CN111285403A - Purification treatment method of manganese sulfate solution - Google Patents
Purification treatment method of manganese sulfate solution Download PDFInfo
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Abstract
The invention provides a purification treatment method of a manganese sulfate solution. The purification treatment method comprises the following steps: step S1, preparing an extraction organic phase, and saponifying the extraction organic phase to obtain a saponified organic phase; step S2, extracting the saponified organic phase with a manganese sulfate solution to obtain a manganese-rich organic phase; step S3, washing the manganese-rich organic phase for the first time by using water to obtain a purified manganese-rich organic phase for the first time; step S4, washing the primary purified manganese-rich organic phase for the second time by using a manganese-containing strong acid solution to obtain a secondary purified manganese-rich organic phase; and step S5, back extraction is carried out on the secondary purified manganese-rich organic phase by using sulfuric acid to obtain high-purity manganese sulfate solution and a regenerated organic phase. Because pure manganese sulfate is not needed to be adopted to carry out manganese conversion saponification on the saponified organic phase, and the washing liquid is cheap water and strong acid solution containing manganese, the purification treatment cost is low.
Description
Technical Field
The invention relates to the technical field of purification of manganese-containing solutions, and particularly relates to a purification treatment method of a manganese sulfate solution.
Background
Manganese and its compounds are one of the important industrial raw materials. In recent years, along with the continuous progress of the electronic chemical industry (such as electrolytic manganese, chemical manganese dioxide, magnetic trimanganese tetroxide and other electronic chemicals with high quality and high purity), the quality of manganese sulfate, which is a raw material for producing the high-standard electronic chemicals, is also attracting much attention. Lithium manganate and ternary materials can replace lithium cobaltate to become main battery anode materials in the coming years, and the consumption of manganese sulfate serving as a main raw material of the lithium manganate and the ternary materials is increased along with the rise of the lithium battery industry.
Manganese ore generally contains certain amounts of calcium, magnesium and other metal impurities. All heavy metal ions in the sulfuric acid leaching solution of the manganese ore can be well purified and removed by adjusting the purification process conditions, but the calcium and magnesium ions in the sulfuric acid leaching solution are very difficult to purify, and the purification effect of calcium and magnesium can directly determine whether a manganese sulfate product can meet the quality requirement of producing a high-performance battery raw material. In a sulfate system, calcium and magnesium ions are mainly purified by using the indissolvability of calcium sulfate and the uniionic effect of magnesium sulfate in high-concentration sulfate ions to ensure that the calcium and magnesium ions are calcium sulfate (CaSO)4) And magnesium sulfate (MgSO)4) The precipitate is separated out in a form, has the effect of removing calcium and magnesium ions, and is further purified by other methods such as ion exchange, salting out crystallization, chemical precipitation, solvent extraction and the like. The solvent extraction method has the advantages of high separation efficiency, low energy consumption, large production capacity, less equipment investment and convenience for continuous industrial operation, and is widely applied.
The traditional production process for removing calcium and magnesium from manganese sulfate by solvent extraction mainly comprises the following steps: chinese patent No. CN106517347B discloses a method for preparing high-purity manganese sulfate by using saponified octyl-decyl acid to perform extraction and back extraction. The raw material used in the method is the higher-price caprylic-capric acid, so that the production cost is higher. The Chinese patent application with the patent application number of 201810313444.9 discloses a method for reducing calcium and magnesium ions in electrolytic manganese qualified liquid, which comprises the steps of adjusting the pH value of the electrolytic manganese qualified liquid and preparing an extraction organic phase; saponifying the extracted organic phase with alkali liquor to obtain a sodium soap organic phase, and carrying out manganese soap treatment on the sodium soap organic phase with a manganese sulfate solution to obtain a manganese soap organic phase; extracting by taking the obtained manganese soap organic phase as an extracting agent and taking the electrolytic manganese qualified liquid with the adjusted pH as an extraction liquid to obtain a calcium-magnesium metal ion loaded organic phase and a deeply purified electrolytic manganese qualified liquid; washing manganese in the obtained organic phase loaded with calcium and magnesium metal ions by using a dilute manganese sulfate solution, and then performing back extraction by using sulfuric acid to obtain a regenerated extracted organic phase and a water phase loaded with calcium and magnesium metal ions. The method needs pure manganese sulfate to carry out manganese soap on the extractant, consumes manganese sulfate, increases the cost and has low magnesium removal rate.
The Chinese patent application with the patent application number of 201410640712.X adopts sulfide to remove heavy metals and Cyanex272 to extract manganese to prepare high-purity manganese sulfate, but because sulfide precipitate particles are small, colloid is easy to form, and separation is difficult, the method has large wastewater discharge, and the imported Cyanex272 extracting agent is expensive and has high cost.
Disclosure of Invention
The invention mainly aims to provide a method for purifying a manganese sulfate solution, which aims to solve the problem of high cost of the purification treatment of the manganese sulfate solution in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for purifying a manganese sulfate solution. The purification treatment method comprises the following steps: step S1, preparing an extraction organic phase, and saponifying the extraction organic phase to obtain a saponified organic phase; step S2, extracting the saponified organic phase with a manganese sulfate solution to obtain a manganese-rich organic phase; step S3, washing the manganese-rich organic phase for the first time by using water to obtain a purified manganese-rich organic phase for the first time; step S4, washing the primary purified manganese-rich organic phase for the second time by using a manganese-containing solution to obtain a secondary purified manganese-rich organic phase; and step S5, back extraction is carried out on the secondary purified manganese-rich organic phase by using sulfuric acid to obtain high-purity manganese sulfate solution and a regenerated organic phase.
