CN108862369A - A method of nano zine oxide is produced using electrolytic zinc acid system leached mud - Google Patents
A method of nano zine oxide is produced using electrolytic zinc acid system leached mud Download PDFInfo
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- CN108862369A CN108862369A CN201810817117.7A CN201810817117A CN108862369A CN 108862369 A CN108862369 A CN 108862369A CN 201810817117 A CN201810817117 A CN 201810817117A CN 108862369 A CN108862369 A CN 108862369A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
This disclosure relates to a kind of method using electrolytic zinc acid system leached mud production nano zine oxide, including a leach step, optional purifying step, desulfurized step, calcium zincates synthesis step, a calcining step, secondary leach step, piezocrystallization step, decompression decomposition step, optional rinse step, secondary clacining step.Disclosed method realizes the secondary use of leached mud while solving environmental issue, it solves to realize its resource utilization while various heavy pollution, sulfate ion as pollution sources is turned waste into wealth by calcium sulfate conversion, calcium zincates synthesis is realized under zinc ammonia environment for the first time, and nano zine oxide is obtained via calcium zincates, without ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, also avoid high temperature and pressure security risk caused by ammonia still process and equipment etching problem, the decomposition condition of ammonium carbonate is creatively utilized in process, the recycling of carbon dioxide is realized by pressure difference.
Description
Technical field
The invention belongs to the comprehensive application technology fields of comprehensive utilization of resources and new material, are related to electrolytic zinc acid system leached mud
Environmental protection treatment and resource utilization, in particular to it is a kind of using electrolytic zinc acid system leached mud production nano zine oxide method.
Background technique
Electrolytic zinc acid system leached mud is the most important pollutant of electrolytic zinc industry, belongs to lead-zinc smelting in national dangerous waste catalogue
Leached mud and the normobaric oxygen leaching that process routine lixiviation process generates and the sulphur slag (leached mud) that pressure leaching generates.The leaching of electrolytic zinc acid system
The problem of Treatment and recovery slagged tap is using being urgent need to resolve.The production of China's zinc simultaneously is ranked the first in the world with consumption, state
Interior zinc resource is not able to satisfy production, needs a large amount of zinc raw material of import every year.A kind of method is developed to realize that electrolytic zinc acid system leaches
The high efficiency resource utilization of zinc in slag has important meaning for solving the problems, such as environmental protection pressure and alleviating domestic zinc raw material supply
Justice.
Calcium zincates tool has been widely used.Negative electrode material of the calcium zincates for alkaline secondary zinc electrode is newly opened up in recent years
Direction, constantly mature and industrialization；Compared with traditional Zinc oxide desulfurizer, calcium zincates are the room temperature of desulphurizing activated component
Desulfurizing agent, Sulfur capacity increase considerably；Calcium zincates are not only conducive to animal as feed addictive and absorb also conducive to reduction environment dirt
Dye.Calcium zincates can also be widely used in glaze, paint, coating additive etc. simultaneously.Calcium zincates can be used for electrolytic zinc and oxygen
Change zinc raw material.
The preparation method of calcium zincates is limited to experimental exploration in the prior art, still immature.For example, Chinese patent
CN1397498A and CN1595688A discloses ball-milling method synthesis calcium zincates, wherein disclosed in Chinese patent CN1397498A
It is by Ca (OH)2It is put into ball grinder with ZnO in the ratio in calcium zincates chemical formula, suitable quantity of water is added, under argon atmospher protection
Ball milling 8-18 hours, product was obtained after then toasting 10-15 hours at 30-80 DEG C；United States Patent (USP) 5,460,899 discloses one
Kind ZnO and Ca (OH)2The method that reaction generates calcium zincates in lye；Use is disclosed in Chinese patent CN2012100305744
The Ca (OH) of soluble zinc salt and stoichiometric ratio2It is made into emulsion and generates calcium zincates.It is needed in the above method high-purity with finished product
It spends zinc oxide or finished product zinc salt is starting material, expensive starting materials, and severe reaction conditions, energy consumption is high, reacts not exclusively, yield
Low, atopic is poor, interferes vulnerable to impurity, total production procedure is with high costs, is unsuitable for industrial applications.
Zinc oxide is a kind of oxide of zinc, is insoluble in water, dissolves in acid and highly basic.Zinc oxide is a kind of common chemistry
Additive, be widely used in plastics, silicate product, synthetic rubber, lubricating oil, paint, ointment, adhesive, food,
In the production of the products such as battery, fire retardant.The band gap and exciton bind energy of zinc oxide are larger, and transparency is high, have excellent normal
Warm luminescent properties have application in the products such as the liquid crystal display, thin film transistor (TFT), light emitting diode of semiconductor field.
