CN114715945A - Method for purifying manganese sulfate solution with high efficiency - Google Patents
Method for purifying manganese sulfate solution with high efficiency Download PDFInfo
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- manganese sulfate
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 78
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 78
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 78
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 57
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 47
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 47
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 47
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 47
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 47
- 239000000706 filtrate Substances 0.000 claims abstract description 43
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 22
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 18
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000600 sorbitol Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000003825 pressing Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- -1 polysiloxane Polymers 0.000 claims description 20
- 229910052935 jarosite Inorganic materials 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 17
- 239000011733 molybdenum Substances 0.000 abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011591 potassium Substances 0.000 abstract description 10
- 229910052700 potassium Inorganic materials 0.000 abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 9
- 229910052708 sodium Inorganic materials 0.000 abstract description 9
- 239000011734 sodium Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 238000011085 pressure filtration Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000011133 lead Substances 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000072 sodium resin Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical group CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical group CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for purifying a manganese sulfate solution with high efficiency, which comprises the steps of putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:0.9-1.2, adding a defoaming agent before putting the manganese carbonate powder, and reacting for 2-4 hours at the temperature of 90-110 ℃ to obtain manganese sulfate ore slurry; adding manganese dioxide powder into the manganese sulfate ore pulp, reacting for 1h under the condition of keeping the pH of the solution at 2.5-3.0, and finally, performing pressure filtration to remove precipitates and obtain a crude filtrate; and adding a neutralizing agent into the rough filtrate to adjust the pH value to 4.5-5.0, then adding barium sulfide and sorbitol, stirring and reacting for 1-2 hours, and then carrying out secondary filter pressing to obtain a filtrate, namely a manganese sulfate solution. The method of the invention adopts the simultaneous operation of molybdenum removal and potassium and sodium removal, and the simultaneous operation of iron removal and weight removal, thereby reducing one procedure, simplifying the production flow, improving the production efficiency, saving the cost, having high purity of the extracted manganese sulfate solution and being easy to realize the industrial production.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for purifying a manganese sulfate solution with high efficiency.
Background
Manganese is used widely, the consumption of which is second to that of iron, more than 90% of manganese ore is used in the steel industry for producing manganese-based ferroalloy, and the rest 10% is used in the industries of nonferrous metallurgy, chemical industry, batteries, electronics, construction, agriculture and the like. Manganese sulfate is a traditional manganese salt product and has wide application. At present, most of domestic manganese sulfate products are in feed grade, such as electrolytic manganese metal used for feed additives and manganese-copper alloys; electrolytic or chemical manganese dioxide for manufacturing high-grade batteries, high-purity manganese carbonate for soft magnetic ferrite materials, trimanganese tetroxide and the like are all produced by taking manganese sulfate as a basic raw material.
In recent years, with the rapid development of the battery industry, the demand for the impurity mass fraction of electrolytic manganese dioxide is becoming more stringent. The key technology for producing high-quality products lies in the deep impurity removal of manganese sulfate solution. In the manganese sulfate solution obtained by sulfuric acid leaching, impurity elements such as potassium, iron, cobalt, nickel, copper, lead, molybdenum, calcium, magnesium and the like exist, and can enter the product in the electrolytic process. In order to remove the impurities, in the traditional process, the pH value of the solution is adjusted to 5.5-6.5 by adding stone powder, so that iron is precipitated and removed, then solid-liquid separation is carried out, sulfides are added to remove heavy metal ions such as cobalt, nickel, copper, lead and the like, solid-liquid separation is carried out again, the pH value of the solution is adjusted to 2.0-3.0, molybdenum removing agent is added, and solid-liquid separation is carried out again to obtain the purified manganese sulfate solution. The method is complicated, the reagent amount is large, the removal of calcium and magnesium still needs to be improved, and the simple deep purification method has very important significance for producing high-quality EMD.
