CN109182757A - A kind of method of zinc hydrometallurgy precipitating alum and removing iron slag minimizing - Google Patents
A kind of method of zinc hydrometallurgy precipitating alum and removing iron slag minimizing Download PDFInfo
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- CN109182757A CN109182757A CN201811221930.4A CN201811221930A CN109182757A CN 109182757 A CN109182757 A CN 109182757A CN 201811221930 A CN201811221930 A CN 201811221930A CN 109182757 A CN109182757 A CN 109182757A
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
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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
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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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- 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
- C22B3/20—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to zinc hydrometallurgy field of metallurgy, a kind of method for specifically disclosing heavy alum slag minimizing of zinc hydrometallurgy.This method mainly include it is neutral leach, neutral leachate precipitating alum and removing iron, five processing steps of Ore Leaching and high acidic oils in neutral leaching residue twice.This method returns once heavy alum process as crystal seed and neutralizer by once heavy alum terminal pH control and secondary heavy alum slag, so that the primary heavy heavy scum amount of iron process before comparing reduces 20% or so, rate containing zinc reduces 5% or more in slag, improve the direct yield of zinc, the content of the impurity such as arsenic antimony in middle supernatant solution is also reduced simultaneously, and the method for the present invention is a kind of heavy iron method of zinc hydrometallurgy of economic and environment-friendly low cost.
Description
Technical field
The invention belongs to zinc hydrometallurgy field of metallurgy, and in particular to a kind of side of zinc hydrometallurgy precipitating alum and removing iron slag minimizing
Method.
Background technique
Zinc abstraction is broadly divided into pyrogenic process and zinc hydrometallurgy at present.Current 80% or more zinc yield both is from wet processing.
Zinc hydrometallurgy main method has conventional lixiviation process, zinc concentrate pressure leaching process and alkaline leaching method etc..Either with zinc concentrate
Or secondary material containing zinc produces zinc ingot metal, and current main wet processing mainly includes based on still being leached with conventional wet lay
Neutral leachings, preneutralization, hot acid leach, precipitating alum and removing iron, and the main distinction is to use different method deferrization process.Mesh
Preceding main deferrization process has jarosite process, goethite process and hematite process, and wherein jarosite process is the most widely to use
Process, be mainly characterized by that operation is easier, low energy consumption, but need to consume certain base reagent.Separation of iron in goethite form slag
Amount is few, and energy consumption is high, and oxidation-reduction process is realized more complicated.Hematite process is relatively high except iron cost of investment, and technology is complicated, operation
Difficulty is bigger, and application is fewer.Discovery is using the removal of the impurity such as arsenic antimony while separation of iron in goethite form during practice
Effect is better than other two kinds, therefore is the producer for producing zinc ingot metal raw material for being especially with zinc secondary resource with secondary zinc oxide,
Majority uses separation of iron in goethite form.
During producing zinc ingot metal as raw material using zinc secondary resource, due to the impurity ratio such as the fluorine of antimony containing arsenic chlorine cobalt nickel in raw material
Higher, impurity content is all gram liter rank or more in general neutrality leachate, it is therefore desirable to will be big absolutely during removing iron
Partial impurities remove, therefore often need during heavy alum by Fe2+Mend 4g/L or more, so that during heavy alum Chen Tie
A large amount of neutralizers are added, cause the heavy alum quantity of slag big, rate containing zinc is relatively high in slag, directly affects the direct yield and energy consumption of zinc.
Summary of the invention
In order to solve the above technical problems, a kind of method that the present invention proposes heavy alum slag minimizing of zinc hydrometallurgy, this method energy
Enough significantly reduce the big problem of the quantity of slag of precipitating alum and removing iron, moreover it is possible to remove the impurity such as most of arsenic antimony fluorine chlorine cobalt in solution, subtract
The light pressure of purification section and the consumption of zinc powder, low production cost, improve zinc direct yield.
