CN106381397A - Method for dechlorinating through zinc ash material ammonia-leaching ion exchange combined process - Google Patents

Method for dechlorinating through zinc ash material ammonia-leaching ion exchange combined process Download PDF

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Publication number
CN106381397A
CN106381397A CN201610852332.1A CN201610852332A CN106381397A CN 106381397 A CN106381397 A CN 106381397A CN 201610852332 A CN201610852332 A CN 201610852332A CN 106381397 A CN106381397 A CN 106381397A
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ammonia
chlorine
zinc
liquid
ion exchange
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Inventor
宋志红
王国良
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JISHOU JINXIANG RESOURCES SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
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JISHOU JINXIANG RESOURCES SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
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Publication of CN106381397A publication Critical patent/CN106381397A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02Working-up flue dust
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/24Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • C22B7/008Wet processes by an alkaline or ammoniacal leaching
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a method for dechlorinating chlorine through a zinc ash material ammonia-leaching ion exchange combined process. The method comprises the following steps of: preparing zinc ash with high chlorine content into pulp, adding ammonia into the pulp to carry out ammonia leaching, and filtering to obtain ammonia-leaching filter residues and ammonia-leaching filtrate, wherein filtrate is returned to pulp preparing and ammonic leaching if chlorine ion concentration is smaller than 80g/L, and a way is made for recycling chlorine salt I if the chlorine ion concentration is greater than 80g/L; rinsing the ammonia-leaching filter residues to obtain rinsing water and rinsed zinc ash, and leaching and purifying the rinsed zinc ash by use of electrodeposition waste liquor to obtain a zinc sulfate solution; deeply removing the chlorine ions of the zinc sulfate solution by use of ion exchange resin, feeding the dechlorinated zinc sulfate solution to carry out electrodeposition to recycle zinc; and after chlorine salt II is produced by dechlorinating an ion exchange desorbed solution, returning ion exchange resin as a desorption reagent. The method disclosed by the invention realizes high-efficiency low-cost dechlorination, which is several times that of treatment limit of an existing dechlorinating process, and also recycle chlorine salts, so that waste is changed into things of value, a new qualified raw material source is provided for electrolytic zinc, wastewater and waste residue emission is avoided, and environment-friendly, economic and social benefits are remarkable.

Description

Zinc gray material ammonia soaks the method that ion exchange process integration removes chlorine
Technical field
The invention belongs to technical field of wet metallurgy, specially zinc gray material ammonia soak ion exchange process integration removes chlorine Method.
Background technology
With the continuous exhaustion of zinc resource, wet production electrolytic zinc is carried out using the zinc gray of high chlorinity and is increasingly subject to To attention.But under normal circumstances, all containing a large amount of chlorine being existed with compound form in zinc gray, typically chloride 1%~30% ?.If do not removed these impurity components, follow-up electrodeposition operation will be had a strong impact on.And how effectively to remove this kind of harmful Impurity is always the problem that people do not resolve.
At present, in zinc abstraction industry, the common method of zinc gray dechlorination has pyrogenic process and two kinds of wet method, and thermal process mainly has many Thorax oven process and kiln process, wet processing mainly has alkali wash.
Multiple hearth furnace method and kiln process principle are by the way of high-temperature roasting, make the chlorine compound in zinc gray evaporate into receipts Removed in dirt ash.This method haves such problems as that high energy consumption, flue gas be many, pollution is big, simultaneously more than collected ash need extra locating Reason, and multiple hearth furnace method needs the coal gas that burns, equipment requirements are very high.
Alkali wash is using more universal method in current zinc abstraction industry, using sodium hydroxide, sodium carbonate wherein Kind or two kinds as basic agent, wet method pulping and washing is carried out to zinc gray.It is excellent that this method has simple to operate, little, instant effect of investment etc. Point, but there is also soda-wash water chlorine ion concentration low (less than 10g/L), water consumption is big, clean result is not thorough, follow-up water process becomes The shortcomings of this is high.When in zinc gray, chlorine total content is higher than 5%, make just to guarantee the removing of chlorine in zinc gray in this way at all Effect.
