CN102828035A - Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process - Google Patents
Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process Download PDFInfo
- Publication number
- CN102828035A CN102828035A CN2012103581252A CN201210358125A CN102828035A CN 102828035 A CN102828035 A CN 102828035A CN 2012103581252 A CN2012103581252 A CN 2012103581252A CN 201210358125 A CN201210358125 A CN 201210358125A CN 102828035 A CN102828035 A CN 102828035A
- Authority
- CN
- China
- Prior art keywords
- acid leaching
- ammonia
- zinc
- leaching slag
- zinc oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting an ammonia process. When the electrolytic zinc acid leaching slag to be treated is leached, 0.3-0.5kg of sodium fluosilicate is added into per cubic meter of ammonia water-ammonium bicarbonate solution, 30-60kg of slaked lime is added into per cubic meter of leaching liquid after leaching, decarbonization reaction is carried out, the ammonia process is applied to treatment on the electrolytic zinc acid leaching slag, and adaptability improvement is carried out on the existing ammonia process; and a decarbonization step is added after a leaching step, and sodium fluosilicate, a surface active agent and dicyanodiamine are added while leaching, on the one hand, the zinc in the electrolytic zinc acid leaching slag is fully recycled; on the other hand, zinc oxide with larger specific surface area can be obtained, and purity of the obtained zinc oxide can reach up to 99.7%, thus the method disclosed by the invention has higher economic value; besides, the method disclosed by the invention has low energy consumption and high efficiency, the treated electrolytic zinc acid leaching slag is changed into general waste from the electrolytic zinc acid leaching slag which is taken as high-risk waste, and the effects of being economic and environment-friendly can be achieved.
Description
Technical field
The present invention relates to a kind of working method of zinc oxide, particularly a kind of working method of high pure zinc oxide.
Background technology
Zinc hydrometallurgy mainly adopts roasting-leaching-electrolytic production technique at present; Zinc content is generally 6-9% by mass ratio in the electrolytic zinc acid leaching slag of discharging; What have can reach 20%, and material phase analysis and X diffraction analysis that acid leaching residue is done show that zinc is mainly with ZnFe in the leached mud
2O
4Form exists, simultaneously, the content 6-12% of sulphur, wherein sulfate radical content is 15-30%, ore deposit, various places calcium, magnesium salts content difference also contain Cu simultaneously
2+, Pb
2+, Cd
2+, Ni
2+, Hg
2+, As
3+Or As
5+Plasma, its roughly mass content be about: copper 1%, plumbous 0.8%, iron 4%, silicon 3%, arsenic 0.3%, silver 0.003%, calcium 12%, magnesium 3%).In order to reclaim these zinc, present treatment process has two kinds of pyrogenic process and wet methods, and pyrogenic process is rotary kiln evaporation method (waelz process) and fuming furnace volatilization method, is the one Chinese patent application of CN101886180 like publication number.Wet method has hot acid to leach or high-temperature pressurizing leaches.The pyrogenic attack technical process is long, and the ME amount is big, and investment is high, and Working environment is relatively poor, needs to consume a large amount of coal-fired or metallurgical coking coal, and benefit is low, and environmental pollution is big.Therefore leach with hot acid usually or high pressure leaches, these methods still exist shortcoming to be: 1. consume a large amount of acid, 2. the pressure of deironing is big, needs to consume more reagent, 3. high-temperature high-pressure apparatus seriously corroded, and the complex equipments investment is bigger; 4. running cost is high, deficiency in economic performance.5. last slag of discharging is an acid slag, brings new pollution to environment, have to take to solidify landfill, not only contaminate environment, and waste resource.
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; The quality percentage composition that high pure zinc oxide generally is meant zinc oxide is 99.7% and above zinc oxide product; High-purity zinc oxide is the indispensable a kind of high-tech functional material of modern industry; 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; Still 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: ammonia-carbon ammonium is a leach liquor; Material containing zinc is leached, and the zinc ammino closes liquid and makes zinc oxide product through purification, ammonia still process crystallization, drying and calcining.
