CN108866332A - 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 PDF

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Publication number
CN108866332A
CN108866332A CN201810817494.0A CN201810817494A CN108866332A CN 108866332 A CN108866332 A CN 108866332A CN 201810817494 A CN201810817494 A CN 201810817494A CN 108866332 A CN108866332 A CN 108866332A
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China
Prior art keywords
zinc
carbonate
calcium
amount
leachate
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CN201810817494.0A
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Chinese (zh)
Inventor
岳辉伟
李世川
龙忠祥
蒋涛
刘权锋
蒋文艺
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Chongqing Dong Qun Technology Co Ltd
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Chongqing Dong Qun Technology Co Ltd
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Priority to CN201810817494.0A priority Critical patent/CN108866332A/en
Publication of CN108866332A publication Critical patent/CN108866332A/en
Priority to CN201980002306.1A priority patent/CN110972482B/en
Priority to PCT/CN2019/087246 priority patent/WO2020019834A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/24Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

This disclosure relates to a kind of low-grade beneficiation method containing zinc ore crude, including leach step, settling step, calcium zincates synthesis step, drying steps.Disclosed method realizes the economic and environment-friendly utilization of ultra-low oxidized zinc ore, it is applied widely, it is not necessarily to 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 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 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;The disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time.

Description

A kind of low-grade beneficiation method containing zinc ore crude
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%, 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%.Flotation of Zinc Oxide needs to be added a large amount of simultaneously Vulcanized sodium carries out vulcanizing treatment, and zinc sulphide needs that after pyrogenic attack, directly as production metallic zinc or zinc oxide could be produced Raw material, energy consumption are high and seriously polluted.
For the wet underwater welding of zinc ore, mainly there are sulfuric acid leaching, Calcium Chloride Method, ammonium chloride method etc. in the prior art. Sulfuric acid leaching is selectively low, can largely leach the solvable silicon in ore, and the colloidal state silicon of generation is difficult to filter, and the acid-hatching of young eggs is raw At a large amount of sulfate slags, great environmental protection treatment pressure is caused;Sulfuric acid leaching also can not 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 first Solid and the first filtrate;
Calcium zincates synthesis step:Calcium hydroxide and/or calcium oxide are added into first filtrate, stirring is reacted, The second solid and the second filtrate is obtained by filtration;
Drying steps:Take second solid to be dried, or by some or all of described first solid with it is described Some or all of second solid mix then drying, obtains finished product.
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%, preferably 100% to 110%.
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 into the leachate that the leach step obtains, and are stirred It mixes, pre-treated solid and intermediate filtrate is obtained by filtration,
Heavy zinc step:The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, stirring, Filtering obtains heavy zinc solid and the first filtrate;
In the drying steps, the pre-treated solid, the heavy zinc solid is taken to mix with second solid, then It is dried;Or the heavy zinc solid is taken to mix with second solid, then it is dried.
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, 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 molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
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%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, in the calcium zincates The object of zinc ammonium complex ion in the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in synthesis step and first filtrate The ratio between amount of matter is 1~1.2:2, preferably 1~1.1:2.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, to the calcium zincates Second filtrate that synthesis step obtains is passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as digestion agent, Circulation is for the extraction containing zinc ore crude.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides:
In the drying steps, not higher than 125 DEG C at a temperature of be dried, the finished product be contain carbonic acid The mixture of calcium, zinc hydroxide and calcium zincates;
Alternatively, in the drying steps, 150~350 DEG C at a temperature of be dried, the finished product is to contain carbon The mixture of sour calcium, zinc oxide and calcium hydroxide.
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, and avoiding existing heating ammonia still process method from destroying ammonia environment causes impurity big The phenomenon that amount co-precipitation.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, greatly reduces the energy consumption of technique, it is thus also avoided that steams Various problems such as water process pressure caused by ammonia, high temperature and pressure security risk and equipment corrosion.
4) disclosed method solves the problems, such as the technique rate of recovery and fine work grade, and raw material needs two after solving vulcanizing treatment The deficiency of secondary treatment process process.
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.
6) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, from the reaction of zinc ammonium complex ion synthesis calcium zincates Selectivity is high, simple and quick.
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.
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 1 to 4)
2. precipitating
Lime is reacted with water
CaO+H2O=Ca (OH)2
Precipitating
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
[Zn(NH3)i]CO3+Ca(OH)2=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
[Zn(NH3)i]CO3+Ca(OH)2=[Zn (NH3)i](OH)2+CaCO3
(integer that i is 1 to 4)
3. calcium zincates synthesize
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O=Ca (OH)2·2Zn(OH)2·2H2O+2iNH3(i be 1 to 4 it is whole Number)
