CN1253589C - Method for wet zinc refining without iron slag - Google Patents
Method for wet zinc refining without iron slag Download PDFInfo
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- CN1253589C CN1253589C CN 03118199 CN03118199A CN1253589C CN 1253589 C CN1253589 C CN 1253589C CN 03118199 CN03118199 CN 03118199 CN 03118199 A CN03118199 A CN 03118199A CN 1253589 C CN1253589 C CN 1253589C
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Abstract
The present invention relates to a zinc hydrometallurgy method without iron residue, which comprises manufacturing processes such as neutral leaching, high-temperature high-acid leaching of neutralized leaching residue, manganese addition by reduction, the extraction of indium and germanium, preliminary purification, deep purification, redundant zinc removing, coprecipitation, ferrite preparation, etc. In the present invention, a de-ironing process in the processes of the zinc hydrometallurgy is cancelled so as not to generate iron slag, and most of iron and a small amount of zinc in zinc ore concentrate are directly manufactured into soft magnetic ferrite material of manganese and the zinc, which has the advantages of great market potential and high price. The indium (germanium) is directly extracted from a reductive solution, which not only greatly simplifies the processes of zinc hydrometallurgy and indium (germanium) recovery, but also eliminates the environmental pollution of sulfur dioxide gas of a low concentration and a large amount of iron slag so as to bring great economic benefit and prominent social benefit.
Description
[technical field] the present invention relates to a kind of slag-free zinc hydrometallurgy method, particularly the no scum Wet-smelting method of the zinc ore concentrate that iron content indium (germanium) is all high.
[background technology] conventional wet zinc smelting method divides two big classes, and a class is the low acid leaching residue of pyrogenic attack, reclaims the plumbous and part dissipated metal of zinc, is the kiln slag of main component but produce a large amount of with iron.Another kind of is full wet process, and promptly the high temperature peracid leaches low acid leaching residue, and zinc-iron separation is carried out in deironing then.On method for removing iron, divide jarosite process, goethite process and hematite process again, but, all produce the scum of a large amount of contaminate environment no matter adopt which kind of method for removing iron.Especially siderotil method deironing, the quantity of slag is more, harder to get along with controlling, but the nearly all full flowsheet of wet zinc smelting of China all adopts the deironing of siderotil method, even the processing of the zinc indium concentrate of iron content very high (13～20%) all is like this, the siderotil quantity of slag that the zinc indium concentrate that this iron content is very high produces in treating processes is surprisingly big especially, and indium mostly enters iron vitriol slag, in order to extract indium, iron vitriol slag must further be handled, cause and carry the indium long flow path, indium recovery is low, produces a large amount of low-concentration sulfur dioxide and ferric oxide residue contamination environment in putting forward the indium process. and germanic zinc ore concentrate germanium in full wet processing disperses, be difficult to reclaim, germanic lower iron vitriol slag is the same with general iron vitriol slag, piles up the slag field for a long time, contaminate environment.
The Mn-Zn soft magnetic ferrite magneticsubstance is a kind of functional materials with wide application prospect that is widely used in fields such as communication, household electrical appliances, computer, transmitter, switch power supply, annual growth is greater than 15%, and traditional method is produced soft magnetic materials with pure metal or pure metal compound; Chinese patent 95110609 discloses a kind of iron filings and manganese ore, zinc cigarette ash of utilizing and has produced the method for soft magnetic materials for raw material, and this method has reduced cost significantly, but scale expand to 10000t/a above after, as the big problem that has been supplied in of the iron filings of source of iron.
[summary of the invention] the object of the present invention is to provide a kind of slag-free zinc hydrometallurgy method, shortens zinc hydrometallurgy and puies forward indium (germanium) flow process, increases substantially metal recovery rate and comprehensive utilization of resources degree, reduces environmental pollution.
