CN110964914B - Method for removing calcium and magnesium in zinc hydrometallurgy process - Google Patents

Method for removing calcium and magnesium in zinc hydrometallurgy process Download PDF

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CN110964914B
CN110964914B CN201911389011.2A CN201911389011A CN110964914B CN 110964914 B CN110964914 B CN 110964914B CN 201911389011 A CN201911389011 A CN 201911389011A CN 110964914 B CN110964914 B CN 110964914B
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tank
thickener
conveying
magnesium
calcium
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CN110964914A (en
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周南方
马宝军
周裕高
汤浅一郎
杨明学
韦勇
王智
侯荣昌
吴少华
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Nandan Nanfang Non Ferrous Metals Co ltd
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Nandan Nanfang Non Ferrous Metals Co ltd
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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
    • 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
    • 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 the technical field of metallurgy, and particularly relates to a method for removing calcium and magnesium in a zinc hydrometallurgy process. Which comprises the following steps: 1) calcium removal: mixing the new liquid, the waste electrolyte and the solution containing CaSO4·2H2Adding the underflow of the O seed crystal thickener into a seed crystal mixing tank, cooling, then feeding the mixture into a ripening tank and a thickener, returning one half of the underflow of the thickener to the seed crystal mixing tank, feeding the other half of the underflow of the thickener into a No. 1 reaction tank, and then adding CaCO3Slurrying, adding into a No. 1 reaction tank to adjust the pH value to 2.5-3, adding waste electrolyte into the No. 1 reaction tank, conveying to a No. 2 reaction tank for reaction, conveying to a centrifugal machine for centrifugation, and obtaining a centrifugal machine calcium-removed filtrate and a centrifugal machine calcium-containing filter residue; 2) magnesium removal: the centrifuge filtrate was fed to a neutralization tank, followed by addition of Ca (OH)2Slurrying, adding into a neutralization tank to adjust the pH value to 8-9, then conveying to a filter press, and conveying the obtained magnesium-containing filtrate to a sewage station for treatment. The method can effectively remove calcium and magnesium ions in the zinc hydrometallurgy system, maintain a reasonable concentration level, greatly reduce the power consumption of zinc electrolysis and save the production cost.

