A method for preparing zinc ferrite material using copper slag and electric furnace dust

Abstract

The application discloses a method for preparing zinc ferrite material by using copper slag and electric furnace dust, wherein the copper slag and the electric furnace dust are mixed to obtain a mixture, the mixture is pressed to obtain a green body, then the green body is subjected to microwave roasting to obtain a roasted body, the roasted body is ground to obtain a ground material, the ground material is immersed in a mixed acid solution to obtain a crude zinc ferrite material product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product, wherein the temperature of the microwave roasting is 500-1000 DEG C, and the time of the microwave roasting is less than or equal to 120 min. The zinc ferrite material with a purity of 99.9% can be obtained under low-temperature and short-time conditions, and the method has the advantages of low production cost, simple process, high product added value, high resource utilization rate, environmental friendliness and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of resource recycling, and particularly relates to a method for preparing zinc ferrite material by using copper slag and electric furnace dust. BACKGROUND

[0002] As the main by-product of electric furnace steelmaking, electric furnace dust contains high zinc and iron resources, and is an important secondary resource. The annual emission of electric furnace dust is about 8 million tons, and is expected to increase to 18 million tons in 2050. Electric furnace dust contains high heavy metal elements (Pb, Cr and Cd) and has extremely fine particle size, which has great potential harm to the environment and human body, and needs harmless treatment. At present, the main treatment trend of electric furnace dust is to recover valuable metals such as Zn and Fe by using pyrometallurgical solid-state reduction process or wet leaching process. However, a large proportion of zinc and iron resources in the dust raw material exist in the form of extremely stable ferrite, which is difficult to reduce and dissolve. Therefore, the recovery rate of zinc and iron from electric furnace dust is low, the recovery cost is high, and the environmental pollution is serious.

[0003] Copper slag is a typical solid waste discharged in the process of copper smelting, which contains high iron, copper, zinc, cobalt, nickel and other important metal elements. About 2-3 tons of copper slag will be discharged for every ton of copper produced, and the global annual emission is close to 70 million tons. Copper slag also contains heavy metals such as Pb and Cd, so it is both an important secondary resource and a hazardous waste. For different chemical compositions, the treatment process of copper slag is slightly different. For copper slag with high copper content, chemical leaching such as H2SO4, H2O2 and (NH4)2SO4 is used to realize the co-extraction of copper, nickel, cobalt, zinc and iron, and the recovery rates can reach 75-93%, 80-95%, 90-98%, 90-97% and 5-37% respectively. For copper in the form of metal or sulfide, flotation process is mainly used for recovery, and the copper recovery rate is generally 67.0%-87.6%. For copper slag with low copper content and high iron content, pyrometallurgical reduction technology is the preferred technology. Generally, 88.1-95.1% of metallic iron is obtained at 1200-1600℃. In general, the treatment of copper slag has problems such as low recovery rate, high recovery cost and serious environmental pollution.

[0004] Zinc ferrite material has excellent catalytic activity, adsorption performance, soft magnetic properties and corrosion and rust resistance, and is widely used in the fields of catalysts, wave-absorbing materials, soft magnetic materials and the like. However, the existing technology has high synthesis temperature of zinc ferrite, long processing time and low product quality. Microwave technology, as an emerging technology, is widely used in the field of metallurgy, has the advantages of low cost, high product quality and cleanliness, and is a potential technology. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application aims to provide a method for preparing zinc ferrite material from copper residue and electric furnace dust, which has simple process, high resource utilization, low production cost, high product added value and environmental friendliness.

[0006] To achieve the above-mentioned object, the technical scheme adopted by the present application is:

[0007] The present application is a method for preparing zinc ferrite material from copper residue and electric furnace dust, which comprises the following steps: mixing copper residue and electric furnace dust to obtain a mixture, pressing the mixture to form a green body, then microwave roasting the green body to obtain a roasted body, grinding the roasted body to obtain a ground material, and immersing the ground material in a mixed acid solution to obtain the zinc ferrite material; the temperature of the microwave roasting is 500-1000 DEG C, and the time of the microwave roasting is less than or equal to 120 min.

