CN102849781B - Method for producing high-purity zinc oxide through fume ash in steel works - Google Patents

Method for producing high-purity zinc oxide through fume ash in steel works Download PDF

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CN102849781B
CN102849781B CN201210357963.8A CN201210357963A CN102849781B CN 102849781 B CN102849781 B CN 102849781B CN 201210357963 A CN201210357963 A CN 201210357963A CN 102849781 B CN102849781 B CN 102849781B
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leaching
zinc
zinc oxide
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ammonia
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CN102849781A (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 zinc oxide through fume ash in steel works. Ammonia-ammonium bicarbonate liquid is used as leaching solvent to perform leaching; 0.3 to 0.5 kg of sodium fluosilicate is added in each cubic meter of the leaching solvent; before an impurity removal step, leaching liquid subjected to leaching is heated to 95 to 105 DEG C to be subjected to ammonia pre-steaming; and by applying ammonia process to the treatment of the fume ash in the steel works and performing adaptive improvement on the existing ammonia process, zinc in the fume ash in the steel works can be rapidly leached completely as far as possible, the zinc in the fume ash in the steel works can be sufficiently recycled, and the purity of zinc oxide obtained can reach more than 99.7 percent. The method has the advantages that the energy consumption is low; the efficiency is high; the leaching solvent is circularly utilized; the problem of zinc load in the fume ash in the steel works is thoroughly solved; not only the requirement of purification of noxious constituent zinc and alkali metal by the steel works is satisfied, and the virtuous cycle of production is achieved, but also valued iron and coal resources in the steel works are recovered, and iron and coal are enriched; and not only energy is saved, but also good economic benefit is created.

Description

A kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide
Technical field
The present invention relates to a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide.
Background technology
At present from the smoke dust of steel mill (comprising that blast-furnace dust, converter ash, electric furnace are grey), claim again flue dust to store ash, one ton of iron and steel of every production will produce the smoke dust of 35～90kg, the general iron content 15～30% of this smoke dust, silicon oxide-containing 4～5%, zinc 5～22%, combustible fixed carbon (C) 25～55%, calcium oxide 2～5%, magnesium oxide 1～2% and titanium, vanadium and basic metal etc.Under usual conditions, generally as the raw material of sintering, produce agglomerate, in steel mill's internal recycling, utilize, along with the enrichment of circulation, enter stove zinc load more and more high, have a strong impact on the normal operation of blast furnace.
The method that restriction blast furnace zinc is loaded at present: the one, restriction circulation smoke dust consumption; The 2nd, smoke dust ore dressing is processed; The 3rd, adopt pyrogenic process and wet processing.The first be not reduce blast furnace zinc load economical, effective means, and bring environmental pollution.The second is that zinc is enriched in tail mud, but iron is smart, three kinds of products imbalances of carbon, tail mud, still loses higher iron, charcoal resource.The third is divided into again pyrogenic process and wet processing, and pyrogenic process has direct sintering, pelletizing facture, direct-reduction process to process.But zinc, lead and basic metal are not resolved yet.Wet method is divided into again acid system and alkaline process, and acid technological process is ripe, and the zinc leaching rate that do not heat up is 80% left and right only, and intensification can reach 95%, but iron is also up to 60%, and deironing difficulty, wastes again iron, and equipment corrosion is serious, does not also reach environmental requirement.But alkaline process leaching rate is lower.It is that zinc leaching rate is low that existing wet method is put forward zinc existing problems general nature, soaks slag and is difficult to recycle, cannot meet the requirement of environmental protection, and equipment corrosion is serious, responsive to ingredient requirement, and technique is difficult to optimize, and productivity effect Di Yu steel mill output does not match etc.Iron and Steel Enterprises in China zinc-containing dust is allocated sintering recycle mode into and blast furnace, SINTERING PRODUCTION and Steel Plant's environment is brought to significant damage at present, very urgent to the processing of dust.
Optimal method is that the selectivity of carrying out zinc leaches, and zinc is entered in solution, and zinc obtains valuable recycling.
On the other hand, high pure zinc oxide generally refers to that the massfraction of zinc oxide is 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.
Produce at present the method for high-purity zinc oxide, it is mainly indirect method, indirect method generally be take zinc ingot metal as raw material, pass through electrolytic reduction, or high-temperature gasification, atmospheric oxidation again condensation collection makes zinc oxide, different zinc ingot metal raw materials, the zinc oxide purity of producing is also different, and this technique is mainly produced the zinc oxide of 99.5%--99.7%.
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: to material containing zinc, use ammonia-carbon ammonium to combine leaching and make zinc ammonia complex liquid, through purification, ammonia still process crystallization, drying and calcining, make zinc oxide product, general zinc oxide content 95-98%.
