CN102826589A - 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 working method of zinc oxide, particularly a kind of working method of high-purity nm zinc oxide.
Background technology
Present smoke dust (comprising blast furnace, converter, electric furnace) from steel mill; Claim the smoke of steel factory ash again; 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%, quicklime 2～5%, Natural manganese dioxide 1～2% and titanium, vanadium and basic metal etc.Under the usual conditions, generally produce agglomerate as the agglomerating raw material, utilize in the steel mill circulating inside, along with the round-robin enrichment, it is more and more high to go into stove zinc load, has a strong impact on the normal operation of blast furnace.
Limit the method for blast furnace zinc load at present: the one, limit is with smoke of steel factory ash consumption; The 2nd, the ore dressing of smoke of steel factory ash is handled; The 3rd, adopt pyrogenic process and wet processing.First kind be not reduce blast furnace zinc load economic, effective means, and bring environmental pollution.Second kind be the zinc enrichment in tail mud, but iron is smart, three kinds of products imbalances of carbon, tail mud, still loses higher iron, charcoal resource.The third is divided into pyrogenic process and wet processing again, and pyrogenic process has direct sintering, pelletizing facture, direct-reduction process to handle.But zinc, lead and basic metal are not resolved yet.Wet method is divided into acid system and alkaline process again, 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 iron again, 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 reach environmental requirement, and equipment corrosion is serious, and is responsive to ingredient requirement, and difficult technique is to optimize, and productivity effect is hanged down and steel mill's output is not complementary etc.The Iron and Steel Enterprises in China zinc-containing dust is allocated sintering recycle mode into and blast furnace, SINTERING PRODUCTION and Iron 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 got in the solution, and zinc obtains valuable recycling.
On the other hand; High pure zinc oxide generally is meant the massfraction of zinc oxide more than 99.7%, and high-purity zinc oxide is the indispensable a kind of high-tech raw material of modern industry, and is of many uses; Be mainly used in 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.
Producing the method for high-purity zinc oxide at present, mainly is indirect method, and indirect method generally is raw material with the zinc ingot metal; Pass through electrolytic reduction; Or high-temperature gasification, atmospheric oxidation condensation and collection again makes zinc oxide, different zinc ingot metal raw materials; The zinc oxide purity of producing is also different, and this technology is mainly produced the zinc oxide of 99.5%--99.7%.
Ammonia process is a kind of domestic 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. because the smoke of steel factory ash contains zinc rate low (generally containing Zn%=5-22), it is low that leach liquor contains zinc concentration, and the leaching agent consumption is big, 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 recovery is low, and iron, charcoal resource reclaim and also do not form complete chain, and the value of smoke dust does not obtain embodying.
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 many special nature; Like non-migrating property, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc.; Utilize its marvellous performance, can make gas sensor, fluor, varistor, UV-preventing material, image recording material, piezoelectric, voltage dependent resistor, effective catalyst, magneticsubstance and plastics film etc. at aspects such as light, electricity, magnetic, sensitivities.
Produce the method for nano zine oxide at present, mainly contain chemical precipitation method, sol-gel method, microemulsion method and hydrothermal synthesis method etc.But the raw material that is adopted all is that zinc content is at zinc baking sand more than 50% or pure zinc salt etc.
Disclosed at present method for producing nanometer-zinc oxide by ammonia leaching technology all is the water at low temperature solution as:
One Chinese patent application numbers 92103230.7 has been announced a kind of improvement technology to the legal production zinc oxide of traditional ammino; With 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), continue heating then and finish, obtain the nano zine oxide of 30-100nn through high-temperature calcination until the decomposition of zinc ammonia complex liquid.
The following problem of this technical patent needs to solve:
After the hydrolysis; Non-dissociated zinc ammonia complex liquid is in the thermal degradation process, and the new zinc subcarbonate that produces can impel the crystal of former hydrolysis to grow up in original nucleating surface continued growth; Cause zinc subcarbonate xln particle diameter inhomogeneous easily, make the finished product particle diameter wayward.
Increase the 4-10 water yield doubly, reduced the efficient of producing in the process, increase energy consumption, increase the rear end cost of water treatment.