Patent CN 105293584 a discloses a method for purifying manganese sulfate solution, which comprises treating manganese sulfate solution with ion exchange resin, wherein the ion exchange resin is chelate resin with dimethyl pyridine group; the chelating resin with the lutidine group is Purolite @ S960; the ion exchange resin treatment also comprises resolution and transformation treatment; the analysis treatment is to use the resin loaded with copper, nickel, cobalt and zinc impurities after adsorption treatment
Resolving sulfuric acid with the concentration of 5-30% to obtain a sulfate solution containing copper, nickel, cobalt and zinc, and recovering valuable metals of copper, nickel, cobalt and zinc; the transformation treatment is to transform the resolved resin into a sodium resin by using liquid alkali with the mass concentration of 4-15%, the transformed sodium resin is introduced into a manganese sulfate solution, the sodium resin is transformed into a manganese resin, and the transformed manganese resin is returned to the adsorption treatment step for impurity removal; in the adsorption treatment process, the manganese sulfate solution to be treated passes through an exchange column loaded with ion exchange resin at the flow speed of 5-15 BV/h, and then
Stopping the adsorption operation when the content of copper, nickel, cobalt and zinc in the solution flowing out of the exchange column exceeds 2 mg/l; and (3) carrying out oil removal treatment before the adsorption treatment of the ion exchange resin, wherein the oil removal treatment is to remove oil from the manganese sulfate solution by microbubble air flotation and remove oil from fibers to obtain the deoiled manganese sulfate solution. The method has the disadvantages of complicated operation, high cost and difficulty in realizing industrial production.
Patent CN 111187806a discloses a method for purifying manganese sulfate solution. The purification 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, performing manganese conversion saponification on the saponified organic phase by using a first manganese sulfate solution to obtain a manganese soap organic phase; step S3, carrying out first extraction on the manganese sulfate solution to be purified by using the saponified organic phase to obtain a manganese-rich organic phase; step S4, washing the manganese-rich organic phase with water to obtain a purified manganese-rich organic phase; step S5, carrying out first back extraction on the purified manganese-rich organic phase by using sulfuric acid to obtain a purified manganese sulfate solution and a first regenerated organic phase; and step S6, performing second extraction by using manganese soap organic phase-relatively purified manganese sulfate solution to obtain high-purity manganese sulfate solution and calcium-magnesium-rich organic phase. Although the method can well remove calcium and magnesium in the manganese sulfate solution, a large amount of organic solvent is consumed, the cost is high, and the industrialization is difficult.
The above background disclosure is only provided to assist understanding of the inventive concept and technical solutions of the present invention, which do not necessarily belong to the prior art of the present patent application, and should not be used to evaluate the novelty and inventive step of the present application in the case that there is no clear evidence that the above content has been disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention provides a method for purifying a manganese sulfate solution with high efficiency aiming at the problems of the existing manganese sulfate solution. The method of the invention adopts the simultaneous operation of molybdenum removal and potassium and sodium removal, and the simultaneous operation of iron removal and weight removal, thereby reducing one procedure, simplifying the production flow, improving the production efficiency, saving the cost, having high purity of the extracted manganese sulfate solution and being easy to realize the industrial production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:0.9-1.2, and reacting at the temperature of 90-110 ℃ for 2-4h to obtain manganese sulfate ore slurry;
(2) adding manganese dioxide powder into the manganese sulfate ore pulp to obtain Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, reacting for 1h under the condition that the pH of the solution is controlled to be 2.5-3.0, and finally, performing pressure filtration to remove the precipitates to obtain a crude filtrate;
(3) and adding a neutralizing agent into the rough filtrate to adjust the pH value to 4.5-5.0, then adding barium sulfide and sorbitol, stirring and reacting for 1-2 hours, and then carrying out secondary filter pressing to obtain a filtrate, namely a manganese sulfate solution.
As a further optimization of the invention: the weight of the barium sulfide and the dosage of the filtrate are 40-60 g: 1L.
As a further optimization of the invention: the volume ratio of the sorbitol to the filtrate is 1-2: 100.
As a further optimization of the invention: and (1) adding a defoaming agent before adding the manganese carbonate powder.