This traditional ammonia process prepares the processing that zinc oxide never is applied to electrolytic zinc acid leaching slag, and major cause is:
1) a large amount of calcium sulfate parcels are arranged in the electrolytic zinc acid leaching slag and make zinc wherein leach difficulty, the recovery is low
2) contain the sulfate radical of 15-30% in the electrolytic zinc acid leaching slag, a large amount of ammonia are converted into ammonium sulfate, and the ammonia consumption is high
3) the zinc ammonia complex liquid direct purification after will leaching, owing to still have a large amount of free ammonias in the liquid, impurity complexing power is strong, purifies to be difficult to thoroughly finally influence the purity of zinc oxide product.
4) owing to have a large amount of sulfate radicals in the solution, in the ammonia still process process, will separate out part of sulfuric acid zinc ammonium double salt, influence zinc oxide purity.
In addition, ammonia leaching process is produced zinc oxide at present, and xln is a zinc subcarbonate; Calcine then, for obtaining high purity product, need be for keeping the sufficiently high decomposition temperature of zinc subcarbonate; General temperature is more than 500 ℃; Like application number is 200610130477.7 one Chinese patent application, and high-temperature calcination will have influence on the specific surface area of zinc oxide, influence the activity of zinc oxide product.
In sum; Processing for electrolytic zinc acid leaching slag; How in the material of the tailings of low zinc content and high impurity content, effectively leach zinc wherein; And obtain highly purified zinc oxide, and overcome the traditional pyrogenic process and the shortcoming of wet method simultaneously, become the industry and need to be resolved hurrily and unsolved technical barrier.
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 electrolytic zinc acid leaching slag is provided and prepares the method for high pure zinc oxide.
The technical scheme that the present invention adopted is: a kind of method of utilizing the electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide may further comprise the steps successively:
Leach pending electrolytic zinc acid leaching slag, purification and impurity removal, ammonia still process crystallization and drying and calcining, it is characterized in that:
Leach pending electrolytic zinc acid leaching slag, leach with ammoniacal liquor-ammonium fluid during leaching; Wherein, NH
3Volumetric molar concentration be 5-6mol/L, CO
2Volumetric molar concentration be 0.85-1.0 mol/L, and in ammoniacal liquor-ammonium fluid of every cubic metre, add the 0.3-0.5kg Sodium Silicofluoride 98min, obtain leaching liquid after the leaching;
After the leaching, the decarburization that heats up, its method is: in every cubic metre of leaching liquid, add 30-60kg white lime, carry out decarburizing reaction, temperature of reaction is more than 60 ℃, control CO
3 2-Concentration≤0.3mol/L, filtering separation then.
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.
Obtain highly purified zinc oxide; Need guarantee that at first the zinc in the electrolytic zinc acid leaching slag can leach as much as possible; Can improve the recovery of zinc so on the one hand, on the other hand, the content of zinc is big more in leach liquor; Foreign matter content is also just more little, could guarantee under equal processing condition, to make more highly purified zinc oxide.
The present invention at first is applied to the processing to electrolytic zinc acid leaching slag with the technology that existing ammonia process prepares zinc oxide, simultaneously, on the technology basis of existing ammonia process, in leaching liquid, adds an amount of Sodium Silicofluoride 98min; And increased the step of decarburization.
Owing to contain a large amount of calcium sulfate (15-30%) in the electrolytic zinc acid leaching slag; Calcium sulfate causes acid environment to be difficult to leach to MOX skinning buffer actions such as zinc oxide, so the present invention adopts ammonia process to leach; Under ammonia-carbon ammonium associating liquid effect; Calcium sulfate is converted into lime carbonate and calcium hydroxide, in switching process, realizes that successively peeling off with zinc ammino contract of calcium sulfate goes on foot; But ultrafine particulates such as calcium hydroxide leach complexing and also play certain inhibition; 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; Realize ultrafine particulate layering come-up, thereby the zinc exposure is immersed in the liquid.
Decarburization is fallen and is added ammonium persulphate in the ammonia process as oxygenant.
