CN109022821B - Method for producing nano zinc oxide by using leached residues of electrolytic zinc acid method - Google Patents
Method for producing nano zinc oxide by using leached residues of electrolytic zinc acid method Download PDFInfo
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Abstract
The disclosure relates to a method for producing nano zinc oxide by using leaching residue of an electrolytic zincate method, which comprises a leaching step, an optional purification step, a desulfurization step, a calcium zincate synthesis step, an optional rinsing step, a calcination step and a calcium-zinc separation step. The method disclosed by the invention realizes secondary utilization of leaching residues while solving the problem of environmental protection, realizes resource utilization while solving the pollution of various heavy metals, does not need ammonia distillation, is simple and easy, and also greatly reduces the energy consumption of the process.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of resources and comprehensive application of new materials, relates to environment-friendly treatment and resource utilization of leaching residues of an electrolytic zincic acid method, and particularly relates to a method for producing nano zinc oxide by using the leaching residues of the electrolytic zincic acid method.
Background
The leaching slag of the electrolytic zincate method is the most main pollutant in the electrolytic zinc industry, and belongs to the leaching slag generated by the conventional leaching method in the lead-zinc smelting process and the sulfur slag (leaching slag) generated by the normal pressure oxygen leaching and the pressure oxygen leaching in the national hazardous waste catalogue. The treatment and resource utilization of the leaching residue by the electrolytic zincate method are problems which need to be solved urgently. Meanwhile, the production and consumption of zinc in China are at the top of the world, domestic zinc resources cannot meet the production, and a large amount of zinc raw materials need to be imported every year. The method is developed to realize the high-efficiency resource utilization of the zinc in the leaching residue of the electrolytic zincic acid method, and has important significance for solving the environmental protection pressure and relieving the domestic zinc raw material supply problem.
Calcium zincate has a wide range of uses. The application of calcium zincate to the negative electrode material of the alkaline secondary zinc electrode is a new direction developed in recent years and is continuously mature and industrialized; compared with the traditional zinc oxide desulfurizer, the calcium zincate is a normal-temperature desulfurizer with desulfurization active components, and the sulfur capacity is greatly increased; the calcium zincate as the feed additive is not only beneficial to the absorption of animals but also beneficial to reducing the environmental pollution. The calcium zincate can also be widely used for glaze, paint, coating additives and the like. Calcium zincate can also be used as raw material for electrolytic zinc and zinc oxide.
The preparation method of calcium zincate in the prior art is limited to experimental exploration and is not mature. For example, Chinese patent CBoth N1397498A and CN1595688A disclose the synthesis of calcium zincate by a ball milling method, wherein, in Chinese patent CN1397498A, Ca (OH)2 and ZnO are put into a ball milling tank according to the proportion in the chemical formula of the calcium zincate, a proper amount of water is added, the ball milling is carried out for 8 to 18 hours under the protection of argon atmosphere, and then the product is obtained after the baking is carried out for 10 to 15 hours at the temperature of 30 to 80 ℃; U.S. Pat. No. 5,460,899 discloses a method of using ZnO and Ca (OH)2A method for generating calcium zincate by reaction in alkali liquor; chinese patent CN2012100305744 discloses a soluble zinc salt and Ca (OH) in a stoichiometric ratio2Preparing into emulsion to generate calcium zincate. In the method, finished high-purity zinc oxide or finished zinc salt is used as a starting raw material, the raw material is expensive, the reaction condition is harsh, the energy consumption is high, the reaction is incomplete, the yield is low, the reaction specificity is poor, the interference of impurities is easy, the total preparation process cost is high, and the method is not suitable for industrial application.
Zinc oxide is an oxide of zinc, is poorly soluble in water, and is soluble in acids and strong bases. Zinc oxide is a commonly used chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint, coating, ointment, adhesive, food, batteries, flame retardant and the like. The zinc oxide has large energy band gap and exciton constraint energy, high transparency and excellent normal temperature luminous performance, and is applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like in the semiconductor field.
