CN109371243A - A kind of method that zinc smelting factory waste acid recycles - Google Patents
A kind of method that zinc smelting factory waste acid recycles Download PDFInfo
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- CN109371243A CN109371243A CN201811319257.8A CN201811319257A CN109371243A CN 109371243 A CN109371243 A CN 109371243A CN 201811319257 A CN201811319257 A CN 201811319257A CN 109371243 A CN109371243 A CN 109371243A
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- zinc
- flue gas
- waste acid
- gas washing
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- 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
Abstract
The present invention relates to a kind of methods that zinc abstraction waste acid recycles, this method is in existing flue gas washing process, zinc carbonate or zinc oxide is added as neutralizer, maintain cleaning solution in certain acidity, to increase waste acid cleaning solution cycle-index, so that waste acid cleaning solution obtains enrichment method, realize the minimizing of waste acid, flue gas washing process is utilized simultaneously, zinc oxide or zinc carbonate are leached, and is laid the foundation for subsequent extraction zinc.After waste acid after enrichment method is removed fluorine, chlorine impurity using absorption method, qualified zinc sulfate solution is obtained, can be used for zinc sulfate or electric zinc production.This method not only solve the current lime neutralisation quantity of slag it is big, it is at high cost, there are problems that secondary pollution, also achieve the efficient utilization of the valuable resources such as sulfuric acid in waste acid, zinc, cadmium, fluorine, have many advantages, such as that simple process, at low cost, valuable metal utilization rate is high, there is preferable industrial application prospect.
Description
Technical field
The present invention relates to a kind of methods that zinc smelting factory waste acid recycles, and in particular to a kind of to utilize zinc smelting factory waste acid
It leaches zinc oxide or zinc carbonate, obtains the solution of zinc sulfate that can be used for electrowinning zinc, while realizing that waste acid is enriched with, reduce waste acid
Discharge capacity belongs to non-ferrous metallurgy field.
Background technique
Waste acid is the common by-products of the indirect smelting process of zinc sulfide concentrates, originates from sulfur dioxide flue gas dynamic wave scrubbing
Cleaning procedure.The main component of waste acid: 40-100g/L sulfuric acid, 50-150mg/L zinc, 30-100mg/L cadmium, 500-800mg/L
Chlorine, 400-1200mg/L fluorine and a small amount of arsenic, lead.According to statistics, one 100,000 tons of zine-smelting plant, daily output waste acid are up to 400-600m3。
Since waste acid yield is big, impurity component is relatively easy, this makes it recycle and utilize the concern by metallargist.
From the point of view of waste acid ingredient, main component be sulfuric acid, but due in waste acid sulfuric acid concentration it is lower, in addition contained by it
Fluorine, chlorine impurity are higher, it is difficult to which direct return system uses.For this purpose, researcher develops extensive research, each tool is proposed
The waste acid processing method of characteristic.These methods are broadly divided into three kinds: 1. direct concentration method, i.e., in dynamic wave flue gas washing system
Extend cleaning solution circulation time, so that sulfuric acid concentration is promoted to 200g/L in waste acid, in this way, which sulfuric acid concentration can meet leaching
Process uses.This method is simple and easy, but the impurity such as fluorine, chlorine are also enriched with synchronous, and the raising of sulfuric acid concentration is so that power
Wave washing system seriously corroded, loses more than gain；2. distillation and concentration method, waste acid is carried out heating distillation by this method, is on the one hand mentioned
On the other hand high sulfuric acid concentration can also remove fluorine, chlorine impurity in waste acid.However fluorine, chlorine impurity removal is complete, it need to be by sulphur
Acid concentration is concentrated into 800g/L or more.Thus, waste acid distillation and concentration not only needs to expend a large amount of steam, equally also faces equipment corruption
The problem of erosion.3. milk of lime is added in lime neutralisation in waste acid, control terminal pH is 8-10, after reacting 3-5h, by waste acid
It is converted into gypsum.This method is simple, but resource utilization is low, also generates a large amount of utilizing waste gypsum slags, brings potential trend of environmental protection
Danger.Nevertheless, in lime it is legal be still the processing of current waste acid prevailing technology, this also shows waste acid recycling from another point of view
Using there are biggish difficulty.In addition to this, technical staff also developed the waste acids such as membrane separation process, ion-exchange processing work
Skill, but these method processing costs are higher, technology maturation is lower, mostly still in the laboratory research stage.
