CN104233373A - Zinc smelting technology for low-zinc high-iron roasting ore by wet method - Google Patents

Zinc smelting technology for low-zinc high-iron roasting ore by wet method Download PDF

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CN104233373A
CN104233373A CN201310235080.4A CN201310235080A CN104233373A CN 104233373 A CN104233373 A CN 104233373A CN 201310235080 A CN201310235080 A CN 201310235080A CN 104233373 A CN104233373 A CN 104233373A
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zinc
iron
temperature
acid
slag
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华兆红
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WUXI SENXIN PRECISION MACHINERY FACTORY
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Abstract

The invention relates to a zinc smelting technology for a low-zinc high-iron roasting ore by a wet method. The technology comprises a leaching process, a purifying process and an electrolyzing process. The technology employs a smelting method that a wet method can solve the problem of lean impurity high-iron raw material, iron removal efficiency is high, and various production consumption and production cost are not increased. The quality of 58% qualified high-purity zinc is greater than or equal to 99.995%, and quality of 42% qualified high purity zinc is greater than or equal to 99.99%.

Description

A kind of low zinc high ferro roasted ore Zinc hydrometallurgy process
Technical field
The present invention relates to low zinc high ferro roasted ore Zinc hydrometallurgy process.
Background technology
In recent years, along with the quickening of process of industrialization, the development of zinc abstraction industry and expansion, more and more in short supply containing zinc raw material both at home and abroad, zinc raw materials quality also progressively declines, and through exploitation and the smelting of decades, Mineral resources constantly reduce and exhaustion, mine grade constantly declines, and constantly adds smelting difficulty.Under these circumstances, the raw material of low-grade high ferro is more and more concerned and uses, and therefore, the exploitation of low-grade high iron material smelting technology is imperative with research.
Later stage sixties high-iron-zinc roasted ore high temperature 20th century of high acidic oils grows up along with succeeding in developing of various method for removing iron.After adopting high temperature high acidic oils that zinc ferrite is decomposed, the iron level in infusion solution, up to about 30g/l, because the iron of this high iron solution effectively can be separated with jarosite process from zinc solution, makes roasted ore hot acid leach and is widely applied.But also there are some shortcomings, as needs consume alkali, slag iron content is low, large and the slag of the quantity of slag to store up performance bad, be unfavorable for environment protection etc., for the deficiency of conventional jarosite process, a kind of novel low stain jarosite process, namely in heavy alum process, neutralizing agent is not added, reduce the loss of valuable metal in slag and improve the pollution of alum slag to environment, its ultimate principle is the composition of adjustment solution before siderotil precipitation, make in heavy alum process, not need to add neutralizing agent and just can reach satisfied de-ferrous effect, this makes thinner by low temperature pre-neutralization or with meutral innersion liquid, or both are combined and are achieved.The iron vitriol slag be settled out, slag iron content is high, and zinc-containing metal is few, and zinc metal recovery rate is high.In order to adapt to the change of market, situation, in order to the survival and development of enterprise, make that production can continue, stable carrying out, the raw material that we also using impurity such as a large amount of zinc grades is low, iron content are higher carries out producing electric zinc, the Practice and pondering of being simultaneously correlated with, zinc roasted ore used containing zinc low be only 35%, on average only have 40%, soluble zinc rate is low reaches 62%, is on average only about 80%, wherein iron content is up to 30%, and siliceous also have about 4.5%.The roasted ore higher to these ferrous contaminants, how effectively deironing, improve the rate of recovery of zinc metal, smelting process to reduce as far as possible and become great problem pendulum in face of us to the pollution of environment, current research free of contamination deironing smelting zinc smelting technique becomes the Focal point and difficult point of zinc industry.
The present invention adopt low stain jarosite sink iron smelt zinc technology adapted to this smelting technology developing direction just, be a kind of novel smelting technology.Groped by a large amount of tests and production, management strictly controls, technique is updated, make low zinc height iron material obtain comparatively ten-strike on production high purity zinc.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of low zinc high ferro roasted ore Zinc hydrometallurgy process.The smelting process of the insurmountable poor assorted high ferro height impurity raw material of described technique hydrometallurgy, de-ironing efficiency is higher, and various production consumes, production cost does not all improve.Qualified high purity zinc 58% quality of output is >=99.995%, 42% quality is >=99.99%.
