CN102863011B - Method of using low-grade zinc oxide ore to produce high-purity nano zinc oxide by means of ammonia process - Google Patents

Method of using low-grade zinc oxide ore to produce high-purity nano zinc oxide by means of ammonia process Download PDF

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CN102863011B
CN102863011B CN201210358094.0A CN201210358094A CN102863011B CN 102863011 B CN102863011 B CN 102863011B CN 201210358094 A CN201210358094 A CN 201210358094A CN 102863011 B CN102863011 B CN 102863011B
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zinc oxide
leaching
low
ammonia
oxide ore
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CN102863011A (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 of using low-grade zinc oxide ore to produce high-purity nano zinc oxide by means of the ammonia process. The method includes: using slaked lime of 3-5% mass of the low-grade zinc oxide ore for activating before leaching, using ammonia water-ammonium bicarbonate solution as leaching agent, adding 0.3-0.5kg of sodium fluorosilicate into per stere of the leaching agent for leaching, purifying for impurity removal, and refining. On one hand, efficient leaching of the low-grade zinc oxide ore is realized, high-purity zinc oxide with large specific surface area can be obtained at low calcinations temperature, and extremely high practical value and economic value are obtained; and on the other hand, the treatment method is low in energy consumption and high in efficiency. Valuable and poisonous heavy metal in the low-grade zinc oxide ore can be leached out for use and cleaned by means of water washing, and accordingly economy, environment friendliness and reasonable utilization of renewable resources are realized.

