CN109295320A - A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material - Google Patents
A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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Abstract
The present invention relates to a kind of methods of normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material, and leaded high iron content zinc sulphide zinc oxide mix material is leached using " middle leaching → acidleach → washery slag " technique, uses MnO2As oxidant, by leach in ore pulp it is ferrous oxidising be ferric iron, catalyst is utilized iron as under effect of sulfuric acid and leaches zinc sulphide, zinc enters solution with zinc sulphate, and sulphur is formed with simple substance and precipitated, thus Leaching Zinc, it can Leaching Zinc, sulfuric acid consumption be low at normal temperature.
Description
Technical field
The present invention relates to a kind of methods of normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material.
Background technique
Zinc sulphide material directly leaches, and sulphur is recycled with simple substance form, has fundamentally avoided SO2Pollution problem.From 20 generation
It is that pressure oxidation is leached, but extraction temperature is higher than 120 DEG C more that discipline has been applied at most since the eighties, and pressure reaches 1600KPa, needs
It to be carried out in autoclave, it is big that there are equipment investments, and equipment material requires height, and safe operation requires the defects of stringent.It carries on the back herein
Under scape, the normal pressure leaching of zinc sulfide concentrates comes into being, the normal pressure leaching that the world uses at present, mainly using oxygen to nearly boiling
Iron in the leachate of (being greater than 90 DEG C) is aoxidized, and utilizing iron as catalyst enables zinc sulphide to leach, and method has leaching
The time is longer (being greater than 7 hours) out, requires height, oxygen demand big oxygen purity, and being blown into a large amount of oxygen makes to leach ore pulp heat
Lose larger, to maintain that a large amount of steam need to be added greater than 90 DEG C of extraction temperature, energy consumption is higher, the lower disadvantage of zinc leaching rate,
And the iron in mineral can be largely leached, sulfuric acid consumption is high, and the processing cost of subsequent iron is high, and high integrated treatment cost makes this
Method is difficult to promote and apply.
Summary of the invention
The object of the present invention is to provide a kind of at low cost, can Leaching Zinc at normal temperature, sulfuric acid consumption is low from containing
The method of normal pressure leaching zinc in the high iron content zinc sulphide zinc oxide mix material of lead.
The technical solution adopted by the present invention to solve the technical problems is:
A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material, by leaded high iron content sulphur
Change zinc zinc oxide mix material to be leached using " middle leaching → acidleach → washery slag " technique, uses MnO2As oxidant, will soak
Out in ore pulp it is ferrous oxidising be ferric iron, under effect of sulfuric acid using ferric iron as catalyst leaching zinc sulphide, zinc with
Zinc sulphate enters solution, and sulphur is formed with simple substance and precipitated, so that Leaching Zinc, makes the leaching of zinc reach maximization, passes through control
Temperature, sulfuric acid concentration and the extraction time of leaching process, control the leaching of iron, not only ensure that sufficient catalytic iron but also have been greatly reduced
It is subsequent to remove iron cost.The leaching of zinc sulphide reaches 90% or more, and manganese powder dosage is about 1.1~1.2 times of theoretical amount, than routine
It smelts and saves 20%, key reaction is as follows:
ZnS+2Fe3++SO4 2-→ZnSO4+2Fe2++S0↓
2FeSO4+MnO2+2H2SO4→Fe2(SO4)3+MnSO4+2H2O
Zinc oxide in material directly generates zinc sulfate with sulfuric acid reaction, passes through control temperature and solution sulfuric acid concentration ferrous acid
Zinc is also dissolved out, and chemical equation is as follows:
ZnO+H2SO4→ZnSO4+H2O
ZnO·Fe2O3+4H2SO4→ZnSO4+Fe2(SO4)3+4H2O。
This method is suitable for the solution system Leaching Zinc that potassium, sodium, ammonia content are more than 30g/L simultaneously, controls in leaching process
20g/L or so sulfuric acid concentration inhibits siderotil to generate, and leaches the solution after completing solid-liquor separation, and a small amount of material can be added and neutralize
PH value is carried out with Jarosite process except iron to 1.5 or so, can also remove iron using the neutralizing hydrolysis precipitation method.
