Patent Application
20160177416
The present invention relates to a method for recovering zinc from electric furnace steelmaking dust and a device for recovering zinc from electric furnace steelmaking dust.
About 30% of crude steel production in Japan is performed by remelting and smelting steel scrap using an electric furnace. Zinc on the surface of a galvanized steel sheet is conventionally volatized and reoxidized during melting of the scrap, and recovered as collected dust. The amount of dust generated in the whole of Japan is 15 kg/ton steel, that is, as much as 500 thousand to 600 thousand tons approximately per year. With the increase of plated steel sheet scrap for vehicles, the amount of dust tends to increase. The dust is generally consisted of ZnFe2O4, ZnO, and the like, which are mainly oxide of iron and/or zinc. Thus it is important how efficiently ZnO is separated from Fe2O3 to recover zinc, which are exhaustible scarce resource, and iron.
Currently, the main method employed both inside and outside Japan as electric furnace dust processing is the Waelz method (see Patent Literature 1, for example). In the Waelz method, using a rotary kiln, electric furnace dust is heated to about 1300° C. by a heavy oil burner after adding carbon materials thereto so as to reduce zinc oxide and volatize zinc as vapor once. However, the generated zinc vapor is reoxidized by CO2 in an atmosphere, and thus zinc is eventually recovered as crude zinc oxide and supplied to zinc-smelting manufactures. Meanwhile, the residue after extracting zinc is discharged to the outside of the furnace, and one part of the residue is recycled as electric furnace materials as clinker, while the major part thereof is processed as roadbed materials, cement materials, or landfilling materials. Recently, the residue has been often stored in electric furnace steel makers or Waelz kiln companies.
As described above, in the Waelz method, zinc originally in an oxide form is reduced to be a metal form once using a large amount of energy, but it is returned to the oxide form eventually. As a result, the zinc oxide in dust is simply separated and concentrated, causing a problem that the efficiency is considerably low from the viewpoint of energy effective use. Moreover, iron components recovered by the Waelz method are low-purity iron oxide, and the reuse rate of iron is also considerably low. Therefore, there has been desired a high-technique effective use employing a new idea not depending on the conventional method, such as conversion into value added iron oxide while reducing input energy.
In order to solve the above-described problem, the present inventors propose the method in which dust with calcium oxide not less than double of the molar amount of iron in the dust added thereto, is kept in air at not lower than 900° C. and not exceeding 1000° C. for not shorter than 60 hours and not exceeding 120 hours, whereby zinc ferrite ZnFe2O4 that is a zinc compound as main component in the dust is converted into zinc oxide ZnO and dicalcium ferrite 2CaO.Fe2O3, as shown in the equation (1), and the generated ZnO and 2CaO.Fe2O3 are magnetically separated from each other by a high magnetic field gradient using a difference in magnetic characteristics between both (see Patent Literature 2, for example).
[Chemical equation 1]
ZnFe2O4(s)+2CaO(s)→ZnO(s)+Ca2Fe2O5(s) (1)
Patent Literature 1: Japanese Patent Application Laid-open No. H9-268332
Patent Literature 2: Japanese Patent Application Laid-open No. 2009-30121
In the method described in Patent Literature 2, it is possible to separate zinc oxide more efficiently than the Waelz method and provide an additional value to iron oxide. However, zinc is recovered as zinc oxide, and there has been desired the development of a method for recovering metal zinc from electric furnace steelmaking dust. Moreover, the method described in Patent Literature 2 has the problem that the heating time when heating electric furnace steelmaking dust with calcium oxide added thereto is 60 hours or longer, which is excessively long.
The present invention has been made in view of such a problem, and aims at providing a method for recovering zinc from electric furnace steelmaking dust and a device for recovering zinc from electric furnace steelmaking dust, which are capable of recovering high-purity metal zinc for relatively short time.
The present inventors has achieved the present invention after conducting an experiment in which electric furnace steelmaking dust is subjected to heat treatment in a non-reducing atmosphere after adding lime thereto and finding that although the volatilization amount of iron and zinc is small regardless of whether CaO is added or not, the major part of any of halogens such as chlorine and fluorine and heavy metal which has high vapor pressure, such as lead and cadmium, is volatilized and removed, and that the concentration of halogens, lead, and cadmium after heat treatment at 1100° C., in particularly, is equal to lower than the analytical limit.
