CN108585026A - A method of producing nanometer calcium zincates using containing zinc ore crude - Google Patents

A method of producing nanometer calcium zincates using containing zinc ore crude Download PDF

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Publication number
CN108585026A
CN108585026A CN201810832651.5A CN201810832651A CN108585026A CN 108585026 A CN108585026 A CN 108585026A CN 201810832651 A CN201810832651 A CN 201810832651A CN 108585026 A CN108585026 A CN 108585026A
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China
Prior art keywords
zinc
calcium
carbonate
zincates
calcium zincates
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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 CN201810832651.5A priority Critical patent/CN108585026A/en
Publication of CN108585026A publication Critical patent/CN108585026A/en
Priority claimed from PCT/CN2019/085932 external-priority patent/WO2020019823A1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00Compounds of zinc
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • 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 which a kind of utilizing the method for producing nanometer calcium zincates containing zinc ore crude, including leach step, optional purifying step, decarbonation process, calcium zincates synthesis step, optional rinse step, drying steps.Disclosed method is combined wet-leaching 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, it solves in ammonia circulation technology because steam brings the environmental issue faced due to water more than needed influences process water balance into, 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 calcium zincates under zinc ammonia environment is realized for the first time.

Description

A method of producing nanometer calcium zincates using containing zinc ore crude
Technical field
The invention belongs to technical field of inorganic chemical industry, be related to the low-grade recycling containing zinc ore crude, more particularly to one The method that kind produces nanometer calcium zincates using low-grade zinc oxide raw ore.
Background technology
The production of China's zinc is ranked the first in the world with consumption, and domestic zinc resource cannot meet production, need import a large amount of every year Zinc raw material.China is one and aoxidizes the abundanter country of zinc resource, 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, the problem insufficient for alleviating 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 that a large amount of vulcanized sodium progress sulphur are added Change is handled, and the zinc after vulcanization package is needed could be directly as production metallic zinc or life after pyrogenic process or pressure oxidation after-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 given birth to 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 commercial Application.
Therefore, existing technique is unsatisfactory to the low-grade utilization containing zinc ore crude.
Calcium zincates tool has been widely used.Negative material of the calcium zincates for alkaline secondary zinc electrode is newly opened up in recent years Direction, constantly ripe and industrialization;Compared with traditional Zinc oxide desulfurizer, calcium zincates are the room temperature of desulphurizing activated component Desulfurizing agent, Sulfur capacity increase considerably;Calcium zincates are not only conducive to animal as feed addictive and absorb also conducive to reduction environment dirt Dye.Calcium zincates can also be widely used in glaze, paint, coating additive etc. simultaneously.
The preparation method of calcium zincates is limited to experimental exploration in the prior art, still immature.For example, Chinese patent CN1397498A and CN1595688A discloses ball-milling method synthesis calcium zincates, disclosed in wherein Chinese patent CN1397498A It is by Ca (OH)2It is put into ball grinder in the ratio in calcium zincates chemical formula with ZnO, suitable quantity of water is added, under argon atmospher protection Ball milling 8-18 hours obtains product after then being toasted 10-15 hours at 30-80 DEG C;United States Patent (USP) 5,460,899 discloses one Kind ZnO and Ca (OH)2The method that reaction generates calcium zincates in lye;Use is disclosed in Chinese patent CN2012100305744 The Ca (OH) of soluble zinc salt and stoichiometric ratio2It is made into emulsion and generates calcium zincates.It is needed in the above method high-purity with finished product It is starting material, expensive starting materials, and severe reaction conditions to spend zinc oxide or finished product zinc salt, and energy consumption is high, and reaction is incomplete, yield Low, atopic is poor, is easily interfered by impurity, and total production procedure is with high costs, is unsuitable for industrial applications.
Invention content
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 by the improvement to zinc oxide ore treatment process present in zinc oxide ore utilization 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 calcium zincates containing zinc ore crude Method includes the following steps:
Leach step:Being mixed containing zinc ore crude and digestion agent after will be levigate, 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, the 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:Activating agent is added into first filtrate, adds calcium hydroxide and/or calcium oxide, 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 dried, a nanometer calcium zincates finished product is obtained.
It is described in the utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates 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 utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates containing zinc ore crude, in institute It states in the leachate that leach step obtains, the concentration (in terms of quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L.
In the utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates 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 utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates containing zinc ore crude, in institute It states in calcium zincates synthesis step, amount and the first filter 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 liquid:2, preferably 1~1.1:2.
In the utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates containing zinc ore crude, to institute State second filtrate that calcium zincates 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 utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates containing zinc ore crude The reaction temperature of calcium zincates synthesis step is 15~90 DEG C, preferably 15~25 DEG C.
It is described in the utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates containing zinc ore crude The time that is stirred to react of calcium zincates synthetic reaction is 15~30 minutes.