Further, the manganese sulfate solution contains: 10 to 50g/L of Mn2+0.1 to 0.5g/L of Ca2+And 5 to 20g/L of Mg2+。
Further, the extracted organic phase comprises a P204 extracting agent and sulfonated kerosene, and the volume ratio of the P204 extracting agent to the sulfonated kerosene is 1: 10-3: 10.
Further, the above saponification process for the extracted organic phase comprises: saponifying the extracted organic phase by using an alkaline solution, wherein the alkaline solution is selected from one or more of a sodium hydroxide solution, a potassium hydroxide solution, ammonia water, a sodium carbonate solution and a potassium carbonate solution, and the saponification rate of saponification is preferably 60-80%; more preferably, the saponification rate is 70 to 80%.
Further, the pH value of the manganese sulfate solution is 2-4, and in the step S2, the volume ratio of the saponified organic phase to the manganese sulfate solution is 1: 2-2: 1; preferably, the extraction in the step S2 is multi-stage extraction, the temperature of each stage of extraction is preferably 20-40 ℃, the time of each stage of extraction is preferably 4-6 min, and the step S2 is preferably carried out 4-6 stages of countercurrent extraction.
Further, in the step S3, the volume ratio of the manganese-rich organic phase to the water is 1:1 to 1: 3; preferably, the first washing in the step S3 is multi-stage washing, the temperature of the first washing in each stage is preferably 20-40 ℃, the washing time of the first washing in each stage is preferably 5-10 min, the standing time of the first washing in each stage is preferably 5-10 min, and 2-4 stages of counter-current washing in the step S3 are preferably carried out.
Further, in step S4, the hydrogen ion concentration of the strong acid solution containing manganese is 0.01 to 0.04mol/L, preferably the strong acid solution containing manganese is a sulfuric acid solution containing manganese or a hydrochloric acid solution containing manganese, preferably the Mn in the strong acid solution containing manganese2+The content of the manganese-rich organic phase is 5-10 g/L, the volume ratio of the first purified manganese-rich organic phase to the manganese-containing strong acid solution is preferably 5: 1-8: 1, the second washing in the step S4 is preferably multi-stage washing, the temperature of the second washing in each stage is preferably 20-40 ℃, the washing time of the second washing in each stage is preferably 10-20 min, the standing time of the second washing in each stage is preferably 30-60 min, and the step S4 is preferably subjected to 2-4 stages of countercurrent washing.
Further, in the step S5, the concentration of sulfuric acid is 4 to 8mol/L, and the volume ratio of the secondary purification manganese-rich organic phase to the sulfuric acid is preferably 1:1 to 1: 3; preferably, the back extraction in the step S5 is multi-stage back extraction, preferably, the temperature of each stage of back extraction is 20-40 ℃, preferably, the time of each stage of back extraction is 4-6 min, and preferably, the step S5 is 2-4 stages of counter-current back extraction.
Further, the regenerated organic phase is returned to step S1 for saponification.
Further, the purification treatment method further comprises the following steps: and sequentially carrying out ultrasonic demulsification oil removal and activated carbon adsorption oil removal on the high-purity manganese sulfate solution to obtain the deoiled high-purity manganese sulfate solution.
By applying the technical scheme of the invention, firstly, the saponified organic phase is used as an extracting agent to carry out first extraction on the manganese sulfate solution, most of manganese ions enter the saponified organic phase to obtain a manganese-rich organic phase, and most of calcium and magnesium ions still remain in the water phase, so that the primary separation of the manganese ions, the calcium ions and the magnesium ions is realized. Secondly, the manganese-rich organic phase is washed for the first time by water, so that a small amount of calcium and magnesium ions attached to the manganese-rich organic phase can be removed preliminarily, and the purified manganese-rich organic phase is obtained for the first time. And then, the primary purified manganese-rich organic phase is washed for the second time by adopting a manganese-containing strong acid solution, so that the ion exchange between calcium and magnesium ions in the primary purified manganese-rich organic phase and manganese ions in the manganese-containing strong acid solution is facilitated in the strong acid solution containing a certain amount of manganese ions. On one hand, calcium and magnesium ions in the primary purified manganese-rich organic phase fully enter the water phase, and the calcium and magnesium ions in the primary purified manganese-rich organic phase are almost removed; on the other hand, the loss of manganese ions in the primary purified manganese-rich organic phase in the washing process is reduced, but the content of the manganese ions in the primary purified manganese-rich organic phase is further increased, and the secondary purified manganese-rich organic phase is obtained. And finally, back-extracting the secondary purified manganese-rich organic phase by using sulfuric acid to obtain a high-purity manganese sulfate solution and a regenerated organic phase. According to the method, manganese ions are gradually separated from calcium ions and magnesium ions through the step-by-step separation process of extraction, first washing, second washing and back extraction of the manganese sulfate solution, so that the calcium ions and the magnesium ions in the manganese sulfate solution are highly purified, and the highly purified manganese sulfate solution is obtained. In the prior art, the process of extracting and removing impurities from manganese soap organic phase to manganese sulfate solution is needed, and then expensive pure manganese sulfate is needed to convert the organic extractant into manganese for saponification. Compared with the prior art, the method does not need to adopt pure manganese sulfate to carry out manganese conversion saponification on the saponified organic phase, and the used washing liquid is cheap water and strong acid solution containing manganese ions, so that the purification treatment cost is low.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the application, the problem of high purification treatment cost of the manganese sulfate solution exists in the prior art, and in order to solve the problem, the application provides a purification treatment method of the manganese sulfate solution.