The leaded high iron content zinc sulphide zinc oxide mix material contains zinc 10.37% as a preferred technical solution, wherein
Vulcanizing Zn content is 6.56%, iron content 6.80%, and contains 12.39% lead.
The middle leaching is neutral continuous leaching as a preferred technical solution, and wherein extraction time is 1.5 hours, and liquid is solid
Than being 3/1~20/1, extraction temperature is 38~45 DEG C, and leach endpoint pH: 5.0~5.2, MnO2 input amount are dry mine quality
0.5%~7%, and solution iron content is less than 10mg/L.
As improvement to above-mentioned technical proposal, the neutral leaching residue send acidic leaching after carrying out pulp using slag washing liquid
Workshop section
The acidleach is acidic leaching as a preferred technical solution, and extraction time is 2.5~3 hours, liquid-solid ratio 3/
1~5/1, extraction temperature is 50~80 DEG C, and leaching process and terminal sulfuric acid concentration are 10~25g/L, MnO2Input amount is neutrality
The 0%~5% of leached mud dry mass.
As improvement to above-mentioned technical proposal, the acidic leaching residue carries out pulp using low zinc solution or clear water and washes
It washs.
The washery slag time as a preferred technical solution, are as follows: 30~45 minutes, liquid-solid ratio was 3/1~4/1, washery slag temperature
Degree is room temperature, and filter-press residues are aqueous less than 35%, and slag washing liquid is less than 10g/L containing zinc.
As improvement to above-mentioned technical proposal, the slag after the washery slag sends receipts lead back to, and slag washing liquid a part is recycled,
Another part returns to acidic leaching.
Below with reference to specific experiment, invention is further explained:
1, the determination of process conditions
Because the potassium in raffinate, sodium, ammonia radical ion total amount are up to 25g/L or so, the temperature in control leaching process should be passed through
Degree, sulfuric acid concentration, extraction time reduce siderotil generation to the greatest extent, and quantity of slag increase is avoided to cause the dilution of lead in slag, refine lead to wet process
Bring difficulty.And then in situation similar in existing production manganese powder consumption, make leaching after the completion of solution divalent concentration of iron
Maintain lower numerical value, it is ensured that filtered solution can carry out the heavy iron of jarosite process, also can choose and be sent to smoke of steel factory
Heavy iron is hydrolyzed in middle leaching section.
2.1 zinc influence of extraction factors
The principal element for influencing zinc leaching rate has: ferric ion concentration in temperature, acidity, extraction time and solution.It is real
Test and 500g raw material (calculating dry mine be 355g) taken to be added in 1.3L raffinate (liquid-solid ratio about 4:1), by control concentrated sulfuric acid dosage,
Extraction time and manganese powder input amount, comparison different acidity leach duration and solution ferric ion concentration to the shadow of zinc leaching rate
It rings, generates control leaching pH < 0.5 to reduce iron vitriol slag.Because steam is insufficient in existing production, it is unable to ensure higher leaching temperature
Degree, experiment respectively with regard under the conditions of 50 DEG C, 60 DEG C, 70 DEG C, zinc, iron leaching situation compare, raw material and raffinate analysis
As shown in table 1, table 2.
1 feedstock analysis of table
| Element | H2O | Zn(complete) | ZnS | ZnSO4 | Pb | Fe(complete) | FeIt (can) | Mn | K | Na | Cl |
| Content (%) | 29.09 | 10.37 | 6.56 | 1.37 | 12.39 | 6.80 | 5.49 | 1.71 | 2.68 | 2.72 | 3.36 |
The analysis of 2 raffinate of table
(1) influence of the temperature to zinc leaching rate
It is leached 2 hours under the conditions of 50 DEG C, 60 DEG C, 70 DEG C, eventually 20~30g/L of acid, solution ferric ion concentration 3~
When 4g/L, not molten Zn content is respectively 3.19%, 2.65%, 2.07% after deducting zinc sulfate in leached mud, as shown in Table 1 raw material
In not molten Zn content be 9%, not molten zinc part leaching rate is respectively 64.56% (50 DEG C), 70.56% (60 DEG C), 77.00%
(70℃).It can be seen that eventually in acid situation close with ferric ion concentration, zinc leaching rate is warm with leaching in identical extraction time
Degree increases and increases, and amplification is 6~7% under conditions present.
