CN102849781A - 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 PDFInfo
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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
Technical field
The present invention relates to a kind of method of utilizing the 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 the usual conditions, generally produce agglomerate as the raw material of sintering, utilize in steel mill's internal recycling, 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.
Limit at present the method for blast furnace zinc load: the one, restriction circulation smoke dust consumption; The 2nd, the 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 the 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, the zinc leaching rate that do not heat up only about 80%, and intensification can reach 95%, but iron is also up to 60%, and the deironing difficulty is wasted again iron, and equipment corrosion is serious, does not also reach environmental requirement.But the alkaline process leaching rate is lower.It is that the zinc leaching rate is low that existing wet method is put forward zinc existing problems general nature, soaks slag and is difficult to recycle, can't meet the requirement of environmental protection, and equipment corrosion is serious, and is responsive to ingredient requirement, and technique is difficult to optimize, and productivity effect is low not to be complementary etc. with steel mill's output.The 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 brought significant damage at present, and is very urgent to the processing of dust.
Optimal method is that the selectivity of carrying out zinc leaches, and zinc is entered in the solution, and zinc obtains valuable recycling.
On the other hand, high pure zinc oxide refers to that generally the oxidation Zn-content 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. all are in great demand to zinc oxide, and purity requirement is very high.
Produce at present the method for high-purity zinc oxide, it mainly is indirect method, indirect method is generally 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 preparation zinc oxide, the general step of ammonia process (ammonia-carbon ammonium associating lixiviation process is produced zinc oxide) comprising at present: use ammonia-carbon ammonium to unite leaching to material containing zinc and make zinc ammonia complex liquid, make zinc oxide product through purification, ammonia still process crystallization, drying and calcining, general zinc oxide content 95-98%.
This traditional ammonia process prepares the processing that zinc oxide never is applied to smoke dust, and major cause is:
1. contain zinc rate low (generally containing Zn%=5-22) because smoke of steel factory is stored ash, it is low that leach liquor contains zinc concentration, and the leaching agent consumption is large, and cost is high, and enterprise can't 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 low deficiency in economic performance of product price.
3. when conventional means leached, the leaching yield of smoke dust was 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 simultaneously the shortcoming of traditional method, become the technical barrier that the industry needs 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 the 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 the smoke of steel factory ash to produce high-purity zinc oxide may further comprise the 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, leach as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in the 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 the 0.3-0.5kg Sodium Silicofluoride, obtain leaching liquid after the leaching;
Before the purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid that will obtain after will leaching is heated to 95-105 ℃ and analyses ammonia, until c (NH in the leaching liquid
3Then)≤3mol/L by adding the 2-4kg ammonium persulphate in every cubic metre the leaching liquid and stirring and carry out abundant oxidation, carries out solid-liquid separation with the liquid after the pre-ammonia still process, and solution enters the purification and impurity removal step.
Purification and impurity removal, ammonia still process crystallization and drying and calcining step all adopt present common ammonia process to prepare the processing parameter of zinc oxide.
Obtain highly purified zinc oxide, need at first to guarantee that the zinc in the smoke dust can leach as much as possible, can improve so on the one hand the rate of recovery of zinc, on the other hand, the content of zinc is larger in leach liquor, foreign matter content is also just less, and guarantee makes more highly purified zinc oxide under equal processing condition.Namely 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 the present invention at first prepares existing ammonia process zinc oxide is applied to the processing to the smoke of steel factory ash, simultaneously, on the technique basis of existing ammonia process, in leaching liquid, add an amount of 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 consumes 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, the ultrafine particulate of gangue also plays certain deadening effect to leaching agent in the smoke dust, in order to address this problem, the present inventor draws by great many of experiments: an amount of 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 more fully is immersed in the leach liquor.
