CN115491499A - Method for separating and recovering strontium from zinc anode mud - Google Patents
Method for separating and recovering strontium from zinc anode mud Download PDFInfo
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- CN115491499A CN115491499A CN202211170111.8A CN202211170111A CN115491499A CN 115491499 A CN115491499 A CN 115491499A CN 202211170111 A CN202211170111 A CN 202211170111A CN 115491499 A CN115491499 A CN 115491499A
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- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 105
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000011701 zinc Substances 0.000 title claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000000498 ball milling Methods 0.000 claims abstract description 33
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims abstract description 22
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 65
- 239000007788 liquid Substances 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910001427 strontium ion Inorganic materials 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 20
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003751 zinc Chemical class 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
- 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
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for separating and recovering strontium from zinc anode mud, which comprises the steps of carrying out wet ball milling on zinc anode mud, and filtering to obtain a filter cake I; then carrying out strontium conversion reaction on the filter cake I and a carbonate solution, and filtering to obtain a filter cake II; leaching the filter cake II at low temperature by using dilute acid to obtain strontium-containing leachate; purifying and removing impurities from the strontium-containing leachate by using a sodium hydroxide solution to obtain a strontium-containing purified solution; and adding a carbonate solution into the strontium-containing purified solution for precipitation reaction to obtain strontium carbonate. The method has the advantages of high strontium recovery rate of 90-99% in the anode mud, high purity of 94-98%, greatly reduced medicament concentration and dosage, environmental friendliness, simple process flow, low requirement on equipment and contribution to large-scale popularization and application.
Description
Technical Field
The invention relates to a method for treating zinc anode slime, in particular to a method for separating and recovering strontium from the zinc anode slime, and belongs to the technical field of chemical industry.
Background
Strontium is a metal with unique physical and chemical properties, and can be widely applied to various fields of electronics, chemical industry, metallurgy, fireworks, military, light industry, medicine, optics and the like. The strontium resource of China is rich and accounts for about one fourth of the global strontium reserves. The rapid development of the metallurgical industry has produced a large amount of strontium-containing secondary resources. The strontium slag is a byproduct generated in the strontium carbonate refining process, and the accumulated strontium slag in China reaches 4500 ten thousand tons and is increased at the rate of 500 ten thousand tons per year. Therefore, the recovery of strontium from the strontium-containing secondary resource is of great significance to environmental requirements and the safety of strontium resources.
The zinc anode mud is produced in the electrodeposition process of a zinc hydrometallurgy system. Strontium carbonate is often added to the cell during electrodeposition to improve the quality of the cathode zinc. Strontium carbonate is first converted to strontium sulfate in the electrolyte and then coprecipitated with lead sulfate. About 40-50 kg of anode sludge is produced for every 1 ton of zinc produced. The anode mud contains various valuable metals such as manganese, zinc, calcium and the like besides strontium and lead. The accumulation treatment mode of the waste anode slime inevitably brings about serious problems of insufficient resource utilization, serious pollution to public health and environment and the like. Therefore, the enhancement of the separation and recovery of strontium from zinc electrolysis anode slime has become a problem that the zinc hydrometallurgy industry has to solve.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention aims to provide a method for separating and recovering strontium from zinc anode slime. The method utilizes ball milling machinery to activate strontium in zinc anode mud to realize (Pb, sr) SO 4 The method has the advantages of high strontium recovery rate, reduction in treatment agent concentration and dosage, environmental friendliness, simple process flow, low requirement on equipment and contribution to large-scale popularization and application.
In order to realize the technical purpose, the invention provides a method for separating and recovering strontium from zinc anode slime, which comprises the steps of carrying out wet ball milling on zinc anode slime, and filtering to obtain a filter cake I; carrying out strontium conversion reaction on the filter cake I and a carbonate solution, and filtering to obtain a filter cake II; leaching the filter cake II at low temperature by using dilute acid to obtain strontium-containing leachate; purifying and removing impurities from the strontium-containing leachate by using a sodium hydroxide solution to obtain a strontium-containing purified solution; and adding a carbonate solution into the strontium-containing purified solution for precipitation reaction to obtain strontium carbonate.
The zinc anode mud is strontium-containing anode mud generated in an electrodeposition process in a zinc hydrometallurgy system, wherein the strontium content is 2-6 wt%.
