CN108866333A - A kind of low-grade beneficiation method containing zinc ore crude - Google Patents
A kind of low-grade beneficiation method 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
- C22B19/02—Preliminary treatment of ores; Preliminary refining of zinc oxide
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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 low-grade beneficiation method containing zinc ore crude, including leach step, settling step, calcining step.Disclosed method realizes the economic and environment-friendly utilization of super low-grade zinc, it is applied widely, realize that the selective crystallization of Zn-ef ficiency separates by balance moving principle under the premise of not destroying solution ammonia environment, without ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, it is thus also avoided that various problems such as water process pressure caused by conventional method ammonia still process, high temperature and pressure security risk and equipment corrosion；Disclosed method solves the problems, such as the technique rate of recovery and fine work grade, and raw material needs secondary treatment technical process after solving the problems, such as vulcanizing treatment；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 the complex art fields of inorganic chemical industry and ore-dressing technique, are related to the low-grade recycling containing zinc ore crude
It utilizes, in particular to a kind of low-grade beneficiation method containing zinc ore crude.
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%.
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, 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 is needed through fire
It could be directly as production metallic zinc or the raw material of production zinc oxide after method or pressure oxidation secondary treatment.
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 in ore zinc silicate, zinc ferrite at
Divide and is 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 leaching rate is paid no attention to
Think, need high temperature to leach, overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, returned from leachate
The process for receiving zinc ingredient 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
The technique that low-grade zinc utilizes at present is high in the presence of energy consumption, recovery rate in ore-dressing is low, causes Heavy environmental pollution, economy
It is worth the problems such as low.The present invention solves above-mentioned present in low-grade zinc utilization ask by the improvement to zinc ore treatment process
Topic.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of low-grade beneficiation method containing zinc ore crude, including
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；
Settling step：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains solid
And filtrate；
Calcining step：The solid that the settling step is obtained is calcined at 850~1050 DEG C, is contained
The mixture of zinc oxide and calcium oxide.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the precipitating
The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in rapid is the amount of the substance of effective carbonate in the leachate
100% to 130%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked to the precipitating
Suddenly the filtrate obtained is passed through carbon dioxide, using the filtrate for being passed through carbon dioxide as digestion agent, recycles for former containing zinc
The extraction of mine.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, the settling step
It is divided into pre-treatment step, heavy zinc step two step carries out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added in the leachate obtained to the leach step, are stirred,
The first solid and intermediate filtrate is obtained by filtration,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to the pre-treatment step, is stirred
It mixes, filters, obtain the second solid and whole filtrate；
In the calcining step, second solid is taken, is calcined at 850~1050 DEG C；Or by described
Some or all of some or all of one solid and described second solid are mixed, and are then carried out at 850~1050 DEG C
Calcining.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, in the pretreatment
The amount of the calcium hydroxide and/or calcium oxide that add in 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%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the heavy zinc
The calcium hydroxide of addition and/or the amount of calcium oxide are in rapid：
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%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, calcining described first
Solid obtains calcium oxide and carbon dioxide, will calcine the carbon dioxide that the first solid obtains and is passed through in the whole filtrate, will be passed through
The whole filtrate of carbon dioxide is as digestion agent, and circulation is for the extraction containing zinc ore crude, oxidation that will calcine first solid and obtain
Calcium circulation is used for pre-treatment step or heavy zinc step.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, in the digestion agent
Total ammonia mass concentration be 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 amount of the substance 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 of the substance containing the 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%~200%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, described former containing zinc
In mine, the existence form of zinc ingredient includes one of zinc oxide, zinc carbonate, zinc silicate or a variety of.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the precipitating
In rapid, reacted in 15~25 DEG C of at a temperature of stirring.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects：
1) by wet-leaching in conjunction with ore-dressing technique, 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-zinc hydroxide balance, passes through under the premise of not destroying solution ammonia environment
Balance moving principle realizes the selective crystallization separation of Zn-ef ficiency.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, substantially reduces
The energy consumption of technique, it is thus also avoided that water process pressure caused by conventional method ammonia still process, high temperature and pressure security risk, equipment burn into
A large amount of ammonia steam volatilization and additional environmental protection treatment are caused various problems such as to bear.
4) disclosed method solves the problems, such as the technique rate of recovery and fine work grade, and resulting combination product can directly be made
For product, the raw material that also can be used as other industrial process is used.
5) 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 6%~15% containing zinc ore crude；Disclosed method is not only technically realized to such low-grade
Effective utilization containing zinc ore crude, 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 (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.
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
CaCO3=CaO+CO2
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 ammonia.
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%~15%, more preferable 6%~8% in digestion agent.It is preferred that
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%~100%.Complexing zinc theory carbonate consumption, which refers to, is fully converted to ammine carbonate zinc for the Zn-ef ficiency in raw ore
The amount of consumed carbonate.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 Zn-ef ficiency in zinc ore crude
The amount of substance, 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, and a's takes
Value is 100%~600%, preferably 150%~200%.The mass concentration of carbonate can convert according to molar concentration in digestion agent.
