CN102826589B - Method for producing high purity nanometer zinc oxide by using ammonia process of steel plant dust - Google Patents
Method for producing high purity nanometer zinc oxide by using ammonia process of steel plant dust Download PDFInfo
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Abstract
The invention discloses a method for producing high purity nanometer zinc oxide by using ammonia process of steel plant dust. According to the method, white lime of 3-5 percent of the mass of steel plant dust is added for activation before leaching, then leaching is carried out with an ammonia-ammonium carbonate solution as the leaching agent, 0.3-0.5kg of sodium fluosilicate is added into the leaching agent per cubic meter, and purification and impurity removal are carried out and then refining treatment is carried out. According to the method, the ammonia process is used for treating steel plant dust, the existing ammonia process is adaptively improved, and high purity nanometer zinc oxide with larger specific surface area can be obtained; and the method has the advantages of low energy consumption and high efficiency, and thoroughly solves the problem of zinc load of steel plant dust as the leaching agent can be recycled, thereby meeting the requirement of purifying the toxic components including zinc and alkali metals and realizing good production circulation.
Description
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
The current smoke dust (comprising blast furnace, converter, electric furnace) from steel mill, claim again smoke of steel factory ash, one ton of iron and steel of every production will produce the smoke of steel factory ash of 35～90kg, the general iron content 15～30% of this smoke of steel factory ash, silicon oxide-containing 4～5%, zinc 5～22%, combustible fixed carbon 25-～55%, calcium oxide 2～5%, magnesium oxide 1～2% and titanium, vanadium and basic metal etc.Under 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.
The method of restriction blast furnace zinc load at present: the one, smoke of steel factory ash consumption for restriction circulation; The 2nd, smoke of steel factory ash ore dressing processing; 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 three kinds of products imbalances of iron essence, carbon, tail mud still lose 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 processing.But zinc, lead and basic metal are resolved not yet.Wet method is divided into again acid system and alkaline process, acid technological process maturation, and only 80% left and right of the zinc leaching rate that do not heat up, 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, and to ingredient requirement sensitivity, technique is difficult to optimize, and productivity effect is low not to match etc. with steel mill's output.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 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 preparing 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 combine 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 is prepared zinc oxide and is never applied to the processing of smoke dust, and major cause is:
1. because smoke of steel factory ash contains 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 of impurity component complexity, 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.
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, fluor, varistor, UV-preventing material, image recording material, piezoelectric, voltage dependent resistor, effective catalyst, magneticsubstance and plastics film etc.
The method of producing at present nano zine oxide, mainly contains chemical precipitation method, sol-gel method, microemulsion method and hydrothermal synthesis method etc.But the raw material adopting is all zinc baking sand or the pure zinc salt etc. of zinc content more than 50%.
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, by the zinc ammonia complex liquid thin up after purifying, make the hydrolysis of part zinc ammonia complex liquid, obtain zinc subcarbonate (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 in thermal degradation process, and the new zinc subcarbonate producing can, in original nucleating surface continued growth, impel the crystal of former hydrolysis to grow up, easily cause zinc subcarbonate xln particle diameter inhomogeneous, make the finished product 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 density is separated out in fact efficiency is high, energy consumption is low, and efficiency that the zinc ammoniacal liquor of lower concentration is separated out is low, energy consumption is high, people be the proportional 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 in zinc oxide process at present, after analysing ammonia, all crystallize out with zinc subcarbonate, decomposition temperature is high, and (zinc hydroxide just makes approximately 125 ℃ of temperature theoretical decomposition, 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 zinc subcarbonate decompose completely.As the Chinese patent application that application number is 200610130477.7, calcining temperature is up to 550 ℃.High-temperature calcination has a strong impact on the specific surface area of zinc oxide and dispersiveness, mobility, then affects its Application Areas.
In sum, for the processing of smoke of steel factory ash, how in the low mineral of zinc content, effectively to leach zinc wherein, and obtain high-purity nm zinc oxide, overcome the shortcoming of traditional 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 efficient recovery smoke of steel factory ash 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 smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide, comprises the following steps:
Leaching smoke of steel factory ash, purification and impurity removal, refinement treatment, ammonia still process crystallization and drying and calcining:
Before leaching smoke of steel factory ash step, in pending smoke of steel factory ash, add white lime to obtain compound, and the maintenance mixture moisture content 8-10% that adds water, then carry out admixture activation, the amount of the white lime adding by weight, is the 3-5% of smoke of steel factory ash;
Smoke of steel factory ash after admixture activation is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=4.5-7mol/L, CO
3 2volumetric molar concentration c (CO
3 2-)=0.95-1.5 mol/L adds 0.3-0.5kg Sodium Silicofluoride in every cubic metre of leaching agent;
After purification and impurity removal, carry out refinement treatment, method is: in purification and impurity removal liquid after treatment, add ammonium phosphate and tensio-active agent, add-on is 1-3kg ammonium phosphate, 10-50g tensio-active agent 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 processing parameter of zinc oxide.