That is, a method for recovering zinc from electric furnace steelmaking dust according to the present invention includes a Ca mixing and heating step for obtaining ZnO and 2CaO.Fe2O3 by mixing electric furnace steelmaking dust with calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust and performing heat treatment in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours [see the Chemical equation (2)], a iron powder mixing step for mixing the ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating step with iron powder of a molar amount not less than the equivalent amount of the molar amount of the ZnO, and compacting the mixture, a reduction and volatilization step for obtaining a solid zinc piece by disposing a green compact by the iron powder mixing step in a decompression container, decompressing and heating the inside of the decompression container to generate zinc vapor [see the Chemical equation (3)], and cooling and coagulating the zinc vapor, and a zinc acquisition step for acquiring lumpy zinc by immersion the zinc piece obtained by the reduction and volatilization step in an NaCl—KCl based multi-component chloride flux having a melting point lower than the melting point of zinc and cooling the solution.
[Chemical equation 2]
ZnFe2O4(s)+2CaO(s)→ZnO(s)+Ca2Fe2O5(s) (2)
ZnO(s)+Fe(s)→Zn(g)+FeO(s) (3)
A device for recovering zinc from electric furnace steelmaking dust according to the present invention includes a Ca mixing and heating means configured to obtain ZnO and 2CaO.Fe2O3 by mixing electric furnace steelmaking dust with calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust and performing heat treatment in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours [see the Chemical equation (2)], an iron powder mixing means configured to mix the ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating means with iron powder of the molar amount not less than the equivalent amount of the molar amount of the ZnO, and compact the mixture, a reduction and volatilization means that includes a decompression container and is configured to obtain a solid zinc piece by disposing a green compact by the iron powder mixing means in the decompression container, decompressing and heating the inside of the decompression container to generate zinc vapor [see the Chemical equation (3)], and cooling and coagulating the zinc vapor, and a zinc acquisition means configured to acquire lumpy zinc by immersion the zinc piece obtained by the reduction and volatilization means in an NaCl—KCl based multi-component chloride flux having a melting point lower than the melting point of zinc and cooling the flux solution.
In the method for recovering zinc from electric furnace steelmaking dust and the device for recovering zinc from electric furnace steelmaking dust according to the present invention, when electric furnace steelmaking dust is mixed with calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust, and heat treatment is performed in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours, it is possible to substantially volatilize and remove halogens such as chlorine and fluorine and heavy metal which has high vapor pressure, such as lead and cadmium, contained in the electric furnace steelmaking dust while hardly volatilizing iron and zinc. Moreover, with the addition of calcium compound, ZnO and 2CaO.Fe2O3 can be obtained by the reaction of the Chemical equation (2) while preventing generation of hardly-reducible and hardly-soluble ZnFe2O4. The heat treatment time is within three hours, which is relatively short, and thus the whole processing for recovering zinc can be performed for short time. Although the method described in Patent Literature 2 can be also used as the Ca mixing and heating step, the heat treatment time becomes as long as 60 hours or longer. The calcium compound to be mixed is quick lime (CaO), lime stones (CaCO3), or slaked lime (Ca(OH)2), for example. Moreover, when calcium ferrite (2CaO.Fe2O3) is melted, an unexpected phenomenon occurs. Thus, even when the heating temperature is higher than 1100° C., it is preferably maintained equal to or lower than a melting point of calcium ferrite (about 1230° C.) so that the calcium ferrite is not melted.
The obtained ZnO and 2CaO.Fe2O3 is reduced after mixing iron powder thereto, whereby zinc vapor is obtained in accordance with the Chemical equation (3), and the zinc vapor is cooled and coagulated to obtain a metal zinc piece. The heat treatment is performed with addition of calcium compound before reduction, and thus the zinc piece in which halogens or heavy metal such as lead is free can be obtained. As the iron powder to be mixed, electrolytic iron powder or turnings (that are one type of iron scrap and cutting chips of carbon steel) can be used, for example. Moreover, the heating temperature for generating zinc vapor may be a boiling point of zinc or higher at reduced pressure.
The recovered metal zinc piece is immersed in NaCl—KCl based multi-component chloride flux for flux processing, whereby an oxide layer on the surface of the zinc piece can be removed, and lumpy and high-purity metal zinc can be recovered. Moreover, 2CaO.Fe2O3 that is the residue after reducing zinc can be recovered as it is and used as a dephosphorization agent in a steelmaking process or an iron source in a blast furnace ironmaking process.
