CN108913887A - A method of zinc oxide is produced using containing zinc ore crude - Google Patents
A method of zinc oxide is produced using containing zinc ore crude Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/34—Obtaining zinc oxide
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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Abstract
This disclosure relates to a kind of method using the production zinc oxide containing zinc ore crude, including a leach step, optional purifying step, decarbonation process, calcium zincates synthesis 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, supplies are recyclable, the calcium zincates synthesis under zinc ammonia environment is realized for the first time, and zinc oxide product is produced via calcium zincates, creatively utilize the decomposition condition of ammonium carbonate, 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 zinc 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, the zinc after vulcanizing package is needed could be directly as production metallic zinc or life after pyrogenic process or pressure oxidation secondary treatment
Produce the raw material of zinc oxide.
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.
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 method packet using the production zinc oxide containing zinc ore crude
Include 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；
Decarbonation process：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：It is passed through the carbon dioxide of pressurization into second leachate, obtains the 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, aoxidized
Zinc product.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, 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 mass concentration of effective carbonate is 8%~
15%.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, described first
Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in leachate is 10~25g/L.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, described one
In secondary leach step, by the concentration of the zinc ammonium complex ion in first leachate being obtained by filtration (in terms of the quality of Zn-ef ficiency)
It is adjusted to 10~25g/L.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, described de-
The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in carbon step is the object of effective carbonate in first leachate
The 100% to 130% of the amount of matter, preferably 100% to 110%.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, in the zinc
In sour calcium synthesis step, it is added into first filtrate in amount and the first filtrate of the substance of calcium hydroxide and/or calcium oxide
The ratio between amount of substance of zinc ammonium complex ion is 1~1.2:2, preferably 1~1.1:2.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, add described
In piezocrystallization step, crystallization pressure is 0.3~0.6MPa.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, subtract described
It presses in decomposition step, the part ammonium carbonate in the third filtrate is made to be decomposed into the reaction of ammonia and carbon dioxide at 70~90 DEG C
At a temperature of carry out.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, to the zinc
Second filtrate that sour calcium synthesis step obtains is passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as first
Digestion agent is recycled for the primary extraction containing zinc ore crude.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, subtract described
It presses in 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) 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 supplies are recyclable, and it is former to solve existing zinc oxide treatment process auxiliary
The problem of expecting bring environmental pollution.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, and produces zinc oxide via calcium zincates and produce
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
Lime is reacted with water
CaO+H2O=Ca (OH)2
Precipitating
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
[Zn(NH3)i]CO3+Ca(OH)2=[Zn (NH3)i](OH)2+CaCO3↓
(integer that i is 1 to 4)
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
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, the first leachate can be used for decarbonization process.
In the first leachate that leaching process obtains, zinc ammonium complex ion concentration is not particularly limited, but preferably in leachate
Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) be 10~25g/L, the treatment effeciency of technique can be made optimal, subsequent
Good yield and purity are obtained in calcium zincates synthesis step, overall economic efficiency is best.If zinc in the liquid of original leaching
The liquid of leaching is also optionally concentrated or is diluted not in preferred scope by ammonium complex ion concentration, will be in leachate
Zinc ammonium complex ion concentration 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 decarburization
In decarbonation process, calcium hydroxide and/or calcium oxide are added into the first leachate, precipitate that (first consolidates
Body), it then filters, the first solid and the first filtrate is separated.Decarbonation process is mainly by carbonate/carbon in the first leachate
Sour hydrogen radical precipitating removes, and most zinc ammonium complex ion is retained in filtrate.
In this step, calcium oxide and/or calcium hydroxide are added into the first leachate.Calcium oxide and/or calcium hydroxide
Additional amount can be determined according to the amount of carbonate effective in the first leachate, preferably this step be added calcium hydroxide and/or
The amount of the substance of calcium oxide be the first leachate in effectively carbonate substance amount 100% to 130%, more preferable 100%
To 110%.It is stirred after calcium oxide and/or calcium hydroxide is added, preferably stirs 1~2 hour, can not only react fully, but also
Energy consumption can be controlled in the reasonable scope.It is filtered after the completion of stirring, filtering resulting first solid main component is carbonic acid
Calcium.If zinc ammonium complex ion excessive concentration in the first leachate of step 1, part zinc ingredient will be in the form of zinc hydroxide and carbon
Sour calcium co-precipitation.The first filtrate is obtained after filtering for carrying out next step, calcium carbonate can then be calcined to calcium oxide and dioxy
Change carbon, realization recycles.