In an exemplary embodiment of the present application, a method for purifying a manganese sulfate solution is provided. The purification treatment method comprises the following steps: step S1, preparing an extraction organic phase, and saponifying the extraction organic phase to obtain a saponified organic phase; step S2, extracting the saponified organic phase with a manganese sulfate solution to obtain a manganese-rich organic phase; step S3, washing the manganese-rich organic phase for the first time by using water to obtain a purified manganese-rich organic phase for the first time; step S4, washing the primary purified manganese-rich organic phase for the second time by using a manganese-containing strong acid solution to obtain a secondary purified manganese-rich organic phase; and step S5, back extraction is carried out on the secondary purified manganese-rich organic phase by using sulfuric acid to obtain high-purity manganese sulfate solution and a regenerated organic phase.
Firstly, a saponified organic phase is used as an extracting agent to carry out first extraction on a manganese sulfate solution, most of manganese ions enter the saponified organic phase to obtain a manganese-rich organic phase, and most of calcium and magnesium ions still remain in a water phase, so that the primary separation of the manganese ions, the calcium ions and the magnesium ions is realized. Secondly, the manganese-rich organic phase is washed for the first time by water, so that a small amount of calcium and magnesium ions attached to the manganese-rich organic phase can be removed preliminarily, and the purified manganese-rich organic phase is obtained for the first time. And then, the primary purified manganese-rich organic phase is washed for the second time by adopting a manganese-containing strong acid solution, so that the ion exchange between calcium and magnesium ions in the primary purified manganese-rich organic phase and manganese ions in the manganese-containing strong acid solution is facilitated in the strong acid solution containing a certain amount of manganese ions. On one hand, calcium and magnesium ions in the primary purified manganese-rich organic phase fully enter the water phase, and the calcium and magnesium ions in the primary purified manganese-rich organic phase are almost removed; on the other hand, the loss of manganese ions in the primary purified manganese-rich organic phase in the washing process is reduced, but the content of the manganese ions in the primary purified manganese-rich organic phase is further increased, and the secondary purified manganese-rich organic phase is obtained. And finally, back-extracting the secondary purified manganese-rich organic phase by using sulfuric acid to obtain a high-purity manganese sulfate solution and a regenerated organic phase. According to the method, manganese ions are gradually separated from calcium ions and magnesium ions through the step-by-step separation process of extraction, first washing, second washing and back extraction of the manganese sulfate solution, so that the calcium ions and the magnesium ions in the manganese sulfate solution are highly purified, and the highly purified manganese sulfate solution is obtained. In the prior art, the process of extracting and removing impurities from manganese soap organic phase to manganese sulfate solution is needed, and then expensive pure manganese sulfate is needed to convert the organic extractant into manganese for saponification. Compared with the prior art, the method does not need to adopt pure manganese sulfate to carry out manganese conversion saponification on the saponified organic phase, and the used washing liquid is cheap water and strong acid solution containing manganese ions, so that the purification treatment cost is low.
The method realizes the separation of manganese ions from calcium ions and magnesium ions by a solvent extraction method, wherein the concentration of each ion in the manganese sulfate solution directly influences the extraction rate of the manganese ions and the purity of the final manganese sulfate solution. In a preferred embodiment of the present application, the manganese sulphate solution comprises: 10 to 50g/L of Mn2+0.1 to 0.5g/L of Ca2+And 5 to 20g/L of Mg2+. The purification method of the application has a particularly prominent effect on improving the magnesium removal rate of the manganese sulfate solution to be purified with the contents of manganese ions, calcium ions and magnesium ions.
The extraction organic phase which can be used in the present application is various, and can be selected by a person skilled in the art from extraction organic phases commonly used in the prior art, preferably, the extraction organic phase comprises a P204 extracting agent and sulfonated kerosene, and the volume ratio of the P204 extracting agent to the sulfonated kerosene is preferably 1: 10-3: 10. On one hand, sulfonated kerosene is used as an inert organic solvent, and on the other hand, sulfonated kerosene is added into a P204 extracting agent for dilution, so that the specific gravity of the P204 extracting agent in an extracted organic phase is reduced, the viscosity of the organic phase is reduced, and the separation of the organic phase and a water phase is facilitated. Moreover, the P204 extracting agent and the sulfonated kerosene have wide sources and lower cost.
In one embodiment of the present application, the saponification of the extracted organic phase comprises: saponifying the extracted organic phase by using an alkaline solution, wherein the alkaline solution is selected from one or more of a sodium hydroxide solution, a potassium hydroxide solution, ammonia water, a sodium carbonate solution and a potassium carbonate solution, and the saponification rate of saponification is preferably controlled to be 60-80%; more preferably, the saponification rate is 70 to 80%.
The P204 extractant is an acidic extractant, and the P204 extractant is involved in ion exchange in the extraction separation process of manganese, calcium and magnesium ions, including H+The exchange of (2). The pH value of the manganese sulfate solution has direct and critical influence on the extraction rate of manganese ions, calcium ions and magnesium ions, and if the pH value of the manganese sulfate solution is too small, the manganese ions are not beneficial to entering an organic phase. In order to reduce H in the saponified organic phase during the extraction+The organic phase is preferably saponified in advance, because of the influence of the pH value of the manganese sulfate solution and the extraction rate of manganese, calcium and magnesium ions. If the saponification rate is too high, the probability of emulsifying the organic phase is increased, which is not favorable for the layering of the organic phase and the aqueous phase, and further influences the separation of the organic phase and the aqueous phase. Therefore, the saponification rate of the saponified organic phase is preferably controlled within the above range.
In a preferred embodiment of the present application, the pH of the manganese sulfate solution is 2 to 4, and in step S2, the volume ratio of the saponified organic phase to the manganese sulfate solution is 1:2 to 2: 1; preferably, the extraction in the step S2 is multi-stage extraction, the temperature of each stage of extraction is preferably 20-40 ℃, the time of each stage of extraction is preferably 4-6 min, and the step S2 is preferably carried out 4-6 stages of countercurrent extraction.
