CN112063839B - Process for preparing manganese sulfate by manganese sulfide wet method - Google Patents
Process for preparing manganese sulfate by manganese sulfide wet method Download PDFInfo
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- CN112063839B CN112063839B CN202010769933.2A CN202010769933A CN112063839B CN 112063839 B CN112063839 B CN 112063839B CN 202010769933 A CN202010769933 A CN 202010769933A CN 112063839 B CN112063839 B CN 112063839B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a process for preparing manganese sulfate by a manganese sulfide wet method in the technical field of wet metallurgy, which comprises the steps of adding manganese sulfide concentrate powder into an acidic solution of an oxidant, and blowing air into the acidic solution to obtain a leaching solution; adding lime into air while bubbling the leachate to adjust the pH value to 5.0, heating to boil, and then filtering to remove iron; adding barium sulfide to remove heavy metal impurities; stirring, heating and concentrating until manganese sulfate is just separated out, stopping heating, stirring and standing for 24h, and filtering to remove calcium and magnesium; heating, concentrating and crystallizing until the crystallization rate is about 60%, and filtering while the solution is hot to obtain manganese sulfate monohydrate; the reaction is mild, the conditions are easy to control, and the problem of hydrogen sulfide generated by a manganese sulfide wet method is perfectly solved; the aim of mild reaction speed can be achieved by using air as an oxidant instead of hydrogen peroxide, and a large amount of cost can be saved; aiming at low requirements of industrial manganese sulfate on calcium and magnesium, the calcium and magnesium are removed by adopting a preconcentration crystallization method, so that the reagent is saved, and fluoride is not introduced.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a process for preparing manganese sulfate by a manganese sulfide wet method.
Background
The sulfur-containing manganese ore mainly comprises manganese carbonate, manganese sulfide, a very small amount of manganese oxide and manganese silicate, the average sulfur content of the ore is about 13%, and the ore is floated to obtain a manganese carbonate concentrate (the sulfur content is less than 0.6%) and a manganese sulfide concentrate (the sulfur content is about 30% and the manganese content is about 50%). Sulfur-containing manganese ore is unpopular because sulfur can be combusted to generate sulfur dioxide gas during sintering, and the problem that the alloy cannot be smelted by a pyrogenic process objectively exists, so that resources are idle; meanwhile, because sulfur in the sulfur-containing manganese ore is negative divalent sulfur, hydrogen sulfide gas is easily generated due to improper condition control in acid leaching in a traditional wet method, and the hydrogen sulfide gas has toxicity and strong pungent smell, so that the ore can not be used in the wet method objectively, a large amount of resources of the sulfur-containing manganese ore are idle, and the sulfur-containing manganese ore can not be used in large quantities. At present, sulfur-containing manganese ore resources are scattered in all parts of the country, the manganese grade is generally relatively high, and the sulfur-containing manganese ore resources are influenced by sulfur and cannot realize due value.
Disadvantage 1: in pyrometallurgy, the raw ore contains a large amount of sulfur, which can cause sulfur dioxide emission when used in combination with other ores, on one hand, causes environmental pollution, and on the other hand, the sulfur dioxide index is consumed very quickly, which causes environmental protection cost to rise.
And (2) disadvantage: in hydrometallurgy, because manganese sulfide has extremely strong reaction activity under an acidic condition, the manganese sulfide can quickly react at a low temperature to generate hydrogen sulfide gas, and the existing reaction system for acid leaching manganese sulfate is generally an open reaction tower, so that a large amount of hydrogen sulfide is released if a condition operation fails in the operation process of workers, and serious accidents of casualties are easily caused.
The disadvantage 3 is that the pyro-and wet-processes for treating the acidic gas require an acidic absorption tower with matching capability to treat the tail gas, and require additional operation cost such as alkali solution cost, alkali solution treatment and the like besides equipment investment.
Disadvantage 4: if the hydrogen peroxide is used as an oxidant, on one hand, the hydrogen peroxide is high in price and belongs to a controlled chemical product; on the other hand, hydrogen peroxide is unstable in solution and is easily decomposed by itself under the condition of other impurities such as Mn ions, and oxygen is generated to separate from the system, so that the reaction efficiency is low, the consumption is increased, and the cost is increased.
Based on the technical scheme, the invention designs a process for preparing manganese sulfate by a manganese sulfide wet method, so as to solve the problems.
