CN108892162A - A method of zinc oxide and compound of calcium carbonate are produced using containing zinc ore crude - Google Patents
A method of zinc oxide and compound of calcium carbonate are produced using containing zinc ore crude Download PDFInfo
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- CN108892162A CN108892162A CN201810817579.9A CN201810817579A CN108892162A CN 108892162 A CN108892162 A CN 108892162A CN 201810817579 A CN201810817579 A CN 201810817579A CN 108892162 A CN108892162 A CN 108892162A
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- zinc
- carbonate
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- oxide
- leachate
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
-
- 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
-
- 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
- C22B3/20—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
This disclosure relates to it is a kind of using the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, include the steps that leach step, optional purification leachate, settling step, optional rinse step, drying and calcining step.Wet-leaching in conjunction with synthesis technology, is realized the economic and environment-friendly utilization of super low-grade zinc by disclosed method, applied widely, is not necessarily to ammonia still process, simple and easy to do, is also greatly reduced the energy consumption of technique, Matter Transfer process is convenient and easy；Disclosed method has energy conservation, low investment, low-cost advantage, solve the environmental issue faced due to steam, which brings water more than needed into, influences process water balance in ammonia circulation technology, solve the problems, such as the technique rate of recovery and fine work grade, the raw material that resulting combination product directly as product, can also can be used as other industrial process uses；Disclosed method pollution is small, and supplies are recyclable, solves the problems, such as existing zinc oxide treatment process auxiliary material bring environmental pollution.
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
Kind utilizes the low-grade method containing zinc ore crude production zinc oxide and compound of calcium carbonate.
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 ore floatation process, external zinc oxide
Mine sorting index is：Zinc grade 36%~40%, the rate of recovery 60%~70%, up to 78%；China's zinc oxide ore sorts finger
It is designated as：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
The problems such as be 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
Vulcanizing treatment, the zinc after vulcanization package need after pyrogenic process or pressure oxidation secondary treatment could directly as production metallic zinc or
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.
In the prior art, ammonia-ammonium carbonate method production zinc oxide or zinc oxide, the technique can be used mainly to use low-grade zinc
In 10% or more the zinc oxide ore containing zinc, economic use value there is no at present for the super low-grade zinc containing zinc 3~6%.?
In existing ammonia-ammonium carbonate method technique, after leaching leachate of the zinc ore acquisition containing zinc ammonia complex with ammonia-ammonium bicarbonate, need to heat
Zinc ammonia complexing liquid steams ammonia, to realize the crystalline deposit of zinc ingredient.But due to the ingredient of low-grade zinc oxide ore composition and work
The economic input that skill is equipped with, when using 3~6% ultralow grade zinc oxide ores, zinc concentration is low in leachate, produces oxygen per ton
Change zinc product and need to complete the evaporation of 50 cubic metres or more zinc ammonia complexing liquid, energy consumption is high, and ammonia is waved during heating evaporation
Hair is not easy to control, be easy to cause environmental issue.Conventional ammonia-ammonium carbonate method produces oxidation zinc technology ammonia still process process using steam simultaneously
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 using containing zinc ore crude production zinc oxide and calcium carbonate
The method of compound includes the following steps：
Leach step：Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein
The digestion agent be ammonia and ammonium hydrogen carbonate mixed aqueous solution or ammonia and the mixed aqueous solution or ammonia of ammonium carbonate, ammonium hydrogen carbonate and
The mixed aqueous solution of ammonium carbonate；
Optionally, leachate obtained in the leach step is purified；
Settling step：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains solid
And filtrate；
Optionally, the solid that the settling step obtains is taken, is rinsed with water；
Drying and calcining step：The solid that the settling step is obtained by filtration is dried, is calcined, zinc oxide is obtained
With compound of calcium carbonate, wherein calcination temperature is 150 DEG C or more, preferably 250~350 DEG C.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the settling step is having in the leachate
The 100% to 130% of the amount of the substance of effect carbonate, preferably 100% to 110%.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the filtrate obtained to the settling step is passed through carbon dioxide, will be passed through the filtrate of carbon dioxide as leaching
Agent is proposed, is recycled for the extraction containing zinc ore crude.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the settling step is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added into the leachate that the leach step obtains, and are stirred
It mixes, filters, obtain the first solid and intermediate filtrate,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, stirring,
Filtering obtains the second solid and whole filtrate；
In the drying and calcining step, second solid is taken to be dried and calcine, or by first solid
Some or all of mixed with some or all of second solid, be then dried and calcine.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the amount of the calcium hydroxide and/or calcium oxide that add in the pre-treatment step is：