Increase decarburization and fall the ammonia step, can eliminate too much free ammonia on the one hand, reduce the complex ability of foreign ion, make foreign ion be able to remove, be beneficial to the raising depuration quality, reduce purifying drug dosage; Can remove carbanion in the solution on the other hand, make to help obtaining the presoma zinc hydroxide deposition that the nucleus size is littler, decomposition temperature is lower in the follow-up deamination hydrolytic process of complex liquid.
Simultaneously, the present inventor draws through a large amount of experiments:, can provide on the one hand to replace CO as decarburizer with white lime
3 2-Ligand OH
-, make CO
3 2-Eliminate and form CaCO
3Deposition, strong slightly in addition alkaline environment help the ferrous metallic impurity deposition that waits, for follow-up purification creates conditions.On the other hand, white lime is inexpensive.
Wherein:
The chemical equation of leaching step is:
ZnO+nNH
3?+H
2O→［Zn(NH
3)n］
2++2OH
-
ZnFe
2O
4?+nNH
3+4H
2O→［Zn(NH
3)n］
2++2Fe(OH)
3?↓+2OH
-
ZnFe
2O
4?+nNH
3+H
2O→［Zn(NH
3)n］
2++Fe
2O
3↓+2OH
-
Zn
2SiO
4?+2nNH
3→?2［Zn(NH
3)n］
2+?+?SiO
4 4-
Zn(OH)
2?+nNH
3?→［Zn(NH
3)n］
2++2OH
-
Zn+nNH
3?+2H
2O→［Zn(NH
3)n］
2++H
2+2OH
-
ZnSO
4+nNH
3→［Zn(NH
3)n］
2++SO
4 2-
N=1～4 wherein;
Chemical reaction in the decarbonation process is:
Ca(OH)
2﹦?Ca
2++2OH
-
Ca
2++?CO
3 2-→CaCO
3↓
NH
3H
2O +?NH
4HCO
3→?2NH
3↑?+CO
2↑?+2H
2O
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 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→?Zn(OH)
2↓+?CO
2↑?+?4NH
3↑；
The chemical equation of drying and calcining:
Zn(OH)
2→ZnO?+?H
2O↑
As preferably: when leaching pending electrolytic zinc acid leaching slag, in ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the Dicyanodiamide of 0.5-1kg and the tensio-active agent of 0.03-0.05kg.
Tensio-active agent and Sodium Silicofluoride 98min mating reaction are played ultrafine particulates such as calcium hydroxide are disperseed, peel off effect.Improve the recovery of zinc, thereby the relative concentration that improves zinc in the leaching liquid more helps the preparation of high pure zinc oxide.
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 electrolytic zinc acid leaching slag of leaching, carry out the ball milling leaching simultaneously.
Utilize the ball milling leaching, destroy the parcel of ultrafine particulate, can improve leaching velocity and leaching yield zinc with mechanical force.
As preferably: in every cubic metre of aforementioned liquids, add the 3-4kg ammonium persulphate during decarburization.
As preferably: after the decarbonation process, add an amount of Neutral ammonium fluoride deliming in the solution, add-on be calcium ion theoretical value in the solution 1.5-2 doubly;
As preferably: add sodium sulphite in the waste liquid after the ammonia still process crystallization and sink zinc, obtain zinc sulphide filter cake and liquid portion after the separation; Add white lime at liquid portion and obtain mixed solution, in whipping process, add tensio-active agent; Mixed solution is carried out the ammonia still process crystallization, and Tc stirs in the ammonia still process process for not being higher than 105 ℃, and stirring velocity is 300-500 rev/min, and the ammonia of effusion reclaims through cooling, obtains the calcium sulfate powder and carries out rinsing, drying, obtains the calcium sulfate product.
Like this, on the one hand the zinc that is not utilized in the crystallization waste liquid is further recycled and obtained zinc sulphide; Can reclaim ammonia on the other hand and utilize again, be used for ammonia and soak etc., practice thrift cost, be beneficial to environmental protection.
Because technical scheme of the present invention; Behind the ammonia still process crystallisation step; The xln that obtains mainly is a zinc hydroxide, and the decomposition temperature of zinc hydroxide is lower than zinc carbonate, adopts 150-300 ℃ temperature to calcine; Can obtain purity 99.7% and above and zinc oxide product bigger serface, specific surface area is generally at 80m/g
2More than.
