CN110228816B - Method for utilizing zinc-containing raw ore through strontium zincate synthesis step - Google Patents

Method for utilizing zinc-containing raw ore through strontium zincate synthesis step Download PDF

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Publication number
CN110228816B
CN110228816B CN201910628407.1A CN201910628407A CN110228816B CN 110228816 B CN110228816 B CN 110228816B CN 201910628407 A CN201910628407 A CN 201910628407A CN 110228816 B CN110228816 B CN 110228816B
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zinc
strontium
carbonate
zincate
raw ore
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CN110228816A (en
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岳辉伟
李世川
龙忠祥
蒋涛
刘权锋
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Chongqing Dongqun Technology Co ltd
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Chongqing Dongqun Technology Co ltd
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Priority to CN201810817444.2A priority Critical patent/CN108913886A/en
Priority to CN201810817129.XA priority patent/CN108913885A/en
Priority to CN201810817471X priority
Priority to CN2018108174442 priority
Priority to CN201810817129X priority
Priority to CN201810817442.3A priority patent/CN108640146A/en
Priority to CN201810817471.XA priority patent/CN108892166A/en
Priority to CN2018108174423 priority
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    • 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
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • 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
    • 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

The present disclosure relates to a method for utilizing zinc-bearing raw ore by a strontium zincate synthesis step, comprising a leaching step, an optional purification step, a decarbonation step, a strontium zincate synthesis step, an optional rinsing step, a drying or calcination step. The method realizes the synthesis of strontium zincate in the zinc-ammonia environment for the first time, has high reaction selectivity for synthesizing the strontium zincate from zinc-ammonia complex ions, is simple and quick, and prepares high value-added products from low-grade raw ores which are difficult to treat in an economic and environment-friendly manner; the method disclosed by the invention is wide in application range, can effectively extract and utilize zinc-containing raw ores in various forms, enriches zinc elements through a strontium zincate synthesis way, solves the problems of process recovery rate and quality grade of fine products, and can be directly used as a product or used as an industrial raw material.

Description

Method for utilizing zinc-containing raw ore through strontium zincate synthesis step
Technical Field
The invention belongs to the technical field of inorganic chemical industry, relates to resource utilization of low-grade zinc-containing raw ore, and particularly relates to a method for utilizing the zinc-containing raw ore, especially the low-grade zinc-containing raw ore, through a strontium zincate synthesis step.
Background
Strontium zincate is a material with a utilization value in the aspects of special ceramics, battery electrodes, fluorescent materials and the like, but the preparation of the strontium zincate is limited to the research in a laboratory at present, and the preparation scale is small and the cost is high. The industrial production method of strontium zincate is not mature, and methods which can be applied in industry and can stably produce strontium zincate and derivative products in large scale are lacked, in particular to a method for producing strontium zincate and derivative products by starting from zinc-containing raw materials with high impurity content.
The process for economically and efficiently preparing various zinc products from a zinc raw material with low zinc content and high impurity content is a technical problem. The current industrial situation particularly urgently needs to solve the problem because the total amount of zinc resources in China is rich, but the overall grade of zinc ores is low, a large amount of dead ores and lean ores cannot be effectively utilized due to the lack of an industrial economic and effective treatment method, a large amount of zinc raw materials have to be imported every year to meet the requirements of production and consumption, and meanwhile, the mining tailings containing 3-5% of zinc oxide and the mineral tailings are stockpiled in a large amount, so that great pressure is caused.
The existing low-grade zinc ore processing technology has a plurality of defects, so that the low-grade zinc ore processing technology is difficult to use in actual production. For example, the process for treating low-grade zinc oxide ore by a pyrogenic process faces elimination due to high energy consumption and large pollution, and does not meet the policy guidance of energy conservation and emission reduction. Flotation is the main process for treating zinc oxide ore at present, but the common problems of low ore dressing recovery rate and low concentrate grade are faced by various flotation processes. The wet extraction of zinc ore has the problems of poor leaching selectivity, unsatisfactory leaching efficiency, difficult recovery after leaching and the like. Therefore, the prior art lacks an economical and effective method for preparing various industrial products from low-grade zinc ores.
Disclosure of Invention
Problems to be solved by the invention
The existing process for utilizing the low-grade zinc oxide ore has the problems of high energy consumption, low recovery rate, serious environmental pollution, low economic value and the like, and a method for economically and effectively utilizing the low-grade zinc ore to prepare various zinc-containing products represented by strontium zincate is lacked. The invention solves the above problem in one or more aspects in the utilization of zinc ore, especially low grade zinc ore, by improving the treatment process.
