CN108950240A - 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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CN108950240A
CN108950240A CN201810817164.1A CN201810817164A CN108950240A CN 108950240 A CN108950240 A CN 108950240A CN 201810817164 A CN201810817164 A CN 201810817164A CN 108950240 A CN108950240 A CN 108950240A
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zinc
carbonate
low
calcium
ore
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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 CN201810817164.1A priority Critical patent/CN108950240A/en
Publication of CN108950240A publication Critical patent/CN108950240A/en
Priority to CN201980002306.1A priority patent/CN110972482B/en
Priority to PCT/CN2019/087246 priority patent/WO2020019834A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • 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
    • C01F11/02—Oxides or hydroxides
    • 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
    • C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/34—Obtaining zinc oxide
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

This disclosure relates to a kind of low-grade beneficiation method containing zinc ore crude, including leach step, decarbonation process, calcium zincates synthesis step, calcining step.Disclosed method is by wet-leaching in conjunction with ore-dressing technique, realize the economic and environment-friendly utilization of super low-grade zinc, it is applied widely, without ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, 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 the deficiency of secondary treatment technical process after solution 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 production 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 low-grade zinc oxide ore, but for zinc oxide floatation process, external zinc oxide Mine sorting index are as follows: 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, zinc sulphide is needed could be directly as production metallic zinc or the raw material of production zinc oxide, energy consumption after pyrogenic attack It is 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: then being mixed after will be levigate containing zinc ore crude and digestion agent 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；
Decarbonation process: calcium oxide and/or calcium hydroxide being added into the leachate, then stirring filters, obtains first Solid and the first filtrate；
Calcium zincates synthesis step: calcium hydroxide and/or calcium oxide being added into first filtrate, and stirring is reacted, The second solid and the second filtrate is obtained by filtration；
Calcining step: second solid is dry, it then calcines, makes contained in the second solid at 650~1050 DEG C Calcium zincates be decomposed into zinc oxide and calcium oxide.
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 are as follows:
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%, preferably 150%~250%.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, the leach step In the obtained leachate, the concentration (in terms of the quality of Zn-ef ficiency) of zinc ammonium complex ion is 10g/L or more, preferably 10~25g/ L。
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the extraction In rapid, the concentration (in terms of the quality of Zn-ef ficiency) of the zinc ammonium complex ion in the obtained leachate is adjusted to 10~25g/L.
In the low-grade beneficiation method containing zinc ore crude that disclosure further embodiment provides, walked in the decarburization 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, in the calcium zincates In synthesis step, zinc ammonia in the amount and the first filtrate of the substance of calcium hydroxide and/or calcium oxide is added into first filtrate The ratio between amount of substance of complex ion 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, the calcium zincates are closed Reaction temperature at step is 15~90 DEG C, preferably 30~60 DEG C, or preferably 15~25 DEG C.
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 Water process pressure caused by ammonia, high temperature and pressure security risk, a large amount of ammonia of equipment burn into steam volatilization and cause additional environmental protection treatment Various problems such as burden.
4) relative to zinc oxide floatation process, disclosed method solves the problems, such as the technique rate of recovery and fine work grade, solution Certainly raw material needs the deficiency of secondary treatment technical process after vulcanizing treatment.
6) disclosed method pollution is small, and supplies are recyclable, and it is former to solve existing zinc oxide treatment process auxiliary The problem of expecting bring environmental pollution.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, 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, in solution (the including but not limited to various liquid such as digestion agent, leachate) " effective carbonate " refers 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. decarburization
Lime is reacted with water
CaO+H2O=Ca (OH)2
Precipitating
Ca(OH)2+(NH4)2CO3=CaCO3↓+2NH3·H2O
Ca(OH)2+NH4HCO3=CaCO3↓+NH3+2H2O
[Zn(NH3)i]CO3+Ca(OH)2=[Zn (NH3)i](OH)2+CaCO3↓
(integer that i is 1 to 4)
The side reaction that may occur:
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(integer that i is 1 to 4)
3. calcium zincates synthesize
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O=Ca (OH)2·2Zn(OH)2·2H2O+2iNH3
(integer that i is 1 to 4)
4. calcining
Ca(OH)2·2Zn(OH)2·2H2O=CaO+2ZnO+5H2O
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, 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 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, can not only obtain satisfied extracting effect, 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 is stirred after oxidation zinc ore crude is mixed with digestion agent, mixing time is not particularly limited, as long as making in raw ore Zinc ingredient be leached, preferably mixing time be 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 de- Carbon 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 10~25g/L. If zinc ammonium complex ion concentration is not in preferred scope in the liquid of original leaching, also optionally the liquid of leaching is carried out dense Contracting or dilution, are adjusted to preferred 10~25g/L range for the zinc ammonium complex ion concentration in leachate.Optionally, if it is necessary, Leachate can be purified with existing method.