The invention adopts the following technical scheme:
A kind of method of the heavy alum slag minimizing of zinc hydrometallurgy, method includes the following steps:
(1) neutral to leach: using secondary zinc oxide as raw material, neutral leaching is done with acid solution, solid-liquor separation after the completion of leaching,
Obtained neutral leachate and neutral leaching residue；
(2) it once sinks alum: neutralizer and oxidant being added in the neutral leachate that step (1) is obtained, carries out goethite
Method removes iron, carries out solid-liquor separation after the reaction was completed, obtains an alum precipitation liquid and heavy alum scum；
(3) secondary heavy alum: the primary heavy alum that step (2) is obtained, which sinks neutralizer to be added and oxidant is added in liquid, carries out needle
Iron ore method removes iron, and solution is carried out dense separation after the reaction was completed, obtains middle supernatant and underflow；
(4) Ore Leaching in: Ore Leaching in the Plus acidic solution progress of the neutral leaching residue that step (1) is obtained is leached and is completed
After carry out solid-liquor separation, obtain a sour not good liquor and sour primary slag；
(5) high acidic oils: carrying out high acidic oils for sour primary slag sulfuric acid or zinc electrolytic waste liquid that step (4) obtains, leaching
Solid-liquor separation is carried out after the completion of out, obtains sour two not good liquors and lead body refuse.
Wherein, above-mentioned zinc hydrometallurgy sinks the method for alum slag minimizing, in step (1), by percentage to the quality, the secondary oxygen
Changing zinc includes component: H2O 0.1~4.0%, Zn 50~68%, Pb5.5~8.6%, As 0.3~1.4%, Sb 0.5~
3.6%, F 0.2~0.7%, Cl 0.2~0.8%.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, acid solution described in step (1) are zinc electrolytic waste liquid
Or step (4) sour not good liquor.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the actual conditions that neutrality described in step (1) leaches
Are as follows: between control terminal pH 3.0~4.5, react liquid-solid ratio L/S=3.5~5 (kg/L), 70~90 DEG C of reaction temperature.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, neutralizer described in step (2) are calcium carbonate and lime
At least one of.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the reaction item of separation of iron in goethite form described in step (2)
Part are as follows: control terminal pH 4.0~4.5, Fe2+Concentration be lower than 1g/L, 70~85 DEG C of reaction temperature, 2~3h of reaction time.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy sinks alum scum through rotary kiln or cigarette described in step (2)
Change the valuable metals such as furnace processing recycling zinc.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, neutralizer described in step (3) are dry powder and lime
At least one of.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, oxidant described in step (2) and step (3) is double
Oxygen water.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the reaction item of separation of iron in goethite form described in step (3)
Part are as follows: control terminal pH 4.5~5.2, Fe2+Concentration be lower than 0.02g/L, 70~85 DEG C of reaction temperature, 2~3h of reaction time.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, middle supernatant described in step (3) are sent into purification work
Sequence, the underflow return to above-mentioned once heavy alum process.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the actual conditions of middle Ore Leaching described in step (4)
Are as follows: control 90~110g/L of reaction end acidity, the reaction time be 2~3h, 70~90 DEG C of reaction temperature.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, acid solution described in step (4) are sulfuric acid or step
(5) sour two not good liquor.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the not good liquor return step (1) of acid one described in step (4)
The neutral leaching process.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the actual conditions of high acidic oils described in step (5)
Are as follows: control 140~180g/L of reaction end acidity, the reaction time be 2~3h, 70~90 DEG C of reaction temperature.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the not good liquor return step (4) of acid two described in step (5)
The middle Ore Leaching process, the lead body refuse recycle the valuable metals such as lead zinc into pyrogenic process lead system.
Wherein, the method for the heavy alum slag minimizing of above-mentioned zinc hydrometallurgy, the solid-liquor separation are divided using plate and frame filter press
From.