It is raw material that the present invention adopts zinc baking sand, Zn in the zinc baking sand 〉=50%, Fe, In, Ge do not limit, with sulfuric acid (waste electrolyte) carry out neutrality leach in immersion liquid and in soak slag, 75～95% zinc enters middle immersion liquid, the centering immersion liquid is produced electric zinc through electrolysis, and remaining zinc (mainly existing with zinc ferrite) is with all iron, indium, germanium, tin, silver, lead etc. soak slag in all entering; Soak slag with sulfuric acid centering and carry out the high temperature peracid and leach, high immersion liquid and height soak slag, wherein Jue Dabufen zinc, iron, indium, copper, cadmium and part germanium enter high immersion liquid, and silver, lead, tin, antimony etc. are enriched in height and soak in the slag; Reduce high valence ion (Fe in the high immersion liquid
+ 3, Cu
+ 2Deng), and according to the proportioning of Mn-Zn soft magnetic ferrite, be the manganese that benchmark adds respective amount with the iron amount, and returning the ferrimanganic slag, most free acids neutralize; Indium with in the extraction process extraction reduced liquid reclaims germanium with the precipitator method; Primary purification is promptly earlier removed Zn with sulfurization-precipitation method
+ 2All heavy metal ion are in addition removed impurity elements such as aluminium, silicon, arsenic, antimony then with neutralisation; Deep purifying and open circuit zinc are promptly further removed detrimental impurity elements such as silicon, aluminium, calcium, magnesium, potassium, sodium and heavy metal, and the unnecessary zinc of opening a way with the double salt precipitation method, make iron in the two clean liquid, manganese, zinc proportioning substantially near stoichiometric; Dosing and co-precipitation, according to principal constituent ionic content in the two clean liquid, allocate the pure compound or the pure metal of the insufficient principal constituent of a small amount of content into, make it to reach the ratio of magneticsubstance principal constituent, carry out co-precipitation with carbon ammonium or carbon ammonium and ammoniacal liquor then and get coprecipitated powder, coprecipitated powder is carried out processing treatment such as pre-burning, doping, ball milling, granulation, pressed compact, sintering, finally make high performance Mn-Zn soft magnetic ferrite.Details are as follows for specific embodiment and condition:
One. the neutral leaching
This process is carried out in sulfuric acid system, and promptly the waste electrolyte with electrowinning zinc leaches zinc baking sand, under the condition near neutral (pH value is about 5), has only the oxide compound and the vitriol dissolving of metals such as zinc, cadmium, copper:
And the compound of metals such as the compound of the iron, indium and the germanium that mainly exist with zinc ferrite, sulfide, lead, tin, silver, antimony, arsenic, aluminium all can not dissolve, and stay in soak in the slag.Neutral leaching condition is: 0～100 ℃ of temperature, and time 0.5～10h, pH value 4.5～5.5, leaching agent acidity 1.5～2.5mol/l determines liquid-solid ratio to contain zinc 90～160g/l in the immersion liquid.
Two. the high temperature peracid leaches
The high temperature peracid leaches and still to carry out in sulfuric acid system, and under high temperature peracid condition, the high oxide of iron such as wustites such as zinc ferrite, ferric oxide all can decompose and enters high immersion liquid:
At Fe
+ 3Effect under, the sulfide of metals such as zinc, copper, cadmium also can oxidation dissolution:
Plumbous, antimony compounds also can react, but generate the vitriol of indissoluble at last, because of unavoidably there being micro-chlorine in the leaching system, silver finally enters residue with silver chloride, tin mainly exists with inert cassiterite form, also stay in residue, and the character of indium compound is similar with the high price iron cpd, all enters leach liquor with effect of sulfuric acid; But germanium is dispersive, and big portion germanium enters leach liquor, and the heterogeneous in-phase germanium dioxide of small part and silicon-dioxide is stayed in the residue. high temperature peracid leaching condition is: 90～100 ℃ of temperature, time 2～10h, liquid-solid ratio 3～9: 1, beginning acidacidity 150～350g/l, whole acidacidity 30～100g/l.
Three. reduction and benefit manganese
High immersion liquid contains high volence metal ion, and indium (germanium) is preceding carrying, and must reduce, and reductive agent can be a gaseous reducing agent, also can be solid reductant, and gaseous reducing agent is SO
2Or H
2S, solid reductant are iron filings or FeS or manganese powder or MnS.
