CN104478140A

CN104478140A - Non-ferrous smelting waste acid purification treatment method

Info

Publication number: CN104478140A
Application number: CN201410690268.2A
Authority: CN
Inventors: 李绪忠; 肖功明; 虢振强; 王水云; 高伟; 卢丽; 赵凌波; 陈林; 吴班; 陈寒秋; 邓涛; 门海芬; 张弘强; 贺迎春; 夏传
Original assignee: HUNAN HESHENG ENERGY SAVING ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd; MINMETALS COPPER (HUNAN) Co Ltd; ZHEJIANG KEFEI TECHNOLOGY Co Ltd; CINF Engineering Corp Ltd
Current assignee: HUNAN HESHENG ENERGY SAVING ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd; MINMETALS COPPER (HUNAN) Co Ltd; ZHEJIANG KEFEI TECHNOLOGY Co Ltd; CINF Engineering Corp Ltd
Priority date: 2014-11-27
Filing date: 2014-11-27
Publication date: 2015-04-01

Abstract

The invention relates to a non-ferrous smelting waste acid purification treatment method which comprises the following steps: (1) adding waste acid into concentrated sulfuric acid, adjusting the acidity to 40-50g/L, adding white ash, extracting at 70-80 DEG C, then, adding zinc oxide to enable the pH to 2.5-3.0, reacting under stirring and filtering; (2) removing chlorine from the filtrate by chloride ion exchange resin and removing fluorine from the filtrate by fluorine ion exchange resin respectively; and (3) respectively carrying out spiral electrodeposition on the liquid after ion exchange to remove arsenic and carrying out spiral electrodeposition to recover zinc. Waste acid treated reaches zero discharge, arsenic in the waste acid can be separated and heavy metal zinc can be recovered, so that the piling problem of waste gypsum residues generated in conventional sewage treatment is solved, thereby achieving zero discharge and comprehensive recovery and utilization of sewage and solid wastes of a lead, zinc and copper joint smelting enterprise.

Description

The dirty acid purification treatment process of a kind of non-ferrous metal metallurgy

Technical field

The invention belongs to smelting field of nonferrous metal, be specifically related to a kind of dirty acid purification treatment process.

Background technology

Dirty acid is the spent acid washing flue gas generation in flue gas during smelting process of preparing sulfuric acid.After non-ferrous metals smelting works' sulfuric acid plant purification section carries out washing, purifying to flue gas during smelting, the impurity such as the arsenic in flue gas, fluorine, chlorine, flue dust enter in recycle acid, when impurity enriched to a certain extent time outside system, discharge a certain amount of dirty acid.The dirt acid that Non-ferrous Metallurgy produces, its acidity is high, heavy metal kind is many and concentration is high, simultaneously containing the arsenic, fluorine, the chlorine that are difficult in a large number remove.Present stage mainly adopts the various methods such as lime stone-gypsum method, chemical precipitation method, lime iron salt method, sulfuration method, embrane method to carry out combined treatment, treatment process exist processing costs high, be difficult to stably reaching standard discharge, water outlet calcium ion concn height reuse difficulty, gypsum tailings stores up the shortcomings such as landfill land occupation stock number is large, reverse osmosis membrane easily blocks, and is difficult to the requirement meeting national environmental protection new policy.How stable removal arsenic, fluorine, chlorine, and spent acid and valuable metal in acid heavy metal containing sewage can be reclaimed become a difficult problem of pendulum in face of Study on Environmental Protection worker.

Summary of the invention

The present invention is directed to the deficiencies in the prior art, provide a kind of non-ferrous metal metallurgy dirty acid purification treatment process, the dirt acid adopting art breading of the present invention to cross reaches zero release, and can isolate arsenic wherein, reclaims heavy metal zinc wherein.

The dirty acid purification treatment process of non-ferrous metal metallurgy of the present invention, step is as follows:

A, dirt acid that is plumbous or zinc abstraction factory is added the vitriol oil regulate acidity to reach 40 ~ 50g/L, add the white cigarette ash (dirty acid and white cigarette ash liquid-solid ratio 40 ~ 50: 1) of copper smelting plant, leach at temperature is 70 ~ 80 DEG C, then the zinc oxide p H adding zinc abstraction factory reaches 2.5 ~ 3.0, stirring reaction, obtains the sewage through primary treatment after filtration.

B, the sewage through primary treatment of step a pumped into the dechlorination of chlorion exchange resin, obtain the sewage through secondary treatment.

C, the sewage through secondary treatment of step b pumped into fluorion exchange resin except fluorine, obtain the sewage through three process.

D, by step c through three times process sewage through eddy flow electrodeposition removing heavy metals and arsenic, obtain through four times process electrodeposition after liquid and electrodeposition slag.

E, the liquid after the electrodeposition of four process of steps d is reclaimed zinc wherein through eddy flow electrodeposition.

The electrodeposition slag of steps d delivers to the recovery system of zinc abstraction factory, reclaims zinc wherein, solidification arsenic wherein.

When chlorion exchange resin in step b reaches capacity, use sulfuric acid counter-current regeneration.Regenerated liquid is hydrochloric acid, recoverable.