Content of the invention
The purpose of the present invention is aiming at the problems referred to above, proposes a kind of zinc gray material ammonia leaching ion exchange process integration removing The method of chlorine, this method can make the chlorine in the zinc gray of high chlorinity effectively be removed, and makes such material pass through wet method zinc abstraction stream Journey is recycled, and during reducing water consumption, simultaneously this method have that ammonia leaching liquid chloride ion-containing concentration is high, flow process is steady Qualitative good the features such as, the deficiencies in the prior art are made up with this.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of zinc gray material ammonia soaks the method that ion exchange process integration removes chlorine, comprises the steps of:
(1) first the zinc gray of high chlorinity is carried out slurrying, in serosity add ammonia carry out ammonia leaching so as in chloride dissolution Or conversion is extracted into ammonia leaching solution, obtain ammonia leaching slag and ammonia leaching liquid after filtering, as chlorine ion concentration is less than 80g/L in filtrate When, return the leaching of slurrying ammonia, such as chlorine ion concentration is then opened a way more than 80g/L and is evaporated reclaiming villaumite one;
(2) ammonia leaching slag is rinsed and is filtered washings and rinsing after zinc gray, to rinsing after zinc gray carry out electrodeposition waste liquid Leach and purify, obtain solution of zinc sulfate;
(3) to the solution of zinc sulfate ion exchange removing chloride ion in step (2) step;Ion exchange resin strippant desorbing Chlorine, after desorbing, liquid enters integral type dechlorination apparatus dechlorination and produces villaumite two, and the ion exchange resin after desorbing recycles.
(4) villaumite two is produced to the integral type dechlorination apparatus dechlorination in step (3), the chloride shift in liquid after making desorbing enters and absorbs Liquid, allows liquid after dechlorination desorbing to be recycled, and returns ion exchange resin and makees strippant.After after absorption, liquid reaches finite concentration Reclaim villaumite two.
Further improvement, described in step (1), the zinc gray of high chlorinity is containing muriatic material containing zinc, and it is substantially Composition is:The 20%-75% of grade containing zinc, chloride 0.5%-30%.
Further improvement, the ammonia of the leaching of slurrying ammonia described in step (1) is one of ammonium hydrogen carbonate, ammonia or two Kind, the feed postition of ammonia can be directly added into for solid or make ammoniacal liquor and add, ammonia dipped process control pH6-10, ammonia leaching temperature 20 ℃—80℃.
Further improvement, in step (2), rinse cycle is single-stage or multi-stage countercurrent rinsing.
Further improvement, described in step (3), strippant is mainly dilution heat of sulfuric acid, and its percentage by weight is:Sulphuric acid 1% 30%, strippant becomes rich in liquid after the desorbing of chlorine after desorbing operation, after integral type dechlorination apparatus dechlorination, obtains After dechlorination desorbing, liquid returns ion exchange resin and recycles.
Further improvement, described in step (4), absorbing liquid is mainly solution of ferrous chloride, and its percentage by weight is:Chlorine Change ferrous 10% 60%, absorbing liquid becomes rich in liquid after the absorption of chlorine after operation through absorbing, and after absorption, liquid reaches finite concentration Reclaim villaumite two afterwards.
The technical characterstic of the present invention is:
High chlorine zinc gray material adopts the leaching of slurrying ammonia and single-stage or multi-stage countercurrent rinsing, can be in the wherein most chlorine of removing Simultaneously it is ensured that ammonia leaching liquid chloride ion-containing concentration is significantly increased, effectively reduce water volume, reduce the cost reclaiming villaumite. In zinc gray after rinsing, a small amount of chlorine of remaining is then removed in liquid after purification and impurity removal by ion exchange dechlorination technology, so protects Demonstrate,prove solution chloride ion in wet method Zn system and be in extremely low level (chlorine ion concentration is less than 300mg/L), meet wet method electrowinning zinc Requirement.After the desorbing by ion-exchange process, liquid returns to the side making strippant use after integral type dechlorination apparatus dechlorination Formula, has reclaimed villaumite, turns waste into wealth, and makes to arrange outside whole method realization no waste water.