In sum; Owing to adopted technique scheme; The invention has the beneficial effects as follows: ammonia process is applied to the processing to the electrolysis acid leaching residue, and existing ammonia process has been carried out adaptation, increasing decarbonation process after the leaching and when leaching, adding Sodium Silicofluoride 98min, tensio-active agent and Dicyanodiamide; Make on the one hand electrolytic zinc acid leaching slag zinc fast, as far as possible fully leach, make that the zinc in the electrolytic zinc acid leaching slag is fully recycled; On the other hand, the present invention preferably adopts lower calcining temperature, can obtain can reaching more than 99.7% than the zinc oxide while purity of bigger serface, has very high economic worth; In addition; Treatment process energy consumption of the present invention is low, efficient is high; Treated electrolytic zinc acid leaching slag; Become general waste (sulfate radical is recycled by-product calcium sulfate powder, and other heavy metals obtain reclaiming) by electrolytic zinc acid leaching slag (because a large amount of acid group and the soluble heavy metals of content) in the removal of impurities process, reached the effect of economic environmental protection as high-risk waste.
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:
A kind of method of utilizing the electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide may further comprise the steps successively:
(1) leaching: get 500 gram electrolytic zinc acid leaching slags (wherein, by quality ratio, containing zinc 8.6%, copper 1.03%, calcium sulfate 32%, cadmium 0.05%, arsenic 0.03%), be milled to 200 orders; Produce 1500ml ammoniacal liquor-ammonium fluid as ammonia leaching solution, wherein NH
3Concentration is 6mol/L, CO
2Concentration is 1mol/L; In ammoniacal liquor-ammonium fluid of every cubic metre, add the 0.3kg Sodium Silicofluoride 98min; Electrolytic zinc acid leaching slag joins and carries out three sections leachings in the above-mentioned ammonia leaching solution, and each section leaching time is 2 hours, after the solid-liquid separation; Zinc 38.7 grams (zinc recovery 90.1%) in the gained zinc ammonia complex liquid, sulfate radical 41.72 grams in the zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: in the decarbonizer of belt stirrer, add 30kg white lime in every cubic metre of leaching liquid, indirect heating to 60 ℃ is worked as CO
3 2-During concentration=0.28mol/L, carry out solid-liquid separation;
(3) purification and impurity removal: add 0.5 gram sodium sulphite in the liquid after (2) step solid-liquid separation, stir 2 hours after-filtration, add 0.2 gram potassium permanganate, stir 2 hours after-filtration;
(4) ammonia still process crystallization: zinc ammonia complex liquid after will purifying filters post-heating ammonia still process, and ammonia distiller stirring velocity PM 600 changes, and treats in the liquid that the zinc oxide mass content is to stop ammonia still process at 0.5% o'clock; Filter then, obtain zinc hydroxide filter cake and filtrating;
(5) add the heavy zinc of sodium sulphite in the filtrating after the ammonia still process crystallization, the separation of reaction back obtains zinc sulphide filter cake and solution; Partly add white lime at solution, and stir and to obtain mixed solution, in whipping process, add tensio-active agent; Mixed solution is carried out the ammonia still process conversion make ammonium sulfate be converted into the calcium sulfate powder, the ammonia still process temperature stirs in the ammonia still process process for not being higher than 105 ℃; Stirring velocity is 300 rev/mins; The ammonia of overflowing reclaims through cooling, and the calcium sulfate powder carries out rinsing, drying, obtains the calcium sulfate powder product;
(6) drying and calcining: the deionized water that the zinc hydroxide filter cake after the filtration adds 200ml respectively carries out three washings; Add 0.05 gram sodium lauryl sulphate in the washing process in the first time, the zinc hydroxide filter cake after the press filtration is put into retort furnace 300 degree calcinings 3 hours.
The zinc oxide quality percentage composition of gained is 99.7%, specific surface area 80m
2/ g.