Means for solving the problems
In order to solve the problems in the prior art, the present disclosure provides a method for utilizing zinc-containing raw ore through strontium zincate synthesis steps, comprising the steps of:
leaching: mixing and stirring ground zinc-containing raw ore and a leaching agent, and then filtering to obtain a leaching agent, wherein the leaching agent is a mixed aqueous solution of ammonia and ammonium bicarbonate, or a mixed aqueous solution of ammonia and ammonium carbonate, or a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate;
optionally, purifying the leachate obtained in the leaching step;
a decarburization step: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
strontium zincate synthesis step: adding strontium hydroxide and/or strontium oxide into the first filtrate, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
optionally, rinsing the second solid with water;
a drying or calcining step: drying the second solid at a temperature not higher than 125 ℃ to obtain a strontium zincate product; or calcining the second solid at the temperature of 150-1050 ℃, mixing the calcined product with water, stirring and filtering to obtain a third solid and a third filtrate, and drying the third solid to obtain a zinc oxide product.
In a method of utilizing zinc-containing raw ore through a strontium zincate synthesis step provided in a further embodiment of the present disclosure, an active agent is added to the first filtrate before adding strontium hydroxide and/or strontium oxide to the first filtrate in the strontium zincate synthesis step.
In a further embodiment of the present disclosure, there is provided a method for utilizing zinc-containing raw ore through a strontium zincate synthesis step, the mass concentration of total ammonia in the leaching agent is 5% to 15%, and the molar concentration of available carbonate in the leaching agent is:
Clixiviant carbonate radical=(nTotal zinc of raw ore-nRaw mineral zinc carbonate)×a/VLixiviant
Wherein the content of the first and second substances,
Clixiviant carbonate radicalIs the molar concentration of available carbonate in the leaching agent,
ntotal zinc of raw oreIs the amount of the zinc element in the zinc-containing raw ore,
nraw mineral zinc carbonateIs the amount of zinc carbonate material in the zinc-bearing raw ore,
VlixiviantIs the volume of the leaching agent,
the value range of a is 100-600%, preferably 150-250%.
In the method for utilizing zinc-containing raw ore through a strontium zincate synthesis step, provided by a further embodiment of the present disclosure, the concentration of zinc ammine complex ions (based on the mass of zinc element) in the leachate obtained in the leaching step is 10-25 g/L.
In a process for utilizing a zinc-containing raw ore by a strontium zincate synthesis step provided in a further embodiment of the present disclosure, the amount of the substance of calcium oxide and/or calcium hydroxide added in the decarbonization step is 100% to 130%, preferably 100% to 110%, of the amount of the substance of available carbonate in the leachate.
In a method for utilizing zinc-containing raw ore through a strontium zincate synthesis step provided in a further embodiment of the present disclosure, in the strontium zincate synthesis step, a ratio of an amount of strontium hydroxide and/or strontium oxide substance added to the first filtrate to an amount of zinc ammine complex ion substance in the first filtrate is 1 to 1.2:2, preferably 1 to 1.1: 2.
In a method for utilizing zinc-containing raw ore through a strontium zincate synthesis step, carbon dioxide is introduced into the second filtrate obtained in the strontium zincate synthesis step, and the second filtrate introduced with the carbon dioxide is used as a leaching agent and is recycled for leaching the zinc-containing raw ore.
In a method of using a zinc-containing raw ore through a strontium zincate synthesis step provided in a further embodiment of the present disclosure, the reaction temperature of the strontium zincate synthesis step is 15 to 90 ℃, preferably 30 to 60 ℃, or preferably 15 to 25 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
The present disclosure achieves the following advantageous technical effects in one or more aspects:
1) the method realizes the synthesis of strontium zincate in the zinc-ammonia environment for the first time, has high reaction selectivity for synthesizing the strontium zincate from zinc-ammonia complex ions, is simple and quick, and prepares high value-added products from low-grade raw ores which are difficult to treat in an economic and environment-friendly manner.
2) The method disclosed by the invention is wide in application range, the ammonia-ammonium bicarbonate leaching system can effectively extract and utilize zinc-containing raw ores in various forms, zinc elements are enriched through a strontium zincate synthesis way, the problems of process recovery rate and quality of fine products are solved, and the obtained product can be directly used as a product and also can be used as an industrial raw material.
3) Breaking the inherent method that the traditional ammonia-ammonium bicarbonate method zinc complex leaching process destroys the complex environment by heating and evaporating ammonia to realize zinc ion crystal separation, the application creatively adds strontium oxide or strontium hydroxide into an ammonium bicarbonate-zinc ammonia complex system to move the balance of zinc ammino-zinc ion-strontium zincate, realizes the selective crystal separation of zinc element by the balance moving principle on the premise of not destroying the dissolved ammonia environment, and avoids the phenomenon of impurity mass coprecipitation caused by the ammonia environment destruction of the existing heating and ammonia evaporation method. The process disclosed by the invention is simple and easy to implement without ammonia distillation, greatly reduces the energy consumption of the process, and also avoids the problems in many aspects such as water treatment pressure, high-temperature and high-pressure potential safety hazards, equipment corrosion and the like caused by ammonia distillation.