Present invention achieves exceed existing alkali cleaning dechlorination process processing limit (the high chlorine zinc gray material of chloride 5%) several times Dechlorination efficiently at low cost, is that electrolytic zinc production provides new acceptable material source.
Substantially free of discharge of wastewater, harmful chlorine becomes valency villaumite side-product to the present invention, is advantageous to environmental protection, to discarded Thing resource utilization degree is high, and economic benefit and social benefit are notable.
Brief description
Fig. 1 is the process chart of the present invention;
Fig. 2 is the structural representation of integral type dechlorination apparatus.
Specific embodiment
Taking pilot production practice as a example further illustrate the positive effect of the present invention below.
Example 1:Certain zinc gray 1 main component is as follows:
Element Zinc % Lead % Chlorine % Ferrum %
Content 56.3 1.2 17.1 1.5
Using following handling process:
(1) slurrying ammonia leaching:By this zinc gray, 6 tons are delivered to pulping tank, and pulping tank is mechanical agitating tank, dischargeable capacity 36m3, Using washings as pulping solution, be mixed into pulping tank to control liquid-solid ratio by returning part ammonia leaching liquid is 6:1, start stirring Device is stirring evenly and then adding into Ammonium bicarbonate food grade, ammonia etc. and carries out ammonia leaching operation, ammonia dipped process control time 1h, 40 DEG C of temperature, regulation Terminal pH is 7.Output ammonia leaching liquid chloride ion-containing 82g/L, open circuit portions are evaporated reclaiming villaumite one;Output ammonia leaching slag contains Chlorine 2.1%.
(2) two sections of countercurrent rinsings:Ammonia leaching slag is rinsed in slurrying tank, using two sections of countercurrent rinsings.Ammonia leaching slag Carry out one section of rinsing first, one section of rinsing, using two-stage nitration washings (chloride ion 10g/L) slurrying rinsing, obtains one section of washings (chlorine Ion 35g/L), one section rinsing slag (chloride 0.9%).One section of rinsing slag carries out two-stage nitration rinsing using water again in slurrying tank, obtains Two-stage nitration washings return one section of rinsing use, (chloride 0.38%) entrance electrodeposition waste liquid leaches and purifies two-stage nitration rinsing slag, gained sulfur Sour zinc solution (chloride ion-containing 1.1g/L) send ion-exchange process dechlorination.
(3) ion exchange dechlorination:Solution of zinc sulfate, through ion exchange resin, instead gives birth to exchange reaction, flow speed control 1.5Be, purified rear (chloride ion-containing 0.28g/L) send Zinc electrolysis to produce zinc.The ion exchange resin of enrichment chlorine is through strippant Desorbing, flow speed control 0.8Be, after desorbing, liquid (4g/L containing zinc, chloride 4.2g/L, containing sulfate radicals 95g/L) enters integral type dechlorination Device dechlorination.
(4) loss of thick fluid chlorine after desorbing:After desorbing, liquid enters integral type dechlorination apparatus, so that chloride ion is transferred to by liquid after desorbing In absorbing liquid, after obtaining dechlorination desorbing, liquid (3.8g/L containing zinc, chloride 0.15g/L, containing sulfate radicals 89g/L) returns ion exchange resin Recycle.Absorbing liquid becomes rich in liquid after the absorption of chlorine through absorbing after operation, and after absorption, liquid reclaims chlorine after reaching finite concentration Salt two.