In such a manner, the method for recovering zinc from electric furnace steelmaking dust and the device for recovering zinc from electric furnace steelmaking dust according to the present invention can efficiently separate zinc oxide in electric furnace steelmaking dust as oxide without reducing the zinc oxide, and recover metal zinc. Furthermore, the iron oxide in the electric furnace steelmaking dust can be recovered as 2CaO.Fe2O3 that becomes a dephosphorization agent in the steelmaking process or an iron source in the blast furnace ironmaking process, allowing the electric furnace steelmaking dust to be recycled almost completely. Moreover, it is also possible to considerably reduce the processing cost of the electric furnace steelmaking dust and input energy.
Furthermore, the method for recovering zinc from electric furnace steelmaking dust according to the present invention may include a Ca mixing and heating step for obtaining ZnO and 2CaO.Fe2O3 by mixing electric furnace steelmaking dust with calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust and performing heat treatment in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours, a leaching step for immersing the ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating step in an alkali or neutral aqueous solution to selectively leach the ZnO in the aqueous solution, and a electrowinning step for electrolizing the aqueous solution in which the ZnO is leached by the leaching step so that zinc is deposited on a cathode.
The device for recovering zinc from electric furnace steelmaking dust according to the present invention may include a Ca mixing and heating means configured to obtain ZnO and 2CaO.Fe2O3 by mixing electric furnace steelmaking dust with calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust and performing heat treatment in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours, a leaching means configured to immerse the ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating means in an alkali or neutral aqueous solution to selectively leach the ZnO in the aqueous solution, and an electrowinning means configured to electrolize the aqueous solution in which the ZnO is leached by the leaching means so that zinc is deposited on a cathode.
In these cases, ZnO and 2CaO.Fe2O3 obtained by heat treatment with addition of calcium compound are immersed in an alkali or neutral aqueous solution, whereby ZnO can be selectively leached in the aqueous solution while hardly immersing 2CaO.Fe2O3 in the aqueous solution. Thus, 2CaO.Fe2O3 can be recovered as residues and used as a dephosphorizing agent in the steelmaking process or an iron source in the blast furnace method. Moreover, the aqueous solution in which ZnO is leached is electrolyzed so that zinc is deposited on a cathode, whereby high-purity metal zinc can be recovered.
In the leaching step in the method for recovering zinc from electric furnace steelmaking dust according to the present invention, it is preferable that the ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating step is immersed in the aqueous solution at not lower than 70° C. and not exceeding 100° C. Moreover, it is preferable that the aqueous solution in the leaching step is a NaOH solution or a NH4Cl solution. In the device for recovering zinc from electric furnace steelmaking dust according to the present invention, it is preferable that the leaching means is configured to immerse the ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating means in the solution at not lower than 70° C. and not exceeding 100° C. Moreover, it is preferable that the aqueous solution in the leaching means is a NaOH solution or a NH4Cl solution. In these cases, all zinc can be efficiently leached into the solution.
According to the present invention, it is possible to provide a method for recovering zinc from electric furnace steelmaking dust and a device for recovering zinc from electric furnace steelmaking dust, which are capable of recovering high-purity metal zinc for relatively short time.
In the following, an embodiment of the present invention will be described with reference to the enclosed drawings.
As illustrated in
As illustrated in
The iron powder mixing means 12 includes a powder compacting device. The iron powder mixing means 12 is configured to mix ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating means 11 with iron powder of a molar amount not less than an equivalent amount of the molar amount of ZnO and compact the mixture using the powder compacting device. Note that the iron powder to be mixed is electrolytic iron powder or turnings, for example.
As illustrated in
As illustrated in
In the following, the method for recovering zinc from electric furnace steelmaking dust according to the embodiment of the present invention will be described with reference to experimental results and the like. The method for recovering zinc from electric furnace steelmaking dust according to the embodiment of the present invention is performed preferably by the device for recovering zinc from electric furnace steelmaking dust according to the embodiment of the present invention. In the method for recovering zinc from electric furnace steelmaking dust according to the embodiment of the present invention, the Ca mixing and heating means 11 first mixes electric furnace steelmaking dust and calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust, and performs heat treatment in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours.