The invention carries out wet ball milling on the zinc anode mud to activate the zinc anode mud, and then adds carbonate solution to carry out chemical reaction with the activated zinc anode mud so as to convert strontium in the zinc anode mud into strontium carbonate (SrCO) which is easy to leach in low-concentration acid liquor 3 ) Therefore, by combining low-concentration acid liquor and low-temperature leaching, the strontium carbonate can be efficiently leached under the condition, only a small amount of impurities such as calcium are contained, and manganese, silicon dioxide, lead and the like are enriched in a slag phase, so that enrichment and separation of strontium can be realized.
As a preferred scheme, the wet ball milling conditions are as follows: the rotating speed is 100-300 r/min, the solid-liquid ratio is 1 g. The rotation speed is more preferably 150 to 250r/min. Further preferred solid-to-liquid ratios are 1g:0.9 to 1.1ml. A more preferred time is 0.9 to 1.1h.
In the ball milling activation process, conditions such as proper liquid-solid ratio, ball milling rotation speed and the like need to be controlled, wherein the excessively high liquid-solid ratio can cause the excessive dispersion of materials, so that the materials are not fully contacted with the balls, the wet ball milling effect is reduced, and the leaching effect is reduced; and the low liquid-solid ratio leads to poor material fluidity, insufficient contact between the materials and the balls, and reduced wet ball milling effect, thereby reducing leaching effect. Meanwhile, the surface activation of the zinc anode slime can be realized by mechanical energy only by controlling the proper ball milling rotating speed.
As a preferred embodiment, the carbonate is at least one of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
As a preferred embodiment, the conditions of the strontium conversion reaction are as follows: the solid-liquid ratio of the filter cake I to the carbonate solution is 1g: 3-4 mL, and the concentration of the carbonate solution is 0.2-0.4 mol/L; the temperature is 85-95 ℃ and the time is 10-20 min. The concentration of the carbonate solution is more preferably 0.25 to 0.33mol/L. In the process of strontium conversion reaction, the liquid-solid ratio is too low, so that the fluidity of the mixed material is poor, and the recovery is influenced; the liquid-solid ratio is too large, which causes resource waste and increases the cost. Meanwhile, the concentration of the carbonate solution is too low, so that the raw materials cannot fully react, and the conversion efficiency of strontium is low; the excessive concentration of carbonate solution increases the consumption of the medicament, and the corresponding benefit cannot be obtained, thereby affecting the economic benefit. In the process of strontium conversion reaction, the higher the temperature is, the higher the strontium conversion efficiency is, and when the temperature is 85-95 ℃, the strontium conversion efficiency is the best. The fuel cost is increased, the cost is increased and the economic benefit is reduced due to overhigh temperature; and the low temperature not only reduces the reaction rate, but also reduces the strontium recovery effect.
As a preferred scheme, the conditions of the dilute acid low-temperature leaching are as follows: taking a dilute acid solution with the concentration of 0.3-0.4 mol/L as a leaching agent, wherein the solid-to-liquid ratio of the filter cake II to the dilute acid solution is 1g:3 to 4mL, the temperature is 20 to 40 ℃, and the time is 5 to 10min. In the process of the dilute acid leaching reaction, the concentration of the dilute acid, the solid-liquid ratio and the reaction temperature need to be controlled within a proper range, which is beneficial to improving the leaching efficiency. If the liquid-solid ratio is too low, the fluidity of the mixed material is poor, and the recovery is influenced; the liquid-solid ratio is too large, so that water resource waste is caused, and the cost is increased. The concentration of the dilute acid solution is too low, the raw materials cannot fully react, and the leaching efficiency is reduced; the excessive concentration of the dilute acid solution can increase the consumption of the medicament, can not obtain corresponding benefits, has higher requirements on equipment and influences economic benefits. In the dilute acid leaching reaction process, when the temperature is 30 ℃, the strontium leaching achieves the best effect. Due to the fact that the temperature is too high, the leaching efficiency of strontium is reduced, the recovery effect of strontium is affected, the consumption of acid and the fuel cost are increased, and the production cost is increased; and if the temperature is too low, the reaction rate is reduced, and the leaching effect of strontium is influenced.
In a preferred embodiment, the dilute acid solution is dilute hydrochloric acid. The dilute hydrochloric acid adopted by the invention has strong acidity, good leaching effect and less waste liquid pollution, and is beneficial to environmental protection. Compared with weak acids such as hydrochloric acid, oxalic acid and the like, the acid leaching effect is relatively poor, and nitric acid leaching generates a large amount of nitrogen-containing waste liquid, so that water eutrophication is easily caused, denitrification treatment is required, and the production cost is increased.