This traditional ammonia process is prepared the processing that zinc oxide is never applied to smoke dust, and major cause is:
1. because smoke of steel factory is stored ash containing zinc rate low (generally containing Zn%=5-22), leach liquor is low containing zinc concentration, and leaching agent consumption is large, and cost is high, and enterprise cannot bear.
2. because impurity component is complicated, what production obtained can only be that common active oxidation zinc product and qualification rate are low, the lower deficiency in economic performance of product price.
3. when conventional means leaches, the leaching yield of smoke dust is low, and the rate of recovery is low, and iron, charcoal resource reclaim and also do not form complete chain, and the value of smoke dust is embodied.
In sum, for the processing of smoke dust, how in the low smoke dust of zinc content, effectively to leach zinc wherein, and obtain high-purity zinc oxide, overcome the shortcoming of traditional method simultaneously, become industry technical barrier urgently to be resolved hurrily.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, provide a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide.
The technical solution used in the present invention is such: a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide, comprises the following steps:
Leaching smoke of steel factory ash, pre-ammonia still process, purification and impurity removal, ammonia still process crystallization and drying and calcining, wherein:
During leaching smoke of steel factory ash, with ammoniacal liquor-ammonium fluid, as leaching agent, leach; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=4.5-7mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=0.95-1.5 mol/L, and in every cubic metre of leaching agent, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
Before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 95-105 ℃ and analyses ammonia, until c (NH in leaching liquid 3)≤3mol/L, is then fully oxidized by adding 2-4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring, and the liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step.
Purification and impurity removal, ammonia still process crystallization and drying and calcining step all adopt current common ammonia process to prepare the processing parameter of zinc oxide.
Obtain highly purified zinc oxide, first need to guarantee that the zinc in smoke dust can leach as much as possible, can improve the rate of recovery of zinc so on the one hand, on the other hand, in leach liquor, the content of zinc is larger, foreign matter content is also just less, and guarantee makes more highly purified zinc oxide under equal processing condition.For the recycling of smoke dust, zinc " soaks and draws " and " removes totally " with impurity, is the technical problem of most critical.
In order to solve the problems of the technologies described above, the technology that first the present invention prepares existing ammonia process zinc oxide is applied to the processing to smoke of steel factory ash, simultaneously, on the technique basis of existing ammonia process, in leaching liquid, add appropriate Sodium Silicofluoride, to solve the problem of " soak and draw "; And before purification and impurity removal, increased the step of pre-ammonia still process, to solve the problem of " removing totally ".
Because the fe content of smoke dust is high, can not leach with strong acid, not only consume a large amount of acid, also make a large amount of strippings such as iron, purify difficulty.Zinc ferrite stripping in acidity is also very slow, so the present invention adopts ammonia process to leach, in smoke dust, the ultrafine particulate of gangue also plays certain deadening effect to leaching agent, in order to address this problem, present inventor draws by great many of experiments: appropriate silicofluoric acid is received and can be abolished ultrafine particulate to containing zinc particle package action, realize ultrafine particulate layering floating, thereby zinc is exposed, it is more fully immersed in leach liquor.
Meanwhile, present inventor draws by great many of experiments: before purification and impurity removal, increase pre-ammonia still process step, reduce on the one hand the free ammonia in solution, lower the complexing coefficient of foreign ion, be beneficial to raising depuration quality, reduce and purify drug dosage.
Wherein:
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 -
Zn 2SiO 4 +2nNH 3→ 2［Zn(NH 3)n］ 2+ + SiO 4 4-
ZnSiO 3+ nNH 3 +2NH 4HCO 3→［Zn(NH 3)n］CO 3+ SiO 2·H 2O+(NH 4) 2CO 3
N=1～4 wherein;
The reaction that pre-ammonia still process process occurs:
NH 3·H 2O+NH 4HCO 3 ——→2NH 3 ↑+CO 2 ↑+2H 2O
（NH 4） 4SiO 4 ——→ SiO 2↓+ 2NH 3↑ + 2H 2O
Ammonium persulphate is as oxygenant, except impurity such as de-iron, manganese, arsenic.