The technical solution adopted in the present invention is:
A kind of low zinc high ferro roasted ore Zinc hydrometallurgy process, its technical process comprises: leach operation, cleaning section, electrowinning process;
(1) operation is leached
To low zinc high ferro raw material production electricity zinc, obtain good economic benefit, key is the zinc metal leaching rate improving raw material, makes the impurity such as iron, silicon can discharge process in time and not allow their impacts produce simultaneously.Have employed multistage counter current volatility process hot acid leaching to low zinc height iron material, this flow process comprises 5 processes: the leaching of meutral innersion, Weak-acid leaching, hot acid, heavy alum and iron vitriol slag pickling.
A, meutral innersion
The object of meutral innersion is dissolved out the zinc metal major part of raw material, makes middle immersion liquid can meet the specification of quality of cleaning section simultaneously.After being equipped with a certain amount of copper removal to sub-sieve thick roasted ore ball mill out, liquid is ground to soak in pumping into together with the thin alum supernatant liquor in lower sand pond with fine sand, dirt sand, manganese powder afterwards during bucket carries out and is soaked, and then pump is clarified to neutral thickener.Control condition is: temperature 65-70 DEG C, time 40-60 minute, terminal pH5.0-5.2.
Meutral innersion major failure and measure have:
(1) meutral innersion bucket blocks up bucket.This mainly because zinc raw material also unreacted to sink to completely and directly barrel at the bottom of the blocking of the pump drainage mouth of pipe.The measure of fixing a breakdown has: 1. slowly add calcining, dirt sand, and calcining, dirt sand press 1:1 even 1:2 input.2. expand liquid-solid ratio, strengthen the consumption of thin alum supernatant liquor.3. thoroughly bucket slag is cleared up.
(2) meutral innersion pulp clarification is bad.Meutral innersion pulp clarification is bad, will cause high, the suspension object height of liquid iron content before purification, make purification zinc consumption excessive, even can cause the pernicious consequence that System Solution cannot normally have enough to meet the need.The main precautionary measures have: soak terminal pH5.2-5.4 in 1. controlling, can not be excessive.2. strengthen polyacrylamide injected volume, promote pulp clarification.3. soak liquid-solid ratio in expanding, strengthen thin alum supernatant liquor consumption, reduce pulp viscosity.4. discharge neutral thickener underflow in time, the front pressurized air of deslagging dispels end slag.5. soak calcining, dirt sand consumption in regulating, add by 1:2.
B, Weak-acid leaching
Weak-acid leaching is equivalent to the pre-neutralization process before heavy alum, and zinc oxide residual in neutral leaching residue is dissolved out when Weak-acid leaching.Control condition is: temperature 70 C, 1.5 hours time, and begin sour 25-30g/l, eventually sour 18-20g/l, peracid supernatant: neutral underflow=1:1.Weak-acid leaching terminal acidity can not be too high, otherwise can make to add during heavy alum calcining and carbon ammonium is too much, and cause heavy alum pulp clarification bad, be unfavorable for the recovery of zinc metal, carbon ammonium consumes also can be increased.Terminal acidity is also not easily too low, otherwise the ammonium jarosite easily generated containing indium causes the loss of indium and iron facile hydrolysis and be unfavorable for clarification.
