CN108913886A - A method of nanometer zincic acid strontium is produced using containing zinc ore crude - Google Patents

A method of nanometer zincic acid strontium is produced using containing zinc ore crude Download PDF

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Publication number
CN108913886A
CN108913886A CN201810817444.2A CN201810817444A CN108913886A CN 108913886 A CN108913886 A CN 108913886A CN 201810817444 A CN201810817444 A CN 201810817444A CN 108913886 A CN108913886 A CN 108913886A
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China
Prior art keywords
zinc
zincic acid
acid strontium
carbonate
nanometer
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CN201810817444.2A
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Chinese (zh)
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 CN201810817444.2A priority Critical patent/CN108913886A/en
Publication of CN108913886A publication Critical patent/CN108913886A/en
Priority claimed from CN201910628407.1A external-priority patent/CN110228816B/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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00Compounds of zinc
    • C01G9/006Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • 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 method using the production nanometer zincic acid strontium containing zinc ore crude, including leach step, optional purifying step, decarbonation process, zincic acid strontium synthesis step, optional rinse step, drying steps.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 synthesis of the nanometer zincic acid strontium under zinc ammonia environment is realized for the first time.

Description

A method of nanometer zincic acid strontium 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 nanometer zincic acid strontium 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, needs to be added a large amount of vulcanized sodium with Flotation of Zinc Oxide simultaneously and carries out Vulcanizing treatment, the zinc after vulcanization package need after pyrogenic process or pressure oxidation secondary treatment could directly as production metallic zinc or Produce the raw material of zinc oxide.
For the wet underwater welding of zinc ore, mainly there are sulfuric acid leaching, Calcium Chloride Method, ammonium chloride method etc. in the prior art. Sulfuric acid leaching is selectively low, can largely leach the solvable silicon in ore, and the colloidal state silicon of generation is difficult to filter, and the acid-hatching of young eggs is raw At a large amount of sulfate slags, great environmental protection treatment pressure is caused;Sulfuric acid leaching also can not be effectively to zinc silicate, the iron in ore The ingredients such as sour zinc are handled.The leaching of the ingredients such as zinc silicate in raw ore, zinc ferrite can not be effectively treated in Calcium Chloride Method, and leaches Rate is undesirable, and high temperature is needed to leach, and overall economic efficiency is bad.And in ammonium chloride method, after being leached to raw ore, from leaching The process that zinc ingredient is recycled in liquid is extremely difficult, is unsuitable for industrial application.
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 side using the production nanometer zincic acid strontium containing zinc ore crude Method includes the following steps:
Leach step:Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein The digestion agent be ammonia and ammonium hydrogen carbonate mixed aqueous solution or ammonia and the mixed aqueous solution or ammonia of ammonium carbonate, ammonium hydrogen carbonate and The mixed aqueous solution of ammonium carbonate;
Optionally, leachate obtained in the leach step is purified;
Decarbonation process:Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains first Solid and the first filtrate;
Zincic acid strontium synthesis step:Activating agent is added into first filtrate, adds strontium hydroxide and/or strontium oxide strontia, Stirring is reacted, and the second solid and the second filtrate is obtained by filtration;
Optionally, second solid is rinsed with water;
Drying steps:Second solid is dry, obtain a nanometer zincic acid strontium finished product.
It is described in the method for the utilization that disclosure further embodiment provides production nanometer zincic acid strontium containing zinc ore crude The mass concentration of total ammonia in digestion 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 nanometer zincic acid strontium containing zinc ore crude, in institute It states in the leachate that leach 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 nanometer zincic acid strontium containing zinc ore crude, in institute The amount for stating the substance of the calcium oxide and/or calcium hydroxide that are added in decarbonation process is the object of effective carbonate in the leachate The 100% to 130% of the amount of matter, preferably 100% to 110%.
In the method for the utilization that disclosure further embodiment provides production nanometer zincic acid strontium containing zinc ore crude, in institute It states in zincic acid strontium synthesis step, the amount and the first filter of the substance of strontium hydroxide and/or strontium oxide strontia is added into first filtrate The ratio between amount of substance of zinc ammonium complex ion is 1~1.2 in liquid:2, preferably 1~1.1:2.
In the method for the utilization that disclosure further embodiment provides production nanometer zincic acid strontium containing zinc ore crude, to institute State second filtrate that zincic acid strontium synthesis step obtains and be passed through carbon dioxide, will be passed through the second filtrate of carbon dioxide as Digestion agent is recycled for the extraction containing zinc ore crude.