Step 2 decarburization
In decarbonation process, calcium hydroxide and/or calcium oxide are added into the leachate containing zinc ammonium complex ion, will leach Effective carbonate in liquid switchs to calcium carbonate.If zinc ammonium complex ion excessive concentration in leachate, it is likely that while soaking Zinc ammonium complex ion-zinc ion-zinc hydroxide balanced sequence in liquid out, a little zinc ingredient may be with zinc hydroxide Form and calcium carbonate are co-precipitated.
In decarbonation process, effective carbonate in the substantially matching leachate of the additive amount of calcium hydroxide and/or calcium oxide Content, for example, the amount of the substance of calcium hydroxide and/or calcium oxide that decarbonation process is added is the object of effective carbonate in leachate The 100% to 130% of the amount of matter, more preferable 100% to 110%.Calcium hydroxide and/or calcium oxide are appropriately added, is facilitated Control process costs, it helps improve the purity and quality of finished product zinc product.
In decarbonation process, 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, and (such as 15~25 DEG C) are reacted particularly preferably at normal temperature, on the one hand saves On the other hand the energy also reduces environmental pollution caused by ammonia volatilization.Mixing time is not particularly limited, and is as long as obtaining precipitating Can, preferably stir 1~2 hour.
It is filtered after stirring, obtains the first solid and the first filtrate.The main component of first solid is calcium carbonate, can quilt Calcining is calcium oxide and carbon dioxide, and realization recycles.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.This step passes through in zinc ammonia environment Lower synthesis calcium zincates, the zinc extracted out is recycled at fractional precipitation.
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 this step and the first filtrate The ratio between amount of matter preferably 1~1.2:2, more preferable 1~1.1:2.Reaction temperature is not particularly limited, and can be such as 15~90 DEG C, preferably 20~90 DEG C, further preferred 30~60 DEG C；Or it is also preferred that 15~25 DEG C of reaction temperature, temperature range tool The advantages of having without heating, energy conservation and reducing ammonia volatilization.Reaction can carry out for 0.5~2 hour after (preferably 0.5~1 hour) Filter, 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, it is however generally that zincic acid calcium component can account for 95% or more of the second solid gross mass；By raw material, whether carry out purification step Suddenly, how purifying step the influence of factors such as carries out, and the chemical combination such as the galvanized iron manganese that is co-precipitated on a small quantity may also be included in the second solid Object.In addition it can be passed through carbon dioxide to the second filtrate, then recycled for the extraction containing zinc ore crude.
Step 4 calcining
Second solid is dry, it is then calcined at 650~1050 DEG C, calcium zincates is made to be decomposed into zinc oxide and calcium oxide.
It is described in detail below in conjunction with embodiment of the embodiment to the disclosure, but those skilled in the art will Understand, the following example is merely to illustrate the disclosure, and is not construed as the restriction to the scope of the present disclosure.It is not specified in embodiment Actual conditions person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer, Being can be with conventional products that are commercially available.
Embodiment 1
Yunnan somewhere zinc ore, Zn content 5.6%, raw ore oxygenation efficiency 96.3%, the zinc ingredient in the mine is based on zinc carbonate Want existence form.
300 grams of oxidation zinc ore crudes are taken, 900 milliliters of ammonia-ammonium bicarbonate mixed liquor (total ammonia mass concentration 10%, carbonate are put into Mass concentration 3%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, filtered Contain zinc (meter is worked as with zinc oxide) 1.632% in liquid, carbonate mass concentration is 4.23% in liquid, and increased portion is divided into raw ore Middle zinc carbonate is brought into.According to inspection data, solvable zinc recovery is 90.79% in leaching process raw ore, and total zinc recovery is 87.43%.
