CN1532297A - Method for wet zinc refining without iron slag - Google Patents
Method for wet zinc refining without iron slag Download PDFInfo
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Abstract
The wet zinc smelting process includes neutral leaching, high temperature and high acid concentration leaching, reducing and replenishing manganese, extracting In and Ge, initial purifying, deep purifying, tapping zinc, coprecipitation, preparing ferrite and other steps. The process has no iron eliminating step producing iron slag, makes soft magnetic Mn-Zn ferrite of great market requirement with most iron and small amount of zinc in the concentrated zinc ore and extracts In and Ge from the original liquid directly, and all these simplifies the wet zinc and indium (germanium) recovering process, raises the In and Ge yield and reduces environmental pollution caused by SO2 fume and iron slag.
Description
The invention relates to a non-iron slag wet-process zinc smelting method, in particular to a non-iron slag wet-process zinc smelting method of zinc concentrate with high iron and indium (germanium).
The conventional zinc hydrometallurgy method is divided into two main types, one is to fire process low acid leaching slag, recover zinc and lead and part of scattered metals, but generate a large amount of kiln slag with iron as a main component. The other is a full wet process, namely leaching low acid leaching slag by high temperature and high acid, and then removing iron to separate zinc and iron. The iron removal method includes jarosite method, goethite method and hematite method, but no matter which iron removal method is adopted, a large amount of iron slag polluting the environment is generated. Particularly, iron is removed by an iron vitriol method, the slag amount is more, and the treatment is more difficult, but almost all zinc smelting processes by a whole wet method in China adopt the iron removal by the iron vitriol method, even the treatment of zinc indium concentrate with high iron content (13-20%) is carried out, the iron vitriol slag amount generated in the treatment process of the zinc indium concentrate with high iron content is more remarkable, most indium enters into iron vitriol slag, in order toextract indium, the iron vitriol slag must be further treated, so that the indium extraction process is long, the indium recovery rate is low, a large amount of low-concentration sulfur dioxide and iron oxide waste slag are generated in the indium extraction process to pollute the environment, germanium is dispersed in the zinc concentrate containing germanium in the whole wet method, the zinc concentrate containing germanium is difficult to recover, the iron vitriol slag with low germanium content is the same as the common iron vitriol slag, a slag field is piled for a long.
The Mn-Zn soft magnetic ferrite magnetic material is a functional material which is widely applied to the fields of communication, household appliances, computers, sensors, switching power supplies and the like and has wide application prospect, the annual growth rate is more than 15 percent, and the traditional method uses pure metal or pure metal compounds to prepare the soft magnetic material; chinese patent 95110609 discloses a method for preparing soft magnetic material by using iron filings, manganese ore and zinc ash as raw materials, which greatly reduces the cost, but the scale is enlarged to more than 10000t/a, and the supply of iron filings as iron source becomes a big problem.
The invention aims to provide a method for smelting zinc by a wet method without iron slag, which shortens the processes of smelting zinc by a wet method and extracting indium (germanium), greatly improves the metal recovery rate and the comprehensive utilization degree of resources and reduces the environmental pollution.