[0008] The method of the present application is the first to use copper residue and electric furnace dust as two kinds of solid waste raw materials to obtain a coarse zinc ferrite product under the condition of microwave roasting, and then to obtain the zinc ferrite material by removing impurities through dilute acid leaching, which realizes the transformation of the toxic waste copper residue and electric furnace dust into high added value spinel zinc ferrite.

[0009] The zinc in the electric furnace dust mainly exists in the form of oxide, silicate and spinel, and the iron in the copper residue mainly exists in the form of oxide; the zinc oxide and zinc silicate can react with various iron oxides to form zinc ferrite spinel under air atmosphere; however, due to the high synthesis temperature of zinc ferrite, long time and high temperature roasting in conventional roasting will cause serious size coarsening of the zinc ferrite product, volatilization of zinc oxide, simultaneous formation of Ca2ZnSi2O7 and other silicate impurities, and serious doping of Ca, Si and other impurity ions in the zinc ferrite, resulting in the decrease of the purity and synthesis rate of the zinc ferrite.

[0010] The inventors have found that the electric furnace dust and copper residue have excellent wave-absorbing performance, and the target product zinc ferrite spinel also has strong wave-absorbing performance; therefore, the inventors utilize the advantages of selective heating and rapid heating of microwave to intensify the solid phase reaction between the copper residue and the electric furnace dust, rapidly form a high-quality coarse zinc ferrite product under low temperature conditions; of course, the conditions of microwave roasting need to be effectively controlled, and only when the conditions are controlled within the present application can high crystallinity and high-quality zinc ferrite material be obtained; if the microwave roasting temperature is too low and the roasting time is too short, the reaction effect of the copper residue and the electric furnace dust will be poor, the reaction of zinc oxide and zinc silicate with iron oxide will be insufficient, the crystallinity of the zinc ferrite will be poor, and the yield will be low; if the microwave roasting temperature is too high and the roasting time is too long, not only will the size of the zinc ferrite product be seriously coarsened, but also the volatilization of zinc oxide will be caused, the reaction of Ca2ZnSi2O7 and other silicate impurities will be promoted, and the doping of Ca, Si and other ions in the zinc ferrite will be promoted, resulting in the decrease of the purity and synthesis rate of the zinc ferrite.

[0011] Preferably, the mass ratio of copper residue to electric furnace dust is 0.30-0.60:1, preferably 0.4-0.6.

[0012] The inventors found that when the mass ratio of copper residue to electric furnace dust is controlled within the above range, the final conversion rate is the highest, which is most conducive to subsequent impurity removal. If the proportion of copper residue is too high, iron oxides will remain, increasing the burden of subsequent impurity removal, causing waste of production cost and reagent. If the proportion of copper residue is too low, the zinc component in the electric furnace dust cannot be completely converted into zinc ferrite, causing waste of zinc resources.

[0013] Preferably, the pressure of the press forming is 20-100 MPa, preferably 40-100, and further preferably 60-80 MPa.

[0014] The inventors found that when the pressure of the press forming is controlled within this range, the effect of roasting is optimal. If the forming pressure is too low, it is not conducive to the occurrence of solid-phase reactions between materials. If the forming pressure is too high, the green body is too tight, and local discharge occurs during microwave roasting, resulting in uneven roasting of the sample.

[0015] Preferably, the temperature of the microwave roasting is 600-900℃, and the time of the microwave roasting is 30-90 min.

[0016] Further preferably, the temperature of the microwave roasting is 700-800℃, and the time of the microwave roasting is 30-60 min.

[0017] Preferably, the power of the microwave roasting is 300-900W, preferably 500-800W, and further preferably 500-700W.