C, high acidic oils
High acidic oils leaches also referred to as hot acid, is to utilize high temperature high acidic oils to dissolve slag at the bottom of Weak-acid leaching thickener, makes the abundant separated and dissolved of zinc ferrite wherein go out zinc metal to improve the leaching yield of zinc.In the During The Fluidized Bed Roast of zinc ore concentrate, when temperature is higher than 650 DEG C, the zinc oxide of generation and ferric oxide are combined into zinc ferrite (ZnOFe2O3), it is a kind of ferrite being insoluble in dilute sulphuric acid, insoluble under general acidic leaching condition, all stay and leach in residue, make slag contain zinc and be greater than 20%.Because zinc ferrite is dissolved in high temperature close to the character in the sulfuric acid of boiling, in production practice, adopt high acidic oils that the zinc ferrite in slag is dissolved.Its reaction is:
ZnO·Fe2O3+4H2SO4=ZnSO4+Fe2(SO4)3+4H2O
In slag, residual ZnS makes 3 valency Fe3+ reduction in solution become divalent iron and dissolve simultaneously.React as follows:
ZnS+Fe2(SO4)3=2FeSO4+ZnSO4+S
Under conventional leaching condition, zinc ferrite dissolves hardly and all enters in slag.In actual production, control hot acid leaching condition: temperature 90 DEG C, begin acid 120 ~ 130g/l, eventually acid 40 ~ 60g/l, 3 ~ 4 hours time, and in slag, zinc ferrite is molten _ and solution degree reaches more than 90%, waste liquid: low sour underflow=1:1.
Under peracid hot acid leaching condition, ZnS is destroyed thoroughly, and in leach liquor, the amount of oxygenant Fe2 (SO4) 3 must be greater than the amount of ZnS.Hot acid leaching condition controls better, and the zinc ferrite in slag is dissolved the more, and 3 valency iron ions are just higher, and it is just more thorough that ZnS is destroyed, and slag is just lower containing zinc, and metal recovery rate is just higher.
Because low zinc height iron material is low and iron, silicone content are high containing zinc, when high acidic oils, iron, silicon are also separated by leaching with zinc, cause difficulty to the press filtration of high acidic oils slag.Therefore, must to high acidic oils elaborate manipulation: 1. do not add the vitriol oil during high leaching, temperature at 65-70 DEG C, sour 35-40g/l eventually.2. reduce vitriol oil consumption, as bad in clarified, vitriol oil consumption is advisable within controlling high acidic oils liquid iron content 40g/l.3. strengthen peracid thickener polyacrylamide consumption, accelerate the clarification of ore pulp.4. dispel slag at the bottom of thickener with pressurized air, accelerate deslagging.5. add appropriate waste water, increase liquid-solid ratio, reduce pulp viscosity.
D, heavy alum process
Heavy alum is under the high temperature conditions, adds appropriate carbon ammonium in Weak-acid leaching supernatant liquor, makes iron, arsenic, antimony form the ammonium jarosite precipitation of indissoluble and remove.This method is at certain temperature and acidity, in Fe2 (SO4) 3 solution of high density, add alkalimetal ion Na+, K+, NH4+ etc., allows the ferric iron in solution generate jarosite crystal settling, simultaneously the impurity such as remove portion arsenic, antimony.In actual production, after supernatant liquor pump is squeezed into heavy alum groove, directly heat with steam, add after Fe2+ is oxidized to Fe3+ by manganese powder, when solution temperature is raised to 85 DEG C, add bicarbonate of ammonia by theoretical amount and sink alum, Controlled acidity pH=1.5, react as follows: 3Fe2 (SO4) 3+2NH4HCO3+10H2O2NH4Fe3 (SO4) 2 (OH) 6 ↓+5H2SO4+2CO2 ↓
Along with the precipitation of iron, will the sulfuric acid of equivalent be had to discharge, for keeping the condition of pH=1.5, adopt calcining (ZnO) to make neutralizing agent, calcining ZnO, Fe2O3 all participate in reaction:
3Fe2(SO4)3+5ZnO+2NH4HCO3+5H2O
2NH4Fe3(SO4)2(OH)6↓+5ZnSO4+2CO2↑
4Fe2(SO4)3+5Fe2O3+6NH4HCO3+15H2O
6NH4Fe3(SO4)2(OH)6↓+6CO2↑
The jarosite generated is insoluble in dilute sulphuric acid, is removed, thus solves the difficulty removing a large amount of iron from supernatant liquor through precipitation, washing and filtration.