According to the invention, zinc calcine is used as a raw material, Zn In the zinc calcine is more than or equal to 50%, Fe, In and Ge are not limited, sulfuric acid (waste electrolyte) is used for neutral leaching to obtain a neutral leaching solution and neutral leaching residues, 75-95% of zinc enters the neutral leaching solution, the neutral leaching solution is electrolyzed to prepare electrozinc, and the rest zinc (mainly existing In zinc ferrite) and all iron, indium, germanium, tin, silver, lead and the like enter the neutral leaching residues; carrying out high-temperature and high-acid leaching on the intermediate leaching residue by using sulfuric acid to obtain high leaching solution and high leaching residue, wherein most of zinc, iron, indium, copper, cadmium and part of germanium enter the high leaching solution, and silver, lead, tin, antimony and the like are enriched in the high leaching residue; reducing high valence ions (Fe) in the high leaching solution+3、Cu+2Etc.) and according to manganeseThe proportion of the zinc soft magnetic ferrite is that manganese with corresponding amount is added by taking the iron amount as a reference, and returns to the iron manganese slag to neutralize most of free acid; extracting indium in the reducing solution by an extraction method, and recovering germanium by a precipitation method; one-time purification, i.e. removing Zn by sulfidation precipitation+2Removing impurity elements such as aluminum, silicon, arsenic, antimony and the like by using a neutralization method except all heavy metal ions; deeply purifying and opening a circuit of zinc, namely further removing harmful impurity elements such as silicon, aluminum, calcium, magnesium, potassium, sodium, heavy metals and the like by using a double-salt precipitation method, and opening a circuit of redundant zinc to ensure that the proportion of iron, manganese and zinc in the second purified liquid is basically close to the theoretical proportion; preparing liquid and coprecipitation, adding a small amount of pure compound or pure metal with insufficient main component content according to the content of main component ions in the two purified liquids to reach the proportion of the main components of the magnetic material, then coprecipitating with ammonium bicarbonate or ammonium bicarbonate and ammonia water to obtain coprecipitation powder, and processing the coprecipitation powder by presintering, doping, ball milling, granulating, compacting, sintering and the like to finally obtain the high-performance manganese-zinc soft magnetic ferrite material. The specific technological process and conditions are detailed as follows:
neutral leaching
The process is carried out in a sulfuric acid system, namely zinc calcine is leached by using waste electrolyte of electrodeposited zinc, and only oxides and sulfates of metals such as zinc, cadmium, copper and the like are dissolved under the condition of being close to neutrality (the PH value is about 5):
the compounds of iron, indium and germanium, sulfide, lead, tin, silver, antimony, arsenic, aluminum and other metals mainly existing in zinc ferrite are not dissolved and remain in the leaching residue. The neutral leaching conditions were: the temperature is 0-100 ℃, the time is 0.5-10 hours, the pH value is 4.5-5.5, the acidity of a leaching agent is 1.5-2.5 mol/l, and the liquid-solid ratio is determined by zinc contained in the leaching solution of 90-160 g/l.
High-temperature high-acid leaching
The high-temperature peracid leaching is still carried out in a sulfuric acid system, and under the condition of high temperature peracid, ferrate such as zinc ferrite and ferric oxide and other ferric oxides are decomposed and enter a high leaching solution:
in Fe+3Under the action of (2), sulfides of metals such as zinc, copper, cadmium and the like are also oxidized and dissolved:
lead and antimony compounds can also react, but insoluble sulfate is finally generated, silver finally enters residues as silver chloride because trace chlorine inevitably exists in a leaching system, tin mainly exists in the residues in an inert cassiterite form, and indium compounds have properties similar to those of high-valence iron compounds and completely enter leaching liquid under the action of sulfuric acid; but the germanium is dispersed, most of the germanium enters the leaching solution, and a small part of the germanium dioxide which is heterogeneous and in phase with the silicon dioxide is left in the residue. The temperature is 90-100 ℃, the time is 2-10 h, the liquid-solid ratio is 3-9: 1, the initial acidity is 150-350 g/l, and the final acidity is 30-100 g/l.
Thirdly, reducing and supplementing manganese
The high leaching solution contains high valence metal ions, and is required to be reduced before indium (germanium) extraction, and the reducing agent can be a gas reducing agent or a solid reducing agent, and the gas reducing agent is SO2Or H2And S, the solid reducing agent is scrap iron or FeS or metal manganese powder or MnS.
The reduction and manganese supplement are combined in the formulas (9) and (10), and in the reduction process, returned ferro-manganese slag is added to neutralize free acid, so that the reduction solution can initially reach the manganese content (based on the iron content) required by the mixture ratio:
the reduction and manganese supplement conditions are as follows: the temperature is 0-100 ℃, the time is 0.5-10 h, the dosage of the reducing agent is 1.05-2.05 times of the theoretical amount, the manganese adding amount is 1.0-1.25 times of the manganese supplementing amount, and the end point acidity is 5-20 g/l. The manganese raw material is non-oxidative manganese salt or manganese ore or metal manganese powder, such as manganese carbonate or manganese carbonate ore, manganese sulfide or manganese sulfide ore, preferably manganese raw material which is also used as reducing agent.