(2) influence of acidity and time to zinc leaching rate
Ferric ion content 7g/L or so in the solution under the conditions of 70 DEG C of extraction temperature, has been respectively compared whole acid 15g/
L, when 32g/L, 62g/L or so, after leaching 2.5 hours and 3 hours, not molten Zn content and leaching rate in leached mud are analyzed, such as table 3
It is shown:
3 different acidity of table and time zinc leach
As it can be seen that improving zinc leaching rate with acid eventually also has growth as the extension zinc leaching rate of extraction time is in growing trend,
But concentrated sulfuric acid consumption amplification is up to 20% or more, and the bigger operating environment of the concentrated acid amount of filling into is more severe in actual production operation, and
As the leaching rate that acid improves iron eventually is substantially increased (described below), causes production cost to increase, comprehensively consider lower actual production
When end acid should control in 20g/L or so, be advisable within extraction time 3 hours.
(3) influence of the ferric ion to zinc leaching rate
Under the conditions of 60 DEG C, liquid-solid ratio 4:1 is leached 2 hours, and by adjusting manganese powder dosage, control is leached when completing three in solution
Valence iron content observes influence of the ferric ion to zinc leaching rate.Under the conditions of 70 DEG C, liquid-solid ratio 4:1 leaching 3 hours, really
Determine ferric iron optimum content in solution, as shown in table 4:
Influence of 4 ferric ion of table to zinc leaching rate
Analysis is it is found that be added without when manganese powder that not molten zinc leaching rate is only 44.45% in raw material, as manganese powder is added in solution
Ferric iron content increases, and zinc leaching rate sharply rises, and slowdown in growth when ferric iron content reaches 6g/L acts on when more than 7g/L
Become unobvious.
2.2 iron influence of extraction factors
The leaching of zinc sulphide needs ferric iron as catalyst, but leaches excessive iron and will lead to acid consumption and except iron cost increases
Add, it is therefore necessary to temperature, acidity, extraction time are investigated, the influence to iron concentration in the material leachate is analyzed, with
Find best immersion zinc condition.
(1) influence of the temperature to iron concentration in solution
It is leached 2 hours under the conditions of 50 DEG C, 60 DEG C, 70 DEG C by 4:1 liquid-solid ratio, eventually acid 25g/L or so, iron content is total in solution
Amount is respectively 4.04g/L, 4.85g/L, 7.63g/L, needs 6~7g/L ferric ion since zinc sulphide leaches, and 70 DEG C
Iron content in leachate is the most suitable.
(2) influence of acidity and time to iron concentration in solution
To determine that suitable leaching is sour eventually and further verifies above-mentioned best galvanizing time, 4:1 liquid is pressed under the conditions of 70 DEG C
It is leached 1.5,2.5,3 hours respectively Gu comparing, iron content when comparing 30g/L and 60g/L end acid in solution, experimental result such as table 5
It is shown:
5 70 DEG C of different acidities of table and time zinc leach
The iron content of leachate improves and is incremented by extension at any time and acid eventually, and the iron that 30g/L is leached when whole sour is more than to need
The amount of asking is few, needed for then largely exceeding when 60g/L is sour eventually, increases on foot except iron cost, therefore the whole acid of leaching process should control
30g/L is hereinafter, the whole acid leached according to zinc above leaches situation should be ideal in 20g/L or so.From current production
From the point of view of the leaching situation of experiment material, 80% or more iron can be leached in the material over time, 3~4:
Solution iron content may be up to 30g/L or so under 1 liquid-solid ratio, so extraction time must control within 3 hours.
