KR101497012B1 - METHOD FOR MANUFACTURING HIGH-PURITY ZnO NANOPOWDER AND HIGH-PURITY ZnO NANOPOWDER MANUFACTURED BY THE METHOD - Google Patents
METHOD FOR MANUFACTURING HIGH-PURITY ZnO NANOPOWDER AND HIGH-PURITY ZnO NANOPOWDER MANUFACTURED BY THE METHOD Download PDFInfo
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- KR101497012B1 KR101497012B1 KR20140059163A KR20140059163A KR101497012B1 KR 101497012 B1 KR101497012 B1 KR 101497012B1 KR 20140059163 A KR20140059163 A KR 20140059163A KR 20140059163 A KR20140059163 A KR 20140059163A KR 101497012 B1 KR101497012 B1 KR 101497012B1
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Abstract
A process for producing a high purity zinc oxide nano powder and a high purity zinc oxide nano powder produced thereby are disclosed. The method for producing high purity zinc oxide nano powder according to the present invention is a method for producing high purity zinc oxide nano powder, comprising the steps of: (a) pre-treating by-products generated in the brass scrap processing step, ; And (b) after the step (a), post-treating the sample to prepare zinc oxide powder. According to the present invention, it is possible to produce a zinc oxide nano powder having a purity of 99.5% or more and a particle size smaller than that of the prior art by calcining a by-product, for example, brass dross and dust generated in the process of recycling brass scrap, as a pretreatment process .
Description
The present invention relates to a method for producing high purity zinc oxide nano powder, and more particularly, to a method for producing a high purity zinc oxide nano powder by calcining a by-product, for example, brass dross and dust generated in the process of recycling brass scrap, Purity zinc oxide nano powder capable of producing a zinc oxide nano powder having a particle size of 100 nm.
In general, zinc oxide is widely used as a vulcanization accelerator for rubber, a reinforcing material for synthetic resin and rubber, a catalyst, a material for electric and electronic parts, a paint, a pigment, a cosmetic, and a medicine.
On the other hand, brass dross and dust are generated in the process of recycling brass scrap and are generally separated into dust generated in the melting process of brass scrap and dross generated in the ball milling process of the slag after melting, However, there are few companies that currently have economical recycling technology, so they are being buried in waste or leaking resources overseas.
Such brass dross and dust have a high quality of zinc of 60 to 90 wt%, but they are difficult to be reused as zinc oxide and zinc metal of high purity because they contain oxides, ceramics, carbides, and other foreign materials, which are raw materials of poor solubility.
The production method of zinc oxide is largely classified into a dry method and a wet method, and the dry method is classified into an indirect method and a direct method. The indirect method is a method for producing zinc oxide powder by heating zinc powder to generate zinc vapor, indirectly heating the vapor to about 1,100 to 1,400 ° C from the outside, and injecting air into the zinc oxide powder. The direct method is a method in which a reducing agent such as coke or coal is added to zinc ore or zinc slag, and the mixture is heated and reduced to vaporize zinc, and the zinc vapor is oxidized in air to obtain zinc oxide. In the case of zinc oxide produced by the direct method, impurities such as Pb, Cd and Al are contained, which makes it difficult to produce high purity zinc oxide. In the case of the indirect method, it is possible to produce high purity zinc oxide, but it has an economical problem because the cost of the zinc raw material is high.
In the case of the wet process, a zinc solution is formed by injecting a solvent such as sulfuric acid into a zinc by-product obtained in various processes, and impurities added to these solutions are precipitated through a precipitant, separated, dried and roasted to prepare zinc oxide powder . An example of zinc oxide production from zinc by-products using such a wet process is disclosed in KR1020050053490, which is a method of manufacturing zinc oxide using byproducts generated in a zinc plating process. The zinc oxide powder has a purity of 95% 0.1 to 1 mu m. In this case, a zinc powder is mainly used as a precipitant for separating impurities of zinc by-products. Removal of impurities using zinc powder is possible by the substitution reaction with Cu, Fe, Cr, Ni, Pb, Cd and Co which are relatively low ionization tendency compared to zinc. However, It is impossible to remove metal such as Al, Mg, Si, Mn, etc. through leaching, and it is impossible to produce a zinc oxide powder of high purity.