4) The method disclosed by the invention realizes leaching and separation of zinc through circulation of carbonate, and solves the environmental protection problem in the ammonia circulation process because the surplus water brought by steam influences the process water balance. The used auxiliary materials have small pollution and low cost, the circulation of the auxiliary materials is realized, and compared with the prior art using high-pollution auxiliary materials, the method disclosed by the invention has obvious advantages in controlling the pollution in the production process.
Detailed Description
Various exemplary embodiments, features and aspects of the disclosure are described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. In some instances, methods, means, reagents and devices well known to those skilled in the art are not described in detail, but those skilled in the art can implement the technical solutions of the present disclosure based on the general knowledge in the art.
The application range of the method disclosed by the invention is not particularly limited, and the method can be widely applied to the utilization of various zinc-containing raw ores. The advantages of the process disclosed herein are particularly pronounced when low grade zinc oxide raw ore is used as a production feedstock. For example, the low-grade zinc-containing raw ore can be zinc-containing raw ore with the zinc content of 3-15%; particularly, before the method, a large amount of zinc-containing raw ores (lean ores and mill tailings) with the zinc content of 3% -6% are stockpiled, the existing various processes cannot utilize the economic value of the zinc-containing raw ores, and great processing pressure is caused.
In the present disclosure, the form of the presence of the zinc component in the zinc-containing raw ore is not particularly limited, for example, the zinc component may be present in one or more forms including, but not limited to, zinc oxide, zinc carbonate, zinc silicate, and the like.
Noun interpretation
As used herein, unless otherwise specified, "zinc ammine carbonate" is a generic term for compounds formed from zinc ammine complex ions and carbonate ions, and includes [ Zn (NH)3)4]CO3(Zinc tetraammine carbonate), [ Zn (NH)3)3]CO3(Triammine Zinc carbonate), [ Zn (NH)3)2]CO3(Diaminozinc carbonate), [ Zn (NH)3)]CO3(zinc monoammonium carbonate), and the like.
In this context, unless otherwise stated, "zinc ammine complex ion" is a generic term for each level of ammine zinc complex ion, and includes [ Zn (NH)3)4]2+(Zinc tetraammine ion), [ Zn (NH)3)3]2+(Triammine Zinc ion), [ Zn (NH)3)2]2+(Diaminato zinc ion), [ Zn (NH)3)]2+(zinc ion ammine), and the like.
As used herein, unless otherwise indicated, "carbonate" in a solution (including but not limited to various liquors such as lixiviants, leachate, and the like) refers to the sum of carbonate and bicarbonate in the solution.
"optional" or "optionally" means that the subsequently described step may or may not be performed, and that the expression includes instances where the subsequently described step is performed and instances where the subsequently described step is not performed.
Chemical reaction formula
1. Leaching
a. Zinc oxide leaching
Extracting agent of ammonia and ammonium bicarbonate
ZnO+(i-1)NH3+NH4HCO3=[Zn(NH3)i]CO3+H2O (i is an integer of 1 to 4)
Ammonia and ammonium carbonate as leaching agents
ZnO+(i-2)NH3+(NH4)2CO3=[Zn(NH3)i]CO3+H2O (i is an integer of 2 to 4)
b. Leaching of zinc hydroxide
Extracting agent of ammonia and ammonium bicarbonate
Zn(OH)2+(i-1)NH3+NH4HCO3=[Zn(NH3)i]CO3+2H2O
(i is an integer of 1 to 4)
Ammonia and ammonium carbonate as leaching agents
Zn(OH)2+(i-2)NH3+(NH4)2CO3=[Zn(NH3)i]CO3+2H2O
(i is an integer of 2 to 4)
c. Zinc carbonate (calamine) leaching
ZnCO3+iNH3=[Zn(NH3)i]CO3(i is an integer of 1 to 4)
d. Zinc silicate leaching
Extracting agent of ammonia and ammonium bicarbonate
ZnSiO3+(i-1)NH3+NH4HCO3=[Zn(NH3)i]CO3+H2O+SiO2
(i is an integer of 1 to 4)
Ammonia and ammonium carbonate as leaching agents
ZnSiO3+(i-2)NH3+(NH4)2CO3=[Zn(NH3)i]CO3+H2O+SiO2
(i is an integer of 2 to 4)
2. Decarburization of carbon
Reaction of lime with water
CaO+H2O=Ca(OH)2
Precipitation of
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
(i is an integer of 1 to 4)
Possible side reactions:
Ca(OH)2+[Zn(NH3)i]CO3=CaCO3↓+Zn(OH)2↓+iNH3
(i is an integer of 1 to 4)
3. Strontium zincate synthesis
2[Zn(NH3)i](OH)2+Sr(OH)2+2H2O=Sr(OH)2·2Zn(OH)2·2H2O+2iNH3
(i is an integer of 1 to 4)
4. Calcination of
Sr(OH)2·2Zn(OH)2·2H2O=Sr(OH)2+2ZnO+4H2O
Sr(OH)2·2Zn(OH)2·2H2O=SrO+2ZnO+5H2O
The concrete process steps
Step 1 extraction
Mixing the ground low-grade zinc-containing raw ore with a prepared leaching agent according to a certain proportion, and stirring and leaching. The leaching agent may be selected from: a mixed aqueous solution of ammonia and ammonium bicarbonate; a mixed aqueous solution of ammonia and ammonium carbonate; a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate.