Fourth, extracting indium (germanium)
By P204And (3) extracting indium from the reducing solution:
the indium extraction conditions are as follows: the temperature is 0-60 ℃, the time is 0.2-10 min, the acidity is 5-20 g/l, the ratio (W/O) is 1-20: 1, and the content of the extractant is 5-30% of P204+200#Extracting kerosene with the number of stages being 1-6; the indium is reversely extracted by hydrochloric acid for loading the organic phase, the reverse extraction equation is the reverse reaction of the formula (11), and the reverse extraction condition is as follows: the temperature is 4-50 ℃, the time is 0.2-10 min, the ratio of (W/O) is 1: 2-10, and the stripping agent component is 2-6 mol/1HCl + 2.5-0.5 mol/1ZnCl2The number of stripping stages is 1-4. In the presence of germanium, extracting germanium by precipitation under the following conditions: the temperature is 0-100 ℃, the time is 0.2-10 h, the pH value is 1.5-3.5, and the dosage of the germanium precipitation agent is 20-80 times of the germanium amount.
Five, primary purification
The sulfidation precipitation method can remove all heavy metal ions except zinc:
the conditions of the sulfidation precipitation are as follows: the temperature is 0-80 ℃, the time is 0.5-10 h, the pH value is 2-4, the dosage of a vulcanizing agent is 1.05-1.5 times of the theoretical amount, and after vulcanization and impurity removal, neutralization, precipitation and impurity removal are carried out:
in addition to aluminum, impurity elements such as silicon, arsenic, antimony, titanium, and tin are removed. The conditions for neutralizing, precipitating and removing impurities are as follows: temperature of 0-80 ℃, time of 0.5-10 h, pH 4.5&5.5, the dosage of PAM (0.1g/l) is 0.1-1.0% of the stock solution. The vulcanizing agent used is alkali metal sulfide Me2S or iron (manganese) sulfide, Me2S is (NH)4)2S or H2S or Na2S, preferably MnS or manganese sulfide ore powder, because it can be used for manganese supplement, reduction and sulfide removal. The neutralizing agent is a neutralizing agent having a low solubility that does not cause local overbasing, such as slaked lime.
Sixth, deep purification and open circuit zinc
Deeply purifying a clean liquid by a double-salt precipitation method:
and (3) washing the double salt by using pure water by utilizing the solubility difference of the double salt until the proportion of iron, manganese and zinc in the washing liquid approximately meets the proportion of the soft magnetic material and the remaining zinc double salt contains little iron and manganese, so that the zinc double salt can be opened. The conditions of deep purification and open circuit zinc are as follows: the temperature is 0-50 ℃, the time is 0.5-10 h, the pH value is 1-3, and the concentration of free ammonium sulfate is 0.2-3.0 mol/l. The operation method and the steps of the double salt precipitation method are as follows: (1) firstly precipitating redundant zinc, opening the circuit to prepare a deep-processing product of the zinc, and then precipitating mixed double salt of iron, manganese and zinc, or (2) completely precipitating the iron, the manganese and the zinc, then washing the iron, the manganese and the zinc by pure water according to the proportion of the manganese-zinc soft magnetic material, wherein more than 95 percent of the residual double salt is zinc double salt, and the circuit can be opened.
Seventhly, depositing ferro-manganese
Precipitating iron and manganese in the double-salt mother liquor by ammonium bicarbonate to recycle, return to the reduction and manganese supplement process, and controlling the mixture ratio:
the conditions for depositing the iron and the manganese are as follows: the temperature is 10-100 ℃, the time is 0.2-10 h, and the dosage of ammonium bicarbonate is 1.05-1.30 times of the theoretical amount. The obtained iron-manganese slag returns to the process of reducing and supplementing manganese, thereby not only neutralizing free acid, but also controlling the proportion.