In general, sodium hydroxide, potassium hydroxide can also be added in pulping solution, the alkaline matter such as sodium carbonate dechlorinates, but its In lixivium, the content of chloride ion at most can only be in 40g/L, and the water consumption in leaching stage and the villaumite now generating reclaim Energy consumption be far above using ammonia or ammonium hydrogen carbonate.But it is using ammonia or the topmost advantage of ammonium hydrogen carbonate, rear Continuous rinse stage, the chlorine residue in leaching slag is easy to be rinsed away, thus rinsing times not only can be reduced, saves money Source, the energy simultaneously increase speed of production, also make chlorine ion concentration in subsequent sulphuric acid zinc solution sufficiently low, thus increasing ion exchange The adsorption efficiency of resin and adsorption effect.Sodium hydroxide and other matter is used according to experiment, in rinse stage, rinses the chlorine residue in slag Content reaches the content being just difficult to reduce chlorine by rinsing when 0.5%, but uses ammonia or ammonium hydrogen carbonate, in rinsing slag Chlorine residue be easy to control below 0.3%, or even can control below 0.2%, thus improving what subsequent production went out The quality of zinc, and substantially increase the organic efficiency of chlorine.
The structure of integral type dechlorination apparatus is as shown in Fig. 2 including reactor 1, absorber 2, adsorber 3, crystallizing evaporator 4, taking out Blower fan 5, chlorine residual measurement instrument 6 and self priming pump 7, reactor 1 by exhaust column 8 connect absorber 2 in the middle part of, the top of absorber 2 with Reactor 1 connects, and absorber 2 is connected with crystallizing evaporator 4, and absorber 2 is connected with self priming pump 7, chlorine residual measurement instrument 6 and air exhauster 5 are located in exhaust column 8, and reactor 1 is connected with adsorber 3.Crystallizing evaporator 4 passes through the bottom of pipeline communication absorber 2.Convulsion Machine 5 is located at exhaust column 8 and the connectivity port of absorber 2.
After after desorbing, liquid enters in reactor 1, air exhauster 5 and self priming pump 7 are opened, and add potassium permanganate to carry out instead in reactor 1 Should, the chloride ion in liquid after making desorbing is changed into the chlorine of gas phase, and chlorine is sent in absorber 2 by air exhauster 5, chlorine and absorber Absorbing liquid reaction in 2, makes the chlorine of gas phase be changed into the chloride ion of liquid phase, and gas recirculation is sent into stirring in reactor 1 and driven away Chlorine, when chlorine residual measurement instrument 6 display chlorine residue is less than 1ppm, air exhauster 5 and self priming pump 7 quit work;After dechlorination desorbing Also it is dissolved with a small amount of chlorine residue in liquid, chlorine residue can be degraded ion exchange resin, therefore cannot be directly used to ion exchange resin dechlorination, After having to pass through adsorber 3 absorption chlorine residue, after dechlorination desorbing, liquid just can return to ion exchange resin recycling.Chloride ion shifts Generate ferric chloride to absorbing liquid, the ferric chloride concentration in absorbing liquid improves constantly simultaneously, when ferric chloride concentration reaches 30- When 60%, extract out and enter crystallizing evaporator 4, obtain ferric chloride side-product.
Example 2:Certain zinc gray 2 main component is as follows:
Element Zinc % Lead % Chlorine % Ferrum %
Content 51.2 2.2 15.9 2.5
Using following handling process:
(1) slurrying ammonia leaching:By this zinc gray, 6 tons are delivered to pulping tank, and pulping tank is mechanical agitating tank, dischargeable capacity 36m3, Using washings as pulping solution, be mixed into pulping tank to control liquid-solid ratio by returning part ammonia leaching liquid is 6:1, start stirring Device is stirring evenly and then adding into ammonium hydrogen carbonate, ammonia etc. and carries out ammonia leaching operation, ammonia dipped process control time 1h, temperature 50 C, regulation Terminal pH is 8.Output ammonia leaching liquid chloride ion-containing 86g/L, open circuit portions are evaporated reclaiming villaumite one;Output ammonia leaching slag contains Chlorine 1.7%.