Therefore, a method for preparing zinc oxide using ammonium chloride (NH 4 Cl) has been reported for the removal of metals having a high ionization tendency. It is possible to remove Al, Mg, Ca and the like which are not dissolved in ammonium chloride by filtration. However, since hydrogen (H 2 ) is generated during the process and the leaching rate of zinc is low, It is not economical in terms of recovery rate.
Accordingly, the present applicant intends to provide a technique for producing zinc oxide nanopowder having a purity of 99.5% or more and a size of 100 nm or less in the above-mentioned brass dross and dust using a wet leaching method.
An object of the present invention is to provide a zinc oxide nanopowder having a particle size of 18 to 100 nm with a purity of 99.5% or more by calcining byproducts such as brass dross and dust generated in the process of recycling brass scrap And a method for producing the high purity zinc oxide nano powder.
The solution to the problem of the present invention is not limited to those mentioned above, and other solutions not mentioned can be clearly understood by those skilled in the art from the following description.
According to an aspect of the present invention, there is provided a method for preparing a high purity zinc oxide nano powder, comprising the steps of: (a) pretreating a by-product generated in a brass scrap process, calcination at a high temperature for a set time; And (b) after the step (a), post-treating the sample to prepare a zinc oxide powder.
Wherein the step (b) comprises: (b1) dissolving the sample after step (a) in a mixed solution; (b2) filtering the slag generated in the step (b1); (b3) adding zinc to the mixed solution through the step (b2); (b4) mixing an aqueous solution of sodium carbonate in the mixed solution after the step (b3); (b5) separating and removing the sodium sulfate by washing with water generated in the step (b4) a 4 ZnCO 3 (OH) generated via the (b4) step; And (b6) may comprise the step of generating the zinc oxide powder to burn the ZnCO 3 (OH) 4.
In the step (b4), a solution in which a dispersant is dissolved in water together with the sodium carbonate aqueous solution may be further mixed.
The dispersing agent may be selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, guar gum, and chitosan.
The mixed solution in the step (b1) may be a mixture of an acidic solution and water.
In step (a), the metal impurities having a higher ionization tendency than zinc may be converted to insoluble spinel compounds. In step (b2), the slag produced in step (b1) may be filtered to remove the insoluble spinel compound.
The step (b3) may include filtering out metal impurities having a lower ionization tendency than the zinc.
Between the step (b2) and the step (b3), a step of heating the mixed solution through the step (b2) to a set temperature may be provided.
The ZnCO 3 (OH) 4 produced in the step (b4) may be in the form of a white gel.
In the step (b6), the combustion process of the ZnCO 3 (OH) 4 may be performed at a temperature of 400 to 1,000 ° C for 1 to 3 hours.
The step (a) may be performed at a temperature of 600 to 1,000 ° C. for 1 to 4 hours.
The zinc oxide powder may have a purity of 99.5% or more and a particle size of 18 to 100 nm.
According to the present invention, zinc oxide nanopowders having a purity of 99.5% or more can be produced by calcining byproducts such as brass dross and dust generated in the process of recycling brass scraps as a pretreatment process.
In addition, zinc oxide nanopowders having a particle size of 18 to 100 nm can be prepared, and the particle size can be further reduced by adding a dispersant.
The effects of the present invention are not limited to those mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.
1 is a flow chart for manufacturing a high purity zinc oxide nano powder manufacturing method according to a first embodiment of the present invention.
FIG. 2 is a flowchart illustrating a method of manufacturing a high purity zinc oxide nano powder according to a second embodiment of the present invention.
FIG. 3 shows the XRD analysis results and the EDS analysis results of the insoluble spinel compound removed through filtration in the high purity zinc oxide nano powder manufacturing method according to the embodiment of the present invention.
4 is an XRD analysis result of ZnCO 3 (OH) 4 as an intermediate product in the method for producing high purity zinc oxide nano powder according to an embodiment of the present invention.