[0018] The inventors found that the microwave roasting power also has a certain influence on the effect of roasting. Too high microwave roasting power will cause the heating rate to be too fast, and the zinc component will volatilize. Too low microwave roasting power cannot provide sufficient roasting temperature.

[0019] Preferably, the mixed acid solution contains HCl, H2SO4, and CH3COOH.

[0020] In the present application, the mixed acid solution containing HCl solution, H2SO4 solution and CH3COOH solution is used for leaching the ground powder obtained after roasting. This is mainly because the powder is obtained by sintering copper slag and electric furnace dust solid waste, so the composition is complex and there are many impurity elements. Different acids have different leaching effects on different elements. HCl and H2SO4 have high leaching rates on Ca, Si, Al, Mg, Na, K and other impurity ions. Among them, HCl and H2SO4 have good effects on the leaching of Si, Na, K, Mg and Al. H2SO4 has high leaching rate on Zn and Fe elements, and HCl has good leaching effect on Ca. However, HCl and H2SO4 have too high leaching on heavy metals Cr and Pb, which does not meet the wastewater discharge standard (Pb < 0.2 mg / L, Cr < 0.5 mg / L), and CH3COOH can inhibit the excessive leaching of Cr and Pb although it has lower leaching effect on impurity ions than HCl and H2SO4. Therefore, using HCl-H2SO4-CH3COOH mixed acid solution as leaching agent can achieve selective leaching, which is more conducive to improving the yield and quality of zinc ferrite product, and can minimize the amount of acid and wastewater discharge.

[0021] Preferably, the mixed acid solution is obtained by mixing HCl solution, H2SO4 solution and CH3COOH solution in a volume ratio of 0.1-0.5:0.1-0.4:0.1-0.8, wherein the concentration of HCl solution is 0.1-0.5 mol / L, the concentration of H2SO4 solution is 0.1-0.5 mol / L, and the concentration of CH3COOH solution is 0.1-0.5 mol / L.

[0022] The inventors found that the amount of HCl, H2SO4 and CH3COOH is crucial. If the ratio is not appropriate, it will not only affect the removal effect of Ca, Si, Al, Mg, Na, K and other impurities, but also cause problems such as Cr and Pb emission exceeding the standard, ZnFe2O4 dissolution, and a large amount of waste liquid.

[0023] Further preferably, the mixed acid solution is obtained by mixing HCl solution, H2SO4 solution and CH3COOH solution in a volume ratio of 0.4-0.5:0.3-0.4:0.1-0.4, wherein the concentration of HCl solution is 0.3-0.5 mol / L, the concentration of H2SO4 solution is 0.3-0.5 mol / L, and the concentration of CH3COOH solution is 0.4-0.5 mol / L.

[0024] Preferably, the liquid-solid volume-mass ratio of the mixed acid solution to the ground powder is 4-10 mL:1 g, preferably 5-7 mL:1 g. Controlling the ratio of mixed acid solution to ground powder within the above range can achieve the best effect of leaching and impurity removal.

[0025] Preferably, the temperature of the leaching is 40-90 DEG C, and the time of the leaching is 30-180 min.

[0026] Further preferably, the temperature of the leaching is 40-60 DEG C, and the time of the leaching is 60-90 min.

[0027] Preferably, the leaching is carried out with the aid of stirring, and the speed of the stirring is 200-400 r / min, preferably 250-350 r / min. The leaching effect can be improved by the stirring.

[0028] Preferably, the zinc ferrite material is nano-sand ground to obtain a nano-sized zinc ferrite material.

[0029] Principle and advantage

[0030] In the prior art, the pyrometallurgical reduction process and the hydrometallurgical process for recovering valuable metals from copper slag and electric furnace dust cannot avoid the need to destroy the stable ferrite spinel structure (such as ZnFe2O4, MnFe2O4, FeCr2O4, Fe3O4, etc.), and require extremely high production costs and harsh production conditions, such as high reduction temperature, long reduction time, high concentration and dosage of leaching agent, etc., and are accompanied by problems such as three-waste discharge and environmental pollution. By converting the main components in copper slag and electric furnace dust into multifunctional zinc ferrite material under low temperature and short time conditions, significant economic benefits and application prospects are achieved.