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 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 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 ions at different levels, into liquid phase.It is carried out after extraction
Filtering, obtains the leachate containing zinc ammonium complex ion, leachate can be used for subsequent heavy zinc process after filtering.Zinc ammonia in leachate
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) in 10g/L
More than, more preferable 10~50g/L.
Step 2 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 switchs to calcium carbonate, while zinc ammonium complex ion-zinc ion-zinc hydroxide balance in leachate
It moves, 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
Zinc conversion is the form of zinc hydroxide precipitation.Preferably, the additive amount of calcium hydroxide and/or calcium oxide is substantially matching
The content of effective carbonate in leachate, for example, the amount of the substance of the calcium hydroxide and/or calcium oxide of precipitation process addition is leaching
Out in liquid the amount of the substance of effective carbonate 100% to 130%, more preferable 100% to 110%.Appropriately add hydroxide
Calcium and/or calcium oxide help to control process costs, it helps improve 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
(such as 15~25 DEG C) are reacted under temperature, on the one hand need not be heated to energy saving, are on the other hand also reduced ammonia volatilization and are made
At environmental pollution.Mixing time is not particularly limited, as long as being precipitated, preferably stirs 1~2 hour.It stirs laggard
Row filtering, resulting solid main component includes zinc hydroxide and calcium carbonate, and resulting filtrate may still contain a small amount of zinc ion
Or zinc ammonium complex ion, but carbon dioxide can be passed through to filtrate, then circulation is used for the low-grade extraction containing zinc ore crude, therefore not shadow
Ring the rate of recovery of integrated artistic.
In further embodiment, the higher mixture of zinc hydroxide percentage, step 2 (precipitating) can be divided into order to obtain
Pretreatment, heavy two step of zinc carry out：
Step 2a 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 Zn content in product and suitably determine.If it is desired to the Zn content in finished product is higher, then it will in pre-treatment step
The most or all of removing of effective carbonate more than needed in leachate.
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 ammonium complex ion
With the amount substantially 1 of carbanion:1 relationship), then show that the effective carbonate for removing and partly or entirely having more than needed in leachate needs
Calcium hydroxide and/or Calcium Oxide Dosage (allowing slightly excessive) to be added.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 2b (heavy zinc) operation.
Step 2b sinks zinc
Calcium hydroxide and/or calcium oxide is added to the resulting intermediate filtrate of step 2a, makes carbonate/bicarbonate in filtrate
Root is converted into calcium carbonate, while zinc ammonium complex ion-zinc ion-zinc hydroxide balance moves in filtrate, zinc ammonium complex ion
It decomposes, zinc ingredient is mainly co-precipitated in the form of zinc hydroxide with calcium carbonate.
In step 2b, the dosage of calcium hydroxide and/or calcium oxide is not particularly limited, as long as making the carbonic acid in filtrate
Root/bicarbonate radical is converted into calcium carbonate, and part zinc conversion is the form of zinc hydroxide precipitation.Preferably, this step
The dosage of middle calcium hydroxide and/or calcium oxide matches substantially with the amount of remaining effectively carbonate in intermediate filtrate, such as this step
The amount of the remaining effectively substance of carbonate is 1 in the amount of the middle substance that calcium hydroxide and/or calcium oxide is added and intermediate filtrate:1,
But also allow certain legitimate skew.
For example, the amount of the substance of the calcium hydroxide and/or calcium oxide that add 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 2b, required calcium hydroxide and/or calcium oxide are added into the resulting intermediate filtrate of step 2a, stirs
Reaction 1~2 hour, reaction preferably carry out under such as 15~25 DEG C of room temperature.It is filtered after reaction, it is filtered to obtain
Liquid is whole filtrate, and 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 2 (precipitating) is divided into step 2a (pretreatment) and step 2b (heavy zinc) two steps carry out, in subsequent step
In rapid 3 (dryings), the second solid for taking step 2b to obtain is dried, and obtains the mixture containing zinc hydroxide and calcium carbonate,
Or some or all of some or all of the first obtained solid of step 2a second solid obtained with step 2b is carried out
It mixes (mixed proportion is in finished product depending on the actual demand of zinc hydroxide ratio height), send to subsequent dry step
Suddenly.
Step 3 calcining
The solid that step 2 (settling step) obtains is calcined under 850~1050 DEG C (preferably 900~950 DEG C), Gu
Zinc hydroxide in body is decomposed into zinc oxide, and Decomposition of Calcium Carbonate is calcium oxide, to obtain the mixing containing zinc oxide and calcium oxide
Object.
If step 2 is divided to for step 2a (pretreatment) and the progress of step 2b (heavy zinc) two steps, take that step 2b obtains the
Two solids are calcined under 850~1050 DEG C (preferably 900~950 DEG C), obtain the mixture of zinc oxide and calcium oxide,
Some or all of some or all of the first solid that step 2a can be obtained second solid obtained with step 2b carries out
Mixing, is then calcined under 850~1050 DEG C (preferably 900~950 DEG C), obtains the mixture of zinc oxide and calcium oxide.
Mixed proportion is in finished product depending on the actual demand of zinc oxide ratio height.