In heavy alum process, acidity raises, and deironing difficulty, so in order to reduce solution iron level as far as possible, must make the precipitation process of yellow ammonium krausite carry out under relatively low acidity (pH=1 ~ 1.5); But can not pH>1.5 or higher, because it's the end pasts acidity, part iron can form ferric hydroxide precipitate, namely affects the strainability of slag, causes again zinc to lose.The precipitation of siderotil is a thermo-negative reaction, and temperature raises, and is conducive to the precipitation of siderotil, controls heavy alum temperature and be greater than 85 DEG C in actual production.Produce and experiment proof, at maintenance pH=1.5, under the condition that temperature is 85 DEG C, the heavy alum time should not be less than 3 hours.
In actual production, when heavy alum pH=1 ~ 1.5, iron is separated out with jarosite crystal, and the clarifying effect of slag is good, and press filtration performance is good, and washing effect is good, and slag is low containing zinc, and the color of slag is yellow.When heavy alum pH=1.7 ~ 2.0, iron is with ironic hydroxide, ferric subsulfate, siderotil form Precipitation, and the clarifying effect of slag, press filtration performance, washing effect inequality, slag is containing zinc higher (10% ~ 11%), and the color of slag is orange.When heavy alum pH=2.0 ~ 3.0, iron is separated out with ferric hydroxide precipitate, because solution iron content is high, defines a large amount of iron hydroxide solution, cannot concentrate, filter, and impact is produced.Control condition is: temperature 95 ~ 100 DEG C, 1 ~ 1.5 hour reaction times, acid of beginning, 15 ~ 20g/l, low sour supernatant liquor iron content 10 ~ 13g/l, eventually acid 5 ~ 10g/l, and terminal iron is less than 1g/l.Iron-removal rate more than 90%.
In heavy alum process, temperature is sufficiently, the Fe2+ brought into calcining during Weak-acid leaching supernatant liquor in considering, whether must contain Fe2+ by sampling analysis before adding carbon ammonium, if any, add appropriate manganese powder and be oxidized to Fe3+.Carbon ammonium will slowly add, and anti-blocking ammonium produces gas in high temperature one decomposes and emits bucket too much.Will control calcining speed of throwing in can not be too fast simultaneously, otherwise can make solution partial over-alkali and molten iron solution, causes pulp clarification bad.React sampling analysis Fe<1.0g/l after a hour, continue stirring reaction 30 minutes, terminal acidity control is advisable at 5 ~ 8g/l, and acidity is too high, then deironing is incomplete, and as too low, then pulp clarification is bad, difficult press filtration, affects the recovery of zinc.Carbon ammonium injected volume to be ensured in addition enough to control liquid Fe<1.0g/l after heavy alum.Carry out heavy alum with sub-sieve fine sand out as far as possible, and add barreled polyacrylamide solution on heavy alum thickener, be beneficial to the clarified separation of ore pulp.
E, pickling
The object of pickling is the calcining dropped in heavy alum process wherein out not improved the rate of recovery of zinc metal by zinc pickling under the condition of peracid of leaching.Control condition is: begin acid 100 ~ 120g/l, temperature 95 DEG C, 2 ~ 3 hours time, vitriol oil 1m3, heavy alum underflow: waste liquid=1:1.Allocate appropriate waste water into when second pickling, be beneficial to press filtration to reduce pulp viscosity, reduce the zinc metal that iron vitriol slag is taken away.
(2) cleaning section
Meutral innersion liquid impurity is more, meet electrolysis process requirement, must carry out purification and impurity removal to it.Adopt reverse antimonic salt method purification process, be divided into: copper removal, except cadmium, except cobalt nickel and deep purifying four sections.
A, copper removal
Use the roasted ore that some cuprics are higher, when other zinc baking sands of arranging in pairs or groups leach, meutral innersion liquid cupric, at 800 ~ 1200g/l, has recovery value.In addition, middle immersion liquid is chloride reaches 1200mg/l, therefore must carry out dechlorination process.Existing centering leach liquor adopts independently except copper process, is also a dechlorination operation simultaneously.After copper is cemented out with elemental form by zinc powder, the chlorine in copper and solution forms cuprous chloride and is formed and precipitate and reach dechlorination effect.Control condition is: temperature 50 C, 1 hour time, theoretical zinc powder consumption Zn:Cu=1:1.After operation controls copper removal, liquid cupric is at below 100mg/l, prevents cupric ion from losing to reclaiming except cadmium operation.