The method of electrolytic zinc acid system leached mud production zinc oxide is disclosed in Chinese patent CN102863007, this method is logical
Cross that ammonia-ammonium bicarbonate is leached, purified to electrolysis zinc leaching residue, ammonia still process crystallization, rinsing and drying and calcining produce zinc oxide, due to electricity
Zn content is lower in solution zinc leaching residue, and zinc concentration is difficult to lead to ammonia still process energy consumption mistake more than 3% in complex liquid in practical applications
Height, simultaneously because a large amount of presence of sulfate radical will increase the environmental protection treatment pressure of technique.
Summary of the invention
Problems to be solved by the invention
The technical solution that the disclosure proposes solves current zinc, and there is lack of raw materials, the good side that zinc oxide is prepared via calcium zincates
Method, the one or more aspects such as the method energy consumption of existing electrolytic zinc acid system leached mud Preparing of Zinc Oxide is high, environmental protection treatment pressure is big
The problem of.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of utilization electrolytic zinc acid system leached mud production nano oxygen
The method for changing zinc, includes the following steps：
Leach step：Electrolytic zinc acid system leached mud and the first digestion agent are mixed, then filters, obtains first
Leachate, wherein first digestion agent is that the mixing of the mixed aqueous solution or ammonia and ammonium carbonate of ammonia and ammonium hydrogen carbonate is water-soluble
The mixed aqueous solution of liquid or ammonia, ammonium hydrogen carbonate and ammonium carbonate；
Optionally, the first leachate obtained in a leach step is purified；
Desulfurized step：Calcium oxide and/or calcium hydroxide are added into first leachate, then stirring is filtered, obtained
First solid and the first filtrate；
Calcium zincates synthesis step：Calcium hydroxide and/or calcium oxide is added to first filtrate, then stirring is filtered, obtained
To the second solid and the second filtrate；
Calcining step：Take second solid to be calcined, calcination temperature be 150~1050 DEG C, preferably 150~
350℃；
Secondary leach step：The second digestion agent is added in the calcined product obtained to a calcining step, stirs, then
Filtering, obtains the second leachate, wherein second digestion agent is the mixed aqueous solution or ammonia and carbonic acid of ammonia and ammonium hydrogen carbonate
The mixed aqueous solution of the mixed aqueous solution or ammonia of ammonium, ammonium hydrogen carbonate and ammonium carbonate；
Piezocrystallization step：Activating agent is added into second leachate, is passed through the carbon dioxide of pressurization, is contained
The slurries of crystallization；
Depressurize decomposition step：The slurries obtained in the piezocrystallization step are filtered in sealed environment,
Third solid and third filtrate are obtained, by the third filtrate decompression to normal pressure, makes the part ammonium carbonate in the third filtrate
It is decomposed into ammonia and carbon dioxide；
Optionally, the third solid is rinsed with water；
Secondary clacining step：The third solid is dry, 450~900 DEG C at a temperature of calcined, be averaged
Partial size is the nano oxidized zinc product of 10~100nm.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, the mass concentration of total ammonia in first digestion agent is 5%~15%, effective carbonate in first digestion agent
The amount of substance is 100%~200% of the amount of the substance of sulfate radical in electrolytic zinc acid system leached mud；It is total in second digestion agent
The mass concentration of ammonia is 6%~12%, and the mass concentration of effectively carbonate is 8%~15% in second digestion agent.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, the zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in first leachate is 10~25g/L.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the desulfurized step is in first leachate
The 100% to 130% of the amount of the substance of sulfate radical, preferably 100% to 110%.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, in the calcium zincates synthesis step, the amount of the substance of calcium hydroxide and/or calcium oxide is added into first filtrate
It is 1~1.2 with the ratio between amount of substance of zinc ammonium complex ion in the first filtrate:2, preferably 1~1.1:2.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, in the piezocrystallization step, crystallization pressure is 0.3~0.6MPa.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, in the decompression decomposition step, the part ammonium carbonate in the third filtrate is made to be decomposed into the anti-of ammonia and carbon dioxide
Should 70~90 DEG C at a temperature of carry out.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, the activating agent is one of calgon, neopelex or a variety of.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, second filtrate obtained to the calcium zincates synthesis step is passed through carbon dioxide, will be passed through the of carbon dioxide
Two filtrates are used for the primary extraction of electrolytic zinc acid system leached mud as the first digestion agent, circulation.