Ammonium sulfate recovery
In order to avoid environmental pollution, the ammonium sulfate in the coprecipitation mother liquor is recovered by a classical method, namely a two-effect evaporation method, and simultaneously, the produced distilled water is returned for use.
Nine. other procedures
The principles and technological conditions of the processing processes of liquid preparation, coprecipitation, presintering, doping, ball milling, granulation, compaction, sintering and the like refer to patent specification No. 95110609.
The present invention features that the iron-removing process in zinc hydrometallurgy is eliminated, no iron slag is produced, most of iron and small amount of zinc in zinc concentrate are directly processed into Mn-Zn soft magnetic ferrite material with large market capacity and high price, and the other feature is that indium (germanium) is directly extracted from reducing liquid. Therefore, the zinc hydrometallurgy and indium (germanium) recovery process is greatly simplified, the indium (germanium) recovery rate is greatly improved, the pollution of low-concentration sulfur dioxide flue gas and a large amount of iron slag to the environment is eliminated, waste is turned into wealth, harm is turned into benefit, iron resources in zinc concentrate are fully utilized, and great economic benefit and remarkable social benefit are brought. The invention makes the zinc hydrometallurgy process generate a great revolution and opens up a new field of production of a novel soft magnetic ferrite material.
Compared with the conventional zinc hydrometallurgy method, the method has the following outstanding advantages: (1) the method has the advantages that an iron removal process is omitted, a zinc smelting process is simplified, (2) alum slag roasting and burned slag indium leaching processes are omitted, an indium (germanium) extracting process is simplified, (3) pollution of iron slag and sulfur dioxide flue gas to the environment is eliminated, (4) the recovery rate of indium (germanium) is improved by more than 20%, and (5) iron resources are utilized with high value; compared with the 95110609 patent technology, the invention also has the following advantages: (1) the problem of iron source supply in large-scale production is solved, (2) the iron source and the zinc source (enough zinc in the original iron slag) are obtained by utilizing waste, and the using amount of sulfuric acid is reduced by about 60%, so that the production cost of the co-precipitation powder for soft magnetism is reduced by more than 20%, and (3) the neutral leaching is carried out to remove most of magnesium, potassium, sodium and other impurity elements in the raw materials, thereby being beneficial to the improvement of the quality of the soft magnetism material.
Description of the drawings the process scheme of the invention is schematically illustrated.
[ detailed description of the invention]
Example 1:
a: neutral leaching
(1) 1354g of concentrated technical sulfuric acid was slowly added to 4500ml of water; (2) 1980g of zinc calcine (with the components (%) of Zn57.21, Fe16.79, Pb0.80, Ag0.01623, In0.0997, Sn0.33 and Cd0.43), (3) stirring and leaching for 2h at 70-80 ℃, (4) adjusting the pH value to about 5 by using 20g of zinc calcine (with the components being the same), filtering the leached slurry and washing the filter cake for several times by using 500ml of water, (6) combining the leaching solution and the washing solution to obtain 5720ml of neutral leaching solution, wherein the neutral leaching solution contains Zn150g/l, Fe<0.1g/l and In<0.001g/l, and (7) drying the filter cake to obtain 997g of neutral leaching residue, with the components (%) of Zn28.69, Fe33.68, Ag0.0326, Pb1.60, In0.20, Sn0.66 and Cd0.22, wherein the zinc leaching rate of the residue is 75%, and iron, indium, silver, tin, lead and the like are nearly one hundred percent of the neutral leaching residue.
B: high temperature peracid leaching
(1) 1387g of industrial concentrated sulfuric acid is added into 4300ml of water; (2) adding 990g of the middle leaching residue, and leaching for 5 hours at the temperature of more than 95 ℃ by stirring; (3) filtering the high leaching slurry, and washing a filter cake for multiple times by using 500ml of water; (4) mixing the extractive solution and lotion to obtain 4950ml extractive solution with the following components (g/l): zn55.63, Fe63.99 (where Fe+348.08)，In0.393，Cd0.43，H2SO436.02, respectively; (5) drying the filter cake to obtain 118.8g of high leaching residue, which comprises the following components in percentage by weight: zn7.08, Fe13.5, In0.028, Ag0.1353, Pb13.03 and Sn5.50, and the leaching rate (%) of the slag is as follows: zn96.95, Fe95.00, In98.32.