It is described in the utilization that disclosure further embodiment provides produces the method for nanometer calcium zincates containing zinc ore crude Activating agent is one or more in calgon, neopelex.
The disclosure also provides the nanometer produced using the method that the utilization of the disclosure produces nanometer calcium zincates containing zinc ore crude The average grain diameter of calcium zincates, the nanometer calcium zincates is 10~100nm.
The effect of invention
The disclosure realizes the Advantageous techniques effect of following one or more aspects:
1) wet-leaching is combined with synthesis technology, realizes the economic and environment-friendly utilization of super low-grade zinc.
2) disclosed method is applied widely, and ammonia-ammonium bicarbonate Leaching Systems can be effectively former containing zinc to 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 makes the balance of zinc ammonium complex ion-zinc ion-calcium zincates move, 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 cycle 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 raw material that the product obtained directly as product, can also can be used as other industrial process uses.
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 environmental pollution that material strip comes.
7) disclosure realizes the synthesis of the calcium zincates under zinc ammonia environment, the especially synthesis of nanometer calcium zincates for the first time.This public affairs It opens from zinc ammonium complex ion and synthesizes nanometer calcium zincates, the selective crystallization point of Zn-ef ficiency is realized by zinc ammonium complex ion balanced sequence From specifically generating nanometer calcium zincates, reactive adaptation is strong, simple and quick, without putting into crystal seed, from low in this way containing zinc ore crude Purity, polymictic cheap raw material set out, and the nanometer calcium zincates for having obtained high-purity under ammonia environment by easy technique produce Product, overall economic efficiency are very high.
Specific implementation mode
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 ".Any embodiment here as illustrated by " exemplary " should not necessarily be construed as Preferred or advantageous over other embodiments.
In addition, in order to which the disclosure is better described, numerous details is given in specific implementation mode below. 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 contains zinc ore crude 3%~15%;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 prodigious 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 of low 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 the compound that zinc ammonium complex ion is formed with carbonate 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 (including but not limited to the 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 the situation carried out including the then described step and the then described step without situation.
Chemical equation
1. extraction
A. zinc oxide extracts
Ammonia is with ammonium hydrogen carbonate as digestion agent
ZnO+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O (integer that i is 1 to 4)
Ammonia is with ammonium carbonate 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 is with ammonium hydrogen carbonate as digestion agent
Zn(OH)2+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+2H2O
(integer that i is 1 to 4)
Ammonia is with ammonium carbonate 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 is with ammonium hydrogen carbonate as digestion agent
ZnSiO3+(i-1)NH3+NH4HCO3=[Zn (NH3)i]CO3+H2O+SiO2
(integer that i is 1 to 4)
Ammonia is with ammonium carbonate 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
Precipitation
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)
Specific process step
Step 1 extracts
Low-grade be mixed in a certain ratio with prepared digestion agent containing zinc ore crude 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 the difference obtained by carbonate amount that zinc carbonate is brought into material, effective carbonate in more preferable digestion agent Amount increase on the basis of zinc theory carbonate consumption is complexed and subtracts the difference obtained by the carbonate amount that zinc carbonate in raw material is brought into Add 50%~150%.It refers to that the Zn-ef ficiency in raw ore is fully converted to ammine carbonate zinc that zinc theory carbonate consumption, which is complexed, The amount of consumed carbonate.Therefore, the molar concentration of effective carbonate may be calculated as in digestion agent:
CDigestion agent carbonate=(nThe total zinc of raw ore-nRaw ore zinc carbonate)×a/VDigestion agent
Wherein, CDigestion agent carbonateFor the molar concentration of effective carbonate 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.
It is complete that the preferred effective carbonate concentration of digestion agent can be such that the zinc in raw ore leaches, and carbonate can be realized in work Cycle 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 the zinc ingredient in raw ore is made to be leached.It is preferred that at normal temperatures into Row extraction, such as extracted at 15~30 DEG C;Also it (such as 30~55 DEG C) can be extracted at slightly higher temperature.It also can 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 (predominantly zinc ammonium complex ions 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 calcium zincates 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 diluted, the zinc ammonium complex ion concentration in leachate is adjusted For preferred 10~25g/L ranges.
Step 2 purifies
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 then addition zinc powder is filtered into line replacement, to Heavy metal contaminants are removed, but other various well known purification methods can also 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 The balanced sequence of zinc ammonium complex ion-zinc ion-zinc hydroxide in raw leachate, a little zinc ingredient may be with hydroxide The form of zinc is co-precipitated with calcium carbonate.
In decarbonation process, effective carbonate in the substantially matching leachate of 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 contributed to 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 Precipitation.The temperature of reaction is not particularly limited, and is particularly preferably reacted at normal temperatures (such as 15~25 DEG C), on the one hand saves The energy, environmental pollution caused by the other hand also reducing ammonia volatilization.Mixing time is not particularly limited, and is as long as obtaining precipitation 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 being co-precipitated with calcium carbonate are also likely to be present in the first solid Zinc.It is calcium oxide and carbon dioxide that the first solid can be calcined, and realization recycles.First filtrate continues on for subsequent zincic acid Calcium synthesizes.
