A kind of method of utilizing low-grade zinc oxide ore to produce high-purity zinc oxide
Technical field
The present invention relates to a kind of method of utilizing low-grade zinc oxide ore to produce high-purity 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, the quality percentage composition that high pure zinc oxide generally refers to zinc oxide is 99.7% and above zinc oxide product, high pure 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 taking 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-volatile salt associating lixiviation process is produced zinc oxide) comprising at present: ammonia-volatile salt is leach liquor, material containing zinc is leached, and zinc ammonia element complex liquid makes zinc oxide product through purification, ammonia still process crystallization, drying and calcining.
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.
In sum, for the processing of low-grade zinc oxide ore, how in low zinc content material, effectively to leach zinc wherein, zinc and other compositions in low-grade zinc oxide ore are effectively recycled, overcome traditional method shortcoming simultaneously, become industry technical barrier urgently to be resolved hurrily.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, provide a kind of method of recycling of low-grade zinc oxide ore.
The technical solution used in the present invention is such: a kind of method of utilizing low-grade zinc oxide ore to produce high-purity zinc oxide, and be mainly ammonia process and prepare zinc oxide, comprise the following steps:
Leach pending low-grade zinc oxide ore, pre-ammonia still process, purification and impurity removal, ammonia still process crystallization and drying and calcining and obtain zinc oxide;
While leaching pending low-grade zinc oxide ore, leach with ammoniacal liquor-ammonium fluid; Wherein, NH
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 the ammoniacal liquor-ammonium fluid of every cubic metre, add 0.3-0.5kg Sodium Silicofluoride, after leaching, obtain leaching liquid;
Before purification and impurity removal step, carry out pre-ammonia still process: leaching liquid is heated to 90-95 DEG C of ammonia still process, remove part free ammonia, steam while being 2.5-3.5mol/L to ammonia concentration in liquid, add the ratio of 4-6kg to add ammonium persulphate to stir oxidation in every cubic metre of leaching liquid again, can also add calcium theoretical consumption 1.5-2 Neutral ammonium fluoride doubly, to go out calcium ion, liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters next step removal step.
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 highly purified zinc oxide, first need to ensure 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.For the recycling of low-grade zinc oxide ore, zinc " soaks and draws " and " removes totally " with impurity, is the technical problem of most critical.
In order to solve the problems of the technologies described above, the technology that 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, in leaching liquid, add appropriate Sodium Silicofluoride, to solve the problem of " soak and draw "; And before purification and impurity removal, increased the step of pre-ammonia still process, to solve the problem of " removing totally ".
Because the 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, in ore, 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.
Meanwhile, present inventor draws by great many of experiments: before purification and impurity removal, increase pre-ammonia still process step, reduce on the one hand the free ammonia in solution, lower the complexing coefficient of foreign ion, be beneficial to raising depuration quality, reduce and purify drug dosage.
Wherein:
The chemical equation of leaching step is:
ZnO+nNH
3 +H
2O→[Zn(NH
3)n]
2++2OH
-
ZnFe
2O
4 +nNH
3+4H
2O→[Zn(NH
3)n]
2++2Fe(OH)
3 ↓+2OH
-
ZnFe
2O
4 +nNH
3+H
2O→[Zn(NH
3)n]
2++Fe
2O
3↓+2OH
-
Zn
2SiO
4 +2nNH
3→ 2[Zn(NH