In the side using electrolytic zinc acid system leached mud production nano zine oxide that disclosure further embodiment provides
In method, in the decompression decomposition step, after the third filtrate decompression to normal pressure：
The carbon dioxide that ammonium carbonate decomposes release is collected, circulation is used for piezocrystallization；
Collection is decompressed to the third filtrate after normal pressure, and circulation is used for secondary extraction.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects：
1) sulfate in electrolytic zinc acid system leached mud is converted into carbonate, metal in the dreg salt is made to be less readily soluble in water and solve
Certainly environmental issue, while realizing the secondary use (can be used as cement and burn the raw material of brick) of leached mud.
2) make in electrolytic zinc acid system leached mud the ammonia such as zinc, copper, cadmium can complex ion enter complex liquid, solve various heavy
Its resource utilization is realized while pollution.
3) turned waste into wealth as the sulfate ion of pollution sources by calcium sulfate conversion.
4) to realize that calcium zincates synthesize under zinc ammonia environment for the first time, and nano zine oxide is obtained via calcium zincates；；From zinc ammino
The reaction selectivity that ion synthesizes calcium zincates is high, simple and quick.
5) technique of the disclosure realizes the leaching and separation of zinc by the circulation of carbonate, solves existing ammonia circulation technology
The middle environmental issue faced due to steam, which brings water more than needed into, influences process water balance.
6) break traditional ammonia-ammonium carbonate method zinc complexing extracting technology by heating evaporation ammonia destroy complexing environment realize zinc from
Calcium oxide or hydrogen-oxygen are added creatively into ammonium sulfate-zinc ammonia complex system by the orthodox practice of sub- Crystallization Separation, the application
Change calcium, moves zinc ammonium complex ion-zinc ion-zinc hydroxide/calcium zincates balance, before not destroying solution ammonia environment
The selective crystallization separation for realizing Zn-ef ficiency by balance moving principle is put, traditional ammonia-ammonium carbonate method zinc complexing extraction work is broken
Skill destroys the orthodox practice that complexing environment realizes zinc ion Crystallization Separation by heating evaporation ammonia, avoids existing heating ammonia still process method
Destroy the phenomenon that ammonia environment causes impurity to be largely co-precipitated.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, greatly reduces work
The energy consumption of skill, it is thus also avoided that high temperature and pressure security risk caused by ammonia still process, a large amount of ammonia of equipment burn into steam volatilization and cause additionally
Environmental protection treatment bear problem.
7) decomposition condition for creatively utilizing ammonium carbonate in process, is made by the circulation that pressure difference realizes carbon dioxide
With.
Specific embodiment
It will be detailed below various exemplary embodiments, feature and the aspect of the disclosure.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, giving numerous details in specific embodiment below in order to which the disclosure is better described.
In some instances, method well known to those skilled in the art, means, reagent and equipment are not described in detail, but ability
Field technique personnel can realize the technical solution of the disclosure according to the general knowledge of this field.
Explanation of nouns
Herein, unless otherwise indicated, " sulfuric acid ammino zinc " is zinc ammonium complex ion and the compound that sulfate radical is formed
General name, including [Zn (NH3)4]SO4(four ammino zinc of sulfuric acid), [Zn (NH3)3]SO4(three ammino zinc of sulfuric acid), [Zn (NH3)2]SO4
(two ammino zinc of sulfuric acid), [Zn (NH3)]SO4(one ammino zinc of sulfuric acid) etc..
Herein, unless otherwise indicated, " zinc ammonium complex ion " is the general name of ammino zinc complex ions at different levels, including [Zn
(NH3)4]2+(four ammino zinc ions), [Zn (NH3)3]2+(three ammino zinc ions), [Zn (NH3)2]2+(two ammino zinc ions), [Zn
(NH3)]2+(an ammino zinc ion) etc..
Herein, unless otherwise indicated, solution (including but not limited to the first digestion agent, the first leachate, the second extraction
The various liquid such as agent) in " effective carbonate " refer to the summation of carbonate and bicarbonate radical in the solution.
" optional " or " optionally " indicates that the then described step can carry out, or can be without, and the table
State include the steps that the then situation carried out and the then described step without situation.