Embodiment 2
A kind of method of utilizing the electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide may further comprise the steps successively:
(1) leaching: get 500 gram electrolytic zinc acid leaching slags (wherein, by quality ratio, containing zinc 9.2%, copper 1.13%, calcium sulfate 30%, cadmium 0.056%, arsenic 0.031%); Produce 1500ml ammoniacal liquor-ammonium fluid as ammonia leaching solution, wherein NH
3Concentration is 5mol/L, CO
2Concentration is 0.85mol/L; In ammoniacal liquor-ammonium fluid of every cubic metre, add the 0.5kg Sodium Silicofluoride 98min, in ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the surfactant SDS of 0.04kg, in ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the Dicyanodiamide of 0.8kg; Electrolytic zinc acid leaching slag joins and carries out three sections leachings in the above-mentioned ammonia leaching solution; The while ball milling, each section leaching time is 2.5 hours, after the solid-liquid separation; Zinc 41.9 grams (zinc recovery 91.2%) in the gained zinc ammonia complex liquid, sulfate radical 58.2 grams in the zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: in the decarbonizer of belt stirrer, add 60kg white lime in every cubic metre of leaching liquid, indirect heating to 90 ℃ is worked as CO
3 2-During concentration=0.26mol/L, discharge mixed solution and add the 4kg ammonium persulphate and stir, continue decarburization and oxidation and remove de-iron, manganese etc., treat CO by every cubic metre
3 2-Carry out solid-liquid separation during=0.04mol/L again, the time of whole stirring decarburization is 12 hours;
(3) purification and impurity removal: add 0.56 gram sodium sulphite in the liquid after (2) step solid-liquid separation, stir 2 hours after-filtration, add 0.2 gram potassium permanganate, stir 2 hours after-filtration;
(4) ammonia still process crystallization: zinc ammonia complex liquid after will purifying filters post-heating ammonia still process, and ammonia distiller stirring velocity PM 600 changes, and treats in the liquid that the zinc oxide mass content is to stop ammonia still process at 0.5% o'clock; Filter then, obtain zinc hydroxide filter cake and filtrating;
(5) drying and calcining: the deionized water that the zinc hydroxide filter cake after the filtration adds 200ml respectively carries out three washings; Add 0.05 gram sodium lauryl sulphate in the washing process in the first time, the zinc hydroxide filter cake after the press filtration is put into retort furnace 150 degree calcinings 4.2 hours.
The flat quality percentage composition of the zinc oxide of gained is 99.85%, specific surface area 86m
2/ g.
Embodiment 3
A kind of method of utilizing the electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide may further comprise the steps successively:
(1) leaching: get 1500 gram acid leaching residues (zinc 9.0%, copper 0.80%, calcium sulfate 30%, cadmium 0.040%, arsenic 0.25%, silicon 3%, arsenic 0.3%, silver 0.003%, magnesium 3%); Produce 1500ml ammoniacal liquor-ammonium fluid as ammonia leaching solution, wherein NH
3Concentration is 5mol/L, CO
2Concentration is 0.95mol/L, in ammoniacal liquor-ammonium fluid of every cubic metre, adds the 0.3kg Sodium Silicofluoride 98min, in ammoniacal liquor-ammonium fluid of every cubic metre, also is added with the surfactant SDS of 0.05kg; In ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the Dicyanodiamide of 0.5kg; Electrolytic zinc acid leaching slag joins and carries out three sections leachings in the above-mentioned ammonia leaching solution, the while ball milling, and each section leaching time is 3.0 hours; After the solid-liquid separation; Obtain leaching liquid, zinc 123.66 grams (zinc recovery 91.6%) in the gained zinc ammonia complex liquid, sulfate radical 165.0 grams in the zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: in the decarbonizer of belt stirrer, add 55kg white lime in every cubic metre of leaching liquid, indirect heating to 95 ℃ is worked as CO
3 2-During concentration=0.3mol/L, discharge mixed solution and add the 3.5kg ammonium persulphate and stir, continue decarburization and oxidation and remove de-iron, manganese etc., treat CO by every cubic metre
3 2-Carry out solid-liquid separation during=0.04mol/L again;
(3) purification and impurity removal: add 1.56 gram sodium sulphite in the liquid after (2) step solid-liquid separation, stir 2 hours after-filtration, add 0.5 gram potassium permanganate, stir 2.5 hours after-filtration;
(4) ammonia still process crystallization: zinc ammonia complex liquid after will purifying filters post-heating ammonia still process, treats in the liquid that the zinc oxide mass content is to stop ammonia still process at 0.5% o'clock; Filter then, obtain zinc hydroxide filter cake and filtrating;
(5) drying and calcining: the deionized water that the zinc hydroxide filter cake after the filtration adds 600ml respectively carries out three washings; The sodium lauryl sulphate that in first time washing process, adds 0.12 gram/cubic meter, the zinc hydroxide filter cake after the press filtration are put into retort furnace 280 and are spent and calcined 3.8 hours.
