CN107779606A - A kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper - Google Patents

A kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper Download PDF

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CN107779606A
CN107779606A CN201710854634.7A CN201710854634A CN107779606A CN 107779606 A CN107779606 A CN 107779606A CN 201710854634 A CN201710854634 A CN 201710854634A CN 107779606 A CN107779606 A CN 107779606A
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copper
liquid
heavy
alum
alkali
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CN107779606B (en
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段良洪
廖谨鹏
刘伟
高海明
王敏杰
廖召军
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CHENZHOU FENGYUE ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working 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
    • C22B7/02—Working-up flue dust
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working 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
    • C22B7/006—Wet processes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Mechanical Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Removal Of Specific Substances (AREA)
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Abstract

The invention discloses a kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, this method includes：Bellamya aeruginosa is by the fluorine chlorine impurity element in the removing Bellamya aeruginosa of alkali cleaning twice, the secondary alkali cleaning slag of Bellamya aeruginosa after alkali cleaning twice passes through neutralization step, leach the valuable metals such as the zinc-copper in Bellamya aeruginosa, liquid carries out heavy copper dechlorination after neutralization, liquid carries out the heavy alum of goethite process twice after dechlorination, remove the iron in solution, arsenic, antimony, the foreign ion such as fluorine and chlorine and the COD for reducing solution, liquid does subsequent purification processing into dense groove after heavy alum, finally enter Zinc electrolysis system, neutralize slag acid leaching residue after once middle acid and a high acidic oils and enter pyrometallurgical smelting of lead system, the valuable metals such as whole technique zinc-copper are effectively reclaimed, fluorine chlorine removal effect is more than 90%.The present invention realizes efficient, inexpensive effective processing to high-fluorine chlorine cigarette ash containing zinc-copper, while also eliminates the influence that Bellamya aeruginosa brings COD higher to Zinc electrolysis.

Description

A kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper
Technical field
The present invention relates to a kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, is a kind of valuable metal wet method such as zinc-copper A kind of new technology for leaching, separating, be enriched with and reclaiming, belongs to heavy metal metallurgy field.
Background technology
In Zinc Hydrometallurgy Process, in electrolyte the exceeded influence to Zinc electrolysis system of the impurity element such as cobalt nickel arsenic antimony compare Greatly, electrodeposition is often caused to burn the accidents such as plate, it is therefore desirable to the concentration of strict control impurity element.Simultaneously when fluorine chlorine in electrolyte The too high increase that will also result in cost of labor and production cost of ion concentration, for example fluorine ion is too high to cause minus plate to corrode, It is relatively difficult to cause manually to shell plate, while minus plate loss rise can be caused indirectly, chloride ion content is too high can heavy corrosion sun Pole plate, cause production cost to rise sharply, therefore control fluorine chlorine ion concentration in zinc electrolyte equally most important.Since in the recent period, by Good situation is always maintained in zinc deficiency and excess market, causes the excellent material source of goods containing zinc etc. in short supply, therefore develops a kind of new technology It is extremely urgent to handle the high zinc material of impurity.Bellamya aeruginosa is a kind of zinc secondary material well, but often frequent in this cigarette ash The foreign metals such as the fluorine chlorine containing high content so that reclaiming the valuable metal in the material becomes difficult.Therefore wet method is being used for reference On the basis of alkali cleaning removing zinc oxide fluorine chlorine technique, Bellamya aeruginosa is pre-processed using alkali washing process, but the effect of de- fluorine and chlorine removal is limited. Therefore on the basis of zinc oxide alkali washing process is summarized, a kind of wet-treating flow for Bellamya aeruginosa, synthetical recovery are developed The valuable metals such as the copper zinc lead in Bellamya aeruginosa.