In addition, if step 2 is carried out in two steps (step 2a：Pretreatment, step 2b：Heavy zinc), then obtained by step 2a 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 2b, absorb the whole filter of carbon dioxide
Liquid can be used for the circulation extraction of low-grade zinc oxide raw ore, and calcium oxide is circularly used in pre-treatment step or heavy zinc step,
It is achieved that in technique carbonate circulation, recycling for material significantly reduce the cost of technique.
It is described in detail below in conjunction with embodiment of the embodiment to the disclosure, but those skilled in the art will
Understand, the following example is merely to illustrate the disclosure, and is not construed as the restriction to the scope of the present disclosure.It is not specified in embodiment
Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer,
Being can be with conventional products that are commercially available.
Embodiment 1
Yunnan somewhere zinc ore, Zn content 11.67%, raw ore oxygenation efficiency 95.2%, the zinc ingredient in the mine are with zinc carbonate
It is primarily present form.
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 after 600 milliliters of extractions is taken, 19.69 grams of calcium oxide are added, is formed for that will participate in
Carbonate more than needed except the carbonate of ammine carbonate zinc, which sinks, to be removed, and is stirred after calcium hydroxide is added, reaction carries out after 1 hour
Filtering.500 milliliters of filtered liquid is taken, 9.29 grams of calcium hydroxides are added for depositing zinc ingredient, stirring carries out at normal temperature
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.
Filtered calcium carbonate is calcined at 950 DEG C with zinc hydroxide mixture, obtains zinc oxide and calcium oxide
Mixture.Analysis, zinc oxide content 47.25% are sampled to mixture.
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 being obtained by filtration after 600 milliliters of extractions is taken, 18.98 grams of calcium hydroxides are added, for shape will to be participated in
It removes at the carbonate more than needed except the carbonate of ammine carbonate zinc is heavy, is stirred after calcium hydroxide is added, reaction 1 hour laggard
Row filtering.It takes filtered liquid to take 500 milliliters, 10.6 grams of calcium hydroxides is added for depositing zinc composition, stir at normal temperature
It is reacted, reaction is 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.
Filtered calcium carbonate is calcined at 950 DEG C with zinc hydroxide mixture, obtains zinc oxide and calcium oxide
Mixture.Analysis, zinc oxide content 47.42% are sampled to mixture.
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 low-grade beneficiation method containing zinc ore crude, which is characterized in that the low-grade beneficiation method packet containing zinc ore crude
Include 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；
Settling step：Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains solid and filter
Liquid；
Calcining step：The solid that the settling step is obtained is calcined at 850~1050 DEG C, is obtained containing oxidation
The mixture of zinc and calcium oxide.
2. the low-grade beneficiation method containing zinc ore crude according to claim 1, which is characterized in that in the settling step
The amount of the substance of the calcium oxide and/or calcium hydroxide of addition is the amount of the substance of effective carbonate in the leachate
100% to 130%.
3. the low-grade beneficiation method containing zinc ore crude according to claim 1 or 2, which is characterized in that walked to the precipitating
Suddenly the filtrate obtained is passed through carbon dioxide, using the filtrate for being passed through carbon dioxide as digestion agent, recycles for former containing zinc
The extraction of mine.
4. the low-grade beneficiation method containing zinc ore crude according to claim 1, which is characterized in that the settling step is divided into
Pre-treatment step, heavy zinc step two step carry out：
Pre-treatment step：Calcium hydroxide and/or calcium oxide are added in the leachate obtained to the leach step, are stirred, filtering
The first solid and intermediate filtrate are obtained,
Heavy zinc step：The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to the pre-treatment step, stirring,
Filtering obtains the second solid and whole filtrate；
In the calcining step, second solid is taken, is calcined at 850~1050 DEG C；Or described first is consolidated
Some or all of some or all of body and described second solid are mixed, and are then calcined at 850~1050 DEG C.
5. the low-grade beneficiation method containing zinc ore crude according to claim 4, which is characterized in that in the pre-treatment step
The calcium hydroxide of middle addition and/or the amount of calcium oxide are：
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. the low-grade beneficiation method containing zinc ore crude according to claim 5, which is characterized in that in the heavy zinc step
The calcium hydroxide of addition and/or the amount of calcium oxide are：
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. according to the described in any item low-grade beneficiation methods containing zinc ore crude of claim 4 to 6, which 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. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 7, which is characterized in that the leaching
The mass concentration for mentioning total ammonia in 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 amount of the substance 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 of the substance containing the 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%~200%.
9. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 8, which is characterized in that described
Containing in zinc ore crude, the existence form of zinc ingredient includes one of zinc oxide, zinc carbonate, zinc silicate or a variety of.
10. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 9, which is characterized in that described
In settling step, reacted in 15~25 DEG C of at a temperature of stirring.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817591.XA CN108866333A (en) | 2018-07-24 | 2018-07-24 | A kind of low-grade beneficiation method 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810817591.XA CN108866333A (en) | 2018-07-24 | 2018-07-24 | A kind of low-grade beneficiation method containing zinc ore crude |
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| Country | Link |
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2018
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