CN108862370A - A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude - Google Patents
A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude Download PDFInfo
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Abstract
This disclosure relates to a kind of method using the production nano zine oxide containing zinc ore crude, including a leach step, optional purifying step, pre-treatment step, heavy zinc step, a calcining step, secondary leach step, piezocrystallization step, decompression decomposition step, optional rinse step, secondary clacining step.Disclosed method is by wet-leaching in conjunction with synthesis technology, realize the economic and environment-friendly utilization of super low-grade zinc, it is applied widely, 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, solve the problems, such as the technique rate of recovery and fine work grade, it pollutes small, material is recyclable, the calcium zincates synthesis under zinc ammonia environment is realized for the first time, and nano oxidized zinc product is produced via calcium zincates, the decomposition condition of ammonium carbonate is creatively utilized in technique, the recycling of carbon dioxide is realized by pressure difference.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be related to the low-grade resource utilization containing zinc ore crude, in particular to one
The method that kind produces nano zine oxide using low-grade zinc oxide raw ore.
Background technique
The production of China's zinc is ranked the first in the world with consumption, and domestic zinc resource is not able to satisfy production, needs import a large amount of every year
Zinc raw material.China is an oxidation zinc resource country more abundant, and zinc metal reserves are about 2800 in China's zinc oxide ore
Ten thousand tons, account for about 27.7% of zinc metal reserves in world's zinc oxide ore.Zinc oxide ore generally zinc grade in China's is low, average grade
Less than 5%, be still unable to the slow-witted mine of economic utilization at present, lean ore reserves account for the overwhelming majority, wherein existing stockpiling containing zinc oxide 3%~
The 5% more than one hundred million tons of mining tailing and milltailings.
Therefore, Efficient Development utilizes low-grade zinc oxide ore resource, for alleviating the insufficient problem of domestic zinc raw material supply
With important strategic importance.
The main technique that low-grade zinc oxide ore utilizes includes：Pyrogenic process produces secondary zinc oxide, due to the high energy consumption of the technique
With high pollution, limited by national industrial policies.
Flotation is the main technique of current processing zinc oxide ore, but for zinc oxide floatation process, external zinc oxide ore
Sorting index is：Zinc grade 36%~40%, the rate of recovery 60%~70%, up to 78%；China's zinc oxide ore sorting index
For：Zinc grade 35%~38%, rate of recovery average out to 68%, up to 73%.Therefore recovery rate in ore-dressing is low, and concentrate grade is low etc.
Problem is common problem existing for domestic and international zinc oxide ore ore dressing, while Flotation of Zinc Oxide needs to be added a large amount of vulcanized sodium and carries out sulphur
Change processing, zinc sulphide is needed could be high directly as production metallic zinc or the raw material of production zinc oxide, energy consumption after pyrogenic attack
And it is seriously polluted.
For the wet underwater welding of zinc ore, mainly there are sulfuric acid leaching, Calcium Chloride Method, ammonium chloride method etc. in the prior art.
Sulfuric acid leaching is selectively low, can largely leach the solvable silicon in ore, and the colloidal state silicon of generation is difficult to filter, and the acid-hatching of young eggs is raw
At a large amount of sulfate slags, great environmental protection treatment pressure is caused；Sulfuric acid leaching also can not be effectively to zinc silicate, the iron in ore
The ingredients such as sour zinc are handled.The leaching of the ingredients such as zinc silicate in raw ore, zinc ferrite can not be effectively treated in Calcium Chloride Method, and leaches
Rate is undesirable, and high temperature is needed to leach, and overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, from leaching
The process that zinc ingredient is recycled in liquid is extremely difficult, is unsuitable for industrial application.