Formula (9) and formula (10) will be reduced and combine and carry out with mending manganese, and in reduction process, also in the ferrimanganic slag that returns of adding and free acid, like this, reduced liquid can tentatively reach the required manganese content of proportioning (is benchmark with the iron amount):
Reduction and mend the manganese condition and be: 0～100 ℃ of temperature, time 0.5～10h, reductive agent consumption are 1.05～2.05 times of theoretical amount, the manganese addition amount is for mending 1.0～1.25 times of manganese amount, terminal point acidity 5～20g/l.The manganese raw material that adds is non-oxidizing manganese salt or manganese ore or manganese powder, such as manganous carbonate or manganese carbonate ore, and manganese sulfide or sulfuration manganese ore, preferably the manganese raw material of double as reductive agent.
Four. extract indium (germanium)
Use P
204Extraction of indium from reduced liquid:
Collection indium condition is: 0～60 ℃ of temperature, and time 0.2～10min, acidity 5～20g/l, compare (W/O)=1～20: 1, extraction agent composition 5～30%P
204+ 200
#Kerosene, 1～6 grade of extraction progression; Load organic phases hydrochloric acid back extraction indium, the back extraction equation is the reversed reaction of formula (11), the back extraction condition is: 4～50 ℃ of temperature, time 0.2～10min, compare (W/O)=1: 2～10, reverse-extraction agent composition 2～6mol/lHCl+2.5～0.5mol/IZnCl
2, 1～4 grade of back extraction progression.Having under the situation of germanium, extract germanium with the precipitator method, heavy germanium condition is: 0～100 ℃ of temperature, time 0.2～10h, pH value 1.5～3.5, heavy germanium agent consumption are 20～80 times of germanium amount.
Five. primary purification
Sulfurization-precipitation method can be removed all heavy metal ion beyond dezincifying:
The condition of sulfide precipitation is: 0～80 ℃ of temperature, time 0.5～10h, pH value 2～4, vulcanizing agent consumption are 1.05～1.5 times of theoretical amount. after the sulfuration removal of impurities, then carry out the neutralization precipitation removal of impurities:
Except aluminium is removed, also have impurity elements such as silicon, arsenic, antimony, titanium, tin to be removed.The condition of neutralization precipitation removal of impurities is: 0～80 ℃ of temperature, and time 0.5～10h, pH value 4.5～5.5, PAM (0.1g/l) consumption is 0.1～1.0% of a former liquid measure.Used vulcanizing agent is alkali metalsulphide Me
2S or iron (manganese) sulfide, Me
2S is (NH
4)
2S or H
2S or Na
2S, preferably MnS or manganese sulfide breeze because it both can be used for mending manganese, can be used for reduction and sulfuration removal of impurities again.Described neutralizing agent is the very little neutralizing agent that can not cause partial over-alkali of a kind of solubleness, such as being slaked lime.
Six. deep purifying and open circuit zinc
With the double salt precipitation method one clean liquid is carried out deep purifying:
Utilize the difference of double salt solubleness, wash double salt with pure water, the ratio of iron, manganese, zinc roughly meets soft magnetic materials proportioning and remaining zinc double salt iron content, manganese seldom the time in washing lotion, and zinc double salt can be opened a way.The condition of deep purifying and open circuit zinc is: 0～50 ℃ of temperature, time 0.5～10h, pH value 1～3, free sulfuric acid ammonium concentration 0.2～3.0mol/l.The working method and the step of double salt precipitation method are: (1) is the unnecessary zinc of precipitation earlier, the deep processed product of open circuit system zinc, redeposition iron, manganese, zinc mixing double salt, or (2) are all precipitated iron, manganese, zinc, wash iron, manganese, zinc with pure water by MnZn soft magnetic materials proportioning then, residual double salt is zinc double salt more than 95%, can open a way it.
Seven. heavy ferrimanganic
With iron and the manganese in the carbon ammonium precipitation double salt mother liquor, return reduction benefit manganese with recycling and cross program control proportioning:
Heavy ferrimanganic condition is: 10～100 ℃ of temperature, time 0.2～10h, carbon ammonium consumption are 1.05～1.30 times of theoretical amount.Gained ferrimanganic slag, it returns reduction and mends the manganese process, both in and free acid, can control proportioning again.
