dregs Generated in Antimony Smelting is studied to [while referring to Xu Li etc., brief talk antimony regulus arsenic-containing waste residue treatment process, tinnery science and technology, 1997, (3): 30-33].Deep arsenic removal technology is comparatively perfect, but it can produce a large amount of waste residues after processing, and causes secondary pollution, is unfavorable for environment protection.Sodium arseniate composite salt method products obtained therefrom at present substantially can only be as glass fining agent, and composition fluctuation is very large, and arsenic content is high, and user is difficult to accept.The arsenic containing solution of a CAM suitable treatment lower concentration, and processing power is low.
Summary of the invention
The problem existing for aforesaid method, the present invention adopts the membrane electrolysis in ion-exchange membrane technique to solve the difficult separation problem of arsenic alkali in leaching liquor of arsenic-containing alkaline dregs, by preparing arsenic acid, sodium hydroxide, improve the economic benefit of enterprise, solved the problem of environmental pollution of antimony smelting arsenic alkali slag simultaneously.
Technical scheme of the present invention is:
(1) the NaOH solution of 1g/L-30g/L concentration or water are added in the cathode compartment of ion-exchange membrane electrolyzer, the sodium arseniate composite salt solution of getting same volume adds in the anolyte compartment of ion-exchange membrane electrolyzer, and anodic dissolution temperature is 30-60 ℃.The anode of ion-exchange membrane electrolyzer is connected with negative pole with the positive pole of external D.C. regulated power supply respectively with negative electrode, and control voltage is 1-12V.Use pH meter to measure anodic dissolution pH value, be less than at 1 o'clock until pH value, electrolysis is complete.
(2) anolyte compartment's solution is shifted out, add slowly ammoniacal liquor, until precipitate not regeneration, by sedimentation and filtration, 35 ℃ of following oven dry, obtain arsenic acid.Cathode chamber solution is shifted out, and concentrated, oven dry, obtains sodium hydroxide.
Described ion-exchange membrane electrolyzer comprises monofilm two-compartment cell, is made up of anolyte compartment, anode, cationic membrane, negative electrode, cathode compartment, and cationic membrane is perfluor cationic exchange membrane.
Described sodium arseniate composite salt solution is the solution after hot water leaching, de-antimony agent leaching, filtration process or again through concentrated, the water-soluble solution of dried sodium arseniate composite salt by antimony smelting arsenic alkali slag.
The know-why of institute of the present invention foundation:
Electrolyzer is divided into cathode compartment and anolyte compartment with cationic exchange membrane, positive plate and negative plate are housed separately, in anolyte compartment, add leaching liquor of arsenic-containing alkaline dregs, in cathode compartment, add water or NaOH solution.Anolyte compartment's anode generation oxidizing reaction under DC electric field effect, sodium ion sees through cationic membrane and enters cathode compartment, and anolyte compartment's pH value in solution reduces, and finally obtains containing H
3asO
4the acidic solution that concentration is higher.And in cathode compartment, there is reduction reaction, water electrolysis produces hydroxide ion, is combined generates sodium hydroxide with sodium ion.Negative electrode and positive electrode reaction is as follows:
Anode: H
2o → O
2↑+4H
++ 4 e
-
Negative electrode: 4H
2o+4e
-→ 2H
2↑+4OH
-
Antianode H that chamber obtains
3asO
4, H
2sO
4, H
2cO
3solution
Due to H
3asO
4be insoluble to NH
3h
2o, by containing the H that concentration is higher
3asO
4in solution, add NH
3h
2o, can be H
3asO
4be precipitated out.
The present invention produces sodium arseniate composite salt solution for the treatment of antimony smelting arsenic alkali slag, and technical process is short, and facility investment is few, has significant economic benefit and environmental benefit.
Embodiment
Following embodiment is intended to further illustrate the present invention, rather than limitation of the invention.
Specific embodiment of the invention sodium arseniate composite salt solution used is taken from Xikuangshan Shanxing Antimony Industry Co., Ltd of Hunan Province, and chemical analysis shows this leaching liquor of arsenic-containing alkaline dregs As
5+concentration is 9.19 g/L.