The content of the invention
The technical problems to be solved by the invention are to propose a kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, the party Method comprises the following steps：
(1) Bellamya aeruginosa alkali one is washed：Using Bellamya aeruginosa as raw material, water is added to do an alkali cleaning according to liquid-solid ratio L/S for 4~6 ︰ 1, instead Oxidant is added during answering, reaction temperature is 60~80 DEG C, and the reaction time is 2~3h, rear to add piece alkali regulation pH value of solution Value, it is 8~11 to control solution terminal pH；An alkali wash water and an alkali cleaning slag are obtained after the completion of alkali cleaning；Alkali wash water Enter sewage plant processing；
(2) Bellamya aeruginosa alkali two is washed：An above-mentioned alkali wash water is done into secondary alkali cleaning, adds water according to liquid-solid ratio L/S to be 4~6 ︰ 1, Additive A is added, reaction temperature is 60~80 DEG C, and the reaction time is 2~3h, while it is 8~11 to control solution terminal pH；It is secondary Secondary alkali wash water and secondary alkali cleaning slag are obtained after the completion of alkali cleaning；
(3) washery slag of Bellamya aeruginosa alkali two neutralizes：Above-mentioned secondary alkali cleaning slag is neutralized, adds water according to liquid-solid ratio L/S to be 4~6 ︰ 1, reaction temperature is 60~85 DEG C, and the reaction time is 2~3h, then adds waste liquid or indium-raffinate regulation solution ph, control Terminal pH is 2~3；After the completion of neutralization, obtain neutralizer and neutralize slag；
(4) the heavy copper dechlorination of neutralizer：Heavy copper dechlorination is done to above-mentioned neutralizer, reducing agent is added into neutralizer so that chlorine Ion forms stannous chloride precipitation with copper ion, and 50~80 DEG C of reaction temperature, the reaction time is 0.5~2h, obtains liquid after heavy copper；
(5) sink copper after liquid once sink alum：A precipitating alum and removing iron is done to liquid after above-mentioned heavy copper, ensures to originate Fe in solution2+It is dense Degree adds lime or dry powder adjusts pH value of solution 3.5~4.0, the amount for adding hydrogen peroxide is weight of iron in 2.5~3.5g/L 2.0~2.2 times, 70~90 DEG C, 2~3h of reaction time of reaction temperature, 20min adds activated carbon before reaction is completed；Reaction is completed, Once sunk alum slag and once sink alum after liquid；
(6) once liquid does secondary heavy alum after heavy alum：Secondary heavy alum is done to liquid after above-mentioned once heavy alum, secondary heavy alum ensures molten Fe is originated in liquid2+Concentration adds lime or dry powder adjusts pH value of solution 4.5~5.0, add hydrogen peroxide in 1.0~1.5g/L Amount be 1.8~2.0 times of weight of iron, 70~90 DEG C, 2~3h of reaction time of reaction temperature, 20min, which is added, before reaction is completed lives Property charcoal, liquid after secondary heavy alum slag and secondary heavy alum is obtained after the completion of secondary heavy alum, the direct press filtration of liquid after secondary heavy alum is beaten with pump Subsequent purification processing is done to dense groove, is directly entered Zinc electrolysis system.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (1), the oxidant is hydrogen peroxide Or manganese powder；Oxidant addition is the 2.5~5% of Bellamya aeruginosa quality.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (1), the oxidant need to slowly add Enter, add time control in 1.0~1.5h.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (2), the additive A is can be with Metal forms the material of precipitation.
Preferably, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (2), it is described can be with metal shape Material into precipitation is sodium carbonate or sodium sulphate.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (4), after the heavy copper in liquid copper from Sub- concentration control is within 0.1g/L.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (4), the reducing agent be iron powder or Person's sodium sulfite.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (5) and (6), the activated carbon plus It is 0.5~1g/L to enter amount.
