CN105755296B - The method of calcium is removed from the solution of zinc sulfate that zinc hydrometallurgy produces - Google Patents
The method of calcium is removed from the solution of zinc sulfate that zinc hydrometallurgy produces Download PDFInfo
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- CN105755296B CN105755296B CN201610187765.XA CN201610187765A CN105755296B CN 105755296 B CN105755296 B CN 105755296B CN 201610187765 A CN201610187765 A CN 201610187765A CN 105755296 B CN105755296 B CN 105755296B
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 159
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 102
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 102
- 239000011575 calcium Substances 0.000 title claims abstract description 71
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 69
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000011701 zinc Substances 0.000 title claims abstract description 47
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 25
- 239000002562 thickening agent Substances 0.000 claims abstract description 53
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 235000009529 zinc sulphate Nutrition 0.000 claims description 57
- 239000011686 zinc sulphate Substances 0.000 claims description 57
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 159000000007 calcium salts Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 41
- 235000011132 calcium sulphate Nutrition 0.000 description 18
- 229940095672 calcium sulfate Drugs 0.000 description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- OKYDTGSQPZBYTF-UHFFFAOYSA-J calcium;magnesium;disulfate Chemical compound [Mg+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OKYDTGSQPZBYTF-UHFFFAOYSA-J 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 208000004434 Calcinosis Diseases 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of method for removing calcium from the solution of zinc sulfate that zinc hydrometallurgy produces, the method that calcium is removed from the solution of zinc sulfate that zinc hydrometallurgy produces is the following steps are included: the cooling solution of zinc sulfate；Thickener is added into the solution of zinc sulfate, and the pH of the solution of zinc sulfate is adjusted to 4.0-4.5；It is added in concentrator with by the solution of zinc sulfate, and stops the solution of zinc sulfate -30 hours 5 hours in the concentrator, to obtain the overflow after the underflow and deliming of calcic.By utilizing the method according to an embodiment of the present invention for removing calcium from the solution of zinc sulfate that zinc hydrometallurgy produces, it can be under the premise of not changing prior art process, greatly alleviate crystallization of the calcium salt in electrolysis process, reduce power consumption, reduce cleaning calcium fouling labour, improves productivity effect.
Description
Technical Field
The invention relates to the field of metallurgy, in particular to a method for removing calcium from a zinc sulfate solution produced by zinc hydrometallurgy.
Background
The impurity removal in the zinc hydrometallurgy process is a necessary procedure, and calcium sulfate impurities are more special and have higher removal difficulty in common impurities.
In the existing zinc hydrometallurgy process, zinc sulfide concentrate is roasted by a fluidized bed furnace to obtain zinc calcine, calcium exists in the zinc calcine as oxide, when the zinc calcine is leached by waste electrolyte from zinc electrodeposition, calcium and magnesium enter neutral leachate along with the leaching of the zinc calcine, and the neutral leachate is subjected to a zinc powder displacement purification impurity removal process to obtain purified zinc sulfate solution (namely purified solution), wherein the temperature of the purified zinc sulfate solution is usually 60-80 ℃. The concentration of calcium in the purified zinc sulfate solution is 300mg/L-600 mg/L. After the calcium sulfate enters a zinc hydrometallurgy solution system, the volume density of purified solution is correspondingly increased, so that the viscosity of the solution is increased, the liquid-solid separation and filtration of ore pulp are difficult, and when calcium salt is crystallized and separated out on the filter cloth, the filter cloth can be blocked, so that the filtration is difficult.
In addition, the purified liquid is forcibly cooled to 35-40 ℃ through an air cooling tower, the solubility of calcium and magnesium sulfates is rapidly reduced along with the continuous reduction of the temperature, the calcium and magnesium are disordered and crystallized, the calcium and magnesium sulfate is disordered and crystallized in the cooling process, and a solution channel is scaled, so that the heat transfer rate of a shell of the heat dissipation equipment and a conveying pipeline is easily reduced, and the production is stopped and overhauled in severe cases.
