CN101698514B - Preparation method of electronic grade high-purity manganese sulfate monohydrate - Google Patents
Preparation method of electronic grade high-purity manganese sulfate monohydrate Download PDFInfo
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- CN101698514B CN101698514B CN2009101933984A CN200910193398A CN101698514B CN 101698514 B CN101698514 B CN 101698514B CN 2009101933984 A CN2009101933984 A CN 2009101933984A CN 200910193398 A CN200910193398 A CN 200910193398A CN 101698514 B CN101698514 B CN 101698514B
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Abstract
The invention discloses a method for preparing manganese sulfate monohydrate by taking electrolytic manganese and industrial sulphuric acid as raw material; the method comprises the following steps: (1) the electrolytic manganese is ground and sieved to obtain manganese powder; the manganese powder is added in the industrial sulphuric acid and is heated to 80-90 DEG C and reacts for 4-12h continuously under the stirring condition, so as to obtain manganese sulphate suspension; the heavy metallic salt content in the manganese sulphate suspension is measured by atomic absorption spectroscopy; (2) the pH of the suspension is adjusted to 3-4, barium sulphide is added and filtration is carried out, so as to obtain filtrate 1; (3) lime stone is added in the filtrate 1, after the pH value is adjusted to be 5-6 and is placed still, so as to obtain the filtrate 2; (4) sodium fluoride is added in the filtrate 2 for reacting 20-26 hours and then is filtered, so as to obtain manganese sulphate solution; (5) after the manganese sulphate solution is concentrated and recrystallized, centrifugal separation, washing, drying and crashing are carried out, thereby obtaining the manganese sulfate monohydrate; the method has simple production process, easy operation, no pollution and low equipment requirements.
Description
Technical field
The invention belongs to chemical production field, particularly a kind of preparation method of electronic grade high-purity manganese sulfate monohydrate.
Background technology
Manganous sulfate is a kind of important chemical product, also is important source material such as main chemical industry, metallurgy, can be used for the production of medicine, papermaking, pottery, electrolytic manganese and the manufacturing of other manganese salt etc.The manganous sulfate manufacturing process comprises: (1) high-temperature roasting method is a raw material with the pyrolusite, though this method is ripe, has long flow path, labour intensity is big, environmental pollution is serious, energy consumption is high, the manganese utilization ratio is low, shortcomings such as waste resource etc.; (2) pickling process is a raw material with the rhodochrosite, and this method need consume a large amount of sulfuric acid, and is strong to equipment corrosion, and filtrate need remove the alkaline earth metal impurity of association in the ore, has strengthened production cost; (3) additive method for example, sulfurous gas method, ferrous sulfate method, manganese monoxide method, hydrocarbon polymer method, utilizes methods such as biogas, rice skin, cane molasses alcohol slops etc. still to be in during theoretic discussion and bench-scale testing explore, and technology is still immature; (4) two ore deposit pickling process, this method is adopted by manganous sulfate producer at present gradually, and its advantage is to have saved the high temperature reduction calcining process, improved operating environment, reduced the consumption of raw material and fuel, the leaching, in and deironing, removing heavy metals all in same reactive tank, once finish, solid-liquid separation is easy.But in actual production, when particularly selecting for use low poor pyrolusite to be raw material, adopt two ore deposit pickling process to be difficult to produce qualified Manganous sulfate monohydrate simply.Existing two ore deposit pickling process are that the manganese ore that adds high Mn content in low poor pyrolusite raw material replenishes the manganese content of raw material in actual production, otherwise can't produce qualified Manganous sulfate monohydrate.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide a kind of preparation method of electronic grade high-purity manganese sulfate monohydrate.
