CN108862371A - A method of zinc oxide is produced using containing zinc ore crude - Google Patents

A method of zinc oxide is produced using containing zinc ore crude Download PDF

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Publication number
CN108862371A
CN108862371A CN201810817318.7A CN201810817318A CN108862371A CN 108862371 A CN108862371 A CN 108862371A CN 201810817318 A CN201810817318 A CN 201810817318A CN 108862371 A CN108862371 A CN 108862371A
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Prior art keywords
zinc
calcium
carbonate
ore
digestion agent
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CN201810817318.7A
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Inventor
岳辉伟
李世川
龙忠祥
蒋涛
刘权锋
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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 CN201810817318.7A priority Critical patent/CN108862371A/en
Publication of CN108862371A publication Critical patent/CN108862371A/en
Priority claimed from CN201980001299.3A external-priority patent/CN110896643B/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00Compounds of zinc
    • C01G9/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Abstract

This disclosure relates to a kind of method using the production zinc oxide containing zinc ore crude, including leach step, optional purifying step, decarbonation process, calcium zincates synthesis step, optional rinse step, calcining step, calcium zinc separating step.Disclosed method is by wet-leaching in conjunction with synthesis technology, realize the economic and environment-friendly utilization of super low-grade zinc, it is applied widely, without ammonia still process, it is simple and easy to do, greatly reduce the energy consumption of technique, also avoid water process pressure caused by ammonia still process, various problems such as high temperature and pressure security risk and equipment corrosion, solves the environmental issue faced due to steam, which brings water more than needed into, influences process water balance in ammonia circulation technology, solve the problems, such as the technique rate of recovery and fine work grade, it pollutes small, supplies are recyclable, the calcium zincates synthesis under zinc ammonia environment is realized for the first time, and zinc oxide product is produced via calcium zincates.

Description

A method of zinc oxide is produced using containing zinc ore crude
Technical field
The invention belongs to technical field of inorganic chemical industry, be related to the low-grade resource utilization containing zinc ore crude, in particular to one The method that kind produces zinc oxide using low-grade zinc oxide raw ore.
Background technique
The production of China's zinc is ranked the first in the world with consumption, and domestic zinc resource is not able to satisfy production, needs import a large amount of every year Zinc raw material.China is an oxidation zinc resource country more abundant, and zinc metal reserves are about 2800 in China's zinc oxide ore Ten thousand tons, account for about 27.7% of zinc metal reserves in world's zinc oxide ore.Zinc oxide ore generally zinc grade in China's is low, average grade Less than 5%, be still unable to the slow-witted mine of economic utilization at present, lean ore reserves account for the overwhelming majority, wherein existing stockpiling containing zinc oxide 3%~ The 5% more than one hundred million tons of mining tailing and milltailings.
Therefore, Efficient Development utilizes low-grade zinc oxide ore resource, for alleviating the insufficient problem of domestic zinc raw material supply With important strategic importance.
The main technique that low-grade zinc oxide ore utilizes includes:Pyrogenic process produces secondary zinc oxide, due to the high energy consumption of the technique With high pollution, limited by national industrial policies.
Flotation is the main technique of current processing zinc oxide ore, but for zinc oxide floatation process, external zinc oxide ore Sorting index is:Zinc grade 36%~40%, the rate of recovery 60%~70%, up to 78%;China's zinc oxide ore sorting index For:Zinc grade 35%~38%, rate of recovery average out to 68%, up to 73%.Therefore recovery rate in ore-dressing is low, and concentrate grade is low etc. Problem is common problem existing for domestic and international zinc oxide ore ore dressing, while Flotation of Zinc Oxide needs to be added a large amount of vulcanized sodium and carries out sulphur Change processing, the zinc after vulcanizing package is needed could be directly as production metallic zinc or life after pyrogenic process or pressure oxidation secondary treatment Produce the raw material of zinc oxide.
For the wet underwater welding of zinc ore, mainly there are sulfuric acid leaching, Calcium Chloride Method, ammonium chloride method etc. in the prior art. Sulfuric acid leaching is selectively low, can largely leach the solvable silicon in ore, and the colloidal state silicon of generation is difficult to filter, and the acid-hatching of young eggs is raw At a large amount of sulfate slags, great environmental protection treatment pressure is caused;Sulfuric acid leaching also can not be effectively to zinc silicate, the iron in ore The ingredients such as sour zinc are handled.The leaching of the ingredients such as zinc silicate in raw ore, zinc ferrite can not be effectively treated in Calcium Chloride Method, and leaches Rate is undesirable, and high temperature is needed to leach, and overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, from leaching The process that zinc ingredient is recycled in liquid is extremely difficult, is unsuitable for industrial application.