Description

A kind of method of utilizing low-grade zinc oxide ore ammonia process to produce high-purity nm 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 nm zinc oxide.
Background technology
The production of zinc oxide product at present is generally carried out roasting with the high ore deposit of zinc content and is become zinc baking sand to make raw material, because it is higher containing zinc rate, lixiviate is relatively easy.Along with exploitation all the year round, higher-grade mineral resources is fewer and feweri, and grade also reduces gradually, and now oneself starts to note the utilization of zinc oxide ore to people.But zinc oxide ore is conventionally containing zinc rate, lower (valuable element content Zn is below 30%; Pb 0.15%; Cu 0.008%; Mn 0.06%), and complicated component, there is gangue content ferric oxide, silicon oxide, calcium oxide, high (the about Fe respectively of content of magnesia in ore mainly with smithsonite, franklinite and lapis calaminaris 2o 34-7%; SiO 23-5%; CaO30-32%; MgO 7-8%).Comprehensive reutilization is worth little, and ore dressing, acidleach to zinc is all more difficult, and beneficiation cost is high, is the long-standing great technical barrier of domestic and international ore dressing.The method of the lixiviate of recent domestic to zinc oxide ore mostly, is used containing the solution of zinc sulfate of strong acid zinc oxide ore is leached, although zinc leaching rate increases, but the iron, the silicon amount that enter solution are also high, deironing difficulty, consumption amount of reagent is large, and it is many that washings is taken away zinc.China's publication, as CN1477217 A improves aforesaid method, first adopts the solution of sulfur acid zinc pH=3-4 to carry out neutrality leaching, then carries out low Ore Leaching technique.But franklinite, lapis calaminaris decompose slowly in low sour situation, and the problems such as leaching efficiency is low, cost is high, environmental pollution still exist.Many metallargists both domestic and external think, zinc content should not be processed by wet-leaching technique separately lower than 20% zinc oxide ore.
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%.
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%.
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 low-grade zinc oxide ore, and major cause is:
1. because mineral are low containing zinc rate, silt content is high, and 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, the conforming product rate of production is low, the low deficiency in economic performance of product price.
3. when conventional means leaches, the leaching yield of zinc ore is low, and waste is large, and the value of zinc ore is not used and embodies.
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 low-grade zinc oxide ore, 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 low-grade zinc oxide ore 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 low-grade zinc oxide ore ammonia leaching process to produce high-purity nm zinc oxide, comprises the following steps:
Leaching low-grade zinc oxide ore makes leaching mother liquor, pre-ammonia still process, purification and impurity removal, refinement treatment, ammonia still process crystallization and drying and calcining, wherein
Before leaching low-grade zinc oxide ore step, in pending low-grade zinc oxide ore, add white lime to obtain compound, and carry out admixture activation, the amount of the white lime adding, by weight, for the 3-5% of low-grade zinc oxide ore, in described compound, the quality percentage composition of water is controlled at 8-10%;
Low-grade zinc oxide ore after admixture activation is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, described leaching agent, wherein c (NH 3)=5.5-7mol/L, c (CO 3 2-)=0.95-1.2 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 low-grade zinc oxide ore, simultaneously, on the technique basis of existing ammonia process, before ammonia soaks step, increase pre-treatment, be in low-grade zinc oxide ore, 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 liquid refinement treatment.
First, obtain highly purified 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, 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 gangue content oxidation content of calcium and magnesium of low-grade zinc oxide ore is high, can not leach with acid system, not only acid consumes greatly, also makes a large amount of calcium, magnesium stripping, purifies difficulty.So the present invention adopts ammonia process to leach, dry hydrate plays loose, the fluffy use that turns into mineral, in ore, the ultrafine particulate of gangue also plays certain buffer action 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.
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 low-grade zinc oxide ore.In order to address the above problem, present inventor, by great many of experiments, after purification and impurity removal, increases liquid refinement treatment step, adds appropriate ammonium phosphate and tensio-active agent, in conjunction with the growth that can effectively suppress xln under high-speed stirring in refined liquid.
Wherein:
Chemical reaction in admixture activation process is:
Ca(OH) 2+ZnCO 3+ →CaCO 3↓+ Zn(OH) 2
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 formula that pre-ammonia still process occurs:
NH 3·H 2O + NH 4HCO 3→ 2NH 3↑ +CO 2↑ +2H 2O
(NH 44SiO 4 → SiO 2↓+ 2NH 3↑ + 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 formula of refined liquid processing:
3[Zn(NH 3)n] 2++ 2(NH 43PO 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) i2++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: the tensio-active agent (as SDS) that is also added with 0.03-0.05kg in ammoniacal liquor-ammonium fluid leaching agent of every cubic metre.
Decreasing by surfactant 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 low-grade zinc oxide ore of leaching, adopt wet ball grinding leaching.
Utilize wet ball grinding leaching, can destroy original crystalline network and carry out the leaching of activation limit, limit, thereby improve leaching efficiency.
As preferably: 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 ore crystalline network (mechanical activation) 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: the leaching liquid obtaining after leaching is heated to 95-105 ℃ and analyses ammonia (pre-ammonia still process), until c (NH in leaching liquid 3)≤3mol/L(reaches zinc ammino and closes near saturated solution, but does not make zinc separate out), then press 2-4kg/m 3add ammonium persulphate and stir and be oxidized completely.Type of heating adopts indirect heating.As c (NH 3when)≤3.5mol/L, zinc ammonia complex liquid approaches saturated, does not make zinc separate out simultaneously; When ammonia still process crystallization, temperature is controlled in 105 ℃, the speed 600-900r/min that ammonia still process container stirs.
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; After pre-ammonia still process, add ammonium persulphate as oxygenant, except impurity such as de-iron, manganese.
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 is lower than 0.3% time, finish ammonia still process and (now finish ammonia still process, owing to containing part of sulfuric acid root in solution, form stable ammonium salt, continue ammonia still process nonsensical, and can produce zinc sulfate ammonium double salt precipitation, affect nano zine oxide quality product).
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.
As preferably: the wherein mixing ore deposit of one or more in smithsonite that described low-grade zinc oxide ore is is 8%~30% containing zinc massfraction, franklinite ore deposit, lapis calaminaris.
Method of the present invention goes for various low-grade zinc oxide ores, applied widely.