Increase pre-ammonia still process step, remove too much free ammonia on the one hand, reduced the complex ability of ammonia, because raise temperature, make silicate colloid and impurity thereof doubt coagulation and form sediment, thereby foreign ion is removed simultaneously, being beneficial to purification, is to make one of high purity product reason; Can remove carbanions a large amount of in solution on the other hand, in subsequent processing complex liquid deamination crystallisation process, be conducive to hydrolysis and obtain zinc hydroxide nucleus, reduce the composition of zinc carbonate, can make one of product reason that specific surface area is large;
Utilize the pyrosol of pre-ammonia still process, add ammonium persulphate to stir and be oxidized, as Fe 3+, AsO 3 3-, Mn 2+produce co-precipitation, reduced follow-up purification difficulty, reduced reagent consumption amount, provide cost savings reaction equation:
5(NH 4) 2S 2O 8 +2Mn 2++8H 2O →2NH 4MnO 4+4(NH 4) 2SO 4 +16H ++ 6SO 4 2-
S 2O 8 2-+Mn 2++2NH 3·H 2O+H 2O→MnO（OH） 2↓ +2NH 4 2++2SO 4 2-+2H +
S 2O 8 2-+2Fe 2+ +6NH 3·H 2O →2SO 4 2-+ 2Fe(OH) 3↓+6NH 4 +
As 2O 3+3H 2O→2H 3AsO 3
2H 3AsO 3+8Fe(OH) 3→(Fe 2O 3) 4As 2O 3·5H 2O↓+10H 2O
AsO 4 3-+Fe 3-→FeAsO 4↓
Ca 2++HCO 3 -+2OH -→ CaCO 3↓+H 2O ；
Zinc ammonia complex liquid after the oxidation of abovementioned steps ammonium persulphate, separation is again through sodium persulfide precipitation of heavy metals impurity, then through separating impurity such as potassium permanganate secondary oxidation iron, manganese, through zinc powder drastic reduction, purification obtains zinc ammino and closes refined liquid again; Reaction equation:
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↓
3Fe 2+ + MnO 4 - + 7H 2O → MnO 2 ↓+ 3Fe(OH) 3↓ + 5H +
3Mn 2+ + 2MnO 4 - +2H 2O → 5MnO 2↓ +4H +
Y 2++ Zn → Zn 2+wherein Y representative of+Y: Cu 2+, Pb 2+, Cd 2+, Ni 2+plasma
The reaction equation of ammonia still process step:
3［Zn(NH 3) 4］CO 3 + H 2O ——→ZnCO 3·2Zn(OH) 2·H 2O ↓ + 12NH 3↑ + 2CO 2↑
During ammonia still process, add sodium hydroxide to improve the reaction formula of pH value:
（NH 4） 2SO 4 + 2NaOH ——→ Na 2SO 4 +2 NH 3↑ +2H 2O
The chemical equation of drying and calcining:
ZnCO 3·2Zn(OH) 2·H 2O→ 3ZnO +3H 2O↑ +CO 2
As preferably: the tensio-active agent that is also added with 0.05-0.1kg in every cubic metre of leaching agent.
The surface energy of decreasing by surfactant solution, with Sodium Silicofluoride mating reaction, increases soaking and permeating, dissolving and the leaching of promotion zinc zinc particle.
As preferably: the Dicyanodiamide that is also added with 0.5-1kg in ammoniacal liquor-ammonium fluid leaching agent of every cubic metre.
Dicyanodiamide, as ammonia stablizer, can reduce the volatilization of ammonia in leaching process, improves leaching Working environment, reduces the loss of ammonia.
As preferably: when the pending smoke dust of leaching, adopt wet ball grinding.
Further: guarantee that extraction time is 50～60 minutes in ball mill, ball mill outlet material is all by 140 mesh sieves.
Utilize ball milling wet extraction, destroyed the crystalline network (reaching mechanical activation) such as zinc ferrite in smoke dust and combined with chemical activations such as tensio-active agents, reach higher leaching velocity and leaching yield.
As preferably: in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution adding is that to add quality percentage composition be 30% sodium hydroxide solution 3-5 liter to every cubic metre of ammonia still process liquid, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process.
In ammonia still process process, when ammonia concentration is lower in zinc ammonia complex liquid, by increasing sodium hydroxid, improve the pH value of liquid, make NH 4 +transfer free NH to 3molecule reaches quick deamination, the object of rapid crystallization.Crystallization velocity is faster, and the chance of impurity parcel crystal is just less, thereby improves the purity of crystal.