Description

Method for removing calcium and magnesium in zinc hydrometallurgy process
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of metallurgy, in particular to a method for removing calcium and magnesium in a zinc hydrometallurgy process.
[ background of the invention ]
The zinc hydrometallurgy is that dilute sulphuric acid (namely waste electrolyte) is used to leach zinc roasted ore to obtain zinc sulfate solution, and zinc is electrodeposited out of the solution by an electrolytic method after purification.
The zinc hydrometallurgy process comprises roasting → leaching → purification → electrolysis → fusion casting, after roasting and leaching, Ca and Mg mainly enter a supernatant solution in leaching in the form of sulfate, and are difficult to remove in the traditional purification process, so that calcium and magnesium are continuously and circularly enriched in a wet system, and the problems of crystallization blockage, current efficiency reduction, energy consumption increase and the like are brought to normal production, and the zinc hydrometallurgy process is regarded as a common problem in the industry. The calcium and magnesium in the zinc hydrometallurgy flow are removed, the labor intensity of manual groove cleaning and pipeline maintenance can be reduced, the processing capacity of filtering equipment is kept, magnesium ions in the electrolyte can be maintained at a reasonable concentration level, the power consumption of zinc electrolysis is reduced, and the production cost is saved.
[ summary of the invention ]
The calcium and magnesium removing process is a process for separating main system from calcium ions in the purified new liquid and magnesium ions in the waste liquid. The new liquid purification method disclosed by the invention has the advantages that the influence of basic zinc sulfate on crystallization and growth of calcium sulfate is reduced under an acidic condition mainly by adjusting the pH value of the solution, the solubility of the calcium sulfate is greatly changed along with the temperature change, the solubility of the calcium sulfate is reduced by reducing the temperature of the new liquid, saturated calcium sulfate is precipitated, crystallized and grown, and the main system is discharged by filtering.
The zinc ions in the waste liquid are precipitated as basic zinc sulfate under the alkaline condition, most of magnesium exists in the solution in an ionic state, and the magnesium is filtered and discharged out of the system. The basic zinc sulfate solid is pulped and sent to remove iron to be used as a neutralizer, and the chemical reaction is as follows (1) - (6):
Ca2++SO4 2-+nH2O＝CaSO4·nH2O↓(s)……………(1)
CaSO4(aq)＝Ca2++SO4 2-……………………………(2)
H2SO4＝HSO4-+H+……………………………(3)
HSO4-＝SO4 2-+H+………………………………(4)
CaCO3+2H+＝Ca2++H2O+CO2………………………(5)
Ca(OH)2+ZnSO4+SO4 2-＝Zn(OH)2SO4↓+CaSO4…………(6)
in order to solve the technical problems in the prior art, based on the principle, the invention adopts the following technical scheme:
a method for removing calcium and magnesium in a zinc hydrometallurgy process comprises the following steps:
1) calcium removal: purifying the new solution, electrolyzing the waste electrolyte, and adding CaSO4·2H2Adding the underflow of the thickener of the O seed crystal into a seed crystal mixing tank for mixing, adjusting the pH to 2-3, then cooling the mixture in a cooling tower, aging the cooled material into a tank, then conveying the tank to the thickener, adding polyaluminium sulfate into the thickener for flocculation to obtain the supernatant of the thickener and the underflow of the thickener, conveying the supernatant of the thickener to an electrolysis process, returning one half of the underflow of the thickener to the seed crystal mixing tank, and the other half of the underflow of the thickener to a No. 1 reaction tank, and then adding CaCO3Slurrying in a slurrying tank, adding into a No. 1 reaction tank, adding waste electrolyte into the No. 1 reaction tank to adjust the pH to 2.5-3, conveying to a No. 2 reaction tank for reaction, and conveying to a centrifugal machine for centrifugation to obtain a centrifuge decalcified filtrate and centrifuge calcium-containing filter residue;
2) magnesium removal: the centrifuge decalcified filtrate was fed to a neutralization tank, followed by Ca (OH)2Slurrying in a slurrying tank, adding a neutralizing tank to adjust the pH value to 8-9, conveying the neutralized material to a filter press, conveying the obtained magnesium-containing filtrate to a sewage station for treatment, slurrying the obtained filter residue, and conveying the slurried filter residue to an iron removal process.
Further, in the seed crystal mixing tank in the step 1), the internal temperature of the seed crystal mixing tank is controlled to be 65-75 ℃, and the material residence time is as follows: the flow rate of the new liquid is 6.7 times of the flow rate of the underflow of the thickener, and the stirring speed is 34 r/min.
Further, in the cooling tower in the step 1), the inlet temperature of the cooling tower is controlled to be 65-75 ℃, and the outlet temperature of the cooling tower is controlled to be 40-50 ℃.
Further, in the ripening tank in the step 1), the internal temperature of the ripening tank is controlled to be 35-45 ℃, and the material retention time is as follows: the stirring speed is 34r/min for more than 60 min.
Further, in the thickener in the step 1), the internal temperature of the thickener is controlled to be 35-40 ℃, the pH value of the supernatant of the thickener is 2-3, and the specific gravity of the underflow of the thickener is as follows: 1.50 to 1.80.