Ammonia-ammonium carbonate method can also be used to be mainly used for containing from zinc ore production zinc oxide or zinc oxide, the technique in the prior art
10% or more zinc oxide ore of zinc there is no economic use value for the ultra-low oxidized zinc ore containing zinc 3~6% at present.Existing
Ammonia-ammonium carbonate method technique in, leached after zinc ore obtains the leachate containing zinc ammonia complex with ammonia-ammonium bicarbonate, need Heating Zn ammonia
Complex liquid steams ammonia, to realize the crystalline deposit of zinc ingredient.But since the ingredient of low-grade zinc oxide ore composition and technique are matched
Standby economic input, when using 3~6% ultralow grade zinc oxide ores, zinc concentration difficulty reaches 20 gram per liters in leachate, life
The evaporation that zinc oxide product per ton needs to complete 50 cubic metres or more zinc ammonia complexing liquid is produced, energy consumption is high, ammonia during heating evaporation
Volatilization it is not easy to control, be easy to cause environmental issue, while existing ammonia-ammonium carbonate method oxidation zinc technology ammonia still process process uses steam
Direct heat exchange mode, the water more than needed that steam is brought into influence water balance, increase the environmental protection treatment pressure of technique；In addition, to guarantee
Zinc concentration in complex liquid needs to improve ammonia concn in leachate, faces ammonia volatilization bring environmental issue.
Therefore, existing technique to it is low-grade containing zinc ore crude using unsatisfactory.
Summary of the invention
Problems to be solved by the invention
Low-grade zinc oxide ore utilizes at present technique exist energy consumption is high, recovery rate in ore-dressing is low, cause Heavy environmental pollution,
The problems such as economic value is low.The present invention is solved present in zinc oxide ore utilization by the improvement to zinc oxide ore treatment process
The above problem.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of side using the production nano zine oxide containing zinc ore crude
Method includes the following steps：
Leach step：Being mixed after will be levigate containing zinc ore crude and the first digestion agent, 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；
Pre-treatment step：Calcium oxide and/or calcium hydroxide are added into first leachate, then stirring is filtered, obtained
To the first solid and the first filtrate；
Heavy zinc step：Calcium hydroxide and/or calcium oxide is added to first filtrate, then stirring filters, obtains second
Solid and the second filtrate；
Calcining step：Take second solid to be calcined, calcination temperature be 150~1050 DEG C, preferably 250~
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, then passes to the carbon dioxide of pressurization, obtains
Slurries containing 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.
It is described in the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude
The mass concentration of total ammonia in first digestion agent is 5%~15%, effective carbonate in first digestion agent it is mole dense
Degree is：
CFirst digestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VFirst digestion agent
Wherein,
CFirst digestion agent carbonateFor the molar concentration of effective carbonate in first digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
VFirst digestion agentFor the volume of first digestion agent,
The value range of a is 100%~600%, preferably 150%~250%；
The mass concentration of total ammonia is 6%~12% in second digestion agent, effective carbonate in second digestion agent
Mass concentration be 8%~15%.
It is described in the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude
Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in first leachate is 10g/L or more, preferably 10~50g/L.
In the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude, in institute
The amount for stating the substance of the calcium oxide and/or calcium hydroxide that are added in pre-treatment step is：
nPretreatment=(nFirst leachate carbonate-nZinc ammonium complex ion)×b
Wherein, nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step, nFirst leachate carbonate
For the amount of the substance of effective carbonate in the first leachate, nZinc ammonium complex ionFor the substance of zinc ammonium complex ion in the first leachate
Amount, the value range of b are 90%≤b≤110%.
In the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude, in institute
It states in heavy zinc step, calcium hydroxide and/or calcium oxide is added into first filtrate, until sediment no longer increases.
In the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude, in institute
It states in piezocrystallization step, crystallization pressure is 0.3~0.6MPa.
In the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude, in institute
It states in decompression decomposition step, the part ammonium carbonate in the third filtrate is made to be decomposed into the reaction of ammonia and carbon dioxide 70~90
It is carried out at a temperature of DEG C.
In the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude, to institute
It states second filtrate that heavy zinc step obtains and is passed through carbon dioxide, the second filtrate of carbon dioxide will be passed through as the first leaching
Agent is proposed, is recycled for the primary extraction containing zinc ore crude.
In the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude, in institute
It states in 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.
It is described in the method for the utilization that disclosure further embodiment provides production nano zine oxide containing zinc ore crude
Activating agent is selected from one of calgon, neopelex or a variety of.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects：
1) by wet-leaching in conjunction with synthesis technology, the economic and environment-friendly utilization of super low-grade zinc is realized.
2) disclosed method is applied widely, and ammonia-ammonium bicarbonate Leaching Systems can be effectively to the former containing zinc of diversified forms
Mine is extracted and is utilized.