[0031] In the present application, the iron oxides in the copper slag and the zinc and iron components in the electric furnace dust have excellent microwave absorption performance, and the microwave technology is used to promote the reaction of the two to synthesize ferrite material with strong wave absorption performance. Not only does this greatly reduce the formation conditions of ferrite and improve the product quality, but also the strong wave absorption performance of ferrite is used to feed back to microwave heating, promoting the low-temperature and short-time formation and growth of ferrite. On the one hand, it can simultaneously recover iron and zinc resources in copper slag and electric furnace dust, avoid resource waste and environmental pollution caused by the destruction of spinel structure in traditional processes, and realize the resource utilization of the two solid wastes. On the other hand, the microwave technology reduces the reaction temperature and time, compresses the production cost, and improves the product quality. The present application not only realizes the simultaneous recovery of valuable metals in copper slag and electric furnace dust, but also obtains zinc ferrite material with excellent performance, realizes the low-cost green transformation of toxic waste copper slag and electric furnace dust into high-value and high-function ferrite material.

[0032] In the present application, the application of microwave roasting technology is one of the key points. On the one hand, the zinc-containing and iron-containing components in the copper slag and the electric furnace dust raw materials have good microwave absorption performance. Therefore, the microwave roasting process can selectively heat and react the zinc-containing components and the iron-containing components. The impurity phases with low microwave absorption performance, such as silicate and feldspar components, have low microwave reaction degree, thereby promoting the formation of the target product ferrite and inhibiting the formation of impurity phases, and realizing the phase directional regulation of the copper slag and the electric furnace dust. On the other hand, the target product ferrite itself is a typical microwave absorber. The strong microwave absorption performance of the ferrite itself ensures the low-temperature rapid crystallization and growth of the ferrite, reduces the production cost of the ferrite, and improves the quality of the ferrite product. Compared with conventional roasting, the microwave roasting temperature is reduced by 400 DEG C, and the roasting time is shortened to 1 / 4.

[0033] In the present application, the microwave roasting conditions are another important factor affecting the synthesis of zinc ferrite. If the microwave roasting temperature is too low and the roasting time is too short, the reaction effect of the copper slag and the dust will be poor, the zinc-containing components and the iron-containing components will not react sufficiently, the zinc ferrite crystallization will be poor, and the yield will be low. If the microwave roasting temperature is too high and the roasting time is too long, not only will the size of the zinc ferrite product be severely coarsened, but also the formation of silicate impurity phases will be caused, and the doping of Ca, Si and other ions in the zinc ferrite will be promoted, resulting in a decrease in the purity and synthesis rate of the zinc ferrite. Too high microwave roasting power will cause the volatilization of the zinc-containing components due to too fast heating rate, and too low microwave roasting power cannot provide sufficient roasting temperature. By adjusting the appropriate microwave roasting conditions, not only high-quality zinc ferrite products can be synthesized, but also the production cost can be significantly reduced.

[0034] Another key point of the present application is the combined use of leaching agents. When leaching the roasting product, the inventors selected HCl, H2SiO4, HNO3, CH3COOH and H3PO4 as five kinds of acidic leaching agents for separate tests. After many tests, it was found that the five kinds of acids can effectively remove most of the impurities in the roasting product. However, different leaching agents have different removal efficiencies for different impurity elements and heavy metals Cr and Pb, which not only affects the purity of the zinc ferrite product, but also has a great influence on wastewater discharge. After many tests, the inventors used HCl-H2SO4-CH3COOH mixed acid solution as the leaching agent, and realized selective leaching by adjusting the concentrations and proportions of the three, which is beneficial to improve the yield and quality of the zinc ferrite product, and can greatly reduce the amount of acid used and meet the wastewater discharge standard.