Chemical equation
1. primary extraction
A. the displacement of sulfate and carbonate/bicarbonate
CaSO4+(NH4)2CO3=CaCO3+(NH4)2SO4
MgSO4+(NH4)2CO3=MgCO3+(NH4)2SO4
PbSO4+(NH4)2CO3=PbCO3+(NH4)2SO4
Or
CaSO4+NH4HCO3=CaCO3+(NH4)2SO4+H2O+CO2
MgSO4+NH4HCO3=MgCO3+(NH4)2SO4+H2O+CO2
PbSO4+NH4HCO3=PbCO3+(NH4)2SO4+H2O+CO2
B. zinc oxide extracts
ZnO+(i-2)NH3+(NH4)2SO4=[Zn (NH3)i]SO4+H2O (integer that i is 2 to 4)
2. desulfurization
CaO+H2O=Ca (OH)2
Ca(OH)2++(NH4)2SO4=CaSO4↓+NH3·H2O
[Zn(NH3)i]SO4+Ca(OH)2=[Zn (NH3)i](OH)2+CaSO4↓
3. calcium zincates synthesize
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O=Ca (OH)2·2Zn(OH)2·2H2O+2iNH3
(integer that i is 1 to 4)
4. primary calcining
Ca(OH)2·2Zn(OH)2·2H2O=Ca (OH)2+2ZnO+4H2O
Or
Ca(OH)2·2Zn(OH)2·2H2O=CaO+2ZnO+5H2O
5. two extractions
ZnO+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O (integer that i is 2 to 4)
6. piezocrystallization
2NH3·H2O+CO2=(NH4)2CO3+H2O
3[Zn(NH3)i]CO3+3H2O=ZnCO3·2Zn(OH)2·H2O+2(NH4)2CO3+(3i-4)NH3(i is 2 to 4
Integer)
7. decompression is decomposed
(NH4)2CO3+H2O=2NH3·H2O+CO2
8. secondary clacining
ZnCO3·2Zn(OH)2·H2O=3ZnO+CO2+3H2O
Specific process step
Step 1 once extracts
Electrolytic zinc acid system leached mud and prepared first digestion agent are mixed in a certain ratio and are stirred extraction, first
Digestion agent can be selected from：The mixed aqueous solution of ammonia and ammonium hydrogen carbonate；The mixed aqueous solution of ammonia and ammonium carbonate；Ammonia, ammonium hydrogen carbonate and
The mixed aqueous solution of ammonium carbonate.It is filtered after extraction, obtains the first leachate.
Total ammonia density and effective carbonate concentration in first digestion agent are not particularly limited, and those skilled in the art can root
According to factors such as sulfate, Zn contents in each batch electrolytic zinc acid system leached mud, selected in conjunction with actual needs.
In the preferred scheme, the mass concentration of total ammonia is 5%~15%, more preferable 6%~8% in the first digestion agent,
Preferred concentration range can reach sufficient extracting effect, and excessive ammonia is avoided to cause waste and environmental issue.
In the preferred scheme, the amount of effective carbonate and sulfate radical in electrolytic zinc acid system leached mud in the first digestion agent
It measures substantially matching, allows certain excess, the sulfate in leached mud is fully converted into carbonate to reach, and do not increase excessively
Add the purpose of subsequent technique processing pressure.For example, the amount of the substance of effective carbonate is the leaching of electrolytic zinc acid system in the first digestion agent
Slag tap middle sulfate radical substance amount 100%~200%.
The weight ratio of first digestion agent and electrolytic zinc acid system leached mud is not particularly limited, as long as zinc ingredient can be leached
?.It is preferred that the weight ratio of digestion agent and electrolytic zinc acid system leached mud is 3:1 to 5:1, satisfied extracting effect can be not only obtained, but also
Avoid the waste of digestion agent.
The temperature of extraction is not particularly limited, as long as being leached the zinc ingredient in electrolytic zinc acid system leached mud.It is excellent
Choosing is extracted at normal temperature, such as is extracted at 15~30 DEG C.After electrolytic zinc acid system leached mud is mixed with digestion agent
It is stirred, mixing time is not particularly limited, and preferably mixing time is 1~4 hour, more preferable 1~2 hour.It stirs laggard
Row filtering.
In leaching process, various metals sulfate conversion in electrolytic zinc acid system leached mud be more indissoluble carbonate from
And be filtered to remove, and Zn-ef ficiency is converted into zinc ammonium complex ion (zinc ammonium complex ion predominantly at different levels), into the first leachate.