Therefore, existing technique to it is low-grade containing zinc ore crude using unsatisfactory.
Summary of the invention
Problems to be solved by the invention
Low-grade zinc oxide ore utilizes at present technique exist energy consumption is high, recovery rate in ore-dressing is low, cause Heavy environmental pollution, The problems such as economic value is low.The present invention is solved present in zinc oxide ore utilization by the improvement to zinc oxide ore treatment process The above problem.
The solution to the problem
In order to solve the problems existing in the prior art, the disclosure provides a kind of method using the production zinc oxide containing zinc ore crude, Include the following steps:
Leach step:Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein The digestion agent be ammonia and ammonium hydrogen carbonate mixed aqueous solution or ammonia and the mixed aqueous solution or ammonia of ammonium carbonate, ammonium hydrogen carbonate and The mixed aqueous solution of ammonium carbonate;
Optionally, leachate obtained in the leach step is purified;
Decarbonation process: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 is added to first filtrate, then stirring is filtered, obtained To the second solid and the second filtrate;
Optionally, second solid is rinsed with water;
Calcining step:Second solid is taken to be calcined, calcination temperature is 150~1050 DEG C, preferably 150~350 DEG C;
Calcium zinc separating step:The calcined product that the calcining step obtains is mixed with water, is stirred, filtering obtains third Solid and third filtrate, the third solid is dry, obtain zinc oxide product.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, the extraction The mass concentration of total ammonia in agent is 5%~15%, and 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%, preferably 150%~250%.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, in the leaching It mentions in the leachate that step obtains, the concentration (in terms of the quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, described de- The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in carbon step is the substance of effective carbonate in the leachate The 100% to 130% of amount, preferably 100% to 110%.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, in the zinc In sour calcium synthesis step, it is added into first filtrate in amount and the first filtrate of the substance of calcium hydroxide and/or calcium oxide The ratio between amount of substance of zinc ammonium complex ion is 1~1.2:2, preferably 1~1.1:2.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, to the zinc Second filtrate that sour calcium synthesis step obtains is passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as extraction Agent is recycled for the extraction containing zinc ore crude.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, the zincic acid The reaction temperature of calcium synthesis step is 15~90 DEG C, preferably 30~60 DEG C, or preferably 15~25 DEG C.
In the method for the utilization that disclosure further embodiment provides production zinc oxide containing zinc ore crude, in the calcium In zinc separating step, it is passed through carbon dioxide to the third filtrate, obtains precipitation of calcium carbonate.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects:
1) by wet-leaching in conjunction with synthesis technology, the economic and environment-friendly utilization of super low-grade zinc is realized.
2) disclosed method is applied widely, and ammonia-ammonium bicarbonate Leaching Systems can be effectively to the former containing zinc of diversified forms Mine is extracted and is utilized.
3) break traditional ammonia-ammonium carbonate method zinc complexing extracting technology by heating evaporation ammonia destroy complexing environment realize zinc from Calcium oxide or hydroxide are added creatively into ammonium bicarbonate-zinc ammonia complex system by the orthodox practice of sub- Crystallization Separation, the application Calcium moves zinc ammonium complex ion-zinc ion-calcium zincates balance, by flat under the premise of not destroying solution ammonia environment The shifting principle that weighs realizes the selective crystallization separation of Zn-ef ficiency, and avoiding existing heating ammonia still process method from destroying ammonia environment causes impurity a large amount of The phenomenon that co-precipitation.The technique of the disclosure is not necessarily to ammonia still process, simple and easy to do, greatly reduces the energy consumption of technique, it is thus also avoided that ammonia still process Various problems such as caused water process pressure, high temperature and pressure security risk and equipment corrosion.
4) leaching and separation that zinc is realized by the circulation of carbonate solve in ammonia circulation technology because steam brings water more than needed into Measure the environmental issue for influencing process water balance and facing.
5) relative to zinc oxide floatation process, disclosed method solves the problems, such as the technique rate of recovery and fine work grade, institute The product obtained can also can be used as the raw material of industry directly as product.