The zinc oxide quality percentage composition of gained is 99.75%, specific surface area 92m
2/ g.
Embodiment 4
A kind of method of utilizing the electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide may further comprise the steps successively:
(1) leaching: 120 tons of raw materials come from Yunnan Chihong Zinc & Germanium Co., Ltd.'s Huize and smelt the acid leaching residue that old factory many decades accumulates, zinc 11.2%, copper 0.91%, lead 1.3%, acid group 27.6%, cadmium 0.03% in the raw material;
Produce 360 cubic metres of ammoniacal liquor-ammonium fluids as ammonia leaching solution, wherein NH
3Concentration is 5.5mol/L, CO
2Concentration is 0.90mol/L, in ammoniacal liquor-ammonium fluid of every cubic metre, adds the 0.36kg Sodium Silicofluoride 98min, in ammoniacal liquor-ammonium fluid of every cubic metre, also is added with the surfactant SDS of 0.045kg; In ammoniacal liquor-ammonium fluid of every cubic metre, also be added with the Dicyanodiamide of 0.42kg; Electrolytic zinc acid leaching slag joins and carries out three sections leachings in the above-mentioned ammonia leaching solution, the while ball milling, and each section leaching time is 3.5 hours; After the solid-liquid separation; Obtain leaching liquid, 12.1 tons on zinc (zinc recovery 90.0%) in the gained zinc ammonia complex liquid, sulfate radical is 13.6 tons in the zinc ammonia complex liquid;
(2) decarburization: the leaching liquid that (1) step the is obtained decarburization that heats up: in the decarbonizer of belt stirrer, add 56kg white lime in every cubic metre of leaching liquid, indirect heating to 97 ℃ is worked as CO
3 2-During concentration=0.26mol/L, discharge mixed solution and add the 3.6kg ammonium persulphate and stir, continue decarburization and oxidation and remove de-iron, manganese etc., treat CO by every cubic metre
3 2-Carry out solid-liquid separation during=0.04mol/L again;
(3) purification and impurity removal: add 1.5kg sodium sulphite at every cubic metre of zinc ammonia complex liquid, stir 2 hours after-filtration, every cubic metre of zinc ammonia complex liquid adds 0.3kg potassium permanganate;
(4) ammonia still process crystallization: zinc ammonia complex liquid after will purifying filters post-heating ammonia still process, and ammonia distiller stirring velocity PM 580 changes, and treats in the liquid that the zinc oxide mass content is to stop ammonia still process at 0.5% o'clock; Filter then, obtain zinc hydroxide filter cake and filtrating;
(5) drying and calcining: the ion exchanged water that the filter cake after the filtration adds by liquid-solid ratio 5:1 carries out three washings, adds 1.25 gram sodium lauryl sulphate in the washing process in the first time, and the zinc hydroxide filter cake after the press filtration is put into retort furnace 160 degree calcinings 2 hours.
The zinc oxide quality percentage composition of gained is 99.82%, specific surface area 85m
2/ g.
