CN102849782B - Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization - Google Patents

Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization Download PDF

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CN102849782B
CN102849782B CN201210358030.0A CN201210358030A CN102849782B CN 102849782 B CN102849782 B CN 102849782B CN 201210358030 A CN201210358030 A CN 201210358030A CN 102849782 B CN102849782 B CN 102849782B
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leaching
zinc oxide
decarburization
smoke
zinc
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CN102849782A (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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SICHUAN JUHONG TECHNOLOGY Co Ltd
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Abstract

The invention discloses a method for producing a high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization. The method includes that an ammonia-water-ammonium-bicarbonate solution is utilized as a leaching agent for leaching, 0.3-0.5kg of sodium fluosilicate is added into the per cubic meter of the leaching agent, and after the leaching, 50-60kg of slaked limes are added in per cubic meter of a leaching agent liquid to perform warming decarburization. According to the method, the ammonia method is applied to smoke dust ash treatment, prior ammonia methods are subjected to adaptable improvement, the leaching speed and the leaching rate of zinc in the smoke dust ash are improved, zinc oxide with a large specific surface area can be obtained, simultaneously the purity can reach above 99.7%, by means of the method, the energy consumption is low, the efficiency is high, the leaching agent can be recycled, the problem of zinc load in the steel mill blast furnace smoke dust can be thoroughly solved, the purifying requirements for harmful ingredients of zinc and alkali metal in the steel mill can be met, virtuous circle of production is achieved, valuable ferrum and carbon resources in the steel mill can be recycled, the ferrum and carbon are enriched, the energy is saved, and good economic benefits are achieved.