Compared with prior art, the beneficial effects of the invention are as follows：Bellamya aeruginosa is by the fluorine in the removing Bellamya aeruginosa of alkali cleaning twice Chlorine impurity element, while destroy the influence for reducing the high COD that brings of Bellamya aeruginosa to electric Zn system Zinc electrolysis, by alkali cleaning twice it The secondary alkali cleaning slag of Bellamya aeruginosa afterwards passes through neutralization step, leaches the valuable metals such as zinc-copper in Bellamya aeruginosa, liquid is sunk after neutralization Copper dechlorinates, and liquid carries out goethite process twice and sinks alum after dechlorination, removes foreign ion and the drop such as iron, arsenic, antimony, fluorine and chlorine in solution The COD of low solution, liquid does subsequent purification processing into dense groove after heavy alum, finally enters Zinc electrolysis system, neutralizes slag by one Acid leaching residue enters the valuable metal such as pyrometallurgical smelting of lead system, whole technique zinc-copper and effectively returned after secondary middle acid and a high acidic oils Receive, fluorine chlorine removal effect is more than 90%.The present invention realizes contains zinc-copper to the existing intractable high-fluorine chlorine of defluorinate chlorine technique Efficient, inexpensive effective processing of cigarette ash, while the influence that Bellamya aeruginosa brings COD higher to Zinc electrolysis is also eliminated, for electricity Zinc production provides new acceptable material source, it is whole it is environmental friendly, economic and social benefit is notable.
Brief description of the drawings
Fig. 1 is the process chart of the wet-treating high-fluorine chlorine of the present invention method of cigarette ash containing zinc-copper.
Embodiment
The invention provides a kind of method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, this method comprises the following steps：
(1) Bellamya aeruginosa alkali one is washed：Using Bellamya aeruginosa as raw material, water is added to do an alkali cleaning according to liquid-solid ratio L/S for 4~6 ︰ 1, instead Oxidant hydrogen peroxide or manganese powder are added during answering, oxidant addition is the 2.5~5% of Bellamya aeruginosa quality, and reaction is warm Spend for 60~80 DEG C, the reaction time is 2~3h, and rear to add piece alkali regulation solution ph, it is 8~11 to control solution terminal pH；One After the completion of secondary alkali cleaning, the fluoride and chloride of solubility are removed, fluorine chlorine is removed in the form of sodium fluoride and sodium chloride, obtained respectively To an alkali wash water and an alkali cleaning slag；Alkali wash water enters sewage plant processing；
(2) Bellamya aeruginosa alkali two is washed：An above-mentioned alkali wash water is done into secondary alkali cleaning, adds water according to liquid-solid ratio L/S to be 4~6 ︰ 1, Additive A is added, introduces A-The fluorine chlorine in insoluble fluorine chlorine compound is replaced, improves fluorine dechlorination rate, reaction temperature is 60~80 DEG C, the reaction time is 2~3h, while it is 8~11 to control solution terminal pH；Secondary alkali wash water and two are obtained after the completion of secondary alkali cleaning Secondary alkali cleaning slag；
(3) washery slag of Bellamya aeruginosa alkali two neutralizes：Above-mentioned secondary alkali cleaning slag is neutralized, adds water according to liquid-solid ratio L/S to be 4~6 ︰ 1, reaction temperature is 60~85 DEG C, and the reaction time is 2~3h, then adds waste liquid or indium-raffinate regulation solution ph, control Terminal pH is 2~3；After the completion of neutralization, obtain neutralizer and neutralize slag；
(4) the heavy copper dechlorination of neutralizer：Heavy copper dechlorination is done to above-mentioned neutralizer, reducing agent is added into neutralizer so that chlorine Ion forms stannous chloride precipitation with copper ion, and 50~80 DEG C of reaction temperature, the reaction time is 0.5~2h, obtains liquid after heavy copper, Copper ion concentration is controlled within 0.1g/L in liquid after heavy copper；