Claims (8)
1. method of utilizing the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure zinc oxide may further comprise the steps:
Leach pending electrolytic zinc acid leaching slag, purification and impurity removal, ammonia still process crystallization and drying and calcining, it is characterized in that:
Leach pending electrolytic zinc acid leaching slag, leach with ammoniacal liquor-ammonium fluid during leaching; Wherein, NH
3Volumetric molar concentration be 5-6mol/L, CO
2Volumetric molar concentration be 0.85-1.0 mol/L, and in ammoniacal liquor-ammonium fluid of every cubic metre, add the 0.3-0.5kg Sodium Silicofluoride 98min, obtain leaching liquid after the leaching;
After the leaching, the decarburization that heats up, its method is: in every cubic metre of leaching liquid, add 30-60kg white lime, carry out decarburizing reaction, temperature of reaction is more than 60 ℃, control CO
3 2-Concentration≤0.3mol/L, filtering separation then.
2. according to the said a kind of method of utilizing the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure zinc oxide of claim 1; It is characterized in that: when leaching pending electrolytic zinc acid leaching slag, 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 the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure 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 the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure zinc oxide of claim 1, it is characterized in that: when leaching pending electrolytic zinc acid leaching slag, utilize ball milling to leach synchronously.
5. according to the said a kind of method of utilizing the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure zinc oxide of claim 1, it is characterized in that: in every cubic metre of aforementioned liquids, add the 3-4kg ammonium persulphate during decarburization.
6. according to the said a kind of method of utilizing the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure zinc oxide of claim 1, it is characterized in that: after the decarbonation process, in liquid, add Neutral ammonium fluoride, the amount of adding is Ca in the solution
2+The 1.5-2.0 of theoretical value doubly.
7. according to the said a kind of method of utilizing the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high-purity zinc oxide of claim 1, it is characterized in that: add the heavy zinc of sodium sulphite in the waste liquid after the ammonia still process crystallization, separate obtaining zinc sulphide filter cake and solution after the reaction; Partly add white lime at solution, and stir and to obtain mixed solution, in whipping process, add tensio-active agent; Mixed solution is carried out the ammonia still process conversion make ammonium sulfate be converted into the calcium sulfate powder, the ammonia still process temperature stirs in the ammonia still process process for not being higher than 105 ℃; Stirring velocity is 300-500 rev/min; The ammonia of overflowing reclaims through cooling, and the calcium sulfate powder carries out rinsing, drying, obtains the calcium sulfate powder product.
8. according to the said a kind of method of utilizing the decarburization of electrolytic zinc acid leaching slag ammonia process to produce high pure zinc oxide of claim 1, it is characterized in that: the temperature of said drying and calcining is 150-300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210358125.2A CN102828035B (en) | 2012-09-25 | 2012-09-25 | Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210358125.2A CN102828035B (en) | 2012-09-25 | 2012-09-25 | Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102828035A true CN102828035A (en) | 2012-12-19 |
| CN102828035B CN102828035B (en) | 2014-06-18 |
Family
ID=47331342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210358125.2A Active CN102828035B (en) | 2012-09-25 | 2012-09-25 | Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102828035B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018745A (en) * | 2015-07-29 | 2015-11-04 | 昆明理工大学 | Method for recovering zinc in oxygen and sulfur mixed zinc ore through synergistic coordination |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109468A1 (en) * | 1982-11-18 | 1984-05-30 | Extramet | Process for the selective recovery of lead from lead sulphides |
| CN1065685A (en) * | 1992-04-28 | 1992-10-28 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
| CN101538648A (en) * | 2009-03-13 | 2009-09-23 | 昆明理工大学 | Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore |
| CN101886180A (en) * | 2010-07-08 | 2010-11-17 | 陕西理工学院 | Method for preparing high-activity zinc oxide from electrolytic zinc leaching slag and lead smelting granulated slag |
| CN102079537A (en) * | 2009-11-27 | 2011-06-01 | 陕西中科纳米材料股份有限公司 | Preparation method of nano zinc oxide and roasting furnace |
-
2012