nPretreatment=(nLeachate 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,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the leachate,
The value of b is 0<B≤110%, the preferably value of b are 90%≤b≤110%.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the amount of the calcium hydroxide and/or calcium oxide that add in the heavy zinc step is：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein,
nHeavy zincTo sink the amount of the substance of calcium hydroxide and/or calcium oxide added in zinc step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the pre-treatment step,
The value of c is 100%≤c≤130%, and preferably the value of c is 100%≤c≤110%.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
It in method, calcines first solid and obtains calcium oxide and carbon dioxide, the carbon dioxide that the first solid obtains will be calcined and be passed through
In the end filtrate, using the whole filtrate for being passed through carbon dioxide as digestion agent, recycles for the extraction containing zinc ore crude, will calcine
The calcium oxide circulation that first solid obtains is used for pre-treatment step or heavy zinc step.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the mass concentration of total ammonia in the digestion agent is 5%~15%, preferably 6%~8%,
The molar concentration of effective carbonate in the digestion agent is：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein,
CDigestion agent carbonateFor the molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount containing the substance of Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount containing the substance of zinc carbonate in zinc ore crude,
VDigestion agentFor the volume of the digestion agent,
The value range of a is 100%~600%, and preferably the value range of a is 150%~250%.
Zinc oxide and compound of calcium carbonate are produced containing zinc ore crude in the utilization that disclosure further embodiment provides
In method, the zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in the leachate is in 10g/L or more, preferably 20~50g/
L。
The disclosure also provides a kind of zinc oxide and nano-calcium carbonate calcium complexes, and the compound according to the utilization of the disclosure by containing
The method of zinc ore crude production zinc oxide and compound of calcium carbonate is prepared, the particle tool of the zinc oxide and compound of calcium carbonate
There is core-shell structure, the kernel of the particle is made of calcium carbonate, and oxide coated by zinc is on the surface of the kernel.
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) calcium oxide or calcium hydroxide are added creatively into ammonium bicarbonate-zinc ammonia complex system, makes zinc ammonium complex ion-zinc
Ion-zinc hydroxide balance moves, to realize the Crystallization Separation of zinc ion, breaks traditional ammonia-ammonium carbonate method zinc complexing
Extracting technology destroys the orthodox practice that complexing environment realizes zinc ion Crystallization Separation by heating evaporation ammonia.The technique of the disclosure
It is simple and easy to do without ammonia still process, it is also greatly reduced the energy consumption of technique, reduces ammonia and steams volatilization and cause additional environmental protection treatment negative
Load.
4) according to disclosed method, in ammonia-ammonium carbonate method zinc complexing extraction low-grade zinc oxide treatment process, ammonium hydroxide
Technique dosage is higher by decades of times compared with the technique dosage of carbonate, using calcium oxide as medium, realizes zinc by the circulation of carbonate
It leaches and separation, Matter Transfer process is convenient and easy；Compared to traditional ammonia-ammonium carbonate method zinc complexing extracting technology with ammonia endless form
Realize that zinc leaches and isolated mode, disclosed method have energy conservation, low investment, low-cost advantage.
5) 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.
6) relative to zinc oxide floatation process, disclosed method solves the problems, such as the technique rate of recovery and fine work grade, institute
The raw material that the combination product obtained directly as product, can also can be used as other industrial process uses.
7) 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.
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.?
Using it is low-grade containing zinc ore crude as raw materials for production when, the advantages of method disclosed herein, is particularly pertinent.For example, low-grade contain zinc ore crude
Zinc content be can be 3%~15% containing zinc ore crude；Particularly, before the disclosure, zinc content is 3%~6% containing zinc
Raw ore (lean ore, milltailings) is largely stored up, and existing various techniques are to can not cause the utilization of existing economic value in fact
Very big processing pressure, and disclosed method is not only technically realized to such low-grade effective benefit containing zinc ore crude
With, and simple process is easy, and 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 (the including but not limited to various liquid such as digestion agent, leachate, intermediate filtrate
Body) 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. 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. precipitating (pretreatment)
Lime is reacted with water
CaO+H2O=Ca (OH)2
Calcium hydroxide reacts with ammonium carbonate/ammonium hydrogen carbonate and (removes carbonate or bicarbonate radical more than needed)
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
3. precipitating (heavy zinc)
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
4. calcining
Zn(OH)2=ZnO+H2O
Specific process step
Step 1 extraction
Low-grade be mixed in a certain ratio containing zinc ore crude and prepared digestion agent after will be levigate is stirred leaching.Leaching
Proposing agent can be selected from：The mixed aqueous solution of ammonia and ammonium hydrogen carbonate；The mixed aqueous solution of ammonia and ammonium carbonate；Ammonia, ammonium hydrogen carbonate and carbon
The mixed aqueous solution of sour ammonium.