As a further optimization of the invention: the addition amount of the defoaming agent is 0.1-0.5% of the manganese carbonate powder.
As a further optimization of the invention: the defoaming agent is a polysiloxane defoaming agent.
As a further optimization of the invention: the neutralizing agent is white mud or/and calcium carbonate powder.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. according to the invention, molybdenum removal and potassium and sodium removal are carried out simultaneously, and iron removal and heavy metal removal are carried out simultaneously, so that one step is completed, one process is reduced, repeated filter pressing is not needed, the pH value is adjusted, the process is simplified, materials and labor are saved, the production efficiency is obviously improved, and industrial production is easy to realize.
2. The content of impurities in the manganese sulfate solution prepared by the method is as follows: co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Cu is less than or equal to 2ppm, Pb is less than or equal to 3.5ppm, K is less than or equal to 20ppm, Mo is less than or equal to 0.05ppm, and the product purity is high.
3. The method adopts the defoaming agent to eliminate a large amount of foam generated in the reaction of manganese carbonate ore and sulfuric acid, can reduce the feeding time, improve the working efficiency, reduce the foam, prevent the overflow of the barrel, ensure the production safety and avoid waste.
4. The invention also adjusts the liquid-solid ratio, adopts a normal temperature leaching method, utilizes the heat generated by the violent reaction of sulfuric acid and manganese carbonate to carry out the reaction, and the whole reaction time is about 4 hours, thereby overcoming the problems of large liquid phase system, about 2 hours of temperature rise time, about 8 hours of total chemical leaching time, long equipment operation time, low equipment utilization rate, large power consumption, high energy consumption and high cost of the traditional method adopting a high temperature leaching method.
5. Sorbitol is added in the method, so that various metal ions can be chelated, and the purity of the manganese sulfate solution is higher.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:0.95, and reacting for 3 hours at the temperature of 95 ℃ to obtain manganese sulfate ore slurry; in the process of adding the manganese carbonate powder, the manganese carbonate powder reacts with sulfuric acid violently to generate a large amount of foam, the manganese carbonate powder is added too fast to cause barrel overflow, the feeding time is too long, and the working efficiency is affected, so that a certain amount of polysiloxane antifoaming agent is added before the manganese carbonate powder is added, and the adding amount of the polysiloxane antifoaming agent is 0.1% of the mass of the manganese carbonate powder.
(2) Adding manganese dioxide powder into the manganese sulfate ore slurry when the reaction time is 3 hours, and adding Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, simultaneously adsorbing molybdenum ions in the solution under an acidic condition by using the specific adsorption effect of manganese dioxide, reacting for 1h under the condition that the pH of the solution is controlled to be 2.5-3.0, finally, performing pressure filtration to remove the precipitates, removing potassium, sodium and molybdenum elements in the solution, and taking a crude filtrate;
(3) adding calcium carbonate powder into the coarse filtrate to adjust pH to 4.5-5.0, and adding Fe3+Complete hydrolysis, qualitative detection of Fe3+After the solution is qualified, adding barium sulfide and sorbitol, wherein the weight ratio of the barium sulfide to the volume ratio of the filtrate is 50g:1L, the volume ratio of the sorbitol to the filtrate is 1:50, stirring and reacting for 1.5h, and removing Cu in the solution2+、Co2+、Ni2+、Pb2+And (3) waiting for heavy metal ions, and performing secondary filter pressing to obtain a filtrate, namely the manganese sulfate solution.
Through detection, the content of impurities in the manganese sulfate solution prepared in the embodiment is as follows: co 1.38ppm, Ni 1.23 ppm, Cu 0.91 ppm, Pb 2.64ppm, K14.80ppm, Mo 0.035 ppm.