Because the pH value of the manganese sulfate solution can directly influence the extraction rate of manganese ions, for the manganese sulfate solution, the extraction rates of manganese ions, calcium ions and magnesium ions in the manganese sulfate solution at different pH values are tested and calculated in advance, so that the pH value of the manganese sulfate solution is determined according to the extraction rates of the manganese ions, the calcium ions and the magnesium ions, and the pH value of the manganese sulfate solution is adjusted to be 2-4 through sulfuric acid. The volume ratio of the saponified organic phase to the manganese sulfate solution, the extraction temperature and the extraction time are controlled, and 4-6-level countercurrent extraction is adopted, so that the extraction rate of manganese ions in the manganese sulfate solution is improved, and the manganese sulfate solution with higher purity is obtained. If the extraction is multi-stage extraction, the volume ratio of each stage of saponified organic phase to the manganese sulfate solution is 1: 2-2: 1 independently
In a preferred embodiment of the present application, in step S3, the volume ratio of the manganese-rich organic phase to water is 1:1 to 1: 3; preferably, the first washing in the step S3 is multi-stage washing, the temperature of the first washing in each stage is preferably 20-40 ℃, the washing time of the first washing in each stage is preferably 5-10 min, the standing time of the first washing in each stage is preferably 5-10 min, and 2-4 stages of counter-current washing in the step S3 are preferably carried out.
And (3) carrying out primary purification on the saponified organic phase to the manganese sulfate solution to obtain a manganese-rich organic phase containing a small amount of calcium and magnesium ions, and carrying out primary washing on the manganese-rich organic phase by adopting water under the washing conditions in order to remove the small amount of calcium and magnesium ions in the manganese-rich organic phase. Wherein, the control of the multilevel countercurrent washing and the washing time is beneficial to improving the washing efficiency and reducing the water consumption. If the washing is carried out in multiple stages, the volume ratio of each manganese-rich organic phase to water is 1: 1-1: 3 independently.
Preferably, in step S4, the hydrogen ion concentration of the strong acid solution containing manganese is preferably 0.01 to 0.04mol/L, the strong acid solution containing manganese is preferably a sulfuric acid solution containing manganese or a hydrochloric acid solution containing manganese, and Mn in the strong acid solution containing manganese is preferably selected2+The content of the manganese-rich organic phase is 5-10 g/L, the volume ratio of the first purified manganese-rich organic phase to the manganese-containing strong acid solution is preferably 5: 1-8: 1, the second washing in the step S4 is preferably multi-stage washing, the temperature of the second washing in each stage is preferably 20-40 ℃, the washing time of the second washing in each stage is preferably 10-20 min, the standing time of the second washing in each stage is preferably 30-60 min, and the step S4 is preferably subjected to 2-4 stages of countercurrent washing. If the washing is multi-stage washing, the volume ratio of the once purified manganese-rich organic phase of each stage to the manganese-containing strong acid solution is respectively 5: 1-8: 1.
And the primary purified manganese-rich organic phase obtained after primary washing contains a very small amount of calcium and magnesium ions, and the primary purified manganese-rich organic phase is subjected to secondary washing by using a manganese-containing strong acid solution, so that the ion exchange between the calcium and magnesium ions in the purified manganese-rich organic phase and the manganese ions in the manganese-containing strong acid solution is more favorably carried out in the strong acid solution containing a certain amount of manganese ions. On one hand, calcium and magnesium ions in the primary purified manganese-rich organic phase fully enter the water phase to almost remove the calcium and magnesium ions; on the other hand, the loss of manganese ions in the primary purified manganese-rich organic phase in the washing process is reduced, but the content of the manganese ions in the primary purified manganese-rich organic phase is further increased, and the secondary purified manganese-rich organic phase is obtained.
In a preferred embodiment of the present application, in step S5, the concentration of sulfuric acid is 4 to 8mol/L, and the volume ratio of the second-purification manganese-rich organic phase to sulfuric acid is preferably 1:1 to 1: 3; preferably, the back extraction in the step S5 is multi-stage back extraction, preferably, the temperature of each stage of back extraction is 20-40 ℃, preferably, the time of each stage of back extraction is 4-6 min, and preferably, the step S5 is 2-4 stages of counter-current back extraction.
And (3) carrying out back extraction on the secondary purified manganese-rich organic phase by using sulfuric acid, and allowing manganese ions to enter a water phase to obtain a high-purity manganese sulfate solution and a regenerated organic phase. The control of the back extraction condition is beneficial to efficiently transferring manganese ions in the organic phase to the aqueous phase to form a high-purity manganese sulfate solution. If the multi-stage back extraction is adopted, the volume ratio of the manganese-rich organic phase of each stage of secondary purification to the sulfuric acid is 1: 1-1: 3.
In one embodiment of the present application, the regenerated organic phase is returned to step S1 for saponification. The recycling of the regenerated organic phase is beneficial to reducing the production cost.
Preferably, the purification treatment method further comprises: and sequentially carrying out ultrasonic demulsification oil removal and activated carbon adsorption oil removal on the high-purity manganese sulfate solution to obtain the deoiled high-purity manganese sulfate solution. And further measuring the content of calcium and magnesium in the deoiled high-purity manganese sulfate solution through atomic absorption, and calculating to obtain the removal rate of calcium and magnesium ions in the manganese sulfate solution.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Preparing a saponified organic phase: taking 1L of manganese sulfate solution, wherein the manganese sulfate solution comprises: mn of 30g/L2+0.3g/L of Ca2+And 15g/L of Mg2+. Adjusting the pH value of a manganese sulfate solution to be 3, controlling the volume ratio of a P204 extractant to sulfonated kerosene to be 1:5, preparing 1L of an organic extractant, and saponifying the organic extractant by using ammonia water with the concentration of 8mol/L to form an ammonia saponification organic phase, wherein the saponification rate is 70%.