6) disclosed method pollution is small, and supplies are recyclable, and it is former to solve existing zinc oxide treatment process auxiliary The problem of expecting bring environmental pollution.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment for the first time, and produces zinc oxide via calcium zincates and produce Product, it is high from the reaction selectivity of zinc ammonium complex ion synthesis calcium zincates, it is simple and quick.
Specific embodiment
It will be detailed below various exemplary embodiments, feature and the aspect of the disclosure.Dedicated word " example herein Property " mean " being used as example, embodiment or illustrative ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as Preferred or advantageous over other embodiments.
In addition, giving numerous details in specific embodiment below in order to which the disclosure is better described. In some instances, method well known to those skilled in the art, means, reagent and equipment are not described in detail, but ability Field technique personnel can realize the technical solution of the disclosure according to the general knowledge of this field.
The scope of application of disclosed method is not particularly limited, and is widely portable to the various utilizations containing zinc ore crude.? When using low-grade zinc oxide raw ore as raw materials for production, the advantages of method disclosed herein, is particularly pertinent.For example, low-grade former containing zinc Mine can be zinc content 3%~15% containing zinc ore crude;Particularly, before the disclosure, zinc content contains 3%~6% Zinc ore crude (lean ore, milltailings) is largely stored up, and existing various techniques are to can not make the utilization of existing economic value in fact At very big processing pressure, and disclosed method is not only technically realized to such low-grade containing the effective of zinc ore crude It utilizes, and simple process is easy, it is low in cost, there is very high economic value.
In the disclosure, the existence form containing zinc ingredient in zinc ore crude is not particularly limited, such as zinc ingredient can be with packet The one or more forms for including but being not limited to zinc oxide, zinc carbonate, zinc silicate etc. exist.
Explanation of nouns
Herein, unless otherwise indicated, " ammine carbonate zinc " is zinc ammonium complex ion and the compound that carbonate is formed General name, including [Zn (NH3)4]CO3(four ammino zinc of carbonic acid), [Zn (NH3)3]CO3(three ammino zinc of carbonic acid), [Zn (NH3)2]CO3 (two ammino zinc of carbonic acid), [Zn (NH3)]CO3(one ammino zinc of carbonic acid) etc..
Herein, unless otherwise indicated, " zinc ammonium complex ion " is the general name of ammino zinc complex ions at different levels, including [Zn (NH3)4]2+(four ammino zinc ions), [Zn (NH3)3]2+(three ammino zinc ions), [Zn (NH3)2]2+(two ammino zinc ions), [Zn (NH3)]2+(an ammino zinc ion) etc..
Herein, unless otherwise indicated, 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=Ca (OH)2+2ZnO+4H2O
Or
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, 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 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 be converted into zinc ammonium complex ion (the zinc ammino formed in leaching process from Son is mainly zinc ammonium complex ions at different levels), into liquid phase.It is filtered, obtains after filtering containing zinc ammonium complex ion after extraction Leachate.Leachate can be used for subsequent decarbonizing process.Zinc ammonium complex ion concentration in leachate is not particularly limited, but preferably Zinc ammonium complex ion concentration (in terms of the quality of Zn-ef ficiency) in leachate is 10~25g/L, and the treatment effeciency of technique can be made optimal, Good yield and purity are obtained in subsequent calcium zincates synthesis step, overall economic efficiency is best.If original leaching The liquid of leaching is also optionally concentrated or is diluted not in preferred scope by zinc ammonium complex ion concentration in liquid, will be soaked The zinc ammonium complex ion concentration in liquid is adjusted to preferred 10~25g/L range out.
Step 2 purification
Step 2 be optional step, it is necessary to when selection carry out step 2.Leachate is purified by known method, Remove the impurity elements such as iron, manganese, lead, copper.A kind of illustrative purification method is that addition zinc powder replace and then filtered, thus Heavy metal contaminants are removed, but other various well known purification methods also can be used.Purifying step helps to improve finished product Purity.
Step 3 decarburization
In decarbonation process, 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.If zinc ammonium complex ion excessive concentration in leachate, it is likely that send out simultaneously Zinc ammonium complex ion-zinc ion-zinc hydroxide balanced sequence in raw leachate, a little zinc ingredient may be with hydroxide The form and calcium carbonate of zinc 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 is particularly preferably reacted at normal temperature (such as 15~25 DEG C), 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, if The concentration of zinc ammonium complex ion is higher in leachate, then some hydroxides with calcium carbonate co-precipitation are also likely to be present in the first solid Zinc.First filtrate continues on for subsequent calcium zincates synthesis.Calcium carbonate in first solid can then be calcined to calcium oxide and two Carbonoxide, realization recycle.
