CN1237192C - Deep purification method of manganese sulfate solution - Google Patents
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Abstract
The invention belongs to extraction of nonferrous metals, and relates to a method for deeply purifying elements such as potassium, molybdenum, iron, cobalt, nickel, copper and the like from a manganese sulfate solution, which is technically characterized by comprising the following steps: adding precipitate or adding reagent to manganese sulfate solution to produce precipitant in the solution and eliminate impurity from the solution. The method not only can extract EMD meeting the requirements of producing performance batteries, but also has the advantages of simple and convenient process, low reagent consumption, low cost and no pollution to the environment.
Description
The technical field is as follows:
the present invention belongs to the field of metal solution purification, and is especially the deep purification of manganese sulfate solution for preparing electrolytic manganese dioxide.
The background art comprises the following steps:
the raw materials for producing Electrolytic Manganese Dioxide (EMD) are generally rhodochrosite, pyrolusite, psilomelane and the like, and a manganese sulfate solution is obtained by leaching with sulfuric acid. The alloy contains impurity elements such as potassium, iron, cobalt, nickel, molybdenum and the like. And can enter into the product EMD during the electrolysis process. The mercury-free alkaline zinc-manganese dioxide battery is very sensitive to impurity elements in the used EMD: when the content of potassium is too high, the crystal form, specific gravity and discharge performance of EMD can be influenced; heavy metals such as copper can cause short circuits in the battery; elements such as iron and molybdenum can cause the battery to climb alkali. To remove these impurities, it is common in industry to remove the iron precipitate by adjusting the pH of the solution to 4.0 to 4.5 by the addition of lime; adding Na into the solution 2 S or introduction of H 2 S, removing heavy metal ions; in order to remove molybdenum, the pH of the solution is adjusted to about 2 again, and H is introduced 2 S makes molybdenum MoS 3 The precipitate is removed. The method is not only complicated and has high reagent consumption, but also H 2 The S gas may pollute the environment. The method for removing molybdenum is not only complex and has large reagent consumption, but also H 2 The S gas pollutes the environment. As for potassium, there is no good removal method, although jarosite (KFe) can be formed with iron 3 (SO 4 ) 2 OH 6 ) Precipitated, but the filtration performance was poor. The simple deep purification method has very important significance for producing high-quality EMD.
According to literature "natural ferro manganese oxide and hydroxide environmental mineralogy research" [ geoscience front edge ] 2004,7 (2): 473-483 notes natural manganese oxideThe compound and the hydroxide have good surface adsorption activity. They can vary in degree under different medium conditionsShows the presence of Cr 6+ 、Pb 2+ 、Hg 2+ 、Cd 2+ 、Cu 2+ 、Zn 2+ 、Co 2+ 、Ni 2+ Heavy metal ion and NO 3- 、PO 4 3- 、F - 、S 2- Adsorption of plasma anions. Ancient enantiomorphous' crypto potassium manganese type hydrated MnO 2 For Na + 、K + Ion exchange selectivity of "proceedings of university of precious state (nature science edition) 18 (2): pages 124-126 report that hydrated manganese oxide is on K + 、Na + And the like has good adsorption exchange performance. "study of Metal cation exchange Capacity of manganese mineral phase of 1 nm" [ oceanographic newspapers ] 1996, 18 (4): pages 56-62, which synthesizes 1nm manganese ore phase and examines Cu for researching the formation mechanism of marine manganese nodule 2+ 、Co 2+ 、Zn 2+ 、Ni 2+ 、Ca 2+ 、Mg 2+ The adsorption of the manganese nodule can better explain the reason that the manganese nodule is rich in copper, nickel and cobalt. Yan Kungtin et al "adsorption of uranium by manganese dioxide in aqueous solution" [ environmental science bulletin ], 1999, 19 (1): on pages 42-46, uranium is adsorbed from an aqueous solution by pyrolusite, and the relationship between the concentration of uranyl ions, temperature, pH and adsorption is studied. People also research and utilize the manganese compound to treat water, soil and atmospheric pollution and obtain better effect. Such as: "the decontamination efficiency of the filtration process is enhanced by manganese dioxide" [ Water supply and drainage ] 1996,4: pages 11-13; "study on removal of phenolic compounds by surface modification of manganese sand" report on environment of Heilongjiang "1998, 22 (1): 5-7 pages; treatment of SO in sulfuric acid tail gas by pyrolusite 2 Experimental study and economic evaluation of "sulfuric acid industry" 1995,3: pages 29-31, 60; "research on pyrolusite flue gas desulfurization" [ journal of university of Sichuan ] 2000, 32 (5): pages 36-39. Different states MnO of Chenhong, etc.) 2 In waste waterAs (III) adsorption study, 1998, environmental science, 18 (2), pp.126-130, arsenic adsorption from wastewater using pyrolusite and discovery of other anions such As PO 4 3- And the presence of competitive adsorption. These indicate that oxides of manganese have a strong ability to adsorb ions, and thus it is entirely possible to remove harmful impurity ions from a manganese sulfate solution by utilizing the adsorption characteristics of manganese compounds.