C: reduction manganese supplement
(1) Taking 4900ml of the high-leaching solution, slowly adding 210g of manganese sulfide ore containing 40% Mn, and reacting at normal temperature for 0.5 h; (2) adding 20.33g of scrap iron, and reacting at the temperature of 70-80 ℃ for 0.5 h; (3) 238.4g of returned ferro-manganese slag (components (%) are Fe16.32 and Mn17.22) is added; (4) filtering the raw material slurry when no ferric ion can be detected in the reducing solution, washing the reducing slag for a plurality of times by using 200ml of water, and combining the washing liquor in the filtrate to obtain 5000ml of reducing solution, wherein the components (g/l) of the reducing solution are as follows: zn54.52, Fe74.49 (Fe among others)+3＜0.5，Mn24.67 percent, In0.385 percent, Cd0.17 percent, acidity of 7.00 percent, manganese recovery rate of 98 percent by liquid meter and cadmium removal rate of 60.66 percent.
D: indium (germanium)
(1) Taking 4500ml of the above reducing solution, and adding 15% of P under the condition of 20 ℃ and phase ratio (W/O) ═ 4: 1204+200#Kerosene two-stage countercurrent extraction was carried out for 2min at a raffinate of 4500ml, with the composition (g/l): zn54.52, Fe74.40, Mn24.67, Cd0.17, In0.00076, indium extraction rate of the solution of 99.80 percent, iron extraction rate of less than 0.2 percent and zinc and manganese extraction rate of almost 0; (2) at 20 ℃ and a phase ratio (W/O) of 1: 5, 4mol/1HCl +1.5mol/1ZnCl2The solution carries out primary back extraction on the loaded organic phase for 2min to obtain 225ml of back extraction solution, wherein the back extraction solution contains 6.85g/l of In, and the indium back extraction rate is 99 percent; (3) replacing indium in the stripping solution by using a zinc sheet, wherein the replaced solution contains 0.137g/l of In, and the replacement rate is 98%; from calcine to sponge indium, the overall recovery of indium was 95.20%.
E: one-time purification
(1) Taking 4400ml of the indium extraction solution, and adjusting the pH value to 3 by using lime milk at normal temperature; (2) slowly adding 20ml of ammonium sulfide (containing S8 percent) and reacting for 0.5 h; (3) regulating pH value to 5 with lime milk at 60-70 deg.C, and stabilizing for 10 min; (4) adding 22ml of PAM (0.1g/l), stirring for 5min, and filtering; (5) the filter cake was washed several times with 200ml of water and the washings were combined in the filtrate to give 4500ml of a neat solution, the composition (g/l) was: zn53.30 percent, Fe72.75 percent, Mn24.12 percent, Cd0.0017 percent, and the cadmium removal rate of the liquid meter is 99 percent.
F: deep purification and open circuit zinc
(1) Taking 4400ml of the above clean liquid, and adjusting the pH value to 2 by using Cp sulfuric acid; (2) adding 2758g of industrial superior ammonium sulfate at 30 ℃, and stirring for 1 h; (3) the double-salt slurry is immediately centrifugally filtered to obtain 4200ml of double-salt mother liquor, and the components (g/l) are as follows: zn0.05, Fe7.97, Mn9.41, (NH)4)2SO4330; the precipitation rate (%) of the double salt on the liquid meter is respectively as follows: zn99.91, Fe89.54, Mn62.76, and 2377g of mixed double salt in addition; (4) the double salt was washed with 6000ml of pure water several times to give 6250ml of a washing solution, the components (g/l) being: fe45.09, Mn10.66, Zn11.68, (NH)4)2SO4156; (5) 226g of ammonium bicarbonate is used for precipitating iron and manganese in the double-salt mother liquor at normal temperature and under the condition that the PH value is 7.5, and the iron and manganese are obtained205.12g of slag, the composition (%) of which is: fe16.35 and Mn19.60, and returning to be used for neutralizing the free acid next time. (6) 748.4g of unwashed zinc double salt containing 21.55 percent of ZnFe, 0.64 percent of FeFe/Zn, 0.0298 percent of Fe/Zn, the purer zinc double salt can be used for preparing zinc products after opening a way and returning to the middle leaching process or dissolving water and then removing iron by a goethite method, and the iron slag returns to the high leaching process.