It is described in the method for the utilization that disclosure further embodiment provides production nanometer zincic acid strontium containing zinc ore crude The reaction temperature of zincic acid strontium synthesis step is 15~90 DEG C, preferably 15~25 DEG C.
It is described in the method for the utilization that disclosure further embodiment provides production nanometer zincic acid strontium containing zinc ore crude The time that is stirred to react of zincic acid strontium synthesis step is 15~30 minutes.
It is described in the method for the utilization that disclosure further embodiment provides production nanometer zincic acid strontium containing zinc ore crude Activating agent is selected from one of calgon, neopelex or a variety of.
The disclosure also provides the Nano-Zinc for producing the method preparation of nanometer zincic acid strontium containing zinc ore crude by the utilization of the disclosure Sour strontium, the average grain diameter of the nanometer zincic acid strontium are 10~100nm.
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 Strontium oxide strontia or hydroxide are added creatively into ammonium bicarbonate-zinc ammonia complex system by the orthodox practice of sub- Crystallization Separation, the application Strontium moves the balance of zinc ammonium complex ion-zinc ion-zincic acid strontium, 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 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 zincic acid strontium under zinc ammonia environment, the especially synthesis of nanometer zincic acid strontium for the first time;From zinc The reaction selectivity that ammonium complex ion synthesizes zincic acid strontium 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.? 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 ammonium 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, " zinc ammonium complex ion " is the general name for a variety of complex ions for having Zn-ef ficiency to participate in, Under the background of this paper, the zinc ammonium complex ion mainly includes zinc ammonium complex ion at different levels, in addition may also relate to zinc and is formed with hydroxyl Complex ions at different levels 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. zincic acid strontium synthesizes
2[Zn(NH3)i](OH)2+Sr(OH)2+2H2O=Sr (OH)2·2Zn(OH)2·2H2O+2iNH3
(integer that i is 1 to 4)
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 will contain after zinc ore crude is mixed with digestion agent and be stirred, mixing time is not particularly limited, as long as making in raw ore Zinc ingredient is leached, and preferably mixing time is 1~4 hour, more preferable 1~2 hour.
In leaching process, the Zn-ef ficiency in raw ore is converted into zinc ammonium complex ion (zinc ammonium complex ion predominantly at different levels), into Enter in liquid phase.It is filtered after extraction, the leachate containing zinc ammonium complex ion is obtained after filtering.Leachate can be used for subsequent 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) it is 10~25g/L, the treatment effeciency of technique can be made optimal, in subsequent zincic acid strontium synthesis step To good yield and purity, overall economic efficiency is best.If zinc ammonium complex ion concentration is not excellent in the liquid of original leaching It selects in range, also optionally the liquid of leaching is concentrated or is diluted, the zinc ammonium complex ion concentration in leachate is adjusted For preferred 10~25g/L range.
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 solid can be calcined as calcium oxide and carbon dioxide, realization recycles.First filtrate continues on for subsequent zincic acid Strontium synthesis.
The synthesis of step 4 zincic acid strontium
Activating agent is added into the first filtrate, strontium hydroxide and/or strontium oxide strontia is then added, stirring is reacted.Activity The preferred calgon of agent or neopelex, the additional amount of activating agent be preferably estimate finished product quality 0.01~ 0.05%.The object of zinc ammonium complex ion in the amount of the substance of the strontium hydroxide and/or strontium oxide strontia 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.The temperature of reaction is not particularly limited, and can be such as 15~90 DEG C, but particularly preferably reacted at normal temperature (such as 15~25 DEG C), it is on the one hand energy saving, it on the other hand also reduces ammonia and waves Environmental pollution caused by hair, while low temperature is more advantageous to control crystallization particle diameter.
Mixing time is not particularly limited, as long as being precipitated, but in order to control crystallization particle diameter, is preferably stirred to react It may filter that after 15~30 minutes, without prolonged reaction and ageing process.The second solid and the second filtrate is obtained by filtration.The The main component of two solids is nanometer zincic acid strontium, it is however generally that zincic acid strontium ingredient can account for 95% or more of the second solid gross mass. It can be passed through carbon dioxide to the second filtrate, then recycled for the extraction containing zinc ore crude.
Step 5 rinsing
This step be optional step, it is necessary to when carry out rinse step.Second solid is rinsed with water, liquid is solid Than 5~10:1, rinsing times 1~2 time.
Step 6 is dry