FIG. 5 is a result of XRD analysis of zinc oxide produced by the method for producing high purity zinc oxide nano powder according to an embodiment of the present invention.
FIG. 6 is a graph showing the results of SEM analysis of zinc oxide prepared by the method of manufacturing high purity zinc oxide nano powder according to an embodiment of the present invention, and measuring the size of the zinc oxide powder.
FIG. 7 is a SEM photograph of a zinc oxide powder according to an embodiment of the present invention to compare the sizes of the zinc oxide powder according to the amount of the dispersant added in the method of manufacturing the zinc oxide nano powder of high purity. FIG.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, It is provided to let you know. Wherein like reference numerals refer to like elements throughout.
The method of manufacturing a high purity zinc oxide nano powder according to a preferred embodiment of the present invention (hereinafter referred to as a "manufacturing method") is a method of manufacturing brass dross and dust generated in the process of recycling brass scrap, To produce a high purity zinc oxide nano powder having a size of 18 to 100 nm with a purity of 99.5% or more. In addition, the embodiment of the present invention can remove metal materials (Al, Mg, Si, Mn, Ca and the like) having higher ionization tendency than zinc by leaching, and can remarkably improve economical efficiency compared with the conventional art.
Hereinafter, the present invention will be described with reference to various embodiments.
As shown in FIG. 1, the manufacturing method according to the first embodiment of the present invention includes a step (S100) of pretreating byproducts generated in a brass scrap processing process, calcination for a set time at a high temperature, And a step (S200) of post-treating the sample (step S100) (i.e., calcined brass dross and dust) to prepare zinc oxide powder.
First, as a pretreatment step, a sample (by-product) generated in a brass scrap process is calcined at a high temperature for a set time (S100). Specifically, brass dross and dust generated in the brass scrap process are calcined at a high temperature. Through the calcination process at such a high temperature, impurities such as a metal substance (X = Al, Mg, Si, Mn, Ca) to an insoluble spinel compound. These insoluble spinel compounds can be removed through wet leaching as described below. Further, the carbon present in the sample can be removed through the calcination process, and the chemical formulas related to the calcination reaction including the above-described metal materials are as follows.
On the other hand, in the present embodiment, the zinc content of the brass dross and dust is preferably 50 wt% or more.
[Chemical Formula 1]
Al 2 O 3 + ZnO - > ZnAl 2 O 4
2MgO + SiO 2 → Mg 2 SiO 4
MnO + Al 2 O 3 → MnAl 2 O 4
3CaO + 2SiO 2 - > Ca 3 Si 2 O 7
C + O 2 - > CO 2
In this embodiment, the calcination process is preferably performed at a temperature of 600 to 1,000 ° C. for 1 to 4 hours, more preferably 700 to 800 ° C. for 2 to 3 hours.
For example, when the calcination temperature is lower than 600 ° C., the complete combustion of the carbon present in the sample does not occur, thereby lowering the purity of the zinc oxide, and the impurity removal for forming the insoluble spinel compound must be performed through the calcination process When the temperature is low, insoluble spinel compound formation becomes difficult.
In addition, when the calcination temperature exceeds 1000 캜, the coagulation phenomenon of the raw powder particles occurs. When the sample is agglomerated, the dissolution process takes a long time in the precipitation process using the acidic aqueous solution in the leaching process.
Further, even when the calcination time is increased to 4 hours or more, the same problems as in the case where the calcination temperature is higher than 1000 deg. C occur. In addition, when the calcination time is less than 1 hour, the insoluble spinel compound is not sufficiently formed through the calcination process, so that metal impurities having a high ionization tendency exist in the sample, which causes the purity of zinc oxide to be produced to be lowered.
To summarize, in this embodiment, before the wet precipitation method is applied to produce zinc oxide from a sample (brass dross and dust), a metal having a higher ionization tendency than zinc existing in the sample is converted into a compound insoluble in the leaching solution It is not dissolved upon leaching but can be precipitated and removed through a wet precipitation process described below. Therefore, in the present embodiment, zinc oxide powder having a high purity of about 99.5% or more can be manufactured in a state of excellent economy as compared with the prior art. Incidentally, the present embodiment has an economical advantage in that the hydrogen treatment cost is not added because there is no need to separately treat hydrogen in comparison with the conventional zinc oxide manufacturing method using ammonium chloride (NH 4 Cl).