(2) two sections of countercurrent rinsings:Ammonia leaching slag is rinsed in slurrying tank, using two sections of countercurrent rinsings.Ammonia leaching slag Carry out first one section rinsing, one section rinsing using two-stage nitration washings (chloride ion 9g/L) slurrying rinsing, obtain one section of washings (chlorine from Sub- 32g/L), one section rinsing slag (chloride 0.7%).One section of rinsing slag carries out two-stage nitration rinsing using water again in slurrying tank, obtains two Section one section of rinsing of washings return uses, (chloride 0.28%) enters the leaching of electrodeposition waste liquid and purifies two-stage nitration rinsing slag, gained sulphuric acid Zinc solution (chloride ion-containing 0.72g/L) send ion-exchange process dechlorination.
(3) ion exchange dechlorination:Solution of zinc sulfate, through ion exchange resin, instead gives birth to exchange reaction, flow speed control 1.5Be, purified rear (chloride ion-containing 0.26g/L) send Zinc electrolysis to produce zinc.The ion exchange resin of enrichment chlorine is through strippant Desorbing, flow speed control 0.8Be, after desorbing, liquid (3.4g/L containing zinc, chloride 3.2g/L, containing sulfate radicals 92g/L) enters integral type and takes off Chlorine device dechlorination.
(4) loss of thick fluid chlorine after desorbing:After desorbing, liquid enters integral type dechlorination apparatus, so that chloride ion is transferred to by liquid after desorbing In absorbing liquid, after obtaining dechlorination desorbing, liquid (3.2g/L containing zinc, chloride 0.11g/L, containing sulfate radicals 86g/L) returns ion exchange resin Recycle.Absorbing liquid becomes rich in liquid after the absorption of chlorine through absorbing after operation, and after absorption, liquid reclaims chlorine after reaching finite concentration Salt two.
Example 3:Certain zinc gray 3 main component is as follows:
Element Zinc % Lead % Chlorine % Ferrum %
Content 60.3 1.1 10.4 0.5
Using following handling process:
(1) slurrying ammonia leaching:By this zinc gray, 6 tons are delivered to pulping tank, and pulping tank is mechanical agitating tank, dischargeable capacity 36m3, Using washings as pulping solution, be mixed into pulping tank to control liquid-solid ratio by returning part ammonia leaching liquid is 6:1, start stirring Device is stirring evenly and then adding into Ammonium bicarbonate food grade, ammonia etc. and carries out ammonia leaching operation, ammonia dipped process control time 1h, 30 DEG C of temperature, regulation Terminal pH is 9.Output ammonia leaching liquid chloride ion-containing 84g/L, open circuit portions are evaporated reclaiming villaumite one;Output ammonia leaching slag contains Chlorine 2.4%.
(2) two sections of countercurrent rinsings:Ammonia leaching slag is rinsed in slurrying tank, using two sections of countercurrent rinsings.Ammonia leaching slag Carry out first one section rinsing, one section rinsing using two-stage nitration washings (chloride ion 9g/L) slurrying rinsing, obtain one section of washings (chlorine from Sub- 33g/L), one section rinsing slag (chloride 1.0%).One section of rinsing slag carries out two-stage nitration rinsing using water again in slurrying tank, obtains two Section one section of rinsing of washings return uses, (chloride 0.48%) enters the leaching of electrodeposition waste liquid and purifies two-stage nitration rinsing slag, gained sulphuric acid Zinc solution (chloride ion-containing 1.0g/L) send ion-exchange process dechlorination.