In fact, the research of the 'method for purifying manganese sulfate solution for electrolytic manganese dioxide' Chinese patent application 96103704.0, by Anderson et al, utilizes this adsorption effect, and they calcine pyrolusite in a rotary kiln, pulverize, pickle with sulfuric acid, filter, wash, dry to obtain an ACM adsorbent, which can be used to remove potassium and molybdenum from the solution. However, this method has the disadvantages that not only the manufacturing process of the ACM is complicated, a special apparatus is required, and a large amount of waste liquid generated during the manufacturing process needs to be disposed. And the addition amount is up to more than 100g/L during adsorption, and the burden of filtration and washing is heavy. And the used adsorbent needs to be desorbed and regenerated by sulfuric acid, and waste water is generated. Therefore, the process of removing impurities by adsorption of the artificially pre-synthesized manganese compound has limitations.
We have focused on the successful use of in situ generated manganese dioxide in chemical analysis to enrich and separate trace elements from solutions. For example, the method for measuring tin, antimony and bismuth in copper by manganese dioxide coprecipitation metal furnace atomic absorption method such as Nemadzu corporation in Kuntian, 1991,4: and 56-61, reacting potassium permanganate with manganese nitrate, enriching tin, antimony and bismuth by a generated manganese dioxide coprecipitation method, and well analyzing the contents of the tin, antimony and bismuth in copper. Umashankar, et al, "Simultaneous registration and registration of statistical amounts of watersamplebycatalytic registration of statistical amounts of rare-glucose reagents for KMnO 4 "" Talanta, 2002, 57 (6): pages 1029-1038, thenThe potassium permanganate is reduced by glucose, the conditions are controlled to almost completely adsorb and enrich trace Al, au, bi, cd, co, cu, fe, mo, ni, pb, ti, V, W, zn and REE in the earth surface and the underground water, and the recovery rate of the elements obtained by analysis is between 96 and 105 percent. Wangxing et al, "manganese oxide hydrate coprecipitation enrichment-polarization Zeeman graphite furnace atomic absorption method for measuring trace antimony in drinking water" [ China Water sanitation (China) 2002, pages 10 (1) 18-20 ], also successfully coprecipitated with manganese dioxide hydrate to enrich trace antimony in drinking water. On the other hand, we have succeeded in removing impurities such As Mo, as, sn, sb, etc. from tungstate solutions by co-precipitation by in-situ formation of copper sulfides.
The invention comprises the following contents:
the invention aims to provide a method for deeply purifying a manganese sulfate solution, which has the advantages of simple process, low reagent consumption, low production cost, no environmental pollution and high quality of electrolytic manganese dioxide, and meets the requirements of battery production.
The prior art inspires that manganese dioxide is generated in situ by adding an oxidant into a manganese sulfate solution and reacting with divalent manganese ions, and potassium and molybdenum ions, iron, cobalt, nickel, copper and other ions in the solution are removed by coprecipitation, so as to meet the requirement of high-quality EMD for producing batteries.
The invention discloses a method for deeply purifying manganese sulfate solution, which is a method for deeply purifying elements such as potassium, molybdenum, iron, cobalt, nickel, copper and the like from the manganese sulfate solution.