Total ammonia density and effective carbonate concentration in digestion agent are not particularly limited, and those skilled in the art can be according to original
The factors such as mine ingredient, grade, are selected in conjunction with actual needs.
In the preferred scheme, the mass concentration of total ammonia is 5%~10%, more preferable 6%~8% in digestion agent, preferably
Concentration range can reach sufficient extracting effect, and avoid excessive ammonia cause waste and environmental issue.
In the preferred scheme, the amount of effective carbonate is to subtract original in complexing zinc theory carbonate consumption in digestion agent
Increase by 0~500% on the basis of difference obtained by the carbonate amount that zinc carbonate is brought into material, effective carbonate in more preferable digestion agent
Amount be complexed zinc theory carbonate consumption subtract difference obtained by the carbonate amount that zinc carbonate in raw material is brought on the basis of increase
Add 50%-150%.Complexing zinc theory carbonate consumption, which refers to, is fully converted to ammine carbonate zinc institute for the Zn-ef ficiency in raw ore
The amount of the carbonate of consumption.Therefore, the molar concentration of effective carbonate may be calculated as in digestion agent：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein, CDigestion agent carbonateFor the molar concentration of carbonate effective in digestion agent, nThe total zinc of raw oreFor containing the Zn-ef ficiency in zinc ore crude
Substance amount, nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude, VDigestion agentFor digestion agent volume, a is coefficient, a's
Value is 100%~600%, preferably 150%~250%.The mass concentration of carbonate can be changed according to molar concentration in digestion agent
It calculates.
The preferred effective carbonate concentration of digestion agent can be such that the zinc in raw ore leaches completely, and carbonate can be realized in work
Circulation in skill, and it is avoided that excessive carbonate causes stress subsequent technique processing.
The granularity containing zinc ore crude after levigate is not particularly limited, as long as zinc ingredient can be leached.It is preferred that containing zinc
The granularity of original ore powder is 120~200 mesh, can not only obtain satisfied extracting effect, but also can control the energy consumption of process of lapping and close
It manages in range.
The weight ratio of 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 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 wave of digestion agent
Take.
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 will contain after zinc ore crude is mixed with digestion agent and be stirred, mixing time is not particularly limited, as long as making in raw ore
Zinc ingredient is leached, and preferably mixing time is 1~4 hour, more preferable 1~2 hour.
In leaching process, the Zn-ef ficiency in raw ore is converted into zinc ammonium complex ion (zinc ammonium complex ion predominantly at different levels), into
Enter in liquid phase.It is filtered after extraction, the leachate containing zinc ammonium complex ion is obtained after filtering, leachate can be used for subsequent heavy
Zinc process.Zinc ammonium complex ion concentration in leachate is not particularly limited, but preferably in leachate zinc ammonium complex ion concentration (with
The quality meter of Zn-ef ficiency) disclosed method overall economic efficiency can be made best in 10g/L or more, more preferable 20~50g/L.
Step 2 purification
Step 2 be optional step, it is necessary to when selection carry out step 2.Leachate is purified by known method,
Remove the impurity elements such as iron, manganese, lead, copper.A kind of illustrative purification method is that addition zinc powder replace and then filtered, thus
Heavy metal contaminants are removed, but other various well known purification methods also can be used.Purifying step helps to improve finished product
Purity.