2.3 optimum conditions are determining and leach situation
In conclusion the best leaching condition of the material are as follows: 70 DEG C of extraction temperature, extraction time 2.5 to 3.0 hours, leaching
Acid 20g/L or so narrows down to liquid-solid ratio to meet the requirement to ferric iron content in solution again in the less iron of leaching eventually out
3:1, manganese powder input amount are about raw material ZnS and MnO21.3 times of reaction theory amount.500g mine is taken to put into 950mL by conditions above
Acidleach is carried out in raffinate, acid leaching residue takes 400g using 500mL tap water pulping and washing 30 minutes after filtering, and experimental data is as follows:
Tailings and current production slag analysis (%) after 6 acid leaching residue of table, washing
| Title | Time | H2O | Zn(complete) | ZnS | ZnSO4 | Pb | Fe(complete) | FeIt (can) | Mn | K | Na | Dry slag (g) |
| 1# acid leaching residue | 2.5h | 39.47 | 4.25 | 1.07 | 2.63 | 11.24 | 4.75 | 3.50 | 2.69 | 2.35 | 5.69 | 362.57 |
| 2# acid leaching residue | 3.0h | 36.11 | 4.06 | 0.79 | 2.56 | 10.14 | 4.45 | 3.29 | 2.74 | 2.28 | 5.07 | 411.58 |
| 1# tailings | 0.5h | 41.18 | 2.79 | 1.38 | 0.70 | 12.70 | 4.80 | 3.10 | 0.88 | 2.24 | 1.86 | 215.28 |
| 2# tailings | 0.5h | 40.68 | 2.64 | 1.18 | 0.70 | 12.42 | 4.90 | 3.69 | 0.91 | 2.16 | 2.40 | 203.58 |
7 pickle liquor of table and slag washing liquid analysis
8 zinc metal balance of table and leaching rate calculate
Manganese powder consumption (80g) is put into raw material dry measure (355g) 22.5%, in leachate divalent iron content be 1.5~
2g/L, from the point of view of ferrous iron situation in table 4, when manganese powder investment ratio reaches 25%, divalent iron content is respectively less than 500mg/L,
The heavy iron of autunezite or the heavy iron of neutralizing hydrolysis can directly be carried out.
During the experiment it was found that washery slag time optimal is 30 minutes or so, the too long washery slag time can make washing lotion
Middle iron content increases, and slag containing zinc without significant change, when being applied to actual production only need to by acid leaching residue pulp it is complete after can mistake
Filter is not necessarily to additional washery slag workshop section.
2, conclusion and technical flow design
(1) 160 tons of the dry measure material is now handled in production, manganese powder usage amount is 40~50 tons, and according to this experiment side
Case handles the material of same amount, and manganese powder usage amount is 36~40 tons, slightly saves.
(2) the final tailings of this experimental program is leaded almost equal with the sulfuric acid lead skim that now produces, and main cause is to improve
The leaching rate of zinc effectively controls the leaching of iron, and most both finishing slag rates are close.
(3) experiment most finishing slag reduces about 50% containing zinc compared with producing tailings, effectively raises the rate of recovery of zinc.
(4) it is leached for effectively control iron, had not only guaranteed enough catalytic irons but also do not exceeded largely, and caused that the production cost increases,
It leaches acidity and the time is emphasis, the leaching that should control 20g/L or so in process of production is sour eventually, and highest must not exceed 35g/L,
Extraction time guarantees that too long extraction time, which will lead to, produces this meaningless increase by 2.5 hours or so.
(5) manganese powder investment must in time, and without ferric iron as catalyst, the normal pressure leaching of zinc sulphide can not be carried out.
(6) if for leaching the material without valuable metals such as lead, indiums, leaching endpoint pH can be controlled 1.0
The time is appropriately extended in left and right, removes most of iron in the form of siderotil, reaches the progress synchronous with heavy iron of leaching zinc.If steam fills
Temperature is increased to 90 DEG C by foot, and the leaching of zinc ferrite will more completely, and siderotil forms speed also faster.
(7) when high material containing indium will extract production indium, the input amount of manganese powder should be adjusted, reduces solution after the completion of leaching as far as possible
In ferric iron, because the ferric iron in solution can reduce the extraction yield of indium and increase significantly organic iron cost of being divided by.
(8) if raw material iron content is reduced to 1.5% or so, it can extend extraction time by reducing liquid-solid ratio, improve temperature
Degree and acidity leach zinc sulphide and zinc ferrite thoroughly, and tailings can be more much lower than current material containing zinc.