Select acrylic board as electrolyzer material, to its processing polished, bond with chloroform, be made into length and be respectively the groove of 14 cm, 9 cm, 9 cm, and add a dividing plate (diameter 4 cm holes are worn in centre) in centre.Length and width of clip is the Nafion perfluoro sulfonic acid membrane of 5 cm 4 cm holes of dividing plate is filled, and electrolyzer is separated into cathode compartment and anolyte compartment like this.
NaOH solution 300 mL that get 3g/L pour in electric tank cathode chamber.Meanwhile, get the above-mentioned leaching liquor of arsenic-containing alkaline dregs of 300 mL and pour anolyte compartment into.Anode uses titanium plate, negative electrode to use stainless steel plate, external D.C. regulated power supply.Start electrolysis, control voltage is 6V.Use pH meter to measure anodic dissolution pH value, be less than at 1 o'clock until pH value, electrolysis is complete.
Anolyte compartment's electrolytic solution is shifted out, add slowly ammoniacal liquor, until precipitate not regeneration, by sedimentation and filtration, through chemical analysis, in filtrate, the content of arsenic is reduced to 0.9452 g/L, and filter residue is dried at 30 ℃, obtains arsenic acid.Anolyte compartment's electrolytic solution is shifted out, dry, obtain sodium hydroxide.
Claims (2)
1. process a method for sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue, it is characterized in that method steps is as follows:
(1) the NaOH solution of 1g/L-30g/L concentration is added in the cathode compartment of ion-exchange membrane electrolyzer, get same volume by antimony smelting arsenic alkali slag through hot water leaching, de-antimony agent is leached, solution after filtration process or again warp are concentrated, the water-soluble solution of dried sodium arseniate composite salt, add ion-exchange membrane electrolyzer anolyte compartment, anodic dissolution temperature is 30-60 ℃, the anode of ion-exchange membrane electrolyzer is connected with negative pole with the positive pole of external direct current power supply respectively with negative electrode, control voltage is 1-12V, use pH meter to measure anodic dissolution pH value, be less than at 1 o'clock until pH value, electrolysis is complete,
(2) anolyte compartment's solution is shifted out, add slowly ammoniacal liquor, until precipitate not regeneration, by sedimentation and filtration, 35 ℃ of following oven dry, obtain arsenic acid, and cathode chamber solution is shifted out, and concentrated, oven dry, obtains sodium hydroxide.
2. a kind of method of processing sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue according to claim 1, it is characterized in that ion-exchange membrane electrolyzer comprises monofilm two-compartment cell, be made up of anolyte compartment, anode, cationic membrane, negative electrode, cathode compartment, cationic membrane is perfluor cationic exchange membrane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110248846.3A CN102330108B (en) | 2011-08-27 | 2011-08-27 | Method for treating sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue |
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|---|---|---|---|
| CN201110248846.3A CN102330108B (en) | 2011-08-27 | 2011-08-27 | Method for treating sodium arsenate composite salt solution in antimony smelting arsenic alkaline residue |
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| CN102330108A CN102330108A (en) | 2012-01-25 |
| CN102330108B true CN102330108B (en) | 2014-05-28 |
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| CN108570684B (en) * | 2017-03-13 | 2020-06-16 | 中国科学院过程工程研究所 | Electrochemical treatment method of arsenic-containing soot |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4961909A (en) * | 1989-11-09 | 1990-10-09 | Comino Ltd. | Process for the manufacture of copper arsenate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111205C (en) * | 2000-10-26 | 2003-06-11 | 罗广福 | Method of treating arsenic alkaline slag from antimony smelting |
| CN100402680C (en) * | 2004-03-31 | 2008-07-16 | 郁南县广鑫冶炼有限公司 | Pollution-free arsenic alkali slage treating technique |
| CN101509080A (en) * | 2009-03-24 | 2009-08-19 | 中南大学 | Method for comprehensively processing stibium smelt arsenic alkaline residue and producing colloid antimony peroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4961909A (en) * | 1989-11-09 | 1990-10-09 | Comino Ltd. | Process for the manufacture of copper arsenate |
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