Beneficial effects of the present invention:
It is high containing zinc in slag the present invention be directed to big using the secondary resource of zinc as the heavy alum scum amount of the zinc hydrometallurgy of raw material at present
Lead to a kind of method of the heavy alum slag minimizing of the low zinc hydrometallurgy proposed of zinc direct yield.This method is by adjusting primary heavy
Underflow is as neutralizer and secondary heavy alum after alum terminal pH and the primary heavy alum of increase, secondary alum precipitation liquid carry out concentrator solid-liquor separation
Slag is added to heavy alum for the first time as crystal seed, so that total heavy alum scum amount largely reduces, rate containing zinc reduces obvious, solution in slag
Impurity removal effect is substantially better than once heavy alum, improves the direct yield of zinc, reduces production cost and energy consumption.Specifically, it compares
The heavy scum amount of a precipitating alum and removing iron technique before reduces 20% or so, and rate containing zinc reduces 5% or more in slag, improves zinc
Direct yield, while the content of the impurity such as arsenic antimony in middle supernatant solution is also reduced, the present invention is a kind of economic and environment-friendly low cost
Zinc hydrometallurgy sinks iron method.
Detailed description of the invention
Fig. 1 is the process flow chart of the heavy alum slag quantitative reduction method of zinc hydrometallurgy described in the embodiment of the present invention 1.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.The following example
It is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.It is all to be based on this hair
In the range of the technology that bright above content is realized is encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Percentage described in following embodiment is mass percent.
Embodiment 1
By 10 tons of secondary zinc oxide (H2O:2.69%, Zn:56.82%, Pb:6.75%, As:1.84%, Sb:2.73%, F:
0.42%, Cl:0.35%) investment surge tank sizes mixing, squeezed into after sizing mixing reactive tank be added in acid leaching liquor or Zinc electrolysis waste liquid be
(Zn 44.89g/L, H+152.6g/L, As 0.0002g/L, Sb 0.0002g/L, F 0.2g/L, Cl 0.95g/L) do neutrality
It leaches, control terminal pH is 3.5 or so, reaction time 2h, and temperature is 80 DEG C, is carried out after the reaction was completed using plate and frame filter press
Solid-liquor separation, sampling analysis neutralizer are Zn154.32g/L；Fe2+4.54g/L, As 1.85g/L, Sb 0.74g/L, F
1.12g/L, Cl 1.65g/L, neutralizer volume 45m after filters pressing3, once heavy alum is according to divalent iron content 3.54g/L in neutralizer
2.0 times of addition hydrogen peroxide carry out once heavy alum, the ferrous iron that 1g/L or so is retained in solution carries out secondary heavy alum, dioxygen is added
Water 318.6L, addition time are 2h, and it is 4.0 or so that lime and calcium carbonate adjusting pH, which is added, reaction time 3h, and reaction temperature is
80 DEG C, solid-liquor separation, an alum precipitation liquid and the heavy separately sampled analytical test of alum slag are carried out using plate and frame filter press after the reaction was completed,
Once liquid result of laboratory test is Fe after heavy alum2+0.98g/L, As 0.02g/L, Sb 0.02g/L, F 0.56g/L, Cl 1.32g/L,
Heavy alum slag result is H2O 53.79%, Zn10.26%, Fe15.31%, once volume is 42m after heavy alum3, secondary heavy alum according to
Hydrogen peroxide 100L is added in 2.2 times of calculating of liquid ferrous ion content after primary heavy alum, and the addition time is 1h, and lime and carbonic acid is added
It is 4.5 or so that calcium, which adjusts pH, reaction time 2h, and reaction temperature is 80 DEG C, directly squeezes into concentrator after the reaction was completed and is sunk
Drop separates, and supernatant sample examination result is Zn148.86g/L, Fe in dense slot2+0.02g/L, As 0.002g/L, Sb
0.003g/L, F 0.37g/L, Cl1.10g/L, underflow return to once heavy alum.It neutralizes after slag is sized mixing and is transferred to middle Ore Leaching slot, it will be high
Acid leaching liquor is squeezed into slot, controls whole acid in 100g/L or so, acid not enough adds the concentrated sulfuric acid, liquid-solid ratio 4:1, and reaction temperature is
80 DEG C, reaction time 2h, plate and frame filter press filters pressing is used after the reaction was completed, and whole acid leaching liquor is leached for neutral, middle acidleach
It slags tap and Zinc electrolysis waste liquid is added does high acidic oils, control acid 140g/L eventually, acidity not enough adds the concentrated sulfuric acid, and liquid-solid ratio is the left side 4:1
The right side, reaction temperature are 80 DEG C, reaction time 2h, use plate and frame filter press filters pressing after the reaction was completed, and middle acid is done in high acid solution return
It leaches, obtained lead mud enters the valuable metals such as pyrogenic process system recycling lead, and lead mud result is H2O 44.95%, Zn7.26%, Pb
18.25%, As 0.21%, Sb6.04%.