(9) the experimental results showed that, zinc sulphide leaching is not high to acidity requirements, it is contemplated that therefrom soaking in production application
Manganese powder is added in section, and more conducively the leaching of zinc sulphide and middle supernatant iron reach extraction and require, but to give special heed in middle leaching thickening pond
Clear quality, in order to avoid fine grained MnO2It is taken away by solution, causes to waste.
Beneficial effects of the present invention:
The method of the present invention provides a kind of method of Leaching Zinc from leaded high iron content zinc sulphide zinc oxide mix material, normal
Pressure is leached, and leaches acidity (sulfuric acid concentration can be down to 10g/L) and temperature (down to 50 DEG C) requires lower, operating condition peace
Complete reliable, energy consumption is lower, environmental-friendly, and the leaching effect of zinc sulphide is prominent, and can effectively inhibit the leaching of iron, using valence
The relatively low pyrolusite of lattice reduces about 30% than conventional method as oxidant, comprehensive production cost.Fly applied to auspicious cloud
Dragon regeneration Science and Technology Co., Ltd.'s wet process Zn system, production procedure is stable, and indices achieve the desired results, and lead passes through
Wet process refining lead technology is effectively recycled, and the maximization of zinc resource utilization rate has been reached, and is that a kind of safely cleaning of low energy consumption is raw
Production technology.
By adopting the above-described technical solution, one kind normal pressure leaching from leaded high iron content zinc sulphide zinc oxide mix material
The method of zinc leaches leaded high iron content zinc sulphide zinc oxide mix material using " middle leaching → acidleach → washery slag " technique,
Use MnO2As oxidant, by leach in ore pulp it is ferrous oxidising be ferric iron, made under effect of sulfuric acid using ferric iron
Zinc sulphide is leached for catalyst, zinc enters solution with zinc sulphate, and sulphur is formed with simple substance and precipitated, thus Leaching Zinc, Ke Yi
Leaching Zinc under room temperature, sulfuric acid consumption are low.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is process flow chart of the invention.
Specific embodiment
A method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material, by leaded high iron content sulphur
Change zinc zinc oxide mix material to be leached using " middle leaching → acidleach → washery slag " technique, uses MnO2As oxidant, will soak
Out in ore pulp it is ferrous oxidising be ferric iron, under effect of sulfuric acid using ferric iron as catalyst leaching zinc sulphide, zinc with
Zinc sulphate enters solution, and sulphur is formed with simple substance and precipitated, so that Leaching Zinc, makes the leaching of zinc reach maximization, passes through control
Temperature, sulfuric acid concentration and the extraction time of leaching process, control the leaching of iron, not only ensure that sufficient catalytic iron but also have been greatly reduced
It is subsequent to remove iron cost.The leaching of zinc sulphide reaches 90% or more, and manganese powder dosage is about 1.1~1.2 times of theoretical amount, than routine
It smelts and saves 20%, key reaction is as follows:
ZnS+2Fe3++SO4 2-→ZnSO4+2Fe2++S0↓
2FeSO4+MnO2+2H2SO4→Fe2(SO4)3+MnSO4+2H2O
Zinc oxide in material directly generates zinc sulfate with sulfuric acid reaction, passes through control temperature and solution sulfuric acid concentration ferrous acid
Zinc is also dissolved out, and chemical equation is as follows:
ZnO+H2SO4→ZnSO4+H2O
ZnO·Fe2O3+4H2SO4→ZnSO4+Fe2(SO4)3+4H2O。
This method is suitable for the solution system Leaching Zinc that potassium, sodium, ammonia content are more than 30g/L simultaneously, controls in leaching process
20g/L or so sulfuric acid concentration inhibits siderotil to generate, and leaches the solution after completing solid-liquor separation, and a small amount of material can be added and neutralize
PH value is carried out with Jarosite process except iron to 1.5 or so, can also remove iron using the neutralizing hydrolysis precipitation method.
The leaded high iron content zinc sulphide zinc oxide mix material contains zinc 10.37%, wherein vulcanization Zn content is 6.56%,
Iron content 6.80%, and contain 12.39% lead.