As preferably: drying and calcining temperature is controlled at 350-450 ℃, and calcination time is 40-80 minute.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows: ammonia process is applied to the processing to smoke of steel factory ash, and existing ammonia process has been carried out to adaptation, when leaching, add Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, the zinc that makes on the one hand smoke of steel factory ash fast, as far as possible fully leach, zinc in smoke of steel factory ash is fully recycled, after leaching, increased pre-ammonia still process step simultaneously, remove unnecessary free ammonia and utilize purification and impurity removal, for making the high-quality zinc oxide of high purity, lay a good foundation; By the processing of the technology of the present invention means, the zinc oxide purity obtaining can reach more than 99.7%, has very high economic worth; Treatment process energy consumption of the present invention is low, efficiency is high, and leaching agent recycle has solved the zinc load problem of steel mill's blast furnace dust up hill and dale, and (basic metal clearance reaches 98% to objectionable constituent zinc and alkali-metal purification requirement both to have met steel mill; Zinc extraction yield is more than 92%), reach the benign cycle of production, reclaimed again iron, the charcoal resource of steel mill's preciousness, iron, charcoal obtain enrichment, iron level is brought up to 18-36% by original 14-28%, charcoal thermal value by original about 1000-3500 kilocalorie/kilogram bring up to 1400-4800 kilocalorie/kilogram; Iron, charcoal recovery utilization rate all reach more than 96%, have not only saved the energy but also created good economic benefit.
Embodiment
Below the present invention is described in detail.
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:
Raw material: Kunming smoke of steel factory ash 1#, its composition by mass percentage (%) is:
Zn9.7% Fe27.14% Pb0.85% Cd0.007% C28% basic metal (k, Na) 2.9%
Method for the preparation of high-purity zinc oxide:
(1) leaching: get 500 grams of smoke dusts 1 #, with 1500ml ammoniacal liquor-ammonium fluid, as leaching agent, leach; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=4.5mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=1.2 mol/L, adds 0.45g Sodium Silicofluoride, carries out three sections of leachings, and each section of leaching time is 2 hours, after solid-liquid separation, and 43.89 grams, zinc (zinc recovery 90.5%) in gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 105 ℃ and analyses ammonia, until c (NH in leaching liquid 3)=3mol/L, then adds 2g ammonium persulphate and stirs, and the liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step;
(3) purification and impurity removal: step (2) gained solution adds 1.32g potassium permanganate to stir 0.5h, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filters, and filtrate adds KMnO 4consumption is 2.7 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(4) ammonia still process crystallization: gained refined liquid is inserted in ammonia distiller and carried out ammonia still process, and 105 ℃ of solution temperatures, until ［ Zn 2+during ］=1.5g/L, stop ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by liquid-solid ratio 5:1 deionized water wash, and washing time 1h, refilters separation, obtains filter cake;
(5) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 450 ℃ of retort furnace calcining 50min, sampling detects and obtains specific surface area is 70m 2/ g, quality percentage composition are 99.73% high-purity zinc oxide.
Embodiment 2
Raw material: the mass percent (%) of southern its composition of smoke of steel factory ash 2# is:
Zn6.2% Fe29.6% Pb0.87% C15.24% Si8.7% basic metal (k, Na) 3.47
Method for the preparation of high-purity zinc oxide:
(1) leaching: get 500 grams of smoke dusts 2 #, with 1500ml ammoniacal liquor-ammonium fluid, as leaching agent, leach; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=7mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=1.5 mol/L, adds 0.75g Sodium Silicofluoride, the surfactant SDS of 0.075g, the Dicyanodiamide of 0.75g; When leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 30 minutes, ball mill outlet material is all by 140 mesh sieves, then carries out three sections and stir leaching, and each section of leaching time is 2 hours, after solid-liquid separation, 28.37 grams, zinc (zinc recovery 91.5%) in gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 105 ℃ and analyses ammonia, until c (NH in leaching liquid 3)=2.8mol/L, then adds 2g ammonium persulphate and stirs, and the liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step;
(3) purification and impurity removal: add 0.85g potassium permanganate to stir 0.5h to step (2) gained solution, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filters, and filtrate adds KMnO 4consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(4) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process in ammonia distiller, 108 ℃ of solution temperatures, in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is 1% time, in ammonia still process equipment, adding quality percentage composition is 30% sodium hydroxide solution 2.5ml, and zinc quality percentage composition lower than 0.3% time, finishes ammonia still process; The emulsion obtaining carries out solid-liquid separation, and filter cake is by liquid-solid ratio 5:1 deionized water wash, and washing time 1h, refilters separation, obtains filter cake;
(5) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 500 ℃ of retort furnace calcining 60min, sampling detects and obtains specific surface area is 72m 2/ g, quality percentage composition are 99.81% high-purity zinc oxide.