(3) ion exchange dechlorination:Solution of zinc sulfate, through ion exchange resin, instead gives birth to exchange reaction, flow speed control 1.5Be, purified rear (chloride ion-containing 0.28g/L) send Zinc electrolysis to produce zinc.The ion exchange resin of enrichment chlorine is through strippant Desorbing, flow speed control 0.8Be, after desorbing, liquid (2.3g/L containing zinc, chloride 4.8g/L, containing sulfate radicals 98g/L) enters integral type and takes off Chlorine device dechlorination.
(4) loss of thick fluid chlorine after desorbing:After desorbing, liquid enters integral type dechlorination apparatus, so that chloride ion is transferred to by liquid after desorbing In absorbing liquid, after obtaining dechlorination desorbing, liquid (2.3g/L containing zinc, chloride 0.09g/L, containing sulfate radicals 91g/L) returns ion exchange resin Recycle.Absorbing liquid becomes rich in liquid after the absorption of chlorine through absorbing after operation, and after absorption, liquid reclaims chlorine after reaching finite concentration Salt two.
Example 4:Certain zinc gray 4 main component is as follows:
Element Zinc % Lead % Chlorine % Ferrum %
Content 58.3 1.3 5.6 0.7
Using following handling process:
(1) slurrying ammonia leaching:By this zinc gray, 6 tons are delivered to pulping tank, and pulping tank is mechanical agitating tank, dischargeable capacity 36m3, Using washings as pulping solution, be mixed into pulping tank to control liquid-solid ratio by returning part ammonia leaching liquid is 6:1, start stirring Device is stirring evenly and then adding into Ammonium bicarbonate food grade, ammonia etc. and carries out ammonia leaching operation, ammonia dipped process control time 1h, temperature 50 C, regulation Terminal pH is 6.Output ammonia leaching liquid chloride ion-containing 84g/L, open circuit portions are evaporated reclaiming villaumite one;Output ammonia leaching slag contains Chlorine 1.4%.
(2) two sections of countercurrent rinsings:Ammonia leaching slag is rinsed in slurrying tank, using two sections of countercurrent rinsings.Ammonia leaching slag Carry out first one section rinsing, one section rinsing using two-stage nitration washings (chloride ion 8g/L) slurrying rinsing, obtain one section of washings (chlorine from Sub- 31g/L), one section rinsing slag (chloride 0.6%).One section of rinsing slag carries out two-stage nitration rinsing using water again in slurrying tank, obtains two Section one section of rinsing of washings return uses, (chloride 0.18%) enters the leaching of electrodeposition waste liquid and purifies two-stage nitration rinsing slag, gained sulphuric acid Zinc solution (chloride ion-containing 0.64g/L) send ion-exchange process dechlorination.
(3) ion exchange dechlorination:Solution of zinc sulfate, through ion exchange resin, instead gives birth to exchange reaction, flow speed control 1.5Be, purified rear (chloride ion-containing 0.23g/L) send Zinc electrolysis to produce zinc.The ion exchange resin of enrichment chlorine is through strippant Desorbing, flow speed control 0.8Be, after desorbing, liquid (2.1g/L containing zinc, chloride 2.4g/L, containing sulfate radicals 90g/L) enters integral type and takes off Chlorine device dechlorination.
(4) loss of thick fluid chlorine after desorbing:After desorbing, liquid enters integral type dechlorination apparatus, so that chloride ion is transferred to by liquid after desorbing In absorbing liquid, after obtaining dechlorination desorbing, liquid (2.0g/L containing zinc, chloride 0.08g/L, containing sulfate radicals 82g/L) returns ion exchange resin Recycle.Absorbing liquid becomes rich in liquid after the absorption of chlorine through absorbing after operation, and after absorption, liquid reclaims chlorine after reaching finite concentration Salt two.
Said method achieves productivity with it was demonstrated that it has very strong adaptability in inside plants, and technology becomes Ripe, dechlorination efficiency is stable, high financial profit.