The middle leaching is neutral continuous leaching, and wherein extraction time is 1.5 hours, and liquid-solid ratio is 3/1~20/1, leaches temperature
Degree is 38~45 DEG C, leaches endpoint pH: 5.0~5.2, MnO2Input amount is the 0.5%~7% of dry mine quality, and solution
Iron content is less than 10mg/L.
The neutral leaching residue carries out pulp Hou Song acidic leaching workshop section using slag washing liquid
The acidleach is acidic leaching, and extraction time is 2.5~3 hours, and liquid-solid ratio is 3/1~5/1, extraction temperature 50
~80 DEG C, leaching process and terminal sulfuric acid concentration are 10~25g/L, MnO2Input amount be neutral leaching residue dry mass 0%~
5%.
The acidic leaching residue carries out pulping and washing using low zinc solution or clear water.
The washery slag time are as follows: 30~45 minutes, liquid-solid ratio was 3/1~4/1, and washery slag temperature is room temperature, and filter-press residues are aqueous
Less than 35%, slag washing liquid is less than 10g/L containing zinc.
Slag after the washery slag sends receipts lead back to, and slag washing liquid a part is recycled, and another part returns to acidic leaching.
Embodiment 1
Material 1, high zinc-iron-containing zinc sulphide material, neutral leaching section leach the zinc oxide in big portion, the dioxy of investment
Changing manganese not only ensure that middle immersion liquid iron content was lower, but also a part of zinc sulphide is enable to leach, and remaining manganese dioxide is not anti-with dilute sulfuric acid
It answers, neutral leaching residue is followed to enter acidic leaching workshop section, analysis is as shown in table 1:
The high zinc-iron-containing zinc sulphide material analyzing of table 1
| Element | H2O | Zn(complete) | ZnS | Zinc ferrite | Pb | Fe(complete) | FeIt (can) | Mn | K | Na |
| Content (%) | 0 | 35.37 | 6.32 | 1.48 | 7.4 | 7.47 | 5.49 | 1.71 | 2.68 | 2.72 |
1, neutral continuous leaching:
Extraction time: 1.5 hours
Liquid-solid ratio: 3/1~20/1 (adjustment is required containing zinc according to solution)
Extraction temperature: 38~45 DEG C (not heating, maintained by reaction heat and diluting concentrated sulfuric acid heat)
Leaching endpoint pH: 5.0~5.2
MnO2Input amount: the 0.5%~7% of dry mine amount
Solution critical impurities index: solution iron content is less than 10mg/L
Substance whereabouts: as used conventional wet lay zinc metallurgy, pressing filtering liquid is sent cleaning shop, extraction vehicle is then sent using extraction process
Between；Neutral leaching residue carries out pulp Hou Song acidic leaching workshop section using slag washing liquid.
2, acidic leaching:
Extraction time: 2.5~3 hours
Liquid-solid ratio: 3/1~5/1
Extraction temperature: 50~80 DEG C (temperature is higher, and ZnS extraction time is shorter)
Leaching process and terminal sulfuric acid concentration: 10~25g/L
MnO2Input amount: the 0%~5% of neutral leaching residue dry measure (puts into the manganese of insufficient investment for leaching section in supplement herein
Powder, depending on iron oxidization condition in solution)
Solution key substance index: solution all iron content is greater than 3g/L, and divalent iron content is less than 100mg/L
Substance whereabouts: pressing filtering liquid carries out heavy iron processing, such as sinks iron using neutralizing hydrolysis, then the liquid after iron that sinks directly send purification or
Zinc is extracted in extraction；Such as using the heavy iron of Jarosite process, then liquid returns to neutral leach after heavy iron；Acidic leaching residue is using low zinc solution or clearly
Water carries out pulping and washing.
3, washery slag:
The washery slag time: 30~45 minutes
Liquid-solid ratio: 3/1~4/1
Washery slag temperature: room temperature
Key index: filter-press residues are aqueous less than 35%, and slag washing liquid is less than 10g/L containing zinc
Substance whereabouts: slag sends receipts lead back to, and slag washing liquid a part is recycled, and another part returns to acidic leaching.