Eight. ammonium sulfate reclaims
Exert oneself environmental pollution for keeping away, the ammonium sulfate classical way in the coprecipitated mother liquor---two-effect evaporation method is reclaimed, and output distilled water returns use simultaneously.
Nine. other processes
The principle of the courses of processing such as dosing, co-precipitation, pre-burning, doping, ball milling, granulation, pressed compact, sintering and technology condition are with reference to No. 95110609 patent specifications.
Characteristics of the present invention are the iron removal in the cancellation flowsheet of wet zinc smelting, do not produce scum, it is big that most iron in the zinc ore concentrate and a spot of zinc directly are processed into market capacity, the Mn-Zn soft magnetic ferrite that price is high, and another characteristics are directly to extract indium (germanium) from reduced liquid.Like this, not only zinc hydrometallurgy and indium (germanium) recovery process is greatly simplified, indium (germanium) rate of recovery significantly improves, and eliminated the pollution of low concentration sulphur dioxide flue gas and a large amount of scums to environment, accomplishing turns waste into wealth, turn harm into good, make the iron resources in the zinc ore concentrate fully obtain utilizing, thereby bring huge economic benefit and remarkable social benefit.The present invention will make Zinc hydrometallurgy process produce great revolution, and open up the production frontier of a brand-new soft magnetic ferrite.
Compare with conventional wet zinc smelting method, the present invention also has following outstanding advantage: (1) cancellation iron removal, simplify the zinc metallurgy flow process, (2) cancellation alum slag roasting and burning slag soak the indium process, simplified and put forward indium (germanium) flow process, (3) eliminated the pollution to environment of scum and sulfur dioxide flue gas, (4) indiums (germanium) rate of recovery improves more than 20%, and (5) iron resources obtains the high value utilization; Compare with No. 95110609 patented technologies, the present invention also has following advantage: (1) has solved the source of iron supply problem of scale operation, (2) source of iron and zinc source (the zinc amount in the former scum is enough) all is sharp useless and get, the sulfuric acid consumption reduces 60% approximately, thereby soft magnetism will reduce more than 20% with the production cost of coprecipitated powder, (3) the neutral leaching removed impurity elements such as most magnesium, potassium, sodium in the raw material, helps the raising of soft magnetic materials quality.
[description of drawings] process flow diagram of the present invention.
[embodiment]
Embodiment 1:
A: the neutral leaching
(1) the dense industrial sulphuric acid of 1354g is joined in the 4500ml water at leisure; (2) (composition (%) is: Zn57.21, Fe16.79, Pb0.80, Ag0.01623, In0.0997, Sn0.33, Cd0.43 to add the 1980g zinc baking sand; (3) at 70～80 ℃ of following agitation leach 2h; (4) transferring pH value with 20g zinc baking sand (composition is the same) is about 5; (5) soak slip in the filtration, and with 500ml water washing filter cake for several times; (6) immersion liquid and washing lotion are merged, immersion liquid 5720ml in getting wherein contains Zn150g/l, Fe＜0.1g/l, In＜0.001g/l; (7) with the filter cake oven dry, soak slag 997g in getting, composition (%) is: Zn28.69, Fe33.68, Ag0.0326, Pb1.60, In0.20, Sn.0.66, it is 75% that Cd0.22, slag meter soak the zinc rate, iron, indium, silver, tin, lead etc. soak slag in almost absolutely entering.
B: the high temperature peracid leaches
(1) the 1387g industry vitriol oil is joined in the 4300ml water; (2) add and to soak slag 990g, agitation leach 5h under the temperature more than 95 ℃ in above-mentioned; (3) filter height and soak slip, repeatedly with 500ml water washing filter cake; (4) immersion liquid and washing lotion are merged, high immersion liquid 4950ml, composition (g/l) is: Zn55.63, Fe63.99 (Fe wherein
+ 348.08), In0.393, Cd0.43, H
2SO
436.02; (5) with the filter cake oven dry, get the high slag 118.8g that soaks, its composition (%) is: Zn7.08, and Fe13.5, In0.028, Ag0.1353, Pb13.03, Sn5.50, slag meter leaching yield (%) is: Zn96.95, Fe95.00, In98.32.