4. dry
Zn(OH)2=ZnO+H2O
Ca(OH)2·2Zn(OH)2·2H2O=Ca (OH)2+2ZnO+4H2O
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%~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%-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 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 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 precipitation process after filtering.Zinc in leachate Ammonium complex ion concentration is not particularly limited, but the zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) preferably in leachate exists 10g/L or more, more preferable 10~50g/L can make disclosed method overall economic efficiency best.It optionally, if it is necessary, can Leachate is purified with existing conventional method.
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 a part of 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 calcium hydroxide and/or calcium oxide that settling step is added 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 It is reacted under temperature (such as 15~25 DEG C), it is on the one hand energy saving, on the other hand also reduce environmental pollution caused by ammonia volatilization. Mixing time is not particularly limited, as long as being precipitated, preferably stirs 1~2 hour.
It is filtered after stirring, obtains the first solid and the first filtrate.The main component of first solid be zinc hydroxide and Calcium carbonate.First filtrate continues on for subsequent calcium zincates synthesis.
The synthesis of step 3 calcium zincates
Calcium hydroxide and/or calcium oxide are added into the first filtrate, stirring is reacted.The hydroxide being added in this step The ratio between amount of substance of zinc ammonium complex ion preferably 1~1.2 in the amount of the substance of calcium and/or calcium oxide and the first filtrate:2, it is more excellent Select 1~1.1:2.Reaction temperature is not particularly limited, and can be such as 15~90 DEG C, preferably 20~90 DEG C, and further preferred 30 ~60 DEG C;Or it is also preferred that 15~25 DEG C of reaction temperature, the temperature range have without heating, energy conservation and reduce ammonia volatilization Advantage.Reaction can be filtered for 0.5~2 hour after (preferably 0.5~1 hour), without prolonged reaction and ageing process. The second solid and the second filtrate is obtained by filtration.The main component of second solid is calcium zincates, in addition can be passed through two to the second filtrate Then carbonoxide is recycled for the extraction containing zinc ore crude.
Step 4 is dry
The ratio of first solid and the second solid according to actual needs is mixed, in the at a temperature of drying not higher than 125 DEG C, is obtained To finished product:Mixture containing calcium carbonate, zinc hydroxide and calcium zincates.Or the first solid and the second solid are needed as practical The ratio mixing wanted obtains finished product in 150~350 DEG C of at a temperature of drying:Contain calcium carbonate, zinc oxide and calcium hydroxide Mixture.The mixed proportion of first solid and the second solid can according in real work to calcium carbonate, hydroxide in mixture The content demand of the various components such as zinc/zinc oxide, calcium zincates and determine.
In addition, in further embodiment, the higher finished product of zinc hydroxide percentage in order to obtain, step 2 (precipitating) Step 2a (pretreatment) can be divided into, step 2b (heavy zinc) two steps carry out:
Step 2a pretreatment
In pre-treatment step, a certain amount of calcium hydroxide and/or oxygen is added in the leachate that obtains to step 1 (extraction) Change the effective carbonate having more than needed in calcium, with leachate and form precipitation of calcium carbonate, thus by effective carbonate more than needed from leachate Middle removing.Effective carbonate more than needed refers to effective carbonate that participation is formed except the carbonate of ammine carbonate zinc.Pretreatment The amount of the calcium hydroxide and/or calcium oxide that are added in step can be appropriate according to the amount of effective carbonate having more than needed in leachate Ground determines.
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 obtain to remove and partly or entirely have more than needed needed for effective carbonate in leachate Calcium hydroxide and/or Calcium Oxide Dosage (allowing certain legitimate skew) to be added.For example, the hydroxide added in this step The amount of the substance of calcium and/or 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 pre-treated solid and intermediate filtrate.Reaction preferably carries out under such as 15~25 DEG C of room temperature.Pre-treated solid it is main Ingredient is 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 switchs to calcium carbonate, while zinc ammonium complex ion-zinc ion-zinc hydroxide balance moves in filtrate, part zinc ammino from Son decomposes, and 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 in the filtrate in filtrate Carbonate/bicarbonate switch to calcium carbonate, part zinc conversion is the form of zinc hydroxide precipitation.Preferably, originally The dosage of calcium hydroxide and/or calcium oxide matches substantially with the amount of remaining effectively carbonate in intermediate filtrate in step, such as this The amount that the substance of remaining effective carbonate in the amount and intermediate filtrate of the substance of calcium hydroxide and/or calcium oxide is added in step is 1:1, allow certain reasonable error;But in view of equilibrium system complicated present in extraction-precipitation solution system, hydrogen can also be made Calcium oxide and/or calcium oxide are suitably excessive, to promote fully reacting.Based on theory matching dosage, calcium hydroxide and/or oxygen Change the excess of calcium preferably no more than 30%, if excess is excessively high, subsequent calcium zincates settling step may be caused Adverse effect.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 (or calcium oxide) is added into the resulting filtrate of step 2a, is stirred to react 1 ~2 hours, reaction preferably carried out under such as 15~25 DEG C of room temperature.It is filtered after reaction, filtered obtained liquid For the first filtrate, the first filtrate is used for subsequent calcium zincates synthesis step;The solid being obtained by filtration is heavy zinc solid, main Ingredient includes zinc hydroxide and calcium carbonate.