Chinese patent CN102863007 discloses a method for producing zinc oxide from leaching residue of electrolytic zincate method, which comprises leaching, purifying, ammonia evaporation crystallization, rinsing, drying and calcining the leaching residue of electrolytic zinc by ammonia-ammonium carbonate to produce zinc oxide, wherein zinc content in the leaching residue of electrolytic zinc is low, zinc concentration in complexing liquid is difficult to exceed 3% in practical application, so that ammonia evaporation energy consumption is too high, and environmental protection processing pressure in the process is increased due to the existence of a large amount of sulfate radicals.
Disclosure of Invention
Problems to be solved by the invention
The technical scheme provided by the disclosure solves the problems that the existing zinc raw material is in shortage, the method for preparing zinc oxide by calcium zincate is good, and the existing method for preparing zinc oxide by leaching residues by an electrolytic zincate method is high in energy consumption, large in environment-friendly treatment pressure and the like.
Means for solving the problems
In order to solve the problems in the prior art, the present disclosure provides a method for producing nano zinc oxide by leaching residue by an electrolytic zincate method, comprising the following steps:
leaching: mixing and stirring leaching residues obtained by an electrolytic zincate method 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;
and (3) desulfurization: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
calcium zincate synthesis step: adding an active agent into the first filtrate, then adding calcium hydroxide and/or calcium oxide, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
optionally, rinsing the second solid with water;
and (3) calcining: calcining the second solid at the temperature of 150-1050 ℃, preferably 150-350 ℃;
calcium and zinc separation: and mixing the calcined product obtained in the calcining step with water, stirring, filtering to obtain a third solid and a third filtrate, and drying the third solid to obtain a nano zinc oxide product with the average particle size of 10-100 nm.
In the method for producing nano zinc oxide by using the electrolytic zincate leaching residue, the mass concentration of total ammonia in the leaching agent is 5-15%, and the amount of available carbonate in the leaching agent is 100-200% of the amount of sulfate in the electrolytic zincate leaching residue.
In the method for producing nano zinc oxide by using the leached residues of the electrolytic zincate method, the concentration of zinc ammine complex ions (based on the mass of zinc element) in the leached solution obtained in the leaching step is 10-25 g/L.
In the method for producing nano zinc oxide by using the leached residues of the electrolytic zincate method provided by the further embodiments of the present disclosure, the amount of the substance of calcium oxide and/or calcium hydroxide added in the desulfurization step is 100% to 130%, preferably 100% to 110% of the amount of the substance of sulfate radical in the leached solution.
In the method for producing nano zinc oxide by using the leached residue of the electrolytic zincate method, in the calcium zincate synthesis step, the ratio of the amount of substances of calcium hydroxide and/or calcium oxide to the amount of substances of zinc ammino ions in the first filtrate is 1-1.2: 2, preferably 1-1.1: 2.
In the method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method provided by the further embodiment of the disclosure, carbon dioxide is introduced into the second filtrate obtained in the calcium zincate synthesis step, and the second filtrate introduced with the carbon dioxide is used as a leaching agent and is recycled for leaching the leaching residue of the electrolytic zincate method.
In the method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method provided by the further embodiment of the disclosure, the reaction temperature of the calcium zincate synthesis step is 15-90 ℃, preferably 15-25 ℃.
In the method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method, the stirring reaction time of the calcium zincate synthesis step is 15-30 minutes.
In the method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method, carbon dioxide is introduced into the third filtrate in the calcium-zinc separation step to obtain calcium carbonate precipitate.
In a method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method, provided by a further embodiment of the disclosure, the active agent is one or more selected from sodium hexametaphosphate and sodium dodecyl benzene sulfonate.
ADVANTAGEOUS EFFECTS OF INVENTION
The present disclosure achieves the following advantageous technical effects in one or more aspects:
1) the sulfate in the leaching slag of the electrolytic zincate method is converted into carbonate, so that the metal salt in the slag is more difficult to dissolve in water, the environmental protection problem is solved, and the secondary utilization of the leaching slag (which can be used as a raw material of cement and fired bricks) is realized.
2) The ammonia such as zinc, copper, cadmium and the like in the leaching residue of the electrolytic zincic acid method can enter the complexing solution by complexing ions, thereby solving the pollution of various heavy metals and realizing the resource utilization of the heavy metals.