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, before ammonia soaks step, increase pre-treatment, be in smoke of steel factory ash, to add white lime to carry out the step of admixture activation, in leaching liquid, add appropriate Sodium Silicofluoride, 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 smoke of steel factory ash can leach as much as possible, can improve so on the one hand the rate of recovery of zinc, on the other hand, in leach liquor, zinc concentration is larger, and impurity concentration relative proportion is just less, can guarantee to make more highly purified zinc oxide under equal processing condition.
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, dry hydrate plays loose, the fluffy use that turns into smoke dust, 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, realizes ultrafine particulate layering floating, thereby zinc is exposed, it is more fully immersed in leach liquor.
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 size and particle size distribution range unsatisfactory, most important reason is constantly the growing up of crystal in treating processes, especially for the raw material processing of this low zinc content of smoke of steel factory ash.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 tensio-active agent, in conjunction with the growth that can effectively suppress xln under high-speed stirring.
Wherein:
Chemical reaction in admixture activation process is:
Ca(OH)
2+ ZnSiO
3+ → CaSiO
3↓+ Zn(OH)
Fe
3+ +3OH
- →Fe(OH)
3↓
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
Zn(OH)
2 +nNH
3 →［Zn(NH
3)n］
2++2OH
-
ZnCO
3+ nNH
3 →［Zn(NH
3)n］CO
3
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 formula 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
［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 smoke of steel factory ash, be also added with the tensio-active agent of 0.03-0.05kg in the ammoniacal liquor-ammonium fluid of every cubic metre, as SDS.
Decreasing by surfactant solution surface energy, with Sodium Silicofluoride mating reaction, the coating function that can abolish ultrafine particulate improves leaching agent penetrating power, further improves the rate of recovery of zinc.
As preferably: the Dicyanodiamide that is also added with 0.5-1kg in the ammoniacal liquor-ammonium fluid 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: in the time of the pending smoke of steel factory ash of leaching, adopt wet ball grinding, activation leaching.
Utilize wet ball grinding leaching, can destroy original crystalline network and carry out the leaching of activation limit, limit, thereby improve leaching efficiency.
Further: guarantee that in ball mill, extraction time is 50～60 minutes, ball mill outlet material is all by 140 mesh sieves.
Utilize ball milling wet extraction, destroyed the crystalline network (mechanical activation) such as zinc ferrite in smoke of steel factory ash and combined with the chemical activation of tensio-active agent and dry hydrate, reach higher leaching velocity.By the mechanical activation of preactivated and ball milling and the adding of promoting agent (Sodium Silicofluoride, SDS etc.) of raw material, obtain higher leaching yield.
As preferably: before purification and impurity removal step, carry out pre-ammonia still process: 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 oxidized completely by adding 2-4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring.Type of heating adopts the mode of indirect heating.As c (NH
3when)≤3mol/L, zinc ammonia complex liquid approaches saturated, does not make zinc separate out simultaneously; When ammonia still process crystallization, temperature is controlled in 105 ℃, and the speed per minute 600-900 of ammonia still process container for stirring turns.
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 on the other hand carbanions a large amount of in solution, 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;
As preferably: in ammonia still process crystallisation 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, add-on is that to add massfraction be 30% sodium hydroxide solution 3-5 liter to every cubic metre of solution, in solution, zinc content lower than 0.3% time, finishes ammonia still process.
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.
Two of object of the present invention, is to provide a kind of high purity and high performance 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 zinc subcarbonate, adopt the temperature of 150-300 ℃ to calcine, can obtain purity 99.7% and above zinc oxide, because the nucleus of zinc hydroxide is less than zinc subcarbonate, so finally can obtain being evenly distributed, particle diameter is 10-30nm, and specific surface area>=100m
2high-quality nanometer Zinc oxide powder more than/g.
In sum, adopt technique scheme, ammonia process is applied to the processing to smoke of steel factory ash, and existing ammonia process is carried out to technological improvement, before leaching, increase activation step and in the time of leaching, added Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, on the one hand smoke of steel factory ash 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 temperature, 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, 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 99% to objectionable constituent zinc and alkali-metal purification requirement both to have met steel mill; Zinc extraction yield is more than 90%), 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 18-38% by original 15-30%, charcoal thermal value by original about 1000-4500 kilocalorie/kilogram bring up to 1600-5200 kilocalorie/kilogram; Iron, charcoal recovery utilization rate all reach more than 98%, have not only saved the energy but also created good economic benefit.