The concentration of total ammonia and the concentration of available carbonate in the leaching agent are not particularly limited, and those skilled in the art can select the concentration according to the actual needs by combining the factors such as raw ore components, grade and the like.
In the preferred scheme, the mass concentration of the total ammonia in the leaching agent is 5-15%, more preferably 6-8%, and the preferred concentration range can achieve sufficient leaching effect and avoid the problems of waste and environmental protection caused by excessive ammonia.
In a preferred scheme, the amount of available carbonate in the leaching agent is increased by 0-500% on the basis of the difference obtained by subtracting the amount of carbonate introduced by zinc carbonate in the raw material from the theoretical consumption of carbonate in complexed zinc, and more preferably, the amount of available carbonate in the leaching agent is increased by 50% -150% on the basis of the difference obtained by subtracting the amount of carbonate introduced by zinc carbonate in the raw material from the theoretical consumption of carbonate in complexed zinc. The consumption of carbonate in the theory of complex zinc is the consumption of carbonate which is used for completely converting zinc element in raw ore into zinc ammonium carbonate. Thus, the molar concentration of available carbonate in the lixiviant can be calculated as follows:
Clixiviant carbonate radical=(nTotal zinc of raw ore-nRaw mineral zinc carbonate)×a/VLixiviant
Wherein, CLixiviant carbonate radicalIs the molar concentration of available carbonate in the lixiviant, nTotal zinc of raw oreIs the amount of material containing zinc element in the zinc raw ore, nRaw mineral zinc carbonateIs the amount of zinc carbonate in the zinc-containing raw ore, VLixiviantIs the volume of the leaching agent, a is a coefficient, and the value of a is 100 to 600 percent, preferably 150 to 250 percent. The mass concentration of carbonate in the lixiviant can be converted according to the molar concentration.
The optimized effective carbonate concentration of the leaching agent can ensure that zinc in raw ore is completely leached, can realize the circulation of carbonate in the process, and can avoid the pressure of excessive carbonate on the subsequent process treatment.
The weight ratio of the leaching agent to the zinc-containing raw ore powder is not particularly limited as long as the zinc component can be leached. Preferably, the weight ratio of the leaching agent to the zinc-containing raw ore powder is 3:1 to 5:1, so that a satisfactory leaching effect can be obtained, and the waste of the leaching agent is avoided.
The leaching temperature is not particularly limited as long as the zinc component in the raw ore is leached. Preferably leaching is carried out at normal temperature, for example leaching is carried out at 15-30 ℃; the leaching may also be carried out at slightly elevated temperatures (e.g., 30-55 ℃). The temperature can be selected according to actual conditions.
The zinc-containing raw ore is mixed with the leaching agent and stirred for a period of time which is not particularly limited as long as the zinc component in the raw ore is leached, and the stirring time is preferably 1 to 4 hours, more preferably 1 to 2 hours.
During leaching, zinc element in raw ore is converted into zinc ammine complex ions (mainly zinc ammine complex ions at each level) and enters into a liquid phase. And filtering after leaching to obtain a leaching solution containing zinc ammonia complex ions. The leachate can be used in the subsequent decarburization process. The concentration of the zinc ammine complex ions in the leachate is not particularly limited, but the concentration of the zinc ammine complex ions (calculated by the mass of the zinc element) in the leachate is preferably 10-25 g/L, so that the treatment efficiency of the process is optimal, good yield and purity are obtained in the subsequent strontium zincate synthesis step, and the comprehensive economic benefit is optimal. If the concentration of the zinc ammine complex ions in the original leached liquid is not in the preferred range, optionally concentrating or diluting the leached liquid, and adjusting the concentration of the zinc ammine complex ions in the leachate to be in the preferred range of 10-25 g/L.