Step 3 precipitating
In settling step, calcium hydroxide and/or calcium oxide are added into the leachate containing zinc ammonium complex ion, will leach
Carbonate/bicarbonate in liquid is converted into calcium carbonate, while zinc ammonium complex ion-zinc ion-zinc hydroxide is flat in leachate
Weighing apparatus moves, and part zinc ammonium complex ion is decomposed, and zinc ingredient is mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In settling step, the additive amount of calcium hydroxide and/or calcium oxide is not particularly limited, as long as making in leachate
Carbonate/bicarbonate is converted into calcium carbonate, and part zinc conversion is the form of zinc hydroxide precipitation.Preferably, hydrogen
The content of effective carbonate in the substantially matching leachate of the additive amount of calcium oxide and/or calcium oxide, for example, precipitation process addition
The amount of the substance of calcium hydroxide and/or calcium oxide is 100% to 130% of the amount of the substance of effective carbonate in leachate, more
It is preferred that 100% to 110%.Calcium hydroxide and/or calcium oxide are appropriately added, helps to control process costs, it helps change
Kind finished product zinc product grade.
In settling step, calcium hydroxide and/or calcium oxide are added into leachate, stirring is reacted, and solid is generated
Precipitating.The temperature of reaction is not particularly limited, but can carry out well since reaction is not necessarily to heating, therefore particularly preferably normal
It is reacted under temperature (such as 15~25 DEG C), it is on the one hand energy saving, on the other hand also reduce environmental pollution caused by ammonia volatilization.
Mixing time is not particularly limited, as long as being precipitated, preferably stirs 1~2 hour.It is filtered after stirring, filters institute
The solid main component obtained is zinc hydroxide and calcium carbonate.Due to specific reaction condition, which has on microcosmic
Composite construction is mainly made of calcium carbonate inside product grain, and zinc hydroxide is covered on the surface of calcium carbonate core.
A small amount of zinc ion or zinc ammonium complex ion may still be contained by filtering resulting filtrate, but can be passed through titanium dioxide to filtrate
Carbon, then circulation is used for the low-grade extraction containing zinc ore crude, therefore does not influence the rate of recovery of integrated artistic.
Step 4 rinsing
Step 4 be optional step, it is necessary to when selection carry out step 4.The solid that step 3 is obtained by filtration is (main
Ingredient is zinc hydroxide and calcium carbonate) add water to be rinsed, liquid-solid ratio 5~10:1, rinsing times 1~2 time.
Step 5 drying and calcining
In this step, by the solid being obtained by filtration in step 3 (being the solid after rinsing if having carried out rinse step)
Calcining is dried, converts zinc oxide for the zinc hydroxide in solid, calcination temperature is 150 DEG C or more, preferably 250~350
DEG C, to obtain containing zinc complexes, main component is zinc oxide and calcium carbonate.It is resulting containing zinc complexes can be directly as rubber
Glue additive or feed addictive also can be used as other industrial uses.Particularly, it is microcosmic upper with core-shell structure copolymer to contain zinc complexes for this
Composite construction, core of the calcium carbonate as sediment, oxide coated by zinc is on the surface of calcium carbonate core.This structure is for compound
The performance that object plays rubber additive is particularly advantageous.
In further embodiment, the higher mixture of zinc hydroxide percentage, step 3 (precipitating) can be divided into order to obtain
Pretreatment, heavy two step of zinc carry out：
Step 3a pretreatment
In pre-treatment step, it is added into leachate in a certain amount of calcium hydroxide and/or calcium oxide, with leachate
Effective carbonate partly or entirely more than needed forms precipitation of calcium carbonate, thus by effective carbonate partly or entirely more than needed from leaching
It is removed in liquid out.Effective carbonate more than needed refers to effective carbonate that participation is formed except the carbonate of ammine carbonate zinc.
The amount of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step is not particularly limited, can be according to whole production
The requirement of zinc hydroxide percentage in product and suitably determine.If it is desired to which the ratio of zinc hydroxide is higher in finished product, then exist
The effective carbonate having more than needed in leachate is partly or entirely removed in pre-treatment step.