[0035] The present application has the characteristics of simple process, low production cost and environmental friendliness. The zinc ferrite material prepared from copper slag and electric furnace dust has excellent gas sensing properties, wave absorption performance, catalytic activity and soft magnetic properties, and has good application prospect. DETAILED DESCRIPTION

[0036] The application will be further described below in connection with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the application, and not all the embodiments. Based on the embodiments of the application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the protection scope of the application.

[0037] The chemical compositions of the copper residue and the electric furnace dust raw material involved in the specific embodiments are shown in Tables 1 and 2 respectively.

[0038] Chemical composition of copper residue (wt%)

[0039]

[0040] Chemical composition of electric furnace dust (wt%)

[0041]

[0042] Comparative Example 1

[0043] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to form a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, the obtained ground material is put into an HCl solution for leaching to obtain a crude product of zinc ferrite material, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0044] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.30;

[0045] The pressing pressure for the pressing forming is 10 MPa;

[0046] The microwave calcination temperature is 400℃, the microwave calcination time is 0 min, and the microwave calcination power is 300 W;

[0047] The leaching agent is an HCl solution with a concentration of 0.1 mol / L;

[0048] The leaching temperature is 20℃, and the leaching time is 0 min;

[0049] The liquid-solid ratio of the leaching solution to the slag grinding material is 2 mL / g;

[0050] The stirring speed is 100 r / min.

[0051] The zinc ferrite synthesis rate in Comparative Example 1 is 50.9%, and the purity of zinc ferrite is 50.1%.

[0052] Comparative Example 2

[0053] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, the obtained powder is put into an H2SO4 solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0054] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.40;

[0055] The pressing forming pressure is 20 MPa;

[0056] The microwave calcination temperature is 500 DEG C, the microwave calcination time is 20 min, and the microwave calcination power is 400 W;

[0057] The leaching agent is an H2SO4 solution with a concentration of 0.2 mol / L;

[0058] The leaching temperature is 30 DEG C, and the leaching time is 10 min;

[0059] The liquid-solid ratio of the leaching liquid to the slag powder is 3 mL / g;

[0060] The stirring speed is 200 r / min.

[0061] In the comparative example 1, the zinc ferrite synthesis rate is 79.6%, and the purity of the zinc ferrite is 57.9%.

[0062] Comparative example 3

[0063] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, the obtained powder is put into an H2SO4 solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0064] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.40;

[0065] The pressing forming pressure is 30 MPa;

[0066] The microwave calcination temperature is 600 DEG C, the microwave calcination time is 30 min, and the microwave calcination power is 500 W;

[0067] The leaching agent is an H2SO4 solution with a concentration of 0.2 mol / L;

[0068] The leaching temperature is 30 DEG C, and the leaching time is 10 min;

[0069] The liquid-solid ratio of the leaching liquid to the slag powder is 3 mL / g;

[0070] The stirring speed is 300 r / min.

[0071] The zinc ferrite synthesis rate in the present comparative example 3 is 79.2%, and the purity of zinc ferrite is 51.2%.

[0072] Comparative example 4

[0073] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, the obtained powder is put into a CH3COOH solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0074] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.45;

[0075] The pressing pressure is 60 MPa;

[0076] The microwave calcination temperature is 1100℃, the microwave calcination time is 90 min, and the microwave calcination power is 1000 W;

[0077] The leaching agent is a CH3COOH solution with a concentration of 1.0 mol / L;

[0078] The leaching temperature is 60℃, and the leaching time is 70 min;

[0079] The liquid-solid ratio of the leaching solution to the slag powder is 4 mL / g;

[0080] The stirring speed is 250 r / min.

[0081] The zinc ferrite synthesis rate in the present comparative example 4 is 91.2%, and the purity of zinc ferrite is 89.2%.