(5) sink copper after liquid once sink alum：A precipitating alum and removing iron is done to liquid after above-mentioned heavy copper, ensures to originate Fe in solution2+It is dense Degree adds lime or dry powder adjusts pH value of solution 3.5~4.0, the amount for adding hydrogen peroxide is weight of iron in 2.5~3.5g/L 2.0~2.2 times, 70~90 DEG C, 2~3h of reaction time of reaction temperature, 20min adds activated carbon before reaction is completed, activated carbon Addition is according to 0.5~1g/L；Reaction is completed, and is once sunk alum slag and once liquid after heavy alum；
(6) once liquid does secondary heavy alum after heavy alum：Secondary heavy alum is done to liquid after above-mentioned once heavy alum, secondary heavy alum ensures molten Fe is originated in liquid2+Concentration adds lime or dry powder adjusts pH value of solution 4.5~5.0, add hydrogen peroxide in 1.0~1.5g/L Amount be 1.8~2.0 times of weight of iron, 70~90 DEG C, 2~3h of reaction time of reaction temperature, 20min, which is added, before reaction is completed lives Property charcoal, the addition of activated carbon is according to 0.5~1g/L；Liquid after secondary heavy alum slag and secondary heavy alum is obtained after the completion of secondary heavy alum, The direct press filtration of liquid after secondary heavy alum is beaten to dense groove with pump and does subsequent purification processing, is directly entered Zinc electrolysis system.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (1), the oxidant need to slowly add Enter, add time control in 1.0~1.5h.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (2), the additive A is can be with Metal forms the material of precipitation, such as sodium carbonate, sodium sulphate material.
Wherein, the method for above-mentioned wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, in step (4), the reducing agent be iron powder or Person's sodium sulfite.
In the inventive method, Bellamya aeruginosa destroys drop by the fluorine chlorine impurity element in the removing Bellamya aeruginosa of alkali cleaning twice Influences of the high COD that low Bellamya aeruginosa is brought to electric Zn system Zinc electrolysis, the secondary alkali cleaning slag of Bellamya aeruginosa after alkali cleaning twice By neutralization step, the valuable metals such as zinc-copper in Bellamya aeruginosa are leached, liquid carries out heavy copper dechlorination after neutralization, and liquid carries out two after dechlorination Secondary goethite process sinks alum, removes the foreign ions such as iron, arsenic, antimony, fluorine and chlorine in solution and reduces the COD of solution, sinks liquid after alum Subsequent purification processing is done into dense groove, finally enters Zinc electrolysis system, neutralizes slag by once middle acid and a high acidic oils Acid leaching residue enters the valuable metal such as pyrometallurgical smelting of lead system, whole technique zinc-copper and effectively reclaimed afterwards, and fluorine chlorine removal effect exists More than 90%.
Below in conjunction with specific embodiment, the present invention will be further explained, but and is not so limited the present invention Protection domain.
Embodiment 1
Take Bellamya aeruginosa (Cu：2.65wt%, Zn：23.62wt%, F：2.26wt%, Cl：8.55wt%) 8t pours into 50m3Instead Answer in groove, add river 40m3, lead to vapour heating to 75 DEG C of stirring reactions to reactive tank, take 200L hydrogen peroxide to be slowly added to solution In, add time control and arrive 1.5h, piece alkali is added in course of reaction, it is 9, reaction time 2h to control reaction end pH, is reacted Solid-liquor separation is carried out after end, liquid enters sewage plant processing, and slag pours into another reactive tank progress alkali two and washed.
40m is passed through toward being equipped with the washery slag reactive tank of alkali one3River, lead to vapour heating to 75 DEG C of stirring reactions to reactive tank, Sodium Carbonate Additive is added in course of reaction, it is 9, reaction time 2h to control reaction end pH, and reaction carries out liquid after terminating and consolidated Separation, liquid enter sewage plant processing, and slag takes a part to do assay, and the washery slag of alkali two enters to be neutralized in next step, and neutralizer does heavy copper Dechlorination, is then sunk alum twice.