3) break traditional ammonia-ammonium carbonate method zinc complexing extracting technology by heating evaporation ammonia destroy complexing environment realize zinc from
Calcium oxide or hydroxide are added creatively into ammonium bicarbonate-zinc ammonia complex system by the orthodox practice of sub- Crystallization Separation, the application
Calcium moves zinc ammonium complex ion-zinc ion-calcium zincates balance, by flat under the premise of not destroying solution ammonia environment
The shifting principle that weighs realizes the selective crystallization separation of Zn-ef ficiency, and avoiding existing heating ammonia still process method from destroying ammonia environment causes impurity a large amount of
The phenomenon that co-precipitation.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, greatly reduces the energy consumption of technique, it is thus also avoided that ammonia still process
Caused high temperature and pressure security risk and equipment etching problem.
4) leaching and separation that zinc is realized by the circulation of carbonate solve in ammonia circulation technology because steam brings water more than needed into
Measure the environmental issue for influencing process water balance and facing.
5) relative to zinc oxide floatation process, disclosed method solves the problems, such as the technique rate of recovery and fine work grade.
6) disclosed method pollution is small, and material is recyclable, solves the techniques such as existing zinc oxide flotation, sulfuric acid leaching
The problem of causing Heavy environmental pollution.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, and produces nano zine oxide via calcium zincates
Product；It is high from the reaction selectivity of zinc ammonium complex ion synthesis calcium zincates, it is simple and quick.
8) 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.
The scope of application of disclosed method is not particularly limited, and is widely portable to the various utilizations containing zinc ore crude.?
When using low-grade zinc oxide raw ore as raw materials for production, the advantages of method disclosed herein, is particularly pertinent.For example, low-grade former containing zinc
Mine can be zinc content 3%~15% containing zinc ore crude；Particularly, before the disclosure, zinc content contains 3%~6%
Zinc ore crude (lean ore, milltailings) is largely stored up, and existing various techniques are to can not make the utilization of existing economic value in fact
At very big processing pressure, and disclosed method is not only technically realized to such low-grade containing the effective of zinc ore crude
It utilizes, and simple process is easy, it is low in cost, there is very high economic value.
In the disclosure, the existence form containing zinc ingredient in zinc ore crude is not particularly limited, such as zinc ingredient can be with packet
The one or more forms for including but being not limited to zinc oxide, zinc carbonate, zinc silicate etc. exist.
Explanation of nouns
Herein, unless otherwise indicated, " ammine carbonate zinc " is zinc ammonium complex ion and the compound that carbonate is formed
General name, including [Zn (NH3)4]CO3(four ammino zinc of carbonic acid), [Zn (NH3)3]CO3(three ammino zinc of carbonic acid), [Zn (NH3)2]CO3
(two ammino zinc of carbonic acid), [Zn (NH3)]CO3(one ammino zinc of carbonic 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. zinc oxide extracts
Ammonia and ammonium hydrogen carbonate are as digestion agent
ZnO+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O (integer that i is 1 to 4)
Ammonia and ammonium carbonate are as digestion agent
ZnO+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O (integer that i is 2 to 4)
B. zinc hydroxide extracts
Ammonia and ammonium hydrogen carbonate are as digestion agent
Zn(OH)2+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 1 to 4)
Ammonia and ammonium carbonate are as digestion agent
Zn(OH)2+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 2 to 4)
C. zinc carbonate (smithsonite) extracts
ZnCO3+iNH3=[Zn (NH3)i]CO3(integer that i is 1 to 4)
D. zinc silicate extracts
Ammonia and ammonium hydrogen carbonate are as digestion agent
ZnSiO3+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 1 to 4)
Ammonia and ammonium carbonate are as digestion agent
ZnSiO3+(i-2)NH3+(NH4)2CO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 2 to 4)
2. decarburization
CaO+H2O=Ca (OH)2
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
3. heavy zinc
Precipitate zinc hydroxide：
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
Form calcium zincates：
2[Zn(NH3)i]CO3+3Ca(OH)2+2H2O=
2CaCO3↓+2Ca(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；
Zn(OH)2=ZnO+H2O
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 1 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
Low-grade be mixed in a certain ratio containing zinc ore crude and prepared first digestion agent after will be levigate is stirred leaching
Out.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, carbonic acid
The mixed aqueous solution of hydrogen ammonium and ammonium carbonate.