C: manganese is mended in reduction
(1) gets above-mentioned high immersion liquid 4900ml, slowly add the sulfuration manganese ore 210g that contains Mn40%, react 0.5h at normal temperatures; (2) add iron filings 20.33g, under 70～80 ℃ temperature, react 0.5h; (3) add the ferrimanganic slag 238.4g return (composition (%) is: Fe16.32, Mn17.22); (4) the reduction slip is filtered in inspection when can not check ferric ion in the reduced liquid, and with 200ml water washing reducing slag for several times, washing lotion is incorporated in the filtrate, gets reduced liquid 5000ml, and its composition (g/l) is: Zn54.52, Fe74.49 (Fe wherein
+ 3＜0.5, Mn24.67, In0.385, Cd0.17, acidity 7.00, liquid meter manganese recovery ratio 98% removes cadmium rate 60.66%.
D: carry indium (germanium)
(1) gets above-mentioned reduced liquid 4500ml, at 20 ℃ and compare under the situation of (W/O)=4: 1, use 15%P
204+ 200
#Kerosene two-stage countercurrent extraction 2min, raffinate is 4500ml, composition (g/l) is: Zn54.52, Fe74.40, Mn24.67, Cd0.17, In0.00076, liquid meter collection indium rate 99.80%, collection iron rate is less than 0.2%, and zinc, manganese percentage extraction are almost 0; (2), use 4mol/l HCl+1.5mol/lZnCl at 20 ℃ and compare under the condition of (W/O)=1: 5
2Solution load organic phases is carried out the one-level back extraction, the time ask 2min, strip liquor 225ml, wherein contain In6.85g/l, indium back extraction ratio 99%; (3) with the indium in the zinc metal sheet displacement strip liquor, displaced liquid contains In0.137g/l, rate of displacement 98%; To the sponge indium, the total yield of indium is 95.20% from calcining.
E: primary purification
(1) gets liquid 4400ml behind the above-mentioned collection indium, transfer pH value to 3 with milk of lime at normal temperatures; (2) slowly add ammonium sulfide (containing S8%) 20ml, reaction 0.5h; (3) under 60～70 ℃, transfer pH value to 5 to stablize 10min with milk of lime again; (4) add PAM (0.1g/l) 22ml, stir the 5min after-filtration; (5) with 200ml washing filter cake for several times, washing lotion is incorporated in the filtrate, gets a clean liquid 4500ml, and composition (g/l) is: Zn53.30, and Fe72.75, Mn24.12, Cd0.0017, the liquid meter removes cadmium rate 99%.
F: deep purifying and open circuit zinc
(1) gets above-mentioned one clean liquid 4400ml, transfer pH value to 2 with Cp sulfuric acid; (2) add industrial top grade ammonium sulfate 2758g down at 30 ℃, stir 1h; (3) double salt of centrifuging at once slip gets double salt mother liquor 4200ml, and composition (g/l) is: Zn0.05, Fe7.97, Mn9.41, (NH
4)
2SO
4330; Liquid meter double salt precipitation rate (%) is respectively: Zn99.91, and Fe89.54, Mn62.76 must mix double salt 2377g in addition; (4) with many washings of pure water 6000ml double salt, must dissolve and wash away liquid 6250ml, composition (g/l) is: Fe45.09, Mn10.66, Zn11.68, (NH
4)
2SO
4156; (5) be iron and the manganese in the precipitation double salt mother liquor under 7.5 the condition with carbon ammonium 226g at normal temperature and pH value, ferrimanganic slag 205.12g, composition (%) is: Fe16.35, Mn19.60 returning neutralization trip acid next time and using.(6) molten zinc double salt 748.4g is washed at the end, contains Zn21.55%, Fe0.64%, and Fe/Zn=0.0298 soaks process or water-soluble back with making the zinc product behind the separation of iron in goethite form during this more purified zinc double salt can be opened a way and be returned, and scum returns height and soaks process.