First leachate is sent to subsequent sulfur removal technology.The concentration of zinc ammonium complex ion is not particularly limited in first leachate, but preferably
The concentration (in terms of the quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L in first leachate, can make the treatment effeciency of technique
It is optimal, good yield and purity are obtained in subsequent calcium zincates synthesis step, overall economic efficiency is best.If original leaching
The liquid of leaching is also optionally concentrated or is diluted not in preferred scope by zinc ammonium complex ion concentration in liquid out,
Zinc ammonium complex ion concentration in leachate is adjusted to preferred 10~25g/L range.
Step 2 purification
Step 2 be optional step, it is necessary to when selection carry out step 2.First leachate is carried out by known method
Purification, the impurity elements such as removal iron, manganese, lead, copper.A kind of illustrative purification method is that addition zinc powder replace then mistake
To remove heavy metal contaminants, but other various well known purification methods also can be used in filter.Purifying step helps to improve
The purity of finished product.
Step 3 desulfurization
In desulfurized step, calcium hydroxide and/or calcium oxide are added into the first leachate containing zinc ammonium complex ion, it will
Sulfate radical in leachate is converted into the calcium sulfate of indissoluble.If zinc ammonium complex ion excessive concentration in the first leachate, having can
Zinc ammonium complex ion-zinc ion-zinc hydroxide balanced sequence in leachate can occur simultaneously, a little zinc ingredient may
It is co-precipitated in the form of zinc hydroxide with calcium sulfate.
In desulfurized step, sulfate radical in substantially matching first leachate of the additive amount of calcium hydroxide and/or calcium oxide
Content, for example, the amount of the substance of calcium hydroxide and/or calcium oxide that desulfurized step is added is the object of sulfate radical in the first leachate
The 100% to 130% of the amount of matter, more preferable 100% to 110%.Calcium hydroxide and/or calcium oxide are appropriately added, is facilitated
Control process costs, it helps improve the purity and quality of finished product zinc product.
In desulfurized step, calcium hydroxide and/or calcium oxide are added into the first leachate, stirring is reacted, and is generated
Solid precipitating.The temperature of reaction is not particularly limited, but can go on smoothly since reaction is not necessarily to heating, therefore particularly preferably normal
It is reacted under temperature (such as 15~25 DEG C), it is on the one hand energy saving, on the other hand also reduce environmental pollution caused by ammonia volatilization.
Mixing time is not particularly limited, as long as being precipitated, preferably stirs 1~2 hour.
It is filtered after stirring, obtains the first solid and the first filtrate.The main component of first solid is calcium sulfate, if
The concentration of zinc ammonium complex ion is higher in leachate, then some hydroxides with calcium sulfate co-precipitation are also likely to be present in the first solid
Zinc.First filtrate continues on for subsequent calcium zincates synthesis.
The synthesis of step 4 calcium zincates
The object of zinc ammonium complex ion in the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in this step and the first filtrate
The ratio between amount of matter preferably 1~1.2:2, more preferable 1~1.1:2.Reaction temperature is not particularly limited, and can be such as 15~90
DEG C, preferably 20~90 DEG C, further preferred 30~60 DEG C；Or it is also preferred that 15~25 DEG C of reaction temperature, temperature range tool
The advantages of having without heating, energy conservation and reducing ammonia volatilization.Reaction can carry out for 0.5~2 hour after (preferably 0.5~1 hour)
Filter, without prolonged reaction and ageing process.The second solid and the second filtrate is obtained by filtration.The main component of second solid is
Calcium zincates.In addition it can be passed through carbon dioxide to the second filtrate, is then leached as the first digestion agent circulation for electrolytic zinc acid system
The extraction of slag.
Step 5 is once calcined
In this step, the second solid for taking step 4 to obtain is calcined, and calcium zincates are decomposed.Calcination temperature 150~
1050 DEG C, preferably 150~350 DEG C.Calcining obtained product is mixture, if calcination temperature is calcined at 150~350 DEG C
Product main component is zinc oxide and calcium hydroxide；If calcined product may contain oxidation using higher calcination temperature
Zinc, calcium hydroxide and/or calcium oxide.
Step 6 two times extractions
It is added and prepares into the mixture containing zinc oxide and calcium hydroxide (or calcium oxide) that a calcining step obtains
The second digestion agent, be stirred extraction, preferably stir 1~4 hour.Second digestion agent can be the mixing of ammonia and ammonium hydrogen carbonate
The mixed aqueous solution of the mixed aqueous solution or ammonia of aqueous solution or ammonia and ammonium carbonate, ammonium hydrogen carbonate and ammonium carbonate, preferably ammonia-carbon
Sour aqueous ammonium, wherein total ammonia mass concentration is 6%~12%, effective carbonate mass concentration is 8%~15%.