Step 4 calcium zincates synthesize
Activating agent is added into the first filtrate, calcium hydroxide and/or calcium oxide is then added, stirring is reacted.Activity The preferred calgon of agent or neopelex, dosage are preferably estimate finished product quality 0.01~0.05%.This The ratio between the amount of substance of the amount of the substance of the calcium hydroxide and/or calcium oxide that are added in step and zinc ammonium complex ion in the first filtrate It is preferred that 1~1.2:2, more preferable 1~1.1:2.The temperature of reaction is not particularly limited, and may, for example, be 15~90 DEG C, but especially It is preferred that (such as 15~25 DEG C) are reacted at normal temperatures, and it is on the one hand energy saving, caused by the other hand also reducing ammonia volatilization Environmental pollution, 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 are obtained after filtering. The main component of second solid be nanometer calcium zincates, it is however generally that zincic acid calcium component can account for the 95% of the second solid gross mass with On.In addition it can be passed through carbon dioxide to the second filtrate, then recycled for the extraction containing zinc ore crude.
Step 5 rinses
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 dried
Second solid is dried at a temperature of not higher than 125 DEG C, is obtained as main component with nanometer calcium zincates Finished product.The average grain diameter of finished product nanometer calcium zincates is 10~100nm.
The embodiment of the disclosure is described in detail below in conjunction with embodiment, 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.
It takes 300 grams to contain 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 (gauge 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 are added, add 2.45 grams of calcium hydroxides For the synthesis of calcium zincates, stirring at normal temperatures is reacted, and reaction is filtered after 0.5 hour, and filtered solid is 105 It is 2 hours dry at DEG C, it is sampled analysis, is 99.65% through examining zincic acid calcium content in solid, average grain diameter 37.1nm.
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.
It takes 300 grams to contain 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 (gauge is worked as with zinc oxide) 1.367% in body, carbonate mass concentration 3.54% in liquid, 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 are added, adds 2 grams of calcium hydroxides and is used for The synthesis of calcium zincates, at normal temperatures stirring are reacted, and reaction is filtered after 0.5 hour, and filtered solid is at 105 DEG C It is 2 hours dry, it is sampled analysis, is 99.49% through examining zincic acid calcium content in solid, average grain diameter 42.3nm.
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 will be apparent from 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 utilizing the method for producing nanometer calcium zincates containing zinc ore crude, which is characterized in that described to be received using the production containing zinc ore crude The method of rice calcium zincates includes the following steps:
Leach step:Being mixed containing zinc ore crude and digestion agent after will be levigate, then filters, obtains leachate, wherein is described Digestion agent is ammonia and the mixed aqueous solution or ammonia of 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, the 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:Activating agent is added into first filtrate, adds calcium hydroxide and/or calcium oxide, 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 dried, a nanometer calcium zincates finished product is obtained.
2. according to claim 1 utilize the method for producing nanometer calcium zincates containing zinc ore crude, which is characterized in that 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%.
3. according to claim 1 or 2 utilize the method for producing nanometer calcium zincates 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 quality of Zn-ef ficiency) of zinc ammonium complex ion is 10~25g/L.
4. according to any one of claims 1 to 3 using the method for producing nanometer calcium zincates containing zinc ore crude, feature exists In the amount of the substance of the calcium oxide and/or calcium hydroxide that are added in the decarbonation process is effective carbon in the leachate The 100% to 130% of the amount of the substance of acid group, preferably 100% to 110%.
5. according to any one of claims 1 to 4 using the method for producing nanometer calcium zincates containing zinc ore crude, feature exists In, in the calcium zincates synthesis step, be added into first filtrate amount of the substance of calcium hydroxide and/or calcium oxide 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. according to any one of claims 1 to 5 using the method for producing nanometer calcium zincates containing zinc ore crude, feature exists In second filtrate obtained to the calcium zincates 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. according to any one of claims 1 to 6 using the method for producing nanometer calcium zincates containing zinc ore crude, feature exists In the reaction temperature of the calcium zincates synthesis step is 15~90 DEG C, preferably 15~25 DEG C.
8. according to any one of claims 1 to 7 using the method for producing nanometer calcium zincates containing zinc ore crude, feature exists In the time that is stirred to react of the calcium zincates synthetic reaction is 15~30 minutes.
9. utilizing the method for producing nanometer calcium zincates containing zinc ore crude according to claim 1 to 8 any one of them, feature exists In the activating agent is one or more in calgon, neopelex.
10. utilizing the nanometer for the method production for producing nanometer calcium zincates containing zinc ore crude by claim 1 to 9 any one of them Calcium zincates, which is characterized in that the average grain diameter of the nanometer calcium zincates is 10~100nm.
CN201810832651.5A 2018-07-26 2018-07-26 A method of producing nanometer calcium zincates using containing zinc ore crude Withdrawn CN108585026A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020019823A1 (en) * 2018-07-24 2020-01-30 重庆东群科技有限公司 Method for producing calcium zincate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020019823A1 (en) * 2018-07-24 2020-01-30 重庆东群科技有限公司 Method for producing calcium zincate

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