G: co-precipitation
(1) gets the above-mentioned liquid 6000ml that dissolves and washes away, carry out dosing and co-precipitation, get coprecipitated powder 676g (being equivalent to mixed oxide 563g) by the method for No. 95110609 patents, its composition (%) is: Fe40.02, Mn9.46, Zn10.37, Si0.0026, Al0.0093, Mg0.0066, Cd0.0014, Pb0.00047, K0.00082, Na0.0022, Cl0.0043, S0.013; Coprecipitated powder foreign matter content, particularly Si, K, Na equal size are very low, and proportioning meets high magnetic permeability soft magnetism requirement (Fe: Mn: Zn=66.87: 15.81: 17.32 (wt.)); (2) above-mentioned coprecipitated powder is carried out process processing such as pre-burning, doping, ball milling, granulation, pressed compact, sintering by No. 95110609 patented methods, produce standard soft magnetism sample ring, the magnetic property measurement result is: μ i6950, Bs436mT, Br118mT, Hc6.0A/m, meets HLR7K brand product standard by Tc135 ℃.
Embodiment 2
A: the neutral leaching
(1) the 9.54kg industry vitriol oil is slowly joined in the 35L water; (2) (composition (%) is: Zn65.764, Fe2.542, Pb1.01, Cd0.942, S2.346, Ag0.01968, Ge0.0082, Ga0.00232) 9.8kg, leaching 1.5h under 75 ℃ to add zinc baking sand; (3) transfer pH value to 5.2 with zinc baking sand (composition is with (2)) 200g; (4) soak slip in the filtration, water 4L washing leaching cake several, washing lotion and filtrate merge, immersion liquid 40.2L in getting, composition (g/l) is: Zn 152.5, Cd2.17, Ge0.26mg/l; (5) filter residue oven dry is soaked slag 2.369kg in getting, and composition (%) is: Zn18.82, and Fe10.68, Cd0.29, S5.56, Ag0.08307, Pb4.26, Ge0.0342, the slag meter soaks zinc rate 93.22%, the germanium rate of recovery 98.80%.
B: the high temperature peracid leaches
(1) the dense industrial sulphuric acid of 1.356kg is slowly joined in the 7L water; (2) add and to soak slag 2.3kg in above-mentioned, at 95～100 ℃ of reaction 5h down; (3) filter height and soak slip, with 1L water washing filter cake for several times, washing lotion merges with filtrate, gets high immersion liquid 8.05L, and its composition (g/l) is: Zn51.89, Fe28.99 (Fe wherein
+ 37.17), Cd0.80, Ge65.2mg/l, H
2SO
438.08 liquid meter leaching yield (%) is: Zn96.50, Fe95.0, Ge66.75; (4) the oven dry filter cake gets the high slag 1.439kg that soaks, and composition (%) is: Ag0.1328, and Pb6.81, Ge0.0182, Zn1.05, Fe0.85 is for reclaiming the good raw material of silver.
C: manganese is mended in reduction
(1) get above-mentioned high immersion liquid 8L, add manganese powder 30.15g, react 1.5h down at 60 ℃, inspected does not go out Fe in the reduced liquid
+ 3(2) add the manganous carbonate 101.43g that contains Mn47%; (3) (wherein contain Fe15.19%, Mn19.60%) 197.69g reacts 0.5h under the situation of no longer heating to add the ferrimanganic slag that returns; (4) filtration reduction slip, with 1L water washing filter cake for several times, washing lotion and filtrate merge, and get reduced liquid 8.06L, and composition (g/l) is: Fe32.50, Mn14.46, Zn51.50, Ge64.71mg/l, H
2SO
412.41.
D: primary purification
(1) gets above-mentioned reduced liquid 8L, add tannin 13g, (2) insulation reaction 20min after transferring pH value to 2.5 and being warmed up to 60～70 ℃; (3) filter slip, for several times with 0.5L hot water wash germanium slag; (4) washing lotion and filtrate merge, and must sink liquid 8.2L behind the germanium, and composition (g/l) is: Fe31.70, Mn14.11, Zn50.24, Ge1.26mg/l, H
2SO
412.11 the liquid meter sinks germanium rate 98%; (5) with the germanium slag at 450～500 ℃ of following calcining 2h, germanium concentrate 10.08g, germanic 5.03%, to germanium concentrate, the rate of recovery of germanium is 65.41% by calcining.