Claims (6)

1. a kind of zinc gray material ammonia soaks the method for ion exchange process integration removing chlorine it is characterised in that comprising the steps of:
(1) first the zinc gray of high chlorinity is carried out slurrying, in serosity add slurrying ammonia carry out ammonia leaching so as in chloride Dissolution or conversion are extracted into ammonia leaching solution, obtain ammonia leaching slag and ammonia leaching liquid after filtering, as chlorine ion concentration in ammonia leaching liquid During less than 80g/L, return the leaching of slurrying ammonia, such as chlorine ion concentration is then opened a way more than 80g/L and is evaporated reclaiming villaumite one;
(2) ammonia leaching slag is rinsed and is filtered washings and rinsing after zinc gray, to rinsing after zinc gray carry out electrodeposition waste liquid Leach and purify, obtain solution of zinc sulfate;
(3) to the solution of zinc sulfate spent ion exchange resin deep removal chloride ion in step (2) step;Ion exchange resin solves Vapor desorbing chlorine, after desorbing, liquid enters integral type dechlorination apparatus dechlorination and produces villaumite two, the ion exchange resin circulation after desorbing Use;
(4) villaumite is produced to the integral type dechlorination apparatus dechlorination in step (3), the chloride shift in liquid after making desorbing enters and absorbs Liquid, allows liquid after dechlorination desorbing to be recycled, and returns ion exchange resin and makees strippant;After after absorption, liquid reaches finite concentration Reclaim villaumite two.
2. zinc gray material ammonia soaks the method for ion exchange process integration removing chlorine it is characterised in that walking according to claim 1 Suddenly the zinc gray of high chlorinity described in (1) is containing muriatic material containing zinc, and its approximate composition is:The 20%- of grade containing zinc 75%th, chloride 0.5%-30%.
3. zinc gray material ammonia soaks the method for ion exchange process integration removing chlorine it is characterised in that walking according to claim 1 Suddenly slurrying ammonia described in (1) is one of ammonium hydrogen carbonate, ammonia or two kinds, and the feed postition of slurrying ammonia can be direct for solid Add or make ammoniacal liquor to add, ammonia dipped process control pH6-10, ammonia 20 DEG C 80 DEG C of temperature of leaching.
4. zinc gray material ammonia soaks the method for ion exchange process integration removing chlorine it is characterised in that walking according to claim 1 Suddenly in (2), rinse cycle is single-stage or multi-stage countercurrent rinsing.
5. zinc gray material ammonia soaks the method for ion exchange process integration removing chlorine it is characterised in that walking according to claim 1 Suddenly described in (3), strippant is mainly dilution heat of sulfuric acid, and its percentage by weight is:Sulphuric acid 1% 30%, strippant is made through desorbing Become rich in liquid after the desorbing of chlorine after industry, after integral type dechlorination apparatus dechlorination, after obtaining dechlorination desorbing, liquid returns ion exchange Resin recycles.
6. zinc gray material ammonia soaks the method for ion exchange process integration removing chlorine it is characterised in that walking according to claim 1 Suddenly described in (4), absorbing liquid is mainly solution of ferrous chloride, and its percentage by weight is:Ferrous chloride 10% 60%, absorbing liquid Become rich in liquid after the absorption of chlorine through absorbing after operation, after absorption, liquid reclaims villaumite two after reaching finite concentration.
CN201610852332.1A 2016-09-27 2016-09-27 Method for dechlorinating through zinc ash material ammonia-leaching ion exchange combined process Pending CN106381397A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN107227466A (en) * 2017-06-26 2017-10-03 郴州市金贵银业股份有限公司 A kind of method that chlorine oxygen copper dechlorination carries copper
CN109897967A (en) * 2019-04-01 2019-06-18 中南大学 A method of separating and recovering zinc from complicated chloride system
CN111411216A (en) * 2020-04-24 2020-07-14 苏州固利环保科技有限公司 Efficient dechlorination method for blast furnace cloth bag ash

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CN109897967B (en) * 2019-04-01 2020-04-21 中南大学 Method for separating and recovering zinc from complex chloride system
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