Simultaneously, the 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 the solution, lower the complexing coefficient of foreign ion, be beneficial to the raising depuration quality, reduce purifying 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 the solution on the other hand, be conducive to hydrolysis in the subsequent processing complex liquid deamination crystallisation process and obtain the zinc hydroxide nucleus, reduce the composition of zinc carbonate, can make one of large product reason of specific surface area;
Utilize the pyrosol of pre-ammonia still process, add the ammonium persulphate stirring and carry out oxidation, such as Fe
3+, AsO
3 3-, Mn
2+Produce co-precipitation, reduced follow-up purification difficulty, reduced the 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 ；
Again through sodium persulfide precipitation of heavy metals impurity, separate impurity through potassium permanganate secondary oxidation iron, manganese etc. through the zinc ammonia complex liquid after the oxidation of abovementioned steps ammonium persulphate, the separation again, purification obtains the zinc ammino and closes refined liquid through the zinc powder drastic reduction 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↑
Add the reaction formula that sodium hydroxide improves the pH value during ammonia still process:
（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 also is added with 0.05-0.1kg in every cubic metre of leaching agent.
The surface energy of decreasing by surfactant solution with the Sodium Silicofluoride mating reaction, increases soaking and permeating, dissolving and the leaching of promotion zinc the zinc particle.
As preferably: the Dicyanodiamide that in every cubic metre ammoniacal liquor-ammonium fluid leaching agent, also is added with 0.5-1kg.
Dicyanodiamide can reduce ammonia emission in the leaching process as the ammonia stablizer, improves the 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, the ball mill outlet material is all by 140 mesh sieves.
Utilize the ball milling wet extraction, destroyed that the crystalline network (reaching mechanical activation) such as zinc ferrite combines with chemical activations such as tensio-active agents in the smoke dust, reach higher leaching velocity and leaching yield.
As preferably: in the ammonia still process crystallisation process, detect at any time liquid zinc content in the ammonia still, when the mass content of zinc during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution that adds is that every cubic metre of ammonia still process liquid adding quality percentage composition is 30% sodium hydroxide solution 3-5 liter, when zinc quality percentage composition is lower than 0.3%, finish ammonia still process.
In the ammonia still process process, when ammonia concentration in the zinc ammonia complex liquid is low, improve the pH value of liquid by increasing sodium hydroxid, make NH
4 +Transfer free NH to
3Molecule reaches quick deamination, the purpose 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: the 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 processing to the smoke of steel factory ash, and existing ammonia process carried out adaptation, when leaching, add Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, on the one hand so that the zinc of smoke of steel factory ash fast, as far as possible fully leach, so that the zinc in the smoke of steel factory ash is fully recycled, after leaching, increased simultaneously pre-ammonia still process step, remove unnecessary free ammonia and utilize purification and impurity removal, lay a good foundation for making the high-quality zinc oxide of high purity; By the processing of the technology of the present invention means, the zinc oxide purity that obtains can reach more than 99.7%, has very high economic worth; Treatment process energy consumption of the present invention is low, efficient is high, and the leaching agent recycle has solved the zinc load problem of steel mill's blast furnace dust up hill and dale, and (the basic metal clearance reaches 98% to objectionable constituent zinc and alkali-metal purification requirement both to have satisfied steel mill; The zinc extraction yield is more than 92%), reach virtuous circle, 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%, and the charcoal thermal value is brought up to 1400-4800 kilocalorie/kilogram by original approximately 1000-3500 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 purpose 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 gram smoke dusts 1
#, leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in the 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 the 0.45g Sodium Silicofluoride, carries out three sections leachings, and each section leaching time is 2 hours, after the solid-liquid separation, and zinc 43.89 grams (zinc recovery 90.5%) in the gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before the purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid that will obtain after will leaching is heated to 105 ℃ and analyses ammonia, until c (NH in the leaching liquid
3Then)=3mol/L adds 2g ammonium persulphate and stirring, and the liquid after the pre-ammonia still process is carried out solid-liquid separation, and solution enters the purification and impurity removal step;
(3) purification and impurity removal: step (2) gained solution adds 1.32g potassium permanganate and stirs 0.5h, adding a small amount of polyacrylamide solution (4mg/L) filters, filtrate is by 1.2 times of adding sodium sulphite of the theoretical amount of deposit 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, 80 ℃ of temperature, and stirring 1h (detecting Fe, Mn qualified) filters, and filtrate is stirred 30min by 2.5 times of adding zinc powders of displacement Cu, Cd, the required theoretical zinc powder of Pb, and temperature 60 C filters, and gets refined liquid;
(4) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 105 ℃ of solution temperatures are until ［ Zn
2+Stop ammonia still process during ］=1.5g/L, the emulsion that obtains 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 dryings of filter cake, 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 gram smoke dusts 2
#, leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in the 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 extraction time is 30 minutes in the ball mill, the ball mill outlet material carries out three sections again and stirs leaching all by 140 mesh sieves, and each section leaching time is 2 hours, after the solid-liquid separation, zinc 28.37 grams (zinc recovery 91.5%) in the gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before the purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid that will obtain after will leaching is heated to 105 ℃ and analyses ammonia, until c (NH in the leaching liquid
3Then)=2.8mol/L adds 2g ammonium persulphate and stirring, and the liquid after the pre-ammonia still process is carried out solid-liquid separation, and solution enters the purification and impurity removal step;
(3) purification and impurity removal: add 0.85g potassium permanganate to step (2) gained solution and stir 0.5h, adding a small amount of polyacrylamide solution (4mg/L) filters, filtrate is by 1.2 times of adding sodium sulphite of the theoretical amount of deposit 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, 80 ℃ of temperature, and stirring 1h (detecting Fe, Mn qualified) filters, and filtrate is stirred 30min by 2.5 times of adding zinc powders of displacement Cu, Cd, the required theoretical zinc powder of Pb, and temperature 60 C filters, and gets refined liquid;
(4) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 108 ℃ of solution temperatures, in the ammonia still process crystallisation process, detect at any time liquid zinc content in the ammonia still, when the mass content of zinc 1% the time, adding quality percentage composition is 30% sodium hydroxide solution 2.5ml in ammonia still process equipment, when zinc quality percentage composition is lower than 0.3%, finishes ammonia still process; The emulsion that obtains 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 dryings of filter cake, 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 gram smoke dusts 3
#, leach as leaching agent with 3000ml ammoniacal liquor-ammonium fluid; Wherein, NH in the 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 extraction time is 45 minutes in the ball mill, the ball mill outlet material carries out three sections again and stirs leaching all by 140 mesh sieves, and each section leaching time is 2 hours, after the solid-liquid separation, zinc 142.45 grams (zinc recovery 92.5%) in the gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before the purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid that will obtain after will leaching is heated to 100 ℃ and analyses ammonia, until c (NH in the leaching liquid
3Then)=2.9mol/L adds 9g ammonium persulphate and stirring, and the liquid after the pre-ammonia still process is carried out solid-liquid separation, and solution enters the purification and impurity removal step;
(3) purification and impurity removal: add 4.3g potassium permanganate to step (2) gained solution and stir 0.8h, adding a small amount of polyacrylamide solution (4mg/L) filters, filtrate is by 1.2 times of adding sodium sulphite of the theoretical amount of deposit 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, 80 ℃ of temperature, and stirring 1h (detecting Fe, Mn qualified) filters, and filtrate is stirred 30min by 2.5 times of adding zinc powders of displacement Cu, Cd, the required theoretical zinc powder of Pb, and temperature 60 C filters, and gets refined liquid;
(4) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 108 ℃ of solution temperatures, in the ammonia still process crystallisation process, detect at any time liquid zinc content in the ammonia still, when the mass content of zinc 1.5% the time, adding quality percentage composition is 30% sodium hydroxide solution 15ml in ammonia still process equipment, when zinc quality percentage composition is lower than 0.3%, finish ammonia still process, the emulsion that obtains 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 dryings of filter cake, 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 gram smoke dusts 4
#, leach as leaching agent with 3000ml ammoniacal liquor-ammonium fluid; Wherein, NH in the 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 extraction time is 80 minutes in the ball mill, the ball mill outlet material carries out three sections again and stirs leaching all by 140 mesh sieves, and each section leaching time is 2 hours, after the solid-liquid separation, zinc 90.01 grams (zinc recovery 92.79%) in the gained zinc ammonia complex liquid;
(2) pre-ammonia still process: before the purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid that will obtain after will leaching is heated to 98 ℃ and analyses ammonia, until c (NH in the leaching liquid
3Then)=2.7mol/L adds 7g ammonium persulphate and stirring, and the liquid after the pre-ammonia still process is carried out solid-liquid separation, and solution enters the purification and impurity removal step;
(3) purification and impurity removal: add 2.7g potassium permanganate to step (2) gained solution and stir 0.8h, adding a small amount of polyacrylamide solution (4mg/L) filters, filtrate is by 1.2 times of adding sodium sulphite of the theoretical amount of deposit 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, 80 ℃ of temperature, and stirring 1h (detecting Fe, Mn qualified) filters, and filtrate is stirred 30min by 2.5 times of adding zinc powders of displacement Cu, Cd, the required theoretical zinc powder of Pb, and temperature 60 C filters, and gets refined liquid;
(4) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 108 ℃ of solution temperatures, in the ammonia still process crystallisation process, detect at any time liquid zinc content in the ammonia still, when the mass content of zinc 1.2% the time, adding quality percentage composition is 30% sodium hydroxide solution 8ml in ammonia still process equipment, when zinc quality percentage composition is lower than 0.3%, finish ammonia still process, the emulsion that obtains 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 dryings of filter cake, obtain powder, through 560 ℃ of retort furnace calcining 75min, sampling detects and obtains specific surface area is 73m
2/ g, quality percentage composition are 99.83% high-purity zinc oxide.