Purpose of the present invention is achieved through the following technical solutions: a kind of is the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, comprises following operation steps:
(1) electrolytic manganese is levigate, cross 300～350 mesh sieves, obtain manganese powder; Manganese powder is joined in the industrial sulphuric acid, continue reaction 4～12h after under agitation condition, being heated to 80～90 ℃, obtain the manganous sulfate suspension liquid, with the content of heavy metallic salt in the Atomic Absorption Spectrometry manganous sulfate suspension liquid;
(2) regulate pH between 3～4 with Wingdale, add barium sulphide and filter, behind reaction 0.5～1h, obtain filtrate 1;
(3) in filtrate 1, add Wingdale, regulate pH value to 5～6, leave standstill 1～2h after-filtration, obtain filtrate 2;
(4) add Sodium Fluoride in filtrate 2, reaction 20～26h after-filtration obtains manganese sulfate solution;
(5) with manganese sulfate solution centrifugation behind 80～90 ℃ of concentrated recrystallizations, washing, drying is pulverized, and obtains the Manganous sulfate monohydrate finished product.
The mass ratio of described industrial sulphuric acid of step (1) and manganese powder is 4: 1～6: 1.
The quality of the described barium sulphide of step (2) is 2 times of lead salt quality in the heavy metallic salt.
The add-on of the described Sodium Fluoride of step (4) is calcium and magnesium ion quality 2 times in the filtrate 2.
The described washing of step (5) is to adopt 60～90 ℃ manganous sulfate saturated solution to wash.
The described exsiccant temperature of step (5) is 120 ℃.
After mother liquor after the described centrifugation of step (5) cooling removed magnesium ion, can recycle after adopting 5wt% sulfuric acid dipping.
A kind of electronic grade high-purity manganese sulfate monohydrate according to method for preparing.
The present invention compared with prior art has following advantage and beneficial effect: (1) production process of the present invention is simple, easy to operate, pollution-free, low for equipment requirements; (2) parameter that is adopted in the inventive method comprises the relation of measuring between temperature of reaction, reaction times and the material, has definitely guaranteed the high-quality of gained sulfuric acid monohydrate manganese product; Prepared Manganous sulfate monohydrate purity reaches more than 99.9995%, the content of metallic impurity iron, lead, zinc, cobalt, cadmium all below 5ppm, the product complete in crystal formation.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) electrolytic manganese is levigate, cross 300 mesh sieves, obtain manganese powder; Manganese powder is joined in the industrial sulphuric acid, continue reaction 12h after under agitation condition, being heated to 80 ℃, obtain the manganous sulfate suspension liquid, with the content of heavy metallic salt in the Atomic Absorption Spectrometry manganous sulfate suspension liquid; The mass ratio of described industrial sulphuric acid and manganese powder is 5: 1;
(2) regulate pH to 3 with Wingdale, add barium sulphide and filter, behind the reaction 1h, obtain filtrate 1; The quality of described barium sulphide is 2 times of lead salt quality in the heavy metallic salt;
(3) in filtrate 1, add Wingdale, regulate pH value to 6, leave standstill the 1h after-filtration, obtain filtrate 2;
(4) add Sodium Fluoride in filtrate 2, reaction 24h after-filtration obtains manganese sulfate solution; The add-on of described Sodium Fluoride is calcium and magnesium ion quality 2 times in the filtrate 2.
(5) with manganese sulfate solution centrifugation behind 80 ℃ of concentrated recrystallizations, adopt 90 ℃ manganous sulfate saturated solution to wash, 120 ℃ of dryings are pulverized, and obtain the Manganous sulfate monohydrate finished product.
After testing, the purity of this Manganous sulfate monohydrate is 99.9995% by percentage to the quality, the content of lead, cadmium, cobalt, zinc, arsenic, iron, aluminium impurity all≤5ppm.
Embodiment 2
(1) electrolytic manganese is levigate, cross 350 mesh sieves, obtain manganese powder; Manganese powder is joined in the industrial sulphuric acid, continue reaction 4h after under agitation condition, being heated to 90 ℃, obtain the manganous sulfate suspension liquid, with the content of heavy metallic salt in the Atomic Absorption Spectrometry manganous sulfate suspension liquid; The mass ratio of described industrial sulphuric acid and manganese powder is 4: 1;
(2) regulate pH to 4 with Wingdale, add barium sulphide and filter, behind the reaction 0.5h, obtain filtrate 1; The quality of described barium sulphide is 2 times of lead salt quality in the heavy metallic salt;
(3) in filtrate 1, add Wingdale, regulate pH value to 6, leave standstill the 1h after-filtration, obtain filtrate 2;
(4) add Sodium Fluoride in filtrate 2, reaction 20h after-filtration obtains manganese sulfate solution; The add-on of described Sodium Fluoride is calcium and magnesium ion quality 2 times in the filtrate 2.