[0082] Comparative example 5

[0083] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a conventional tube furnace to obtain a calcined body. The calcined body is ground, the obtained powder is put into a HCl-H2SO4-CH3COOH solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0084] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.4;

[0085] The pressing pressure is 40 MPa;

[0086] The conventional roasting temperature is 900 DEG C, and the roasting time is 180 min;

[0087] The leaching agent is an HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.2 mol / L, the H2SO4 concentration is 0.2 mol / L, the CH3COOH concentration is 0.2 mol / L, the volume ratio of HCl is 0.2, the volume ratio of H2SO4 is 0.2, and the volume ratio of CH3COOH solution is 0.6.

[0088] The leaching temperature is 60 DEG C, and the leaching time is 120 min;

[0089] The liquid-solid ratio of the leaching solution to the slag grinding material is 6 mL / g;

[0090] The stirring speed is 300 r / min.

[0091] In the comparative example 5, the zinc ferrite synthesis rate is 79.9%, and the zinc ferrite purity is 91.3%.

[0092] Example 1

[0093] The copper slag powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is roasted and cooled in a microwave tube furnace to obtain a roasted body. The roasted body is ground, the obtained ground material is put into an HCl-H2SO4-CH3COOH solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0094] The mass ratio of the copper slag to the zinc-containing electric furnace dust is 0.3;

[0095] The pressing forming pressure is 20 MPa;

[0096] The microwave roasting temperature is 500 DEG C, the microwave roasting time is 0 min, and the microwave roasting power is 300 W;

[0097] The leaching agent is an HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.1 mol / L, the H2SO4 concentration is 0.1 mol / L, the CH3COOH concentration is 0.1 mol / L, the volume ratio of HCl is 0.1, the volume ratio of H2SO4 is 0.1, and the volume ratio of CH3COOH solution is 0.8.

[0098] The leaching temperature is 40 DEG C, and the leaching time is 30 min;

[0099] The liquid-solid ratio of the leaching solution to the slag grinding material is 4 mL / g;

[0100] The stirring speed is 200 r / min.

[0101] The synthesis rate of zinc ferrite in this embodiment 1 is 80.2%, and the purity of zinc ferrite is 80.4%.

[0102] Embodiment 2

[0103] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, and the obtained ground material is put into an HCl-H2SO4-CH3COOH solution for leaching to obtain a crude product of zinc ferrite material, and the crude product is subjected to nano sanding treatment to obtain a nano zinc ferrite product.

[0104] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.4;

[0105] The pressing forming pressure is 40 MPa;

[0106] The microwave calcination temperature is 600°C, the microwave calcination time is 15 min, and the microwave calcination power is 400 W;

[0107] The leaching agent is an HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.2 mol / L; the H2SO4 concentration is 0.2 mol / L, the CH3COOH concentration is 0.2 mol / L, the volume ratio of the HCl is 0.2, the volume ratio of the H2SO4 is 0.2, and the volume ratio of the CH3COOH solution is 0.6.

[0108] The leaching temperature is 50°C, and the leaching time is 60 min;

[0109] The liquid-solid ratio of the leaching solution to the slag grinding material is 5 mL / g;

[0110] The stirring speed is 250 r / min.

[0111] The synthesis rate of zinc ferrite in this embodiment 2 is 92.6%, and the purity of zinc ferrite is 88.8%.

[0112] Embodiment 3

[0113] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, and the obtained ground material is put into an HCl-H2SO4-CH3COOH solution for leaching to obtain a crude product of zinc ferrite material, and the crude product is subjected to nano sanding treatment to obtain a nano zinc ferrite product.