The synthesis of step 4 calcium zincates
Calcium hydroxide and/or calcium oxide is added in the first filtrate obtained to step 3, and stirring is reacted.Add in this step The ratio between the amount of the substance of the calcium hydroxide and/or calcium oxide that enter and amount of substance of zinc ammonium complex ion in the first filtrate preferably 1~ 1.2:2, more preferable 1~1.1:2.Reaction temperature is not particularly limited, and can be such as 15~90 DEG C, preferably 20~90 DEG C, into Preferably 30~60 DEG C of one step;Or it is also preferred that 15~25 DEG C of reaction temperature, the temperature range have without heating, energy conservation and subtract The advantages of few ammonia volatilization.Reaction can be filtered for 0.5~2 hour after (preferably 0.5~1 hour), without prolonged reaction And ageing process.It is filtered, is obtained with calcium zincates the second solid as main component and the second filtrate after reaction.It can also be to It is passed through carbon dioxide in second filtrate, using the second filtrate for being passed through carbon dioxide as digestion agent, is recycled for containing zinc ore crude Extraction.
The rinsing of step 5 calcium zincates
Step 5 be optional step, it is necessary to when selection carry out step 5.In steps of 5, for based on calcium zincates The second solid for wanting ingredient, adds water to be rinsed, and liquid-solid ratio is 5~10:1, rinsing times are 1-2 times.
Step 6 calcining
In this step, it takes the second solid to be calcined, decomposes calcium zincates.Calcination temperature can be 150~1050 DEG C, It is preferred that 150~350 DEG C.Calcining obtained product is mixture, if calcination temperature is at 150~350 DEG C, calcined product is main Ingredient is zinc oxide and calcium hydroxide;If calcined product contains zinc oxide, calcium hydroxide using higher calcination temperature And/or calcium oxide.
The separation of step 7 calcium zinc
Water is insoluble in view of zinc oxide, and calcium hydroxide (or calcium oxide) is water-soluble or is dissolved in water after reacting with water, therefore Water solubility using zinc oxide and calcium hydroxide (or calcium oxide) is poor, realizes zinc oxide and calcium hydroxide (or calcium oxide) Separation.
In this step, calcined product step 6 obtained is mixed with water, is stirred, and filtering obtains third solid and third Filtrate.The main component of third solid is zinc oxide, and the solute in third filtrate is mainly calcium hydroxide.Third solid is done It is dry, obtain zinc oxide product.And for third filtrate, it can be passed through carbon dioxide to it and obtain precipitation of calcium carbonate, also can be recycled Third filtrate supplies other purposes.
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 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) 1.632% in body, carbonate mass concentration 4.23% in liquid, increased portion is divided into raw ore 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 leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
600 milliliters of purified leachates are taken, 14.55 grams of calcium oxide are added, for precipitating carbonate, after reaction 1 hour It is filtered.
500 milliliters of filtered liquid is taken, synthesis of 2.45 grams of calcium hydroxides for calcium zincates is added, stirring carries out anti- It answers, reaction is filtered after 1 hour, is obtained after filtering with calcium zincates solid as main component.
Calcium zincates solid is dried 2 hours at 105 DEG C, then is calcined 2 hours through 300 DEG C, calcium zincates are decomposed into oxygen Change zinc and calcium hydroxide.
The water of 300 times of quality is added to zinc oxide and calcium hydroxide, stirs 1 hour, is then filtered, filtered oxygen It is 2 hours dry at 105 DEG C to change zinc, analysis of testing, the content of zinc oxide is 99.73% in 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 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, liquid after filtering Zinc oxide 1.367%, carbonate mass concentration 3.54% in liquid are pressed in body, increased portion is divided into the zinc carbonate in raw ore and brings into. According to inspection data, solvable zinc recovery is 91.35% in leaching process raw ore, and total zinc recovery is 87.26%.
The leachate containing zinc ammonium complex ion being obtained by filtration is subjected to purified treatment.
600 milliliters of purified leachates are taken, 12.18 grams of calcium oxide are added, for precipitating carbonate, after reaction 1 hour It is filtered.
500 milliliters of filtered liquid is taken, synthesis of 2 grams of calcium hydroxides for calcium zincates is added, stirring is reacted, instead It is filtered, obtains after filtering with calcium zincates solid as main component after answering 1 hour.