Next, as a post-treatment step, a sample (brass dross and dust) that has undergone the step S100 is wet-leached to prepare zinc oxide powder (S200).
As shown in FIG. 1, the step S200 includes a step S210 of dissolving a sample subjected to the calcination step S100 in a mixed solution, a step S220 of filtering the slag generated in the step S210, and a step S220 A step S230 of heating the coarse mixed solution to a set temperature, a step S240 of adding zinc to the mixed solution obtained in the step S230, a step S250 of mixing the sodium carbonate aqueous solution into the mixed solution obtained in the step S240, separating the ZnCO 3 (OH) 4 produced through the S250 step and the resulting zinc oxide powder and the step (S260) of removing and washing the sodium sulfate produced from the S250 step, the combustion of a ZnCO 3 (OH) 4 (S270 ).
First, the calcined sample is dissolved in an acidic aqueous solution, for example, a mixed solution of one of sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ) and hydrochloric acid (HCl) and water (S210). In the step S210 may be dissolved by putting the sample in a sulfuric acid aqueous solution, and wherein by the reaction of zinc sulfate (ZnSO4), the metal compound ((Me) SO 4) is formed associated formula is as follows:
(2)
Sample + H 2 SO 4 + H 2 O → ZnSO 4 + H 2 O + (Me) SO 4 + slag (ZnAl 2 O 4 , Mg 2 SiO 4 , MnAl 2 O 4 , Ca 3 Si 2 O 7 , CO 2 Etc)
Here, Me = Cu, Fe, Cr, Ni, Pb, Cd, Co, etc.
Meanwhile, in this embodiment, an acidic aqueous solution is used in step S210 for easily wet-leaching the insoluble spinel compound in a step S220 described below. Brass dross and dust include various metal impurities except zinc, and it is preferable to use an acidic aqueous solution for selectively separating only zinc. It is also possible to remove impurities which are not dissolved in the acidic aqueous solution. Of course, there is a method of carrying out a wet precipitation process using a basic aqueous solution. However, when a basic aqueous solution is used, hydrogen is generated and problems in economical efficiency occur. Since the reaction rate of the acidic aqueous solution is relatively fast and the leaching rate is high, It is preferable to use
Next, the slag generated in step S210 is filtered (S220). That is, in step S220, the precipitated slag is filtered to remove the insoluble spinel compound (ZnAl 2 O 4 , Mg 2 SiO 4 , MnAl 2 O 4 , Ca 3 Si 2 O 7 , CO 2 Etc.). As a result, it becomes possible to produce a zinc oxide powder having a high purity of 99.5% or more in purity, as described above.
Subsequently, the mixed solution from step S220, that is, the mixed solution from which the insoluble spinel compound has been removed, is heated to a set temperature (S230). In addition, it is preferable to heat the reaction vessel containing the mixed solution described above to a set temperature through a separate heating device, and keep the heated temperature constant so that the temperature does not drop even when the step S240, which will be described later, is performed .
As described above, by heating the mixed solution, a metal (for example, Cu, Fe, Cr, Ni) that is relatively low in ionization tendency as compared with zinc (powder or bar state) , Pb, Cd, Co) can be increased.
In this embodiment, such a heating temperature is preferably approximately 40 to 50 占 폚.
For example, when the mixed solution is heated to less than 40 ° C in step S230, the effect of increasing the rate of substitution reaction between metals having a relatively low ionization tendency is less than that of zinc and zinc. On the other hand, , And evaporation of the mixed solution due to heating occurs.
In addition, in the case of an acidic aqueous solution, the base material is water (H 2 O). When this acidic aqueous solution is heated, the base water is evaporated at 100 ° C. Thus, when the water serving as the base of the aqueous solution is evaporated, the solubility of the entire aqueous solution is reduced.