The oxidant used in the method is one or a combination of more of hydrogen peroxide, persulfuric acid, sodium peroxydisulfate, nitric acid, nitrous acid, sodium nitrite, oxygen, ozone, chlorine, hypochlorous acid, calcium hypochlorite, sodium chlorate, potassium perchlorate, perchloric acid, calcium peroxide, sodium percarbonate, potassium percarbonate, sodium manganate, potassium manganate, barium manganate, calcium manganate, permanganic acid, sodium permanganate, potassium permanganate, barium permanganate, calcium permanganate, sodium ferrate, potassium ferrate and barium ferrate; or generating suspended particle manganese dioxide through electro-oxidation.
MnSO solution treated by the method 4 The concentration is 15 g/L-saturation, and the pH value of the solution is 1.5-6.
The reaction conditions of the method are as follows: the oxidant is added to ensure that the generated manganese oxide precipitate is 0.1-50g/L, the reaction temperature is 10-100 ℃, and the reaction time is 10 minutes-5 hours.
The method for adding the oxidant comprises the following steps: directly and continuously introducing gas oxide into the solution; other oxidants are added in solution or as solid powders, but after addition, gentle stirring is required to promote dissolution homogenization.
When the method generates the suspended particle manganese dioxide through electrooxidation, the concentration of manganese sulfate in the solution is 30-100 g/L, the concentration of sulfuric acid is 100-300 g/L, and the current density of an anode is 10～60A/dm 2 The temperature is 5-80 ℃, and the generated suspended manganese oxide is precipitated by 0.1-50g/L through electrooxidation.
The deep purification method of the manganese sulfate solution not only can extract EMD meeting the requirements of battery production, but also has simple and convenient process, low reagent consumption, low cost and no pollution to the environment.
The specific implementation mode is as follows:
the present invention will be described in detail below with reference to examples.
Example 1 manganese sulfate10L of solution containing MnSO 4 150g/L, potassium 500ppm, molybdenum 0.5ppm, cobalt 0.1g/L, nickel 0.1g/L, iron 0.4g/L, copper 0.06g/L, pH 4.0. Under the conditions of stirring speed of 150rpm and temperature of 80 ℃, slowly adding 100g/L sodium permanganate solution 200mL for 30 minutes, stopping stirring, keeping the temperature for 2 hours, and filtering. The concentration of impurity ions in the purified solution is as follows: 80ppm of potassium, 0.02ppm of molybdenum, 3ppm of cobalt, 5ppm of nickel, 2ppm of iron and 3ppm of copper.
Example 2 manganese sulfate solution 10L, containing MnSO 4 150g/L, 500ppm of potassium, 0.5ppm of molybdenum, 0.1g/L of cobalt, 0.1g/L of nickel, 1g/L of iron and 0.05g/L of copper, and the pH value is 4.5. Under the conditions of stirring speed of 150rpm and temperature of 10 ℃, 30% hydrogen peroxide solution 50mL is slowly added, stirring is stopped after 30 minutes, heat preservation is continued for 4 hours, and filtration is carried out. The concentration of impurity ions in the purified solution is as follows: 85ppm of potassium, 0.02ppm of molybdenum, 4ppm of cobalt, 4ppm of nickel, 1.5ppm of iron and 2ppm of copper.
Example 3 manganese sulfate solution 10L, containing MnSO 4 50g/L, potassium 200ppm, molybdenum 0.4ppm, iron 1g/L, pH 1.5. Under the condition of 40 ℃, slowly adding 200mL of 10% NaClO solution, then uniformly stirring, standing for reacting for 2 hours, and filtering. The concentration of impurity ions in the purified solution is as follows: 82ppm of potassium, 0.02ppm of molybdenum and 1.5ppm of iron.
Example 4 manganese sulfate solution 10L, containing MnSO 4 100g/L, 600ppm of potassium, 0.4ppm of molybdenum, 1g/L of iron and 5 of pH. At a temperature of 85-90 deg.C, chlorine gas is introduced at a flow rate of 100mL/min for 1.5 hours (taking care to disperse the chlorine gas well), and thenStanding for 2 hours, and filtering. The concentration of impurity ions in the purified solution is as follows: 95ppm of potassium, 0.02ppm of molybdenum and 2ppm of iron.