[0114] The mass ratio of the copper residue to the zinc-containing electric furnace dust is 0.45;

[0115] The compression molding pressure is 60 MPa;

[0116] The microwave roasting temperature is 700 DEG C, the microwave roasting time is 30 min, and the microwave roasting power is 500 W;

[0117] The leaching agent is HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.3 mol / L; the H2SO4 concentration is 0.3 mol / L, the CH3COOH concentration is 0.3 mol / L, the HCl volume ratio is 0.3, the H2SO4 volume ratio is 0.3, and the CH3COOH solution volume ratio is 0.4.

[0118] The leaching temperature is 60 DEG C, and the leaching time is 90 min;

[0119] The liquid-solid ratio of the leaching solution to the slag abrasive is 6 mL / g;

[0120] The stirring speed is 300 r / min.

[0121] The zinc ferrite synthesis rate in this embodiment 3 is 94.9%, and the zinc ferrite purity is 96.7%.

[0122] Embodiment 4

[0123] The copper slag powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is compression molded to obtain a green body, and the green body is roasted and cooled in a microwave tube furnace to obtain a roasted body. The roasted body is ground, the obtained ground abrasive is put into HCl-H2SO4-CH3COOH solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0124] The mass ratio of the copper slag to the zinc-containing electric furnace dust is 0.50;

[0125] The compression molding pressure is 60 MPa;

[0126] The microwave roasting temperature is 800 DEG C, the microwave roasting time is 45 min, and the microwave roasting power is 600 W;

[0127] The leaching agent is HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.3 mol / L; the H2SO4 concentration is 0.4 mol / L, the CH3COOH concentration is 0.4 mol / L, the HCl volume ratio is 0.4, the H2SO4 volume ratio is 0.4, and the CH3COOH solution volume ratio is 0.2.

[0128] The leaching temperature is 60 DEG C, and the leaching time is 90 min;

[0129] The liquid-solid ratio of the leaching solution to the slag abrasive is 7 mL / g.

[0130] The stirring speed is 300 r / min.

[0131] The zinc ferrite synthesis rate in this embodiment 4 is 97.9%, and the purity of zinc ferrite is 96.7%.

[0132] Embodiment 5

[0133] The copper slag powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, and the obtained powder abrasive is put into an HCl-H2SO4-CH3COOH solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0134] The mass ratio of the copper slag to the zinc-containing electric furnace dust is 0.55;

[0135] The pressing forming pressure is 80 MPa;

[0136] The microwave calcination temperature is 800°C, the microwave calcination time is 60 min, and the microwave calcination power is 700 W;

[0137] The leaching agent is an HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.4 mol / L; the H2SO4 concentration is 0.4 mol / L, the CH3COOH concentration is 0.5 mol / L, the volume ratio of HCl is 0.5, the volume ratio of H2SO4 is 0.4, and the volume ratio of CH3COOH solution is 0.1.

[0138] The leaching temperature is 80°C, and the leaching time is 120 min;

[0139] The liquid-solid ratio of the leaching solution to the slag abrasive is 8 mL / g;

[0140] The stirring speed is 400 r / min.

[0141] The zinc ferrite synthesis rate in this embodiment 5 is 97.2%, and the purity of zinc ferrite is 97.8%.

[0142] Embodiment 6

[0143] The copper slag powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is pressed to obtain a green body, and the green body is calcined and cooled in a microwave tube furnace to obtain a calcined body. The calcined body is ground, and the obtained powder abrasive is put into an HCl-H2SO4-CH3COOH solution for leaching to obtain a zinc ferrite material crude product, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0144] the mass ratio of the copper residue to the electric furnace dust containing zinc is 0.60;

[0145] the pressure of the press forming is 100 MPa;

[0146] the microwave roasting temperature is 900 ℃, the microwave roasting time is 90 min, and the microwave roasting power is 800 W;

[0147] the leaching agent is an HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.5 mol / L; the H2SO4 concentration is 0.5 mol / L, the CH3COOH concentration is 0.5 mol / L, the volume ratio of the HCl is 0.5, the volume ratio of the H2SO4 is 0.1, and the volume ratio of the CH3COOH solution is 0.4.