As a preferred scheme, the purification process is as follows: adjusting the pH value of the strontium-containing leaching solution to 12-13 by adopting a sodium hydroxide solution with the concentration of 8-12 mol/L, and filtering. The most preferable pH value adjusting range is 12.5-12.7.
As a preferred scheme, when the solid-to-liquid ratio in the dilute acid low-temperature leaching process is 1g: when the volume is 3mL, adjusting the pH value of the leachate to 12.5 by adopting a sodium hydroxide solution in the purification process; when the solid-liquid ratio in the low-temperature leaching process of dilute acid is 1g: and when the volume is 4mL, the pH value of the leachate is adjusted to 12.7 by adopting a sodium hydroxide solution in the purification process. When the pH value of the strontium-containing leachate is adjusted to 12.5-12.7 by sodium hydroxide solution, part of metal ion impurities in the leachate can be precipitated, thereby improving the recovery purity of strontium. In the purification and impurity removal process, the concentration of the sodium hydroxide solution is controlled to be 10mol/L, which is beneficial to improving the purification efficiency.
As a preferred embodiment, the precipitation reaction conditions are: the mol ratio of the carbonate ions in the carbonate solution to the strontium ions in the strontium-containing purified solution is 1.05-1.1: 1. the temperature is 20-40 ℃, and the time is 5-10 min. In the strontium precipitation reaction process, controlling the molar ratio of carbonate ions in the carbonate solution to strontium ions in the purification solution to be 1.05-1.1: 1 better strontium recovery effect can be obtained.
As a preferred embodiment, the carbonate solution is a saturated solution. A further preferred carbonate solution is a sodium carbonate solution.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The method adopts the combined means of mechanochemical ball milling, low-acid low-temperature leaching, precipitation reaction and the like to realize the high-efficiency conversion of strontium in the zinc anode slime and the high-efficiency separation of metal impurities, the recovery rate of the obtained strontium reaches 90-99 percent, and the purity of the strontium product can reach 94-98 percent.
(2) Strontium in low-zinc anode mud is efficiently converted into acid solution which is easily dissolved in low concentration by adopting a mechanochemical ball milling technologyStrontium carbonate (SrCO) 3 ) Thereby realizing the high-efficiency leaching of strontium under the low-concentration acid liquor and realizing the separation of strontium and impurities.
(3) The method is simple, greatly reduces the concentration and the dosage of the medicament, is environment-friendly, has low requirement on equipment, and is beneficial to large-scale popularization and application.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples. These examples are only for better understanding of the present invention and do not limit the scope of the present invention.
Example 1
The embodiment provides a method for separating and recovering strontium from zinc anode slime, which comprises the following specific steps:
(1) 100g of strontium-containing zinc anode mud (components are shown in table 1) is placed into a ball milling tank with the volume of 1L for mechanochemical ball milling, and the solid-liquid ratio is controlled to be 1g:1ml, the ball milling speed is 200r/min, and the ball milling time is 1h.
(2) Mixing the mechanochemical ball-milled product with 0.25mol/L sodium carbonate solution, and controlling the solid-liquid ratio to be 1g:4ml, the leaching temperature is 95 ℃, the time is 20min, and the filter cake containing strontium carbonate is obtained by filtration.
(3) Mixing a filter cake containing strontium carbonate with 0.3mol/L hydrochloric acid, and controlling the solid-liquid ratio to be 1g:4ml, the leaching temperature is 30 ℃, the time is 10min, and the leaching product is filtered to obtain strontium-containing filtrate.
(4) Adding 10mol/L sodium hydroxide solution into the strontium-containing filtrate to adjust the pH value to 12.7, and filtering to obtain strontium-containing purified liquid.
(5) Mixing the strontium-containing purified liquid with a saturated sodium carbonate solution for precipitation reaction, and controlling the molar ratio of carbonate ions to strontium in the purified liquid to be 1.1:1, the reaction temperature is 30 ℃, the reaction time is 10 minutes, a reaction product is filtered to obtain a solid, and the solid is dried to obtain the strontium carbonate.
By calculation, under the implementation condition, the strontium recovery rate is 98.29%, and the product purity is 97.61%.