Next, in step S230, zinc is added to the mixed solution heated or heated to the set temperature (S240). At this time, zinc can be applied in various forms such as powder, rod, and bar.
The chemical formula related to step S240 is as follows. Through the reaction shown below, a metal having a lower ionization tendency than zinc is precipitated to the bottom through a substitution reaction with zinc. On the other hand, precipitated metal impurities, that is, metal impurities having a lower ionization tendency than zinc can be separated and removed through a filter paper or the like.
(3)
ZnSO 4 + H 2 O + (Me) SO 4 + Zn -> ZnSO 4 + Me + H 2 O
Here, Me = Cu, Fe, Cr, Ni, Pb, Cd, Co, etc.
Next, the aqueous solution of sodium carbonate is mixed with the mixed solution through step S240 (S250). In step S240, a mixed solution in which metal impurities having a lower ionization tendency than zinc is removed is mixed with an aqueous solution of sodium carbonate (Na 2 CO 3 ). At this time, white gelcoat ZnCO 3 (OH) 4 is formed through the following chemical reaction.
[Chemical Formula 4]
ZnSO 4 + Na 2 CO 3 → ZnCO 3 (OH) 4 + Na 2 SO 4
Next, remove the ZnCO 3 (OH) 4 produced through the steps S250 and similarly washed with water to remove the sodium sulfate (Na 2 SO 4) generated in step S250 (S260).
Specifically, in step S260, ZnCO 3 (OH) 4 in the form of a white gel was separated from the solution by using a specific gravity difference, washed with water several times, and then washed with sodium sulfate (Na 2 SO 4 ) . The separated ZnCO 3 (OH) 4 is preferably dried for the set time for subsequent work.
Next, ZnCO 3 (OH) 4 separated in step S 260 is burned to produce zinc oxide powder (S 270).
Specifically, high purity zinc oxide powder is prepared by pulverizing ZnCO 3 (OH) 4 in the form of a white gel over a certain amount of time and then heating it for a certain period of time. The formula for this is as follows.
[Chemical Formula 5]
2ZnCO 3 (OH) 4 + O 2 → 2ZnO +
In addition, in step S270, ZnCO 3 (OH) 4 is heated to a predetermined temperature or higher to burn ZnCO 3 (OH) 4 , thereby decomposing ZnO, CO 2 and H 2 O into zinc oxide. The heating temperature range is preferably 400 to 1,000 占 폚, and most preferably 450 to 600 占 폚.
For example, when the heating temperature is lower than 400 ° C., there arises a problem that undissolved ZnCO 3 (OH) 4 is present, and when the heating temperature exceeds 1,000 ° C., the particle size of the produced zinc oxide powder is increased Lt; / RTI >
The heating time is suitably from 1 to 3 hours. When the heating time is less than 1 hour, undissolved ZnCO 3 (OH) 4 is present. On the other hand, when the heating time exceeds 3 hours, the particle size of the zinc oxide powder increases.
Next, as another embodiment, the manufacturing method according to the second embodiment of the present invention is a method for manufacturing a zinc oxide nano powder having a smaller particle size than the zinc oxide powder produced by the manufacturing method according to the first embodiment will be.
The manufacturing method according to the second embodiment of the present invention includes steps S100, S210, S220, S230, and S240 of the first embodiment in the same manner as the first embodiment.
2, in the second embodiment of the present invention, a solution obtained by dissolving an aqueous solution of sodium carbonate and a dispersant in the mixed solution obtained in step S240 is further mixed (S250) The same goes.
Preferably, the dispersant is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, guar gum, and chitosan.
On the other hand, when the dispersant is not added, the zinc oxide nano powder produced through the combustion of ZnCO 3 (OH) 4 is recovered as a zinc oxide powder having a larger particle size by the binding of powder as time progresses in step S270 There is a disadvantage in that
However, when the dispersing agent is further added as in the second embodiment of the present invention, the dispersing agent acts as a coating agent on the zinc oxide nano powder produced in step S270, thereby preventing the increase of the powder size due to the bonding between the powders .