In conclusion the prior art is to waste acid processing, there are problems, and such as at high cost, seriously corroded, this makes zinc smelting
Refinery is forced still to handle waste acid using lime neutralisation, thus how to realize the efficient utilization of zinc smelting factory waste acid, is
The big urgent problem to be solved of industry one.
Summary of the invention
For the prior art to waste acid processing there are at high cost, seriously corroded, problems, this hair such as be difficult to efficiently to utilize
Bright purpose is to be to provide a kind of method for efficiently utilizing waste acid, and this method is by being added zinc oxide during flue gas washing
Or zinc carbonate not only can effectively control waste acid acidity as neutralizer, solve waste acid as cycle-index increase leads to acid
Degree rises bring etching problem, and waste acid is made to obtain enrichment method, reduces discharge capacity, and can also be achieved zinc oxide or zinc carbonate exists
The direct leaching of washing system eliminates leaching equipment, while in waste acid cyclic process, so that fluorine, chlorine impurity concentration obtain
It effectively improves, to be conducive to subsequent removal of impurities, this method simple process achieves noticeable achievement, and is conducive to promote and apply.
In order to achieve the above technical purposes, the present invention provides a kind of method that zinc smelting factory waste acid recycles, the party
During method is flue gas washing, be added zinc oxide in flue gas washing liquid and/or zinc carbonate neutralizer carry out in primary and, with control
The pH of tobacco curing gas washing liquid is in 1.2~1.8 ranges, when zinc ion concentration in flue gas washing liquid is more than 140g/L, lead division
Point flue gas washing liquid, while supplementing the new flue gas washing liquid of corresponding amount and zinc oxide and/or zinc carbonate neutralizer continues cigarette
Gas washing；Zinc carbonate neutralizer is added in extension flue gas washing liquid to carry out in secondary and to control flue gas washing liquid
It after pH is in 2.5~3.5 ranges, is separated by solid-liquid separation, is separated by solid-liquid separation gained slag phase and returns to the reuse of flue gas washing process, solid-liquid point
Fluorine and chlorine impurity are removed by absorption method from gained liquid phase, obtain solution of zinc sulfate.
Preferred scheme, the control of flue gas washing liquid recycle stream amount are 15~50m3/ h, zinc oxide and/or zinc carbonate neutralizer
The addition speed of opposite flue gas washing liquid is 0.6~1.6t/h.If when flue gas washing liquid pH > 1.8, neutralizer charging need to be reduced
Speed；If pH < 1.2 need to increase neutralizer charging rate.
Preferred scheme, the amount for drawing flue gas washing liquid is the 60~80% of flue gas washing liquid total volume；Preferably flue gas
The 70% of cleaning solution total volume.
Preferred scheme, liquid phase remove the process of fluorine and chlorine impurity by absorption method are as follows: are made using copper-aluminium composite oxide
Adsorbent is removed altogether for fluorine chlorine, passes through fluorine and chlorine impurity in two sections of counter-current process adsorbing and removing liquid phases.Two sections of adverse current works can be used
Skill, can not only realize the deep removal of fluorine chlorine, but also be conducive to the absorption of copper-aluminium composite oxide saturation.Copper-aluminium of the invention is compound
Oxide is that the mixed preparing of 1:3~5 forms in molar ratio for cuprous oxide and activated alumina.Cuprous oxide and activated alumina rub
You are than being preferably 1:4.
More preferably scheme, copper-aluminium composite oxide are 60~150kg/m with respect to the dosage of liquid phase3, adsorption temp 30
~60 DEG C, adsorption time is 40~120min.
More preferably scheme, the granularity of the copper-aluminium composite oxide is less than 15 μm.
More preferably scheme, after the copper-aluminium composite oxide for adsorbing fluorine and chlorine to saturation uses alkali liquid washing regeneration treatment,
It reuses.
More preferably scheme, the lye are 0.5~2M NaOH solution, and wash temperature is 30~70 DEG C, and wash time is
30~80min.
Preferred scheme, flue gas washing process use dynamic wave system, this is well known in industry.
The present invention realizes the efficient utilization of waste acid.In general, sulfuric acid concentration is lower in waste acid, it is difficult to be utilized, add
Fluorine, cl concn it is relatively low, this to fluorine, chlorine removing bring certain difficulty.The effective of waste acid is realized in the prior art
It recycles, it is necessary to try to improve sulfuric acid concentration in waste acid, this is a big common recognition of industry.Technical solution of the present invention, key exist
In by introducing zinc oxide or zinc carbonate in flue gas washing system as neutralizer, the addition speed of control neutralizer can be passed through
It spends to adjust the acidity of waste acid cleaning solution, so, even if improving the cycle-index of waste acid cleaning solution, will not bring because of acid
Degree rises bring etching problem can also be achieved zinc oxide or zinc carbonate and is washing so as to realize the enrichment method of waste acid
The direct leaching of system eliminates leaching equipment, while in waste acid cyclic process, so that fluorine, chlorine impurity concentration obtain effectively
It improves, to be conducive to subsequent removal of impurities.
It is accounted with 100,000 tons of zinc smelting factoryes, produces 500m daily3Waste acid waste liquid, the 45g/L containing acid, fluorine, chlorine, Zn content are respectively
723,582,47mg/L.If, so that cleaning solution recycles 5 days, being washed during circulation by the way that zinc oxide is added in flue gas washing liquid
Liquid acidity maintains 20g/L, so, wants 5 × 500=2500m of output within originally 5 days3Waste acid waste liquid, and use present invention side
After method, 5 days only output 500m3Liquid, and the waste acid liquid of output containing zinc up to 136g/L, fluorine, cl concn be respectively 3615,
2910mg/L.Therefore, it after using this method, can not only realize the minimizing of waste acid, can also be achieved the recycling of waste acid, it is really real
Show and has achieved many things at one stroke.
The present invention is in zinc abstraction sulfur dioxide flue gas washing process by introducing zinc oxide or carbon in flue gas washing liquid
Sour zinc neutralizer can maintain the acidity of flue gas washing liquid by controlling the charging rate of neutralizer, so that it is being circulated throughout
Cheng Zhong, will not because of acidity rising and cause equipment accelerated corrosion.And using the strong mass transfer effect of dynamic wave system, so that oxygen
Change zinc or zinc carbonate is efficiently leached by waste acid in flue gas washing liquid, to save leaching equipment；In addition, in control acidity cyclic process
In, waste acid measures effective decrement, while fluorine, chlorine impurity are enriched with conducive to the development of subsequent cleaning procedure.
Compared with prior art, present invention has the advantage that
(1) present invention process process is simple, at low cost, it is easy to accomplish industrialization.
(2) present invention is high to waste acid resource utilization, can sufficiently recycle sulfuric acid, the zinc, cadmium resource in waste acid.
(3) the efficient mass transfer effect that dynamic wave scrubbing is taken full advantage of using the present invention, can realize neutralizer using waste acid
The efficient leaching of middle zinc, while saving zinc oxide and leaching equipment investment.
(4) present invention is environmental-friendly, eliminates the pollution of gypsum tailings caused by existing waste acid lime neutralisation treatment technique
Problem.
(5) present invention realizes the enrichment method of waste acid, can greatly reduce the discharge of waste acid.
Detailed description of the invention
Fig. 1 is that waste acid recycles principle process flow chart.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits protective scope of the claims.
Embodiment 1:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc oxide fumes (Zn:75.2%, granularity is less than 200 mesh: >=95%) be neutralizer,
Zinc oxide fumes are added into flue gas washing liquid circulating slot according to the charging rate of 0.7-0.8t/h, control cleaning solution pH is 1.3
Left and right, washing flow quantity are 36m3Cleaning solution in circulating slot is pumped into neutralization chamber, while after reacting 144h in circulating slot by/h
The isometric new water of middle supplement.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 3.2.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:134g/L, Cl:5232mg/L, F:2201mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 45 DEG C, and 85kg/m is added3Copper-aluminium composite oxide reaction 50min after, mistake
Filter is purified liquid (Zn:136g/L, Cl:476mg/L, F:42mg/L), and scavenging solution is pumped into main production system and carries out electric zinc or sulphur
Sour zinc production.Purification slag is added in alkali cleaning regeneration tank, 0.8M NaOH solution is added, is 55 DEG C of agitator treatings in temperature
After 50min, regenerated copper-aluminium composite oxide adsorbent is can be obtained in filtering, can return to cleaning procedure use, alkali wash water supplement
It is recycled after NaOH.
Comparative example 1:
35m is added in neutralization chamber3Zinc smelting factory waste acid (H2SO4: 112g/L, Cl:845mg/L, F:427mg/L), then
Under agitation, into neutralization chamber, (Zn:75.2%, granularity is less than 200 mesh: >=95%), by solution for addition zinc oxide fumes
It is 3.2 that pH, which is neutralized to pH,.Then it filters, collects neutralize filter residue and filtrate (Zn:68g/L, Cl:982mg/L, F:511mg/ respectively
L).Neutralizing filter residue send fuming furnace to handle, and neutralizes filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 45 DEG C, and 45kg/m is added3Copper-aluminium composite oxide reaction 50min after, mistake
Filter is purified liquid (Zn:69g/L, Cl:451mg/L, F:45mg/L), and scavenging solution is pumped into main production system and carries out electric zinc or sulfuric acid
Zinc production.Purification slag is added in alkali cleaning regeneration tank, 0.8M NaOH solution is added, is 55 DEG C of agitator treating 50min in temperature
Afterwards, regenerated copper-aluminium composite oxide adsorbent can be obtained in filtering, can return to cleaning procedure use, and alkali wash water supplements NaOH
After be recycled.
Comparative example 1 is with the difference of embodiment 1: in comparative example 1, the circulation collection of waste acid cleaning solution is not carried out,
Acidity is only 112g/L, if direct circulation is enriched with, equipment corrosion aggravation adversely affects normal production.Thus work as acidity
More than 100g/L, new waste acid cleaning solution is needed to change.According to the data of comparative example 1, the waste acid without circulation collection, for aoxidizing
There is no problem for the leaching and purification of zinc, but gained scavenging solution zinc concentration is lower, only 69g/L, if returning to main system production
Electric zinc easily causes the water swellable problem of main system, and if produce sulfuric acid zinc product, then be concentrated by evaporation higher cost, economy
It is poor.Simultaneously as not carrying out circulation collection, waste acid yield is caused to increase by 1 times or more compared with embodiment 1.Thus, to it is low at
Originally, high efficiency utilizes waste acid, it is necessary to carry out circulation collection processing to waste acid.
Embodiment 2:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc oxide fumes (Zn:75.2%, granularity is less than 200 mesh: >=95%) be neutralizer,
Zinc oxide fumes are added into flue gas washing liquid circulating slot according to the charging rate of 1.1t/h, control cleaning solution pH is 1.7 or so,
Washing flow quantity is 20m3Cleaning solution in circulating slot is pumped into neutralization chamber, while supplementing in circulating slot by/h after reacting 120h
Isometric new water.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 2.8.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:142g/L, Cl:5601mg/L, F:2425mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 50 DEG C, and 110kg/m is added3Copper-aluminium composite oxide reaction 75min after,
Be obtained by filtration scavenging solution (Zn:144g/L, Cl:364mg/L, F:37mg/L), scavenging solution be pumped into main production system carry out electric zinc or
Zinc sulfate production.Purification slag is added in alkali cleaning regeneration tank, 0.9M NaOH solution is added, is 65 DEG C of agitator treatings in temperature
After 40min, regenerated copper-aluminium composite oxide adsorbent is can be obtained in filtering, can return to cleaning procedure use, alkali wash water supplement
It is recycled after NaOH.
Comparative example 2:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc oxide fumes (Zn:75.2%, granularity is less than 200 mesh: >=95%) be neutralizer,
Zinc oxide fumes are added into flue gas washing liquid circulating slot according to the charging rate of 1.1t/h, control cleaning solution pH is 3.6 right, is washed
Washing flow quantity is 20m3There is crystal after reacting 38h in/h in circulation fluid, deposit occurs in circulation trench bottom, solution viscosity compared with
Greatly, can not continue to wash work.
By the waste acid cleaning solution filtering in circulating slot, collects neutralize filter residue and filtrate (Zn:55g/L, Cl:1124mg/ respectively
L, F:402mg/L), filtrate is pumped into purification tank.
Controlling purification tank reaction temperature is 50 DEG C, and 40kg/m is added3Copper-aluminium composite oxide reaction 75min after, mistake
Filter is purified liquid (Zn:54g/L, Cl:421mg/L, F:42mg/L), and scavenging solution is pumped into main production system and carries out electric zinc or sulfuric acid
Zinc production.Purification slag is added in alkali cleaning regeneration tank, 0.9M NaOH solution is added, is 65 DEG C of agitator treating 40min in temperature
Afterwards, regenerated copper-aluminium composite oxide adsorbent can be obtained in filtering, can return to cleaning procedure use, and alkali wash water supplements NaOH
After be recycled.
Comparative example 2 is with the difference of embodiment 2: pH higher of the comparative example 2 in waste acid cleaning solution cyclic process, this makes
It obtains zinc and reacts a large amount of zinc sulfite precipitating (crystal) of generation with sulfur dioxide in flue gas, that is to say, that as pH higher, wash
Washing liquid not only can be absorbed sulfur trioxide, can be with sulfur dioxide absorption, this makes the cycle performance of cleaning solution be deteriorated, the damage of sulphur
Lose aggravation.In addition, in this case, there is no problem for the removing of fluorine, chlorine, but zinc causes to purify due to forming zinc sulfite
Zinc concentration is lower in liquid, is unfavorable for subsequent processing.
Embodiment 3:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc carbonate (Zn 55.6%, granularity is less than 200 mesh: >=97%) be neutralizer, according to
Zinc oxide fumes are added into flue gas washing liquid circulating slot for the charging rate of 0.9t/h, and control cleaning solution pH is 1.5 or so, washing
Flow quantity is 42m3Cleaning solution in circulating slot is pumped into neutralization chamber by/h after reacting 150h, while the bodies such as supplement in circulating slot
Long-pending new water.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 2.6.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:127g/L, Cl:4507mg/L, F:1844mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 35 DEG C, and 96kg/m is added3Copper-aluminium composite oxide reaction 85min after, mistake
Filter is purified liquid (Zn:128g/L, Cl:411mg/L, F:41mg/L), and scavenging solution is pumped into main production system and carries out electric zinc or sulphur
Sour zinc production.Purification slag is added in alkali cleaning regeneration tank, 1.5M NaOH solution is added, is 65 DEG C of agitator treatings in temperature
After 35min, regenerated copper-aluminium composite oxide adsorbent is can be obtained in filtering, can return to cleaning procedure use, alkali wash water supplement
It is recycled after NaOH.
Embodiment 4:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc carbonate (Zn 55.6%, granularity is less than 200 mesh: >=97%) be neutralizer, according to
Zinc oxide fumes are added into flue gas washing liquid circulating slot for the charging rate of 1.4t/h, and control cleaning solution pH is 1.6 or so, washing
Flow quantity is 30m3Cleaning solution in circulating slot is pumped into neutralization chamber by/h after reacting 128h, while the bodies such as supplement in circulating slot
Long-pending new water.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 2.9.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:146g/L, Cl:5684mg/L, F:2437mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 35 DEG C, and 135kg/m is added3Copper-aluminium composite oxide reaction 105min after,
Be obtained by filtration scavenging solution (Zn:147g/L, Cl:355mg/L, F:32mg/L), scavenging solution be pumped into main production system carry out electric zinc or
Zinc sulfate production.Purification slag is added in alkali cleaning regeneration tank, 1.2M NaOH solution is added, is 45 DEG C of agitator treatings in temperature
After 60min, regenerated copper-aluminium composite oxide adsorbent is can be obtained in filtering, can return to cleaning procedure use, alkali wash water supplement
It is recycled after NaOH.
Embodiment 5:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc oxide fumes (Zn:64.8%, granularity is less than 200 mesh: >=92%) be neutralizer,
Zinc oxide fumes are added into flue gas washing liquid circulating slot according to the charging rate of 1.2t/h, control cleaning solution pH is 1.4 or so,
Washing flow quantity is 35m3Cleaning solution in circulating slot is pumped into neutralization chamber, while supplementing in circulating slot by/h after reacting 130h
Isometric new water.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 3.1.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:133g/L, Cl:5108mg/L, F:2016mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 55 DEG C, and 75kg/m is added3Copper-aluminium composite oxide reaction 120min after,
It is obtained by filtration scavenging solution (Zn136g/L, Cl:474mg/L, F:46mg/L), scavenging solution is pumped into main production system and carries out electric zinc or sulphur
Sour zinc production.Purification slag is added in alkali cleaning regeneration tank, 1.0M NaOH solution is added, is 60 DEG C of agitator treatings in temperature
After 75min, regenerated copper-aluminium composite oxide adsorbent is can be obtained in filtering, can return to cleaning procedure use, alkali wash water supplement
It is recycled after NaOH.
Embodiment 6:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc oxide fumes (Zn:75.2%, granularity is less than 200 mesh: >=95%) be neutralizer,
Zinc oxide fumes are added into flue gas washing liquid circulating slot according to the charging rate of 0.9t/h, control cleaning solution pH is 1.5 or so,
Washing flow quantity is 32m3Cleaning solution in circulating slot is pumped into neutralization chamber, while supplementing in circulating slot by/h after reacting 136h
Isometric new water.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 3.0.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:131g/L, Cl:5115mg/L, F:2307mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 45 DEG C, and 65kg/m is added3Copper-aluminium composite oxide reaction 50min after, filtering
Obtain one section of scavenging solution (Zn:133g/L, Cl:792mg/L, F:104mg/L).One section of scavenging solution is pumped into purification tank and carries out two sections only
Change 55 DEG C, 50kg/m is added3Copper-aluminium composite oxide reaction 40min after, be obtained by filtration two sections of scavenging solutions (Zn:135g/L,
Cl:306mg/L, F:24mg/L), two sections of scavenging solutions are pumped into main production system and carry out electric zinc or zinc sulfate production.By purification slag
It is added in alkali cleaning regeneration tank, 1.2M NaOH solution is added, after temperature is 45 DEG C of agitator treating 60min, filtering be can be obtained
Regenerated copper-aluminium composite oxide adsorbent can return to cleaning procedure use, be recycled after alkali wash water supplement NaOH.
Embodiment 7:
The present invention is new on flue gas washing liquid circulating slot based on the existing sulfur dioxide flue gas washing system of zinc smelting factory
Increase pH monitoring and quantifying feed system.With zinc carbonate (Zn 55.6%, granularity is less than 200 mesh: >=97%) be neutralizer, according to
Zinc oxide fumes are added into flue gas washing liquid circulating slot for the charging rate of 1.2t/h, and control cleaning solution pH is 1.2 or so, washing
Flow quantity is 30m3Cleaning solution in circulating slot is pumped into neutralization chamber by/h after reacting 152h, while the bodies such as supplement in circulating slot
Long-pending new water.
Zinc carbonate is added in neutralization chamber, pH value of solution is neutralized to pH is 2.5.Then filter, respectively collect neutralize filter residue and
Filtrate (Zn:126g/L, Cl:4716mg/L, F:1882mg/L).Neutralize filter residue return flue gas washing system makes as neutralizer
With, and neutralize filtrate and be pumped into purification tank.
Controlling purification tank reaction temperature is 35 DEG C, and 135kg/m is added3Embodiment 4 in regenerated copper-aluminum composite oxide
After object reacts 105min, scavenging solution (Zn:127g/L, Cl:422mg/L, F:44mg/L) is obtained by filtration, scavenging solution is pumped into main production
System carries out electric zinc or zinc sulfate production.Purification slag is added in alkali cleaning regeneration tank, 1.0M NaOH solution is added, in temperature
After 45 DEG C of agitator treating 50min, regenerated copper-aluminium composite oxide adsorbent is can be obtained in filtering, can return to cleaning procedure
It uses, is recycled after alkali wash water supplement NaOH.
Claims (8)
1. a kind of method that zinc smelting factory waste acid recycles, it is characterised in that: during flue gas washing, in flue gas washing liquid
Zinc oxide and/or zinc carbonate neutralizer is added once to be neutralized, to control the pH of flue gas washing liquid in 1.2~1.8 ranges,
When zinc ion concentration in flue gas washing liquid is more than 140g/L, extension flue gas washing liquid, while supplementing the new flue gas of corresponding amount
Cleaning solution and zinc oxide and/or zinc carbonate neutralizer continue flue gas washing；It is added in extension flue gas washing liquid
Zinc carbonate neutralizer carries out secondary neutralization, after controlling the pH of flue gas washing liquid in 2.5~3.5 ranges, is separated by solid-liquid separation, solid-liquid
Separating obtained slag phase returns to flue gas washing process and reuses, and it is miscellaneous by absorption method removing fluorine and chlorine to be separated by solid-liquid separation gained liquid phase
Matter obtains solution of zinc sulfate.
2. the method that a kind of zinc smelting factory waste acid according to claim 1 recycles, it is characterised in that: flue gas washing liquid
Circular flow control is 15~50m3/ h, zinc oxide and/or zinc carbonate neutralizer are 0.6 with respect to the addition speed of flue gas washing liquid
~1.6t/h.
3. the method that a kind of zinc smelting factory waste acid according to claim 1 recycles, it is characterised in that: draw flue gas and wash
The amount for washing liquid is the 60~80% of flue gas washing liquid total volume.
4. the method that a kind of zinc smelting factory waste acid according to claim 1 recycles, it is characterised in that: liquid phase passes through suction
The process of attached method removing fluorine and chlorine impurity are as follows: adsorbent is removed as fluorine chlorine using copper-aluminium composite oxide altogether, it is inverse by two sections
Flow fluorine and chlorine impurity in technique adsorbing and removing liquid phase.
5. the method that a kind of zinc smelting factory waste acid according to claim 4 recycles, it is characterised in that: copper-aluminium is compound
Oxide is 60~150kg/m with respect to the dosage of liquid phase3, adsorption temp is 30~60 DEG C, and adsorption time is 40~120min.
6. the method that a kind of zinc smelting factory waste acid according to claim 4 recycles, it is characterised in that: the copper-aluminium
The granularity of composite oxides is less than 15 μm.
7. the method that a kind of zinc smelting factory waste acid according to claim 4 recycles, it is characterised in that: absorption fluorine and chlorine
To saturation copper-aluminium composite oxide using after alkali liquid washing regeneration treatment, reuse.
8. the method that a kind of zinc smelting factory waste acid according to claim 7 recycles, it is characterised in that: the lye is
0.5~2M NaOH solution, wash temperature are 30~70 DEG C, and wash time is 30~80min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110156068A (en) * | 2019-06-24 | 2019-08-23 | 广东璞睿泰科环保科技有限公司 | A kind of zinc abstraction waste acid Comprehensive recycle technology |
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