TABLE 1 certain Zinc Anode slime composition, wt.%
Example 2
The embodiment provides another method for separating and recovering strontium from zinc anode slime, which comprises the following specific steps:
(1) 100g of strontium-containing zinc anode mud (components are shown in table 1) is placed into a ball milling tank with the volume of 1L for mechanochemical ball milling, and the solid-liquid ratio is controlled to be 1g:0.9ml, the ball milling speed is 200r/min, and the ball milling time is 1h.
(2) Mixing the mechanochemical ball-milled product with 0.33mol/L sodium carbonate solution, and controlling the solid-liquid ratio to be 1g:3ml, leaching temperature of 85 ℃ for 10min, and filtering to obtain a filter cake containing strontium carbonate.
(3) Mixing a filter cake containing strontium carbonate with 0.4mol/L hydrochloric acid, and controlling the solid-liquid ratio to be 1g:3ml, the leaching temperature is 30 ℃, the time is 5min, and the leaching product is filtered to obtain strontium-containing filtrate.
(4) Adding 10mol/L sodium hydroxide solution into the strontium-containing filtrate to adjust the pH value to 12.5, and filtering to obtain purified liquid.
(5) Mixing the purified solution with a saturated sodium carbonate solution for precipitation reaction, and controlling the molar ratio of carbonate ions to strontium in the purified solution to be 1.05:1, the reaction temperature is 30 ℃, the reaction time is 5 minutes, a reaction product is filtered to obtain a solid, and the solid is dried to obtain the strontium carbonate.
By calculation, under the implementation condition, the recovery rate of strontium is 92.47%, and the product purity is 94.89%.
Example 3
The third method for separating and recovering strontium from zinc anode slime is provided in the embodiment and comprises the following specific steps:
(1) 100g of strontium-containing zinc anode mud (the components are shown in table 1) is taken and put into a ball milling tank with the volume of 1L for mechanochemical ball milling, and the solid-liquid ratio is controlled to be 1g:1.1ml, the ball milling speed is 200r/min, and the ball milling time is 1.1h.
(2) Mixing the mechanochemical ball-milled product with 0.25mol/L sodium carbonate solution, wherein the solid-liquid ratio is 1g:4ml, leaching temperature is 90 ℃, time is 10min, and filtering is carried out to obtain a filter cake containing strontium carbonate.
(3) Mixing a filter cake containing strontium carbonate with 0.3mol/L hydrochloric acid, and controlling the solid-liquid ratio to be 1g:4ml, the leaching temperature is 30 ℃, the time is 10min, and the leaching product is filtered to obtain strontium-containing filtrate.
(4) Adding 10mol/L sodium hydroxide solution into the strontium-containing filtrate to adjust the pH value to 12.7, and filtering to obtain purified liquid.
(5) Mixing the purified solution with a saturated sodium carbonate solution for precipitation reaction, and controlling the molar ratio of carbonate ions to strontium in the purified solution to be 1.1:1, the reaction temperature is 30 ℃, the reaction time is 10 minutes, a reaction product is filtered to obtain a solid, and the solid is dried to obtain the strontium carbonate.
By calculation, under the implementation condition, the strontium recovery rate is 90.36%, and the product purity is 95.1%.
Example 4
This example provides a third method for separating and recovering strontium from zinc anode slime, which includes the following steps:
(1) 100g of strontium-containing zinc anode mud (the components are shown in table 1) is taken and put into a ball milling tank with the volume of 1L for mechanochemical ball milling, and the solid-liquid ratio is controlled to be 1g:0.9ml, the ball milling speed is 200r/min, and the ball milling time is 0.9h.
(2) Mixing the mechanochemical ball-milled product with 0.33mol/L sodium carbonate solution, and controlling the solid-liquid ratio to be 1g:3ml, leaching temperature of 85 ℃ for 10min, and filtering to obtain a filter cake containing strontium carbonate.
(3) Mixing a filter cake containing strontium carbonate with 0.4mol/L hydrochloric acid, and controlling the solid-liquid ratio to be 1g:3ml, leaching temperature of 30 ℃ for 5min, and filtering the leaching product to obtain strontium-containing filtrate.
(4) Adding 10mol/L sodium hydroxide solution into the strontium-containing filtrate to adjust the pH value to 12.5, and filtering to obtain purified liquid.
(5) Mixing the purified solution with a saturated sodium carbonate solution for precipitation reaction, and controlling the molar ratio of carbonate ions to strontium in the purified solution to be 1.05:1, the reaction temperature is 30 ℃, the reaction time is 5 minutes, a reaction product is filtered to obtain a solid, and the solid is dried to obtain the strontium carbonate.