Example 2
A method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:1, and reacting for 4 hours at the temperature of 90 ℃ to obtain manganese sulfate ore slurry; in the process of adding the manganese carbonate powder, the manganese carbonate powder reacts with sulfuric acid violently to generate a large amount of foam, the manganese carbonate powder is added too fast to cause barrel overflow, the feeding time is too long, and the working efficiency is affected, so that a certain amount of polysiloxane antifoaming agent is added before the manganese carbonate powder is added, and the adding amount of the polysiloxane antifoaming agent is 0.3% of the mass of the manganese carbonate powder.
(2) Adding manganese dioxide powder into the manganese sulfate ore slurry when the reaction time is 4 hours, and adding Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, simultaneously adsorbing molybdenum ions in the solution under an acidic condition by using the specific adsorption effect of manganese dioxide, reacting for 1h under the condition that the pH of the solution is controlled to be 2.5-3.0, finally, performing pressure filtration to remove the precipitates, removing potassium, sodium and molybdenum elements in the solution, and taking a crude filtrate;
(3) adding lime mud neutralizer into the coarse filtrate to adjust pH to 4.5-5.0, and adjusting Fe content3+Complete hydrolysis, qualitative detection of Fe3+After the solution is qualified, adding barium sulfide and sorbitol, wherein the weight ratio of the barium sulfide to the volume ratio of the filtrate is 40g:1L, the volume ratio of the sorbitol to the filtrate is 1:100, stirring for reaction for 2 hours, and removing Cu in the solution2+、Co2+、Ni2+、Pb2+And (3) waiting for heavy metal ions, and performing secondary filter pressing to obtain a filtrate, namely the manganese sulfate solution.
Through detection, the content of impurities in the manganese sulfate solution prepared in the embodiment is as follows: co 1.62ppm, Ni 0.93ppm, Cu 1.37ppm, Pb 1.82ppm, K12.50 ppm, Mo 0.020 ppm.
Example 3
A method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:0.9, and reacting for 2.5 hours at the temperature of 105 ℃ to obtain manganese sulfate ore slurry; in the process of adding the manganese carbonate powder, the manganese carbonate powder reacts with sulfuric acid violently to generate a large amount of foam, the manganese carbonate powder is added too fast to cause barrel overflow, the feeding time is too long, and the working efficiency is affected, so that a certain amount of polysiloxane antifoaming agent is added before the manganese carbonate powder is added, and the adding amount of the polysiloxane antifoaming agent is 0.4% of the mass of the manganese carbonate powder.
(2) Adding manganese dioxide powder into the manganese sulfate ore pulp when the reaction time is 2.5 hoursOf Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, simultaneously adsorbing molybdenum ions in the solution under an acidic condition by using the specific adsorption effect of manganese dioxide, reacting for 1h under the condition that the pH of the solution is controlled to be 2.5-3.0, finally, performing pressure filtration to remove the precipitates, removing potassium, sodium and molybdenum elements in the solution, and taking a crude filtrate;
(3) adding calcium carbonate neutralizer into the coarse filtrate to adjust pH to 4.5-5.0, and adjusting Fe content3+Complete hydrolysis, qualitative detection of Fe3+After the solution is qualified, adding barium sulfide and sorbitol, wherein the weight ratio of the barium sulfide to the volume ratio of the filtrate is 60g:1L, the volume ratio of the sorbitol to the filtrate is 1:50, stirring for reaction for 1h, and removing Cu in the solution2+、Co2+、Ni2+、Pb2+And (3) waiting for heavy metal ions, and performing secondary filter pressing to obtain a filtrate, namely the manganese sulfate solution.
Through detection, the content of impurities in the manganese sulfate solution prepared in the embodiment is as follows: co 0.83ppm, Ni 1.82ppm, Cu 1.69ppm, Pb 2.01ppm, K9.82ppm, Mo 0.028 ppm.
Example 4
A method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:1.1, and reacting for 2 hours at the temperature of 100 ℃ to obtain manganese sulfate ore slurry; in the process of adding the manganese carbonate powder, the manganese carbonate powder reacts with sulfuric acid violently to generate a large amount of foam, the manganese carbonate powder is added too fast to cause barrel overflow, the feeding time is too long, and the working efficiency is affected, so that a certain amount of polysiloxane antifoaming agent is added before the manganese carbonate powder is added, and the adding amount of the polysiloxane antifoaming agent is 0.2% of the mass of the manganese carbonate powder.