Embodiment 2
By 10 tons of secondary zinc oxide (H2O:0.43%, Zn:60.00%, Pb:8.00%, As:1.03%, Sb:0.75%, F:
0.31%, Cl:0.40%) investment surge tank sizes mixing, squeezed into after sizing mixing reactive tank be added in acid leaching liquor or Zinc electrolysis waste liquid be
(Zn 46.53g/L, H+158.28g/L, As 0.0002g/L, Sb 0.0002g/L, F 0.18g/L, Cl 1.05g/L) it does
Property leach, control terminal pH be 3.5 or so, reaction time 2h, temperature be 80 DEG C, after the reaction was completed using plate and frame filter press into
Row solid-liquor separation, sampling analysis neutralizer result are Zn166.55g/L, Fe2+3.86g/L, As 1.54g/L, Sb 0.43g/L, F
0.61g/L, Cl 1.60g/L, neutralizer volume 46m after filters pressing3, once heavy alum is according to divalent iron content 2.86g/L in neutralizer
2.0 times of addition hydrogen peroxide carry out once heavy alum, the ferrous iron that 1g/L or so is retained in solution carries out secondary heavy alum, dioxygen is added
Water 270L, addition time are 2h, and it is 4.0 or so that lime and calcium carbonate adjusting pH, which is added, reaction time 3h, reaction temperature 80
DEG C, solid-liquor separation is carried out using plate and frame filter press after the reaction was completed, an alum precipitation liquid and the heavy separately sampled analytical test of alum slag, one
Liquid result of laboratory test is Fe after secondary heavy alum2+1.02g/L, As 0.032g/L, Sb 0.041g/L, F 0.56g/L, Cl 1.32g/L,
Heavy alum slag result is H2O 51.22%, Zn 11.32%, Fe12.17%, once volume is 44m after heavy alum3, secondary heavy alum according to
Hydrogen peroxide 100L is added in 2.2 times of calculating of liquid ferrous ion content after primary heavy alum, and the addition time is 1h, and lime and carbonic acid is added
It is 4.5 or so that calcium, which adjusts pH, reaction time 2h, and reaction temperature is 80 DEG C, directly squeezes into dense slot after the reaction was completed and is sunk
Drop separates, and supernatant sample examination result is Zn155.82g/L, Fe in dense slot2+0.02g/L, As 0.003g/L, Sb
0.005g/L, F 0.35g/L, Cl1.15g/L, underflow return to once heavy alum.It neutralizes after slag is sized mixing and is transferred to middle Ore Leaching slot, it will be high
Acid leaching liquor is squeezed into slot, controls whole acid in 110g/L or so, acid not enough adds the concentrated sulfuric acid, liquid-solid ratio 4:1, and reaction temperature is
80 DEG C, reaction time 2h, plate and frame filter press filters pressing is used after the reaction was completed, and whole acid leaching liquor is leached for neutral, middle acidleach
It slags tap and Zinc electrolysis waste liquid is added does high acidic oils, control acid 150g/L eventually, acidity not enough adds the concentrated sulfuric acid, and liquid-solid ratio is the left side 4:1
The right side, reaction temperature are 80 DEG C, reaction time 2h, use plate and frame filter press filters pressing after the reaction was completed, and middle acid is done in high acid solution return
It leaches, obtained lead mud enters the valuable metals such as pyrogenic process system recycling lead, and lead mud result is H2O 40.65%, Zn6.22%, Pb
21.61%, As 0.16%, Sb1.48%.