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 raw ore ingredient, grades, 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,
The 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 is subtracted in complexing zinc theory carbonate consumption in the first digestion agent
It goes on the basis of difference obtained by the carbonate amount that zinc carbonate is brought into raw material to increase by 0~500%, effective carbon in more preferable digestion agent
The amount of acid group subtracts the basis of difference obtained by the carbonate amount that zinc carbonate in raw material is brought into complexing zinc theory carbonate consumption
Upper increase 50%-150%.Complexing zinc theory carbonate consumption, which refers to, is fully converted to ammine carbonate for the Zn-ef ficiency in raw ore
The amount of carbonate consumed in zinc.Therefore, the molar concentration of effective carbonate may be calculated as in the first digestion agent：
CFirst digestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VFirst digestion agent
Wherein, CFirst digestion agent carbonateFor the molar concentration of carbonate effective in the first digestion agent, nThe total zinc of raw oreFor containing in zinc ore crude
The amount of the substance of Zn-ef ficiency, nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude, VFirst digestion agentFor the first digestion agent volume,
A is coefficient, and the value of a is 100%~600%, preferably 150%~250%.The mass concentration of carbonate can in first digestion agent
It is converted according to molar concentration.
The preferred effective carbonate concentration of first digestion agent can be such that the zinc in raw ore leaches completely, and can realize carbonate
Circulation in process, and it is avoided that excessive carbonate causes stress subsequent technique processing.
The weight ratio of first digestion agent and the powder containing zinc ore crude is not particularly limited, as long as zinc ingredient can be leached.
It is preferred that the weight ratio of the first digestion agent and the powder containing zinc ore crude is 3:1 to 5:1, satisfied extracting effect can be not only obtained, but also avoid
The waste of one digestion agent.
The temperature of extraction is not particularly limited, as long as being leached the zinc ingredient in raw ore.It is preferred that at normal temperature into
Row extraction, such as extracted at 15~30 DEG C；It (such as 30~55 DEG C) can also be extracted at a temperature of slightly higher.It can also root
Suitable temperature is selected according to physical condition.
It is stirred after oxidation zinc ore crude is mixed with the first digestion agent, mixing time is not particularly limited, as long as making original
Zinc ingredient in mine is leached, and preferably mixing time is 1~4 hour, more preferable 1~2 hour.
In a leaching process, the Zn-ef ficiency in raw ore is converted into zinc ammonium complex ion (the zinc ammonia formed in leaching process
Complex ion is mainly zinc ammonium complex ion at different levels), into liquid phase.Be filtered after extraction, obtained after filtering containing zinc ammino from
First leachate of son.Zinc ammonium complex ion concentration in first leachate is not particularly limited, but in preferably the first leachate
Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) can make disclosed method in 10g/L or more, more preferable 10~50g/L
Overall economic efficiency is best.
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 pretreatment
In pre-treatment step, calcium hydroxide and/or calcium oxide are added into the first leachate, is stirred to react 1~2 hour
After be filtered, obtain the first solid and the first filtrate.Reaction preferably carries out under such as 15~25 DEG C of room temperature.This step is main
Be by participate in ammine carbonate zinc formed carbonate except effective carbonate more than needed be converted into calcium carbonate (the first solid) from
And be filtered to remove, and the zinc ammonium complex ion of the overwhelming majority is retained in the first filtrate.In addition, obtaining by main component of calcium carbonate
One solid can also be calcined to calcium oxide and carbon dioxide, and realization recycles.
The calcium hydroxide and/or oxygen being added from the angle for mitigating subsequent technique processing pressure, preferred pretreatment step
The amount of the amount and effective carbonate more than needed in the first leachate of changing calcium matches.For example, having in the first leachate of detection
Carbonate total concentration is imitated, in conjunction with leachate total volume, calculates in leachate and participates in except the carbonate that ammine carbonate zinc is formed
Effective carbonate more than needed amount (for ammine carbonate zinc, the amount of zinc ammonium complex ion and carbanion substantially 1:1 closes
System), then show that the effective carbanion for removing and partly or entirely having more than needed in leachate needs calcium hydroxide and/or oxygen to be added
Change calcium dosage (allowing slightly excessive).For example, the amount of the substance of the calcium hydroxide and/or calcium oxide that add in this step can be pressed
Formula calculates：
nPretreatment=(nFirst leachate carbonate-nZinc ammonium complex ion)×b
Wherein, nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step, nFirst leachate carbonate
For the amount of the substance of effective carbonate in the first leachate, nZinc ammonium complex ionFor the substance of zinc ammonium complex ion in the first leachate
Amount, b is coefficient.The value range of b preferably 90%≤b≤110%.