Further, in the reaction tank No. 1 and the reaction tank No. 2 in the step 1), the internal temperature of the reaction tank is controlled to be 65-75 ℃, and the pH value is 2.5-3.0.
Further, in the neutralization tank in the step 1), the internal temperature of the neutralization tank is controlled to be 65-75 ℃, and the pH value is 8.0-9.0.
Further, the CaCO3Slurrying and Ca (OH)2The concentration of the slurried solution was 500 g/l.
Further, the CaCO3The purity of the product is more than or equal to 95 percent, and the granularity is-200 meshes; the Ca (OH)2The purity of the product is more than or equal to 90 percent, and the granularity is-300 meshes.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. after the invention is adopted, the calcium content of the new liquid and the waste electrolyte is reduced to 0.2-0.4g/l, and the magnesium content of the new liquid and the waste electrolyte is respectively reduced to 1g/l and 10 g/l.
2. The calcium and magnesium crystal adhesion amount in the fresh liquid cooling tower is reduced, the system cleaning frequency and personnel are reduced, and the cleaning frequency is reduced from 1 time per month to 1 time per year or even is not required to be cleaned.
3. A last defense line for removing impurities in the new liquid is established, the treated liquid can not re-dissolve after entering the electrolytic bath, and the electrolytic power consumption is reduced.
4. The crystallization in the cooling tower is reduced, and the working efficiency is improved.
5. The produced gypsum carries out 10% of water in a part of the system, and meanwhile, the thickening equipment increases the evaporation capacity of the cooling tower and improves water expansion.
6. The blockage situation of the liquid pipeline in the factory is reduced, the service life of the detection instrument can be prolonged, and the repair cost can be reduced.
[ description of the drawings ]
FIG. 1 is a process flow diagram of the present invention.
[ detailed description ] embodiments
Example 1
A method for removing calcium and magnesium in a zinc hydrometallurgy process comprises the following steps:
1) calcium removal: purifying the new solution, electrolyzing the waste electrolyte, and adding CaSO4·2H2Adding the underflow of the thickener of the O seed crystal into a seed crystal mixing tank for mixing, controlling the internal temperature of the seed crystal mixing tank to be 65-75 ℃, and the retention time of materials: the flow rate of the new liquid is 6.7 times of the flow rate of the underflow of the thickener, and the stirring speed is 34 r/min; adjusting the pH value to 2-3, then cooling the mixture in a cooling tower, controlling the inlet temperature of the cooling tower to be 65-75 ℃ and the outlet temperature to be 40-50 ℃; feeding the cooled material into a ripening tank, controlling the temperature inside the ripening tank to be 35-45 ℃, and keeping the material retention time: the stirring speed is 34r/min for more than 60 min; and then conveying the mixture to a thickener, adding polyaluminium sulfate into the thickener for flocculation, controlling the internal temperature of the thickener to be 35-40 ℃, the pH value of supernatant of the thickener to be 2-3, and the specific gravity of underflow of the thickener: 1.50 to 1.80; obtaining the supernatant fluid of the thickener and the underflow of the thickener, delivering the supernatant fluid of the thickener to an electrolysis process, returning one half of the underflow of the thickener to the seed crystal mixing tank, and the other half to the No. 1 reaction tank, and then, CaCO3Slurrying in a slurrying tank, adding the slurried slurry into a No. 1 reaction tank, adding waste electrolyte into the No. 1 reaction tank to adjust the pH value to 2.5-3, conveying the slurry to a No. 2 reaction tank for reaction, and controlling the internal temperature of the No. 1 reaction tank and the No. 2 reaction tank to be 65-75 ℃ and the pH value to be 2.5-3.0; then conveying the mixture to a centrifugal machine for centrifugation to obtain a calcium-removed filtrate of the centrifugal machine and calcium-containing filter residue of the centrifugal machine;
2) magnesium removal: the centrifuge decalcified filtrate was fed to a neutralization tank, followed by Ca (OH)2Slurrying in a slurrying tank, adding a neutralizing tank to adjust the pH value, controlling the internal temperature of the neutralizing tank to be 65-75 ℃ and the pH value to be 8.0-9.0; and conveying the neutralized materials to a filter press, conveying the obtained magnesium-containing filtrate to a sewage station for treatment, slurrying the obtained filter residue, and conveying to an iron removal process.
In this example, the CaCO3And Ca (OH)2The concentration of the slurried solution is 500 g/l; the CaCO3The purity of the product is more than or equal to 95 percent, and the granularity is-200 meshes(ii) a The Ca (OH)2The purity of the product is more than or equal to 90 percent, and the granularity is-300 meshes.
The process flow diagram of example 1 is shown in fig. 1.
Through 2 years of operation observation, in a zinc wet system, the calcium content of the new liquid and the waste liquid is reduced to 0.3-0.4g/l, the magnesium content of the new liquid and the waste liquid is respectively reduced to 1g/l and 10g/l, and the concentration level is maintained, so that the power consumption of zinc electrolysis is greatly reduced, and the production cost is saved.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims (4)