(5) with manganese sulfate solution centrifugation behind 80 ℃ of concentrated recrystallizations, adopt 60 ℃ manganous sulfate saturated solution to wash, 120 ℃ of dryings are pulverized, and obtain the Manganous sulfate monohydrate finished product.
After testing, the purity of this Manganous sulfate monohydrate is 99.9999% by percentage to the quality, the content of lead, cadmium, cobalt, arsenic, iron, aluminium, antimony, impurity all≤5ppm.
Embodiment 3
(1) electrolytic manganese is levigate, cross 320 mesh sieves, obtain manganese powder; Manganese powder is joined in the industrial sulphuric acid, continue reaction 10h after under agitation condition, being heated to 80 ℃, obtain the manganous sulfate suspension liquid, with the content of heavy metallic salt in the Atomic Absorption Spectrometry manganous sulfate suspension liquid; The mass ratio of described industrial sulphuric acid and manganese powder is 6: 1;
(2) regulate pH to 3 with Wingdale, add barium sulphide and filter, behind the reaction 0.8h, obtain filtrate 1; The quality of described barium sulphide is 2 times of lead salt quality in the heavy metallic salt;
(3) in filtrate 1, add Wingdale, regulate pH value to 6, leave standstill the 1h after-filtration, obtain filtrate 2;
(4) add Sodium Fluoride in filtrate 2, reaction 20h after-filtration obtains manganese sulfate solution; The add-on of described Sodium Fluoride is calcium and magnesium ion quality 2 times in the filtrate 2.
(5) with manganese sulfate solution centrifugation behind 85 ℃ of concentrated recrystallizations, adopt 70 ℃ manganous sulfate saturated solution to wash, 120 ℃ of dryings are pulverized, and obtain the Manganous sulfate monohydrate finished product.
After testing, the purity of this Manganous sulfate monohydrate is 99.9995% by percentage to the quality, the content of lead, cadmium, cobalt, arsenic, iron, aluminium, antimony, impurity all≤5ppm.
Embodiment 4
(1) electrolytic manganese is levigate, cross 340 mesh sieves, obtain manganese powder; Manganese powder is joined in the industrial sulphuric acid, continue reaction 8h after under agitation condition, being heated to 80 ℃, obtain the manganous sulfate suspension liquid, with the content of heavy metallic salt in the Atomic Absorption Spectrometry manganous sulfate suspension liquid; The mass ratio of described industrial sulphuric acid and manganese powder is 4: 1;
(2) regulate pH to 3.5 with Wingdale, add barium sulphide and filter, behind the reaction 1h, obtain filtrate 1; The quality of described barium sulphide is 2 times of lead salt quality in the heavy metallic salt;
(3) in filtrate 1, add Wingdale, regulate pH value to 6, leave standstill the 1h after-filtration, obtain filtrate 2;
(4) add Sodium Fluoride in filtrate 2, reaction 26h after-filtration obtains manganese sulfate solution; The add-on of described Sodium Fluoride is calcium and magnesium ion quality 2 times in the filtrate 2.
(5) with manganese sulfate solution centrifugation behind 85 ℃ of concentrated recrystallizations, adopt 80 ℃ manganous sulfate saturated solution to wash, 120 ℃ of dryings are pulverized, and obtain the Manganous sulfate monohydrate finished product.