(2) Adding manganese dioxide powder into the manganese sulfate ore slurry when the reaction time is 2 hours, and adding Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitate, simultaneously adsorbing molybdenum ions in the solution under acidic condition by using the specific adsorption effect of manganese dioxide,keeping the pH of the solution at 2.5-3.0, reacting for 1h, filter-pressing, removing precipitate, removing potassium, sodium and molybdenum elements in the solution, and collecting crude filtrate;
(3) adding calcium carbonate neutralizer into the coarse filtrate to adjust pH to 4.5-5.0, and adjusting Fe content3+Complete hydrolysis, qualitative detection of Fe3+After the solution is qualified, adding barium sulfide and sorbitol, wherein the weight ratio of the barium sulfide to the volume ratio of the filtrate is 45g:1L, the volume ratio of the sorbitol to the filtrate is 1:80, stirring for reaction for 1h, and removing Cu in the solution2+、Co2+、Ni2+、Pb2+And (3) waiting for heavy metal ions, and performing secondary filter pressing to obtain a filtrate, namely the manganese sulfate solution.
Through detection, the content of impurities in the manganese sulfate solution prepared in the embodiment is as follows: co 1.55ppm, Ni 1.72 ppm, Cu 1.22ppm, Pb 2.08ppm, K15.62 ppm, Mo 0.042 ppm.
Example 5
A method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:1.2, and reacting for 2 hours at the temperature of 95 ℃ to obtain manganese sulfate ore slurry; in the process of adding the manganese carbonate powder, the manganese carbonate powder reacts with sulfuric acid violently to generate a large amount of foam, the manganese carbonate powder is added too fast to cause barrel overflow, the feeding time is too long, and the working efficiency is affected, so that a certain amount of polysiloxane antifoaming agent is added before the manganese carbonate powder is added, and the adding amount of the polysiloxane antifoaming agent is 0.3% of the mass of the manganese carbonate powder.
(2) Adding manganese dioxide powder into the manganese sulfate ore slurry when the reaction time is 2 hours, and adding Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, simultaneously adsorbing molybdenum ions in the solution under an acidic condition by using the specific adsorption effect of manganese dioxide, reacting for 1 hour under the condition of keeping the pH of the solution at 2.5-3.0, finally, performing filter pressing to remove the precipitates, removing potassium, sodium and molybdenum elements in the solution, and taking a crude filtrate;
(3) adding lime mud neutralizer into the coarse filtrate to adjust pH to 4.5-5.0, and adjusting Fe content3+Complete hydrolysis, qualitative detection of Fe3+After the barium sulfide solution is qualified, adding barium sulfide and sorbitol, wherein the weight ratio of the barium sulfide to the volume ratio of the filtrate is 55g to 1L, the volume ratio of the sorbitol to the filtrate is 1 to 100, stirring and reacting for 1.5h, and removing Cu in the solution2+、Co2+、Ni2+、Pb2+And (3) waiting for heavy metal ions, and performing secondary filter pressing to obtain a filtrate, namely the manganese sulfate solution.
Through detection, the content of impurities in the manganese sulfate solution prepared in the embodiment is as follows: co 1.62ppm, Ni 1.65ppm, Cu 1.31ppm, Pb 2.69ppm, K15.92ppm, Mo 0.05 ppm.
Example 6
A method for purifying a manganese sulfate solution with high efficiency comprises the following steps:
(1) putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:1.05, and reacting for 3 hours at the temperature of 100 ℃ to obtain manganese sulfate ore slurry; in the process of adding the manganese carbonate powder, the manganese carbonate powder reacts with sulfuric acid violently to generate a large amount of foam, the manganese carbonate powder is added too fast to cause barrel overflow, the feeding time is too long, and the working efficiency is affected, so that a certain amount of polysiloxane antifoaming agent is added before the manganese carbonate powder is added, and the adding amount of the polysiloxane antifoaming agent is 0.2% of the mass of the manganese carbonate powder.