After three sections of processing, tailings analysis is as shown in table 2:
The analysis of the high zinc-iron-containing zinc sulphide tailings of table 2
| Element | H2O | Zn(complete) | ZnS | ZnSO4 | Pb | Fe(complete) | FeIt (can) | Mn | Zinc ferrite |
| Content (%) | 32 | 2.07 | 0.56 | 0.70 | 14.47 | 5.83 | 3.10 | 0.88 | 0.78 |
Zinc leaching rate: 96.97%
Vulcanization zinc leaching rate: 91.14%
Embodiment 2
Material 2, the low high iron content zinc sulphide material of zinc, the material are other workshop leached muds, because zinc oxide content is lower, directly
Row acidic leaching and washery slag are tapped into, material analyzing is as shown in table 3:
The high iron content zinc sulphide material analyzing of the low zinc of table 3
1, acidic leaching:
Extraction time: 2.5~3 hours
Liquid-solid ratio: 3/1~5/1
Extraction temperature: 50~80 DEG C (temperature is higher, and ZnS extraction time is shorter)
Leaching process and terminal sulfuric acid concentration: 15~25g/L
MnO2Input amount: the 7%~9% of neutral leaching residue dry measure
Solution key substance index: solution all iron content is greater than 3g/L, and divalent iron content is less than 100mg/L
Substance whereabouts: pressing filtering liquid carries out heavy iron processing, such as sinks iron using neutralizing hydrolysis, then the liquid after iron that sinks directly send purification or
Zinc is extracted in extraction；Such as using the heavy iron of Jarosite process, then liquid is incorporated to neutral leaching after heavy iron；Acidic leaching residue is using low zinc solution or clearly
Water carries out pulping and washing.
2, washery slag:
The washery slag time: 30~45 minutes
Liquid-solid ratio: 3/1~4/1
Washery slag temperature: room temperature
Key index: filter-press residues are aqueous less than 35%, and slag washing liquid is less than 10g/L containing zinc
Substance whereabouts: slag sends receipts lead back to, and slag washing liquid a part is recycled, and another part returns to acidic leaching.
After double diffusion, tailings analysis is as shown in table 2:
Table 4 is low containing the high iron content zinc sulphide tailings analysis of zinc
| Element | H2O | Zn(complete) | ZnS | ZnSO4 | Pb | Fe(complete) | FeIt (can) | Mn | Zinc ferrite |
| Content (%) | 30.68 | 1.64 | 0.48 | 0.50 | 12.77 | 4.90 | 3.69 | 0.91 | 0.63 |
The total leaching rate of zinc: 89.01%
Vulcanization zinc leaching rate: 92.68%
Embodiment 3
Material 2, the low iron content zinc sulphide material of low zinc, the material are other workshop leached muds, because lower containing zinc, directly progress
Acidic leaching and washery slag, material analyzing are as shown in table 3:
The high iron content zinc sulphide material analyzing of the low zinc of table 3
| Element | H2O | Zn(complete) | ZnS | Zinc ferrite | Pb | Fe(complete) | Mn | K | Na |
| Content (%) | 33.33 | 5.41 | 4.12 | 1.03 | 12.76 | 1.48 | 1.38 | 2.90 | 11.04 |
1, acidic leaching:
Extraction time: 3~3.5 hours
Liquid-solid ratio: 3/1~4/1
Extraction temperature: 80 DEG C
Leaching process and terminal sulfuric acid concentration: 25~30g/L
MnO2Input amount: the 7%~9% of neutral leaching residue dry measure
Solution key substance index: solution all iron content is greater than 3g/L, and divalent iron content is less than 100mg/L
Substance whereabouts: pressing filtering liquid uses the heavy iron of Jarosite process, and liquid is incorporated to neutral leaching after heavy iron；Acidic leaching residue uses low zinc
Solution or clear water carry out pulping and washing.
2, washery slag:
The washery slag time: 30~45 minutes
Liquid-solid ratio: 3/1~4/1
Washery slag temperature: room temperature
Key index: filter-press residues are aqueous less than 35%, and slag washing liquid is less than 10g/L containing zinc
Substance whereabouts: slag sends receipts lead back to, and slag washing liquid a part is recycled, and another part returns to acidic leaching.