Step 4 sinks zinc
The purpose of this step is that the zinc ammonium complex ion conversion solid in the first filtrate precipitates.In this step,
Calcium hydroxide and/or calcium oxide is added to the first filtrate, stirring is reacted, zinc ammonium complex ion-zinc ion-in the first filtrate
Zinc hydroxide/zincic acid calcium balance moves, and zinc ammonium complex ion is decomposed, and a part of zinc ingredient is in the form of zinc hydroxide and carbon
Sour calcium co-precipitation, another part are converted into calcium zincates and precipitate.
In this step, calcium hydroxide and/or calcium oxide are preferably added to until sediment no longer increases.
The reaction temperature of this step is not particularly limited, and can be such as 15~90 DEG C, but since reaction is without heating just
It can carry out, therefore particularly preferably be reacted under room temperature (15~25 DEG C) well, on the one hand need not heat to save energy
On the other hand environmental pollution caused by ammonia volatilization is also reduced in source.
It is filtered after reaction, the second solid and the second filtrate is obtained by filtration.Second solid is mainly zinc hydroxide, zincic acid
The mixture of calcium and calcium carbonate.It can be passed through carbon dioxide to the second filtrate, then recycled for the extraction containing zinc ore crude.
Step 5 is once calcined
In this step, the second solid for taking step 4 to obtain is calcined, and calcination temperature is 150~1050 DEG C, preferably
250~350 DEG C.By calcining, the zinc hydroxide in the second solid is made to be converted into zinc oxide, calcium zincates decompose.If calcining temperature
Degree is at 250~350 DEG C, then calcined product main component is zinc oxide, calcium hydroxide and calcium carbonate.If using higher calcining
Temperature, then calcium hydroxide, calcium carbonate are also possible to be further converted to calcium oxide.
Step 6 two times extractions
Configured second digestion agent is added in the calcined product obtained to a calcining step, is stirred extraction, it is excellent
Choosing stirring 1~4 hour.Second digestion agent can be the mixed aqueous solution of ammonia and ammonium hydrogen carbonate or the mixing water of ammonia and ammonium carbonate
The mixed aqueous solution of solution or ammonia, ammonium hydrogen carbonate and ammonium carbonate, preferably ammonia-ammonium carbonate solution, wherein the quality of total ammonia is dense
Degree is 6%~12%, and the mass concentration of effective carbonate is 8%~15%.
In this step, the calcium hydroxide (or calcium oxide) in a calcined product in the second digestion agent with water, have
It imitates carbonate reaction and generates precipitation of calcium carbonate, the zinc oxide in a calcined product is then converted into ammine carbonate zinc ([Zn (NH3)i]
CO3, i be 1 to 4 integer) enter liquid phase.Be filtered to remove precipitation of calcium carbonate after the reaction was completed, the filtrate being obtained by filtration be containing
Second leachate of zinc ammonium complex ion is used for subsequent piezocrystallization step.
Step 7 piezocrystallization
Activating agent is added into the second leachate, carbon dioxide gas is then pressed into the second leachate, makes the second leaching
Free ammonia in liquid is converted to ammonium carbonate, and zinc ingredient then loses Complexation conditions, is precipitated in the form of basic zinc carbonate.Activating agent is excellent
Calgon or neopelex are selected, dosage is preferably estimate finished product quality 0.01~0.05%.
Crystallization pressure control is 0.3~0.6MPa, which is better than high temperature.Due to the carbon in aqueous solution
Sour ammonium reaches 70 DEG C under normal pressure voluntarily to be decomposed, and the recycling that pressure difference realizes carbon dioxide can be industrially efficiently used,
The consumption of technique carbon dioxide is reduced, therefore the preferred reaction temperature control of this step is at 70~90 DEG C.This step is contained
There are the slurries of basic zinc carbonate 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.The average grain diameter of nano zine oxide 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
Yunnan somewhere zinc ore, Zn content 11.67%, raw ore oxygenation efficiency 95.2%, the zinc ingredient in the mine are with zinc carbonate
It is primarily present form.