One Chinese patent application numbers 200610130477.7 has been announced a kind of improvement technology to the legal production zinc oxide of traditional ammino; With zinc ammonia complex liquid; Mix with the hot water of 1:2-20 or the mother liquor of heat continuously; Mother liquor circulates behind heat tracing and is used for the hydrolysis of zinc ammonia complex liquid, makes the nano zine oxide of 10-50nn.
The following problem of this technical patent needs to solve:
Ammonia can not be separated fully after the mother liquor hydrolysis, repeats to superpose not reach the effect of hydrolysis, is zinc ammonia complex liquid the most at last and the mixing of zinc ammonia complex liquid.
More than two kinds of patents in fact all be to manage at low temperatures; Utilize the Macrodilution of water to make the pH value of solution slight the change taken place and hydrolysis crystallization acquisition part nano junction crystal, only actually relies on the slight change of pH value can only obtain few a part of hydrolysis (ammonia solvent is write music line chart, can find from zinc oxide) under the situation when zinc concentration is higher.The efficient separated out of the zinc ammoniacal liquor of high density is high in fact, energy consumption is low, and the efficient that the zinc ammoniacal liquor of lower concentration is separated out is low, energy consumption is high, the people be the proportional that adds big flood to produce nano zine oxide be feasible technically, but may not be feasible aspect economic benefit.
In addition, at present ammonia leaching process is produced in the zinc oxide process, all crystallizes out with zinc subcarbonate after analysing ammonia; Decomposition temperature is high, and (zinc hydroxide just makes about 125 ℃ of temperature theoretical the decomposition; About 300 ℃ of zinc carbonate), for obtaining high purity product, must guarantee sufficiently high decomposition temperature; General controlled temperature just can make zinc subcarbonate decompose fully more than 500 ℃.Like application number is 200610130477.7 one Chinese patent application, and calcining temperature is up to 550 ℃.High-temperature calcination has a strong impact on specific surface area and dispersiveness, the flowability of zinc oxide, influences its Application Areas then.
In sum,, 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 the technical barrier that the industry needs to be resolved hurrily for the processing of smoke of steel factory ash.
Summary of the invention
One of goal of the invention of the present invention is: to 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 scheme that the present invention adopts is such: a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide may further comprise the 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 and obtain compound, and add water maintenance mixture moisture content 8-10%; Carry out admixture activation then; The amount of the white lime that is added by weight, is the 3-5% of smoke of steel factory ash;
Smoke of steel factory behind admixture activation ash is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in the said 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 the 0.3-0.5kg Sodium Silicofluoride 98min in every cubic metre of leaching agent;
Behind purification and impurity removal, carry out refinement treatment, method is: in the liquid after purification and impurity removal is handled, add ammonium phosphate and tensio-active agent, add-on is 1-3kg ammonium phosphate, a 10-50g tensio-active agent in the liquid after every cubic metre of purification and impurity removal is handled;
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.
The technology that the present invention at first prepares zinc oxide with existing ammonia process is applied to the processing to the smoke of steel factory ash, simultaneously, and on the technology basis of existing ammonia process; Before ammonia soaks step, increased pre-treatment, promptly add the step that white lime carries out admixture activation in the smoke of steel factory ash; In leaching liquid, add an amount of Sodium Silicofluoride 98min, in addition simultaneously; Behind purification and impurity removal, increased the step of refinement treatment.
At first; Obtain highly purified zinc oxide, need guarantee that at first the zinc in the smoke of steel factory ash can leach as much as possible, can improve the recovery of zinc so on the one hand; On the other hand; Zinc concentration is big more in leach liquor, and the impurity concentration relative proportion is just more little, can guarantee under equal processing condition, to make more highly purified zinc oxide.
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, dry hydrate plays loose, the fluffy usefulness that turns into to smoke dust; 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 through a large amount of experiments: an amount of silicofluoric acid is received and can be abolished ultrafine particulate to containing zinc particle package action, realizes ultrafine particulate layering come-up; Thereby zinc is exposed, it more fully is immersed in the leach liquor.