G: coprecipitation
(1) 6000ml of the washing solution was taken, and solution preparation and coprecipitation were carried out by the method of patent No. 95110609 to obtain 676g of coprecipitated powder (equivalent to 563g of mixed oxide) which had the following components (%): fe40.02, Mn9.46, Zn10.37, Si0.0026, Al0.0093, Mg0.0066, Cd0.0014, Pb0.00047, K0.00082, Na0.0022, C10.0043 and S0.013; the content of impurities of the coprecipitation powder, particularly the content of Si, K, Na and the like is very low, and the mixture ratio meets the soft magnetic requirement of high magnetic permeability (Fe: Mn: Zn: 66.87: 15.81: 17.32 (wt.))); (2) the coprecipitation powder is processed by processes of pre-sintering, doping, ball milling, granulating, compacting, sintering and the like according to a patent No. 95110609, a standard soft magnetic sample ring is prepared, and the magnetic performance measurement result is as follows: mu i6950, Bs436mT, Br118mT, Hc6.0A/m and Tc135 ℃ meet the HLR7K brand product standard.
Example 2
A: neutral leaching
(1) Slowly adding 9.54kg of industrial concentrated sulfuric acid into 35L of water; (2) adding 9.8kg of zinc calcine (with the components of (%) Zn65.764, Fe2.542, Pb1.01, Cd0.942, S2.346, Ag0.01968, Ge0.0082 and Ga0.00232), and leaching at 75 ℃ for 1.5 h; (3) adjusting pH to 5.2 with 200g zinc calcine (the same components as (2)); (4) filtering the soaking slurry, washing the filter cake with 4L of water for several times, and mixing the washing liquid with the filtrate to obtain 40.2L of soaking solution, which comprises the following components (g/L): zn152.5, Cd2.17, Ge0.26mg/l; (5) drying filter residues to obtain 2.369kg of middle leaching residues, wherein the components are as follows: zn18.82, Fe10.68, Cd0.29, S5.56, Ag0.08307, Pb4.26, Ge0.0342, and the zinc leaching rate of slag is 93.22 percent, and the recovery rate of germanium is 98.80 percent.
B: high temperature peracid leaching
(1) Slowly adding 1.356kg concentrated industrial sulfuric acid into 7L water; (2) adding 2.3kg of the middle leaching residue, and reacting for 5h at 95-100 ℃; (3) the high leaching slurry was filtered and the number of filter cakes was washed with 1L of waterNext, the wash solution was combined with the filtrate to give 8.05L of high-grade infusion, which had the following composition (g/L): zn51.89, Fe28.99 (wherein Fe)+37.17)，Cd0.80，Ge65.2mg/l，H2SO438.08, the leaching rate (%) of the liquid meter is: zn96.50, Fe95.0, Ge66.75; (4) drying the filter cake to obtain 1.439kg of high leaching residue, wherein the components are as follows: ag0.1328, Pb6.81, Ge0.0182, Zn1.05 and Fe0.85, which are good raw materials for recovering silver.