In this step, it once calcines in the calcium hydroxide (or calcium oxide) and the second digestion agent in obtained mixture
Carbonate/bicarbonate reaction generates precipitation of calcium carbonate, and the zinc oxide in mixture is then converted into ammine carbonate zinc ([Zn
(NH3)i]CO3, i be 1 to 4 integer).It is filtered to remove precipitation of calcium carbonate after the reaction was completed, the filtrate being obtained by filtration is to contain zinc
Second leachate of ammonium complex ion is used for subsequent piezocrystallization step.
Step 7 piezocrystallization
Activating agent, the preferred calgon of activating agent or neopelex, dosage are added into the second leachate
Preferably estimate the 0.01~0.05% of finished product quality.Then the carbon dioxide gas of pressurization is pressed into the second leachate, made
Free ammonia in second leachate is converted to ammonium carbonate, and zinc ingredient then loses Complexation conditions, is precipitated in the form of basic zinc carbonate.
Crystallization pressure control is 0.3~0.6MPa, which is better than high temperature.Since the ammonium carbonate in aqueous solution is normal
Pressure, which reaches 70 DEG C, voluntarily to decompose, and can industrially efficiently use the recycling that pressure difference realizes carbon dioxide, reduce technique
The consumption of carbon dioxide, therefore the preferred reaction temperature control of this step is at 70~90 DEG C.This step is obtained containing alkali formula carbon
The slurries of sour zinc crystal, send to next step.
Step 8 decompression is decomposed
The slurries for completing crystallization are filtered in sealed environment (environment for maintaining pressurized state), obtain third solid
With third filtrate.The main component of third solid is basic zinc carbonate, and third dissolved in filtrate has ammonium carbonate.Third filtrate is subtracted
It is depressed into normal pressure, the part ammonium carbonate in third filtrate is made to be decomposed into ammonia and carbon dioxide.The carbon dioxide gas released is available
In circulation piezocrystallization, ammonia is mainly existed in solution in the form of free ammonia.Preferred decomposition reaction temperature is 70~90 DEG C,
It is reacted 1~2 hour in atmospheric pressure environment at this temperature, ammonium carbonate can decompose about 60~70% in aqueous solution.Decomposition reaction
Liquid afterwards has Complexation conditions again, can recycle for secondary extraction.
Step 9 rinsing
Step 9 be optional step, it is necessary to when selection carry out step 9.The main component that step 8 is obtained is alkali formula
The third solid of zinc carbonate adds water to be rinsed, liquid-solid ratio 5~10:1, rinsing times 1~2 time.
Step 10 secondary clacining
By the third solid drying that main component is basic zinc carbonate, then calcined, 450~900 DEG C of calcination temperature.
Basic zinc carbonate decomposes, and obtains nano zine oxide solid, and average grain diameter is 10~100nm.
It is described in detail below in conjunction with embodiment of the embodiment to the disclosure, but those skilled in the art will
Understand, the following example is merely to illustrate the disclosure, and is not construed as the restriction to the scope of the present disclosure.It is not specified in embodiment
Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer,
Being can be with conventional products that are commercially available.
Embodiment 1
Sichuan company electrolytic zinc acid system leached mud, Zn content 8.46%, sulfur content 14.09%.
2000 grams of electrolytic zinc acid system leached muds are taken, 10000 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration is put into
10%, carbonate mass concentration 5.5%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then carried out
It filters, zinc (meter is worked as with zinc oxide) 1.47%, sulfate radical mass concentration 8.8% in liquid is contained in filtered liquid.According to
Inspection data, zinc recovery 86.9%.
The zinc ammonia complexing liquid zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
256.7 grams of calcium oxide are added to purified zinc ammonia complexing liquid and are used for precipitated sulfur acid group, reaction carried out after 1 hour
Filter.
Synthesis of 18 grams of calcium hydroxides for calcium zincates is added, stirring is filtered after 1 hour.Solid will be obtained by filtration to obtain
It is 2 hours dry at 105 DEG C, then calcined 2 hours through 300 DEG C, calcium zincates are decomposed into zinc oxide and calcium hydroxide.
50 grams of calcined solids are taken, 500 milliliters of ammonia-ammonium carbonate mixed liquor (ammonia mass concentration 10%, carbonate is added
Mass concentration 12%) it is stirred extraction, mixing time is 2 hours, is then filtered.