At present, the most common method for removing calcium is an air cooling tower cooling and calcium removing method, which generally takes purified liquid at about 60-85 ℃ as a treatment object and reduces the temperature of the purified liquid from about 60-85 ℃ to about 42 ℃ or from about 42 ℃ to about 34 ℃. With the reduction of the temperature, the solubility of the calcium sulfate is reduced and the calcium sulfate is crystallized and separated out, but the actual effect of the cooling and calcium removal process is not very ideal because the calcium sulfate is slowly crystallized in the cooling process. In the zinc electrolysis section, calcium ions deposit in the form of dihydrate gypsum on the wall of the electrolytic bath, the anode plate, even the cathode and the infusion pipeline. The dihydrate gypsum is a poor conductor, and is separated out together with manganese dioxide on an anode plate, so that anode mud is thickened, the resistance is increased, the voltage of a tank is high, the power consumption is increased, even an interelectrode short circuit is caused, and the phenomenon that the cathode zinc is re-dissolved is also common. In order to avoid the problems, the grooves must be frequently cut, and the labor intensity is high.
In order to supplement the effects of temperature reduction and calcium removal, an improved scheme is proposed, zinc sulfate which is cooled to 42 ℃ by a cooling tower solution is pumped into a thickener, and purified solution (42 ℃) stays in the thickener for 3-5 hours, aiming at growing and depositing crystals of calcium sulfate and magnesium, so that the calcium sulfate and the magnesium sulfate are further separated, but the solubility of the calcium sulfate and the magnesium sulfate is still high in the process, the crystallization is slow, and the contents of the calcium and the magnesium in the purified solution are still high.
Patent application No. CN200610031895.0 discloses a method for removing calcium ions from zinc sulfate solution. The method introduces ultrasonic waves into the thickener, takes the ultrasonic waves as a crystallizer, promotes the calcium sulfate in the purified liquid to be converted into a crystalline state from an ionic state, and shortens the crystallization time. But there is no significant improvement in the residual calcium content of the solution and the cost is also increased due to the increase of equipment.
Patent application No. CN02806244.2 discloses a method for removing calcium from zinc-treated sulfate solutions. Adding anhydrous calcium sulfate seed crystal into the purified liquid at 85 deg.c, and stirring slowly to crystallize, separate and deposit calcium sulfate in the form of anhydrous calcium sulfate. According to the method, on the premise of adding seed crystals, calcium ions are converted into anhydrous calcium sulfate with lower solubility and more stable property, and the concentration of liquid calcium is reduced by 400-500 mg/L after calcium is removed. However, the calcium concentration is still high, and simultaneously, the solubility of magnesium is increased, so that the aim of removing magnesium cannot be fulfilled.
Disclosure of Invention
The present application is based on the discovery and recognition by the inventors of the following facts and problems: the inventors of the present application have conducted intensive and repeated studies and investigations in order to remove calcium from zinc sulphate solution produced by zinc hydrometallurgy. Calcium sulfate has three different forms: calcium sulfate dihydrate, calcium sulfate hemihydrate, and calcium sulfate anhydrite. After the zinc sulphate solution is cooled, the calcium sulphate in the zinc sulphate solution is mainly crystallized and separated out in the form of calcium sulphate dihydrate. The solubility and sedimentation rate of calcium sulfate in the zinc sulfate solution are in important relation with the solution temperature, the retention time in a thickener, whether a thickener is added or not and the pH value of the zinc sulfate solution.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, the present invention proposes a method for removing calcium from a zinc sulphate solution produced by zinc hydrometallurgy, which method is effective in removing calcium ions from the zinc sulphate solution.
The method for removing calcium from zinc sulfate solution produced by zinc hydrometallurgy according to the embodiment of the invention comprises the following steps: cooling the zinc sulphate solution; adding a thickener into the zinc sulfate solution, and adjusting the pH of the zinc sulfate solution to 4.0-4.5; and adding the zinc sulphate solution to a thickener and allowing the zinc sulphate solution to remain in the thickener for 5-30 hours to obtain a calcium containing underflow and a calcium depleted overflow.
By utilizing the method for removing calcium from the zinc sulfate solution produced by zinc hydrometallurgy, the crystallization of calcium salt in an electrolysis process can be greatly relieved, the power consumption is reduced, the labor force for cleaning calcium scale is reduced, and the production benefit is improved on the premise of not changing the existing process flow.
In addition, the method for removing calcium from zinc sulfate solution produced by zinc hydrometallurgy according to the above embodiment of the present invention may also have the following additional technical features:
according to one embodiment of the invention, the temperature of the zinc sulphate solution is cooled from 60-80 ℃ to 35-40 ℃ by means of an air cooling tower.
According to one embodiment of the invention the pH of the zinc sulphate solution is adjusted to 4.35.