Description

A kind of method of utilizing the decarburization of smoke of steel factory ash ammonia process to produce high-purity zinc oxide
Technical field
The present invention relates to a kind of production method of zinc oxide, particularly a kind of production method of high-purity zinc oxide.
Background technology
The current smoke dust (comprising blast-furnace dust, converter ash, electric furnace ash) from steel mill, 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 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, restriction circulation smoke dust consumption; The 2nd, smoke dust 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 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 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.
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 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
One of the object of the invention is: for the problem of above-mentioned existence, provide a kind of method of effectively utilizing smoke of steel factory ash to prepare high-purity zinc oxide.
The technical solution used in the present invention is such: a kind of method of utilizing the decarburization of smoke of steel factory ash ammonia process to produce high-purity zinc oxide, comprise the following steps,
Leaching smoke of steel factory ash, decarburization, purification and impurity removal, ammonia still process crystallization and drying and calcining, wherein:
Leaching smoke of steel factory ash leaches as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=5.5-7mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=0.95-1.2 mol/L, and in every cubic metre of leaching agent, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
After leaching, in gained leaching liquid, zinc oxide concentration is controlled at 50-60g/L, the decarburization that heats up, and its method is: in every cubic metre of leaching liquid, add 50-60kg white lime, be heated with stirring to 90-98 ℃, work as CO 2concentration≤0.3mol/L adds 3-4kg ammonium persulphate in every cubic metre of aforementioned liquids, continues stir decarburization and oxidizing reaction occurs, until c (CO 2)≤0.1mol/L, c (NH 3)≤3mol/L, then filtering separation,
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 high-purity zinc oxide, first need to guarantee that the zinc in low-grade zinc oxide ore 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, 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.
The technology that first the present invention prepares existing ammonia process zinc oxide is applied to the processing to smoke dust; Meanwhile, on the technique basis of existing ammonia process, in leaching liquid, add appropriate Sodium Silicofluoride; And increase the step of decarburization.
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;
Increase decarburization and fall ammonia step, can eliminate too much free ammonia on the one hand, reduce the complex ability of foreign ion, make foreign ion be removed (doubting coagulation as silicic acid isocolloid ion at high temperature forms sediment), be beneficial to raising depuration quality, reduce and purify drug dosage; Can remove on the other hand carbanion in solution, make to be conducive to obtain the zinc hydroxide that crystalline core size is less, decomposition temperature is lower in the follow-up deamination hydrolytic process of complex liquid and precipitate.
Meanwhile, present inventor draws by great many of experiments:, can provide on the one hand and replace CO as decarburizer with white lime 3 2-ligand OH -, make CO 3 2-eliminate and form CaCO 3precipitation, slightly strong alkaline environment contributes to the metallic impurity ion precipitations such as iron ion in addition, for follow-up purification creates conditions.On the other hand, milk of lime is inexpensive.
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
Wherein n=1~4;
Chemical reaction in decarbonation process is:
Ca(OH) 2﹦ Ca 2+ +2OH -
Ca 2++ CO 3 2-→CaCO 3
NH 3·H 2O + NH 4HCO 3——→ 2NH 3↑ +CO 2↑ +2H 2O
The reaction occurring in purification and impurity removal process:
S 2O 8 2-+ Mn 2++ 2NH 3·H 2O + H 2O→ Mn O(OH) 2↓ + 2NH 4 ++2SO 4 2-+ 2H +
S 2O 8 2-+2Fe 2+ +6H 2O →2SO 4 2-+ 2Fe(OH) 3↓+ 6H +
AsO 4 3- + Fe 3- → FeAsO 4
AsO 3 3- + S 2O 8 2-+ H 2O → 2SO 4 2- + AsO 4 3-+ 2H +
2H 3AsO 3 + 8Fe(OH) 3 → (Fe 2O 3) 4As 2O 3·5H 2O↓ +10H 2O
M 2++ S 2→ MS ↓ M represents Cu 2+, Pb 2+, Cd 2+, Ni 2+hg 2+plasma
As 3+ + S 2-→As 2S 3
Y 2++ Zn → Zn 2+wherein Y representative of+Y: Cu 2+, Pb 2+, Cd 2+, Ni 2+plasma;
The reaction equation of ammonia still process step:
[Zn(NH 3) i2++2OH - ——→ Zn(OH) 2↓+ iNH 3
[ Zn (NH 3) isO 4+ 2NH 3h 2o---→ Zn (OH) 2↓+iNH 3↑+(NH 4) 2sO 4wherein i=1~4
The chemical equation of drying and calcining:
Zn(OH) 2→ZnO + H 2O↑
As preferably: be also added with the Dicyanodiamide of 0.5-1kg and the tensio-active agent of 0.03-0.05kg in every cubic metre of ammoniacal liquor-ammonium fluid leaching agent, as SDS.
Tensio-active agent can reduce solution surface energy, and 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 added with 0.5-1kg at ammoniacal liquor-ammonium fluid leaching agent of every cubic metre.
Dicyanodiamide, as ammonia stablizer, can reduce the volatilization of ammonia in leaching process, improves Working environment, reduces the loss of ammonia.
As preferably: in the time of the pending smoke dust of leaching, adopt wet ball grinding leaching.
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 the chemical activation of tensio-active agent and dry hydrate, reach higher leaching velocity and leaching yield.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: after decarbonation process completes, add Neutral ammonium fluoride in liquid, the amount adding is Ca in solution 2+the 1.5-2.0 of theoretical value doubly.
Two of object of the present invention, is to provide a kind of high purity and high performance zinc oxide, and the technical scheme adopting is: on aforesaid technical scheme basis, the temperature of drying and calcining adopts 200-300 ℃.
Due to technical scheme of the present invention, after ammonia still process crystallisation step, what obtain is nearly all zinc hydroxide, the decomposition temperature of zinc hydroxide is lower than zinc subcarbonate, adopt the temperature of 200-300 ℃ to calcine, can obtain the zinc oxide product of purity at 99.7% above bigger serface, specific surface area>=100m 2/ g, low temperature calcination dispersiveness, mobility are all more excellent.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows: ammonia process is applied to the processing of smoke dust, and existing ammonia process is carried out to adaptation, before leaching, increase activation step and in the time of leaching, added Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, improved on the one hand zinc leaching velocity and the leaching yield in smoke dust.On the other hand, the present invention preferably adopts lower calcining temperature, can obtain can reaching more than 99.7% compared with the zinc oxide while purity of bigger serface, has very high 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 18-37% by original 14-30%, charcoal thermal value by original about 1000-3000 kilocalorie/kilogram bring up to 1500-4500 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
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: 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 #, 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 43.89 grams, zinc (zinc recovery 90.5%) in gained zinc ammonia complex liquid;
(2) decarburization: after leaching, in gained leaching liquid, zinc oxide concentration is controlled at 50g/L, the decarburization that heats up, its method is: in leaching liquid, add 60g white lime, be heated with stirring to 90 ℃, work as CO 2concentration=0.3mol/L adds 3g ammonium persulphate in aforementioned liquids, continues stir decarburization and oxidizing reaction occurs, until c (CO 2)=0.1mol/L, c (NH 3)=3mol/L, then filtering separation;
(3) purification and impurity removal: add 1.32g potassium permanganate to stir 0.5h in the liquid after separating to step (2), 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, 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 and carried out ammonia still process, vapour pressure import 0.5MPa/cm in ammonia distiller 2, 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;
(5) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 300 ℃ of retort furnace calcining 60min, sampling detects and obtains purity ZnO%=99.76%, specific surface area 73m 2the high-purity zinc oxide powder of/g.
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 #, 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, 28.37 grams, zinc (zinc recovery 91.5%) in gained zinc ammonia complex liquid;
(2) decarburization: after leaching, in gained leaching liquid, zinc oxide concentration is controlled at 60g/L, the decarburization that heats up, its method is: in leaching liquid, add 25g white lime, be heated with stirring to 98 ℃, work as CO 2concentration=0.28mol/L adds 2g ammonium persulphate in aforementioned liquids, continues stir decarburization and oxidizing reaction occurs, until c (CO 2)=0.09mol/L, c (NH 3)=2.8mol/L, then filtering separation;
(3) decalcification: after decarbonation process completes, add Neutral ammonium fluoride in liquid, the amount adding is Ca in solution 2+1.5 times of theoretical value;
(4) purification and impurity removal: think to add 0.85g potassium permanganate to stir 0.5h in the liquid after decalcification, 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, 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;
(5) ammonia still process crystallization: gained refined liquid is inserted in ammonia distiller and carried out ammonia still process, and 108 ℃ 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 200 ℃ of retort furnace calcining 60min, sampling detects and obtains purity ZnO%=99.82%, specific surface area 79m 2the high-purity zinc oxide powder of/g.
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 #, leach as leaching agent with 3000ml ammoniacal liquor-ammonium fluid; 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; 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, 142.45 grams, zinc (zinc recovery 92.5%) in gained zinc ammonia complex liquid;
(2) decarburization: after leaching, in gained leaching liquid, zinc oxide concentration is controlled at 56g/L, the decarburization that heats up, its method is: in leaching liquid, add 174g white lime, be heated with stirring to 95 ℃, work as CO 2concentration=0.27mol/L adds 10.8g ammonium persulphate in aforementioned liquids, continues stir decarburization and oxidizing reaction occurs, until c (CO 2)=0.085mol/L, c (NH 3)=2.3mol/L, then filtering separation;
(3) decalcification: after decarbonation process completes, add Neutral ammonium fluoride in liquid, the amount adding is Ca in solution 2+2.0 times of theoretical value;
(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, and obtains refined liquid;
(5) ammonia still process crystallization: gained refined liquid is inserted in ammonia distiller and carried out ammonia still process, and 108 ℃ 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 250 ℃ of retort furnace calcining 80min, sampling detects and obtains purity ZnO%=99.82%, specific surface area 76m 2the high-purity zinc oxide powder of/g.
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 #, 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, 90.01 grams, zinc (zinc recovery 92.79%) in gained zinc ammonia complex liquid;
(2) decarburization: after leaching, in gained leaching liquid, zinc oxide concentration is controlled at 52g/L, the decarburization that heats up, its method is: in leaching liquid, add 112g white lime, be heated with stirring to 96 ℃, work as CO 2concentration=0.29mol/L adds 8g ammonium persulphate in aforementioned liquids, continues stir decarburization and oxidizing reaction occurs, until c (CO 2)=0.095mol/L, c (NH 3)≤2.6mol/L, then filtering separation;
(3) decalcification: after decarbonation process completes, add Neutral ammonium fluoride in liquid, the amount adding is Ca in solution 2+1.8 times of theoretical value;
(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, and obtains refined liquid;
(5) ammonia still process crystallization: gained refined liquid is inserted in ammonia distiller and carried out ammonia still process, and 108 ℃ 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 280 ℃ of retort furnace calcining 70min, sampling detects and obtains purity ZnO%=99.80%, specific surface area 76m 2the high-purity zinc oxide powder of/g.