Secondary alkali cleaning slag is neutralized, 40m is passed through toward being equipped with secondary alkali cleaning slag reactive tank3River, give reactive tank logical steaming Vapour is heated up to 75 DEG C of stirring reactions, reaction time 2.5h, then adds indium-raffinate regulation solution ph, controls the terminal pH to be 3；After the completion of neutralization, obtain neutralizer and neutralize slag；
The heavy copper dechlorination of neutralizer：Heavy copper dechlorination is done to above-mentioned neutralizer, reducing agent-iron powder is added into neutralizer so that Chlorion forms stannous chloride precipitation with copper ion, 70 DEG C, reaction time 1.5h of reaction temperature, obtains liquid after heavy copper, heavy copper Copper ion concentration is controlled within 0.1g/L in liquid afterwards；
Liquid once sinks alum after heavy copper：A precipitating alum and removing iron is done to liquid after above-mentioned heavy copper, ensures to originate Fe in solution2+Concentration exists 3.0g/L, add lime regulation pH value of solution 3.5, the amount for adding hydrogen peroxide is 2.2 times of weight of iron, 80 DEG C of reaction temperature, reaction Time 3h, 20min adds activated carbon before reaction is completed, and the addition of activated carbon is added according to 0.6g/L；Reaction is completed, and obtains one Liquid after secondary heavy alum slag and once heavy alum；
Once liquid does secondary heavy alum after heavy alum：Secondary heavy alum is done to liquid after above-mentioned once heavy alum, secondary heavy alum ensures solution Middle starting Fe2+Concentration is in 1.0g/L, and adding lime regulation pH value of solution, the amount for adding hydrogen peroxide is 2.0 times of weight of iron, instead 4.5 80 DEG C, reaction time 3h of temperature is answered, 20min adds activated carbon before reaction completion, and the addition of activated carbon is according to 1g/L；It is secondary heavy Liquid after secondary heavy alum slag and secondary heavy alum is obtained after the completion of alum, the direct press filtration of liquid after secondary heavy alum is beaten to dense groove with pump after doing Continuous purified treatment, is directly entered Zinc electrolysis system.
Through assay, twice alkali cleaning slag, neutralize after liquid, heavy copper dechlorination and alum precipitation liquid result of laboratory test is as follows twice：
The washery slag alkali cleaning situation table of 1 alkali of table two
Element F Cl Cu Zn F removal efficiencies Cl removal efficiencies
The washery slag of alkali two (%) 0.24 0.36 3.62 32.27 92.74 97.16
The washery slag infusion solution situation table of 2 alkali of table two
From the point of view of result of laboratory test, Bellamya aeruginosa is after alkali cleaning twice, dechlorination rate 97.16%, and fluorine removal efficiency is 92.74%, it can reach requirement of the Zn system to fluorine chlorine in Bellamya aeruginosa raw material, from the point of view of subsequent handling, after neutralizing heavy alum, Fluorine chlorine and COD are further reduced in solution, can be reached in claimed range.
Embodiment 2
Take Bellamya aeruginosa (Cu：2.65%, Zn：23.62%, F：2.26%, Cl：8.55%) 8t pours into 50m3In reactive tank, Add the washing lotion 40m of alkali two in example 13, lead to vapour heating to 75 DEG C of stirring reactions to reactive tank, take 200L hydrogen peroxide to be slowly added to In solution, adding time control and arrive 1.5h, addition piece alkali in course of reaction, it is 10, reaction time 2h to control reaction end pH, Reaction carries out solid-liquor separation after terminating, liquid enters sewage plant processing, and slag pours into another reactive tank progress alkali two and washed.
40m is passed through toward being equipped with the washery slag reactive tank of alkali one3River, lead to vapour heating to 75 DEG C of stirring reactions to reactive tank, Sodium Carbonate Additive is added in course of reaction, it is 10, reaction time 2h to control reaction end pH, and reaction carries out liquid after terminating and consolidated Separation, liquid enter sewage plant processing, and slag takes a part to do assay, and the washery slag of alkali two enters to be neutralized in next step, and neutralizer does heavy copper Dechlorination, is then sunk alum twice.