C: reduction manganese supplement
(1) Adding 30.15g of manganese metal powder into 8L of the high-leaching solution, reacting at 60 ℃ for 1.5h, and detecting no Fe in the reducing solution+3(ii) a (2) Adding 101.43g of manganese carbonate containing 47% of Mn; (3) 197.69g of returned ferro-manganeseslag (containing 15.19 percent of Fe15 and 19.60 percent of Mn19) is added and reacted for 0.5h under the condition of no heating; (4) filtering the raw material slurry, washing the filter cake with 1L of water for several times, and combining the washing liquid with the filtrate to obtain 8.06L of reducing solution, wherein the components (g/L) are as follows: fe32.50, Mn14.46, Zn51.50, Ge64.71mg/l, H2SO412.41。
D: one-time purification
(1) Taking 8L of the reducing solution, adjusting the pH value to 2.5, heating to 60-70 ℃, adding 13g of tannin, and (2) keeping the temperature and reacting for 20 min; (3) filtering the slurry, washing the germanium residue for several times by using 0.5L hot water; (4) the washing liquid is combined with the filtrate to obtain 8.2L of germanium-precipitated liquid, and the components (g/L) are as follows: fe31.70, Mn14.11, Zn50.24, Ge1.26mg/l, H2SO412.11, the germanium precipitation rate is 98 percent by liquid meter; (5) and calcining the germanium slag at 450-500 ℃ for 2 hours to obtain 10.08g of germanium concentrate, wherein the germanium content is 5.03%, and the recovery rate of germanium is 65.41% from the calcine to the germanium concentrate.
E. F, G in the same manner as in example 1, a coprecipitated powder 512.10g (corresponding to 426.50g of mixed oxide) was obtained, the composition (%) of which was: fe41.65, Mn13.98, Zn4.56, Si0.0028, Al0.022, Ca0.048, Mg0.0046, Cd0.0021, Pb0.0027, K0.00033, Na0.0024, Cl0.0052 and S0.025; the content of impurity elements in the coprecipitation powder is still very low, the mixture ratio accords with the requirement of low-power consumption soft magnetic ferrite (Fe: Mn: Zn: 69.20: 23.22: 7.58(wt.)), the coprecipitation powder is made into a standard sample ring according to the ferrite process of patent No. 95110609, and the measured magnetic performance is as follows: mu.i 2380, Bs514mT, Br92mT, Hc15.2A/m, Tc235 ℃, Pcv(25KHz，200mT)/kw·m-3：125(25℃)，85(60℃)，83(80℃)，94(100℃)，Pcv(100KHz，200mT)/kw·m-3: 650(25 ℃), 435(60 ℃), 405(80 ℃), 400(100 ℃); the product quality exceeds PC30Is close to Pc40The requirements of the brand.
Claims (8)
1. A zinc hydrometallurgy method without iron slag is characterized in that: the method comprises the steps of firstly, performing neutral leaching on zinc calcine, separating iron, indium and germanium, enabling 75-95% of zinc to enter a middle leaching solution to prepare electric zinc, performing high-temperature high-acid leaching on middle leaching residues, reducing the high leaching solution, supplementing manganese and neutralizing free acid according to the proportion of the manganese-zinc soft magnetic ferrite, then extracting indium or germanium from the reducing solution, purifying and removing impurities after extracting indium (germanium), opening a path of redundant zinc, finally, finely adjusting the proportion of iron, manganese and zinc in deep purification solution, performing coprecipitation, and preparing manganese-zinc soft magnetic ferrite magnetic material from coprecipitation powder through processing processes such as presintering, doping, ball milling, granulating, blank pressing, sintering and the like; the specific process conditions are as follows:
(1) carrying out neutral leaching on the zinc calcine by using 1.5-2.5 mol/l of sulfuric acid or waste electrolyte, wherein the leaching conditions are as follows: the temperature is 0-100 ℃, the time is 0.5-10 h, the pH value is 4.5-5.5, and the concentration of zinc in the immersion liquid is 90-160 g/l;
(2) carrying out high-temperature and high-acid leaching on the medium leaching residue by using sulfuric acid, wherein the high-temperature leaching temperature is 90-100 ℃, the time is 2-10 hours, the liquid-solid ratio is 3-9: 1, the initial acid is 150-350 g/l, and the final acid is 30-100 g/l;