3)n]
2+ + SiO
4 4-
Zn(OH)
2 +nNH
3 →[Zn(NH
3)n]
2++2OH
-
ZnCO
3+nNH
3→[Zn(NH
3)n]
2++CO
3 2-
Wherein n=1~4;
The reaction that pre-ammonia still process process occurs:
NH
3·H
2O+NH
4HCO
3 —→2NH
3 ↑+CO
2 ↑+2H
2O
(NH
4)
4SiO
4 ——→ SiO
2↓+ 4NH
3↑ + 2H
2O
Ca
2+ +2NH
4F ——→ CaF
2↓+2NH
4 +
Utilize the pyrosol of pre-ammonia still process, add ammonium persulphate to stir and be oxidized, as Fe
3+, AsO
3 3-, Mn
2+produce co-precipitation, reduced follow-up purification difficulty, reduced reagent consumption amount, provide cost savings reaction equation:
5(NH
4)
2S
2O
8 +2Mn
2++8H
2O →2NH
4MnO
4+4(NH
4)
2SO
4 +16H
++ 6SO
4 2-
S
2O
8 2-+Mn
2++2NH
3·H
2O+H
2O→MnO(OH)
2↓ +2NH
4 2++2SO
4 2-+2H
+
S
2O
8 2-+2Fe
2+ +6NH
3·H
2O →2SO
4 2-+ 2Fe(OH)
3↓+6NH
4 +
As
2O
3+3H
2O→2H
3AsO
3
2H
3AsO
3+8Fe(OH)
3→(Fe
2O
3)
4As
2O
3·5H
2O↓+10H
2O
AsO
4 3-+Fe
3-→FeAsO
4↓
Zinc ammonia complex liquid after the oxidation of abovementioned steps ammonium persulphate, separation is again through sodium persulfide precipitation of heavy metals impurity, then through separating impurity such as potassium permanganate secondary oxidation iron, manganese, through zinc powder drastic reduction, purification obtains zinc ammino and closes refined liquid again; Reaction equation:
M
2++ S
2→ MS ↓ M represents Cu
2+, Pb
2+, Cd
2+, Ni
2+hg
2+plasma
As
3+ + S
2-→As
2S
3↓
3Fe
2+ + MnO
4 - + 7H
2O → MnO
2 ↓+ 3Fe(OH)
3↓ + 5H
+
3Mn
2+ + 2MnO
4 - +2H
2O → 5MnO
2↓ +4H
+
Y
2++ Zn → Zn
2+wherein Y representative of+Y: Cu
2+, Pb
2+, Cd
2+, Ni
2+plasma
The reaction equation of ammonia still process step:
3[Zn(NH
3)
4]CO
3 + H
2O ——→ZnCO
3·2Zn(OH)
2·H
2O ↓ + 12NH
3↑ + 2CO
2↑
The chemical equation of drying and calcining:
ZnCO
3·2Zn(OH)
2·H
2O——→ 3ZnO +3H
2O↑ +CO
2
As preferably: while leaching pending low-grade zinc oxide ore, be also added with the Dicyanodiamide of 0.5-1kg and the tensio-active agent of 0.03-0.05kg in the ammoniacal liquor-ammonium fluid of every cubic metre.
The surface energy of decreasing by surfactant solution, with Sodium Silicofluoride mating reaction, increases soaking and permeating, dissolving and the leaching of promotion zinc zinc particle.
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: the leaching mode of low-grade zinc oxide ore, adopts wet-milling activation to leach.
As preferably: in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is during at 1-1.5%, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution adding is that to add quality percentage composition be 30% sodium hydroxide solution 3-5 liter to every cubic metre of ammonia still process liquid, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process.
In ammonia still process process, in the time that ammonia concentration is lower in zinc ammonia complex liquid, improve the pH value of liquid by increasing sodium hydroxid, make NH
4 +transfer free NH to
3molecule reaches quick deamination, the object of rapid crystallization.Crystallization velocity is faster, and the chance of impurity parcel crystal is just less, thereby improves the purity of xln.
As preferably: described drying and calcining temperature is 350-450 DEG C.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows:
Ammonia process is applied to the processing of low-grade zinc oxide ore, and existing ammonia process has been carried out to adaptation, in the time of leaching, add Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, improved on the one hand zinc leaching velocity and the leaching yield in low-grade zinc oxide ore; The present invention adopts the calcining temperature of 350-450 DEG C, and available zinc oxide purity can reach more than 99.7%, has very high economic worth; In addition, treatment process energy consumption of the present invention is low, efficiency is high, leaching agent recycle.Soak slag through leaching the end of processing, do not destroy original mineral composition structure, still can brickmaking etc. have reached economic environmental protection dual purpose.