Secondary alkali cleaning slag is neutralized, 40m is passed through toward being equipped with secondary alkali cleaning slag reactive tank3River, give reactive tank logical steaming Vapour is heated up to 75 DEG C of stirring reactions, reaction time 2h, then adds indium-raffinate regulation solution ph, it is 3 to control terminal pH； After the completion of neutralization, obtain neutralizer and neutralize slag；
The heavy copper dechlorination of neutralizer：Heavy copper dechlorination is done to above-mentioned neutralizer, reducing agent-iron powder is added into neutralizer so that Chlorion and copper ion form stannous chloride precipitation, 80 DEG C, reaction time 1h of reaction temperature, obtain liquid after heavy copper, sink after copper Copper ion concentration control is within 0.1g/L in liquid；
Liquid once sinks alum after heavy copper：A precipitating alum and removing iron is done to liquid after above-mentioned heavy copper, ensures to originate Fe in solution2+Concentration exists 2.5g/L, add lime regulation pH value of solution 4, the amount for adding hydrogen peroxide is 2.1 times of weight of iron, 90 DEG C of reaction temperature, during reaction Between 2h, 20min adds activated carbon before reaction is completed, and the addition of activated carbon adds according to 1.0g/L；Reaction is completed, and is obtained once Liquid after heavy alum slag and once heavy alum；
Once liquid does secondary heavy alum after heavy alum：Secondary heavy alum is done to liquid after above-mentioned once heavy alum, secondary heavy alum ensures solution Middle starting Fe2+Concentration is in 1.0g/L, and adding lime regulation pH value of solution, the amount for adding hydrogen peroxide is 1.8 times of weight of iron, instead 5.0 90 DEG C, reaction time 2h of temperature is answered, 20min adds activated carbon before reaction completion, and the addition of activated carbon is according to 1g/L；It is secondary heavy Liquid after secondary heavy alum slag and secondary heavy alum is obtained after the completion of alum, the direct press filtration of liquid after secondary heavy alum is beaten to dense groove with pump after doing Continuous purified treatment, is directly entered Zinc electrolysis system.
Through assay, twice alkali cleaning slag, neutralize after liquid, heavy copper dechlorination and alum precipitation liquid result of laboratory test is as follows twice：
The washery slag alkali cleaning situation table of 3 alkali of table two
Element F Cl Cu Zn F removal efficiencies Cl removal efficiencies
The washery slag of alkali two (%) 0.31 0.37 3.47 30.65 90.37 96.94
The washery slag infusion solution situation table of 4 alkali of table two
From the point of view of result of laboratory test, Bellamya aeruginosa is after the accumulation of salt in the surface soil one is washed, alkali two is washed, dechlorination rate 96.94%, fluorine removal efficiency For 90.37%, it can reach requirement of the Zn system to fluorine chlorine in Bellamya aeruginosa raw material, from the point of view of subsequent handling, by neutralizing heavy alum Afterwards, fluorine chlorine and COD are further reduced in solution, can be reached in claimed range.
Embodiment 3
Take Bellamya aeruginosa (Cu：3.21%, Zn：29.96%, F：1.96%, Cl：5.23%) 8t pours into 50m3In reactive tank, Add river 40m3, lead to vapour heating to 80 DEG C of stirring reactions to reactive tank, take 250L hydrogen peroxide to be slowly added in solution, add Time control adds piece alkali to 1.5h in course of reaction, it be 8, reaction time 2h control reaction end pH, and it is laggard to react end Row solid-liquor separation, liquid enter sewage plant processing, and slag pours into another reactive tank progress alkali two and washed.
40m is passed through toward being equipped with the washery slag reactive tank of alkali one3River, lead to vapour heating to 80 DEG C of stirring reactions to reactive tank, Sodium Carbonate Additive is added in course of reaction, it is 8, reaction time 2h to control reaction end pH, and reaction carries out liquid after terminating and consolidated Separation, liquid enter sewage plant processing, and slag takes a part to do assay, and the washery slag of alkali two enters to be neutralized in next step, and neutralizer does heavy copper Dechlorination, is then sunk alum twice.