And (3) extraction: and (3) performing 5-stage countercurrent extraction on the ammoniated saponified organic phase relative to the manganese sulfate solution to obtain a manganese-rich organic phase and a calcium-magnesium-containing water phase. Wherein the volume ratio of each stage of saponified organic phase to manganese sulfate solution is 3:2, the extraction temperature of each stage is 25 ℃, and the extraction time of each stage is 5 min.
First washing: and (3) carrying out 3-stage countercurrent washing on the manganese-rich organic phase by adopting water to obtain a primary purified manganese-rich organic phase. Wherein the volume ratio of the manganese-rich organic phase to the water in each stage is 1:2, the washing temperature in each stage is 25 ℃, the washing time in each stage is 8min, and the standing time in each stage is 8 min.
And (3) second washing: and carrying out 3-stage countercurrent washing on the primary purified manganese-rich organic phase by adopting a manganese-containing sulfuric acid solution to obtain a secondary purified manganese-rich organic phase and a calcium-magnesium-containing water phase. Wherein the volume ratio of the once purified manganese-rich organic phase to the manganese-containing sulfuric acid solution in each stage is 6:1, the washing temperature in each stage is 25 ℃, the washing time in each stage is 15min, the standing time in each stage is 45min, the hydrogen ion concentration of the manganese-containing sulfuric acid solution is 0.03mol/L, and Mn in the manganese-containing sulfuric acid solution is2+The content was 8 g/L.
Back extraction: and 3-stage countercurrent back extraction is carried out on the secondary purified manganese-rich organic phase by adopting sulfuric acid with the concentration of 6mol/L to obtain high-purity manganese sulfate solution and a regenerated organic phase. Wherein the volume ratio of the secondary purified manganese-rich organic phase to the sulfuric acid at each stage is 1:2, the temperature of the back extraction at each stage is 25 ℃, and the time of the back extraction at each stage is 5 min.
And returning the regenerated organic phase to the prepared saponified organic phase, and sequentially performing ultrasonic demulsification oil removal and activated carbon adsorption oil removal on the high-purity manganese sulfate solution to obtain the deoiled high-purity manganese sulfate solution. And further measuring the content of calcium and magnesium in the deoiled high-purity manganese sulfate solution through atomic absorption, wherein the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.3% and 97.5% through calculation.
Example 2
Example 2 differs from example 1 in that the manganese sulfate solution in example 2 contains: mn of 10g/L2+0.1g/L of Ca2+And 5g/L of Mg2+. The removal rate of calcium ions in the manganese sulfate solution is 99.3 percent and the removal rate of magnesium ions is 97.1 percent through calculation.
Example 3
Example 3 differs from example 1 in that the manganese sulfate solution in example 3 contains: 50g/L Mn2+0.5g/L of Ca2+And 20g/L of Mg2+. The removal rate of calcium ions in the manganese sulfate solution is 99.3 percent and the removal rate of magnesium ions is 96.9 percent through calculation.
Example 4
Example 4 differs from example 1 in that the manganese sulfate solution in example 4 contains: 50g/L Mn2+0.9g/L of Ca2+And 35g/L of Mg2+. The removal rate of calcium ions in the manganese sulfate solution is 99.0% and the removal rate of magnesium ions is 92.1% through calculation.
Example 5
Example 5 is different from example 1 in that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.1% and 96.2% by calculation when the pH of the manganese sulfate solution is adjusted to 2 in example 5.
Example 6
Example 6 is different from example 1 in that the pH of the manganese sulfate solution was adjusted to 4 in example 6, and it was found by calculation that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.2% and 92.6%, respectively.
Example 7
Example 7 is different from example 1 in that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.1% and 92.2% by calculation when the pH value of the manganese sulfate solution is adjusted to 1 in example 7.
Example 8
Example 8 is different from example 1 in that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.1% and 91.3% by calculation when the pH of the manganese sulfate solution is adjusted to 6 in example 8.
Example 9
Example 9 differs from example 1 in that the organic extractant used in example 9 was saponified with 320g/L sodium hydroxide solution to form a sodium-saponified organic phase, wherein the saponification rate was 60%. The removal rate of calcium ions in the manganese sulfate solution is 99.4% and the removal rate of magnesium ions is 97.3% through calculation.
Example 10
Example 10 differs from example 1 in that the organic extractant used in example 10 was saponified with a sodium carbonate solution having a concentration of 100g/L to form a sodium-saponified organic phase, wherein the saponification rate was 80%. The removal rate of calcium ions in the manganese sulfate solution is 99.2 percent and the removal rate of magnesium ions is 96.4 percent through calculation.
Example 11
Example 11 differs from example 1 in that the organic extractant used in example 11 was saponified with a 500g/L potassium carbonate solution to form a potassium saponified organic phase, wherein the saponification rate was 90%. The removal rate of calcium ions in the manganese sulfate solution is 98.9 percent and the removal rate of magnesium ions is 92.1 percent through calculation.
Example 12
Example 12 is different from example 1 in that the volume ratio of the P204 extractant to the sulfonated kerosene in example 12 is 1:10, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.2% and 96.4% by calculation.
Example 13
Example 13 is different from example 1 in that the volume ratio of the P204 extractant to the sulfonated kerosene in example 13 is 3:10, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.3% and 95.4% by calculation.
Example 14
Example 14 is different from example 1 in that the volume ratio of the P204 extractant to the sulfonated kerosene in example 14 is 2:5, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.4% and 92.1% respectively.