Disclosure of Invention
The invention aims to provide a process for preparing manganese sulfate by a manganese sulfide wet method, which aims to solve the problems of violent reaction, difficult control of conditions and high cost in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a process for preparing manganese sulfate by a manganese sulfide wet method comprises the following steps:
the method comprises the following steps: leaching, namely adding manganese sulfide concentrate powder into an acid solution of soluble ferrite by adopting a hydrometallurgical process, and blowing air into the solution simultaneously, so that manganese sulfide is quickly oxidized into sulfur or sulfate ions in the solution, thereby inhibiting the generation of hydrogen sulfide gas and obtaining leaching slag and leaching liquid;
step two: removing iron, namely obtaining a leaching solution which is a crude manganese sulfate solution, adding lime into air while blowing to adjust the pH value to 4.5-5.5, heating to boiling, and filtering to remove iron to obtain the manganese sulfate solution;
step three: after iron removal, adding barium sulfide into the manganese sulfate solution to remove heavy metal impurities;
step four: stirring, heating and concentrating after removing heavy metal impurities until manganese sulfate is just separated out, stopping heating, stirring and standing for more than 20 hours, and filtering to remove calcium and magnesium;
step five: heating, concentrating and crystallizing the manganous sulfate solution in the step until the crystallization rate is 50-70%, and filtering while the solution is hot to obtain manganese sulfate monohydrate and mother liquor.
Preferably, the soluble ferrite of step one is sodium ferrate.
Preferably, the solution is tested for iron-free in step two with a potassium thiocyanate indicator.
Preferably, step two adjusts the pH to 5.0.
Preferably, step four is left to stand for 24 h.
Preferably, the mother liquor in the fifth step is continuously and circularly heated, concentrated and crystallized.
Preferably, the mother liquor obtained in the fifth step is mixed with the manganese sulfate liquor after heavy metal impurities are removed for reuse.
Preferably, the crystallization rate in the fifth step is 60%.
Compared with the prior art, the invention has the beneficial effects that: aiming at the characteristics of strong activity and easy reaction with acid of manganese sulfide, the invention introduces the oxidant salt which can directly react with the manganese sulfide to be converted into manganese ions, sulfur and sulfate radicals under the acidic condition.
The aim of mild reaction speed can be achieved by using air as an oxidant instead of hydrogen peroxide, and a large amount of cost can be saved;
aiming at low requirements of industrial manganese sulfate on calcium and magnesium, the calcium and magnesium are removed by adopting a preconcentration crystallization method, reagents are saved, no fluoride is introduced, and the produced manganese sulfate can be used as feed-grade manganese sulfate or fertilizer-grade manganese sulfate and has high market applicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A process for preparing manganese sulfate by a manganese sulfide wet method comprises the following steps:
the method comprises the following steps: leaching, namely adding manganese sulfide concentrate powder into an acid solution of soluble ferrite by adopting a hydrometallurgical process, and blowing air into the solution simultaneously, so that manganese sulfide is quickly oxidized into sulfur or sulfate ions in the solution, thereby inhibiting the generation of hydrogen sulfide gas and obtaining leaching slag and leaching liquid;
step two: removing iron, namely obtaining a leaching solution which is a crude manganese sulfate solution, adding lime into air while blowing to adjust the pH value to 4.5-5.5, heating to boiling, and filtering to remove iron to obtain the manganese sulfate solution;
step three: after iron removal, adding barium sulfide into the manganese sulfate solution to remove heavy metal impurities;
step four: stirring, heating and concentrating after removing heavy metal impurities until manganese sulfate is just separated out, stopping heating, stirring and standing for more than 20 hours, and filtering to remove calcium and magnesium;
step five: heating, concentrating and crystallizing the manganous sulfate solution in the step until the crystallization rate is 50-70%, and filtering while the solution is hot to obtain manganese sulfate monohydrate and mother liquor.
Further, in the first step, sodium ferrate is used as the soluble ferrite.
Further, in step two, the solution was tested for iron-free using a potassium thiocyanate indicator.
Further, the pH is adjusted to 5.0 in the second step.
And further, standing for 24 hours in the fourth step.
Further, the mother liquor in the fifth step is continuously and circularly heated, concentrated and crystallized.
And further, mixing the mother liquor obtained in the fifth step with the manganese sulfate liquor after heavy metal impurities are removed for reuse.
Further, the crystallization rate in the fifth step is 60%.
One embodiment of the invention:
experiment one: preparing sodium ferrate into an acid solution, blowing gas, slowly adding manganese sulfide concentrate powder, reacting for 30min, and filtering to obtain reaction slag and manganese sulfate solution.
Experiment two: heating the leachate to 85 ℃, adding lime 1 into air while blowing to adjust the pH value to 5.0, taking a small amount of filtered clear liquid, testing the clear liquid by using an iron indicator until no iron exists, heating the clear liquid to boiling, and filtering the clear liquid to remove iron to obtain 300ml of manganese sulfate liquid.