B, except cadmium
Cadmium content in meutral innersion liquid, at about 100mg/l, is easy to by zinc dust precipitation out.Control condition is: temperature 60 C, 1 hour time, pH4.6 ~ 5.2.Mainly throw in the deep purifying slag of four purifications during displacement cadmium, utilize wherein unnecessary unreacted zinc powder to consume to reduce purification zinc powder.As removed containing cadmium is high-leveled and difficult in solution, then separately add appropriate zinc powder, after controlling to remove cadmium, in liquid, cadmium content is less than 100mg/l.
C, except cobalt nickel
Content is at 5 ~ 10mg/l in meutral innersion liquid for cobalt, and nickel is at about 3 ~ 5mg/l, and content is not high, but is difficult to removing.High temperature antimonic salt method is adopted to carry out except cobalt nickel.Using copper sulfate, stibium trioxide powder as activator at 85 DEG C, the overvoltage of cobalt nickel reduce after with zinc dust precipitation out.Control condition is: temperature 85 DEG C, 1 hour time, and pH4.6 ~ 5.2, zinc powder consumption is every barrel and adds 30kg.
D, deep purifying
Mainly in order to ensure electrolysis new liquid quality, the impurity such as copper, cadmium, nickel, germanium of the rear liquid remnants of anti-three purifications thoroughly removes deep purifying.Control condition is: temperature 90 DEG C, 1 hour time, and pH5.2 ~ 5.4, zinc powder consumption is every barrel of 200kg.When deep purifying operates, drop into appropriate potassium permanganate, make the ferrous iron in solution, arsenic, antimony with ironic hydroxide hydrolysis absorption removing.After deep purifying, liquid is extracted in stationary tank and deposits, and regularly carry out press filtration to remove the impurity such as calcium, magnesium, iron, cobalt, nickel, germanium, arsenic, antimony wherein precipitated to slag at the bottom of stationary tank, filter-press residues returns the zinc metal leaching and reclaim wherein.
(3) electrowinning process
During electrolysis adopts, current density is produced in acid, electrolysis waste solution Zn40 ~ 50g/l, H2SO4160 ~ 200g/l, sour zinc than 3.5 ~ 4.5, current density 400 ~ 550A/m2.As the crux operation that electric zinc is produced, electrolysis workshop section must strictly regulate operation, and strengthening groove manages: 1. periodic cleaning electrolyzer, and the slotting cycle is one month.2. the negative plate remaining zinc metal sheet can not go up groove.3. the negative plate without plastic insulation bar can not go up groove.4. the negative plate of corrosion hole is had can not to go up groove.5. insert timely school plate after plate at every turn, prevent cathode-anode plate contact short circuit.6. keep each electrolyzer normal discharge, stop to block up, Pu phenomenon.7. normal groove temperature is controlled within the scope of 38 ~ 42 DEG C.If system chlorion is higher, in the fluctuation of 800 ~ 1300g/l scope, therefore, for ensureing zinc metal sheet quality, Strontium carbonate powder amount is added comparatively greatly, consumption 250kg every day.Gained electrolytic zinc plate surface crystallization is fine and close, and without big particle, without tiny pin hole, quality is good, leaded below 0.0030%.
The present invention has the following advantages:
(1) the present invention carries out process optimization, equipment de-sign and reasonable disposition in conjunction with low zinc height iron material composition feature, to low stain volatility process hot acid leaching process study, obtain the meutral innersion in low zinc high ferro roasted ore leaching process, Weak-acid leaching, hot acid leach, heavy alum and iron vitriol slag pickling, a series of key technology such as the purification of dense, zinc liquid and deep purifying, filtration, electrolysis, Optimizing Process Parameters etc.; Solve the Quantitative Separation of zinc and iron, copper, lead, cadmium, cobalt, nickel and other impurity in sulfuric acid medium, after making process, solution of zinc sulfate reaches the requirement of production electrolysis high purity zinc.