Example 15
Example 15 differs from example 1 in that in the extraction, the volume ratio of each stage of saponified organic phase to manganese sulfate solution in example 15 is 1:2, the extraction temperature of each stage is 20 ℃, the extraction time of each stage is 4min, 4 stages of countercurrent washing are adopted, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.4% and 95.7% by calculation.
Example 16
Example 16 is different from example 1 in that in the extraction, the volume ratio of each stage of saponified organic phase to manganese sulfate solution in example 16 is 2:1, the extraction temperature of each stage is 40 ℃, the extraction time of each stage is 6min, 6 stages of countercurrent washing are adopted, and the removal rate of calcium ions and magnesium ions in the manganese sulfate solution is 99.2% and 96.7% respectively.
Example 17
Example 17 differs from example 1 in that in the extraction, the volume ratio of each stage of saponified organic phase to manganese sulfate solution in example 17 is 4:1, the extraction temperature of each stage is 30 ℃, the extraction time of each stage is 2min, 1 stage of countercurrent washing is adopted, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.3% and 92.5%.
Example 18
Example 18 differs from example 1 in that in the first washing process, the volume ratio of the manganese-rich organic phase to water in each stage of example 18 is 1:1, the washing temperature in each stage is 20 ℃, the washing time in each stage is 5min, the standing time in each stage is 5min, and the manganese-rich organic phase is subjected to 2-stage countercurrent washing by using water, so that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.1% and 97.2%.
Example 19
Example 19 differs from example 1 in that, in the first washing process, the volume ratio of the manganese-rich organic phase to water in each stage of example 19 is 1:3, the washing temperature in each stage is 40 ℃, the washing time in each stage is 10min, the standing time in each stage is 10min, the manganese-rich organic phase is subjected to 4-stage countercurrent washing by using water, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.3% and 97.4%.
Example 20
Example 20 differs from example 1 in that in the first washing process, the volume ratio of the manganese-rich organic phase to water in each stage of example 20 is 2:1, the washing time in each stage is 3min, the standing time in each stage of washing is 3min, and the manganese-rich organic phase is subjected to 1-stage countercurrent washing by using water, so that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.2% and 91.8%.
Example 21
Example 21 differs from example 1 in that, in the second washing process, the volume ratio of the first-stage purified manganese-rich organic phase to the manganese-containing sulfuric acid solution in example 21 is 5:1, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.1% and 96.1%.
Example 22
Example 22 differs from example 1 in that in the second washing process, the volume ratio of the first-stage purified manganese-rich organic phase to the manganese-containing sulfuric acid solution in example 22 is 8:1, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.0% and 95.4%.
Example 23
Example 23 differs from example 1 in that in the second washing, the volume ratio of the first-stage purified manganese-rich organic phase to the manganese-containing sulfuric acid solution in example 23 was 10:1, and it was found by calculation that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.2% and 92.1%, respectively.
Example 24
Example 24 differs from example 1 in that in example 24, the washing time of each stage was 10min, the standing time of each stage was 30min, and the manganese-rich organic phase was subjected to 2-stage counter-current washing with water, whereby the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were found to be 99.4% and 97.3%, respectively.
Example 25
Example 25 differs from example 1 in that in example 25, the washing time of each stage is 20min, the standing time of each stage is 60min, and the manganese-rich organic phase is subjected to 4-stage countercurrent washing with water, so that the removal rate of calcium ions and magnesium ions in the manganese sulfate solution is 99.3% and 98.2%, respectively.
Example 26
Example 26 differs from example 1 in that in example 26, the washing time of each stage was 3min, the standing time of each stage was 10min, and the manganese-rich organic phase was subjected to 1-stage counter-current washing with water, whereby the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were found to be 99.1% and 91.5%, respectively.
Example 27
Example 27 differs from example 1 in that the hydrogen ion concentration of the sulfuric acid solution containing manganese in example 27 was 0.01mol/L, and it was found by calculation that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.4% and 98.1%, respectively.
Example 28
Example 28 differs from example 1 in that the hydrogen ion concentration of the manganese-containing sulfuric acid solution in example 28 was 0.04mol/L, and it was found by calculation that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.1% and 97.6%, respectively.
Example 29
Example 29 differs from example 1 in that the hydrogen ion concentration of the manganese-containing sulfuric acid solution in example 29 was 0.008mol/L, and it was found by calculation that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.3% and 91.2%, respectively.
Example 30
Example 30 is different from example 1 in that the hydrogen ion concentration of the sulfuric acid solution containing manganese in example 30 was 0.06mol/L, and it was found by calculation that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.1% and 92.2%, respectively.
Example 31
Example 31 is different from example 1 in that the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution were 99.1% and 97.8% respectively, as calculated from the manganese-containing hydrochloric acid solution used in example 31.
Example 32
Example 32 differs from example 1 in that the Mn in the manganese-containing sulfuric acid solution in example 322+The content is 10g/L, and the removal rate of calcium ions and magnesium ions in the manganese sulfate solution is 99.4% and 97.8% respectively.
Example 33
Example 33 differs from example 1 in that Mn in the manganese-containing sulfuric acid solution in example 332+The content is 5g/L, and the removal rate of calcium ions and magnesium ions in the manganese sulfate solution is 99.1% and 97.6% respectively.
Example 34
Example 34 differs from example 1 in that Mn in the sulfuric acid solution containing manganese in example 342+The content is 3g/L, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.2% and 92.7%.
Example 35
Example 35 differs from example 1 in that the Mn in the manganese-containing sulfuric acid solution in example 352+The content of the manganese sulfate solution is 13g/L, and the removal rate of calcium ions and magnesium ions in the manganese sulfate solution is 99.3% and 91.5% respectively.