Two of object of the present invention, is to provide a kind of high purity and highly active 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 low-grade zinc oxide ore, 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 low-grade zinc oxide ore 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 nanometer zinc oxide precursor of the little and narrowly distributing 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.In low-grade zinc oxide ore, there are valency and harmful heavy metal all to be leached and utilize and through washing totally, reached the reasonable utilization of economic environmental protection and renewable resource.
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, own ammonium sulfate in binding soln, 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: Yunnan zinc oxide ore 1 #, its composition is: Zn15.48%. Fe18. 20%. Si027. 94%, its zinc thing coordinates and is divided into zinc carbonate 9.49%, zinc silicate 2. 12%. zinc sulphide 0. 7 3%, automolite 3.14 %.
Method for the preparation of high-purity nm zinc oxide:
(1) activation: get 500g zinc oxide ore 1 #, adding 15g white lime to obtain compound, and carry out admixture activation, in described compound, the quality percentage composition of water is controlled at 8%, and the admixture activation time is 36 hours;
(2) leaching: by the low-grade zinc oxide ore after admixture activation 1 #leach as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent 3volumetric molar concentration c (NH 3)=5.5mol/L, CO 3 2-volumetric molar concentration c (CO 3 2-)=1.2 mol/L adds Sodium Silicofluoride by the amount of adding 0.3kg Sodium Silicofluoride in every cubic metre of leaching agent in leaching agent; Adding up to leaching time is 3 hours, and temperature is 25-40 ℃; After solid-liquid separation, 69.7 grams, zinc in gained zinc ammonia complex liquid; The leaching yield of zinc oxide ore zinc is 90.1%;
(3) purification and impurity removal: add 2.1g potassium permanganate to stir 0.5h in the leaching liquid that obtains after leaching, 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) refinement treatment, in purification and impurity removal liquid after treatment, adds ammonium phosphate and tensio-active agent, and add-on is 1kg ammonium phosphate, 50g surfactant SDS in every cubic metre of purification and impurity removal liquid after treatment, obtains refined liquid;
(5) 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 the washing of liquid-solid ratio 5:1 clear water, 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%=99.76%; Tap density 0.26g/m 2, median size 14.2nm (XRD live width method), specific surface area 102m 2the high-purity nm Zinc oxide powder of/g.
Embodiment 2
Raw material: zinc oxide ore 2 #, its composition is: Zn9.67%. Fe19.33%. Si026. 63%, its zinc thing of CaO28.34% coordinates and is divided into zinc carbonate 12.28%, zinc silicate 2. 37%. zinc sulphide 0. 8 2%, automolite 3. 20%.
Method for the preparation of high-purity zinc oxide:
(1) activation: get 500g zinc oxide ore 2 #, adding 25g white lime to obtain compound, and carry out admixture activation, in described compound, the quality percentage composition of water is controlled at 9%, and the admixture activation time is 36 hours;
(2) leaching: by the zinc oxide ore after admixture activation 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-)=1.2 mol/L, adds respectively the surfactant SDS of 0.5kg Sodium Silicofluoride, 0.05kg, the Dicyanodiamide of 0.5kg in every cubic metre of leaching agent; In the time of leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 60 minutes, ball mill outlet material is all by 140 mesh sieves, and adding up to leaching time is 3 hours, and temperature is 25-40 ℃; 44.28 grams, zinc in gained zinc ammonia complex liquid; The leaching yield 91.58% of zinc oxide ore zinc;
(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 by adding 4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring;
(4) purification and impurity removal: add 1.33g potassium permanganate to stir 0.5h in the leaching liquid that obtains after leaching, 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) refinement treatment, in purification and impurity removal liquid after treatment, adds ammonium phosphate and tensio-active agent, and add-on is 3kg ammonium phosphate, 10g surfactant SDS in every cubic metre of purification and impurity removal liquid after treatment, obtains refined liquid;
(6) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process, vapour pressure import 0.6MPa/cm in ammonia distiller 2108 ℃ of solution temperatures, in ammonia still process crystallisation process, in every cubic metre of ammonia still process liquid, also adding massfraction is 5% sodium stearate solution 3L, detect at any time liquid zinc content in ammonia still process equipment, when zinc content is 1% time, 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 3 liters of 30% sodium hydroxide solutions, zinc quality percentage composition is lower than 0.3% time, finish ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by the washing of liquid-solid ratio 5:1 clear water, washing time 1h, refilter separation, obtain filter cake;
(7) drying and calcining: 100 ℃ of filter cakes are dry, obtain powder, through 150 ℃ of retort furnace calcining 70min, sampling detects and obtains purity ZnO%=99.89%; Tap density 0.21g/m 2, median size 12.5nm (XRD live width method), specific surface area 115m 2the high-purity zinc oxide powder of/g.
Embodiment 3
Raw material: zinc oxide ore 3 #, its composition is: Zn13.6%. Fe18.67%. Si027.83%, its zinc thing of CaO29.92% coordinates and is divided into zinc carbonate 7.96%, zinc silicate 2. 21%. zinc sulphide 0.76%, automolite 2.67%.
Method for the preparation of high-purity zinc oxide:
(1) activation: get 1t zinc oxide ore 3 #, adding 40kg white lime to obtain compound, and carry out admixture activation, in described compound, the quality percentage composition of water is controlled at 10%, and the admixture activation time is 42 hours;
(2) leaching: by the zinc oxide ore after admixture activation 3 #leach as leaching agent with 3000L 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 0.4kg Sodium Silicofluoride, 0.1kg, the Dicyanodiamide of 1kg in every cubic metre of leaching agent; 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, and adding up to leaching time is 3.5 hours, and temperature is 25-40 ℃; 124.86 kilograms, zinc in gained zinc ammonia complex liquid, the zinc leaching rate 91.8% of low-grade zinc oxide;
(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 by adding 2kg ammonium persulphate in the leaching liquid of every cubic metre and stirring;
(4) purification and impurity removal: add 3.75kg potassium permanganate to stir 0.8h in the leaching liquid that obtains after leaching, 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) refinement treatment, in purification and impurity removal liquid after treatment, adds ammonium phosphate and tensio-active agent, and add-on is 1kg ammonium phosphate, 50g surfactant SDS in every cubic metre of purification and impurity removal liquid after treatment, obtains refined liquid;
(6) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process, vapour pressure import 0.8MPa/cm in ammonia distiller 2108 ℃ of solution temperatures, in ammonia still process crystallisation process, in every cubic metre of ammonia still process liquid, also adding massfraction is 5% sodium stearate solution 5L, detect at any time liquid zinc content in ammonia still process equipment, when zinc content is 1.5% time, 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 5 liters of 30% sodium hydroxide solutions, zinc quality percentage composition is lower than 0.3% time, finish ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by the washing of liquid-solid ratio 5:1 clear water, washing time 1h, refilter separation, obtain filter cake;
(7) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 220 ℃ of retort furnace calcining 70min, sampling detects and obtains purity ZnO%=99.83%; Tap density 0.26g/m 2, median size 12.9nm (XRD live width method), specific surface area 106m 2the high-purity nm Zinc oxide powder of/g.