When fluorion exchange resin in step c reaches capacity, use alum liquor counter-current regeneration.Regenerated liquid obtains aluminum fluoride solid after precipitation, and supernatant liquor is sulfuric acid, equal recoverable.

The present invention adopts ion exchange resin method fluorine and chlorine removal, principle is: when chloride, that fluorine is high solution of zinc sulfate enters into chlorine, fluorion exchange column respectively, the sulfate radical that chlorion, fluorion will replace on respective resin respectively, thus from solution, chlorine, fluorine are removed.After resin absorption for some time, reach capacity state, in order to absorption and resolve chlorine, fluorion process in do not introduce new ion, often select sulfuric acid as the parsing agent of chlorion exchange resin, Tai-Ace S 150 is as the parsing agent of fluorion exchange resin.

Compared with traditional electrodeposition technology, eddy flow electrodeposition technology can carry out selection electrodeposition in many metallic solutions that target metal ions concentration is lower, and obtains high purity metal product.Eddy flow electrodeposition cathodic reaction: metal (or metalloid) positively charged ion obtains electronics at negative electrode and forms metal (or metalloid): Zn ²⁺+ 2e ^-=Zn, As ³⁺+ 3e ^-=As; Anodic reaction: anode has several possible reaction, topmost reaction is that the Water oxidize in solution produces oxygen, and reacts as follows: 2H ₂o=O ₂+ 4H ⁺+ 4e ^-.When the metal concentration in electrolytic solution reduces, be difficult to ensure that metal does not produce other reaction in cathodic reduction, when metal concentration is lower, the most incident chemical reaction is the generation of hydrogen, reacts as follows: 2H ⁺+ 2e ^-=H ₂.

Dirty acid is first carried out acid adjustment and meutral innersion by the present invention, and then adopt ion exchange resin method fluorine and chlorine removal, the decreasing ratio of step b chlorine can reach 95%, and the decreasing ratio of step c fluorine can reach 90%.Adopt the arsenic removal of eddy flow electrodeposition technology, reclaim zinc, the decreasing ratio of steps d arsenic can reach 99.2%, the decreasing ratio of zinc can reach 60%.Chlorine, fluorine, arsenic removal rate are stablized, and form open circuit to the chlorine in system, fluorine, arsenic.Do not introduce calcium ion and direct reuse in water treatment, decrease the possibility of pipe-line equipment fouling, what solve traditional wastewater process generation gypsum tailings stores up problem.The present invention reaches plumbous zinc-copper associating smelting enterprise sewage, the zero release of solid waste and synthetical recovery and utilization.Method treatment effect of the present invention is stable, efficient, simple to operate; Technical process is short, and floor space is few; Cost is low, energy-conserving and environment-protective.

Accompanying drawing explanation

Accompanying drawing 1 is present invention process schema.

Embodiment

For the ease of understanding the present invention, give detailed description by embodiment below.

White cigarette ash is flue gas dust collection gained cigarette ash in Metal smelting process, and general Contents of Main Components scope is: Pb 48 ~ 50%, As 13 ~ 15%, Zn 3 ~ 4%.

Embodiment 1

The present embodiment dirty acid used is from first factory and second factory, but the dirty acidacidity gap of two factories is large, F content lower than standard level, so first carried out the allotment of acidity and F content.

(1) acid adjustment and middle leaching

1. be to mix at 2: 1 by volume by the dirt acid of first factory and second factory, to make the dirty acidacidity of process have more typicalness, then to add the 60mL vitriol oil to the acidity of solution be 43g/L, simultaneously for adding 8.8g NaF, makes F content more meet the F content of the dirty acid of typical case; After mixing, each component content sees the following form:

2. add the white cigarette ash of 100g and leach 1h at temperature is 70 ~ 80 DEG C, keeping temperature-stable slowly to add ZnO gradually again, is 2.5-3.0 by the acidity adjustment pH value of solution, and when pH value no longer changes, stopped reaction, filters.The ZnO amount added is 170g, and leached mud net weight is 142.3g, and the slag rate of reaction process is 52.7%.The composition of filtrate and filter residue sees the following form:

Table 1-1-1 leach liquor and leached mud composition

Lower as can be seen from the leaching yield of table 1-1-1, Pb, be mainly present in leached mud, arsenic also has 1.71% to be present in leached mud.

(2) strong-basicity styrene series anion exchange resin is except Cl ^-

1. adsorb: carry out ion-exchange with peristaltic pump rotating speed for above-mentioned leach liquor following current (upper entering and lower leaving) is sent into resin column by 60rdm (flow velocity is for 1800mL/h);

2. resolve and regenerate: treating Cl in effluent liquid ^-during too high levels, illustrate that resin reaches capacity, stop absorption, regenerate by the sulfuric acid adverse current (bottom in and top out) of 2N, detect Cl in regenerated liquid ^-content.After having regenerated, wash post 1 hour by pure water adverse current, then following current washes post to water outlet pH value >=2.