The synthesis of step 4 calcium zincates
Calcium hydroxide and/or calcium oxide is added in the first filtrate obtained to step 3, and stirring is reacted.Add in this step
The ratio between the amount of the substance of the calcium hydroxide and/or calcium oxide that enter and amount of substance of zinc ammonium complex ion in the first filtrate 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, into
Preferably 30~60 DEG C of one step；Or it is also preferred that 15~25 DEG C of reaction temperature, the temperature range have without heating, energy conservation and subtract
The advantages of few ammonia volatilization.Reaction can be filtered for 0.5~2 hour after (preferably 0.5~1 hour), without prolonged reaction
And ageing process.It is filtered after reaction, the second solid based on calcium zincates and the second filtrate is obtained by filtration, it can be to the second filter
Liquid is passed through carbon dioxide, then recycles 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 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 contains zinc oxide, hydrogen using higher calcination temperature
Calcium oxide 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, the calcium hydroxide in mixture is reacted with effective carbonate in the second digestion agent generates calcium carbonate
It precipitates, the zinc oxide in mixture is then converted into ammine carbonate zinc ([Zn (NH3)i]CO3, i be 1 to 4 integer).Reaction is completed
After be filtered to remove precipitation of calcium carbonate, the filtrate being obtained by filtration is the second leachate containing zinc ammonium complex ion, for subsequent plus
Piezocrystallization step.
Step 7 piezocrystallization
Carbon dioxide gas is pressed into the second leachate, the free ammonia in the second leachate is made to be converted to ammonium carbonate, zinc at
Divide and then lose Complexation conditions, is precipitated in the form of basic zinc carbonate.Crystallization pressure control is 0.3~0.6MPa, the process reaction
Temperature low temperature is better than high temperature.It can voluntarily decompose since the ammonium carbonate in aqueous solution reaches 70 DEG C under normal pressure, can industrially have
Effect realizes the recycling of carbon dioxide using pressure difference, reduces the consumption of technique carbon dioxide, therefore this step is preferably anti-
Answer temperature control at 70~90 DEG C.This step obtains the slurries containing 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 zinc oxide solid.
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 5.6%, raw ore oxygenation efficiency 96.3%, the zinc ingredient in the mine is based on zinc carbonate
Want existence 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 3%) 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) 1.632%, carbonate mass concentration 4.23% in liquid, increased portion is divided into
Zinc carbonate in raw ore is brought into.According to inspection data, solvable zinc recovery is 90.79% in leaching process raw ore, total zinc recovering
Rate is 87.43%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
145 grams of calcium oxide are added to purified leachate, for precipitating carbonate, reaction is filtered after 1 hour.
5000 milliliters of filtered liquid is taken, synthesis of 24.5 grams of calcium hydroxides for calcium zincates is added, stirring carries out anti-
It answers, reaction is filtered after 1 hour, is obtained after filtering with calcium zincates solid as main component.
Calcium zincates solid is dried 2 hours at 105 DEG C, then is calcined through 300 DEG C.
80 grams of calcined solids are taken, 800 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.
After filtered filtrate is heated to 70 DEG C be placed in reaction kettle in, will compression carbon dioxide gas be passed through reaction kettle into
Row reaction, pressure control stop the addition of carbon dioxide when zinc concentration is lower than 0.5% in liquid in 0.3MPa, inspection by sampling,
Positive press filtration device is pumped into 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, gained zinc oxide product is through check analysis, wherein zinc oxide content
99.76%.
Embodiment 2
Chongqing somewhere zinc ore, Zn content 4.7%, raw ore oxygenation efficiency 95.52%, the zinc ingredient in the mine is based on zinc silicate
Want existence form.