The zinc ammonia complexing liquid being obtained by filtration after 600 milliliters of extractions is taken, 14.55 grams of calcium oxide are added, for precipitating carbonate, Reaction is filtered after 1 hour.500 milliliters of filtered liquid is taken, synthesis of 2.41 grams of calcium hydroxides for calcium zincates is added, Stirring is reacted at normal temperature, and reaction is filtered after 1 hour, and the solid being obtained by filtration is dried at 105 DEG C, then It is calcined 2 hours through 950 DEG C, is then sampled analysis.Contain zinc oxide 71.26% in calcined product.
Embodiment 2
Chongqing somewhere zinc ore, Zn content 4.7%, raw ore oxygenation efficiency 95.52%, the zinc ingredient in the mine is based on zinc silicate Want existence form.
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 3%) in be stirred extraction, extraction temperature room temperature, mixing time is 2 hours, is then filtered, filtered liquid Contain zinc (meter is worked as with zinc oxide) 1.367%, carbonate mass concentration 3.54% in liquid in body, increased portion is divided into carbon in raw ore Sour zinc is brought into.According to inspection data, solvable zinc recovery is 91.35% in leaching process raw ore, and total zinc recovery is 87.26%.
The zinc ammonia complexing liquid being obtained by filtration after 600 milliliters of extractions is taken, 12.18 grams of calcium oxide are added, for precipitating carbonate, Reaction is filtered after 1 hour.500 milliliters of filtered liquid is taken, synthesis of 1.99 grams of calcium hydroxides for calcium zincates is added, Stirring is reacted at normal temperature, and reaction is filtered after 1 hour, and the solid being obtained by filtration is dried at 105 DEG C, then It is calcined 2 hours through 950 DEG C, is then sampled analysis.Contain zinc oxide 71.08% in calcined product.
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 (8)

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: then being mixed after will be levigate containing zinc ore crude and digestion agent 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；
Decarbonation process: calcium oxide and/or calcium hydroxide being 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 being added into first filtrate, and stirring is reacted, and filter Obtain the second solid and the second filtrate；
Calcining step: second solid is dry, it is then calcined at 650~1050 DEG C, makes zinc contained in the second solid Sour calcium is decomposed into zinc oxide and calcium oxide.
2. the low-grade beneficiation method containing zinc ore crude according to claim 1, which is characterized in that total in the digestion agent The mass concentration of ammonia is 5%~15%, preferably 6%~8%,
The molar concentration of effective carbonate in the digestion agent are as follows:
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%, preferably 150%~250%.
3. the low-grade beneficiation method containing zinc ore crude according to claim 1 or 2, which is characterized in that the leach step In the obtained leachate, the concentration (in terms of the quality of Zn-ef ficiency) of zinc ammonium complex ion is 10g/L or more, preferably 10~25g/ L。
4. the low-grade beneficiation method containing zinc ore crude according to claim 1 or 2, which is characterized in that walked in the extraction In rapid, the concentration (in terms of the quality of Zn-ef ficiency) of the zinc ammonium complex ion in the obtained leachate is adjusted to 10~25g/L.
5. the low-grade beneficiation method containing zinc ore crude according to any one of claims 1 to 4, which is characterized in that described The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in decarbonation process is the substance of effective carbonate in the leachate Amount 100% to 130%, preferably 100% to 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 described In calcium zincates synthesis step, amount and the first filtrate of the substance of calcium hydroxide and/or calcium oxide are added into first filtrate The ratio between amount of substance of middle zinc ammonium complex ion is 1~1.2:2, preferably 1~1.1:2.
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 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.
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 zinc The reaction temperature of sour calcium synthesis step is 15~90 DEG C, preferably 30~60 DEG C, or preferably 15~25 DEG C.
CN201810817164.1A 2018-07-24 2018-07-24 A kind of low-grade beneficiation method containing zinc ore crude Withdrawn CN108950240A (en)

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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: 20181207