2000 grams of oxidation zinc ore crudes are taken, 6000 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonic acid are put into
Root mass concentration 5%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, after filtering
Liquid in ingredient containing zinc (meter is worked as with zinc oxide) 3.374%, carbonate mass concentration 6.21% in liquid, increased portion is divided into
Zinc carbonate in raw ore is brought into.According to inspection data, solvable zinc recovery is 91.11% in leaching process raw ore, total zinc recovering
Rate is 86.74%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
5000 milliliters of purified leachate is taken, 195 grams of calcium oxide are added, for that will participate in being formed the carbon of ammine carbonate zinc
Carbonate more than needed except acid group, which sinks, to be removed.It is filtered after being stirred to react 1 hour.
115 grams of calcium oxide are added to filtered liquid and are used for depositing zinc ingredient.Stirring is reacted, after reaction 1 hour
It is filtered.
The zinc hydroxide being obtained by filtration, calcium carbonate and zincic acid calcium compound is dry, then calcined 2 hours at 300 DEG C.Through
Sampling analysis, zinc oxide content is 52.36% in calcined product.
200 grams of calcined products are taken, 1600 milliliters of ammonia-ammonium carbonate mixed liquor (total ammonia mass concentration 10%, carbonate is added
Mass concentration 12%) it is stirred extraction, mixing time is 2 hours, is then filtered.Zinc ingredient is dense in filtered filtrate
Spending (working as meter with zinc oxide) is 6.52%.
30 milligrams of neopelexes are added to filtered filtrate, are placed in reaction kettle after filtrate is heated to 70 DEG C
In, compression carbon dioxide gas is passed through reaction kettle and is reacted, pressure is controlled in 0.3MPa, inspection by sampling, when zinc in liquid
Concentration stops the addition of carbon dioxide when being lower than 0.5%, be pumped into positive press filtration device and be 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, the nano oxidized zinc product of gained is through check analysis, and wherein zinc oxide contains
Amount is 99.76%, average grain diameter 21.6nm.
Embodiment 2
Chongqing somewhere zinc ore, Zn content 12.93%, raw ore oxygenation efficiency 94.82%, the zinc ingredient in the mine are with zinc silicate
It is primarily present form.
2000 grams of oxidation zinc ore crudes are taken, 6000 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonic acid are put into
Root mass concentration 6%) in be stirred extraction, 50 DEG C of extraction temperature, mixing time is 2 hours, is then filtered, after filtering
Liquid in ingredient containing zinc (meter is worked as with zinc oxide) 3.681%, carbonate mass concentration 6.34% in liquid, increased portion is divided into
Zinc carbonate in raw ore is brought into.According to inspection data, solvable zinc recovery is 90.07% in leaching process raw ore, total zinc recovering
Rate is 85.41%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
5000 milliliters of purified leachates are taken, 190 grams of calcium oxide are added, for that will participate in being formed the carbon of ammine carbonate zinc
Carbonate more than needed except acid group, which sinks, to be removed.It is filtered after being stirred to react 1 hour.
130 grams of calcium hydroxides are added to filtered liquid and are used for depositing zinc ingredient, stirring is reacted, and is reacted 1 hour
After be filtered.
The zinc hydroxide being obtained by filtration, calcium carbonate and zincic acid calcium compound is dry, then calcined 2 hours at 300 DEG C.Through
Sampling analysis, zinc oxide content is 52.51% in calcined product.
200 grams of calcined products are taken, 1600 milliliters of ammonia-ammonium carbonate mixed liquor (total ammonia mass concentration 10%, carbonate are put into
Mass concentration 12%) in be stirred extraction, mixing time is 2 hours, is then filtered.Zinc ingredient in filtered filtrate
Concentration (working as meter with zinc oxide) is 6.53%.
30 milligrams of neopelexes are added to filtered filtrate, are placed in reaction kettle after filtrate is heated to 70 DEG C
In, compression carbon dioxide gas is passed through reaction kettle and is reacted, pressure 0.3MPa, inspection by sampling, when zinc is dense in liquid are controlled
The addition for stopping carbon dioxide when degree is lower than 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
99.8%, average grain diameter 17.6nm.