According to one embodiment of the present invention, the thickener is selected from at least one of organic thickener #920, polyaluminium sulfate, polyaluminium chloride and organic thickener # 4125.
According to one embodiment of the invention, the thickener is used in an amount of 5ppm to 100 ppm.
According to one embodiment of the invention the concentration of calcium in the zinc sulphate solution is 400-800mg/L, the concentration of zinc is 130-180 g/L and the concentration of magnesium is 5-30 g/L.
According to one embodiment of the invention the zinc concentration in the zinc sulphate solution is between 170g/L and 180g/L and the magnesium concentration is between 20g/L and 30 g/L.
According to one embodiment of the invention the underflow has a zinc content of less than 20 wt% and a calcium content of more than 10 wt%.
According to one embodiment of the invention, the concentration of calcium in the overflow is less than 100 mg/L.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention.
The application provides a method for removing calcium from zinc sulfate solution produced by zinc hydrometallurgy. The method for removing calcium from zinc sulfate solution produced by zinc hydrometallurgy according to the embodiment of the invention comprises the following steps:
cooling the zinc sulphate solution;
adding a thickening agent into the zinc sulfate solution, and adjusting the pH value of the zinc sulfate solution to 4.0-4.5; and
the zinc sulphate solution is added to the thickener and allowed to stay in the thickener for 5-30 hours to obtain a calcium containing underflow and a calcium depleted overflow.
Wherein, the thickening agent can be added into the zinc sulfate solution, and then the pH value of the zinc sulfate solution is adjusted to 4.0-4.5. Or the pH value of the zinc sulfate solution is adjusted to 4.0-4.5, and then the thickening agent is added into the zinc sulfate solution. If the thickener is added, which results in a change in the pH of the zinc sulphate solution, the pH of the zinc sulphate solution is adjusted.
According to the method for removing calcium from the zinc sulfate solution produced by zinc hydrometallurgy, the temperature of the zinc sulfate solution is reduced, and the retention time of the zinc sulfate solution in the thickener is prolonged, so that slow crystallization and precipitation of calcium sulfate in the zinc sulfate solution in the form of calcium sulfate dihydrate are facilitated.
More importantly, according to the method for removing calcium from the zinc sulfate solution produced by zinc hydrometallurgy, the pH value of the zinc sulfate solution is adjusted to 4.0-4.5, so that the viscosity of the zinc sulfate solution can be reduced, the slag amount can be reduced, and the deposition of calcium sulfate dihydrate crystals is facilitated. Further, by adding a thickener to the zinc sulfate solution, crystallization of fine calcium sulfate dihydrate can be promoted.
That is, by cooling the zinc sulphate solution, extending the residence time of the zinc sulphate solution in the thickener, adding the thickener to the zinc sulphate solution and adjusting the pH of the zinc sulphate solution, the sedimentation rate of calcium sulphate can be significantly increased, thereby significantly reducing the concentration of calcium ions in the zinc sulphate solution.
Therefore, by using the method for removing calcium from the zinc sulfate solution produced by zinc hydrometallurgy according to the embodiment of the invention, the crystallization of calcium salt in an electrolysis process can be greatly relieved on the premise of not changing the existing process flow, the power consumption is reduced, the labor force for cleaning calcium scale is reduced, and the production benefit is improved.
The zinc sulfate solution can be purified zinc sulfate solution obtained by a zinc powder replacement purification impurity removal process, namely purified solution. Wherein the concentration of calcium in the zinc sulfate solution is 400-800mg/L, the concentration of zinc is 130-180 g/L, and the concentration of magnesium is 5-30 g/L.
In some examples of the invention, the zinc concentration in the zinc sulphate solution is between 170g/L and 180g/L and the magnesium concentration is between 20g/L and 30 g/L.
The inventors of the present application have found, through intensive and repeated studies and investigations, that the solubility and sedimentation rate of calcium sulfate in a zinc sulfate solution have an important relationship with the concentration of zinc sulfate and the concentration of magnesium sulfate in the zinc sulfate solution. Specifically, the concentration of calcium ions in the zinc sulfate solution decreases as the concentration of sulfates such as zinc sulfate, magnesium sulfate, etc. in the zinc sulfate solution increases.
Therefore, the concentration of the calcium ions in the zinc sulfate solution can be obviously reduced by enabling the concentration of the zinc in the zinc sulfate solution to be 170g/L-180g/L and the concentration of the magnesium to be 20g/L-30 g/L. Specifically, the calcium concentration in the overflow from the thickener is less than 100 mg/L. In other words, after calcium removal, the concentration of calcium ions in the zinc sulphate solution is less than 100 mg/L.
In addition, the higher the concentration of sulfate such as zinc sulfate and magnesium sulfate in the zinc sulfate solution is, the lower the concentration of calcium ions in the zinc sulfate solution after calcium removal is, i.e., the better the calcium removal effect is.
In some embodiments of the invention, the zinc sulphate solution may be cooled from 60-80 ℃ to 35-40 ℃ using an air cooling tower. Specifically, zinc sulfate solution (60-80 ℃) containing 400-800mg/L, Zn140-180g/L, Mg10-30g/L of Ca is conveyed to an air cooling tower through a pump, and the zinc sulfate solution is forcibly cooled to 35-40 ℃ in the air cooling tower.
Adjusting the pH value of the zinc sulfate solution after cooling, and adding a thickening agent. Wherein the pH of the zinc sulphate solution may be adjusted with sulphuric acid. In one embodiment of the invention, the pH of the zinc sulphate solution is adjusted to 4.35. Therefore, the viscosity of the zinc sulfate solution can be further reduced, the amount of slag can be further reduced, and the deposition of calcium sulfate dihydrate crystals is more facilitated.
In one specific example of the present invention, the thickener is at least one selected from the group consisting of organic thickener #920, polyaluminum sulfate, polyaluminum chloride, and organic thickener # 4125. In other words, one thickener may be added to the zinc sulphate solution, or several thickeners may be added to the zinc sulphate solution.
Advantageously, the thickener is used in an amount of 5ppm to 100 ppm. That is, the concentration of the thickener in the zinc sulfate solution is 5ppm to 100 ppm.
The zinc sulphate solution is then transported by means of a pump to a thickener where it stays for 10-30 hours. Finally, the bottom flow of calcium-magnesium sulfate is discharged from the bottom of the thickener periodically, and the zinc sulfate solution overflowed from the thickener enters an electrolysis section.
Wherein, the content of zinc in the underflow of calcium magnesium sulfate discharged from the bottom of the thickener is less than 20wt percent, and the content of calcium is more than 10wt percent. The concentration of calcium in the zinc sulphate solution overflowed from the thickener is less than 200 mg/L. Advantageously, the concentration of calcium in the zinc sulphate solution overflowing from the thickener is less than 100 mg/L.
Example 1
2L of zinc sulfate solution is taken, the temperature of the zinc sulfate solution is 75 ℃, the concentration of calcium in the zinc sulfate solution is 500mg/L, the concentration of zinc in the zinc sulfate solution is 170g/L, and the concentration of magnesium in the zinc sulfate solution is 30 g/L. The pH of the zinc sulphate solution was adjusted to 4.0-4.5 using sulphuric acid, 20ppm of thickener was added to the zinc sulphate solution and stirred slowly with a glass rod for 2 minutes.
The zinc sulphate solution is placed in a water bath and the temperature of the zinc sulphate solution is maintained between 35 ℃ and 40 ℃. After the zinc sulfate solution stays in the water bath for about 20 hours, the overflow is sent for analysis, and the concentration of calcium in the zinc sulfate solution which overflows is reduced to 120 mg/L.
Example 2
2L of zinc sulfate solution is taken, the temperature of the zinc sulfate solution is 75 ℃, the concentration of calcium in the zinc sulfate solution is 500mg/L, the concentration of zinc in the zinc sulfate solution is 160g/L, and the concentration of magnesium in the zinc sulfate solution is 30 g/L. The pH of the zinc sulphate solution was adjusted to 4.0-4.5 using sulphuric acid, 20ppm of thickener was added to the zinc sulphate solution and stirred slowly with a glass rod for 2 minutes.
The zinc sulphate solution is placed in a water bath and the temperature of the zinc sulphate solution is maintained between 35 ℃ and 40 ℃. After the zinc sulfate solution stays in the water bath for about 20 hours, the overflow is sent for analysis, and the concentration of calcium in the zinc sulfate solution which overflows is reduced to 180 mg/L.
Example 3
2L of zinc sulfate solution is taken, the temperature of the zinc sulfate solution is 75 ℃, the concentration of calcium in the zinc sulfate solution is 500mg/L, the concentration of zinc in the zinc sulfate solution is 160g/L, and the concentration of magnesium in the zinc sulfate solution is 10 g/L. The pH of the zinc sulphate solution was adjusted to 4.0-4.5 using sulphuric acid, 20ppm of thickener was added to the zinc sulphate solution and stirred slowly with a glass rod for 2 minutes.
The zinc sulphate solution is placed in a water bath and the temperature of the zinc sulphate solution is maintained between 35 ℃ and 40 ℃. After the zinc sulfate solution stays in the water bath for about 20 hours, the overflow is sent for analysis, and the concentration of calcium in the zinc sulfate solution which overflows is reduced to 200 mg/L.
Example 4
2L of zinc sulfate solution is taken, the temperature of the zinc sulfate solution is 75 ℃, the concentration of calcium in the zinc sulfate solution is 500mg/L, the concentration of zinc in the zinc sulfate solution is 150g/L, and the concentration of magnesium in the zinc sulfate solution is 10 g/L. The pH of the zinc sulphate solution was adjusted to 4.0-4.5 using sulphuric acid, 20ppm of thickener was added to the zinc sulphate solution and stirred slowly with a glass rod for 2 minutes.
The zinc sulphate solution is placed in a water bath and the temperature of the zinc sulphate solution is maintained between 35 ℃ and 40 ℃. After the zinc sulfate solution stays in the water bath for about 30 hours, the overflow is sent for analysis, and the concentration of calcium in the zinc sulfate solution which overflows is reduced to 200 mg/L.
Example 5
2L of zinc sulfate solution is taken, the temperature of the zinc sulfate solution is 65 ℃, the concentration of calcium in the zinc sulfate solution is 500mg/L, the concentration of zinc in the zinc sulfate solution is 150g/L, and the concentration of magnesium in the zinc sulfate solution is 10 g/L. The pH of the zinc sulphate solution is adjusted to 4.0-4.5 with sulphuric acid. The zinc sulfate solution is conveyed to a 180L thickener by a pump, a three-way pipe is adopted to introduce 30ppm of a thickening agent in the conveying process, and the temperature of the zinc sulfate solution in the thickener is maintained at 35-40 ℃ by the flow rate.
After the zinc sulfate solution stays in the thickener for about 10 hours, the overflow is sent for analysis, and the concentration of calcium in the zinc sulfate solution which overflows is reduced to 220 mg/L.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (7)
1. A method for removing calcium from a zinc sulfate solution produced by zinc hydrometallurgy is characterized by comprising the following steps:
cooling the zinc sulphate solution;
adding a thickener into the zinc sulfate solution, and adjusting the pH of the zinc sulfate solution to 4.0-4.5; and
adding the zinc sulphate solution into a thickener and allowing the zinc sulphate solution to stay in the thickener for 5-30 hours so as to obtain a calcium-containing underflow and a calcium-removed overflow; wherein,
the concentration of calcium in the zinc sulfate solution is 400-800mg/L, the concentration of zinc is 170-180 g/L, and the concentration of magnesium is 20-30 g/L.
2. The method of claim 1, characterized in that the temperature of the zinc sulphate solution is cooled from 60-80 ℃ to 35-40 ℃ by means of an air cooling tower.
3. The method of removing calcium from a zinc sulphate solution produced by zinc hydrometallurgy according to claim 1, characterised in that the pH of the zinc sulphate solution is adjusted to 4.35.
4. The method for removing calcium from zinc sulfate solution produced by zinc hydrometallurgy according to claim 1, wherein the thickener is one or more of organic thickener #920, polyaluminium sulfate, polyaluminium chloride and organic thickener # 4125.
5. The method of removing calcium from zinc sulphate solution produced by zinc hydrometallurgy according to claim 1, characterised in that the thickener is used in an amount of 5ppm to 100 ppm.
6. The method of removing calcium from a zinc sulphate solution produced by zinc hydrometallurgy according to claim 1, characterised in that the zinc content of the underflow is less than 20% by weight and the calcium content is more than 10% by weight.
7. The method of removing calcium from a zinc sulphate solution produced by zinc hydrometallurgy according to claim 1, characterised in that the concentration of calcium in the overflow is less than 100 mg/L.
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| CN110964914B (en) * | 2019-12-30 | 2021-09-03 | 南丹县南方有色金属有限责任公司 | Method for removing calcium and magnesium 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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