Secondly; Obtain nano level zinc oxide; Need to suppress growing up of crystal grain; Why size is unsatisfactory with particle size distribution range for the nano zine oxide that existing ammonia process production obtains, and most important reason is that crystalline is constantly grown up 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, the present inventor is through a large amount of experiments, behind purification and impurity removal; Increase the step of refinement treatment; In the solution after purification and impurity removal is handled, add an amount of ammonium phosphate and tensio-active agent, in conjunction with the growth that can effectively suppress xln under the high-speed stirring.
Wherein:
Chemical reaction in the 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
N=1～4 wherein;
The reaction that takes place in the 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: when leaching pending smoke of steel factory ash, in ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the tensio-active agent of 0.03-0.05kg, like SDS.
Tensio-active agent reduces the solution surface ability, and with the Sodium Silicofluoride 98min mating reaction, the coating effect that can abolish ultrafine particulate improves the leaching agent penetrating power, further improves the recovery of zinc.
As preferably: the Dicyanodiamide that in ammoniacal liquor-ammonium fluid of every cubic metre, also is added with 0.5-1kg.
Dicyanodiamide can reduce the volatilization of ammonia in the leaching process as the ammonia stablizer, improves the leaching Working environment, reduces the loss of ammonia.
As preferably: when the pending smoke of steel factory ash of leaching, adopt wet ball grinding, the activation leaching.
Utilize the 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 extraction time is 50～60 minutes in the ball mill, the ball mill outlet material is all through 140 mesh sieves.
Utilize the ball milling wet extraction, destroyed that crystalline network (mechanical activation) such as zinc ferrite combines with the chemical activation of tensio-active agent and dry hydrate in the smoke of steel factory ash, reach higher leaching velocity.Activation in advance and the mechanical activation of ball milling and the adding of promoting agent (Sodium Silicofluoride 98min, SDS etc.) through raw material have obtained higher leaching yield.
As preferably: before the purification and impurity removal step, carry out preparatory ammonia still process: the leaching liquid that will obtain after will leaching is heated to 95-105 ℃ and analyses ammonia, c (NH in leaching liquid
3)≤3mol/L, it is complete to carry out oxidation by adding 2-4kg ammonium persulphate and stirring in every cubic metre the leaching liquid then.Type of heating adopts the mode of indirect heating.As c (NH
3During)≤3mol/L, zinc ammonia complex liquid does not make zinc separate out simultaneously near saturated; During the ammonia still process crystallization, temperature is controlled in 105 ℃, and the speed PM 600-900 of ammonia still process container for stirring changes.
The reaction of ammonia still process process generation in advance:
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 removes impurity such as de-iron, manganese, arsenic as oxygenant
Increase preparatory 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 make foreign ion be able to remove 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, help 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 big product reason of specific surface area;
As preferably: in the ammonia still process crystallisation process; Solution zinc concentration in the detection at any time ammonia still process container; When zinc content during at 1-1.5%, add sodium hydroxide solution in the container, add-on is that to add massfraction be 30% sodium hydroxide solution 3-5 liter to every cubic metre of solution; Zinc content is lower than at 0.3% o'clock in the solution, finishes ammonia still process.
In the ammonia still process later stage, when zinc concentration in the complex liquid is low,, can make NH through adding the pH value of sodium hydroxid raising liquid
4 +Ion transfers NH to
3Molecule reaches the effect of analysing ammonia, rapid crystallization formation nanometer zinc hydroxide nucleus fast.
As preferably: it is 5% octadecoic acid natrium solution 3-5L that every cubic metre of ammonia still process liquid adds mass percent.
In the ammonia still process process, add octadecoic acid natrium, make the nano junction crystal of generation receive the sealing parcel, no longer continue to grow up.
Two of the object of the invention provides a kind of high purity and high performance nano zine oxide, and the technical scheme that is adopted is that the temperature of drying and calcining adopts 150-300 ℃.
Because technical scheme of the present invention, behind the ammonia still process crystallisation step, what obtain mainly is zinc hydroxide; The decomposition temperature of zinc hydroxide is lower than zinc subcarbonate; Adopt 150-300 ℃ temperature to calcine, can obtain purity 99.7% and above zinc oxide, because the nucleus of zinc hydroxide is less than zinc subcarbonate; Particle diameter is 10-30nm so finally can obtain being evenly distributed, and specific surface area>=100m
2The high-quality nanometer Zinc oxide powder that/g is above.