After testing, the purity of this Manganous sulfate monohydrate is 99.9997% by percentage to the quality, the content of lead, cadmium, cobalt, arsenic, iron, aluminium, antimony, impurity all≤5ppm.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. one kind is the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, it is characterized in that comprising following operation steps:
(1) electrolytic manganese is levigate, cross 300～350 mesh sieves, obtain manganese powder; Manganese powder is joined in the industrial sulphuric acid, continue reaction 4～12h after under agitation condition, being heated to 80～90 ℃, obtain the manganous sulfate suspension liquid, with the content of heavy metallic salt in the Atomic Absorption Spectrometry manganous sulfate suspension liquid;
(2) regulate pH to 3～4 with Wingdale, add barium sulphide and filter, behind reaction 0.5～1h, obtain filtrate 1;
(3) in filtrate 1, add Wingdale, regulate pH value to 5～6, leave standstill 1～2h after-filtration, obtain filtrate 2;
(4) add Sodium Fluoride in filtrate 2, reaction 20～26h after-filtration obtains manganese sulfate solution;
(5) with manganese sulfate solution centrifugation behind 80～90 ℃ of concentrated recrystallizations, washing, drying is pulverized, and obtains the Manganous sulfate monohydrate finished product.
2. according to claim 1 a kind of be the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, it is characterized in that: the mass ratio of described industrial sulphuric acid of step (1) and manganese powder is 4: 1～6: 1.
3. according to claim 1 a kind of be the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, it is characterized in that: the quality of the described barium sulphide of step (2) is 2 times of lead salt quality in the heavy metallic salt.
4. according to claim 1 a kind of be the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, it is characterized in that: the add-on of the described Sodium Fluoride of step (4) is calcium and magnesium ion quality 2 times in the filtrate 2.
5. according to claim 1 a kind of be the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, it is characterized in that: the described washing of step (5) is to adopt 60～90 ℃ manganous sulfate saturated solution to wash.
6. according to claim 1 a kind of be the method for feedstock production Manganous sulfate monohydrate with electrolytic manganese and industrial sulphuric acid, it is characterized in that: the described exsiccant temperature of step (5) is 120 ℃.
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| CN101875507B (en) * | 2010-08-04 | 2012-10-24 | 湖南汇通科技有限责任公司 | preparation method of high purity manganese sulfate monohydrate |
| CN102674467B (en) * | 2012-05-23 | 2014-02-12 | 贵州红星发展股份有限公司 | Preparation method of manganese sulfate and manganese sulfate product prepared by same |
| CN102923783A (en) * | 2012-11-23 | 2013-02-13 | 湖南特种金属材料厂 | Battery grade high-purity manganese sulfate monohydrate and preparation method thereof |
| CN103011298A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for production of high purity manganese sulfate by using metal manganese sheet as raw material |
| CN105218172B (en) * | 2015-10-30 | 2018-08-21 | 灵丘县兴光矿业发展有限责任公司 | A method of producing potash magnesium sulphate fertilizer and manganese sulfate |
| CN106756023A (en) * | 2016-12-26 | 2017-05-31 | 湖南稀土金属材料研究院 | The method that depth separates calcium and magnesium impurity in manganese sulfate |
| CA3211620A1 (en) * | 2022-09-02 | 2023-11-17 | Korea Zinc Co., Ltd. | Method for producing manganese(ii) sulfate monohydrate from by-product of zinc refining process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884099A (en) * | 2006-07-07 | 2006-12-27 | 广西大学 | Method for preparing manganese sulfate by reduction leaching of manganese ore using discard molasses and sulfuric acid |
| CN101337692A (en) * | 2008-08-21 | 2009-01-07 | 广西远辰锰业有限公司 | Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material |
| CN101412543A (en) * | 2008-11-18 | 2009-04-22 | 湖北开元化工科技股份有限公司 | Preparation of high purity manganese sulfate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884099A (en) * | 2006-07-07 | 2006-12-27 | 广西大学 | Method for preparing manganese sulfate by reduction leaching of manganese ore using discard molasses and sulfuric acid |
| CN101337692A (en) * | 2008-08-21 | 2009-01-07 | 广西远辰锰业有限公司 | Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material |
| CN101412543A (en) * | 2008-11-18 | 2009-04-22 | 湖北开元化工科技股份有限公司 | Preparation of high purity manganese sulfate |
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