After double diffusion, tailings analysis is as shown in table 2:
Table 4 is low containing the high iron content zinc sulphide tailings analysis of zinc
| Element | H2O | Zn(complete) | ZnS | ZnSO4 | Pb | Fe(complete) | FeIt (can) | Mn | Zinc ferrite |
| Content (%) | 32 | 1.12 | 0.32 | 0.5 | 12.70 | 1.29 | 0.41 | 1.65 | 0.27 |
The total leaching rate of zinc: 88.54%
Vulcanization zinc leaching rate: 92.23%.
The above shows and describes the basic principle, main features and advantages of the invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of method of the normal pressure leaching zinc from leaded high iron content zinc sulphide zinc oxide mix material, it is characterised in that: will contain
The high iron content zinc sulphide zinc oxide mix material of lead is leached using " middle leaching → acidleach → washery slag " technique, uses MnO2As oxygen
Agent, by leach ore pulp in it is ferrous oxidising be ferric iron, under effect of sulfuric acid using ferric iron as catalyst leaching sulphur
Change zinc, zinc enters solution with zinc sulphate, and sulphur is formed with simple substance and precipitated, thus Leaching Zinc, key reaction is as follows:
ZnS+2Fe3++SO4 2-→ZnSO4+2Fe2++S0↓
2FeSO4+MnO2+2H2SO4→Fe2(SO4)3+MnSO4+2H2O
Zinc oxide in material directly generates zinc sulfate with sulfuric acid reaction, by controlling temperature and solution sulfuric acid concentration zinc ferrite also
It is dissolved out, chemical equation is as follows:
ZnO+H2SO4→ZnSO4+H2O
ZnO·Fe2O3+4H2SO4→ZnSO4+Fe2(SO4)3+4H2O。
2. as described in claim 1 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
Be characterized in that: the leaded high iron content zinc sulphide zinc oxide mix material contains zinc 10.37%, wherein vulcanization Zn content is
6.56%, iron content 6.80%, and contain 12.39% lead.
3. as described in claim 1 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
Be characterized in that: the middle leaching is neutral continuous leaching, and wherein extraction time is 1.5 hours, and liquid-solid ratio is 3/1~20/1, is leached
Temperature is 38~45 DEG C, leaches endpoint pH: 5.0~5.2, MnO2Input amount is the 0.5%~7% of dry mine quality, and molten
Liquid iron content is less than 10mg/L.
4. as claimed in claim 3 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
Be characterized in that: the neutral leaching residue carries out pulp Hou Song acidic leaching workshop section using slag washing liquid.
5. as described in claim 1 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
Be characterized in that: the acidleach is acidic leaching, and extraction time is 2.5~3 hours, and liquid-solid ratio is 3/1~5/1, and extraction temperature is
50~80 DEG C, leaching process and terminal sulfuric acid concentration are 10~25g/L, MnO2Input amount is the 0% of neutral leaching residue dry mass
~5%.
6. as claimed in claim 5 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
Be characterized in that: the acidic leaching residue carries out pulping and washing using low zinc solution or clear water.
7. as described in claim 1 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
It is characterized in that: the washery slag time are as follows: 30~45 minutes, liquid-solid ratio was 3/1~4/1, and washery slag temperature is room temperature, and filter-press residues are aqueous
Less than 35%, slag washing liquid is less than 10g/L containing zinc.
8. as claimed in claim 7 from leaded high iron content zinc sulphide zinc oxide mix material normal pressure leaching zinc method,
Be characterized in that: the slag after the washery slag sends receipts lead back to, and slag washing liquid a part is recycled, and another part returns to acidic leaching.
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| CN114085989A (en) * | 2021-11-24 | 2022-02-25 | 白银有色集团股份有限公司 | Method for adjusting manganese in zinc hydrometallurgy system |
| CN115404354A (en) * | 2022-10-11 | 2022-11-29 | 云南金鼎锌业有限公司 | Method for improving zinc leaching rate of zinc-containing material by wet smelting |
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