By calculation, under the implementation condition, the strontium recovery rate is 95.7%, and the product purity is 96.35%.
Comparative example 1
On the basis of example 1, the solid-to-liquid ratio in the ball milling process was adjusted to 1g:3ml, adjusting the ball milling time to 0.5h, and keeping other conditions unchanged.
It was calculated that the strontium recovery was only 34.83% under the comparative example conditions.
Comparative example 2
In addition to example 1, the reaction temperature in the sodium carbonate conversion reaction of step (2) was adjusted to 50 ℃ and the reaction time was adjusted to 5min, while the other conditions were kept constant.
It was calculated that the strontium recovery under the comparative example conditions was only 47.32%.
Comparative example 3
On the basis of example 1, the leaching temperature in the acid leaching reaction in step (3) was adjusted to 90 ℃, and other conditions were kept unchanged.
The strontium recovery was calculated to be only 57.58% under the comparative example conditions.
Comparative example 4
On the basis of the example 1, the molar ratio of carbonate ions in the precipitation reaction in the step (5) to strontium in the leaching solution is adjusted to 1:1, other conditions were kept unchanged.
It was calculated that under the conditions of this comparative example, the strontium recovery was 80.28% and the purity was 95.34%.
In conclusion, through analysis of comparative examples, for zinc anode slime, mechanochemical ball milling and sodium carbonate conversion-low-concentration hydrochloric acid low-temperature leaching can obviously improve the recovery efficiency, and the method has simple process flow and low requirement on equipment, and is suitable for industrial large-scale production.
Claims (9)
1. A method for separating and recovering strontium from zinc anode slime is characterized by comprising the following steps: carrying out wet ball milling on the zinc-containing anode mud, and filtering to obtain a filter cake I; carrying out strontium conversion reaction on the filter cake I and a carbonate solution, and filtering to obtain a filter cake II; leaching the filter cake II at low temperature by using dilute acid to obtain strontium-containing leachate; purifying and removing impurities from the strontium-containing leachate by using a sodium hydroxide solution to obtain a strontium-containing purified solution; and adding a carbonate solution into the strontium-containing purified solution for precipitation reaction to obtain strontium carbonate.
2. The method for separating and recovering strontium from zinc anode slime according to claim 1, wherein: the wet ball milling conditions are as follows: the rotating speed is 100-300 r/min; the solid-liquid ratio is 1g:0.5 to 1.5ml; the time is 0.5 to 1.5 hours.
3. The method for separating and recovering strontium from zinc anode slime according to claim 1, wherein: the carbonate solution contains at least one carbonate of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
4. The method for separating and recovering strontium from zinc anode slime according to claim 1 or 2, characterized in that: the conditions of the strontium conversion reaction are as follows: the solid-liquid ratio of the filter cake I to the carbonate solution is 1g: 3-4 mL, and the concentration of the carbonate solution is 0.2-0.4 mol/L; the temperature is 85-95 ℃ and the time is 10-20 min.
5. The method for separating and recovering strontium from zinc anode slime as set forth in claim 1, characterized in that: the low-temperature leaching conditions of the dilute acid are as follows: taking a dilute acid solution with the concentration of 0.3-0.4 mol/L as a leaching agent, wherein the solid-liquid ratio of the filter cake II to the dilute acid solution is 1g:3 to 4mL, the temperature is 20 to 40 ℃, and the time is 5 to 10min.
6. The method for separating and recovering strontium from zinc anode slime as set forth in claim 5, characterized in that: the dilute acid solution is dilute hydrochloric acid.
7. The method for separating and recovering strontium from zinc anode slime according to claim 1, wherein: the purification and impurity removal process comprises the following steps: adjusting the pH value of the strontium-containing leaching solution to 12-13 by adopting a sodium hydroxide solution with the concentration of 8-12 mol/L, and filtering.
8. The method for separating and recovering strontium from zinc anode slime as set forth in claim 1 or 7, characterized in that: the precipitation reaction conditions are as follows: the mol ratio of carbonate ions in the carbonate solution to strontium ions in the strontium-containing purified solution is 1.05-1.1, the temperature is 20-40 ℃, and the time is 5-10 min.
9. The method for separating and recovering strontium from zinc anode slime as set forth in claim 1, characterized in that: the carbonate solution is a saturated solution.
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