Calcium zincates solid is dried 2 hours at 105 DEG C, then is calcined 2 hours through 300 DEG C, calcium zincates are decomposed into oxygen Change zinc and calcium hydroxide.
The water of 300 times of quality is added to zinc oxide and calcium hydroxide, stirs 1 hour, is then filtered, filtered oxygen Change zinc dry analysis of testing in 2 hours at 105 DEG C, the content of zinc oxide is 99.57% in 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 method using the production zinc oxide containing zinc ore crude, which is characterized in that described to produce zinc oxide using containing zinc ore crude Method include the following steps:
Leach step:Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein is described Digestion agent is the mixed aqueous solution or ammonia of ammonia and ammonium hydrogen carbonate and mixed aqueous solution or ammonia, the ammonium hydrogen carbonate and carbonic acid of ammonium carbonate The mixed aqueous solution of ammonium;
Optionally, leachate obtained in the leach step is purified;
Decarbonation process: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 is added to first filtrate, then stirring is filtered, obtain the Two solids and the second filtrate;
Optionally, second solid is rinsed with water;
Calcining step:Second solid is taken to be calcined, calcination temperature is 150~1050 DEG C, preferably 150~350 DEG C;
Calcium zinc separating step:The calcined product that the calcining step obtains is mixed with water, is stirred, filtering obtains third solid It is with third filtrate, the third solid is dry, obtain zinc oxide product.
2. the method according to claim 1 using the production zinc oxide containing zinc ore crude, which is characterized in that
The mass concentration of total ammonia in the digestion agent is 5%~15%, effective carbonate in the digestion agent it is mole dense Degree 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%, preferably 150%~250%.
3. the method according to claim 1 or 2 using the production zinc oxide containing zinc ore crude, which is characterized in that in the leaching It mentions in the leachate that step obtains, the concentration (in terms of the quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L.
4. the method according to any one of claims 1 to 3 using the production zinc oxide containing zinc ore crude, which is characterized in that The amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the decarbonation process is effective carbonate in the leachate The 100% to 130% of the amount of substance, preferably 100% to 110%.
5. the method according to any one of claims 1 to 4 using the production zinc oxide containing zinc ore crude, which is characterized in that In the calcium zincates synthesis step, the amount and first of the substance of calcium hydroxide and/or calcium oxide is added into first filtrate The ratio between amount of substance of zinc ammonium complex ion is 1~1.2 in filtrate:2, preferably 1~1.1:2.
6. the method according to any one of claims 1 to 5 using the production zinc oxide containing zinc ore crude, which is characterized in that Second filtrate that the calcium zincates synthesis step obtains is passed through carbon dioxide, and the second filtrate for being passed through carbon dioxide is made For digestion agent, recycle for the extraction containing zinc ore crude.
7. the method according to any one of claims 1 to 6 using the production zinc oxide containing zinc ore crude, which is characterized in that institute The reaction temperature for stating calcium zincates synthesis step is 15~90 DEG C, preferably 30~60 DEG C, or preferably 15~25 DEG C.
8. the method according to any one of claims 1 to 7 using the production zinc oxide containing zinc ore crude, which is characterized in that In the calcium zinc separating step, it is passed through carbon dioxide to the third filtrate, obtains precipitation of calcium carbonate.
CN201810817318.7A 2018-07-24 2018-07-24 A method of zinc oxide is produced using containing zinc ore crude Withdrawn CN108862371A (en)

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CN201980001299.3A CN110896643B (en) 2018-07-24 2019-04-24 Method for producing zinc-containing compound or zinc oxide from zinc-containing raw ore through intermediate step of calcium zincate synthesis
PCT/CN2019/084003 WO2020019777A1 (en) 2018-07-24 2019-04-24 Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020019834A1 (en) * 2018-07-24 2020-01-30 重庆东群科技有限公司 Mineral processing method for low-grade zinc-containing raw ore
WO2020019777A1 (en) * 2018-07-24 2020-01-30 重庆东群科技有限公司 Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020019834A1 (en) * 2018-07-24 2020-01-30 重庆东群科技有限公司 Mineral processing method for low-grade zinc-containing raw ore
WO2020019777A1 (en) * 2018-07-24 2020-01-30 重庆东群科技有限公司 Method for producing zinc-containing complex or zinc oxide using zinc-containing raw ore via intermediate step for synthesis of calcium zincate

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