By the second solid not higher than 125 DEG C at a temperature of be dried, obtain as main component with nanometer zincic acid strontium Finished product.10~100nm of average grain diameter of finished product nanometer zincic acid strontium.
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 is 4.23% in liquid, and 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 zinc ammonia complexing liquid being obtained by filtration is subjected to purified treatment.
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, 3 milligrams of neopelexes, 4.46 grams of strontium oxide strontias are added for zincic acid The synthesis of strontium, stirring is reacted at normal temperature, and reaction is filtered after 1 hour, and filtered solid is dry 2 at 105 DEG C Hour, it is sampled analysis, being examined zincic acid content of strontium in solid is 99.57%, average grain diameter 32.7nm.
Embodiment 2
Chongqing somewhere zinc ore, Zn content 4.7%, raw ore oxygenation efficiency 95.52%, in zinc ingredient with zinc silicate be mainly deposit In 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 is subjected to purified treatment.
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, 3 milligrams of neopelexes, 3.67 grams of strontium oxide strontias are for zincic acid strontium Synthesis, stirring is reacted at normal temperature, and reaction is filtered after 1 hour, and filtered solid is 2 hours dry at 105 DEG C, It is sampled analysis, being examined zincic acid content of strontium in solid is 99.53%, average grain diameter 38.3nm.
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 method using the production nanometer zincic acid strontium containing zinc ore crude, which is characterized in that described to be received using the production containing zinc ore crude The method of rice zincic acid strontium includes the following steps:
Leach step:Being mixed after will be levigate containing zinc ore crude and digestion agent, then filters, obtains leachate, wherein is described Digestion agent is the mixed aqueous solution or ammonia of ammonia and ammonium hydrogen carbonate and mixed aqueous solution or ammonia, the ammonium hydrogen carbonate and carbonic acid of ammonium carbonate The mixed aqueous solution of ammonium;
Optionally, leachate obtained in the leach step is purified;
Decarbonation process:Calcium oxide and/or calcium hydroxide are added into the leachate, then stirring filters, obtains the first solid With the first filtrate;
Zincic acid strontium synthesis step:Activating agent is added into first filtrate, adds strontium hydroxide and/or strontium oxide strontia, stirs It is reacted, the second solid and the second filtrate is obtained by filtration;
Optionally, second solid is rinsed with water;
Drying steps:Second solid is dry, obtain a nanometer zincic acid strontium finished product.
2. the method according to claim 1 using the production nanometer zincic acid strontium 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 nanometer zincic acid strontium containing zinc ore crude, which is characterized in that in institute It states in the leachate that leach 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 claim 1 or 2 using the production nanometer zincic acid strontium containing zinc ore crude, which is characterized in that in institute The amount for stating the substance of the calcium oxide and/or calcium hydroxide that are added in decarbonation process is the object of effective carbonate in the leachate The 100% to 130% of the amount of matter, preferably 100% to 110%.
5. the method according to any one of claims 1 to 4 using the production nanometer zincic acid strontium containing zinc ore crude, feature exist In, in the zincic acid strontium synthesis step, be added into first filtrate amount of the substance of strontium hydroxide and/or strontium oxide strontia with The ratio between amount of substance of zinc ammonium complex ion is 1~1.2 in first filtrate:2, preferably 1~1.1:2.
6. the method according to any one of claims 1 to 5 using the production nanometer zincic acid strontium containing zinc ore crude, feature exist In second filtrate obtained to the zincic acid strontium synthesis step is passed through carbon dioxide, will be passed through the second of carbon dioxide Filtrate recycles as digestion agent for the extraction containing zinc ore crude.
7. the method according to any one of claims 1 to 6 using the production nanometer zincic acid strontium containing zinc ore crude, feature exist In the reaction temperature of the zincic acid strontium synthesis step is 15~90 DEG C, preferably 15~25 DEG C.
8. the method according to any one of claims 1 to 7 using the production nanometer zincic acid strontium containing zinc ore crude, feature exist In the time that is stirred to react of the zincic acid strontium synthesis step is 15~30 minutes.
9. the method according to any one of claims 1 to 8 using the production nanometer zincic acid strontium containing zinc ore crude, feature exist In, the activating agent be selected from one of calgon, neopelex or a variety of.
10. passing through the described in any item nanometers using the method preparation for producing nanometer zincic acid strontium containing zinc ore crude of claim 1 to 9 Zincic acid strontium, which is characterized in that the average grain diameter of the nanometer zincic acid strontium is 10~100nm.
CN201810817444.2A 2018-07-24 2018-07-24 A method of nanometer zincic acid strontium is produced using containing zinc ore crude Withdrawn CN108913886A (en)

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CN201910628407.1A CN110228816B (en) 2018-07-24 2019-07-12 Method for utilizing zinc-containing raw ore through strontium zincate synthesis step

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Application publication date: 20181130