In the present embodiment, the addition amount of the dispersing agent is suitably in the range of 1 to 10 g (0.1 to 1 wt%) of the dispersing agent in 1 L of water, and the optimum condition is a range of 1 to 5 g (0.1 to 0.5 wt% .
For example, when the amount of the dispersant is less than 0.1 wt% with respect to water, the particle size of the zinc oxide powder may increase during the combustion process because the dispersant does not appear, wt.%, the particle size of the zinc oxide nano powder does not become smaller, so that there is an economic disadvantage due to addition of the dispersant content. That is, the dispersant prevents the aggregation of the zinc oxide nanoparticles during the combustion process, thereby preventing the increase of the particle size of the zinc oxide powder.
In summary, the method for producing a high purity zinc oxide nano powder according to an embodiment of the present invention includes the steps of removing impurities (Al, Mg, Si, Mn, Ca) having a higher ionization tendency than zinc, Wet precipitation method. Then, the brass dross and dust are calcined at a temperature of about 600 to 1,000 DEG C for 1 to 4 hours before the wet precipitation step to produce a zinc oxide having a higher ionization tendency than zinc existing in the sample (brass dross and dust) Converts the metal to a compound that is insoluble in the leach solution. It is also possible to produce a high purity zinc oxide nano powder having a purity of 99.5% or more and having a particle size of 30 to 100 nm through the removal of the zinc oxide powder by dissolving in the wet leaching, The size can be controlled to about 18 nm.
Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples.
Example 1: The sample subjected to the calcination process is wet-leached to prepare zinc oxide nano powder
The brass scrap processing company collected the brass dross and dust and conducted the experiment. The composition of the collected brass dross and dust was analyzed by ICP-AES and automatic element analyzer.
Table 1 below shows the results of carbon analysis by ICP analysis and automatic element analysis of brass dross and dust. The brass dross contains 56.75wt% of zinc and the impurities are 13.13wt% of copper, 5.7wt% of aluminum, 4.43wt% of silicon, Impurities of Pb, Fe, Sn, Ni, Sb, Mn, Ca, P and F were confirmed. Brass dust contains 72.9wt% of zinc (Zn), and the impurities are 4.49wt% aluminum, 2.13wt% silicon and other Cu, Pb, Fe, Sn, Ni, Sb, Mn , And impurities of F were confirmed.
Prior to the wet precipitation process (experiment) described above, 200 g of brass dross and dust were calcined at 700 ° C. for 2 hours to remove metal impurities with a higher ionization tendency than zinc. Through the calcination process, metal impurities with higher ionization tendency than zinc were formed into insoluble spinel compounds. The carbon in the sample was also removed through the calcination process.
The sample calcined at high temperature was added to a mixed solution of 200 g of 98% sulfuric acid (H 2 SO 4 ) and 500 ml of water (H 2 O) to dissolve and form zinc sulfate (ZnSO 4 ), and the slag was filtered to remove insoluble spinel compound .
After the mixed solution from which the insoluble spinel compound had been removed was heated to 50 캜, a zinc rod having a diameter of 10 to 15 cm was immersed for 30 minutes. Accordingly, a metal having a lower ionization tendency than zinc is precipitated through a substitution reaction with zinc.
The precipitated metal impurities were separated and removed through a filter paper. The mixed solution from which impurities were removed was mixed with 1 L of water and 150 g of sodium carbonate (Na 2 CO 3 ) to form a white gel-like ZnCO 3 (OH) 4 .
ZnCO 3 (OH) 4 was separated from the mixed solution using a specific gravity difference. After washing with water several times, sodium sulfate (Na 2 SO 4 ) was separated and removed using a filter paper. The separated gel form of ZnCO 3 (OH) 4 was then dried at 100 ° C for one day.
Thereafter, the dried ZnCO 3 (OH) 4 was pulverized using a mortar and heated at 500 ° C. for 3 hours to prepare zinc oxide powder.
Example 2: Calcined zinc nanoparticles were prepared by wet-leaching the calcined sample, and in order to reduce the particle size in the intermediate process Dispersant Additional input
A dispersing agent was added for particle refinement of the zinc oxide nano powder. Poly Vinyl Pyrrolidone was used as the dispersing agent and zinc sulfate (ZnSO 4 ) with metal impurities removed in the zinc oxide manufacturing process was added to the dispersant.