Claims (7)

1. a method of utilizing the decarburization of smoke of steel factory ash ammonia process 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:
Leaching smoke of steel factory ash leaches as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=5.5-7mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=0.95-1.2 mol/L, and in every cubic metre of leaching agent, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
After leaching, in gained leaching liquid, zinc oxide concentration is controlled at 50-60g/L, the decarburization that heats up, and its method is: in every cubic metre of leaching liquid, add 50-60kg white lime, be heated with stirring to 90-98 ℃, work as CO 2concentration≤0.3mol/L adds 3-4kg ammonium persulphate in every cubic metre of aforementioned liquids, continues stir decarburization and oxidizing reaction occurs, until c (CO 2)≤0.1mol/L, c (NH 3)≤3mol/L, then filtering separation.
2. a kind of method of utilizing the decarburization of smoke of steel factory ash ammonia process 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 the decarburization of smoke of steel factory ash ammonia process 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 the decarburization of smoke of steel factory ash ammonia process to produce high-purity zinc oxide according to claim 1, is characterized in that: in the time of the pending smoke dust of leaching, adopt wet ball grinding.
5. a kind of method of utilizing the decarburization of smoke of steel factory ash ammonia process 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 the decarburization of smoke of steel factory ash ammonia process to produce high-purity zinc oxide according to claim 1, is characterized in that: after decarbonation process completes, in liquid, add Neutral ammonium fluoride, the amount adding is Ca in solution 2+the 1.5-2.0 of theoretical value doubly.
7. a kind of method of utilizing the decarburization of smoke of steel factory ash ammonia process to produce high-purity zinc oxide according to claim 1, is characterized in that: the temperature of described drying and calcining is 200-300 ℃.
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