3) Calcium oxide or calcium hydroxide is creatively added into an ammonium sulfate-zinc ammonia complex system to move the balance of zinc ammonia complex ions-zinc hydroxide/calcium zincate, thereby realizing the crystallization separation of zinc ions and 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 the crystallization separation of zinc ions. The process disclosed by the invention is simple and easy to implement without ammonia distillation, and the energy consumption of the process is greatly reduced.
4) Sulfate ions as a pollution source are converted into valuables by calcium sulfate.
5) The synthesis of calcium zincate is realized for the first time in the zinc ammonia environment, and the nano zinc oxide is obtained through the calcium zincate; the reaction selectivity of synthesizing calcium zincate from the zinc ammine complex ions is high, simple and rapid.
6) The process disclosed by the invention realizes leaching and separation of zinc through circulation of carbonate, and solves the environmental protection problem in the existing ammonia circulation process because the surplus water brought by steam influences the process water balance.
7) The method breaks 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 crystallization separation, creatively adds calcium oxide or calcium hydroxide into an ammonium bicarbonate-zinc ammonia complex system to shift the balance of zinc ammonia complex ions-zinc hydroxide/calcium zincate, realizes the selective crystallization separation of zinc element by a balance shift principle on the premise of not destroying the dissolved ammonia environment, and avoids the phenomenon of impurity 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 of high-temperature and high-pressure potential safety hazards caused by ammonia distillation, equipment corrosion and extra environmental protection treatment burden caused by evaporation and volatilization of a large amount of ammonia.
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.
Noun interpretation
As used herein, unless otherwise indicated, "zinc ammonium sulfate" is a generic term for compounds formed from zinc ammine complex ions and sulfate radicals, and includes [ Zn (NH)3)4]SO4Zinc tetra-ammino sulfate and Zn (NH)3)3]SO4(triamino zinc sulfate), [ Zn (NH)3)2]SO4Zinc diammine sulfate and Zn (NH)3)]SO4(zinc ammonium sulfate), 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. Replacement of sulfate with carbonate/bicarbonate
CaSO4+(NH4)2CO3＝CaCO3+(NH4)2SO4
MgSO4+(NH4)2CO3＝MgCO3+(NH4)2SO4
PbSO4+(NH4)2CO3＝PbCO3+(NH4)2SO4
Or
CaSO4+NH4HCO3＝CaCO3+(NH4)2SO4+H2O+CO2
MgSO4+NH4HCO3＝MgCO3+(NH4)2SO4+H2O+CO2
PbSO4+NH4HCO3＝PbCO3+(NH4)2SO4+H2O+CO2
b. Zinc oxide leaching
ZnO+(i-2)NH3+(NH4)2SO4＝[Zn(NH3)i]SO4+H2O (i is an integer of 2 to 4)
2. Desulfurization of
CaO+H2O＝Ca(OH)2
Ca(OH)2++(NH4)2SO4＝CaSO4↓+NH3·H2O
[Zn(NH3)i]SO4+Ca(OH)2＝[Zn(NH3)i](OH)2+CaSO4↓
3. Calcium zincate synthesis
2[Zn(NH3)i](OH)2+Ca(OH)2+2H2O＝Ca(OH)2·2Zn(OH)2·2H2O+2iNH3
(i is an integer of 1 to 4)
4. Calcination of
Ca(OH)2·2Zn(OH)2·2H2O＝Ca(OH)2+2ZnO+4H2O
Or
Ca(OH)2·2Zn(OH)2·2H2O＝CaO+2ZnO+5H2O
The concrete process steps
Step 1 extraction
Mixing the leaching residue of electrolytic zincate method with prepared leaching agent according to a certain proportion, stirring and leaching, wherein the leaching agent can 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. Leaching and filtering to obtain a leaching solution.
The concentration of total ammonia and the concentration of available carbonate in the leaching agent are not particularly limited, and the concentration can be selected by a person skilled in the art according to the factors such as the sulfate content and the zinc content in the leaching residue of the electrolytic zinc acid method of each batch and the actual requirement.
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 preferable scheme, the amount of available carbonate in the leaching agent is approximately matched with the amount of sulfate radicals in the leaching residue of the electrolytic zincic acid method, and a certain excess is allowed so as to achieve the purposes of fully converting sulfate in the leaching residue into carbonate and not excessively increasing the treatment pressure of a subsequent process. For example, the amount of available carbonate in the leaching agent is 100% to 200% of the amount of sulfate in the leaching residue of the electrolytic zinc acid method.