Secondary alkali cleaning slag is neutralized, 40m is passed through toward being equipped with secondary alkali cleaning slag reactive tank3River, give reactive tank logical steaming Vapour is heated up to 85 DEG C of stirring reactions, reaction time 2h, then adds indium-raffinate regulation solution ph, controls the terminal pH to be 2.5；After the completion of neutralization, obtain neutralizer and neutralize slag；
The heavy copper dechlorination of neutralizer：Heavy copper dechlorination is done to above-mentioned neutralizer, reducing agent-sodium sulfite is added into neutralizer, So that chlorion forms stannous chloride precipitation with copper ion, 60 DEG C, reaction time 2h of reaction temperature, liquid after heavy copper is obtained, is sunk Copper ion concentration is controlled within 0.1g/L in liquid after copper；
Liquid once sinks alum after heavy copper：A precipitating alum and removing iron is done to liquid after above-mentioned heavy copper, ensures to originate Fe in solution2+Concentration exists 3.0g/L, add lime regulation pH value of solution 4, the amount for adding hydrogen peroxide is 2.2 times of weight of iron, 70 DEG C of reaction temperature, during reaction Between 3h, 20min adds activated carbon before reaction is completed, and the addition of activated carbon adds according to 0.5g/L；Reaction is completed, and is obtained once Liquid after heavy alum slag and once heavy alum；
Once liquid does secondary heavy alum after heavy alum：Secondary heavy alum is done to liquid after above-mentioned once heavy alum, secondary heavy alum ensures solution Middle starting Fe2+Concentration is in 1.0g/L, and adding lime regulation pH value of solution, the amount for adding hydrogen peroxide is 2.0 times of weight of iron, instead 4.5 Temperature 70 C is answered, reaction time 3h, 20min adds activated carbon before reaction is completed, and the addition of activated carbon is according to 0.5g/L；It is secondary Liquid after secondary heavy alum slag and secondary heavy alum is obtained after the completion of heavy alum, the direct press filtration of liquid after secondary heavy alum is beaten to dense groove with pump and done Subsequent purification processing, is directly entered Zinc electrolysis system.
Through assay, twice alkali cleaning slag, neutralize after liquid, heavy copper dechlorination and alum precipitation liquid result of laboratory test is as follows twice：
The washery slag alkali cleaning situation table of 5 alkali of table two
Element F Cl Cu Zn F removal efficiencies Cl removal efficiencies
The washery slag of alkali two (%) 0.21 0.4 3.84 35.88 90.37 96.94
The washery slag infusion solution situation table of 6 alkali of table two
From the point of view of result of laboratory test, Bellamya aeruginosa is after alkali one is washed, alkali two is washed, dechlorination rate 93.61%, and fluorine removal efficiency is 91.05%, it can reach requirement of the Zn system to fluorine chlorine in Bellamya aeruginosa raw material, from the point of view of subsequent handling, after neutralizing heavy alum, Fluorine chlorine and COD are further reduced in solution, can be reached in claimed range.
Described above is the preferred embodiments of the present invention, it is noted that for those skilled in the art, is not being taken off On the premise of structure of the present invention, various modifications and improvements can be made, these should also be as being considered as protection scope of the present invention, These are all without the practicality for influenceing the effect of the invention implemented and this patent.