2000 grams of oxidation zinc ore crudes are taken, 6000 milliliters of ammonia-ammonium bicarbonate mixed liquor (ammoniacal liquor mass concentration 10%, carbonic acid is put into
Root mass concentration 3%) 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) 1.367%, carbonate mass concentration 3.54% in liquid, increased portion is divided into
Zinc carbonate in raw ore is brought into.According to inspection data, solvable zinc recovery is 91.35% in leaching process raw ore, total zinc recovering
Rate is 87.26%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
145 grams of calcium oxide are added to purified leachate, for precipitating carbonate, reaction is filtered after 1 hour.
5000 milliliters of filtered liquid is taken, synthesis of 20 grams of calcium hydroxides for calcium zincates is added, stirring is reacted,
Reaction is filtered after 1 hour, is obtained after filtering with calcium zincates solid as main component.
Calcium zincates solid is dried 2 hours at 105 DEG C, then is calcined through 300 DEG C.
80 grams of calcined solids are taken, 800 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.
After filtered filtrate is heated to 70 DEG C be placed in reaction kettle in, will compression carbon dioxide gas be passed through reaction kettle into
Row reaction, controls pressure 0.3MPa, and inspection by sampling stops the addition of carbon dioxide when zinc concentration is lower than 0.5% in liquid, takes out
Enter positive press filtration device to be 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%.
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 zinc oxide containing zinc ore crude, which is characterized in that described to produce zinc oxide using containing zinc ore crude
Method include 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；
Decarbonation process：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：It is passed through the carbon dioxide of pressurization into second leachate, obtains the slurries containing 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 zinc oxide production
Product.
2. the method according to claim 1 using the production zinc oxide containing zinc ore crude, which is characterized in that first extraction
The mass concentration of total ammonia in 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 mass concentration of effective carbonate is 8%~
15%.
3. the method according to claim 1 or 2 using the production zinc oxide containing zinc ore crude, which is characterized in that described first
Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in leachate is 10~25g/L.
4. the method according to claim 1 or 2 using the production zinc oxide containing zinc ore crude, which is characterized in that described one
In secondary leach step, by the concentration of the zinc ammonium complex ion in first leachate being obtained by filtration (in terms of the quality of Zn-ef ficiency)
It is adjusted to 10~25g/L.
5. according to the method according to any one of claims 1 to 4 using the production zinc oxide containing zinc ore crude, feature exists
In the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the decarbonation process is having in first leachate
The 100% to 130% of the amount of the substance of effect carbonate, preferably 100% to 110%.
6. the method according to any one of claims 1 to 5 using the production zinc oxide containing zinc ore crude, which is characterized in that
In the calcium zincates synthesis step, the amount and first of the substance of calcium hydroxide and/or calcium oxide is added into first filtrate
The ratio between amount of substance of zinc ammonium complex ion is 1~1.2 in filtrate:2, preferably 1~1.1:2.
7. the method according to any one of claims 1 to 6 using the production zinc oxide containing zinc ore crude, which is characterized in that
In the piezocrystallization step, crystallization pressure is 0.3~0.6MPa.
8. the method according to any one of claims 1 to 7 using the production zinc oxide containing zinc ore crude, which is characterized in that
In the decompression decomposition step, make the part ammonium carbonate in the third filtrate be decomposed into the reaction of ammonia and carbon dioxide 70~
It is carried out at a temperature of 90 DEG C.
9. the method according to any one of claims 1 to 8 using the production zinc oxide containing zinc ore crude, which is characterized in that
Second filtrate that the calcium zincates synthesis step obtains 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.
10. the method according to any one of claims 1 to 9 using the production zinc oxide containing zinc ore crude, which 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.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817517.8A CN108913887A (en) | 2018-07-24 | 2018-07-24 | A method of zinc oxide is produced using containing zinc ore crude |
| CN201980002439.9A CN110972479B (en) | 2018-07-24 | 2019-05-27 | Method for producing zinc oxide by twice leaching method |
| PCT/CN2019/088490 WO2020019854A1 (en) | 2018-07-24 | 2019-05-27 | Method for producing zinc oxide by means of double leaching |
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| CN201810817517.8A CN108913887A (en) | 2018-07-24 | 2018-07-24 | A method of zinc oxide is produced using containing zinc ore crude |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 |
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