[Heating Test when Calcium Compound is Added to Electric Furnace Steelmaking Dust]
Regarding the case in which an equivalent amount of quick lime (CaO) is added to the electric furnace steelmaking dust shown in Table 1 and the mixture is heated for three hours, the relation between the holding temperature and the volatilization volume of zinc (Zn), iron (Fe), chlorine (Cl), fluorine (F), lead (Pb), and cadmium (Cd) was investigated. The result is illustrated in
As illustrated in
Moreover, it was confirmed that when CaO is added, the volatilization and removal of halogens, lead, and cadmium does not progress unless the temperature is higher than the case where CaO is not added. However, when the dust is heated without adding CaO thereto, ZnO, which occupies 30 to 40% of zinc in the dust, reacts with Fe2O3 in the dust to be converted into hardly-reducible and hardly-soluble ZnFe2O4 by the equation (4). Thus, the addition of CaO is necessary to prevent generation of ZnFe2O4.
[Chemical equation 3]
ZnO(s)+Fe2O3(s)→ZnFe2O4(s) (4)
In order to confirm this, the X-ray diffraction patterns of the dust after heat treatment were investigated. The result is shown in
Furthermore, when the dust is heated without adding CaO thereto, the major part of ZnCl2, which generally occupies about 10% in zinc contained in the dust, is volatilized, and the loss of zinc cannot be avoided. By contrast, it is experimentally demonstrated that the volatilization loss of zinc is hardly occurred by adding CaO, and the addition of CaO is advantageous also from the viewpoint of the yield of zinc.
In this test, CaO was used as calcium compound. However, it can be easily assumed, from the Chemical equations (5) and (6) based on the dissociation temperature or dissociation vapor pressure of thermodynamics, and experimentally confirmed that the same effects can be obtained also in the case where lime stones (CaCO3) or slaked lime (Ca(OH)2) is used.
[Chemical equation 4]
CaCO3(s)→CaO(s)+CO2(g) (5)
Ca(OH)2(s)→CaO(s)+H2O(g) (6)
Based on the above-described test result, when electric furnace steelmaking dust is mixed with calcium compound containing Ca of a molar amount not less than an equivalent amount of the molar amount of Fe in the electric furnace steelmaking dust, and heat treatment is performed in a non-reducing atmosphere at not lower than 960° C. and not exceeding 1100° C. for one to three hours, it is possible to substantially volatilize and remove halogens such as chlorine and fluorine and heavy metal which has high vapor pressure, such as lead and cadmium, contained in the electric furnace steelmaking dust while hardly volatilizing iron and zinc. Moreover, with the addition of calcium compound, ZnO and 2CaO.Fe2O3 can be obtained while preventing generation of hardly-reducible and hardly-soluble ZnFe2O4. The heat treatment time is within three hours, which is relatively short, and thus the whole processing for recovering zinc can be performed for short time.
Next, the iron powder mixing means 12 mixes ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating means 11 with iron powder of a molar amount not less than an equivalent amount of the molar amount of ZnO and compacts the mixture. Such a green compact 1 is disposed in the decompression container 21, and the reduction and volatilization means 13 decompresses the inside of the decompression container 21 while heating it to 1000° C. or higher so as to generate zinc vapor 2. Then, the zinc vapor 2 is cooled and coagulated to obtain the solid metal zinc piece 3. The metal zinc piece 3 is flake-shaped or granular-shaped.
[Zinc Reduction Test after Addition of Iron Powder]
There was prepared a dust sample heated in air at 1100° C. for three hours after adding thereto CaO not less than the iron concentration in electric furnace steelmaking dust, and electrolytic iron powder was added to the dust sample so that the molar ratio of ZnO/Fe becomes 1, and mixed and compacted to be set in the sample holding container 22 of the reduction and volatilization means 13 in
The X-ray diffraction patterns of a zinc piece recovered from the surface of the low-temperature condensation pipe 24 is illustrated in
The same experiment was performed using turnings instead of electrolytic iron powder as reduction materials. Also in this case, zinc vapor can be generated in accordance with the Chemical equation (3). It was confirmed that the same result as the case of electrolytic iron powder is obtained by adding turnings of an equivalent amount of double of electrolytic iron powder in order to secure a contact area between iron and ZnO. However, it is clear that if the grain size of turnings is sufficiently small, an excessive addition amount can be less.
Based on the above-described test result, in the method for recovering metal zinc by reducing and volatilizing zinc oxide with metal iron, high-purity zinc cannot be obtained unless halogens, lead, and the like are removed preliminarily. That is, the iron reduction and volatilization method can recover metal zinc not mixed with halogens and heavy metal such as lead, in combination with the lime treatment. Note that 2CaO.Fe2O3 that is the residue after reducing zinc can be recovered as it is and used as a dephosphorizing agent in the steelmaking process or an iron source in the blast furnace ironmaking process.