In sum; Adopt technique scheme, ammonia process is applied to the processing to the smoke of steel factory ash, and existing ammonia process has been carried out technological improvement; Before leaching, increase activation step and when leaching, added Sodium Silicofluoride 98min, tensio-active agent and Dicyanodiamide; The smoke of steel factory ash has reached efficient leaching on the one hand, and subsequent handling increases preparatory ammonia still process and in the ammonia still process process, adds resistance change agent to suppress the crystalline growth, obtains the little and uniform nanometer zinc oxide precursor of particle diameter of particle diameter; On the other hand, the lower calcining temperature of this preferred employing can obtain the high-purity nm zinc oxide (purity can reach 99.7%) than bigger serface, has very high practical value and economic worth; In addition, 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 99% to objectionable constituent zinc and alkali-metal purification requirement both to have satisfied steel mill; The zinc extraction yield is more than 90%); Reach the benign cycle of production, reclaimed valuable iron, the charcoal resource of steel mill again, iron, charcoal obtain enrichment; Iron level is brought up to 18-38% by original 15-30%, and the charcoal thermal value is brought up to 1600-5200 kilocalorie/kilogram by original about 1000-4500 kilocalorie/kilogram; Iron, charcoal recovery utilization rate all reach more than 98%, have not only practiced thrift the energy but also created good economic benefit.
Innovative point of the present invention mainly contains: ⑴ increases preparatory ammonia still process to be handled, and drives too much free ammonia earlier away, when ammonia still process, reaches the purpose of rapid crystallization; ⑵ in the ammonia still process process, when ammonia concentration in the zinc ammonia complex liquid is low,, reach the purpose of analysing ammonia fast through adding the pH value of sodium hydroxid raising liquid; ⑶ add tensio-active agent (like SDS), ammonium phosphate in zinc ammonia complex liquid, can effectively control the growth of nano zine oxide nucleus; ⑷ utilize the power of steam to realize high-speed stirring, the crystallization of control nano zine oxide;
Embodiment
Do detailed explanation in the face of the present invention down.
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification 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%
Be used to prepare the method for high-purity nm zinc oxide:
(1) activation: get 500g smoke of steel factory ash 1#, add 15g white lime and obtain compound, and add water maintenance mixture moisture content 8%, carry out admixture activation then, soak time is 36 hours;
(2) leaching: with the ash of the smoke of steel factory behind the admixture activation 1
#Leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in the said 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 98min, carries out three sections leachings, and each section leaching time is 2 hours, after the solid-liquid separation, and zinc 44.38 grams (zinc recovery 91.5%) in the gained zinc ammonia complex liquid;
(3) purification and impurity removal: add 1.33g potassium permanganate and stir 0.5h, add a small amount of polyacrylamide solution (4mg/L) and filter, filtrating is extraordinarily gone into sodium sulphite by 1.2 of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb; Temperature, 70 ℃, churning time 2h; Filter, filtrating adds KMnO
4Consumption is 2.7 times of Fe amount, and 80 ℃ of temperature stir 1h (detect Fe, Mn is qualified), filters, and filtrating is extraordinarily gone into zinc powder by 2.5 of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and 60 ℃ of temperature are filtered;
(4) refinement treatment: in the liquid after purification and impurity removal is handled, add 1g ammonium phosphate, 0.05g surfactant SDS, obtain refined liquid;
(5) 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;
(6) drying and calcining: 105 ℃ of dryings of filter cake, 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
Be used to prepare the method for high-purity nm zinc oxide:
(1) activation: get 500g smoke of steel factory ash 2#, add 25g white lime and obtain compound, and add water maintenance mixture moisture content 10%, carrying out the admixture activation soak time then is 36 hours;
(2) leaching: with the ash of the smoke of steel factory behind the admixture activation 2
#Leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in the said 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 98min, 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 through 140 mesh sieves, and each section leaching time is 2 hours; After the solid-liquid separation, zinc 28.46 grams (zinc recovery 91.8%) in the gained zinc ammonia complex liquid;
(3) ammonia still process in advance: the leaching liquid that will obtain after will leaching is heated to 95 ℃ and analyses ammonia, c (NH in leaching liquid