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 zinc oxide:
(1) leaching: by 500g low-grade zinc oxide ore 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 DEG C; After solid-liquid separation, 68.5 grams, zinc in gained zinc ammonia complex liquid; The leaching yield of zinc oxide ore zinc is 88.5%;
(2) pre-ammonia still process: leaching liquid is heated to 90 DEG C of ammonia still processs, remove part free ammonia, steam while being 2.5mol/L to ammonia concentration in liquid, add the ratio of 5kg to add ammonium persulphate in every cubic metre of leaching liquid again, liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step;
(3) purification and impurity removal: add 2.1g potassium permanganate to stir 0.5h in the liquid after pre-ammonia still process, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 DEG C, churning time 2h, filters, and filtrate adds KMnO
4consumption is 2.7 times of Fe amount, and 80 DEG C 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 DEG C 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;
(5) drying and calcining: 105 DEG C of filter cakes are dry, obtain powder, through 450 DEG C of retort furnace calcining 40min, sampling detects and obtains purity ZnO%=99.70%, specific surface area 72m
2the high-purity 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) leaching: by 500g zinc oxide ore 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 Sodium Silicofluoride, SDS and Dicyanodiamide by the amount of Dicyanodiamide of the surfactant SDS, the 0.5kg that add 0.5kg Sodium Silicofluoride, 0.05kg in every cubic metre of leaching agent respectively; In the time of leaching, adopt ball milling, and ensure 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 DEG C; 42.7 grams, zinc in gained zinc ammonia complex liquid; The leaching yield 88.3% of zinc oxide ore zinc;
(2) pre-ammonia still process: leaching liquid is heated to 95 DEG C of ammonia still processs, remove part free ammonia, steam while being 3.5mol/L to ammonia concentration in liquid, then add the ratio of 4kg to add ammonium persulphate in every cubic metre of leaching liquid, liquid after pre-ammonia still process is carried out to solid-liquid separation, and solution enters purification and impurity removal step;
(3) purification and impurity removal: add 1.28g potassium permanganate to stir 0.5h in the liquid after pre-ammonia still process, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 DEG C, churning time 2h, filters, and filtrate adds KMnO
4consumption is 3.5 times of Fe amount, and 80 DEG C 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 0.6MPa/cm in ammonia distiller
2108 DEG C of solution temperatures, in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is 1% time, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution adding is that to add quality percentage composition be 3 liters of 30% sodium hydroxide solutions to every cubic metre of ammonia still process liquid, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process, and the emulsion obtaining carries out solid-liquid separation, filter cake is by the washing of liquid-solid ratio 5:1 clear water, washing time 1h, refilters separation, obtains filter cake;
(5) drying and calcining: 105 DEG C of filter cakes are dry, obtain powder, through 420 DEG C of retort furnace calcining 50min, sampling detects and obtains purity ZnO%=99.73%, specific surface area 80m
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) leaching: by 1t zinc oxide ore 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 Sodium Silicofluoride, SDS and Dicyanodiamide by the amount of Dicyanodiamide of the surfactant SDS, the 1kg that add 0.4kg Sodium Silicofluoride, 0.1kg in every cubic metre of leaching agent respectively; In the time of leaching, adopt ball milling, and ensure 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 DEG C; After solid-liquid separation, 119.95 kilograms, zinc in gained zinc ammonia complex liquid; The leaching yield of zinc oxide ore zinc is 88.19%;
(2) pre-ammonia still process: the leaching liquid obtaining after leaching is heated to 105 DEG C and analyses ammonia, until c (NH in leaching liquid
3)=2.5mol/L, then by adding 6kg ammonium persulphate in the leaching liquid of every cubic metre and stirring;
(3) purification and impurity removal: add 3.6kg potassium permanganate to stir 0.8h in the liquid after pre-ammonia still process, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of precipitate C u, Cd, the required sodium sulphite of Pb, temperature, 70 DEG C, churning time 2h, filters, and filtrate adds KMnO
4consumption is 3.5 times of Fe amount, and 80 DEG C 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 0.8MPa/cm in ammonia distiller
2108 DEG C of solution temperatures, in ammonia still process crystallisation process, detect at any time liquid zinc content in ammonia still, when the mass content of zinc is 1.5% time, in ammonia still process equipment, add sodium hydroxide solution, the sodium hydroxide solution adding is that to add quality percentage composition be 5 liters of 30% sodium hydroxide solutions to every cubic metre of ammonia still process liquid, zinc quality percentage composition lower than 0.3% time, finishes ammonia still process, and the emulsion obtaining carries out solid-liquid separation, filter cake is by the washing of liquid-solid ratio 5:1 clear water, washing time 1h, refilters separation, obtains filter cake;
(5) drying and calcining: 105 DEG C of filter cakes are dry, obtain powder, through 350 DEG C of retort furnace calcining 45min, sampling detects and obtains purity ZnO%=99.83%, specific surface area 83m
2the high-purity zinc oxide powder of/g.