Embodiment 3
Raw material: certain smoke of steel factory ash 3# of southwest, its composition is by mass percentage:
Zn 15.4% Fe32.53% Pb0.67% C25.28% Si 8.67% basic metal (k, Na) 2.52%
Method for the preparation of high-purity zinc oxide:
(1) leaching: get 1000 grams of smoke dusts 3 #, with 3000ml ammoniacal liquor-ammonium fluid, as leaching agent, leach; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=5.8mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=1.15 mol/L, adds respectively the surfactant SDS of 1.2g Sodium Silicofluoride, 0.3g, the Dicyanodiamide of 3g; When leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 45 minutes, ball mill outlet material is all by 140 mesh sieves, then carries out three sections and stir leaching, and each section of leaching time is 2 hours, after solid-liquid separation, 142.45 grams, zinc (zinc recovery 92.5%) in gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 100 ℃ and analyses ammonia, until c (NH in leaching liquid 3)=2.9mol/L, then adds 9g ammonium persulphate and stirs, and the liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step;
(3) purification and impurity removal: add 4.3g potassium permanganate to stir 0.8h to step (2) gained solution, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filters, and filtrate adds KMnO 4consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(4) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process in ammonia distiller, 108 ℃ of solution temperatures, in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is 1.5% time, in ammonia still process equipment, adding quality percentage composition is 30% sodium hydroxide solution 15ml, zinc quality percentage composition is lower than 0.3% time, finish ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by liquid-solid ratio 5:1 deionized water wash, washing time 1h, refilter separation, obtain filter cake;
(5) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 580 ℃ of retort furnace calcining 70min, sampling detects and obtains specific surface area is 75m 2/ g, quality percentage composition are 99.79% high-purity zinc oxide.
Embodiment 4
Raw material: Kunming smoke of steel factory ash 4#, its composition is by mass percentage:
Zn 9.7% Fe27.14% Pb0.85% Cd0.007% C 28% basic metal (k, Na) 2.9%
Method for the preparation of high-purity zinc oxide:
(1) leaching: get 1000 grams of smoke dusts 4 #, with 3000ml ammoniacal liquor-ammonium fluid, as leaching agent, leach; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=6.2mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=1.25 mol/L, adds respectively the surfactant SDS of 1.35g Sodium Silicofluoride, 0.6g, the Dicyanodiamide of 2.4g; When leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 80 minutes, ball mill outlet material is all by 140 mesh sieves, then carries out three sections and stir leaching, and each section of leaching time is 2 hours, after solid-liquid separation, 90.01 grams, zinc (zinc recovery 92.79%) in gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 98 ℃ and analyses ammonia, until c (NH in leaching liquid 3)=2.7mol/L, then adds 7g ammonium persulphate and stirs, and the liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step;
(3) purification and impurity removal: add 2.7g potassium permanganate to stir 0.8h to step (2) gained solution, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filters, and filtrate adds KMnO 4consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(4) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process in ammonia distiller, 108 ℃ of solution temperatures, in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is 1.2% time, in ammonia still process equipment, adding quality percentage composition is 30% sodium hydroxide solution 8ml, zinc quality percentage composition is lower than 0.3% time, finish ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by liquid-solid ratio 5:1 deionized water wash, washing time 1h, refilter separation, obtain filter cake;
(5) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 560 ℃ of retort furnace calcining 75min, sampling detects and obtains specific surface area is 73m 2the high-purity zinc oxide that/g, quality percentage composition are 99.83%.

Claims (7)

1. a method of utilizing smoke of steel factory ash to produce high-purity zinc oxide, comprises the following steps:
Leaching smoke of steel factory ash, purification and impurity removal, ammonia still process crystallization and drying and calcining, is characterized in that:
During leaching smoke of steel factory ash, with ammoniacal liquor-ammonium fluid, as leaching agent, leach; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=4.5-7mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=0.95-1.5 mol/L, and in every cubic metre of leaching agent, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
Before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 95-105 ℃ and analyses ammonia, until c (NH in leaching liquid 3)≤3mol/L, then, by adding 2-4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring, carries out solid-liquid separation by the liquid after pre-ammonia still process, and solution enters purification and impurity removal step.
2. a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide according to claim 1, is characterized in that: the tensio-active agent that is also added with 0.05-0.1kg in every cubic metre of leaching agent.
3. a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide according to claim 2, is characterized in that: the Dicyanodiamide that is added with 0.5-1kg at the leaching agent of every cubic metre.
4. a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide according to claim 1, is characterized in that: when the pending smoke dust of leaching, adopt wet ball grinding.
5. a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide according to claim 4, is characterized in that: guarantee that extraction time is 50～60 minutes in ball mill, ball mill outlet material is all by 140 mesh sieves.
6. a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide according to claim 1, it is characterized in that: in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution adding 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 smoke of steel factory ash to produce high-purity zinc oxide according to claim 1, is characterized in that: described drying and calcining temperature is 350-450 ℃.
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