Claims (8)

  1. A kind of 1. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper, it is characterised in that this method comprises the following steps：
    (1) Bellamya aeruginosa alkali one is washed：Using Bellamya aeruginosa as raw material, water is added to do an alkali cleaning according to liquid-solid ratio L/S for 4~6 ︰ 1, reaction During add oxidant, reaction temperature is 60~80 DEG C, and the reaction time be 2~3h, rear to add piece alkali regulation solution ph, is controlled Solution terminal pH processed is 8~11；An alkali wash water and an alkali cleaning slag are obtained after the completion of alkali cleaning；One time alkali wash water enters sewage Stand processing；
    (2) Bellamya aeruginosa alkali two is washed：An above-mentioned alkali wash water is done into secondary alkali cleaning, adds water according to liquid-solid ratio L/S to be 4~6 ︰ 1, is added Additive A, reaction temperature are 60~80 DEG C, and the reaction time is 2~3h, while it is 8~11 to control solution terminal pH；Secondary alkali cleaning After the completion of obtain secondary alkali wash water and secondary alkali cleaning slag；
    (3) washery slag of Bellamya aeruginosa alkali two neutralizes：Above-mentioned secondary alkali cleaning slag is neutralized, adds water according to liquid-solid ratio L/S to be 4~6 ︰ 1, instead It is 60~85 DEG C to answer temperature, and the reaction time is 2~3h, then adds waste liquid or indium-raffinate regulation solution ph, controls terminal PH is 2~3；After the completion of neutralization, obtain neutralizer and neutralize slag；
    (4) the heavy copper dechlorination of neutralizer：Heavy copper dechlorination is done to above-mentioned neutralizer, reducing agent is added into neutralizer so that chlorion Stannous chloride precipitation is formed with copper ion, 50~80 DEG C of reaction temperature, the reaction time is 0.5~2h, obtains liquid after heavy copper；
    (5) sink copper after liquid once sink alum：A precipitating alum and removing iron is done to liquid after above-mentioned heavy copper, ensures to originate Fe in solution2+Concentration exists 2.5~3.5g/L, lime or dry powder is added to adjust pH value of solution 3.5~4.0, the amount for adding hydrogen peroxide is the 2.0 of weight of iron ~2.2 times, 70~90 DEG C, 2~3h of reaction time of reaction temperature, 20min adds activated carbon before reaction is completed；Reaction is completed, and is obtained To once sinking alum slag and once liquid after heavy alum；
    (6) once liquid does secondary heavy alum after heavy alum：Secondary heavy alum is done to liquid after above-mentioned once heavy alum, secondary heavy alum ensures in solution Originate Fe2+Concentration adds lime or dry powder adjusts pH value of solution 4.5~5.0, add the amount of hydrogen peroxide in 1.0~1.5g/L For 1.8~2.0 times of weight of iron, 70~90 DEG C, 2~3h of reaction time of reaction temperature, 20min adds activity before reaction is completed Charcoal, obtain liquid after secondary heavy alum slag and secondary heavy alum after the completion of secondary heavy alum, by the direct press filtration of liquid after secondary heavy alum with pump beat to Dense groove does subsequent purification processing, is directly entered Zinc electrolysis system.
  2. A kind of 2. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 1, it is characterised in that step (1) in, the oxidant is hydrogen peroxide or manganese powder；Oxidant addition is the 2.5~5% of Bellamya aeruginosa quality.
  3. A kind of 3. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 1, it is characterised in that step (1) in, the oxidant need to be slowly added to, and add time control in 1.0~1.5h.
  4. A kind of 4. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 1, it is characterised in that step (2) in, the additive A is that the material of precipitation can be formed with metal.
  5. A kind of 5. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 4, it is characterised in that step (2) in, the material that precipitation can be formed with metal is sodium carbonate or sodium sulphate.
  6. A kind of 6. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 1, it is characterised in that step (4) in, copper ion concentration is controlled within 0.1g/L in liquid after the heavy copper.
  7. A kind of 7. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 1, it is characterised in that step (4) in, the reducing agent is iron powder or sodium sulfite.
  8. A kind of 8. method of wet-treating high-fluorine chlorine cigarette ash containing zinc-copper according to claim 1, it is characterised in that step (5) and in (6), the addition of the activated carbon is 0.5~1g/L.
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CN112609081A (en) * 2020-11-27 2021-04-06 郴州丰越环保科技有限公司 Method for producing electrolytic zinc by using high thallium zinc oxide

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