3)=2.8mol/L adds 2g ammonium persulphate and stirring then;
(4) purification and impurity removal: add 0.83g potassium permanganate and stir 0.5h, add a small amount of polyacrylamide solution (4mg/L) and filter, filtrating is extraordinarily gone into sodium sulphite by 1.2 of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb; Temperature, 70 ℃, churning time 2h; Filter, filtrating adds KMnO
4Consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detect Fe, Mn is qualified), filters, and filtrating is extraordinarily gone into zinc powder by 2.5 of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and 60 ℃ of temperature are filtered;
(5) refinement treatment: in the liquid after purification and impurity removal is handled, add 1g ammonium phosphate, 0.02g surfactant SDS, obtain refined liquid;
(6) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 108 ℃ of solution temperatures are in the ammonia still process crystallisation process; Also add massfraction and be 5% octadecoic acid natrium solution 1.5ml, liquid zinc content in the detection at any time ammonia still process equipment, when zinc content 1% the time; Adding quality percentage composition is 30% sodium hydroxide solution 2.5ml in ammonia still process equipment, and zinc quality percentage composition is lower than at 0.3% o'clock, stops 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;
(7) drying and calcining: 105 ℃ of dryings of filter cake, 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%
Be used to prepare the method for high-purity nm zinc oxide:
(1) activation: get 1kg smoke of steel factory ash 3
#, add 40g white lime and obtain compound, and add water maintenance mixture moisture content 9%, carrying out the admixture activation soak time then is 42 hours;
(2) leaching: with the ash of the smoke of steel factory behind the admixture activation 3
#Leach as leaching agent with 3000mL ammoniacal liquor-ammonium fluid; Wherein, NH in the said 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 the surfactant SDS of 1.2g Sodium Silicofluoride 98min, 0.3g, the Dicyanodiamide of 3g respectively; 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 through 140 mesh sieves, and each section leaching time is 2 hours; After the solid-liquid separation, zinc 143.5 grams (zinc recovery 93.18%) in the gained zinc ammonia complex liquid;
(3) ammonia still process in advance: the leaching liquid that will obtain after will leaching is heated to 105 ℃ and analyses ammonia, c (NH in leaching liquid
3)=2.6mol/L adds 6g ammonium persulphate and stirring then;
(4) purification and impurity removal: add 4.3g potassium permanganate and stir 0.8h, add a small amount of polyacrylamide solution (4mg/L) and filter, filtrating is extraordinarily gone into sodium sulphite by 1.2 of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb; Temperature, 70 ℃, churning time 2h; Filter, filtrating adds KMnO
4Consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detect Fe, Mn is qualified), filters, and filtrating is extraordinarily gone into zinc powder by 2.5 of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and 60 ℃ of temperature are filtered;
(5) refinement treatment: in the liquid after purification and impurity removal is handled, add 3g ammonium phosphate, 0.15g surfactant SDS, obtain refined liquid;
(6) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 108 ℃ of solution temperatures are in the ammonia still process crystallisation process; Also add massfraction and be 5% octadecoic acid natrium solution 15ml, liquid zinc content in the detection at any time ammonia still process equipment, when zinc content 1% the time; Adding quality percentage composition is 30% sodium hydroxide solution 15ml in ammonia still process equipment, and zinc quality percentage composition is lower than at 0.3% o'clock, stops 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;
(7) drying and calcining: 105 ℃ of dryings of filter cake, 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%
Be used to prepare the method for high-purity zinc oxide:
(1) activation: get 1kg smoke of steel factory ash 4
#, add 45g white lime and obtain compound, and add water maintenance mixture moisture content 8.5%, carrying out the admixture activation soak time then is 50 hours;
(2) leaching: with the ash of the smoke of steel factory behind the admixture activation 3
#Leach as leaching agent with 3000mL ammoniacal liquor-ammonium fluid; Wherein, NH in the said 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 the surfactant SDS of 1.35g Sodium Silicofluoride 98min, 0.6g, the Dicyanodiamide of 2.4g respectively; 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 through 140 mesh sieves, and each section leaching time is 2 hours; After the solid-liquid separation, zinc 90.11 grams (zinc recovery 92.9%) in the gained zinc ammonia complex liquid;