The cause of deterioration of the quality of the metal zinc piece recovered by the reduction and volatilization means 13 is an oxide layer on the deposit surface, and the oxide (zinc oxide) is only and most important impurities. Thus, subsequently, in order to remove the oxide layer on the surface of the zinc piece, the zinc acquisition means 14 immerses the zinc piece obtained by the reduction and volatilization means 13 in NaCl—KCl based multi-component chloride flux having a melting point lower than the melting point of zinc. Thereafter, the flux is cooled, whereby lumpy zinc can be obtained.
[Test for Immersion Zinc Piece in Flux]
A test for immersion zinc was performed using NaCl—KCl based multi-component chloride flux having a melting point lower than the melting point of Zn. Both the zinc piece and the flux were introduced in an alumina crucible and reimmersed at 450° C. The zinc piece, which was flake-shaped and granular-shaped with an oxidized surface before immersion, became a substantially fine ingot after flux dissolution. As a result of chemical analysis, the purity of zinc was 99% or higher.
Based on the test result, the recovered metal zinc piece is immersed in NaCl—KCl based multi-component chloride flux for carrying out on the flux processing, whereby the oxide layer on the surface of the zinc piece can be removed, and lumpy and high-purity metal zinc can be recovered.
In such a manner, the method for recovering zinc from electric furnace steelmaking dust and the device for recovering zinc from electric furnace steelmaking dust according to the embodiment of the present invention can efficiently separate zinc oxide in electric furnace steelmaking dust as oxide without reducing the zinc oxide, and recover metal zinc. Furthermore, the iron oxide in the electric furnace steelmaking dust can be recovered as 2CaO.Fe2O3 that becomes a dephosphorizing agent in the steelmaking process or an iron source in the blast furnace ironmaking process, allowing the electric furnace steelmaking dust to be recycled almost completely. Moreover, it is also possible to considerably reduce the processing cost of the electric furnace steelmaking dust and input energy.
As illustrated in
In this case, in the method for recovering zinc from electric furnace steelmaking dust according to the embodiment of the present invention, the Ca mixing and heating means 11 converts zinc ferrite in the electric furnace steelmaking dust into zinc oxide that can be easily immersed both in acid and alkali. Thus, zinc in the dust can be leached entirely in the solution. Here, in order to use 2CaO.Fe2O3 that is the residue after recovering zinc as an ironmaking raw material or dephosphorizing flux, it is not preferable to dissolve 2CaO.Fe2O3 as well as zinc. For this reason, the dust is introduced not in acid solution but in an aqueous alkali NaOH solution or an aqueous neutral NH4Cl solution in which 2CaO.Fe2O3 is not immersed basically. That is, ZnO and 2CaO.Fe2O3 obtained by the Ca mixing and heating means 11 are immersed in the NaOH solution or the NH4Cl solution at not lower than 70° C. and not exceeding 100° C. to selectively leach ZnO in the solution.
[ZnO Leaching Test]
1 g of electric furnace steelmaking dust lime-treated by the Ca mixing and heating means 11 was introduced to 300 ml of alkali 2M-NaOH solution to perform a test for investigating the influence of solution concentration and the influence of a temperature on the zinc leaching rate. The temperature of the aqueous solution was set to 25° C., 40° C., 50° C., and 70° C. The result of the leaching test is illustrated in
It was confirmed experimentally that all zinc in lime-treated dust can be leached also with an NH4Cl solution instead of the aqueous NaOH solution. When the aqueous NH4Cl solution is used, zinc leaching is occurred more rapidly than the case using the aqueous NaOH solution. However, the pH of the solution is close to neutral, and thus around 10% of 2CaO.Fe2O3 is leached into the solution. Thus, the aqueous NH4Cl solution is slightly inferior to the aqueous NaOH solution from the viewpoint of the yield of 2CaO.Fe2O3.
Based on the above-described test result, ZnO and 2CaO.Fe2O3 obtained by heat treatment with addition of calcium compound are immersed in an alkali or neutral aqueous solution, whereby ZnO can be selectively leached in the aqueous solution while hardly immersion 2CaO.Fe2O3 in the aqueous solution. Thus, 2CaO.Fe2O3 can be recovered as residues and used as a dephosphorizing agent in the steelmaking process or an iron source in the blast furnace ironmaking process.
Next, the aqueous solution in which ZnO is leached by the leaching means 31 is electrolyzed by the electrowinning means 32. Thus, zinc can be deposited on the cathode, and high-quality metal zinc can be recovered.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-157305 | Jul 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/069184 | 7/18/2014 | WO | 00 |