Such as：Effective carbonate total concentration in leachate is detected, in conjunction with leachate total volume, calculates and is participated in leachate
Ammine carbonate zinc formed carbonate except effective carbonate more than needed amount (for ammine carbonate zinc, zinc ammino from
The amount substantially 1 of son and carbanion:1 relationship), then obtain the effective carbonate for removing and partly or entirely having more than needed in leachate
Need calcium hydroxide and/or Calcium Oxide Dosage to be added (allowing slightly excessive).For example, the calcium hydroxide added in this step
And/or the amount of the substance of calcium oxide can be calculated as follows：
nPretreatment=(nLeachate 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, nLeachate carbonateFor
The amount of the substance of effective carbonate in leachate, nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in leachate, b is to be
Number.The value range of b can be such as 0<B≤110%：If it is desired to effective carbonate more than needed is substantially removed, then b
Value can be such as 90%≤b≤110%；If it is desired to only remove a part effective carbonate more than needed, then the value of b can
Think such as 60%≤b<90% or 30%≤b<60% or 0<b<30%.Under conditions of 90%≤b≤110%,
This technique can be made to obtain the high final product of zinc grade.
Required calcium hydroxide and/or calcium oxide are added into leachate, are filtered after being stirred to react 1~2 hour, mistake
Filter to obtain the first solid and intermediate filtrate.Reaction preferably carries out under such as 15~25 DEG C of room temperature.The main component of first solid
For calcium carbonate.Intermediate filtrate is taken to enter step 3b (heavy zinc) operation.
Step 3b sinks zinc
Calcium hydroxide and/or calcium oxide is added to the resulting intermediate filtrate of step 3a, is converted into the carbonate in filtrate
Calcium carbonate, while zinc ammonium complex ion-zinc ion-zinc hydroxide balance moves in filtrate, part zinc ammonium complex ion is decomposed,
Zinc ingredient is mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In step 3b, the dosage of calcium hydroxide and/or calcium oxide is not particularly limited, as long as making the zinc ingredient in filtrate
It is converted into the form of zinc hydroxide precipitation.Preferably, the dosage of calcium hydroxide and/or calcium oxide and intermediate filter in this step
The amount of remaining effective carbonate matches substantially in liquid, such as the substance of calcium hydroxide and/or calcium oxide is added in this step
Amount and the amount of the substance of remaining effective carbonate in intermediate filtrate are 1:1, allow certain error；But in view of extraction-precipitating
Complicated equilibrium system present in solution system, can also make calcium hydroxide and/or calcium oxide suitably excessive, to promote to have reacted
Entirely.Based on theory matching dosage, the excess of calcium hydroxide and/or calcium oxide is preferably no more than 30%, if excessive
Degree is excessively high, not only increases process costs, it is also possible to reduce the grade of finished product zinc product.
For example, the molal quantity of the calcium hydroxide and/or calcium oxide added in heavy zinc step can be calculated as follows：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein, nHeavy zincFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in heavy zinc step, nLeachate carbonateTo leach
The amount of the substance of effective carbonate in liquid, nPretreatmentFor the substance of the calcium hydroxide and/or calcium oxide that are added in pre-treatment step
Amount, c is coefficient, the value of c preferably 100%≤c≤130%, more preferable 100%≤c≤110%.
In step 3b, required calcium hydroxide and/or calcium oxide are added into the resulting filtrate of step 3a, is stirred to react
1~2 hour, reaction preferably carried out under such as 15~25 DEG C of room temperature.It is filtered after reaction, filtered obtained liquid
For whole filtrate, whole filtrate may still contain a small amount of zinc ion or zinc ammonium complex ion, but can be passed through carbon dioxide to whole filtrate, then
Circulation is used for the low-grade extraction containing zinc ore crude, therefore does not influence the rate of recovery of integrated artistic；Filtering obtained solid is known as second
Solid, main component include zinc hydroxide and calcium carbonate.
If step 3 is carried out in two steps (step 3a：Pretreatment, step 3b：Heavy zinc), then can take that step 3b obtains the
Two solids carry out subsequent rinsing, drying and calcining step, obtain zinc oxide-compound of calcium carbonate；Or step 3a can be taken to obtain
Some or all of first solid arrived is mixed with some or all of the second obtained solid of step 3b, is then carried out
Subsequent rinsing, drying and calcining step, obtain zinc oxide-compound of calcium carbonate, mixed proportion is not particularly limited, according to reality
Demand in production to Zn content in finished product suitably selects mixed proportion.
In addition, if step 3 is carried out in two steps (step 3a：Pretreatment, step 3b：Heavy zinc), then obtained by step 3a filtering
Solid (the first solid) main component be calcium carbonate, can 900 DEG C~1100 DEG C at a temperature of the first solid is calcined,
Calcium oxide and carbon dioxide are obtained, carbon dioxide can be absorbed by the resulting whole filtrate of step 3b, absorb the whole filter of carbon dioxide
Liquid can be used for the circulating leaching of low-grade zinc oxide raw ore, and calcium oxide is circularly used in settling step, it is achieved that work
The circulation of carbonate in skill, recycling for material significantly reduce the cost of technique.