Sodium carbonate in
The dried samples were subjected to a combustion process at 500 ° C for 2 hours to prepare zinc oxide nanopowder.
Comparative Example : Manufacture of zinc oxide nanopowder by wet leaching of sample not subjected to calcination process
The rest of the process was carried out in the same manner as in Example 1 except that the sample was not calcined.
Insoluble Spinel Confirm removal of the compound
Figure 3 shows the results of XRD analysis and EDS analysis of the insoluble spinel compound removed through filtration. As shown in FIG. 3 (a), the major component of the impurities removed through filtration was zinc spinel (ZnAl 2 O 4 ), and a trace amount of Al-Si compound was also confirmed as shown in FIG. 3 (b).
In other words, it can be confirmed from the XRD analysis that ZnAl 2 O 4 is formed through the reaction of Al 2 O 3 and ZnO. As a result of EDS analysis, it was confirmed that a trace amount of Si was removed by the present calcination process in addition to Al 2 O 3 .
ZnCO 3 ( OH ) 4 Confirmation of the formation of
Figure 4 is a ZnCO 3 intermediates (OH) and XRD analysis results of the four, XRD analysis results are ZnSO 4 and Na 2 ZnCO 3 than the CO 3 by a reaction generally known ZnCO 3 of (OH) 4 to determine the formed there was.
ZnO Confirm the creation of
5 shows the XRD analysis results of the zinc oxide thus produced. 5, it can be confirmed that the final product is ZnO, and impurities other than zinc oxide can not be confirmed.
Identify particle size of zinc oxide nano powder
FIG. 6 shows the result of measuring the size of zinc oxide powder through SEM analysis. FIG. 6 shows that zinc oxide nanopowders having a size of 100 nm or less were produced.
Wet leaching method including calcination process ( Example One, Example 2) and purity of the zinc oxide nano powder prepared by the wet leaching method Comparative Example Comparison of purity of zinc oxide nano powder prepared by using
Table 2 compares the ICP-AES analysis results of the zinc oxide powder with the zinc oxide results prepared in Examples 1 and 2 and the conventional process (wet precipitation process in which the calcination process is omitted). In case of zinc oxide without calcination process, the purity was 95.4%, but when metal impurities with high ionization tendency were removed by calcination process, the purity was 99.8%.
[Table 2] ICP-AES analysis of zinc oxide powder
Dispersant Characterization through addition
FIG. 7 is a SEM photograph showing the size of the zinc oxide powder according to the addition amount of the dispersant. 7 (b) shows the result when 1.6 g of the dispersant is added. Fig. 7 (c) shows the result when the dispersant is added. Fig. 7 FIG. 7 (d) shows the result of measuring the zinc oxide powder size when 4.8 g of the dispersant was added, and FIG. 7 (e) shows the zinc oxide powder size when the dispersant 6.4 g was added. to be.
As can be seen from FIG. 7, specifically, FIG. 7 (e), it can be seen that as the amount of the dispersing agent increases, the zinc oxide powder size decreased from about 40 nm to about 17.9 nm.
Although the present invention has been described with reference to the accompanying drawings and the preferred embodiments described above, the present invention is not limited thereto but is limited by the following claims. Accordingly, those skilled in the art will appreciate that various modifications and changes may be made thereto without departing from the spirit of the following claims.
S100: calcination step S200: zinc oxide nanopowder manufacturing step
Claims (13)
(a) calcining a brass dross and brass dust; And
(b) preparing a zinc oxide powder from the sample after the step (a)
The step (b)
(b1) dissolving the sample after step (a) in a mixed solution;
(b2) filtering the slag generated in the step (b1);
(b3) adding zinc to the mixed solution through the step (b2);
(b4) mixing an aqueous solution of sodium carbonate in the mixed solution after the step (b3);
(b5) separating and removing the sodium sulfate by washing with water generated in the step (b4) a 4 ZnCO 3 (OH) generated via the (b4) step; And
(b6) the ZnCO 3 (OH) method for producing high-purity nano zinc oxide powder comprising the step of generating a zinc oxide powder by burning a 4.