(3) the conditions of high-immersion liquid reduction and manganese supplement are that the temperature is 0-100 ℃, the time is 0.5-10 h, the dosage of a reducing agent is 1.05-2.05 times of the theoretical amount, the manganese adding amount is 1.0-1.25 times of the theoretical amount of manganese supplement, and the end point acidity is 5-20 g/l;
(4) extracting indium from the reducing solution by an extraction method, and recovering germanium by a precipitation method, wherein the indium extraction conditions are as follows: the temperature is 4-60 ℃, the time is 0.2-10 min, the acidity is 5-20 g/l, and the ratio is as follows: 1-20% of W/O, and the organic phase composition is as follows: 5 to 30% of P204+200 kerosene, extraction grade 1-6 grade; the condition of backward extraction of indium is as follows: the temperature is 4-50 ℃, the time is 0.2-10 min, and compared with (W/O) 1/(2-10), the stripping agent: 2 to 6mol/l HCl +2.5 to 0.5mol/l ZnCl2On the contraryThe extraction grade number is 1-4; the germanium precipitation conditions are as follows: the temperature is 0-100 ℃, the time is 0.1-10 h, the pH value is 1.5-3.5, and the dosage of the germanium precipitation agent is 10-80 times of the germanium amount;
(5) the liquid after extracting indium (germanium) is purified for one time, heavy metal is removed by a sulfurizing precipitation method, impurity elements such as aluminum, silicon, arsenic, antimony, tin and the like are removed by a neutralization method, and the conditions for removing heavy metal are as follows: the temperature is 0-80 ℃, the time is 0.5-10 h, the pH value is 2-4, and the dosage of a vulcanizing agent is 1.5-15 times of the theoretical amount; the neutralization and impurity removal conditions are as follows: the temperature is 0-80 ℃, the time is 0.5-10 h, the pH value is 4.5-5.5, and the flocculating agent amount is as follows: PAM (0.1g/l) is 0.1-1.0% of the solution after indium extraction;
(6) the purified liquid is deeply purified and zinc is opened by a double-salt precipitation method under the following conditions: temperature of 0-50 ℃, time of 0.5-10 h, pH value of 1-3, free (NH)4)2SO4The concentration is 0.2 to 3.0 mol/l.
2. The method of claim 1, wherein: the zinc calcine is produced by fluidizing (boiling) oxidizing roasting of various zinc concentrates, and particularly is zinc calcine containing iron, indium or germanium.
3. The method of claim 1, wherein: the reducing agent can be a gaseous reducing agent or a solid reducing agent, and the gaseous reducing agent is SO2Or H2And S, the solid reducing agent is scrap iron or FeS or metal manganese powder or MnS.
4. The method of claim 1, wherein: the manganese raw material is non-oxidative manganese salt or manganese ore or metal manganese powder, such as manganese carbonate or manganese carbonate ore, manganese sulfide or manganese sulfide ore, and preferably the manganese raw material which also serves as a reducing agent.
5. The method according to claim 1, wherein the vulcanizing agent is an alkali metal sulfide Me2S or iron (manganese) sulfide, Me2S is (NH)4)2S or H2S or Na2S is preferably MnS or manganese sulfide ore powder becauseIt can be used for manganese supplement, reduction and sulfurization for removing impurities.
6. The method of claim 1, wherein: the neutralizing agent is a neutralizing agent having a low solubility that does not cause local overbasing, such as slaked lime.
7. The method of claim 1, wherein: the operation method and the steps of the double salt precipitation method are as follows: (1) firstly precipitating redundant zinc, opening the circuit to prepare a deep-processing product of the zinc, and then precipitating mixed double salt of iron, manganese and zinc, or (2) completely precipitating the iron, the manganese and the zinc, then washing the iron, the manganese and the zinc by pure water according to the proportion of the manganese-zinc soft magnetic material, wherein more than 95 percent of the residual double salt is zinc double salt, and the circuit can be opened.
8. The method of claim 1, wherein: the iron-manganese slag is obtained by precipitating the double-salt mother liquor by ammonium bicarbonate, returns to the process of reducing and manganese supplementing, not only neutralizes free acid, but also can control the proportion.
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