Example 36
Example 36 is different from example 1 in that in stripping, in example 36, sulfuric acid with a concentration of 4mol/L is used for carrying out 2-stage countercurrent stripping on the secondary purified manganese-rich organic phase, the volume ratio of the secondary purified manganese-rich organic phase to the sulfuric acid at each stage is 1:1, the stripping temperature at each stage is 10 ℃, the stripping time at each stage is 4min, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.3% and 95.4% through calculation.
Example 37
Example 37 is different from example 1 in that in the stripping, in example 37, sulfuric acid with the concentration of 8mol/L is used for carrying out 4-stage countercurrent stripping on the secondary purified manganese-rich organic phase, the volume ratio of the secondary purified manganese-rich organic phase to the sulfuric acid at each stage is 1:3, the stripping temperature at each stage is 30 ℃, the stripping time at each stage is 6min, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.1% and 96.2% through calculation.
Example 38
Example 38 differs from example 1 in that in the stripping, in example 38, sulfuric acid with a concentration of 1mol/L is used to perform 1-stage counter-current stripping on the twice-purified manganese-rich organic phase, the volume ratio of the twice-purified manganese-rich organic phase to the sulfuric acid at each stage is 1:3, the stripping temperature at each stage is 30 ℃, the stripping time at each stage is 4min, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are calculated to be 99.3% and 93.5%.
Example 39
Example 39 differs from example 1 in that the manganese sulfate solution in example 39 contains: 20g/L Mn2+0.2g/L of Ca2+And 10g/L of Mg2+. The removal rate of calcium ions in the manganese sulfate solution is 99.5 percent and the removal rate of magnesium ions is 98.6 percent through calculation.
Example 40
Example 40 is different from example 1 in that the extractant in example 40 is P507, and the removal rate of calcium ions and the removal rate of magnesium ions in the manganese sulfate solution are respectively 99.2% and 95.6%.
Comparative example
Taking qualified electrolytic manganese solution, wherein the qualified electrolytic manganese solution comprises: 20g/L Mn2+0.2g/L of Ca2+10g/L of Mg2+100g/L of (NH)4)2SO4(ii) a Adjusting the pH value of the electrolytic manganese qualified liquid to 4 by adopting 2mol/L sulfuric acid solution, wherein an extraction organic phase consists of an extracting agent and 260# sulfonated kerosene, the extracting agent is a combined extracting agent formed by combining P507 and Cyanex272 in a volume ratio of 3:2, and the combined extracting agent is diluted by 260# sulfonated kerosene until the volume concentration of the combined extracting agent is 35%; saponifying the extracted organic phase by using 30 wt% NaOH alkali liquor, wherein the saponification rate is controlled at 40%, and forming a sodium soap organic phase; the obtained sodium soap hasAnd saponifying the organic phase by a manganese sulfate solution with the manganese content of 30g/L, controlling the ratio of the sodium soap organic phase to the manganese sulfate solution to be 5:1, and converting the sodium soap organic phase into the manganese soap organic phase by adopting 4-level countercurrent manganese soap.
And (3) extraction: and (3) taking the manganese soap organic phase and the flow ratio of the organic phase to the water phase in the electrolytic manganese qualified liquid with the adjusted pH value to be 4:1, enabling the two phases to fully react, exchanging calcium and magnesium ions in the electrolytic manganese qualified liquid solution with manganese ions in the manganese soap organic phase, enabling the calcium and magnesium ions to be combined with the organic phase, enabling the manganese ions to enter the water phase again, and obtaining the organic phase loaded with calcium and magnesium metal ions and the electrolytic manganese qualified liquid subjected to deep purification after the impurity removal process is finished.
Washing: and washing manganese in the obtained organic phase loaded with calcium and magnesium metal ions by using a dilute manganese sulfate solution with the concentration of 0.1g/L, controlling the volume ratio of the organic phase to the water phase to be 10:1, and washing the manganese by adopting 3-stage countercurrent so that the manganese ions in the organic phase enter the water phase, and continuously loading the calcium and magnesium ions in the organic phase to obtain the manganese-removed organic phase loaded with the calcium and magnesium metal ions.
Back extraction: and (2) carrying out back extraction on the manganese-removed organic phase loaded with calcium and magnesium metal ions by adopting sulfuric acid with the concentration of 4.5mol/L, controlling the flow ratio of the loaded organic phase to the water phase to be 1:4, and carrying out 4-stage countercurrent regeneration to obtain a regenerated extracted organic phase and a water phase loaded with calcium and magnesium metal ions, wherein the regenerated extracted organic phase can be recycled in the process of preparing the extracted organic phase.
The removal rate of calcium ions in the qualified electrolytic manganese solution processed by the steps reaches 98.9 percent, and the removal rate of magnesium ions is 90.0 percent.