Step 2 purification
Step 2 is an optional step, and step 2 is optionally performed, if necessary. Purifying the leachate by a known method to remove impurity elements such as iron, manganese, lead, copper and the like. An exemplary purification method is to add zinc powder for displacement and then filtering to remove heavy metal contaminants, but various other known purification methods may be used. The purification step helps to increase the purity of the final product.
Step 3 decarburization
In the decarbonization step, calcium hydroxide and/or calcium oxide is added into the leachate containing the zinc-ammonia complex ions, and carbonate/bicarbonate radicals in the leachate are converted into calcium carbonate. If the concentration of the zinc ammine complex ions in the leachate is too high, equilibrium shift of zinc ammine complex ions-zinc hydroxide in the leachate may occur at the same time, and a very small portion of the zinc component may be co-precipitated with calcium carbonate in the form of zinc hydroxide.
In the decarbonising step, the amount of calcium hydroxide and/or calcium oxide added substantially matches the amount of available carbonate in the leach solution, for example, the amount of calcium hydroxide and/or calcium oxide species added in the decarbonising step is 100% to 130%, more preferably 100% to 110% of the amount of available carbonate species in the leach solution. Proper addition of calcium hydroxide and/or calcium oxide is helpful for controlling the process cost and improving the purity and quality of the finished zinc product.
In the decarbonization step, calcium hydroxide and/or calcium oxide are added into the leaching solution, and the mixture is stirred for reaction to generate solid precipitate. The reaction temperature is not particularly limited, and particularly, the reaction is preferably carried out at normal temperature (for example, 15 to 25 ℃), so that on one hand, energy is saved, and on the other hand, environmental pollution caused by ammonia volatilization is reduced. The stirring time is not particularly limited as long as a precipitate is obtained, and stirring is preferably performed for 1 to 2 hours.
And filtering after stirring to obtain a first solid and a first filtrate. The primary component of the first solid is calcium carbonate, and if the concentration of zinc ammine ions in the leach solution is high, some zinc hydroxide co-precipitated with the calcium carbonate may also be present in the first solid. The first solid can be calcined into calcium oxide and carbon dioxide for recycling. The first filtrate continues to be used for subsequent strontium zincate synthesis.
Step 4 strontium zincate Synthesis
Adding strontium hydroxide and/or strontium oxide into the first filtrate, and stirring for reaction. If a reaction product having a minute particle size is desired, the first filtrate is added with an activating agent, and then strontium hydroxide and/or strontium oxide is added, followed by stirring for reaction. The active agent is preferably sodium hexametaphosphate or sodium dodecyl benzene sulfonate, and the addition amount of the active agent is preferably 0.01-0.05% of the estimated final product mass.
The ratio of the amount of strontium hydroxide and/or strontium oxide added in this step to the amount of zinc ammine complex ion in the first filtrate is preferably 1 to 1.2:2, more preferably 1 to 1.1: 2. The reaction temperature is not particularly limited, and may be, for example, 15 to 90 ℃, preferably 20 to 90 ℃, and more preferably 30 to 60 ℃; or the reaction temperature of 15-25 ℃ is preferably selected, the temperature range has the advantages of no need of heating, energy conservation and reduction of ammonia volatilization, and the low temperature is more favorable for controlling the crystal grain size.
After reacting for 15 minutes to 2 hours, filtering can be carried out without long-time reaction and aging processes. Particularly, the filtering is carried out after the stirring reaction is carried out for 15-30 minutes, and the shorter stirring reaction time is beneficial to controlling the grain size of the crystal. Filtering to obtain a second solid and a second filtrate. The main component of the second solid is strontium zincate, and generally, the strontium zincate component may account for 95% or more of the total mass of the second solid. Carbon dioxide may be passed to the second filtrate and then recycled for leaching of the zinc containing raw ore.
Step 5 rinsing
This step is an optional step, and a rinsing step is performed if necessary. And rinsing the second solid with water, wherein the liquid-solid ratio is 5-10: 1, and the rinsing times are 1-2.
Step 6 drying or calcining
The first scheme of the step is to dry the second solid at a temperature not higher than 125 ℃ to obtain a final product with strontium zincate as a main component. If the activator is added in the strontium zincate synthesis step, the step is dried to obtain the nanometer strontium zincate product, and the average grain size of the nanometer strontium zincate product is 10-100 nm.