Experiment three: taking 300ml of manganese sulfate solution, heating the manganese sulfate solution to 60 ℃ in a constant-temperature water bath kettle, adding 1.5 times of theoretical amount of industrial-grade barium sulfide (55% effective), stirring and reacting for 1 hour, stopping heating, standing for 24 hours, and filtering to obtain the weight-removed manganese sulfate solution.
Experiment four: and (3) evaporating the heavy manganese sulfate liquid to be just turbid, stopping heating and stirring, standing for 24 hours, and filtering to obtain the manganese sulfate liquid with primary calcium and magnesium removed.
Experiment five: heating, concentrating and crystallizing the manganese sulfate solution with calcium and magnesium removed initially until the crystallization rate is about 60%, filtering while the solution is hot to obtain manganese sulfate monohydrate and mother liquor, and recycling the mother liquor or mixing the mother liquor with the removed heavy manganese sulfate solution of the next batch for reuse. The indexes of the obtained manganese sulfate product are as follows:
assay data of manganese sulfate
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A process for preparing manganese sulfate by a manganese sulfide wet method is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: leaching, namely adding manganese sulfide concentrate powder into an acid solution of soluble ferrite by adopting a hydrometallurgical process, and blowing air into the solution simultaneously, so that manganese sulfide is quickly oxidized into sulfur or sulfate ions in the solution, thereby inhibiting the generation of hydrogen sulfide gas and obtaining leaching slag and leaching liquid;
step two: removing iron, namely obtaining a leaching solution which is a crude manganese sulfate solution, adding lime into air while blowing to adjust the pH value to 4.5-5.5, heating to boiling, and filtering to remove iron to obtain the manganese sulfate solution;
step three: after iron removal, adding barium sulfide into the manganese sulfate solution to remove heavy metal impurities;
step four: stirring, heating and concentrating after removing heavy metal impurities until manganese sulfate is just separated out, stopping heating, stirring and standing for more than 20 hours, and filtering to remove calcium and magnesium;
step five: heating, concentrating and crystallizing the manganous sulfate solution in the step until the crystallization rate is 50-70%, and filtering while the solution is hot to obtain manganese sulfate monohydrate and mother liquor.
2. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: step one, sodium ferrate is adopted as soluble ferrate.
3. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: and in the second step, a potassium thiocyanate indicator is used for testing the solution to be free of iron.
4. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: and step two, adjusting the pH value to 5.0.
5. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: and step four, standing for 24 hours.
6. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: and step five, continuously circularly heating, concentrating and crystallizing the mother liquor.
7. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: and mixing the mother liquor obtained in the step five with the manganese sulfate liquor after heavy metal impurities are removed for reuse.
8. The process for preparing manganese sulfate by using a manganese sulfide wet method according to claim 1, wherein the manganese sulfide wet method comprises the following steps: and step five, the crystallization rate is 60 percent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740243A (en) * | 1984-12-31 | 1988-04-26 | Ensci, Inc. | Metal value recovery from metal sulfide containing ores |
| CN102329957A (en) * | 2011-09-09 | 2012-01-25 | 西南科技大学 | Method for continuously leaching sulfide ore by using synergy of autotrophic ore leaching bacteria and heterotrophic ore leaching bacteria |
| CN105331813A (en) * | 2015-11-03 | 2016-02-17 | 中南大学 | Method for inhibiting H2S generation in process of extracting manganese through manganese ore acid leaching |
| CN106693081A (en) * | 2016-11-28 | 2017-05-24 | 西藏淇华生物科技有限公司 | Method for preparing nuclear magnetic resonance development material and application |
| CN107012337A (en) * | 2017-04-01 | 2017-08-04 | 贵州大龙汇成新材料有限公司 | The method of enriching and recovering nickel cobalt from manganese-containing waste |
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- 2020-08-04 CN CN202010769933.2A patent/CN112063839B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740243A (en) * | 1984-12-31 | 1988-04-26 | Ensci, Inc. | Metal value recovery from metal sulfide containing ores |
| CN102329957A (en) * | 2011-09-09 | 2012-01-25 | 西南科技大学 | Method for continuously leaching sulfide ore by using synergy of autotrophic ore leaching bacteria and heterotrophic ore leaching bacteria |
| CN105331813A (en) * | 2015-11-03 | 2016-02-17 | 中南大学 | Method for inhibiting H2S generation in process of extracting manganese through manganese ore acid leaching |
| CN106693081A (en) * | 2016-11-28 | 2017-05-24 | 西藏淇华生物科技有限公司 | Method for preparing nuclear magnetic resonance development material and application |
| CN107012337A (en) * | 2017-04-01 | 2017-08-04 | 贵州大龙汇成新材料有限公司 | The method of enriching and recovering nickel cobalt from manganese-containing waste |
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