The weight ratio of the leaching agent to the electrolytic zincate process leaching residue is not particularly limited as long as the zinc component can be leached. Preferably, the weight ratio of the leaching agent to the leaching residue of the electrolytic zincate method is 3:1 to 5:1, so that not only can a satisfactory leaching effect be obtained, but also the waste of the leaching agent is avoided.
The leaching temperature is not particularly limited as long as the zinc component in the leaching residue of the electrolytic zincate process is leached. Preferably, the leaching is carried out at ambient temperature, for example at 15 to 30 ℃. The leaching residue of the electrolytic zincate method and the leaching agent are mixed and stirred, the stirring time is not particularly limited, and the stirring time is preferably 1 to 4 hours, more preferably 1 to 2 hours. After stirring, filtration was carried out.
In the leaching process, a plurality of metal sulfates in the leaching residue of the electrolytic zincate method are converted into more insoluble carbonates to be filtered and removed, and zinc elements are converted into zinc ammine complex ions (mainly zinc ammine complex ions at each stage) to enter the leaching solution. The leachate is sent to the subsequent desulfurization process. The concentration of the zinc ammine complex ions in the leachate is not particularly limited, but the concentration (by mass of the zinc element) of the zinc ammine complex ions in the leachate is preferably 10-25 g/L, so that the treatment efficiency of the process can be optimized, good yield and purity can be obtained in the subsequent calcium 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 desulfurization
In the desulfurization step, calcium hydroxide and/or calcium oxide is added into the leachate containing zinc ammine complex ions to convert sulfate radicals in the leachate into insoluble calcium sulfate. 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 sulfate in the form of zinc hydroxide.
In the desulfurization step, calcium hydroxide and/or calcium oxide is added in an amount approximately matching the sulfate radical content in the leachate, for example, the amount of the substance of calcium hydroxide and/or calcium oxide added in the desulfurization step is 100% to 130%, more preferably 100% to 110%, of the amount of the substance of sulfate radical in the leachate. 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 desulfurization step, calcium hydroxide and/or calcium oxide is added into the leaching solution, and the mixture is stirred for reaction to generate solid precipitate. The reaction temperature is not particularly limited, but since the reaction can be smoothly carried out without heating, it is particularly preferable to carry out the reaction at room temperature (for example, 15 to 25 ℃), which not only saves energy but also reduces environmental pollution caused by ammonia volatilization. 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 sulphate, and if the concentration of zinc ammine ions in the leach solution is high, some zinc hydroxide co-precipitated with the calcium sulphate may also be present in the first solid. The first filtrate continues to be used for the subsequent calcium zincate synthesis.
Step 4 calcium zincate Synthesis
And adding an activating agent into the first filtrate, then adding calcium hydroxide and/or calcium oxide, and stirring for reaction. The active agent is preferably sodium hexametaphosphate or sodium dodecyl benzene sulfonate, and the dosage is preferably 0.01-0.05 percent of the estimated quality of the final product. The ratio of the amount of the calcium hydroxide and/or calcium oxide to the amount of the 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 ℃, but it is particularly preferable to carry out the reaction at normal temperature (for example, 15 to 25 ℃), so that on the one hand, energy is saved, on the other hand, environmental pollution caused by ammonia volatilization is reduced, and meanwhile, the low temperature is more favorable for controlling the crystal grain size.
The stirring time is not particularly limited as long as precipitation is obtained, but in order to control the crystal particle size, it is preferable that the stirring reaction is carried out for 15 to 30 minutes and then filtration is carried out without a long-term reaction and aging process. Filtering to obtain a second solid and a second filtrate. The main component of the second solid is calcium zincate. In addition, carbon dioxide can be introduced into the second filtrate and then recycled for leaching of the leaching residue of the electrolytic zincate method.
Step 5 calcium zincate rinse
Step 5 is an optional step, and step 5 is optionally performed, if necessary. In the step 5, adding water into the second solid with calcium zincate as a main component for rinsing, wherein the liquid-solid ratio is 5-10: 1, and the rinsing times are 1-2 times.