Example 5 manganese sulfate solution 10L, containing MnSO 4 100g/L, 600ppm of potassium, 0.4ppm of molybdenum, 1g/L of iron and 5 of pH. Under the condition of the temperature of 75-80 ℃, the flow rate is 100mL/mOzone in for 1 hour (care was taken to disperse the ozone well) then allowed to stand for 2 hours and filtered. The impurity ion concentration of the purified solution is as follows: 80ppm of potassium, 0.02ppm of molybdenum and 1ppm of iron.
Example 6 manganese sulfate solution 10L, containing MnSO 4 50g/L, potassium 200ppm, molybdenum 0.4ppm, iron 1g/L, pH 6. Under the conditions of stirring speed of 250rpm and temperature of 100 ℃, 5g of NaClO solid is added in 4 times, the time interval is 10, 20 and 40 minutes in sequence, 20 g of NaClO solid is added in total, and after 2 hours of reaction, filtration is carried out. The concentration of impurity ions in the purified solution is as follows: 82ppm of potassium, 0.02ppm of molybdenum and 2ppm of iron.
Example 7 manganese sulfate solution 10L, containing MnSO 4 150g/L, potassium 500ppm, molybdenum 0.5ppm, cobalt 0.1g/L, nickel 0.1g/L, iron 0.4g/L, copper 0.06g/L, pH 4.0. Under the conditions of stirring speed of 150rpm and temperature of 80 ℃, 100mL of sodium permanganate solution with the concentration of 100g/L is slowly added, 30mL of 30% hydrogen peroxide solution is added, stirring is stopped after 30 minutes, heat preservation is continued for 2 hours, and filtering is carried out. The impurity ion concentration of the purified solution is as follows: 80ppm of potassium, 0.02ppm of molybdenum, 3ppm of cobalt, 5ppm of nickel, 2ppm of iron and 3ppm of copper.
Example 8 manganese sulfate solution 10L, containing MnSO 4 30g/L, molybdenum 0.3ppm, pH 6. Adding K under the conditions of stirring speed of 400rpm and temperature of 10 DEG C 2 MnO 4 Solid 15g, reaction after 5 hours filter. The concentration of impurity molybdenum in the purified solution is 0.02ppm.
Example 9 manganese sulfate solution 10L, containing MnSO 4 30g/L, molybdenum 0.3ppm, pH 6. Under the conditions of stirring speed of 400rpm and temperature of 80 ℃, addingNaClO 3 15g of solid, react for 2 hours and then filter. The impurity ion concentration of the purified solution is as follows: 82ppm of potassium and 0.02ppm of molybdenum.
Example 10 manganese sulfate solution 10L, containing MnSO 4 130g/L，500ppm of potassium and 0.45ppm of molybdenum, and the pH value is 4.5. Adding NaMnO under the conditions of stirring speed of 200rpm and temperature of 90 DEG C 4 12 g of solid, react for 3 hours and then filter. The concentration of impurity ions in the purified solution is as follows: 78ppm of potassium and 0.02ppm of molybdenum.
Example 11 manganese sulfate solution 10L, containing MnSO 4 130g/L, potassium 500ppm, molybdenum 0.5ppm, pH 4. 20 g of sodium dithionite solid was added thereto at a stirring speed of 150rpm and a temperature of 85 ℃ to react for 5 hours, followed by filtration. The concentration of impurity ions in the purified solution is as follows: 82ppm of potassium and 0.02ppm of molybdenum.
Example 12 manganese sulfate solution 10L, containing MnSO 4 100g/L, 600ppm of potassium, 0.6ppm of molybdenum, 1g/L of iron and 5 of pH. Adding NaClO at 85-90 deg.c 4 30g of solid, stirring for 1.5 hours, then standing for 2 hours, and filtering. The concentration of impurity ions in the purified solution is as follows: 95ppm of potassium, 0.02ppm of molybdenum and 2ppm of iron.