- 2012-09-25 CN CN201210358125.2A patent/CN102828035B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0109468A1 (en) * | 1982-11-18 | 1984-05-30 | Extramet | Process for the selective recovery of lead from lead sulphides |
| CN1065685A (en) * | 1992-04-28 | 1992-10-28 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
| CN101538648A (en) * | 2009-03-13 | 2009-09-23 | 昆明理工大学 | Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore |
| CN102079537A (en) * | 2009-11-27 | 2011-06-01 | 陕西中科纳米材料股份有限公司 | Preparation method of nano zinc oxide and roasting furnace |
| CN101886180A (en) * | 2010-07-08 | 2010-11-17 | 陕西理工学院 | Method for preparing high-activity zinc oxide from electrolytic zinc leaching slag and lead smelting granulated slag |
Non-Patent Citations (1)
| Title |
|---|
| 彭清静等: "氨浸-碳化法制活性氧化锌", 《化工生产与技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018745A (en) * | 2015-07-29 | 2015-11-04 | 昆明理工大学 | Method for recovering zinc in oxygen and sulfur mixed zinc ore through synergistic coordination |
| CN105018745B (en) * | 2015-07-29 | 2017-09-22 | 昆明理工大学 | A kind of method for cooperateing with coordination to reclaim zinc in oxysulphied zinc ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102828035B (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105293564A (en) | Method for recycling zinc-containing dust ash in steel plant | |
| US9528170B2 (en) | Method for producing a high-purity nanometer zinc oxide from steel plant smoke and dust by ammonia decarburization | |
| CN102863007B (en) | Method for producing high-purity nano-zinc oxide by ammonia method using electrolytic zinc acid-leaching residues | |
| CN102849783B (en) | Production method of high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarbonization | |
| US9512502B2 (en) | Method for producing a high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarburization | |
| CN102838158B (en) | Method for producing high-purity nano-zinc oxide by ammonia decarburization of electrolytic zinc acid-leaching residues | |
| CN102828025A (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN111647754A (en) | Comprehensive utilization method of zinc-containing dust and sludge in steel plant | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN105439192A (en) | Comprehensive utilization method for zinc oxide ore | |
| CN110775998A (en) | System and method for producing nano zinc oxide by industrially recycling zinc | |
| CN102828034B (en) | Method for producing high-purity zinc oxide through decarbonization on low-grade zinc oxide ore by adopting ammonia process | |
| CN102230080B (en) | Method for zinc raw material dechlorination in zinc hydrometallurgy | |
| CN102828033B (en) | Method for recycling electrolytic zinc acid leaching slag | |
| CN102849782B (en) | Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization | |
| CN102839282A (en) | Method for producing high-purity nano zinc oxide from low-grade zinc oxide ores | |
| CN102863009B (en) | Method of using low-grade zinc oxide ore to produce high-purity zinc oxide | |
| CN110844932A (en) | Method for producing nano zinc oxide by recovering zinc in zinc-containing solid waste of steel plant | |
| CN102826588B (en) | Method for producing high-purity nanometer zinc oxide by using ammonia process decarburization of steel plant dust | |
| CN102863011B (en) | Method of using low-grade zinc oxide ore to produce high-purity nano zinc oxide by means of ammonia process | |
| CN102828035B (en) | Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process | |
| CN102863008B (en) | Method for producing high-purity zinc oxide by ammonia method using low-grade zinc oxide ores | |
| CN108588413A (en) | A method of producing nano zine oxide using containing zinc ore crude | |
| CN104060109A (en) | Method for extracting vanadium by virtue of leaching | |
| CN211545970U (en) | System for producing nano zinc oxide by industrially recycling zinc |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: West high tech Zone Fucheng Road in Chengdu city of Sichuan Province in 610041 399, 9 17 storey building No. 11 Applicant after: SICHUAN JUHONG TECHNOLOGY CO., LTD. Address before: West high tech Zone Fucheng Road in Chengdu city of Sichuan Province in 610041 399, 9 17 storey building No. 11 Applicant before: Sichuan Juhong Technology Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: SICHUAN JUHONG TECHNOLOGY CO., LTD. TO: SICHUAN XINHONG TECHNOLOGY CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20121219 Assignee: Hanyuan zinc hung Technology Limited Assignor: SICHUAN JUHONG TECHNOLOGY CO., LTD. Contract record no.: 2016510000020 Denomination of invention: Method for producing high-purity zinc oxide through decarbonization on electrolytic zinc acid leaching slag by adopting ammonia process Granted publication date: 20140618 License type: Common License Record date: 20160920 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |