CN102863007B - Method for producing high-purity nano-zinc oxide by ammonia method using electrolytic zinc acid-leaching residues - Google Patents

Method for producing high-purity nano-zinc oxide by ammonia method using electrolytic zinc acid-leaching residues Download PDF

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CN102863007B
CN102863007B CN201210358014.1A CN201210358014A CN102863007B CN 102863007 B CN102863007 B CN 102863007B CN 201210358014 A CN201210358014 A CN 201210358014A CN 102863007 B CN102863007 B CN 102863007B
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ammonia
zinc
acid leaching
electrolytic zinc
purity
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CN102863007A (en
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陈尚全
李时春
李晓红
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SICHUAN JUHONG TECHNOLOGY Co Ltd
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Abstract

The invention discloses a method for producing high-purity nano-zinc oxide by an ammonia method using electrolytic zinc acid-leaching residues. The method comprises the following steps of: adding slaked lime being 1-5% of the mass of electrolytic zinc acid-leaching residues before a leaching step to perform activation, then leaching with ammonia-ammonium bicarbonate solution, adding 0.3-0.5kg of sodium fluorosilicate to per cubic meter of ammonia-ammonium bicarbonate solution, and refining after performing purification and impurity removal. According to the method for producing high-purity nano-zinc oxide by ammonia method using electrolytic zinc acid-leaching residues, the electrolytic zinc acid-leaching residues can be leached efficiently, the high-purity nano-zinc oxide with the purity up to above 99.7% can be obtained, and the high-purity nano-zinc oxide has high practical value and economic value; all the valuable and harmful heavy metals in the electrolytic zinc acid-leaching residues are leached and utilized, so that the obtained final leaching residues are converted from electrolytic zinc acid-leaching residues as high hazard wastes into ordinary solid wastes, the environment is protected, and the resources are rationally utilized.

Description

A kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide
Technical field
The present invention relates to a kind of production method of zinc oxide, particularly a kind of production method of high-purity nm zinc oxide.
Background technology
Zinc hydrometallurgy mainly adopts the production technology of roasting-leaching-electrolysis at present, in the electrolytic zinc acid leaching slag of discharge, zinc content is counted in mass ratio and is generally 6-9%, what have can reach 20%, and the material phase analysis that acid leaching residue is done and X diffraction analysis show, in leached mud, zinc is mainly with ZnFe 2o 4,zinc silicate form exists, meanwhile, the mass content 6-12% of sulphur, wherein the mass content of sulfate radical is 15-30%, ore deposit, various places calcium, magnesium salts content difference also contain Cu simultaneously 2+, Pb 2+, Cd 2+, Ni 2+, Hg 2+, As 3+plasma, its roughly mass content be about: copper 1%, plumbous 0.8%, iron 4%, silicon 3%, arsenic 0.3%, silver 0.003%, calcium 12%, magnesium 3%.In order to reclaim these zinc, current processing method has two kinds of pyrogenic process and wet methods at present, and pyrogenic process is rotary kiln evaporation method (waelz process) and fuming furnace volatility process, as the publication number Chinese patent application that is CN101886180.Wet method has hot acid to leach or high-temperature pressurizing leaches.Pyrogenic attack technological process is long, and maintenance of equipment amount is large, invests highly, and working environment is poor, need to consume a large amount of coal-fired or metallurgical coking coal, and benefit is low, and environmental pollution is large.Therefore conventionally leach with hot acid or high pressure leaching, these methods still existent defect are: 1. consume a large amount of acid, 2. the pressure of deironing is large, need to consume more reagent, 3. high-temperature high-pressure apparatus seriously corroded, and the complicated investment of equipment is larger; 4. operating cost is high, deficiency in economic performance.5. last slag of discharging is acid slag, brings new pollution to environment, have to take solidify & bury, not only contaminated environment, and waste resource.
Optimal method is to carry out the selective leaching of zinc, and zinc is entered in solution, and zinc obtains valuable recycling
The zinc oxide product of the mass fraction that high-purity zinc oxide generally refers to zinc oxide more than 99.7%, high-purity zinc oxide is the indispensable a kind of high-tech raw material of modern industry, of many uses, be mainly used in the tens of kinds of industry and enterprises such as glass, feed, pottery, dyestuff, paint, papermaking, rubber, agricultural chemicals, oil refining, zinc-plated, special steel material, alloy, science and techniques of defence, no matter be glass, papermaking, or rubber, oil refining etc. are all in great demand to zinc oxide, and purity requirement is very high.
Nano zine oxide (ZnO) be a kind of particle diameter between 1-100 nm, novel high function fine inorganic product geared to the 21st century, show much special character, as non-migrating, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc., utilize its marvellous performance at aspects such as optical, electrical, magnetic, sensitivities, can manufacture gas sensor, fluorophor, rheostat, UV-preventing material, image recording material, piezoelectric, piezo-resistance, effective catalyst, magnetic material and plastic sheeting etc.
The method of producing at present nano zine oxide, mainly contains chemical precipitation method, sol-gel process, microemulsion method and hydrothermal synthesis method etc.But the raw material adopting is all zinc calcine or the pure zinc salt etc. of zinc content more than 50%.
Ammonia process is a kind of common method of preparing zinc oxide, the general step of ammonia process (ammonia-carbon ammonium associating lixiviation process is produced zinc oxide) comprising at present: ammonia-carbon ammonium is leachate, material containing zinc is leached, and zinc ammonia element complex liquid makes zinc oxide product through purification, ammonia still process crystallization, drying and calcining.
This traditional ammonia process is prepared zinc oxide and is never applied to the processing of electrolytic zinc acid leaching slag, and main cause is:
1) in electrolytic zinc acid leaching slag, have a large amount of calcium sulfate parcels and make zinc wherein leach difficulty, the rate of recovery is low
2) in electrolytic zinc acid leaching slag, contain the sulfate radical of 15-30%, a large amount of ammonia are converted into ammonium sulfate, and ammonia consumption is high.
3) conventional method, by the zinc ammonia complex liquid direct purification after leaching, is removed heavy metal with zinc replacement as last, owing to there being a large amount of free ammonias in solution, impurity complexing power is strong, easily produce back dissolving phenomenon, affect clean-up effect, finally affect the purity of zinc oxide product
4) owing to there is a large amount of ammonium sulfate in liquid, in ammonia still process process, will separate out part of sulfuric acid zinc ammonium double salt, finally affect zinc oxide purity.
Current published method for producing nanometer-zinc oxide by ammonia leaching technology is all lower temperature hydrolytic precipitation method as:
Chinese Patent Application No. 92103230.7 has been announced a kind of improvement technology for the legal production zinc oxide of traditional ammino, zinc ammonia complex liquid after purifying is diluted with water, make the hydrolysis of part zinc ammonia complex liquid, obtain basic zinc carbonate (zinc hydroxide is 2:1 with the ratio of zinc carbonate), then continue heating until the decomposition of zinc ammonia complex liquid is complete, obtain the nano zine oxide of 30-100nn through high-temperature calcination.
The following problem of this technical patent needs to solve:
After hydrolysis, non-dissociated zinc ammonia complex liquid is adding in thermal decomposition process, and the new basic zinc carbonate producing can, in original nucleating surface continued growth, impel the crystal of former hydrolysis to grow up, easily cause basic zinc carbonate crystalline solid particle diameter inhomogeneous, make final products particle diameter wayward.
Increase the 4-10 water yield doubly, reduced the efficiency of producing in process, increase energy consumption, increase rear end cost of water treatment.
Chinese Patent Application No. 200610130477.7 has been announced a kind of improvement technology for the legal production zinc oxide of traditional ammino, by zinc ammonia complex liquid, mix with the hot water of 1:2-20 or the mother liquor of heat continuously, mother liquor is cycled to used in the hydrolysis of zinc ammonia complex liquid after heating and thermal insulation, makes the nano zine oxide of 10-50nn.
The following problem of this technical patent needs to solve:
After mother liquor hydrolysis, ammonia can not be separated completely, repeats stack and does not reach the effect of hydrolysis, is zinc ammonia complex liquid the most at last and the mixing of zinc ammonia complex liquid.
Above two kinds of patents are in fact all to manage at low temperatures, utilize the Macrodilution of water to make the pH value of solution slight change occur and hydrolysis crystallization acquisition part Nanocrystal, only actually relies on the slight change of pH value can only obtain few part hydrolysis (can find from zinc oxide) in situation in the time that zinc concentration is higher ammonia solvent is write music line chart.The zinc ammoniacal liquor of high concentration is separated out in fact efficiency is high, energy consumption is low, and efficiency that the zinc ammoniacal liquor of low concentration is separated out is low, energy consumption is high, people be the proportional quantities that adds flood to produce nano zine oxide be feasible technically, but may not be feasible aspect economic benefit.
In addition, ammonia leaching process is produced zinc oxide at present, crystalline solid is high (first approximately 125 ℃ of the temperature that make of zinc hydroxide decomposition of basic zinc carbonate decomposition temperature, approximately 300 ℃ of zinc carbonates), for obtaining high purity product, must guarantee sufficiently high decomposition temperature, general control temperature more than 500 ℃, just can make basic zinc carbonate decompose completely.As the Chinese patent application that application number is 200610130477.7, calcining heat is up to 550 ℃.High-temperature calcination has a strong impact on specific area and the activity thereof of zinc oxide, then has influence on its application.
In sum, for the processing of electrolytic zinc acid leaching slag, how in the material of low content zinc, effectively to leach zinc wherein, and obtain the zinc oxide of high-purity Nano-class, need to overcome traditional pyrogenic process and the shortcoming of wet method simultaneously, become industry technical barrier urgently to be resolved hurrily.
Summary of the invention
One of goal of the invention of the present invention is: for the problem of above-mentioned existence, the zinc in a kind of effective recovery electrolytic zinc acid leaching slag is provided and prepares the method for high-purity nm zinc oxide.
The technical solution used in the present invention is such: a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide, comprises the following steps:
Leach pending electrolytic zinc acid leaching slag, purification and impurity removal, ammonia still process crystallization and drying and calcining,
Before leaching pending electrolytic zinc acid leaching slag step, in pending electrolytic zinc acid leaching slag, add white lime to carry out admixture activation, the amount of the white lime adding, by weight, is the 1-5% of pending electrolytic zinc acid leaching slag;
Electrolytic zinc acid leaching slag after activation is leached with ammoniacal liquor-ammonium fluid; Wherein, NH 3molar concentration c (NH 3)=5-6mol/L, CO 3 2-molar concentration c (CO 3 2-)=0.9-1.2 mol/L adds 0.3-0.5kg prodan in the ammoniacal liquor-ammonium fluid of every cubic metre;
After purification and impurity removal, carry out refinement treatment, method is: in purification and impurity removal liquid after treatment, add ammonium phosphate and surfactant, addition is 1-3kg ammonium phosphate, 10-50g surfactant in every cubic metre of purification and impurity removal liquid after treatment;
Purification and impurity removal, ammonia still process crystallization and drying and calcining step all adopt current common ammonia process to prepare the technological parameter of zinc oxide.
The technology that first the present invention prepares existing ammonia process zinc oxide is applied to the processing to electrolytic zinc acid leaching slag, simultaneously, on the technique basis of existing ammonia process, before ammonia soaks step, increase pretreatment, it is the step that adds white lime to activate in electrolytic zinc acid leaching slag, in leaching liquid, add appropriate prodan, in addition simultaneously, after purification and impurity removal, increase the step of refinement treatment.
First, obtain highly purified zinc oxide, first need to guarantee that the zinc in electrolytic zinc acid leaching slag can leach as much as possible, can improve so on the one hand the rate of recovery of zinc, on the other hand, in leachate, zinc concentration is larger, and impurity concentration relative scale is just less, can guarantee to make more highly purified zinc oxide under equal process conditions.
Owing to containing a large amount of calcium sulfate (15-30%) in electrolytic zinc acid leaching slag, the ultrafine dusts such as calcium sulfate play buffer action to leaching agent, cause acid environment to leach, so the present invention adopts ammonia process to leach, under the effect of ammonia-carbon ammonium associating liquid, calcium sulfate is converted into calcium carbonate and calcium hydroxide, in conversion process, accelerates infiltration and the stripping of leaching agent thereby form space; But calcium hydroxide also has certain sealing process to leaching, and in order to address this problem, present inventor draws by great many of experiments: appropriate fluosilicic acid is received and can be abolished ultrafine dust to containing zinc particle parcel, realizes ultrafine dust layering floating.
Meanwhile, present inventor draws by great many of experiments: the adding of appropriate white lime, on the one hand can in and remaining sulfuric acid in acid leaching residue; Can increase on the other hand the OH in leaching environment -, improve the activation grade of ammonia and the leaching rate of zinc; Again on the one hand, OH -can make crystallization product in subsequent step be converted into zinc hydroxide by zinc carbonate.
Secondly, obtain nano level zinc oxide, need to suppress growing up of crystal grain, existing ammonia process produce the nano zine oxide that obtains why particle size and particle size distribution range unsatisfactory, most important reason is constantly the growing up of crystal in processing procedure, especially for the raw material processing of this low zinc content of electrolytic zinc acid leaching slag.In order to address the above problem, present inventor is by great many of experiments, after purification and impurity removal, increase the step of refinement treatment, in purification and impurity removal solution after treatment, add appropriate ammonium phosphate and surfactant, in conjunction with the growth that can effectively suppress crystalline solid under high-speed stirred.