Claims (9)

1. utilize low-grade zinc oxide ore ammonia process to produce a method for high-purity nm zinc oxide, comprise the following steps:
Leaching low-grade zinc oxide ore, purification and impurity removal, ammonia still process crystallization and drying and calcining, is characterized in that:
Before leaching low-grade zinc oxide ore step, in pending low-grade zinc oxide ore, add white lime to obtain compound, and carry out admixture activation, the amount of the white lime adding, by weight, for the 3-5% of low-grade zinc oxide ore, in described compound, the quality percentage composition of water is controlled at 8-10%;
Low-grade zinc oxide ore after admixture activation is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, c (NH in described leaching agent 3)=5.5-7mol/L, c (CO 3 2-)=0.95-1.2 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 low-grade zinc oxide ore ammonia process to produce high-purity nm zinc oxide according to claim 1, it is characterized in that: while leaching pending low-grade zinc oxide ore, 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 low-grade zinc oxide ore 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 low-grade zinc oxide ore ammonia process to produce high-purity nm zinc oxide according to claim 1, is characterized in that: in the time of the pending low-grade zinc oxide ore of leaching, utilize wet ball grinding leaching.
5. a kind of method of utilizing low-grade zinc oxide ore 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 low-grade zinc oxide ore 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)≤3.5mol/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 low-grade zinc oxide ore 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 3-5 liter, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process.
8. a kind of method of utilizing low-grade zinc oxide ore 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 low-grade zinc oxide ore 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 ℃.
CN201210358094.0A 2012-09-25 2012-09-25 Method of using low-grade zinc oxide ore to produce high-purity nano zinc oxide by means of ammonia process Expired - Fee Related CN102863011B (en)

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