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 tensio-active agent (as SDS), ammonium phosphate, can effectively control the growth of nano zine oxide nucleus; (4) utilize the power of steam to realize high-speed stirring, control nano zine oxide crystallization;
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
Raw material: the smoke of steel factory ash 1# of Kunming steel mill, 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 nm zinc oxide:
(1) activation: get 500g smoke of steel factory ash 1#, add 15g white lime to obtain compound, and the maintenance mixture moisture content 8% that adds water, then carrying out admixture activation, soak time is 36 hours;
(2) leaching: by the smoke of steel factory ash 1 after admixture activation
#leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; 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 44.38 grams, zinc (zinc recovery 91.5%) in gained zinc ammonia complex liquid;
(3) purification and impurity removal: add 1.33g 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 deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filter, 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;
(4) refinement treatment: in purification and impurity removal liquid after treatment, add 1g ammonium phosphate, 0.05g surfactant SDS, obtain refined liquid;
(5) 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+when ］=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;
(6) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 300 ℃ of retort furnace calcining 50min, sampling detects and obtains purity ZnO%=99.72%; Tap density 0.25g/m
2, specific surface area 103m
2the high-purity zinc oxide powder of/g.
Embodiment 2
Raw material: the mass percent (%) of southern its composition of the smoke of steel factory ash 2# of steel mill is:
Zn6.2% Fe29.6% Pb0.87% C15.24% Si8.7% basic metal (k, Na) 3.47
Method for the preparation of high-purity nm zinc oxide:
(1) activation: get 500g smoke of steel factory ash 2#, add 25g white lime to obtain compound, and the maintenance mixture moisture content 10% that adds water, then carrying out admixture activation soak time is 36 hours;
(2) leaching: by the smoke of steel factory ash 2 after admixture activation
#leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; 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; In the time of 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, 28.46 grams, zinc (zinc recovery 91.8%) in gained zinc ammonia complex liquid;
(3) pre-ammonia still process: the leaching liquid obtaining after leaching is heated to 95 ℃ and analyses ammonia, until c (NH in leaching liquid
3)=2.8mol/L, then adds 2g ammonium persulphate and stirs;
(4) purification and impurity removal: add 0.83g 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 deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filter, 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;
(5) refinement treatment: in purification and impurity removal liquid after treatment, add 1g ammonium phosphate, 0.02g surfactant SDS, obtain refined liquid;
(6) 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, also adding massfraction is 5% sodium stearate solution 1.5ml, detect at any time liquid zinc content in ammonia still process equipment, when zinc content is 1% time, in ammonia still process equipment, adding quality percentage composition is 30% sodium hydroxide solution 2.5ml, zinc quality percentage composition lower than 0.3% time, stops ammonia still process, and the emulsion obtaining carries out solid-liquid separation, filter cake is by liquid-solid ratio 5:1 deionized water wash, washing time 1h, refilters separation, obtains filter cake;
(7) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 150 ℃ of retort furnace calcining 80min, sampling detects and obtains purity ZnO%=99.85%; Tap density 0.23g/m
2, specific surface area 110m
2the high-purity zinc oxide powder of/g.
Embodiment 3
Raw material: certain smoke of steel factory ash 3# of steel mill 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 nm zinc oxide:
(1) activation: get 1kg smoke of steel factory ash 3
#, add 40g white lime to obtain compound, and the maintenance mixture moisture content 9% that adds water, then carrying out admixture activation soak time is 42 hours;
(2) leaching: by the smoke of steel factory ash 3 after admixture activation
#leach as leaching agent with 3000mL ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=5.6mol/L, CO
3 2-volumetric molar concentration c (CO
3 2-)=1.05 mol/L, adds respectively the surfactant SDS of 1.2g Sodium Silicofluoride, 0.3g, the Dicyanodiamide of 3g; In the time of 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, 143.5 grams, zinc (zinc recovery 93.18%) in gained zinc ammonia complex liquid;
(3) pre-ammonia still process: the leaching liquid obtaining after leaching is heated to 105 ℃ and analyses ammonia, until c (NH in leaching liquid
3)=2.6mol/L, then adds 6g ammonium persulphate and stirs;
(4) purification and impurity removal: add 4.3g potassium permanganate to stir 0.8h, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filter, 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;
(5) refinement treatment: in purification and impurity removal liquid after treatment, add 3g ammonium phosphate, 0.15g surfactant SDS, obtain refined liquid;
(6) 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, also adding massfraction is 5% sodium stearate solution 15ml, detect at any time liquid zinc content in ammonia still process equipment, when zinc content is 1% time, in ammonia still process equipment, adding quality percentage composition is 30% sodium hydroxide solution 15ml, zinc quality percentage composition lower than 0.3% time, stops ammonia still process, and the emulsion obtaining carries out solid-liquid separation, filter cake is by liquid-solid ratio 5:1 deionized water wash, washing time 1h, refilters separation, obtains filter cake;
(7) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 250 ℃ of retort furnace calcining 80min, sampling detects and obtains purity ZnO%=99.83%; Tap density 0.24g/m
2, specific surface area 117m
2the high-purity zinc oxide powder of/g.