3 milligrams of neopelexes are added in filtered filtrate, is placed in reaction kettle, will press after being heated to 70 DEG C
Contracting carbon dioxide gas is passed through reaction kettle and is reacted, and pressure is controlled in 0.3MPa, inspection by sampling, when zinc concentration is lower than in liquid
The addition for stopping carbon dioxide when 0.5% is pumped into positive press filtration device and is filtered.
The basic zinc carbonate being obtained by filtration is by liquid-solid ratio 10:1 adds water to be rinsed twice, and the basic zinc carbonate after rinsing exists
It is 2 hours dry at 105 DEG C, then calcined 2 hours through 800 DEG C, gained zinc oxide product is through check analysis, wherein zinc oxide content
99.76%, average grain diameter 47.1nm.
Embodiment 2
Yunnan company electrolytic zinc acid system leached mud, Zn content 7.98%, sulfur content 16.01%.
2000 grams of electrolytic zinc acid system leached muds are taken, 10000 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration is put into
10%, carbonate mass concentration 6%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then carried out
It filters, zinc (meter is worked as with zinc oxide) 1.367% is contained in filtered liquid, sulfate radical mass concentration is 9.61% in liquid.Root
According to inspection data, zinc recovery 86.63%.
The zinc ammonia complexing liquid zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
280 grams of calcium oxide are added to purified zinc ammonia complexing liquid and are used for precipitated sulfur acid group, reaction carried out after 1 hour
Filter.
Synthesis of 16 grams of calcium hydroxides for calcium zincates is added, stirring is filtered after 1 hour.Solid will be obtained by filtration to obtain
It is 2 hours dry at 105 DEG C, then calcined 2 hours through 300 DEG C, calcium zincates are decomposed into zinc oxide and calcium hydroxide.
50 grams of calcined solids are taken, 500 milliliters of ammonia-ammonium carbonate mixed liquor (ammonia mass concentration 10%, carbonate is put into
Mass concentration 12%) in be stirred extraction, mixing time is 2 hours, is then filtered.
3 milligrams of neopelexes are added in filtered filtrate, is placed in reaction kettle, will press after being heated to 70 DEG C
Contracting carbon dioxide gas is passed through reaction kettle and is reacted, and controls pressure 0.3MPa, inspection by sampling, when zinc concentration is lower than in liquid
The addition for stopping carbon dioxide when 0.5% is pumped into positive press filtration device and is filtered.
Filtered basic zinc carbonate presses liquid-solid ratio 10:1 adds water to be rinsed twice, and the basic zinc carbonate after rinsing exists
It dry 2 hours at 105 DEG C, then calcines 2 hours through 800 DEG C, gained zinc oxide product is through check analysis, wherein zinc oxide content
99.80%, average grain diameter 42.3nm.
The presently disclosed embodiments is described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.The selection of term used herein, purport
In principle, the practical application or to the technological improvement in market for best explaining each embodiment, or make the art its
Its those of ordinary skill can understand each embodiment disclosed herein.
Claims (10)
1. a kind of method using electrolytic zinc acid system leached mud production nano zine oxide, which is characterized in that described to utilize electrolytic zinc
The method of acid system leached mud production nano zine oxide includes the following steps：
Leach step：Electrolytic zinc acid system leached mud and the first digestion agent are mixed, then filters, obtains the first leaching
Liquid, wherein first digestion agent is the mixed aqueous solution or ammonia of ammonia and ammonium hydrogen carbonate and the mixed aqueous solution of ammonium carbonate, or
The mixed aqueous solution of ammonia, ammonium hydrogen carbonate and ammonium carbonate；
Optionally, the first leachate obtained in a leach step is purified；
Desulfurized step：Calcium oxide and/or calcium hydroxide are added into first leachate, then stirring filters, obtains first
Solid and the first filtrate；
Calcium zincates synthesis step：Calcium hydroxide and/or calcium oxide is added to first filtrate, then stirring is filtered, obtain the
Two solids and the second filtrate；
Calcining step：Second solid is taken to be calcined, calcination temperature is 150~1050 DEG C, preferably 150~350 DEG C；
Secondary leach step：The second digestion agent is added in the calcined product obtained to a calcining step, stirs, then mistake
Filter, obtains the second leachate, wherein second digestion agent is the mixed aqueous solution or ammonia and ammonium carbonate of ammonia and ammonium hydrogen carbonate
Mixed aqueous solution or ammonia, ammonium hydrogen carbonate and ammonium carbonate mixed aqueous solution；
Piezocrystallization step：Activating agent is added into second leachate, is passed through the carbon dioxide of pressurization, obtains containing crystallization
Slurries；
Depressurize decomposition step：The slurries obtained in the piezocrystallization step are filtered in sealed environment, are obtained
The third filtrate decompression to normal pressure decomposes the part ammonium carbonate in the third filtrate by third solid and third filtrate
For ammonia and carbon dioxide；
Optionally, the third solid is rinsed with water；
Secondary clacining step：The third solid is dry, 450~900 DEG C at a temperature of calcined, obtain average grain diameter
For the nano oxidized zinc product of 10~100nm.