Wherein a solution in which a dispersing agent is dissolved in water together with the sodium carbonate aqueous solution is further mixed in the step (b4).
Wherein the dispersant is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, guar gum, and chitosan. The method of claim 1, wherein the dispersing agent is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, guar gum and chitosan.
Wherein the mixed solution in the step (b1) is a mixture of an acidic solution and water.
In the step (a), a metal impurity having a higher ionization tendency than zinc is converted into an insoluble spinel compound,
Wherein the insoluble spinel compound is removed by filtering the slag generated in the step (b1) in the step (b2).
Wherein the step (b3) comprises filtering and removing metal impurities having a lower ionization tendency than the zinc.
Wherein the step of heating the mixed solution through the step (b2) to a set temperature is provided between the step (b2) and the step (b3).
Wherein the ZnCO 3 (OH) 4 produced in step (b4) is in the form of a white gel.
Wherein the burning process of the ZnCO 3 (OH) 4 is performed at a temperature of 400 to 1,000 ° C. for 1 to 3 hours in the step (b6).
Wherein the step (a) is performed at a temperature of 600 to 1,000 ° C. for 1 to 4 hours.
Wherein the zinc oxide powder has a purity of 99.5% or more and a particle size of 18 to 100 nm.
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| CN108996541A (en) * | 2018-08-08 | 2018-12-14 | 沈海红 | A kind of preparation method of nano zine oxide and nano-zinc oxide composite material and preparation method thereof |
| KR20200044485A (en) * | 2018-10-19 | 2020-04-29 | 한일화학공업주식회사 | Method for manufacturing high-purity nano zinc oxide powder and surface-coated high-purity nano zinc oxide powder |
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| KR20030046950A (en) * | 2001-12-07 | 2003-06-18 | 박성 | A method for preparaing ZnO nanopowder |
| KR100625521B1 (en) * | 2005-06-21 | 2006-09-20 | 심재윤 | Production of ultra fine zinc oxide particle from zinc ash and the products thereby |
| KR101128880B1 (en) * | 2011-06-23 | 2012-03-26 | 홍상휘 | Method for manufacturing highgrade zinc oxide |
| JP2013256443A (en) * | 2003-09-30 | 2013-12-26 | Jx Nippon Mining & Metals Corp | High purity zinc oxide powder, method for producing the same, and high purity zinc oxide target and high purity zinc oxide thin film |
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| KR20030046950A (en) * | 2001-12-07 | 2003-06-18 | 박성 | A method for preparaing ZnO nanopowder |
| JP2013256443A (en) * | 2003-09-30 | 2013-12-26 | Jx Nippon Mining & Metals Corp | High purity zinc oxide powder, method for producing the same, and high purity zinc oxide target and high purity zinc oxide thin film |
| KR100625521B1 (en) * | 2005-06-21 | 2006-09-20 | 심재윤 | Production of ultra fine zinc oxide particle from zinc ash and the products thereby |
| KR101128880B1 (en) * | 2011-06-23 | 2012-03-26 | 홍상휘 | Method for manufacturing highgrade zinc oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108996541A (en) * | 2018-08-08 | 2018-12-14 | 沈海红 | A kind of preparation method of nano zine oxide and nano-zinc oxide composite material and preparation method thereof |
| CN108996541B (en) * | 2018-08-08 | 2020-09-01 | 沈海红 | Preparation method of nano zinc oxide, nano zinc oxide composite material and preparation method thereof |
| KR20200044485A (en) * | 2018-10-19 | 2020-04-29 | 한일화학공업주식회사 | Method for manufacturing high-purity nano zinc oxide powder and surface-coated high-purity nano zinc oxide powder |
| KR102134260B1 (en) | 2018-10-19 | 2020-07-15 | 한일화학공업주식회사 | Method for manufacturing high-purity nano zinc oxide powder and surface-coated high-purity nano zinc oxide powder |
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