The second scheme of the step is to calcine the second solid to decompose strontium zincate. The calcination temperature is 150-1050 ℃, preferably 150-350 ℃. The product obtained by calcining is a mixture, and if the mixture is calcined at the temperature of 150-350 ℃, the main components of the calcined product are zinc oxide and strontium hydroxide; if calcined at higher temperatures, the strontium hydroxide may be further converted to strontium oxide. Since zinc oxide is poorly soluble in water and strontium hydroxide is readily soluble in water (or strontium oxide reacts with water to form strontium hydroxide which is soluble in water), the calcined product can be mixed with water, stirred, and filtered to obtain a third solid and a third filtrate. The main component of the third solid is zinc oxide and the solute in the third filtrate is mainly strontium hydroxide. And drying the third solid to obtain a final product with zinc oxide as a main component. If the activating agent is added in the strontium zincate synthesis step, the nano-scale zinc oxide product can be obtained after calcination, and the average particle size of the nano-scale zinc oxide product is 10-100 nm. And for the third filtrate, carbon dioxide can be introduced to the third filtrate to obtain strontium carbonate precipitate, and the third filtrate can also be recycled for other purposes.
Embodiments of the present disclosure will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present disclosure and should not be construed as limiting the scope of the present disclosure. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The zinc content of the zinc ore in some places in Yunnan province is 5.6%, the oxidation rate of raw ore is 96.3%, and the zinc component in the ore takes zinc carbonate as a main existing form.
300 g of zinc-containing raw ore is taken and put into 900 ml of ammonia-ammonium bicarbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 3 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the filtered liquid contains 1.632 percent of zinc (calculated by zinc oxide equivalent), the mass concentration of carbonate in the liquid is 4.23 percent, and the increased part is introduced by zinc carbonate in the raw ore. According to the test data, the recovery rate of soluble zinc in the raw ore in the leaching process is 90.79%, and the total recovery rate of zinc is 87.43%.
And purifying the filtered zinc-ammonia complex solution.
And adding 14.55 g of calcium oxide into 600 ml of zinc-ammonia complex solution obtained by leaching and filtering for precipitating carbonate, reacting for 1 hour, and filtering.
And (3) taking 500 ml of filtered liquid, adding 4.46 g of strontium oxide for synthesizing strontium zincate, stirring at normal temperature for reaction, filtering after 1 hour of reaction, drying the filtered solid at 105 ℃ for 2 hours, sampling and analyzing, and testing that the content of strontium zincate in the solid is 99.57%.
Example 2
In the zinc ore in Chongqing, the zinc content is 4.7%, the oxidation rate of raw ore is 95.52%, and the zinc component in the ore takes zinc silicate as a main existing form.
300 g of zinc-containing raw ore is taken and put into 900 ml of ammonia-ammonium bicarbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 3 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc (calculated by zinc oxide equivalent) in the filtered liquid is 1.367 percent, the mass concentration of carbonate in the liquid is 3.54 percent, and the part of the zinc-containing raw ore is added by zinc carbonate in the raw ore. According to the test data, the recovery rate of soluble zinc in the raw ore in the leaching process is 91.35%, and the total recovery rate of zinc is 87.26%.
And purifying the filtered zinc-ammonia complex solution.
Taking 600 ml of zinc-ammonia complex liquid obtained by leaching and filtering, adding 12.18 g of calcium oxide for precipitating carbonate, reacting for 1 hour, and filtering.
And (3) adding 3.67 g of strontium oxide into 500 ml of filtered liquid for synthesizing strontium zincate, stirring at normal temperature for reaction, filtering after 1 hour of reaction, drying the filtered solid at 105 ℃ for 2 hours, sampling and analyzing, and testing that the content of strontium zincate in the solid is 99.53%.
Example 3
The difference from example 1 is that in example 3, calcium oxide is added to the zinc-ammonia complex solution obtained by leaching to precipitate carbonate, then the solution is filtered, 500 ml of the filtered solution is taken, 3 mg of sodium dodecyl benzene sulfonate is added, and 4.46 g of strontium oxide is added for synthesizing strontium zincate. The rest of the steps and the amounts of the reagents in example 3 are the same as in example 1.
The final product was sampled and analyzed, and the strontium zincate content in the solid was checked to be 99.57% and the average particle size was 32.7 nm.
Example 4
The difference from example 2 is that in example 4, calcium oxide is added to the zinc-ammonia complex solution obtained by leaching to precipitate carbonate, then the solution is filtered, 500 ml of the filtered solution is taken, 3 mg of sodium dodecyl benzene sulfonate is added, and then 3.67 g of strontium oxide is added for synthesizing strontium zincate. The rest of the steps and the amounts of the reagents in example 4 are the same as in example 2.
The final product was sampled and analyzed, and the strontium zincate content in the solid was checked to be 99.53%, and the average particle size was 38.3 nm.
Example 5
The zinc content of the zinc ore in some places in Yunnan province is 5.6%, the oxidation rate of raw ore is 96.3%, and the zinc component in the ore takes zinc carbonate as a main existing form.
300 g of zinc-containing raw ore is taken and put into 900 ml of ammonia-ammonium carbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 3 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc (calculated by zinc oxide equivalent) is 1.632 percent in the filtered liquid, the mass concentration of carbonate in the liquid is 4.23 percent, and the increased part is brought by the zinc carbonate in the raw ore. According to the test data, the recovery rate of soluble zinc in the raw ore in the leaching process is 90.79%, and the total recovery rate of zinc is 87.43%.
And purifying the leaching solution containing the zinc ammine complex ions obtained by filtering.
And taking 600 ml of purified leachate, adding 14.55 g of calcium oxide for precipitating carbonate, reacting for 1 hour, and filtering.
And taking 500 ml of filtered liquid, adding 4.46 g of strontium oxide for synthesizing strontium zincate, stirring for reaction, filtering after 1 hour of reaction, and filtering to obtain a solid with strontium zincate as a main component.
The strontium zincate solid is dried for 2 hours at 105 ℃ and then calcined for 2 hours at 300 ℃, and the strontium zincate is decomposed into zinc oxide and strontium hydroxide.
Adding water 300 times the mass of zinc oxide and strontium hydroxide, stirring for 1 hour, filtering, drying the filtered zinc oxide at 105 ℃ for 2 hours, and inspecting and analyzing to obtain the product with the zinc oxide content of 99.56%.
Example 6
In the zinc ore in Chongqing, the zinc content is 4.7%, the oxidation rate of raw ore is 95.52%, and the zinc component in the ore takes zinc silicate as a main existing form.
300 g of zinc oxide raw ore is taken and put into 900 ml of ammonia-ammonium carbonate mixed solution (the mass concentration of total ammonia is 10 percent, and the mass concentration of carbonate is 3 percent) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then filtration is carried out, 1.367 percent of zinc oxide and 3.54 percent of carbonate in the liquid are added into the filtered liquid, and the zinc oxide is carried in by the zinc carbonate in the raw ore. According to the test data, the recovery rate of soluble zinc in the raw ore in the leaching process is 91.35%, and the total recovery rate of zinc is 87.26%.
And purifying the leaching solution containing the zinc ammine complex ions obtained by filtering.
Taking 600 ml of purified leachate, adding 12.18 g of calcium oxide for precipitating carbonate, reacting for 1 hour, and filtering.
And taking 500 ml of filtered liquid, adding 3.36 g of strontium oxide for synthesizing strontium zincate, stirring for reaction, filtering after 1 hour of reaction, and filtering to obtain a solid with strontium zincate as a main component.
The strontium zincate solid is dried for 2 hours at 105 ℃ and then calcined for 2 hours at 300 ℃, and the strontium zincate is decomposed into zinc oxide and strontium hydroxide.
Adding water 300 times the mass of zinc oxide and strontium hydroxide, stirring for 1 hour, filtering, drying the filtered zinc oxide at 105 ℃ for 2 hours, and detecting and analyzing to obtain the product with the zinc oxide content of 99.53%.
Example 7
The difference from example 5 is that in example 7, calcium oxide is added to the zinc-ammonia complex solution obtained by leaching to precipitate carbonate, and then the solution is filtered, 500 ml of the filtered solution is taken, 3 mg of sodium dodecyl benzene sulfonate is added, and 4.46 g of strontium oxide is added for synthesizing strontium zincate. The rest of the steps and the amounts of the reagents in example 7 are the same as those in example 5.
The obtained final product was sampled and analyzed, and it was checked that the content of zinc oxide in the final product was 99.63% and the average particle size of zinc oxide was 34.6 nm.
Example 8
The difference from example 6 is that in example 8, calcium oxide is added to the zinc-ammonia complex solution obtained by leaching to precipitate carbonate, and then the solution is filtered, 500 ml of the filtered solution is taken, 3 mg of sodium dodecyl benzene sulfonate is added, and then 3.67 g of strontium oxide is added for synthesizing strontium zincate. The rest of the steps and the amount of the reagents in example 6 are the same as those in example 8.