The heavy zinc solid that pre-treated solid that step 2a (pretreatment) obtains, step 2b (heavy zinc) can be obtained with it is subsequent The second solid that step 3 (calcium zincates synthesis) obtains according to actual needs ratio mixing, then not higher than 125 DEG C at a temperature of It is dried, obtains finished product:The mixture of calcium carbonate, zinc hydroxide and calcium zincates;Or 150~350 DEG C at a temperature of It is dry, obtain finished product:The mixture of calcium carbonate, zinc oxide and calcium hydroxide.What step 2b (heavy zinc) can also be obtained is heavy The ratio mixing of the second solid that zinc solid and subsequent step 3 (calcium zincates synthesis) obtain according to actual needs, is then being not higher than It is dried at a temperature of 125 DEG C, obtains finished product:Mixture containing calcium carbonate, zinc hydroxide and calcium zincates;Or It is dry at a temperature of 150~350 DEG C, obtain finished product:Mixture containing calcium carbonate, zinc oxide and calcium hydroxide.Mixing ratio Example can be determined according to the actual demand of zinc component ratio in finished product.
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, and the solid being obtained by filtration is calcium carbonate and zinc hydroxide mixture.
Remaining Zn content (working as meter with zinc oxide) is 15.12 gram per liters in filtered fluid, adds 2.21 grams of oxygen It is stirred after changing calcium, reaction is filtered after 1 hour, remaining Zn content (working as meter with zinc oxide) in filtered filtrate It is 2.3 gram per liters, the solid being obtained by filtration is mainly containing the mixture of calcium zincates.
The mixture of calcium carbonate, zinc hydroxide is merged with the mixture mainly containing calcium zincates, is done at 250 DEG C Dry, the mixture after drying is sampled analysis, and Zn content (working as meter with zinc oxide) is 43.4% in 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, and the solid being obtained by filtration is calcium carbonate and zinc hydroxide mixture.
Remaining Zn content (working as meter with zinc oxide) is 15.03 gram per liters in filtered fluid, adds 2.26 grams of oxygen It is stirred after changing calcium, reaction is filtered after 1 hour, remaining Zn content (working as meter with zinc oxide) in filtered filtrate It is 1.9 gram per liters, the solid being obtained by filtration is mainly containing the mixture of calcium zincates.
The mixture of calcium carbonate, zinc hydroxide is merged with the mixture mainly containing calcium zincates, is done at 250 DEG C Dry, the mixture after drying is sampled analysis, and Zn content (working as meter with zinc oxide) is 43.3% in 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 the first solid With the first filtrate;
Calcium zincates synthesis step:Calcium hydroxide and/or calcium oxide are added into first filtrate, stirring is reacted, and is filtered Obtain the second solid and the second filtrate;
Drying steps:Second solid is taken to be dried, or by some or all of described first solid and described second Some or all of solid mix then drying, obtains finished product.
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%, preferably 100% to 110%.
3. the low-grade beneficiation method containing zinc ore crude according to claim 1 or 2, which is characterized in that 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 into the leachate that the leach step obtains, and are stirred, Pre-treated solid and intermediate filtrate is obtained by filtration,
Heavy zinc step:The intermediate filtrate addition calcium hydroxide and/or calcium oxide obtained to pre-treatment step, is stirred, filtering, Obtain heavy zinc solid and the first filtrate;
In the drying steps, takes the pre-treated solid, the heavy zinc solid to mix with second solid, then carry out It is dry;Or the heavy zinc solid is taken to mix with second solid, then it is dried.
4. the low-grade beneficiation method containing zinc ore crude according to claim 3, 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%.
5. the low-grade beneficiation method containing zinc ore crude according to claim 3 or 4, which is characterized in that 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%.
6. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 5, 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 molar concentration of effective carbonate in the digestion agent,
nThe total zinc of raw oreFor the amount of the substance containing the Zn-ef ficiency in zinc ore crude,
nRaw ore zinc carbonateFor the amount of the substance containing the zinc carbonate in zinc ore crude,
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%.
7. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 6, which is characterized in that described Zinc ammino in the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in calcium zincates synthesis step and first filtrate from The ratio between amount of substance of son is 1~1.2:2, preferably 1~1.1:2.
8. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 7, which is characterized in that described Second filtrate that calcium zincates synthesis step obtains is passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as leaching Agent is proposed, is recycled for the extraction containing zinc ore crude.
9. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 8, it is characterised in that:
In the drying steps, not higher than 125 DEG C at a temperature of be dried, the finished product be contain calcium carbonate, hydrogen The mixture of zinc oxide and calcium zincates;
Alternatively, in the drying steps, 150~350 DEG C at a temperature of be dried, the finished product is to contain carbonic acid The mixture of calcium, zinc oxide and calcium hydroxide.
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.
CN201810817494.0A 2018-07-24 2018-07-24 A kind of low-grade beneficiation method containing zinc ore crude Withdrawn CN108866332A (en)

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CN201810817494.0A CN108866332A (en) 2018-07-24 2018-07-24 A kind of low-grade beneficiation method containing zinc ore crude
CN201980002306.1A CN110972482B (en) 2018-07-24 2019-05-16 Beneficiation method for low-grade zinc-containing raw ore
PCT/CN2019/087246 WO2020019834A1 (en) 2018-07-24 2019-05-16 Mineral processing method for low-grade zinc-containing raw ore

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Application publication date: 20181123