Embodiment 4
Raw material: the smoke of steel factory ash 4# of Kunming steel mill, 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) activation: get 1kg smoke of steel factory ash 4
#, add 45g white lime to obtain compound, and the maintenance mixture moisture content 8.5% that adds water, then carrying out admixture activation soak time is 50 hours;
(2) leaching: by the smoke of steel factory ash 3 after admixture activation
#leach as leaching agent with 3000mL ammoniacal liquor-ammonium fluid; 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; In the time of 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, 90.11 grams, zinc (zinc recovery 92.9%) in gained zinc ammonia complex liquid;
(3) pre-ammonia still process: the leaching liquid obtaining after leaching is heated to 105 ℃ and analyses ammonia, until c (NH in leaching liquid
3)=2.6mol/L, then adds 6g ammonium persulphate and stirs;
(4) purification and impurity removal: add 2.7g potassium permanganate to stir 0.8h, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filter, 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;
(5) refinement treatment: in purification and impurity removal liquid after treatment, add 4g ammonium phosphate, 0.08g surfactant SDS, obtain refined liquid;
(6) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process in ammonia distiller, 105 ℃ of solution temperatures, in ammonia still process crystallisation process, also adding massfraction is 5% sodium stearate solution 8ml, detect at any time liquid zinc content in ammonia still process equipment, when zinc content is 1% time, in ammonia still process equipment, adding quality percentage composition is 30% sodium hydroxide solution 8ml, zinc quality percentage composition lower than 0.3% time, stops ammonia still process, and the emulsion obtaining carries out solid-liquid separation, filter cake is by liquid-solid ratio 5:1 deionized water wash, washing time 1h, refilters separation, obtains filter cake;
(7) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 260 ℃ of retort furnace calcining 80min, sampling detects and obtains purity ZnO%=99.85%; Tap density 0.27g/m
2, specific surface area 116m
2the high-purity zinc oxide powder of/g.
Claims (9)
1. a method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm 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:
Before leaching smoke of steel factory ash step, in pending smoke of steel factory ash, add white lime to obtain compound, and the maintenance mixture moisture content 8-10% that adds water, then carry out admixture activation, the amount of the white lime adding by weight, is the 3-5% of smoke of steel factory ash;
Smoke of steel factory ash after admixture activation is leached as leaching agent with ammoniacal liquor-ammonium fluid; 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 adds 0.3-0.5kg Sodium Silicofluoride in every cubic metre of leaching agent;
After purification and impurity removal, carry out refinement treatment, method is: in purification and impurity removal liquid after treatment, add ammonium phosphate and tensio-active agent, add-on is 1-3kg ammonium phosphate, 10-50g tensio-active agent in every cubic metre of purification and impurity removal liquid after treatment.
2. a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide according to claim 1, it is characterized in that: while leaching pending smoke of steel factory ash, in the ammoniacal liquor-ammonium fluid of every cubic metre, be also added with the tensio-active agent of 0.03-0.05kg.
3. a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide according to claim 2, is characterized in that: the Dicyanodiamide 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 smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide according to claim 1, is characterized in that: in the time of the pending smoke of steel factory ash of leaching, utilize wet ball grinding activation leaching.
5. a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide according to claim 4, is characterized in that: guarantee that in ball mill, extraction time is 50～60 minutes, ball mill outlet material is all by 140 mesh sieves.
6. a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide according to claim 1, is characterized in that: 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 oxidized completely by adding 2-4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring.
7. a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm 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 process equipment, when zinc content is during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, add-on be every cubic metre of ammonia still process liquid to add quality percentage composition be 30% sodium hydroxide solution 3-5L, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process.
8. a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide according to claim 7, is characterized in that: in every cubic metre of ammonia still process liquid, also adding massfraction is 5% sodium stearate solution 3-5L.
9. a kind of method of utilizing smoke of steel factory ash 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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