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.
300 grams are taken containing zinc ore crude, is put into 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate matter
Amount concentration 5%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, filtered fluid
Middle zinc mass concentration 3.374% (calculate by zinc oxide is then 4.2%), carbonate mass concentration 6.21% in liquid, increased portion
It is divided into zinc carbonate in raw ore to bring into.According to inspection data, solvable zinc recovery is 91.11% in leaching process raw ore, and total zinc returns
Yield is 86.74%.
The zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
600 milliliters of purified zinc ammonia complexing liquid are taken, 19.69 grams of calcium oxide are added, form ammine carbonate for that will participate in
Carbonate more than needed except the carbonate of zinc, which sinks, to be removed, and is stirred after calcium hydroxide is added, reaction is filtered after 1 hour.
Take 500 milliliters of filtered liquid, 9.29 grams of calcium hydroxides be added for depositing zinc ingredient, stir at normal temperature into
Row reaction, reaction are filtered after 1 hour.
Remaining Zn content (working as meter with zinc oxide) is 15.12 gram per liters in filtered fluid, due to can be in production
The partially liq is used for the circulating leaching of raw material, does not influence the rate of recovery of integrated artistic.
Add water (liquid-solid ratio 10 to the calcium carbonate and zinc hydroxide mixture being obtained by filtration:1) it is rinsed twice, after rinsing
Mixture it is dry after calcined 2 hours at 300 DEG C, obtain the compound of calcium carbonate and zinc oxide.Through check analysis, this is multiple
Close zinc oxide content 37.5% in object, calcium carbonate content 62.2%.
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.
300 grams are taken containing zinc ore crude, is put into 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate matter
Measure concentration 6%) in carry out heating stirring extraction, 50 DEG C of extraction temperature, mixing time 2 hours, be then filtered, liquid after filtering
Zinc mass concentration 3.681% in body, carbonate mass concentration 6.34% in liquid, increased portion are divided into zinc carbonate in raw ore and bring into.
According to inspection data, solvable zinc recovery 90.07% in leaching process raw ore, total zinc recovery 85.41%.
The zinc ammonia complexing liquid zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
600 milliliters of purified zinc ammonia complexing liquid are taken, 18.98 grams of calcium hydroxides are added, form carbonic acid ammonia for that will participate in
Carbonate more than needed except the carbonate of conjunction zinc, which sinks, to be removed, and is stirred after calcium hydroxide is added, reaction is filtered after 1 hour.
Take 500 milliliters of filtered liquid, 10.6 grams of calcium hydroxides be added for depositing zinc composition, stir at normal temperature into
Row reaction, reaction are filtered after 1 hour.
Remaining Zn content (working as meter with zinc oxide) is 15.03 gram per liters in filtered fluid, due to can be in production
The partially liq is used for the circulating leaching of raw material, does not influence the rate of recovery of integrated artistic.
Add water (liquid-solid ratio 10 to filtered calcium carbonate and zinc hydroxide mixture:1) it is rinsed twice, after rinsing
It is being calcined 2 hours at 300 DEG C after mixture is dry, is obtaining the compound of calcium carbonate and zinc oxide.Through check analysis, this is compound
Zinc oxide content 37.7% in object, calcium carbonate content 62.1%.
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 utilize the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, which is characterized in that described using containing zinc
The method of raw ore production zinc oxide and compound of calcium carbonate includes the following steps：
Leach step：Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein is described
Digestion agent is the mixed aqueous solution or ammonia of ammonia and ammonium hydrogen carbonate and mixed aqueous solution or ammonia, the ammonium hydrogen carbonate and carbonic acid of ammonium carbonate
The mixed aqueous solution of ammonium；
Optionally, leachate obtained in the leach step is purified；
Settling step：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains solid and filter
Liquid；
Optionally, the solid that the settling step obtains is taken, is rinsed with water；
Drying and calcining step：The solid that the settling step is obtained by filtration is dried, is calcined, zinc oxide and carbon are obtained
Sour calcium complexes, wherein calcination temperature is 150 DEG C or more, preferably 250~350 DEG C.