(2) quantity of slag reduces, greatly improves the pollution of iron vitriol slag to environment.Aborning, before siderotil precipitation, the composition of adjustment solution, makes not need to add neutralizing agent in precipitation process and just can reach satisfied de-ferrous effect, make thinner by low temperature pre-neutralization or with meutral innersion liquid, or both are combined and are achieved.Therefore, the great advantage of this low stain jarosite process does not need to add neutralizing agent, precipitable go out iron vitriol slag, the quantity of slag is few, and iron content is high, few containing valuable metals such as zinc, reduces the pollution level to environment.
(3) advantages such as low stain jarosite process is comparatively advanced method for removing iron, and it has, and production efficiency is high, slag is low containing zinc, the Metal smelting rate of recovery is high, production cost is low, environmental pollution is little.
(4) smelting process of the insurmountable poor assorted high ferro height impurity raw material of the present invention standard law hydrometallurgy, de-ironing efficiency is higher, and various production consumes, production cost does not all improve.
(5) qualified high purity zinc 58% quality of output is >=99.995%, 42% quality is >=99.99%.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment one
A kind of low zinc high ferro roasted ore Zinc hydrometallurgy process, its technical process comprises: leach operation, cleaning section, electrowinning process;
The main component of described low zinc high ferro roasted ore is: Zn, 35-45%; Fe, 28-31%; SiO2,3.5-4.9%, soluble zinc rate 62-86%.
(1) operation is leached
Have employed multistage counter current volatility process hot acid leaching to low zinc height iron material, this flow process comprises 5 processes: the leaching of meutral innersion, Weak-acid leaching, hot acid, heavy alum and iron vitriol slag pickling.
A, meutral innersion
Control condition is: temperature 65-70 DEG C, time 40-60 minute, terminal pH5.0-5.2.
B, Weak-acid leaching
Control condition is: temperature 70 C, 1.5 hours time, and begin sour 25-30g/l, eventually sour 18-20g/l, peracid supernatant: neutral underflow=1:1.
C, high acidic oils
High acidic oils condition: temperature 90 DEG C, begin acid 120 ~ 130g/l, eventually acid 40 ~ 60g/l, 3 ~ 4 hours time, and in slag, zinc ferrite is molten _ and solution degree reaches more than 90%, waste liquid: low sour underflow=1:1.
D, heavy alum process
After supernatant liquor pump is squeezed into heavy alum groove, directly heat with steam, add after Fe2+ is oxidized to Fe3+ by manganese powder, when solution temperature is raised to 85 DEG C, add bicarbonate of ammonia by theoretical amount and sink alum, Controlled acidity pH=1.5, along with the precipitation of iron, will the sulfuric acid of equivalent be had to discharge, for keeping the condition of pH=1.5, adopt calcining (ZnO) to make neutralizing agent, calcining ZnO, Fe2O3 all participate in reaction; The jarosite generated is insoluble in dilute sulphuric acid, is removed, thus solves the difficulty removing a large amount of iron from supernatant liquor through precipitation, washing and filtration.
Control condition is: temperature 95 ~ 100 DEG C, 1 ~ 1.5 hour reaction times, acid of beginning, 15 ~ 20g/l, low sour supernatant liquor iron content 10 ~ 13g/l, eventually acid 5 ~ 10g/l, and terminal iron is less than 1g/l.Iron-removal rate more than 90%.
E, pickling
Control condition is: begin acid 100 ~ 120g/l, temperature 95 DEG C, 2 ~ 3 hours time, vitriol oil 1m3, heavy alum underflow: waste liquid=1:1.Allocate appropriate waste water into when second pickling, be beneficial to press filtration to reduce pulp viscosity, reduce the zinc metal that iron vitriol slag is taken away.
(2) cleaning section
Adopt reverse antimonic salt method purification process, be divided into: copper removal, except cadmium, except cobalt nickel and deep purifying four sections.
A, copper removal
Control condition is: temperature 50 C, 1 hour time, theoretical zinc powder consumption Zn:Cu=1:1.After operation controls copper removal, liquid cupric is at below 100mg/l, prevents cupric ion from losing to reclaiming except cadmium operation.