Embodiment 3
By 10 tons of secondary zinc oxide (H2O:0.33%, Zn:62.52%, Pb:6.05%, As:0.62%, Sb:1.17%, F:
0.55%, Cl:0.63%) investment surge tank size mixing, squeezed into after sizing mixing reactive tank be added in acid leaching liquor or Zinc electrolysis waste liquid (Zn
45.83g/L；H+152.96g/L, As 0.0002g/L, Sb 0.0002g/L, F 0.19g/L, Cl 0.90g/L) do neutral leaching
Out, control terminal pH is 3.0 or so, reaction time 2h, and temperature is 80 DEG C, carries out liquid using plate and frame filter press after the reaction was completed
Gu separation, sampling analysis neutralizer result is Zn162.13g/L；Fe2+5.21g/L, As 1.12g/L, Sb 0.40g/L, F
1.25g/L, Cl 1.88g/L, neutralizer volume 45m after filters pressing3, once heavy alum is according to divalent iron content 4.21g/L in neutralizer
2.0 times of addition hydrogen peroxide carry out once heavy alum, the ferrous iron that 1g/L or so is retained in solution carries out secondary heavy alum, dioxygen is added
Water 421L, addition time are 2h, and it is 4.5 or so that lime and calcium carbonate adjusting pH, which is added, reaction time 3h, reaction temperature 80
DEG C, solid-liquor separation is carried out using plate and frame filter press after the reaction was completed, an alum precipitation liquid and the heavy separately sampled analytical test of alum slag, one
Liquid result of laboratory test is Fe after secondary heavy alum2+0.92g/L, As 0.01g/L, Sb 0.011g/L, F 0.62g/L, Cl 1.40g/L sink
Alum slag result is H2O 52.35%, Zn12.24%, Fe14.72%, once volume is 43m after heavy alum3, secondary heavy alum is according to one
Hydrogen peroxide 90L is added in 2.2 times of calculating of liquid ferrous ion content after secondary heavy alum, and the addition time is 1h, and lime and calcium carbonate is added
Adjusting pH is 4.5 or so, reaction time 2h, and reaction temperature is 80 DEG C, directly squeezes into dense slot after the reaction was completed and is settled
It separates, supernatant sample examination result is Zn153.39g/L, Fe in dense slot2+0.02g/L, As 0.002g/L, Sb 0.002g/
L, F 0.40g/L, Cl1.21g/L, underflow return to once heavy alum.It neutralizes after slag is sized mixing and is transferred to middle Ore Leaching slot, by high acidic oils
Liquid is squeezed into slot, and controlling acid eventually, in 100g/L or so, acid not enough adds the concentrated sulfuric acid, liquid-solid ratio 4:1, and reaction temperature is 80 DEG C,
Reaction time is 2h, uses plate and frame filter press filters pressing after the reaction was completed, and whole acid leaching liquor is leached for neutral, and middle acid leaching slag adds
Enter Zinc electrolysis waste liquid and do high acidic oils, control acid 160g/L eventually, acidity not enough adds the concentrated sulfuric acid, and liquid-solid ratio is 4:1 or so, reaction
Temperature is 80 DEG C, reaction time 2h, uses plate and frame filter press filters pressing after the reaction was completed, and high acid solution return is done middle Ore Leaching, obtained
To lead mud enter the pyrogenic process system recycling valuable metals such as lead, lead mud result is H2O 41.37%, Zn6.05%, Pb
16.42%, As 0.10%, Sb2.68%.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of method of the heavy alum slag minimizing of zinc hydrometallurgy, which is characterized in that method includes the following steps:
(1) neutral to leach: using secondary zinc oxide as raw material, to do neutral leaching with acid solution, solid-liquor separation after the completion of leaching obtains
Neutral leachate and neutral leaching residue；
(2) it once sinks alum: neutralizer and oxidant being added in the neutral leachate that step (1) is obtained, carries out goethite process and removes