The purification treatment costs of example 39 and comparative example were calculated, and the calculation results of the purification treatment costs of example 39 and comparative example are shown in table 1. The same object can be treated, and the cost can be reduced by adopting the method for purifying the manganese sulfate solution.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
firstly, a saponified organic phase is used as an extracting agent to carry out first extraction on a manganese sulfate solution, most of manganese ions enter the saponified organic phase to obtain a manganese-rich organic phase, and most of calcium and magnesium ions still remain in a water phase, so that the primary separation of the manganese ions, the calcium ions and the magnesium ions is realized. Secondly, the manganese-rich organic phase is washed for the first time by water, so that a small amount of calcium and magnesium ions attached to the manganese-rich organic phase can be removed preliminarily, and the purified manganese-rich organic phase is obtained for the first time. Secondly, washing the primary purified manganese-rich organic phase for the second time by using a manganese-containing strong acid solution, and performing ion exchange between calcium and magnesium ions in the primary purified manganese-rich organic phase and manganese ions in the manganese-containing strong acid solution in the strong acid solution containing a certain amount of manganese ions, so that on one hand, the calcium and magnesium ions in the primary purified manganese-rich organic phase fully enter the water phase, and the calcium and magnesium ions in the primary purified manganese-rich organic phase are almost removed; on the other hand, the loss of manganese ions in the primary purified manganese-rich organic phase in the washing process is reduced, but the content of the manganese ions in the primary purified manganese-rich organic phase is further increased, and the secondary purified manganese-rich organic phase is obtained. And finally, back-extracting the secondary purified manganese-rich organic phase by using sulfuric acid to obtain a high-purity manganese sulfate solution and a regenerated organic phase. According to the method, manganese ions are gradually separated from calcium ions and magnesium ions through the step-by-step separation process of extraction, first washing, second washing and back extraction of the manganese sulfate solution, so that the calcium ions and the magnesium ions in the manganese sulfate solution are highly purified, and the highly purified manganese sulfate solution is obtained. In the prior art, the process of extracting and removing impurities from manganese soap organic phase to manganese sulfate solution is needed, and then expensive pure manganese sulfate is needed to convert the organic extractant into manganese for saponification. Compared with the prior art, the method does not need to adopt pure manganese sulfate to carry out manganese conversion saponification on the saponified organic phase, and the used washing liquid is cheap water and strong acid solution containing manganese ions, so that the purification treatment cost is low.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A purification treatment method of a manganese sulfate solution is characterized by comprising the following steps:
step S1, preparing an extraction organic phase, and saponifying the extraction organic phase to obtain a saponified organic phase;
step S2, extracting the saponified organic phase with a manganese sulfate solution to obtain a manganese-rich organic phase;
step S3, washing the manganese-rich organic phase for the first time by using water to obtain a purified manganese-rich organic phase for the first time;
step S4, washing the primary purified manganese-rich organic phase for the second time by using a manganese-containing strong acid solution to obtain a secondary purified manganese-rich organic phase; and
and step S5, back-extracting the secondary purified manganese-rich organic phase by using sulfuric acid to obtain a high-purity manganese sulfate solution and a regenerated organic phase.
2. The purification treatment method according to claim 1, wherein the manganese sulfate solution contains: 10 to 50g/L of Mn2+0.1 to 0.5g/L of Ca2+And 5 to 20g/L of Mg2+。
3. The purification treatment method according to claim 1, wherein the extracted organic phase comprises a P204 extracting agent and sulfonated kerosene, and the volume ratio of the P204 extracting agent to the sulfonated kerosene is 1: 10-3: 10.
4. The purification process of claim 1, wherein the saponifying of the extracted organic phase comprises:
saponifying the extracted organic phase by adopting an alkaline solution, wherein the alkaline solution is selected from one or more of a sodium hydroxide solution, a potassium hydroxide solution, ammonia water, a sodium carbonate solution and a potassium carbonate solution, and preferably, the saponification rate of saponification is 60-80%; more preferably, the saponification rate is 70 to 80%.
5. The purification treatment method according to claim 1, wherein the pH value of the manganese sulfate solution is 2-4, and the volume ratio of the saponified organic phase to the manganese sulfate solution in step S2 is 1: 2-2: 1; preferably, the extraction in the step S2 is multi-stage extraction, the temperature of each stage of extraction is preferably 20-40 ℃, the time of each stage of extraction is preferably 4-6 min, and the step S2 is preferably performed with 4-6 stages of countercurrent extraction.
6. The purification treatment method according to claim 1, wherein in step S3, the volume ratio of the manganese-rich organic phase to the water is 1:1 to 1: 3; preferably, the first washing in the step S3 is multi-stage washing, preferably, the temperature of each stage of the first washing is 20-40 ℃, preferably, the washing time of each stage of the first washing is 5-10 min, preferably, the standing time of each stage of the first washing is 5-10 min, and preferably, the step S3 is performed with 2-4 stages of counter-current washing.
7. The purification treatment method according to claim 1, wherein in step S4, the hydrogen ion concentration of the strong acid solution containing manganese is 0.01 to 0.04mol/L, preferably the strong acid solution containing manganese is a sulfuric acid solution containing manganese or a hydrochloric acid solution containing manganese, preferably Mn in the strong acid solution containing manganese2+The content of the manganese-rich organic phase is 5-10 g/L, the volume ratio of the primary purified manganese-rich organic phase to the manganese-containing strong acid solution is preferably 5: 1-8: 1, the second washing in the step S4 is preferably multi-stage washing, the temperature of each stage of the second washing is preferably 20-40 ℃, the washing time of each stage of the second washing is preferably 10-20 min, the standing time of each stage of the second washing is preferably 30-60 min, and the step S4 is preferably performed with 2-4 stages of countercurrent washing.
8. The purification treatment method according to claim 1, wherein in step S5, the concentration of the sulfuric acid is 4 to 8mol/L, and the volume ratio of the secondary purification manganese-rich organic phase to the sulfuric acid is preferably 1:1 to 1: 3; preferably, the back extraction in the step S5 is multi-stage back extraction, preferably, the temperature of each stage of back extraction is 20-40 ℃, preferably, the time of each stage of back extraction is 4-6 min, and preferably, the step S5 is 2-4 stages of counter-current back extraction.
9. The purification process of claim 1, wherein the regenerated organic phase is returned to step S1 for saponification.
10. The purification process of claim 1, further comprising: and sequentially carrying out ultrasonic demulsification oil removal and activated carbon adsorption oil removal on the high-purity manganese sulfate solution to obtain the deoiled high-purity manganese sulfate solution.
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