B, except cadmium
Control condition is: temperature 60 C, 1 hour time, pH4.6 ~ 5.2.Mainly throw in the deep purifying slag of four purifications during displacement cadmium, utilize wherein unnecessary unreacted zinc powder to consume to reduce purification zinc powder.As removed containing cadmium is high-leveled and difficult in solution, then separately add appropriate zinc powder, after controlling to remove cadmium, in liquid, cadmium content is less than 100mg/l.
C, except cobalt nickel
Control condition is: temperature 85 DEG C, 1 hour time, pH4.6 ~ 5.2.
D, deep purifying
Control condition is: temperature 90 DEG C, 1 hour time, pH5.2 ~ 5.4.When deep purifying operates, drop into appropriate potassium permanganate, make the ferrous iron in solution, arsenic, antimony with ironic hydroxide hydrolysis absorption removing.After deep purifying, liquid is extracted in stationary tank and deposits, and regularly carry out press filtration to remove the impurity such as calcium, magnesium, iron, cobalt, nickel, germanium, arsenic, antimony wherein precipitated to slag at the bottom of stationary tank, filter-press residues returns the zinc metal leaching and reclaim wherein.
(3) electrowinning process
During electrolysis adopts, current density is produced in acid, electrolysis waste solution Zn40 ~ 50g/l, H2SO4160 ~ 200g/l, sour zinc than 3.5 ~ 4.5, current density 400 ~ 550A/m2.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (4)

1. a low zinc high ferro roasted ore Zinc hydrometallurgy process, its technical process comprises: leach operation, cleaning section, electrowinning process;
(1) operation is leached
Have employed multistage counter current volatility process hot acid leaching to low zinc height iron material, this flow process comprises 5 processes: the leaching of meutral innersion, Weak-acid leaching, hot acid, heavy alum and iron vitriol slag pickling;
A, meutral innersion
Control condition is: temperature 65-70 DEG C, time 40-60 minute, terminal pH5.0-5.2;
B, Weak-acid leaching
Control condition is: temperature 70 C, 1.5 hours time, and begin sour 25-30g/l, eventually sour 18-20g/l, peracid supernatant: neutral underflow=1:1;
C, high acidic oils
High acidic oils condition: temperature 90 DEG C, begin acid 120 ~ 130g/l, eventually acid 40 ~ 60g/l, 3 ~ 4 hours time, and in slag, zinc ferrite is molten _ and solution degree reaches more than 90%, waste liquid: low sour underflow=1:1;
D, heavy alum process
Control condition is: temperature 95 ~ 100 DEG C, 1 ~ 1.5 hour reaction times, acid of beginning, 15 ~ 20g/l, low sour supernatant liquor iron content 10 ~ 13g/l, eventually acid 5 ~ 10g/l, and terminal iron is less than 1g/l; Iron-removal rate more than 90%;
E, pickling
Control condition is: begin acid 100 ~ 120g/l, temperature 95 DEG C, 2 ~ 3 hours time, vitriol oil 1m3, heavy alum underflow: waste liquid=1:1;
(2) cleaning section
Adopt reverse antimonic salt method purification process, be divided into: copper removal, except cadmium, except cobalt nickel and deep purifying four sections;
A, copper removal
Control condition is: temperature 50 C, 1 hour time, theoretical zinc powder consumption Zn:Cu=1:1; After operation controls copper removal, liquid cupric is at below 100mg/l, prevents cupric ion from losing to reclaiming except cadmium operation;
B, except cadmium
Control condition is: temperature 60 C, 1 hour time, pH4.6 ~ 5.2;
C, except cobalt nickel
Control condition is: temperature 85 DEG C, 1 hour time, pH4.6 ~ 5.2;
D, deep purifying
Control condition is: temperature 90 DEG C, 1 hour time, pH5.2 ~ 5.4;
(3) electrowinning process
During electrolysis adopts, current density is produced in acid, electrolysis waste solution Zn40 ~ 50g/l, H2SO4160 ~ 200g/l, sour zinc than 3.5 ~ 4.5, current density 400 ~ 550A/m2.
2. technique according to claim 1, allocates appropriate waste water into when second pickling, is beneficial to press filtration to reduce pulp viscosity, reduces the zinc metal that iron vitriol slag is taken away.