(2) Adding manganese dioxide powder into the manganese sulfate ore slurry when the reaction time is 3 hours, and adding Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, simultaneously adsorbing molybdenum ions in the solution under an acidic condition by using the specific adsorption effect of manganese dioxide, reacting for 1 hour under the condition of keeping the pH of the solution at 2.5-3.0, finally, performing filter pressing to remove the precipitates, removing potassium, sodium and molybdenum elements in the solution, and taking a crude filtrate;
(3) adding calcium carbonate neutralizer into the coarse filtrate to adjust pH to 4.5-5.0, and adjusting Fe content3+Complete hydrolysis, qualitative detection of Fe3+After the solution is qualified, adding barium sulfide and sorbitol, wherein the weight ratio of the barium sulfide to the volume ratio of the filtrate is 60g:1L, the volume ratio of the sorbitol to the filtrate is 1:50, stirring for reaction for 2 hours, and removing Cu in the solution2+、Co2+、Ni2+、Pb2+And (3) waiting for heavy metal ions, and performing secondary filter pressing to obtain a filtrate, namely the manganese sulfate solution.
Through detection, the content of impurities in the manganese sulfate solution prepared in the embodiment is as follows: co 0.93ppm, Ni 1.03 ppm, Cu 1.24ppm, Pb 2.08ppm, K12.38ppm, Mo 0.031 ppm.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments and it is not intended to limit the invention to the specific embodiments described. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (8)
1. A method for purifying a manganese sulfate solution with high efficiency is characterized by comprising the following steps: the method comprises the following steps:
putting manganese carbonate powder and concentrated sulfuric acid into a reaction kettle according to the mass ratio of 1:0.9-1.2, and reacting at the temperature of 90-110 ℃ for 2-4h to obtain manganese sulfate ore slurry;
adding manganese dioxide powder into the manganese sulfate ore pulp to obtain Fe2+Conversion of Fe3+Converting the produced Fe3+And K+、Na+Reacting to form jarosite and jarosite precipitates, reacting for 1h under the condition that the pH of the solution is controlled to be 2.5-3.0, and finally, performing filter pressing to remove the precipitates and taking a crude filtrate;
and adding a neutralizing agent into the rough filtrate to adjust the pH value to 4.5-5.0, then adding barium sulfide and sorbitol, stirring and reacting for 1-2 hours, and then carrying out secondary filter pressing to obtain a filtrate, namely a manganese sulfate solution.
2. The method for purifying manganese sulfate solution with high efficiency as set forth in claim 1, wherein: the weight of the barium sulfide and the dosage of the filtrate are 40-60 g: 1L.
3. The method for purifying manganese sulfate solution with high efficiency as set forth in claim 1, wherein: the volume ratio of the sorbitol to the filtrate is 1-2: 100.
4. The method for purifying manganese sulfate solution with high efficiency as set forth in claim 1, wherein: and (1) adding a defoaming agent before adding the manganese carbonate powder.
5. The method for purifying manganese sulfate solution with high efficiency as set forth in claim 4, wherein: the addition amount of the defoaming agent is 0.1-0.5% of the manganese carbonate powder.
6. The method for purifying manganese sulfate solution with high efficiency as set forth in claim 1, wherein: the defoaming agent is a polysiloxane defoaming agent.
7. The method for purifying manganese sulfate solution with high efficiency as set forth in claim 1, wherein: the neutralizing agent is white mud or/and calcium carbonate powder.
8. The method for the high-efficiency purification of a manganese sulfate solution as set forth in any one of claims 1 to 7, wherein: the content of impurities in the manganese sulfate solution prepared in the step (3) is as follows: co is less than or equal to 2ppm, Ni is less than or equal to 2ppm, Cu is less than or equal to 2ppm, Pb is less than or equal to 3.5ppm, K is less than or equal to 20ppm, and Mo is less than or equal to 0.05 ppm.
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