Step 6 calcination
In this step, the second solid is calcined to decompose the calcium zincate. The calcination temperature is 150-1050 ℃, preferably 150-350 ℃. The product obtained by calcining is a mixture, and if the calcining temperature is 150-350 ℃, the main components of the calcined product are zinc oxide and calcium hydroxide; if higher calcination temperatures are used, the calcined product may contain zinc oxide, calcium hydroxide and/or calcium oxide.
Step 7 calcium Zinc separation
Since zinc oxide is difficult to dissolve in water, and calcium hydroxide (or calcium oxide) is soluble in water or soluble in water after reaction with water, the separation of zinc oxide and calcium hydroxide (or calcium oxide) can be realized by utilizing the water solubility difference of zinc oxide and calcium hydroxide (or calcium oxide).
In this step, the calcined product obtained in step 6 is mixed with water, stirred, and filtered to obtain a third solid and a third filtrate. The solute in the third filtrate is mainly calcium hydroxide, carbon dioxide can be introduced into the third filtrate to obtain calcium carbonate precipitate, and the third filtrate can also be recycled for other purposes. And drying the third solid to obtain a nano zinc oxide product. The average grain diameter of the nano zinc oxide is 10-100 nm.
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 leaching residue of the electrolytic zinc acid method of Sichuan company is 8.46 percent, and the sulfur content is 14.09 percent.
200 g of electrolytic zinc acid leaching residue is put into 1000 ml of ammonia-ammonium carbonate mixed solution (the total ammonia mass concentration is 10%, and the carbonate mass concentration is 5.5%) for stirring and leaching, the leaching temperature is normal temperature, the stirring time is 2 hours, then the filtering is carried out, the zinc content (calculated by zinc oxide equivalent) in the filtered liquid is 1.47%, and the sulfate radical mass concentration in the liquid is 8.8%. According to the inspection data, the zinc recovery rate is 86.9%.
And purifying the filtered zinc-ammonia complex solution.
500 ml of purified zinc-ammonia complex solution is taken, 25.67 g of calcium oxide is added for precipitating sulfate radicals, and filtration is carried out after reaction for 1 hour.
3 mg of sodium dodecylbenzenesulfonate and 1.8 g of calcium hydroxide were added to the filtered liquid for calcium zincate synthesis, and the mixture was stirred for 1 hour and then filtered. The solid obtained by filtering is dried for 2 hours at 105 ℃, and then calcined for 2 hours at 300 ℃, and the calcium zincate is decomposed into zinc oxide and calcium hydroxide.
Adding 300 times of water into zinc oxide and calcium hydroxide, stirring for 1 hour, filtering, drying the filtered zinc oxide at 105 deg.C for 2 hours, and inspecting and analyzing to obtain the product with zinc oxide content of 99.56% and zinc oxide average particle size of 32.7 nm.
Example 2
The zinc content of the leaching residue obtained by the electrolytic zinc acid method of a company in Yunnan is 7.98 percent, and the sulfur content is 16.01 percent.
200 g of electrolytic zinc acid leaching residue is put into 1000 ml of ammonia-ammonium carbonate mixed solution (the total ammonia mass concentration is 10 percent, and the carbonate mass concentration is 6 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 content (calculated by zinc oxide equivalent) in the filtered liquid is 1.367 percent, and the sulfate radical mass concentration in the liquid is 9.61 percent. According to the inspection data, the zinc recovery rate is 86.63%.
And purifying the filtered zinc-ammonia complex solution.
And taking 500 ml of purified zinc-ammonia complex solution, adding 28 g of calcium oxide for precipitating sulfate radicals, reacting for 1 hour, and filtering.
3 mg of sodium dodecyl benzene sulfonate and 1.6 g of calcium hydroxide are added into the filtered liquid for synthesizing calcium zincate, and the filtering is carried out after the stirring for 1 hour. The solid obtained by filtering is dried for 2 hours at 105 ℃, and then calcined for 2 hours at 300 ℃, and the calcium zincate is decomposed into zinc oxide and calcium hydroxide.