Iron carries out solid-liquor separation after the reaction was completed, obtains an alum precipitation liquid and heavy alum scum；
(3) secondary heavy alum: the primary heavy alum that step (2) is obtained, which sinks neutralizer to be added and oxidant is added in liquid, carries out goethite
Method removes iron, and solution is carried out dense separation after the reaction was completed, obtains middle supernatant and underflow；
(4) Ore Leaching in: it is laggard to leach completion for Ore Leaching in the Plus acidic solution progress of the neutral leaching residue that step (1) is obtained
Row solid-liquor separation obtains a sour not good liquor and sour primary slag；
(5) high acidic oils: sour primary slag sulfuric acid or zinc electrolytic waste liquid that step (4) obtains are subjected to high acidic oils, leached
At rear carry out solid-liquor separation, sour two not good liquors and lead body refuse are obtained.
2. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that in step (1), with matter
Percentages are measured, the secondary zinc oxide includes component: H2O 0.1~4.0%, Zn 50~68%, Pb 5.5~8.6%, As
0.3~1.4%, Sb 0.5~3.6%, F 0.2~0.7%, Cl 0.2~0.8%.
3. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (1)
Acid solution is zinc electrolytic waste liquid or step (4) sour not good liquor；
The actual conditions that neutrality described in step (1) leaches are as follows: between control terminal pH 3.0~4.5, react liquid-solid ratio L/S=
3.5~5 (kg/L), 70~90 DEG C of reaction temperature.
4. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (2)
Neutralizer is at least one of calcium carbonate and lime；
The reaction condition of the separation of iron in goethite form are as follows: control terminal pH 4.0~4.5, Fe2+Concentration is lower than 1g/L, reaction temperature
70~85 DEG C, 2~3h of reaction time.
The heavy alum scum is through the valuable metals such as rotary kiln or fuming furnace processing recycling zinc.
5. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (3)
Neutralizer is at least one of dry powder and lime；Oxidant described in step (2) and step (3) is hydrogen peroxide.
6. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (3)
The reaction condition of separation of iron in goethite form are as follows: control terminal pH4.5~5.2, Fe2+Concentration is lower than 0.02g/L, reaction temperature 70~85
DEG C, 2~3h of reaction time；
Middle supernatant described in step (3) is sent into cleaning procedure, and the underflow returns to above-mentioned once heavy alum process.
7. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (4)
The actual conditions of middle Ore Leaching are as follows: control 90~110g/L of reaction end acidity, the reaction time be 2~3h, reaction temperature 70~
90℃。
8. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (4)
Acid solution is sulfuric acid or step (5) sour two not good liquor；
The not good liquor return step (1) of acid one described in step (4) the neutral leaching process.
9. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (5)
The actual conditions of high acidic oils are as follows: control 140~180g/L of reaction end acidity, the reaction time be 2~3h, reaction temperature 70~
90℃。
10. the method for the heavy alum slag minimizing of zinc hydrometallurgy according to claim 1, which is characterized in that described in step (5)
Sour two not good liquor return steps (4) the middle Ore Leaching process, the lead body refuse recycle the valuable metals such as lead zinc into pyrogenic process lead system.
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| CN117604243B (en) * | 2024-01-23 | 2024-04-26 | 昆明理工大学 | Efficient zinc extraction method for zinc calcine |
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