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 the production nano zine oxide containing zinc ore crude, which is characterized in that described to be received using the production containing zinc ore crude
The method of rice zinc oxide includes the following steps：
Leach step：Being mixed after will be levigate containing zinc ore crude and the first digestion agent, 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；
Pre-treatment step：Calcium oxide and/or calcium hydroxide are added into first leachate, then stirring is filtered, obtain the
One solid and the first filtrate；
Heavy zinc step：Calcium hydroxide and/or calcium oxide is added to first filtrate, then stirring filters, obtains the second solid
With the second filtrate；
Calcining step：Second solid is taken to be calcined, calcination temperature is 150~1050 DEG C, preferably 250~350 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, then passes to 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, 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 the production nano zine oxide containing zinc ore crude, which is characterized in that described first
The mass concentration of total ammonia in digestion agent is 5%~15%, and the molar concentration of effective carbonate in first digestion agent is：
CFirst digestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VFirst digestion agent
Wherein,
CFirst digestion agent carbonateFor the molar concentration of effective carbonate in first digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
VFirst digestion agentFor the volume of first digestion agent,
The value range of a is 100%~600%, preferably 150%~250%；
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 the production nano zine oxide containing zinc ore crude, which is characterized in that described
Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in first leachate is 10g/L or more, preferably 10~50g/L.
4. according to the method according to any one of claims 1 to 3 using the production nano zine oxide containing zinc ore crude, feature
It is, the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the pre-treatment step is：
nPretreatment=(nFirst leachate carbonate-nZinc ammonium complex ion)×b
Wherein, nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step, nFirst leachate carbonateIt is
The amount of the substance of effective carbonate in one leachate, nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the first leachate, b
Value range be 90%≤b≤110%.
5. the method according to any one of claims 1 to 4 using the production nano zine oxide containing zinc ore crude, feature exist
In, in the heavy zinc step, addition calcium hydroxide and/or calcium oxide into first filtrate, until sediment no longer increases
Mostly stop.
6. the method according to any one of claims 1 to 5 using the production nano zine oxide containing zinc ore crude, feature exist
In in the piezocrystallization step, crystallization pressure is 0.3~0.6MPa.
7. the method according to any one of claims 1 to 6 using the production nano zine oxide containing zinc ore crude, feature exist
In making the part ammonium carbonate in the third filtrate be decomposed into the reaction of ammonia and carbon dioxide in the decompression decomposition step
70~90 DEG C at a temperature of carry out.
8. the method according to any one of claims 1 to 7 using the production nano zine oxide containing zinc ore crude, feature exist
In second filtrate obtained to the heavy zinc step is passed through carbon dioxide, and the second filtrate for being passed through carbon dioxide is made
For the first digestion agent, recycle for the primary extraction containing zinc ore crude.
9. the method according to any one of claims 1 to 8 using the production nano zine oxide containing zinc ore crude, feature exist
In 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.
10. the method according to any one of claims 1 to 9 using the production nano zine oxide containing zinc ore crude, feature exist
In, the activating agent be selected from one of calgon, neopelex or a variety of.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817265.9A CN108862370A (en) | 2018-07-24 | 2018-07-24 | A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude |
| PCT/CN2019/088490 WO2020019854A1 (en) | 2018-07-24 | 2019-05-27 | Method for producing zinc oxide by means of double leaching |
| CN201980002439.9A CN110972479B (en) | 2018-07-24 | 2019-05-27 | Method for producing zinc oxide by twice leaching method |
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| CN201810817265.9A CN108862370A (en) | 2018-07-24 | 2018-07-24 | A method of nano zine oxide being produced under zinc ammonia complexing environment using containing zinc ore crude |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019854A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing zinc oxide by means of double leaching |
| CN110817930A (en) * | 2019-07-25 | 2020-02-21 | 重庆东群科技有限公司 | Method for producing zinc ammonium carbonate |
| CN110817935A (en) * | 2019-07-25 | 2020-02-21 | 重庆东群科技有限公司 | Method for preparing high-purity zinc oxide by utilizing zinc renewable resources |
-
2018
- 2018-07-24 CN CN201810817265.9A patent/CN108862370A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020019854A1 (en) * | 2018-07-24 | 2020-01-30 | 重庆东群科技有限公司 | Method for producing zinc oxide by means of double leaching |
| CN110817930A (en) * | 2019-07-25 | 2020-02-21 | 重庆东群科技有限公司 | Method for producing zinc ammonium carbonate |
| CN110817935A (en) * | 2019-07-25 | 2020-02-21 | 重庆东群科技有限公司 | Method for preparing high-purity zinc oxide by utilizing zinc renewable resources |
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