Claims (7)
1. one kind is utilized the grey method of producing high-purity zinc oxide of smoke of steel factory, may further comprise the 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, leach as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in the 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 the 0.3-0.5kg Sodium Silicofluoride, obtain leaching liquid after the leaching;
Before the purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid that will obtain after will leaching is heated to 95-105 ℃ and analyses ammonia, until c (NH in the leaching liquid
3Then)≤3mol/L by adding the 2-4kg ammonium persulphate in every cubic metre the leaching liquid and stirring, carries out solid-liquid separation with the liquid after the pre-ammonia still process, and solution enters the purification and impurity removal step.
2. described 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 also is added with 0.05-0.1kg in every cubic metre of leaching agent.
3. described 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 every cubic metre leaching agent.
4. described 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. described a kind of method of utilizing smoke of steel factory ash to produce high-purity zinc oxide according to claim 4, it is characterized in that: guarantee that extraction time is 50～60 minutes in ball mill, the ball mill outlet material is all by 140 mesh sieves.
6. described 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 the ammonia still process crystallisation process, detect at any time liquid zinc content in the ammonia still, when the mass content of zinc during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution that adds is that every cubic metre of ammonia still process liquid adding quality percentage composition is 30% sodium hydroxide solution 3-5 liter, when zinc quality percentage composition is lower than 0.3%, finishes ammonia still process.
7. described 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: described drying and calcining temperature is 350-450 ℃.
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| CN107099672A (en) * | 2017-05-16 | 2017-08-29 | 中国恩菲工程技术有限公司 | The recovery method of the fume from steel making containing zinc |
| CN112744856A (en) * | 2021-01-12 | 2021-05-04 | 李发武 | Method for producing zinc oxide for ceramic glaze by using hot-dip galvanizing ash |
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| CN102168190A (en) * | 2010-12-23 | 2011-08-31 | 中南大学 | Method for enrichment of vanadium from stone coal mine in a manner of low consumption and high efficiency |
| CN102515252A (en) * | 2011-12-28 | 2012-06-27 | 韶关凯鸿纳米材料有限公司 | Film-coating production technology for nano zinc oxide |
| CN102583503A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Method for preparing activated zinc oxide by utilizing high-arsenic secondary zinc oxide resource ammonia-ammonium process |
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| CN102583503A (en) * | 2011-01-18 | 2012-07-18 | 郴州市金贵银业股份有限公司 | Method for preparing activated zinc oxide by utilizing high-arsenic secondary zinc oxide resource ammonia-ammonium process |
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| CN107099672A (en) * | 2017-05-16 | 2017-08-29 | 中国恩菲工程技术有限公司 | The recovery method of the fume from steel making containing zinc |
| CN107099672B (en) * | 2017-05-16 | 2019-02-26 | 中国恩菲工程技术有限公司 | The recovery method of the fume from steel making containing zinc |
| CN112744856A (en) * | 2021-01-12 | 2021-05-04 | 李发武 | Method for producing zinc oxide for ceramic glaze by using hot-dip galvanizing ash |
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