E, F, G step make coprecipitated powder 512.10g (being equivalent to mixed oxide 426.50g) with embodiment 1, and its composition (%) is: Fe41.65, Mn13.98, Zn4.56, Si0.0028, Al0.022, Ca0.048, Mg0.0046, Cd0.0021, Pb0.0027, K0.00033, Na0.0024, Cl0.0052, S0.025; Coprecipitated powder impurity content is still very low, proportioning meets the requirement (Fe: Mn: Zn=69.20: 23.22: 7.58 (wt.)) of low-power dissipation soft magnetic ferrite, this coprecipitated powder is made standard rings by No. 95110609 patent ferrite technologies, the magnetic property that records is: μ i2380, Bs514mT, Br92mT, Hc15.2A/m, Tc235 ℃, P
Cv(25KHz, 200mT)/kwm
-3: 125 (25 ℃), 85 (60 ℃), 83 (80 ℃), 94 (100 ℃), P
Cv(100KHz, 200mT)/kwm
-3: 650 (25 ℃), 435 (60 ℃), 405 (80 ℃), 400 (100 ℃); Quality product surpasses P
C30Near P
C40The requirement of brand.
Claims (1)
1. slag-free zinc hydrometallurgy method is characterized in that: at first zinc baking sand is carried out neutrality and leach, make 75～95% zinc enter middle immersion liquid, separate with iron, indium, germanium, middle immersion liquid is produced electric zinc through electrolysis; In soak slag and carry out the high temperature peracid and leach, reduce high immersion liquid, and be benchmark with the iron amount according to the proportioning of Mn-Zn soft magnetic ferrite, mend manganese and with in the ferrimanganic slag that returns and free acid with the manganese raw material, from reduced liquid, extract indium or germanium then, extract indium or germanium solution afterwards and carry out primary purification and deep purifying, and the unnecessary zinc of opening a way, at last, carry out dosing to dissolveing and washing away liquid, fine tuning is the proportioning of ferrimanganic zinc wherein, carries out co-precipitation then, coprecipitated powder is made the Mn-Zn soft magnetic ferrite magneticsubstance through pre-burning, doping, ball milling, granulation, pressed compact, sintering, and its concrete processing condition are:
(1) sulfuric acid with 1.5～2.5mol/l carries out the neutrality leaching to zinc baking sand, and neutral leaching condition is: temperature is 0～100 ℃; Time is 0.5～10h; PH value=4.5～5.5; Zinc concentration is 90～160g/l in the immersion liquid;
(2) soak slag in and carry out the leaching of high temperature peracid with sulfuric acid, the high condition of soaking is: temperature is 90～100 ℃; Time is 2～10h; Liquid-solid ratio is 3～9: 1; The beginning acidacidity is 150～350g/l, and whole acidacidity is 30～100g/l;
(3) high immersion liquid reduction combines with benefit manganese and carries out, and also adds in the ferrimanganic slag that returns and free acid, reduces and mend the manganese condition to be: temperature is 0～100 ℃; Time is 0.5～10h; The reductive agent consumption is 1.05～2.05 times of theoretical amount; The manganese addition amount is for mending 1.0～1.25 times of manganese amount; Terminal point acidity 5～20g/l, reductive agent are iron filings or manganese powder, and the manganese raw material is non-oxidizing manganese salt or manganese ore or manganese powder;
(4) reduced liquid extracts indium with extraction process, reclaims germanium with the precipitator method, and collection indium condition is: temperature is 0～60 ℃; Time is 0.2～10min; Acidity is 5～20g/l; Compare: W/O=1～20; Organic phase is formed: 5～30%P
204+ No. 200 kerosene; Extraction progression is 1～6 grade; Back extraction indium condition is: temperature is 4～50 ℃; Time is 0.2～10min; Compare: W/O=1/ (2～10); Reverse-extraction agent is formed: 2～6mol/lHCl+2.5～0.5mol/lZnCl
2Back extraction progression is 1～4 grade; Heavy germanium condition is: temperature is 0～100 ℃; Time is 0.2～10h; PH value=1.5～3.5; Heavy germanium agent consumption is 20～80 times of germanium amount;