Example 13 manganese sulfate solution 10L, containing MnSO 4 150g/L, potassium 550ppm, molybdenum 0.7ppm, iron 1g/L, pH 1.5. At the temperature of 80 ℃,30 g of sodium percarbonate is added, then the mixture is stirred evenly and stands for reaction for 2 hours, and then the mixture is filtered. The impurity ion concentration of the purified solution is as follows: 82ppm of potassium, 0.02ppm of molybdenum and 1ppm of iron.
Example 14 manganese sulfate solution 10L, containing MnSO 4 150g/L, potassium 550ppm, molybdenum 0.7ppm, iron 1g/L, pH 3.5. 30g of calcium hypochlorite is added under the condition of 80 ℃, then the mixture is stirred evenly and stands for reaction for 2 hours, and then the mixture is filtered. The impurity ion concentration of the purified solution is as follows: 82ppm of potassium, 0.02ppm of molybdenum and 1ppm of iron.
Example 15 manganese sulfate solution 10L, containing MnSO 4 150g/L, molybdenum 0.7ppm, iron 1g/L, pH 4.5. 30g of potassium ferrate is added at the temperature of 80 ℃, then the mixture is stirred evenly and stands for reaction for 2 hours, and then the mixture is filtered. Impurities in purified solutionIon concentrationThe degree is as follows: 0.02ppm of molybdenum and 2ppm of iron.
Example 16 manganese sulfate solution 10L, containing MnSO 4 150g/L, 500ppm of potassium, 0.5ppm of molybdenum, 0.1g/L of cobalt, 0.1g/L of nickel, 1g/L of iron and 0.05g/L of copper, and the pH value is 4.5. 250mL of 30 percent hydrogen peroxide solution is added within 20 minutes under the conditions that the stirring speed is 150rpm and the temperature is 80 ℃, attention is paid to prevent overflowing, and filtering is carried out after the addition is finished. The concentration of impurity ions in the purified solution is as follows: 85ppm of potassium, 0.02ppm of molybdenum, 4ppm of cobalt, 4ppm of nickel, 1.5ppm of iron and 2ppm of copper.
Example 17 manganese sulfate solution 10L, containing MnSO 4 30g/L, potassium 500ppm, molybdenum 0.3ppm, pH 6. At a stirring speed of 400rpm and a temperature of 75 ℃, 15g of calcium peroxide solid was added, reacted for 5 hours, and then filtered. The impurity ion concentration of the purified solution is as follows: 82ppm of potassium and 0.02ppm of molybdenum.
Example 18 manganese sulfate solution 10L, containing MnSO 4 150g/L, 500ppm of potassium, 0.5ppm of molybdenum, 0.1g/L of cobalt, 0.1g/L of nickel, 1g/L of iron and 0.05g/L of copper, and the pH value is 4.5. 250mL of concentrated nitric acid was added to the solution at a stirring speed of 150rpm and a temperature of 80 ℃ over 20 minutes, and the solution was stirred for 2 hours and filtered. The concentration of impurity ions in the purified solution is as follows: 95ppm of potassium, 0.02ppm of molybdenum, 4.5ppm of cobalt, 5ppm of nickel, 3ppm of iron and 3ppm of copper.
Example 19 manganese sulfate solution 10L, containing MnSO 4 50g/L, potassium 200ppm, molybdenum 0.4ppm, iron 1g/L, pH 6. Adding NaNO under the conditions of stirring speed of 250rpm and temperature of 100 DEG C 2 55 g of solid, react for 2 hours and then filter. The impurity ion concentration of the purified solution is as follows: 82ppm of potassium, 0.02ppm of molybdenum and 2ppm of iron.
Example 20 manganese sulfate solution 10L, containing MnSO 4 30g/L, potassium 500ppm, molybdenum 0.3ppm, pH 6. Under the conditions of stirring speed of 400rpm and temperature of 75 deg.C, adding45 g of sodium percarbonate solid is added, and after 5 hours of reaction, filtration is carried out. The impurity ion concentration of the purified solution is as follows: 82ppm of potassium and 0.02ppm of molybdenum.