[0148] the leaching temperature is 90 ℃, and the leaching time is 150 min;

[0149] the liquid-solid ratio of the leaching solution to the slag abrasive is 9 mL / g;

[0150] the stirring speed is 300 r / min.

[0151] In this embodiment 6, the synthesis rate of zinc ferrite is 96.4%, and the purity of zinc ferrite is 97.8%.

[0152] Embodiment 7

[0153] The copper residue powder and the electric furnace dust powder are mixed according to a certain mass ratio to obtain a mixture, the mixture is press-formed to obtain a green body, and the green body is roasted and cooled in a microwave tube furnace to obtain a roasted body. The roasted body is ground, the obtained ground abrasive is put into an HCl-H2SO4-CH3COOH solution for leaching to obtain a crude product of zinc ferrite material, and the crude product is subjected to nano sand grinding treatment to obtain a nano zinc ferrite product.

[0154] the mass ratio of the copper residue to the electric furnace dust containing zinc is 0.55;

[0155] the pressure of the press forming is 100 MPa;

[0156] the microwave roasting temperature is 1000 ℃, the microwave roasting time is 120 min, and the microwave roasting power is 900 W;

[0157] the leaching agent is an HCl-H2SO4-CH3COOH solution, the HCl concentration is 0.5 mol / L; the H2SO4 concentration is 0.5 mol / L, the CH3COOH concentration is 0.5 mol / L, the volume ratio of the HCl is 0.2, the volume ratio of the H2SO4 is 0.1, and the volume ratio of the CH3COOH solution is 0.7.

[0158] The leaching temperature is 80℃, and the leaching time is 180 min;

[0159] The liquid-solid ratio of the leaching liquid to the residue grinding material is 10 mL / g;

[0160] The stirring speed is 400 r / min.

[0161] The zinc ferrite synthesis rate in this example 7 is 96.5%, and the zinc ferrite purity is 94.3%.

[0162] It is obvious for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application, therefore, the embodiments should be regarded as exemplary and non-limiting from any point of view, the scope of the present application is defined by the appended claims rather than the above description, therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be encompassed in the present application.

[0163] Furthermore, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, the description manner of the specification is only for the sake of clarity, those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be properly combined to form other embodiments which can be understood by those skilled in the art.

Claims

1. A method for preparing a zinc ferrite material using copper slag and electric furnace dust, characterized by: Mix copper residue and electric furnace dust to obtain a mixture, press the mixture to obtain a green body, then microwave the green body to obtain a sintered body, grind the sintered body to obtain a ground material, and immerse the ground material in a mixed acid solution to obtain a zinc ferrite material; the temperature of the microwave sintering is 700-800 ℃, and the time of the microwave sintering is ≤120 min; The mixed acid solution is obtained by mixing HCl solution, H2SO4 solution and CH3COOH solution in a volume ratio of 0.1-0.5:0.1-0.4:0.1-0.8, wherein the concentration of the HCl solution is 0.1-0.5 mol / L, the concentration of the H2SO4 solution is 0.1-0.5 mol / L, and the concentration of the CH3COOH solution is 0.1-0.5 mol / L; The liquid-solid volume-mass ratio of the mixed acid solution to the ground material is 4-10 mL:1 g.

2. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The mass ratio of the copper residue to the electric furnace dust is 0.30-0.60:

1.

3. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The pressure of the press molding is 20-100 MPa.

4. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The time of the microwave sintering is 30-90 min.

5. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The power of the microwave sintering is 300-900 W.

6. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The temperature of the immersion is 40-90 ℃, and the time of the immersion is 30-180 min.

7. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The immersion is assisted by stirring, and the stirring speed is 200-400 r / min.

8. The method for preparing zinc ferrite material by using copper slag and electric furnace dust according to claim 1, characterized in that: The zinc ferrite material is nanometer ground to obtain a nanometer zinc ferrite material.

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