2. according to claim 1 using the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, feature exists
In the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the settling step is effective carbon in the leachate
The 100% to 130% of the amount of the substance of acid group, preferably 100% to 110%.
3. according to claim 1 or 2 utilize the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, feature
It is, the filtrate obtained to the settling step is passed through carbon dioxide, will be passed through the filtrate of carbon dioxide as extraction
Agent is recycled for the extraction containing zinc ore crude.
4. according to claim 1 using the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, feature exists
In the settling step is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added into the leachate that the leach step obtains, and are stirred,
Filtering obtains the first solid and intermediate filtrate,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, is stirred, filtering,
Obtain the second solid and whole filtrate；
In the drying and calcining step, second solid is taken to be dried and calcine, or by the portion of first solid
Point or all mixed with some or all of second solid, be then dried and calcine.
5. according to claim 4 using the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, feature exists
In the amount of the calcium hydroxide and/or calcium oxide that add in the pre-treatment step is：
nPretreatment=(nLeachate 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,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nZinc ammonium complex ionFor the amount of the substance of the zinc ammonium complex ion in the leachate,
The value of b is 0<B≤110%, the preferably value of b are 90%≤b≤110%.
6. according to claim 4 or 5 utilize the method containing zinc ore crude production zinc oxide and compound of calcium carbonate, feature
It is, the amount of the calcium hydroxide and/or calcium oxide that add in the heavy zinc step is：
nHeavy zinc=(nLeachate carbonate-nPretreatment)×c
Wherein,
nHeavy zincTo sink the amount of the substance of calcium hydroxide and/or calcium oxide added in zinc step,
nLeachate carbonateFor the amount of the substance of effective carbonate in the leachate,
nPretreatmentFor the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in the pre-treatment step,
The value of c is 100%≤c≤130%, and preferably the value of c is 100%≤c≤110%.
7. the method containing zinc ore crude production zinc oxide and compound of calcium carbonate is utilized according to claim 4 to 6 is described in any item,
It is characterized in that,
It calcines first solid and obtains calcium oxide and carbon dioxide,
The obtained carbon dioxide of the first solid will be calcined to be passed through in the whole filtrate, will be passed through the whole filtrate of carbon dioxide as
Digestion agent is recycled for the extraction containing zinc ore crude,
The calcium oxide circulation that the first solid obtains will be calcined and be used for pre-treatment step or heavy zinc step.
8. according to any one of claims 1 to 7 utilize the method containing zinc ore crude production zinc oxide and compound of calcium carbonate,
It is characterized in that, the mass concentration of total ammonia in the digestion agent is 5%~15%, preferably 6%~8%,
The molar concentration of effective carbonate in the digestion agent is：
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein,
CDigestion agent carbonateFor the molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount containing the substance of Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount containing the substance of zinc carbonate in zinc ore crude,
VDigestion agentFor the volume of the digestion agent,
The value range of a is 100%~600%, and preferably the value range of a is 150%~250%.
9. producing zinc oxide and compound of calcium carbonate using containing zinc ore crude according to according to any one of claims 1 to 8
Method, which is characterized in that zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in the leachate is excellent in 10g/L or more
Select 20~50g/L.
10. utilizing the method for producing zinc oxide and compound of calcium carbonate containing zinc ore crude by the way that claim 1 to 9 is described in any item
The zinc oxide and compound of calcium carbonate of preparation, which is characterized in that the particle of the zinc oxide and compound of calcium carbonate has nucleocapsid
The kernel of composite construction, the particle is made of calcium carbonate, and oxide coated by zinc is on the surface of the kernel.
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| CN201810817579.9A CN108892162A (en) | 2018-07-24 | 2018-07-24 | A method of zinc oxide and compound of calcium carbonate are produced using containing zinc ore crude |
| CN201910573953.XA CN110184456A (en) | 2018-07-24 | 2019-06-28 | A kind of low-grade utilization method containing zinc ore crude |
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| CN110724831A (en) * | 2019-10-31 | 2020-01-24 | 重庆赛迪热工环保工程技术有限公司 | Carbon circulating system and method for producing zinc oxide by industrially recycling zinc |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110724831A (en) * | 2019-10-31 | 2020-01-24 | 重庆赛迪热工环保工程技术有限公司 | Carbon circulating system and method for producing zinc oxide by industrially recycling zinc |
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