Example 21 manganese sulfate solution 10L, containing MnSO 4 15g/L, molybdenum 0.4ppm, pH 6. Chlorine gas was introduced at a flow rate of 100mL/min at a temperature of 85 to 90 ℃ for 1.5 hours (taking care to disperse the chlorine gas well), and then allowed to stand for 2 hours and filtered. The impurity ion concentration of the purified solution is as follows: 95ppm of potassium, 0.02ppm of molybdenum and 2ppm of iron.
Example 22 manganese sulfate solution 10L, containing MnSO 4 30g/L, molybdenum 0.3ppm, pH 6. Adding BaMnO under the conditions of stirring speed of 400rpm and temperature of 10 DEG C 4 35 g of solid, react for 5 hours and then filter. The concentration of impurity molybdenum in the purified solution is 0.02ppm.
Example 23. An electrolytic cell was charged with 10L of a manganese sulfate solution containing MnSO 4 100g/L，H 2 SO 4 250g/L, 0.5ppm Mo, stirring speed of electrolyte at 250rpm, and anode current density at 35A/dm 2 At 65 ℃ and 7000 coulombs of electricity, stirring was continued for 1 hour, and the mixture was allowed to stand for 0.5 hour and filtered. The concentration of impurity molybdenum in the purified solution is 0.02ppm.
Claims (2)
1. A method for deeply purifying a manganese sulfate solution is characterized in that under proper technical conditions, an oxidant is added into the manganese sulfate solution, a small part of bivalent manganese in the solution is precipitated after oxidation, and impurities in the solution are removed in a coprecipitation mode, and the method is characterized in that:
(1) the oxidant used is one or a combination of more of hydrogen peroxide, persulfuric acid, sodium peroxodisulfate, nitric acid, nitrous acid, sodium nitrite, oxygen, ozone, chlorine, hypochlorous acid, calcium hypochlorite, sodium chlorate, potassium chlorate, sodium perchlorate, potassium perchlorate, perchloric acid, calcium peroxide, sodium percarbonate, potassium percarbonate, sodium manganate, potassium manganate, barium manganate, calcium manganate, permanganate, sodium permanganate, potassium permanganate, barium permanganate, calcium permanganate, sodium ferrate, potassium ferrate and barium ferrate; or generating suspended particle manganese dioxide through electrooxidation;
(2) MnSO of the treated solution 4 The concentration is 15 g/L-saturation, and the pH value of the solution is 1.5-6;
(3) the reaction conditions are as follows: adding oxidant to precipitate the generated manganese oxide at 0.1-50g/L, at 10-100 deg.c for 10 min-5 hr;
(4) the method for adding the oxidant comprises the following steps: directly and continuously introducing gas oxide into the solution; other oxidants are added in solution or as solid powders, but after addition, gentle stirring is required to promote dissolution homogenization.
2. The method for the deep purification of manganese sulfate solution as claimed in claim 1, characterized in that: when the suspended particle manganese dioxide is generated by electrooxidation, the concentration of manganese sulfate in the solution is 30-100 g/L, the concentration of sulfuric acid is 100-300 g/L, and the current density of the anode is 10-60A/dm 2 The temperature is 10-80 ℃, and the generated suspended manganese oxide is precipitated by electrooxidation to be 0.1-50g/L.
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| CN110240204A (en) * | 2019-06-28 | 2019-09-17 | 贵州大学 | A kind of method that the nano hydrated manganese oxide depth of new life removes molybdenum in manganese sulfate solution |
| CN113262799B (en) * | 2021-05-18 | 2023-08-11 | 中国人民解放军陆军勤务学院 | FeOOH cladding Mn 3 O 4 Composite material, preparation method and application thereof |
-
2002
- 2002-11-26 CN CN 02150085 patent/CN1237192C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122411A (en) * | 2013-02-05 | 2013-05-29 | 中南大学 | Cyclic and comprehensive utilization method of sodium-free mangano-manganic oxide production mother solution |
| CN103122411B (en) * | 2013-02-05 | 2014-08-27 | 中南大学 | Cyclic and comprehensive utilization method of sodium-free mangano-manganic oxide production mother solution |
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