Adding 300 times of water into zinc oxide and calcium hydroxide, stirring for 1 hr, filtering, drying at 105 deg.C for 2 hr, and analyzing to obtain product with zinc oxide content of 99.62% and average particle size of 34.7 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 (14)
1. The method for producing the nano zinc oxide by using the leaching residues of the electrolytic zincic acid method is characterized by comprising the following steps of:
leaching: mixing and stirring leaching residues obtained by an electrolytic zincate method 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;
and (3) desulfurization: adding calcium oxide and/or calcium hydroxide into the leachate, stirring, and then filtering to obtain a first solid and a first filtrate;
calcium zincate synthesis step: adding an active agent into the first filtrate, then adding calcium hydroxide and/or calcium oxide, stirring for reaction, and filtering to obtain a second solid and a second filtrate;
optionally, rinsing the second solid with water;
and (3) calcining: calcining the second solid at the temperature of 150-1050 ℃;
calcium and zinc separation: and mixing the calcined product obtained in the calcining step with water, stirring, filtering to obtain a third solid and a third filtrate, and drying the third solid to obtain a nano zinc oxide product with the average particle size of 10-100 nm.
2. The method for producing nano zinc oxide by using the leaching residue of the electrolytic zinc acid method according to claim 1, wherein in the calcining step, the calcining temperature is 150-350 ℃.
3. The method for producing nano zinc oxide by using the leached residues of the electrolytic zinc acid method according to claim 1, wherein the mass concentration of total ammonia in the leaching agent is 5-15%, and the amount of available carbonate in the leaching agent is 100-200% of the amount of sulfate in the leached residues of the electrolytic zinc acid method.
4. The method for producing nano zinc oxide by using the leached residues of the electrolytic zincate method according to any one of claims 1 to 3, wherein the concentration of zinc ammine complex ions in terms of the mass of zinc element in the leached solution obtained in the leaching step is 10 to 25 g/L.
5. The method for producing nano zinc oxide by using the leached residues of the electrolytic zincate process according to any one of claims 1 to 3, characterized in that the amount of the substance of calcium oxide and/or calcium hydroxide added in the desulfurization step is 100 to 130% of the amount of the substance of sulfate radical in the leached solution.
6. The method for producing nano zinc oxide by using the leached residues of the electrolytic zincate process according to claim 5, wherein the amount of the substance of calcium oxide and/or calcium hydroxide added in the desulfurization step is 100 to 110% of the amount of the substance of sulfate radical in the leached solution.
7. The method for producing nano zinc oxide by using the leached residues of the electrolytic zincate method according to any one of claims 1 to 3, wherein in the calcium zincate synthesis step, the ratio of the amount of the substance of calcium hydroxide and/or calcium oxide to the amount of the substance of zinc ammine complex ion in the first filtrate is 1-1.2: 2.
8. The method for producing nano zinc oxide by using the leached residues of the electrolytic zincate method according to claim 7, wherein in the calcium zincate synthesis step, the ratio of the amount of the substance of calcium hydroxide and/or calcium oxide added to the first filtrate to the amount of the substance of zinc ammine complex ion in the first filtrate is 1-1.1: 2.
9. The method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method according to any one of claims 1 to 3, wherein carbon dioxide is introduced into the second filtrate obtained in the calcium zincate synthesizing step, and the second filtrate introduced with carbon dioxide is used as a leaching agent to be recycled for leaching the leaching residue of the electrolytic zincate method.
10. The method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method according to any one of claims 1 to 3, wherein the reaction temperature of the calcium zincate synthesis step is 15-90 ℃.
11. The method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method according to claim 10, wherein the reaction temperature of the calcium zincate synthesis step is 15-25 ℃.
12. The method for producing nano zinc oxide by using the leaching residue of the electrolytic zincate method according to any one of claims 1 to 3, wherein the stirring reaction time of the calcium zincate synthesis step is 15 to 30 minutes.
13. The method for producing nano zinc oxide by using the leached residues of the electrolytic zincate method according to any one of claims 1 to 3, characterized in that in the calcium-zinc separation step, carbon dioxide is introduced into the third filtrate to obtain calcium carbonate precipitate.
14. The method for producing nano calcium zincate by using the leaching residue of the electrolytic zincate method according to any one of claims 1 to 3, wherein the active agent is one or more selected from sodium hexametaphosphate and sodium dodecyl benzene sulfonate.
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