3. technique according to claim 1, mainly throws in the deep purifying slag of four purifications during displacement cadmium, utilize wherein unnecessary unreacted zinc powder to consume to reduce purification zinc powder; As removed containing cadmium is high-leveled and difficult in solution, then separately add appropriate zinc powder, after controlling to remove cadmium, in liquid, cadmium content is less than 100mg/l.
4. technique according to claim 1, when deep purifying operates, drops into appropriate potassium permanganate, makes the ferrous iron in solution, arsenic, antimony with ironic hydroxide hydrolysis absorption removing; After deep purifying, liquid is extracted in stationary tank and deposits, and regularly carry out press filtration to remove the impurity such as calcium, magnesium, iron, cobalt, nickel, germanium, arsenic, antimony wherein precipitated to slag at the bottom of stationary tank, filter-press residues returns the zinc metal leaching and reclaim wherein.
CN201310235080.4A 2013-06-13 2013-06-13 Zinc smelting technology for low-zinc high-iron roasting ore by wet method Pending CN104233373A (en)

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CN105568317A (en) * 2015-12-31 2016-05-11 株洲冶炼集团股份有限公司 High-grade zinc electrolysis preparing method and application thereof
CN105586496A (en) * 2016-03-29 2016-05-18 河南国玺超纯金属材料有限公司 Process for industrial production of high-purity zinc
CN106893872A (en) * 2016-12-27 2017-06-27 河南豫光锌业有限公司 A kind of method of zinc hydrometallurgy deeply purifying and removing cobalt
CN107010673A (en) * 2017-04-18 2017-08-04 中国恩菲工程技术有限公司 The method for preparing the mixture of hydration siderotil and ferric subsulfate
CN108913893A (en) * 2018-07-29 2018-11-30 桂林理工大学 A kind of zinc hydrometallurgy zinc powder consumption-reducing method
CN109295320A (en) * 2018-11-14 2019-02-01 云南祥云飞龙再生科技股份有限公司 A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material
CN110129585A (en) * 2019-06-06 2019-08-16 何耀 A kind of method of Purification of zinc sulfate solution removing heavy metals
CN114107656A (en) * 2021-11-24 2022-03-01 白银有色集团股份有限公司 Method for reducing consumption of zinc-manganese ore powder produced by wet smelting
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CN105568317A (en) * 2015-12-31 2016-05-11 株洲冶炼集团股份有限公司 High-grade zinc electrolysis preparing method and application thereof
CN105586496A (en) * 2016-03-29 2016-05-18 河南国玺超纯金属材料有限公司 Process for industrial production of high-purity zinc
CN106893872A (en) * 2016-12-27 2017-06-27 河南豫光锌业有限公司 A kind of method of zinc hydrometallurgy deeply purifying and removing cobalt
CN107010673A (en) * 2017-04-18 2017-08-04 中国恩菲工程技术有限公司 The method for preparing the mixture of hydration siderotil and ferric subsulfate
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CN108913893A (en) * 2018-07-29 2018-11-30 桂林理工大学 A kind of zinc hydrometallurgy zinc powder consumption-reducing method
CN109295320A (en) * 2018-11-14 2019-02-01 云南祥云飞龙再生科技股份有限公司 A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material
CN110129585A (en) * 2019-06-06 2019-08-16 何耀 A kind of method of Purification of zinc sulfate solution removing heavy metals
CN114107656A (en) * 2021-11-24 2022-03-01 白银有色集团股份有限公司 Method for reducing consumption of zinc-manganese ore powder produced by wet smelting
CN114107660A (en) * 2021-11-24 2022-03-01 白银有色集团股份有限公司 High-germanium raw material zinc hydrometallurgy process
CN115305347A (en) * 2022-08-27 2022-11-08 苏州金之翼新材料科技有限公司 Method for preparing zinc ferrite from neodymium iron boron waste
CN115369237A (en) * 2022-09-21 2022-11-22 云南驰宏资源综合利用有限公司 Method for balancing production and consumption of manganese ions in zinc smelting
CN115369237B (en) * 2022-09-21 2023-08-22 云南驰宏资源综合利用有限公司 Method for balancing production consumption of zinc smelting manganese ions
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