Repeat Adsorption and desorption and regeneration tests, and compare the content data of Cl:

Before absorption

3.12g/L

After absorption	0.156g/L
		Extrusion rate	95％

(3) weakly basic styrene type anion exchange resin is except F ^-

1. adsorb: be that above-mentioned leach liquor following current feeding resin column is carried out ion-exchange by 60rdm (flow velocity is 1800mL/h) with rotating speed;

2. resolve and regenerate: treating F in effluent liquid ^-during too high levels, stop absorption, with the alum liquor counter-current regeneration of 180g/L.After having regenerated, then wash post 1 hour by pure water adverse current, then post is washed in following current.

Repeat Adsorption and desorption and regeneration tests, and compare the content data of F.

G/L before absorption	1.35
		G/L after absorption	0.154、0.115、0.123
Extrusion rate %	90.3

(4) eddy flow electrodeposition removal of impurities

Adopt eddy flow electrowinning plant to test, electrodeposition condition is as follows:

Current density A/m ²	Internal circulating load m ³/h	Temperature	PH value	Time
					1500	200	Room temperature	2.5～3.0	1h

According to electrolytic condition, to draw before and after electrodeposition each metal removal situation in solution:

Table 1-1-2 eddy flow electrodeposition removal of impurities situation

Dry and carry out composition analysis to electrodeposition slag:

Table 1-1-3 eddy flow electrodeposition electrodeposition slag ingredient content

Composition	As	Cu	Zn	Pb	F	Cl	Cd	In
									Quality %	3.19	0.043	45.58	1.03	0.325	0.176	1.68	0.0084

As can be seen from table 1-1-1 and 1-1-2, through leaching process, Pb is mainly present in leached mud, and in leach liquor, Pb content is 0.0031g/L; After ion-exchange, the decreasing ratio of F and Cl can reach 90% and 96% respectively; After eddy flow electrodeposition, the As in leach liquor can take off to 0.033g/L, and decreasing ratio reaches 99.2%; Zn is reduced to 10.1g/L by 24.47g/L.

Embodiment 2

The present embodiment uses liquid after the removal of impurities of embodiment 1 electrodeposition to investigate, and proceeds the situation of eddy flow electrodeposition electrowinning zinc.

After electrodeposition removing impurities, in liquid, Zn content is lower, adds zinc sulfate, and preparing Zn content is respectively the solution of zinc sulfate of 50g/L and 100g/L.

Use clean water equipment, then the solution of zinc sulfate of 3L is injected electrolytic solution storage tank, start magnetic drive pump, circulation is carried out 5 minutes to solution; Eddy flow electrodeposition parameter gets solution circulated amount 600L/hr, arranges current density and carries out electrodeposition experiment.In process of the test, recording voltage at set intervals during electrolysis, calculates its average cell voltage; And analyze the acidity of each time period, whole experimentation record is in table 1:

Table 1 experimentation record

Through the eddy flow electrodeposition of 2.5 hours, stop, open eddy flow electrowinning plant, take out starting sheet, obtain zine plate, zine plate is peeled off from negative electrode, the zinc pipe obtained.Be weighed as 52.2g, calculate current efficiency 85.6%, zinc power consumption 3333.3kWh/t Zn.

Claims

1. the dirty acid purification treatment process of non-ferrous metal metallurgy, comprises the steps:

(1) in dirty acid, add the vitriol oil, regulate acidity to reach 40 ~ 50g/L, add white cigarette ash, leach at temperature is 70 ~ 80 DEG C, then add zinc oxide and make pH reach 2.5 ~ 3.0, stirring reaction also filters;

(2) filtrate dechlorinated respectively by chlorion exchange resin, fluorion exchange resin is except fluorine;

(3) by the liquid after ion-exchange respectively through the arsenic removal of eddy flow electrodeposition, eddy flow electrodeposition reclaim zinc.

2. the dirty acid purification treatment process of non-ferrous metal metallurgy according to claim 1, it is characterized in that dirty acid is for plumbous or the dirty acid of zinc abstraction, white cigarette ash is Copper making cigarette ash.

3. the dirty acid purification treatment process of non-ferrous metal metallurgy according to claim 1 and 2, is characterized in that in step (1), dirty acid and white cigarette ash add by liquid-solid ratio 40 ~ 50: 1.

4. the dirty acid purification treatment process of non-ferrous metal metallurgy according to claim 1, is characterized in that step (2) chlorion exchange resin used and fluorion exchange resin are styrene series anion exchange resin.

5. the dirty acid purification treatment process of the non-ferrous metal metallurgy according to claim 1 or 4, is characterized in that step (2) ion-exchange flow velocity is 1700 ~ 1800mL/h.

6. the dirty acid purification treatment process of the non-ferrous metal metallurgy according to claim 1,2 or 4, is characterized in that step (3) eddy flow electrodeposition arsenic removal condition is: temperature 70 ~ 80 DEG C, current density 1200 ~ 1500A/m ², electrolytic solution pH 2.5 ~ 3.0; Eddy flow electrodeposition reclaims zink rod part: temperature 70 ~ 80 DEG C, current density 400 ~ 500A/m ², electrolytic solution pH 2.5 ~ 3.0.