The obtained final product was sampled and analyzed, and it was checked that the content of zinc oxide in the final product was 99.57% and the average particle size of zinc oxide was 30.6 nm.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (10)

1. A method for utilizing a zinc-containing raw ore through a strontium zincate synthesis step, characterized in that the method for utilizing a zinc-containing raw ore through a strontium zincate synthesis step comprises the steps of:
leaching: mixing and stirring ground zinc-containing raw ore and a leaching agent, and then filtering to obtain a leaching agent, wherein the leaching agent is a mixed aqueous solution of ammonia and ammonium bicarbonate, or a mixed aqueous solution of ammonia and ammonium carbonate, or a mixed aqueous solution of ammonia, ammonium bicarbonate and ammonium carbonate;
optionally, purifying the leachate obtained in the leaching step;
a decarburization step: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
strontium zincate synthesis step: adding strontium hydroxide and/or strontium oxide into the first filtrate, stirring for reaction at the reaction temperature of 30-60 ℃ or 15-25 ℃, and filtering to obtain a second solid and a second filtrate;
optionally, rinsing the second solid with water;
a drying or calcining step: drying the second solid at a temperature not higher than 125 ℃ to obtain a strontium zincate product; or calcining the second solid at the temperature of 150-1050 ℃, mixing the calcined product with water, stirring and filtering to obtain a third solid and a third filtrate, and drying the third solid to obtain a zinc oxide product.
2. The method of claim 1, wherein an active agent is added to the first filtrate before adding strontium hydroxide and/or strontium oxide to the first filtrate in the strontium zincate synthesis step.
3. A method according to claim 1, characterized in that the mass concentration of total ammonia in the leaching agent is 5-15%, and the molar concentration of available carbonate in the leaching agent is:
Clixiviant carbonate radical=(nTotal zinc of raw ore-nRaw mineral zinc carbonate)×a/VLixiviant
Wherein the content of the first and second substances,
Clixiviant carbonate radicalIs the molar concentration of available carbonate in the leaching agent,
ntotal zinc of raw oreIs the amount of the zinc element in the zinc-containing raw ore,
nraw mineral zinc carbonateIs the amount of zinc carbonate material in the zinc-bearing raw ore,
VlixiviantIs the volume of the leaching agent,
the value range of a is 100-600%.
4. The method of utilizing zinc-containing raw ore through strontium zincate synthesis step according to claim 3, wherein a is in a range of 150% to 250%.
5. The method according to any one of claims 1 to 4, wherein the leachate obtained in the leaching step contains zinc ammine complex ions in an amount of 10 to 25g/L in terms of the mass of zinc element.
6. The method according to any one of claims 1 to 4, wherein the amount of the substance of calcium oxide and/or calcium hydroxide added in the decarbonation step is 100 to 130% of the amount of the substance of available carbonate in the leachate.
7. The method according to claim 6, characterized in that the amount of calcium oxide and/or calcium hydroxide added in the decarbonization step is 100 to 110% of the amount of available carbonate in the leachate.
8. The method for utilizing zinc-containing raw ore through a strontium zincate synthesis step according to any one of claims 1 to 4, wherein in the strontium zincate synthesis step, the ratio of the amount of the substance of strontium hydroxide and/or strontium oxide to the amount of the substance of zinc ammine complex ion in the first filtrate is 1-1.2: 2.
9. The method according to claim 8, wherein the ratio of the amount of strontium hydroxide and/or strontium oxide to the amount of zinc ammine complex ion in the first filtrate in the strontium zincate synthesis step is 1 to 1.1: 2.
10. The method according to any one of claims 1 to 4, wherein carbon dioxide is introduced into the second filtrate obtained in the strontium zincate synthesis step, and the second filtrate introduced with carbon dioxide is used as a leaching agent and recycled for leaching of the zinc-containing raw ore.
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CN201810817444.2A CN108913886A (en) 2018-07-24 2018-07-24 A method of nanometer zincic acid strontium is produced using containing zinc ore crude
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CN102242262A (en) * 2011-04-02 2011-11-16 中南大学 Method for treating low-grade zinc oxide ore by using weakly alkaline amino acid salt system
CN102849783A (en) * 2012-09-25 2013-01-02 四川巨宏科技有限公司 Production method of high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarbonization
CN105967222A (en) * 2015-06-08 2016-09-28 江苏大学 Method for directly preparing zinc oxide by zinc-containing flue dust in steel factory through wet processing

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1396117A (en) * 2002-06-13 2003-02-12 山东小鸭集团有限责任公司 Process for preparing nano zinc oxide
CN102242262A (en) * 2011-04-02 2011-11-16 中南大学 Method for treating low-grade zinc oxide ore by using weakly alkaline amino acid salt system
CN102849783A (en) * 2012-09-25 2013-01-02 四川巨宏科技有限公司 Production method of high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarbonization
CN105967222A (en) * 2015-06-08 2016-09-28 江苏大学 Method for directly preparing zinc oxide by zinc-containing flue dust in steel factory through wet processing

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