(5) solution behind extraction indium or the germanium carries out primary purification, removes the heavy metal in addition that dezincifies with sulfurization-precipitation method, removes impurity element aluminium, silicon, arsenic, antimony, titanium, tin with the neutralization precipitation method; The condition of sulfurization-precipitation method is: temperature is 0～80 ℃; Time is 0.5～10h; PH value=2～4; The vulcanizing agent consumption is 1.05～1.5 times of theoretical amount; Neutralization precipitation removal of impurities condition is: temperature is 0～80 ℃; Time is 0.5～10h; PH value=4.5～5.5; Flocculation agent is that concentration is the PAM of 0.1g/l, its consumption be after carrying indium or carrying germanium liquid 0.1～1.0%, vulcanizing agent is (NH
4)
2The neutralizing agent that S, neutralization precipitation use is a slaked lime;
(6) one clean liquid carry out deep purifying with the double salt precipitation method, and its condition is: temperature is 0～50 ℃; Time is 0.5～10h; PH value=1～3; Free (NH
4)
2SO
4Concentration is 0.2～3.0mol/l, gets double salt mother liquor and double salt; The method of open circuit zinc is: wash double salt with pure water, the ratio of iron, manganese, zinc roughly meets soft magnetic materials proportioning and remaining zinc double salt iron content, manganese seldom the time in dissolveing and washing away liquid, open circuit zinc double salt;
(7) carry out dosing, co-precipitation, pre-burning, doping, ball milling, granulation, pressed compact, sintering to dissolveing and washing away liquid, to produce Mn-Zn soft magnetic ferrite;
(8) double salt mother liquor carbon ammonium precipitation iron and manganese, its condition is: temperature is 10～100 ℃; Time is 0.2～10h; Carbon ammonium consumption is 1.05～1.3 times of theoretical amount, and gained ferrimanganic slag returns reduction and mends the manganese process, with in and free acid.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI118226B (en) * | 2005-12-29 | 2007-08-31 | Outokumpu Technology Oyj | A method for recovering rare metals in a zinc leaching process |
| CN100374589C (en) * | 2006-06-07 | 2008-03-12 | 祥云县飞龙实业有限责任公司 | Combined process for organic solvent extracting zinc and wet zinc refining |
| CN101886272B (en) * | 2010-01-08 | 2011-11-23 | 中南大学 | Method for extracting indium and preparing iron oxide by slag-free zinc hydrometallurgy of zinc concentrate |
| CN102021605B (en) * | 2010-12-27 | 2011-11-30 | 株洲科能新材料有限责任公司 | Purification and regeneration method of indium electrolysis waste liquid |
| CN102199706B (en) * | 2011-05-21 | 2013-05-15 | 南京中锗科技股份有限公司 | Method for comprehensively recovering valuable metal in diode core |
| CN102614979B (en) * | 2012-03-29 | 2014-04-23 | 中南大学 | Method for recycling iron in multilevel magnetic separation mode from zinc hydrometallurgy process |
| CN102703695A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for comprehensively recovering iron and germanium from zinc calcine containing high iron and high indium |
| CN102876888A (en) * | 2012-10-18 | 2013-01-16 | 广西华锡集团股份有限公司 | Zinc hydrometallurgy production process |
| CN103911511B (en) * | 2014-04-28 | 2016-08-17 | 北京矿冶研究总院 | Method for removing iron from zinc solution |
| CN105463212B (en) * | 2015-11-30 | 2017-06-16 | 来宾华锡冶炼有限公司 | A kind of method for producing zinc metal sheet from indium displaced liquid and reclaiming ammonium chloride |
| CN105420755B (en) * | 2015-12-28 | 2017-06-16 | 长沙赛恩斯环保科技有限公司 | The method of arsenic removing in zinc sulphate electrolyte |
| CN106086407A (en) * | 2016-06-23 | 2016-11-09 | 广东佳纳能源科技有限公司 | The recovery method of manganese in a kind of nickel cobalt leachate |
| CN110764545B (en) * | 2019-10-24 | 2020-11-27 | 中南大学 | Method for controlling pH value in neutral leaching process of zinc hydrometallurgy |
| CN114107656B (en) * | 2021-11-24 | 2023-07-21 | 白银有色集团股份有限公司 | Method for reducing consumption of zinc-manganese ore powder produced by wet process |
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