2. the method according to claim 1 using electrolytic zinc acid system leached mud production nano zine oxide, which is characterized in that
The mass concentration of total ammonia in first digestion agent is 5%~15%, the substance of effective carbonate in first digestion agent
Amount be 100%~200% of the amount of the substance of sulfate radical in electrolytic zinc acid system leached mud；
The mass concentration of total ammonia is 6%~12% in second digestion agent, the matter of effective carbonate in second digestion agent
Measuring concentration is 8%~15%.
3. the method according to claim 1 or 2 using electrolytic zinc acid system leached mud production nano zine oxide, feature exist
In the zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in first leachate is 10~25g/L.
4. the method according to any one of claims 1 to 3 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the desulfurized step is first leachate
In sulfate radical substance amount 100% to 130%, preferably 100% to 110%.
5. the method according to any one of claims 1 to 4 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, in the calcium zincates synthesis step, the substance of calcium hydroxide and/or calcium oxide is added into first filtrate
Amount and the first filtrate in the ratio between the amount of substance of zinc ammonium complex ion be 1~1.2:2, preferably 1~1.1:2.
6. the method according to any one of claims 1 to 5 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, in the piezocrystallization step, crystallization pressure is 0.3~0.6MPa.
7. the method according to any one of claims 1 to 6 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, in the decompression decomposition step, the part ammonium carbonate in the third filtrate is made to be decomposed into ammonia and carbon dioxide
Reaction 70~90 DEG C at a temperature of carry out.
8. the method according to any one of claims 1 to 7 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, the activating agent is one of calgon, neopelex or a variety of.
9. the method according to any one of claims 1 to 8 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, second filtrate obtained to the calcium zincates synthesis step is passed through carbon dioxide, will be passed through carbon dioxide
The second filtrate as the first digestion agent, circulation is used for the primary extraction of electrolytic zinc acid system leached mud.
10. the method according to any one of claims 1 to 9 using electrolytic zinc acid system leached mud production nano zine oxide,
It is characterized in that, in the decompression decomposition step, after the third filtrate decompression to normal pressure：
The carbon dioxide that ammonium carbonate decomposes release is collected, circulation is used for piezocrystallization；
Collection is decompressed to the third filtrate after normal pressure, and circulation is used for secondary extraction.
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| CN110724831A (en) * | 2019-10-31 | 2020-01-24 | 重庆赛迪热工环保工程技术有限公司 | Carbon circulating system and method for producing zinc oxide by industrially recycling zinc |
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| CN102838158A (en) * | 2012-09-25 | 2012-12-26 | 四川巨宏科技有限公司 | Method for producing high-purity nano-zinc oxide by ammonia decarburization of electrolytic zinc acid-leaching residues |
| CN104512952A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | Method of recovering and reutilizing zinc from zinc ammonia solution |
| CN105129839A (en) * | 2015-08-22 | 2015-12-09 | 湖南华信稀贵科技有限公司 | Method for producing micron-grade zinc oxide with high fluorine and chlorine crude zinc oxide as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102838158A (en) * | 2012-09-25 | 2012-12-26 | 四川巨宏科技有限公司 | Method for producing high-purity nano-zinc oxide by ammonia decarburization of electrolytic zinc acid-leaching residues |
| CN104512952A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | Method of recovering and reutilizing zinc from zinc ammonia solution |
| CN105129839A (en) * | 2015-08-22 | 2015-12-09 | 湖南华信稀贵科技有限公司 | Method for producing micron-grade zinc oxide with high fluorine and chlorine crude zinc oxide as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110724831A (en) * | 2019-10-31 | 2020-01-24 | 重庆赛迪热工环保工程技术有限公司 | Carbon circulating system and method for producing zinc oxide by industrially recycling zinc |
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