Wherein:
Chemical reaction in activation process is:
Ca(OH) 2+CO 3 2-→CaCO 3↓+2OH -
2NH 3·H 2O + CaSO 4 →Ca(OH) 2 ↓+(NH 4) 2SO 4
NH 4HCO 3+ NH 3·H 2O+ CaSO 4 →CaCO 3↓+(NH 4) 2SO 4+H 2O
Fe 3+ +3OH - →Fe(OH) 3↓
Fe 2+ +2OH - →Fe(OH) 2↓；
The chemical equation of leaching step is:
ZnO+nNH 3 +H 2O→［Zn(NH 3)n］ 2++2OH -
ZnFe 2O 4 +nNH 3+4H 2O→［Zn(NH 3)n］ 2++2Fe(OH) 3 ↓+2OH -
ZnFe 2O 4 +nNH 3+H 2O→［Zn(NH 3)n］ 2++Fe 2O 3↓+2OH -
ZnSiO 3+ nNH 3 +2NH 4HCO 3→［Zn(NH 3)n］CO 3+ SiO 2·H 2O+(NH 4) 2CO 3
Zn(OH) 2 +nNH 3 →［Zn(NH 3)n］ 2++2OH -
Zn+nNH 3 +2H 2O→［Zn(NH 3)n］ 2++ H 2+ 2OH -
ZnSO 4+nNH 3→［Zn(NH 3)n］ 2++SO 4 2-
Wherein n=1～4;
The reaction occurring in purification and impurity removal process:
S 2O 8 2-+ Mn 2++ 2NH 3·H 2O + H 2O→ Mn O（OH） 2↓ + 2NH 4 ++2SO 4 2-+ 2H +
S 2O 8 2-+2Fe 2+ +6H 2O →2SO 4 2-+ 2Fe(OH) 3↓+ 6H +
AsO 4 3- + Fe 3- → FeAsO 4↓
AsO 3 3- + S 2O 8 2-+ H 2O → 2SO 4 2- + AsO 4 3-+ 2H +
2H 3AsO 3 + 8Fe(OH) 3 → (Fe 2O 3) 4As 2O 3·5H 2O↓ +10H 2O
M 2++ S 2→ MS ↓ M represents Cu 2+, Pb 2+, Cd 2+, Ni 2+hg 2+plasma
As 3+ + S 2-→As 2S 3↓
Y 2++ Zn → Zn 2+wherein Y representative of+Y: Cu 2+, Pb 2+, Cd 2+, Ni 2+plasma;
The reaction equation of refinement treatment:
3［Zn(NH 3)n］ 2++ 2（NH 4） 3PO 4+ 6OH -→［Zn(NH 3)n］ 3(PO 4) 2+ 6NH 3·H 2O
The reaction equation of ammonia still process step:
［Zn(NH 3) i］ 2++2OH -= Zn(OH) 2↓+ iNH 3↑ i =1～4
A small amount of CO in solution 3 2-can there is following hydrolysis:
［Zn(NH 3) 4］CO 3+H 2O→ZnCO 3·2Zn(OH) 2·H 2O↓+16NH 3↑；
The chemical equation of drying and calcining:
Zn(OH) 2→ZnO + H 2O↑
ZnCO 3·2Zn(OH) 2·H 2O → 3ZnO +3H 2O↑ +CO 2
As preferably: while leaching pending electrolytic zinc acid leaching slag, be also added with the surfactant of 0.03-0.05kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
Decreasing by surfactant surface energy, with prodan mating reaction, the coating function that can abolish ultrafine dust improves leaching agent penetrating power, further improves the rate of recovery of zinc.
As preferably: the dicyanodiamine that is also added with 0.5-1kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
Dicyanodiamine, as ammonia stabilizing agent, can reduce the volatilization of ammonia in leaching process, improves leaching working environment, reduces the loss of ammonia.
As preferably: in the time of the pending electrolytic zinc acid leaching slag of leaching, adopt wet ball grinding, activation leaching.
Utilize wet ball grinding leaching, can destroy original lattice structure and carry out the leaching of activation limit, limit, thereby improve leaching efficiency.
As preferably: before purification and impurity removal step, carry out pre-ammonia still process: leaching liquid is heated to 90-98 ℃ and carries out ammonia still process, steam to ammonia concentration in liquid be 2.5-3.5mol/L; Then add 2-4kg ammonium persulfate to stir oxidation by every cubic metre of leaching liquid and reach preliminary purification; When ammonia still process crystallization, temperature is controlled in 105 ℃, and the speed 300-500 per minute stirring in ammonia still process equipment turns.
Increase pre-ammonia still process step, remove on the one hand too much free ammonia, reduce the complexing power of impurity, make foreign ion be easy to remove, reduce and purify drug dosage, improve depuration quality; Can remove on the other hand carbanions a large amount of in solution, while making the hydrolysis of complex liquid deamination, be conducive to obtain zinc hydroxide nucleus precipitation, reduce the composition of zinc carbonate;
As preferably: in ammonia still process crystallization process, detect at any time solution zinc concentration in ammonia still process container, when zinc content is during at 1-1.5%, in container, add sodium hydroxide solution, addition is that to add mass fraction be 30% sodium hydroxide solution 3-5 liter to every cubic metre of solution, in solution, zinc content is lower than 0.3% time, finish ammonia still process and (now finish ammonia still process, owing to containing a large amount of sulfate radicals in solution, form stable ammonium salt, continue ammonia still process nonsensical, and can produce zinc sulfate ammonium double salt precipitation, affect nano zine oxide product quality).
In the ammonia still process later stage, in the time that zinc concentration is lower in complex liquid, by adding sodium hydroxid to improve the pH value of liquid, can make NH 4 +ion transfers NH to 3molecule reaches the effect of analysing fast ammonia, rapid crystallization formation nanometer zinc hydroxide nucleus.
As preferably: it is 5% Sodium stearate solution 3-5L that every cubic metre of ammonia still process liquid adds mass percent.
In ammonia still process process, add Sodium stearate, make the Nanocrystal producing be subject to sealing parcel, no longer continue to grow up.
As preferably: add vulcanized sodium to sink zinc in crystallization raffinate, separate and obtain zinc sulphide filter cake.Filtrate adds white lime again, mixed liquor is stirred to intensification ammonia still process and transform, and temperature is not for higher than 105 ℃, mixing speed is 300-500 rev/min, and the ammonia of effusion is by cooling recycling, and ammonium sulfate is converted into crystal of calcium sulfate body simultaneously, then carry out rinsing, dry, obtain calcium sulfate powder.Turn waste into wealth, realize processing and recycling to water.
Two of object of the present invention, is to provide a kind of high-purity and highly active nano zine oxide, and the technical scheme adopting is that the temperature of drying and calcining adopts 150-300 ℃.
Due to technical scheme of the present invention, after ammonia still process crystallisation step, what obtain is mainly zinc hydroxide, the decomposition temperature of zinc hydroxide is lower than basic zinc carbonate, adopt the temperature of 250-350 ℃ to calcine, can obtain purity 99.7% and above zinc oxide, because the nucleus of zinc hydroxide is less than basic zinc carbonate, so finally can obtain being evenly distributed, particle diameter is 10-30nm, and specific area>=100m 2high-quality nanometer Zinc oxide powder more than/g.
In sum, adopt technique scheme, ammonia process is applied to the processing to electrolysis acid leaching residue, and existing ammonia process is carried out to technological improvement, before leaching, increase activation step and in the time of leaching, added prodan, surfactant and dicyanodiamine, on the one hand electrolytic zinc acid leaching slag has reached efficient leaching, and subsequent handling increases pre-ammonia still process and in ammonia still process process, adds resistive agent to suppress the growth of crystal, obtains the little and uniform nanometer zinc oxide precursor of particle diameter of particle diameter; On the other hand, this preferably adopts lower calcining heat, can obtain the high-purity nm zinc oxide (purity can reach 99.7%) compared with bigger serface, has very high practical value and economic worth; In addition, processing method energy consumption of the present invention is low, efficiency is high.In electrolytic zinc acid leaching slag, there are valency and harmful heavy metal all to be leached utilization and clean through washing.Obtain soaking slag from becoming general solid refuse as the electrolytic zinc acid leaching slag of high-risk discarded object eventually, reached the reasonable utilization of economic environmental protection and regenerated resources.
Innovative point of the present invention mainly contains: (1) increase pre-ammonia still process processing, first drive too much free ammonia away, reach the object of rapid crystallization in the time of ammonia still process; (2), in ammonia still process process, in the time that ammonia concentration is lower in zinc ammonia complex liquid, by adding sodium hydroxid to improve the pH value of liquid, reach the object of analysing fast ammonia; (3) in zinc ammonia complex liquid, add surfactant (as SDS), ammonium phosphate, own ammonium sulfate in binding soln, can effectively control the growth of nano zine oxide nucleus; (4) utilize the power of steam to realize high-speed stirred, control nano zine oxide crystallization;
The specific embodiment
The present invention is described in detail below.
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity nano zinc oxide, comprise the following steps successively:
(1) activation: get 500 grams of electrolytic zinc acid leaching slags (wherein, by quality ratio, containing zinc 8.6%, copper 1.03%, calcium sulfate 32%, cadmium 0.05%, arsenic 0.03%), add 25 grams of white limes to activate, soak time is 36 hours;
(2) leaching: produce 1500ml ammonia leaching solution, wherein NH 3concentration is 6mol/L, CO 3 2-concentration is 1mol/L, in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.3kg prodan, electrolytic zinc acid leaching slag after activation is joined and in above-mentioned ammonia leaching solution, carries out three sections of leachings, each section of leaching time is 2 hours, after Separation of Solid and Liquid, 38.9 grams, zinc (zinc recovery 90.5%) in gained zinc ammonia complex liquid, 41.92 grams of sulfate radicals in zinc ammonia complex liquid;
(3) purification and impurity removal: add 0.5 gram of vulcanized sodium at zinc ammonia complex liquid, stir after 2 hours and filter, add 0.2 gram of potassium permanganate, stir after 2 hours and filter;
(4) refining: in purification and impurity removal liquid after treatment, in every cubic metre of purification and impurity removal liquid after treatment, to add 2kg ammonium phosphate, 30g surfactant SDS;
(5) ammonia still process crystallization: heating ammonia still process after the zinc ammonia complex liquid after refinement treatment is filtered, ammonia distiller mixing speed per minute 600 turns, and stops ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(6) drying and calcining: the zinc hydroxide after filtration adds respectively the deionized water of 200ml to carry out three washings, adding 0.05 gram of lauryl sodium sulfate in washing process for the first time, zinc hydroxide after washing adds 150ml ethanol to wash, and the zinc hydroxide after press filtration is put into Muffle furnace 250 degree calcining 3 hours;
Made nano zine oxide average grain diameter 12.7nm(XRD live width method), quality percentage composition is 99.7%, specific area 106m 2/ g.
Embodiment 2
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity nano zinc oxide, comprise the following steps successively:
(1) activation: get 500 grams of acid leaching residues (zinc 7.6%, copper 0.83%, calcium sulfate 28%, cadmium 0.045%, arsenic 0.02%), add 5 grams of white limes to activate, soak time is 40 hours;
(2) leaching: produce 1500ml ammonia leaching solution, wherein NH 3concentration is 5mol/L, CO 3 2-concentration is 1.2mol/L, adds 0.5kg prodan in the ammoniacal liquor-ammonium fluid of every cubic metre, and in the ammoniacal liquor-ammonium fluid of every cubic metre, is also added with the surfactant SDS of 0.04kg; In the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the dicyanodiamine of 0.8kg; Electrolytic zinc acid leaching slag after activation is joined in above-mentioned ammonia leaching solution and carries out three sections of leachings, ball milling when leaching, each section of leaching time is 2.5 hours, after Separation of Solid and Liquid, 34.9 grams, zinc (zinc recovery 91.8%) in gained zinc ammonia complex liquid, 37.7 grams of sulfate radicals in zinc ammonia complex liquid;
(3) pre-ammonia still process: leaching liquid is heated to 90 ℃, and every cubic metre of leaching liquid adds 2kg ammonium persulfate, then carries out ammonia still process, steam to ammonia concentration in liquid be 3.5mol/L;
(4) purification and impurity removal: add 0.6 gram of vulcanized sodium at zinc ammonia complex liquid, stir after 2 hours and filter, add 0.2 gram of potassium permanganate, stir after 2 hours and filter;
(5) refining: in purification and impurity removal liquid after treatment, in every cubic metre of purification and impurity removal liquid after treatment, to add 1kg ammonium phosphate, 10g surfactant SDS;
(6) ammonia still process crystallization: heating ammonia still process after the zinc ammonia complex liquid after refinement treatment is filtered, ammonia distiller mixing speed per minute 900 turns, and temperature is controlled in 105 ℃, stops ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(7) in the filtrate after ammonia still process crystallization, add vulcanized sodium to react, after reaction, separate and obtain solid zinc sulphide and liquid part; Add white lime in liquid part, and stir obtain mixed liquor, in whipping process, add surfactant SDS; Mixed liquor is carried out to ammonia still process crystallization, and crystallization temperature is 100 ℃, in ammonia still process process, stirs, and mixing speed is 300 revs/min, and the ammonia of separating out is by cooling recovery, and the calcium sulfate after crystallization carries out rinsing, dry, obtains calcium sulfate powder;
(8) drying and calcining: the zinc hydroxide filter cake after filtration adds respectively the deionized water of 200ml to carry out three washings, adding 0.05 gram of lauryl sodium sulfate in washing process for the first time, zinc hydroxide after washing adds 150ml ethanol to wash, and the zinc hydroxide after press filtration is put into Muffle furnace 150 degree calcining 3.5 hours;
Made nano zine oxide average grain diameter 11.5nm (XRD live width method), quality percentage composition is 99.75%, specific area 110m 2/ g.
Embodiment 3
Utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity nano zinc oxide, comprise the following steps successively:
(1) activation: get 1500 grams of acid leaching residues (zinc 9.0%, copper 0.80%, calcium sulfate 30%, cadmium 0.040%, arsenic 0.25%, silicon 3%, arsenic 0.3%, silver 0.003%, magnesium 3%), add 45 grams of white limes to activate, soak time is 48 hours;
(2) leaching: produce 1500ml ammonia leaching solution, wherein NH 3concentration is 5.5mol/L, CO 3 2-concentration is 0.9mol/L, adds 0.5kg prodan in the ammoniacal liquor-ammonium fluid of every cubic metre, and in the ammoniacal liquor-ammonium fluid of every cubic metre, is also added with the surfactant SDS of 0.03kg; In the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the dicyanodiamine of 1kg; Electrolytic zinc acid leaching slag after activation is joined and in above-mentioned ammonia leaching solution, carries out three sections of leachings, ball milling when leaching, each section of leaching time is 2.5 hours, after Separation of Solid and Liquid, 124.2 grams, zinc (zinc recovery 92.0%) in gained zinc ammonia complex liquid, 165.0 grams of sulfate radicals in zinc ammonia complex liquid;
(3) pre-ammonia still process: leaching liquid is heated to 98 ℃, and every cubic metre of leaching liquid adds 1kg ammonium persulfate, then carries out ammonia still process, steam to ammonia concentration in liquid be 3.0mol/L;
(4) purification and impurity removal: add 0.6 gram of vulcanized sodium at zinc ammonia complex liquid, stir after 2 hours and filter, add 0.2 gram of potassium permanganate, stir after 2 hours and filter;
(5) refining: in purification and impurity removal liquid after treatment, in every cubic metre of purification and impurity removal liquid after treatment, to add 3kg ammonium phosphate, 50g surfactant SDS;
(6) ammonia still process crystallization: heating ammonia still process after the zinc ammonia complex liquid after refinement treatment is filtered, ammonia distiller mixing speed per minute 800 turns, and temperature is controlled in 105 ℃, stops ammonia still process when zinc oxide mass content is 0.5% in liquid; Then filter, obtain zinc hydroxide filter cake and filtrate;
(7) in the filtrate after ammonia still process crystallization, add vulcanized sodium to react, after reaction, separate and obtain solid zinc sulphide and liquid part; Add white lime in liquid part, and stir obtain mixed liquor, in whipping process, add surfactant; Mixed liquor is carried out to ammonia still process crystallization, and crystallization temperature is 102 ℃, in ammonia still process process, stirs, and mixing speed is 500 revs/min, and the ammonia of separating out is by cooling recovery, and the calcium sulfate after crystallization carries out rinsing, dry, obtains calcium sulfate powder;
(8) drying and calcining: the zinc hydroxide filter cake after filtration adds respectively the deionized water of 200ml to carry out three washings, adding 0.05 gram of lauryl sodium sulfate in washing process for the first time, zinc hydroxide after washing adds 150ml ethanol to wash, and the zinc hydroxide after press filtration is put into Muffle furnace 250 degree calcining 1.5 hours;
Made nano zine oxide average grain diameter 10.8nm (XRD live width method), quality percentage composition is 99.80%, specific area 118m 2/ g.
Embodiment 4
120 tons of raw materials, come from Yunnan Chihong Zinc & Germanium Co., Ltd.'s Huize and smelt the acid leaching residue that old factory many decades accumulates, zinc 11.2%, copper 0.91%, lead 1.3%, acid group 27.6%, cadmium 0.03% in raw material.
(1) activation: add 2.5 tons of white limes to carry out admixture activation in above-mentioned raw materials, soak time is 46 hours;
(2) leaching: produce 360m 3ammonia leaching solution, wherein NH 3concentration is 5.6mol/L, CO 3 2-concentration is 1.1mol/L, in the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.4kg prodan, electrolytic zinc acid leaching slag after activation is joined and in above-mentioned ammonia leaching solution, carries out three sections of leachings, and in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the surfactant SDS of 0.045kg; In the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the dicyanodiamine of 0.8kg; Ball milling when leaching, each section of leaching time is 2.6 hours, Gu after Separation of Solid and Liquid, 12.23 tons, zinc (zinc recovery 91.0%) in gained zinc ammonia complex liquid, 13.7 tons of sulfate radicals in zinc ammonia complex liquid;
Authoritative institution's " Yunnan Province's environmental monitoring central station " that leached mud is specified through Environmental Protection Agency of Yunnan Province carries out scene sampling and leaching test, and waste meets the general solid waste standard of I class in " general industrial solid waste storage, disposal site pollute control criterion " (GB18599-2001);
(3) pre-ammonia still process: leaching liquid is heated to 96 ℃, and every cubic metre of leaching liquid adds 3kg ammonium persulfate, then carries out ammonia still process, steam to ammonia concentration in liquid be 3.2mol/L;
(4) purification and impurity removal: add 1.5kg vulcanized sodium at every cubic metre of zinc ammonia complex liquid, stir after 2 hours and filter, every cubic metre of zinc ammonia complex liquid adds 0.3kg potassium permanganate, stirs after 2 hours and filters;
(5) refining: in purification and impurity removal liquid after treatment, in every cubic metre of purification and impurity removal liquid after treatment, to add 3kg ammonium phosphate, 50g surfactant SDS;
(6) ammonia still process crystallization: heating ammonia still process after the zinc ammonia complex liquid after refinement treatment is filtered, ammonia distiller mixing speed per minute 700 turns, and controls temperature at 105 ℃; When zinc oxide mass content is 0.5% in liquid, stop ammonia still process; Then filter, obtain zinc hydroxide filter cake and filtrate;
(7) in the filtrate after ammonia still process crystallization, add vulcanized sodium to react, after reaction, separate and obtain solid zinc sulphide and liquid part; Add white lime in liquid part, and stir obtain mixed liquor, in whipping process, add surfactant; Mixed liquor is carried out to ammonia still process crystallization, and crystallization temperature is 103 ℃, in ammonia still process process, stirs, and mixing speed is 400 revs/min, and the ammonia of separating out is by cooling recovery, and the calcium sulfate after crystallization carries out rinsing, dry, obtains calcium sulfate powder;
(8) drying and calcining: drying and calcining: the filter cake after filtration adds ion exchange water to carry out three washings by liquid-solid ratio 5:1, in washing process for the first time, add the lauryl sodium sulfate of 1.25 grams/cubic metre, zinc hydroxide filter cake after washing adds ethanol to wash by liquid-solid ratio 1-5:1, and the zinc hydroxide after press filtration is put into Muffle furnace 180 degree calcining 3.5 hours;
Made nano zine oxide average grain diameter 12.6nm (XRD live width method), quality percentage composition is 99.78%, specific area 116m 2/ g.

Claims (9)

1. utilize electrolytic zinc acid leaching slag ammonia process to produce a method for high-purity nm zinc oxide, comprise the following steps:
Leach pending electrolytic zinc acid leaching slag, purification and impurity removal, ammonia still process crystallization and drying and calcining, it is characterized in that:
Before leaching pending electrolytic zinc acid leaching slag step, in pending electrolytic zinc acid leaching slag, add white lime to carry out admixture activation, the amount of the white lime adding, by weight, is the 1-5% of pending electrolytic zinc acid leaching slag;
Electrolytic zinc acid leaching slag after activation is leached with ammoniacal liquor-ammonium fluid; Wherein, NH 3molar concentration c (NH 3)=5-6mol/L, CO 3 2-molar concentration c (CO 3 2-)=0.9-1.2 mol/L adds 0.3-0.5kg prodan in the ammoniacal liquor-ammonium fluid of every cubic metre;
After purification and impurity removal, carry out refinement treatment, method is: in purification and impurity removal liquid after treatment, add ammonium phosphate and surfactant, addition is 1-3kg ammonium phosphate, 10-50g surfactant in every cubic metre of purification and impurity removal liquid after treatment.
2. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 1, it is characterized in that: while leaching pending electrolytic zinc acid leaching slag, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the surfactant of 0.03-0.05kg.
3. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 2, is characterized in that: the dicyanodiamine that is also added with 0.5-1kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
4. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 1, is characterized in that: in the time of the pending electrolytic zinc acid leaching slag of leaching, utilize wet ball grinding activation leaching.
5. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 1, it is characterized in that: before purification and impurity removal step, carry out pre-ammonia still process: leaching liquid is heated to 90-98 ℃ and carries out ammonia still process, steam to ammonia concentration in liquid be 2.5-3.5mol/L, rear every cubic metre of zinc ammoniacal liquor adds 2-4kg ammonium persulfate to stir oxidation; Ammonia still process crystallization stage, temperature is controlled in 105 ℃, and the speed of ammonia still process container for stirring 300-500 per minute turns.
6. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 1, it is characterized in that: in ammonia still process crystallization process, detect at any time liquid zinc content in ammonia still process equipment, when zinc content is during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, addition be every cubic metre of ammonia still process liquid to add quality percentage composition be 30% sodium hydroxide solution 3-5 liter, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process.
7. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 6, is characterized in that: in every cubic metre of ammonia still process liquid, also adding mass fraction is 5% Sodium stearate solution 3-5L.
8. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 1, it is characterized in that: in the residual solution after ammonia still process crystallization, add vulcanized sodium to precipitate remaining zinc, after precipitation, separate and obtain zinc sulphide filter cake, the dry zinc sulphide product that obtains; Filtrate adds white lime again, under agitation adds surfactant; By mixed liquor indirectly heat up ammonia still process transform, make ammonium sulfate be converted into crystal of calcium sulfate, conversion temperature is not for higher than 105 ℃, in ammonia still process process, mixing speed is 300-500 rev/min, the ammonia of overflowing is by cooling recovery, crystal of calcium sulfate after conversion carries out rinsing, dry, obtains calcium sulfate powder byproduct.
9. a kind of method of utilizing electrolytic zinc acid leaching slag ammonia process to produce high-purity nm zinc oxide according to claim 1, is characterized in that: the temperature of described drying and calcining is 150-300 ℃.
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