(3) ammonia still process in advance: the leaching liquid that will obtain after will leaching is heated to 105 ℃ and analyses ammonia, c (NH in leaching liquid
3)=2.6mol/L adds 6g ammonium persulphate and stirring then;
(4) purification and impurity removal: add 2.7g potassium permanganate and stir 0.8h, add a small amount of polyacrylamide solution (4mg/L) and filter, filtrating is extraordinarily gone into sodium sulphite by 1.2 of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb; Temperature, 70 ℃, churning time 2h; Filter, filtrating adds KMnO
4Consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detect Fe, Mn is qualified), filters, and filtrating is extraordinarily gone into zinc powder by 2.5 of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and 60 ℃ of temperature are filtered;
(5) refinement treatment: in the liquid after purification and impurity removal is handled, add 4g ammonium phosphate, 0.08g surfactant SDS, obtain refined liquid;
(6) ammonia still process crystallization: the gained refined liquid inserted carry out ammonia still process in the ammonia distiller, 105 ℃ of solution temperatures are in the ammonia still process crystallisation process; Also add massfraction and be 5% octadecoic acid natrium solution 8ml, liquid zinc content in the detection at any time ammonia still process equipment, when zinc content 1% the time; Adding quality percentage composition is 30% sodium hydroxide solution 8ml in ammonia still process equipment, and zinc quality percentage composition is lower than at 0.3% o'clock, stops 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;
(7) drying and calcining: 105 ℃ of dryings of filter cake, 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. method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide 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:
Before leaching smoke of steel factory ash step, in pending smoke of steel factory ash, add white lime and obtain compound, and add water maintenance mixture moisture content 8-10%; Carry out admixture activation then; The amount of the white lime that is added by weight, is the 3-5% of smoke of steel factory ash;
Smoke of steel factory behind admixture activation ash is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in the said 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 the 0.3-0.5kg Sodium Silicofluoride 98min in every cubic metre of leaching agent;
Behind purification and impurity removal, carry out refinement treatment, method is: in the liquid after purification and impurity removal is handled, add ammonium phosphate and tensio-active agent, add-on is 1-3kg ammonium phosphate, a 10-50g tensio-active agent in the liquid after every cubic metre of purification and impurity removal is handled.
2. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 1; It is characterized in that: when leaching pending smoke of steel factory ash, in ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the tensio-active agent of 0.03-0.05kg.
3. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 2, it is characterized in that: the Dicyanodiamide that in ammoniacal liquor-ammonium fluid of every cubic metre, also is added with 0.5-1kg.
4. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 1, it is characterized in that: when the pending smoke of steel factory of leaching is grey, utilize wet ball grinding activation leaching.
5. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 4, it is characterized in that: guarantee that extraction time is 50～60 minutes in the ball mill, the ball mill outlet material is all through 140 mesh sieves.
6. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 1, it is characterized in that: the leaching liquid that will obtain after will leaching is heated to 95-105 ℃ and analyses ammonia, c (NH in leaching liquid
3)≤3mol/L, it is complete to carry out oxidation by adding 2-4kg ammonium persulphate and stirring in every cubic metre the leaching liquid then.
7. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 1; It is characterized in that: in the ammonia still process crystallisation process, liquid zinc content in the detection at any time ammonia still process equipment is when zinc content during at 1-1.5%; In ammonia still process equipment, add sodium hydroxide solution; Add-on is that every cubic metre of ammonia still process liquid adding quality percentage composition is 30% sodium hydroxide solution 3-5L, and zinc quality percentage composition is lower than at 0.3% o'clock, finishes ammonia still process.
8. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 7, it is characterized in that: also add massfraction in every cubic metre of ammonia still process liquid and be 5% octadecoic acid natrium solution 3-5L.
9. according to the said a kind of method of utilizing smoke of steel factory ash ammonia process to produce high-purity nm zinc oxide of claim 1, it is characterized in that: the temperature of said drying and calcining is 150-300 ℃.
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