1. A method for removing calcium and magnesium in a zinc hydrometallurgy process is characterized by comprising the following steps:
1) calcium removal: purifying the new solution, electrolyzing the waste electrolyte, and adding CaSO4·2H2Adding the underflow of the thickener of the O seed crystal into a seed crystal mixing tank for mixing, adjusting the pH to 2-3, then cooling the mixture in a cooling tower, aging the cooled material into a tank, then conveying the tank to the thickener, adding polyaluminium sulfate into the thickener for flocculation to obtain the supernatant of the thickener and the underflow of the thickener, conveying the supernatant of the thickener to an electrolysis process, returning one half of the underflow of the thickener to the seed crystal mixing tank, and the other half of the underflow of the thickener to a No. 1 reaction tank, and then adding CaCO3Slurrying in a slurrying tank, adding into a No. 1 reaction tank, adding waste electrolyte into the No. 1 reaction tank to adjust the pH to 2.5-3, conveying to a No. 2 reaction tank for reaction, and conveying to a centrifugal machine for centrifugation to obtain a centrifuge decalcified filtrate and centrifuge calcium-containing filter residue;
in the seed crystal mixing tank, the internal temperature of the seed crystal mixing tank is controlled to be 65-75 ℃, and the material residence time is as follows: the flow rate of the new liquid is 6.7 times of the flow rate of the underflow of the thickener, and the stirring speed is 34 r/min;
in the cooling tower, the inlet temperature of the cooling tower is controlled to be 65-75 ℃, and the outlet temperature is controlled to be 40-50 ℃;
in the ripening tank, the temperature in the ripening tank is controlled to be 35-45 ℃, and the material retention time is as follows: the stirring speed is 34r/min for more than 60 min;
in the thickener, the internal temperature of the thickener is controlled to be 35-40 ℃, the pH value of supernatant fluid of the thickener is 2-3, and the specific gravity of underflow of the thickener is as follows: 1.50 to 1.80;
in the No. 1 reaction tank and the No. 2 reaction tank, the internal temperature of the reaction tank is controlled to be 65-75 ℃, and the pH value is 2.5-3.0;
2) magnesium removal: the centrifuge decalcified filtrate was fed to a neutralization tank, followed by Ca (OH)2Slurrying in a slurrying tank, adding a neutralizing tank to adjust the pH value to 8-9, conveying the neutralized material to a filter press, conveying the obtained magnesium-containing filtrate to a sewage station for treatment, slurrying the obtained filter residue, and conveying the slurried filter residue to an iron removal process.
2. The method for removing calcium and magnesium in the zinc hydrometallurgy process as claimed in claim 1, wherein in the neutralization tank of the step 1), the internal temperature of the neutralization tank is controlled to be 65-75 ℃, and the pH value is controlled to be 8.0-9.0.
3. The method for removing calcium and magnesium in a zinc hydrometallurgy process of claim 1, wherein the CaCO3Slurrying and Ca (OH)2The concentration of the slurried solution was 500 g/l.
4. The method for removing calcium and magnesium in the zinc hydrometallurgy process of claim 3, wherein the CaCO3The purity of the product is more than or equal to 95 percent, and the granularity is-200 meshes; the Ca (OH)2The purity of the product is more than or equal to 90 percent, and the granularity is-300 meshes.
CN201911389011.2A 2019-12-30 2019-12-30 Method for removing calcium and magnesium in zinc hydrometallurgy process Active CN110964914B (en)

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CN114438328B (en) * 2021-12-30 2023-09-22 云锡文山锌铟冶炼有限公司 Device and method for producing zinc sulfate leaching solution in zinc hydrometallurgy process
CN114438319B (en) * 2021-12-30 2023-12-08 云锡文山锌铟冶炼有限公司 Method for treating calcium and magnesium in zinc hydrometallurgy process

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US4437953A (en) * 1981-06-02 1984-03-20 Electrolytic Zinc Company Of Australasia Limited Process for solution control in an electrolytic zinc plant circuit
FI110268B (en) * 2001-03-09 2002-12-31 Outokumpu Oy Process for removing calcium from sulfate solutions in a zinc process
CN100450942C (en) * 2006-10-20 2009-01-14 云南冶金集团总公司技术中心 Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution
CN105755296B (en) * 2016-03-29 2018-12-28 云南华联锌铟股份有限公司 The method of calcium is removed from the solution of zinc sulfate that zinc hydrometallurgy produces

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