CN103145188A - Purifying method of manganese sulfate monohydrate - Google Patents
Purifying method of manganese sulfate monohydrate Download PDFInfo
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- CN103145188A CN103145188A CN2013100981402A CN201310098140A CN103145188A CN 103145188 A CN103145188 A CN 103145188A CN 2013100981402 A CN2013100981402 A CN 2013100981402A CN 201310098140 A CN201310098140 A CN 201310098140A CN 103145188 A CN103145188 A CN 103145188A
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- manganese sulfate
- sulfate monohydrate
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Abstract
The invention discloses a purifying method of manganese sulfate monohydrate. The method comprises the following steps: using industrial manganese sulfate monohydrate as raw material, dissolving in high-pure water, adsorbing by organic amine modified starch chelating agent, filtering by a cellulose acetate film, evaporating and concentrating the obtained filtrate, cooling, separating crystal, washing the obtained crystal by using high-pure water, drying to obtain purified manganese sulfate monohydrate. According to the detection analysis, the impurity metal ion content in the purified manganese sulfate monohydrate achieves the index value that the impurity metal ion required by food and medicine is less than 1ppm. The organic amine modified starch chelating agent adopted by the invention is low in cost, good in impurity-removing effect and is biodegradable. The manganese sulfate monohydrate obtained through the purifying method disclosed by the invention is stable in quality, environment-friendly and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of purification process of manganese sulfate monohydrate, particularly relate to a kind ofly utilize the starch sequestrant of organic amine modification to adsorb, the method for acetyl cellulose membrane filtration purifying manganese sulfate monohydrate.
Background technology
Manganese sulfate monohydrate is a kind of purposes inorganic salt very widely, it is one of important trace element fertilizer, as fodder additives, its reagent specification is often made titrimetry ammonium, silver, tellurium, oxymuriate, bromate and periodate, in addition, often make mordant, colored glaze manufacturing and paint siccative etc. in scientific research, production.The manganese sulfate monohydrate heating removes crystal water and can make anhydrous manganous sulfate, anhydrous manganous sulfate is except such use, reagent is measured in the trace analysis that also can be used for more high analyte requirement, not only be used for analyzing, synthesizing on biological medicine etc., or good bulk drug, nutritional additive, and be the important component part of arginine kinase, prolinase, pyruvate carboxylase; Mn ion activates the effect of plurality of enzymes in addition, is the partial hydrolysis enzyme, the activator of the enzyme that washes away dike slopes, Starch phosphorylase, coring enzyme etc., has the growth of promotion, strengthens immunity and improves the effects such as animal reproduction performance.
In prior art, make with extra care with the manganese sulfate monohydrate of technical grade, the content of its foreign metal ion all more than 3ppm, is difficult to reach scientific research, medicine manganese sulfate monohydrate foreign metal ion used need be controlled at the index request in 1ppm.Disclosing respectively as Chinese patent CN101875507A, CN1222486A adopts chemical precipitation method to produce the method for POV manganese, but because the method process is complicated, and when containing complexing agent in solution, complexing agent makes heavy metal be in dissolved state, can not form precipitation of hydroxide, residual heavy metal concentration is high, can't meet the requirement of environmental protection, in product after processing simultaneously, the content of foreign metal ion is still higher, does not meet index request.
Summary of the invention
Problem to be solved by this invention is to provide a kind of purification process of manganese sulfate monohydrate, with the higher deficiency of foreign metal ion content in the sulfuric acid monohydrate manganese product that overcomes prior art production.
Technical conceive of the present invention is such:
Take industrial manganese sulfate monohydrate as raw material, add in high purity water and dissolve, through the absorption of starch sequestrant, the acetyl cellulose membrane filtration of organic amine modification, the filtrate that obtains is through evaporation, concentrated, crystallization, with xln with high purity water wash, drying, namely obtain the manganese sulfate monohydrate of purifying.
Particularly, the purification process of manganese sulfate monohydrate of the present invention comprises the steps:
Industrial manganese sulfate monohydrate is added in high purity water dissolve, the starch sequestrant that adds the organic amine modification, stirred under normal temperature condition 4～6 hours, filter and remove this sequestrant, filtrate is evaporated at 90～110 ℃ of temperature, is concentrated after acetyl cellulose filters, carry out suction filtration after cooling crystallization, the xln that obtains washs with the high purity water of 5～10 ℃, and is dry under 100～120 ℃ of conditions, obtains the manganese sulfate monohydrate of purifying.
In aforesaid method, the anti-resistance of ratio of described high purity water is greater than 17M Ω .cm, and the mass volume ratio of described industrial manganese sulfate monohydrate and high purity water is 1:5～10g/ml.
The preparation method of the starch sequestrant of described organic amine modification is referring to the report of Master degree candidate's paper " the preparation and property research of natural polymeric chelant " of the Hu Chunhong of Tianjin University of Technology, and the present invention repeats no more.The mass ratio of the starch sequestrant of described industrial manganese sulfate monohydrate and organic amine modification is 1:0.01～0.02, g/g.
The aperture of described acetyl cellulose film is 0.10～00.22 μ m.
The high purity water mass volume ratio of described xln and washing is 1:1～2, g/ml.
The manganese sulfate monohydrate that obtains with the above-mentioned purification process of the present invention, analyze after testing, the content of foreign metal ion reaches food, medical required foreign metal ion lower than the desired value of 1ppm, meets the technical requirement that US Federal Communication Committee (FCC) (version in 1996) food chemistry pharmacopeia proposes manganese sulfate as food additive.
Beneficial effect of the present invention:
1, the present invention adopts starch sequestrant through the organic amine modification as the agent of foreign metal ion remaval, problem is processed in the toxicological harmless that can solve the manganese sulfate solution that contains complex compound and foreign metal ion, the starch sequestrant that utilizes the organic amine modification at normal temperatures can with manganese sulfate solution in the foreign metal ion react rapidly and generate water-fast chelating precipitation, thereby reach the purpose of removing the foreign metal ion.
2, after the present invention carries out the toxicological harmless processing under the plurality of impurities metal ion coexists situation, but meet the requirement of environmental protection, also can play one's part to the full to foreign metal complexing salt in synthetics, and it is fast to have precipitation, aftertreatment is easy, stablize nontoxicly, without characteristics such as secondary public hazards, can be widely used in manganous sulfate toxicological harmless processing links.
3, it is cheap that the present invention adopts the starch sequestrant of organic amine modification, and good impurity removing effect is biodegradable.
4, the manganese sulfate monohydrate constant product quality that obtains with purification process of the present invention, environmentally friendly, be suitable for suitability for industrialized production.
Embodiment
The present invention is described further below by specific embodiment, but embodiment does not limit protection scope of the present invention.Need to prove, following examples are only unrestricted in order to technical scheme of the present invention to be described.Although with reference to preferred embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not break away from the scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
Embodiment 1
in the reaction unit of agitator is housed, add than the high purity water 500ml of anti-resistance greater than 17M Ω .cm, industry manganese sulfate monohydrate 100g, under room temperature after stirring and dissolving, add the starch sequestrant 1g through the organic amine modification, stirring at normal temperature 6 hours, the filtering sequestrant, gained liquid via hole diameter is that the acetyl cellulose film of 0.22 μ m filters, filtrate is evaporated at the temperature of 90～110 ℃, concentrated, carry out suction filtration after cooling crystallization, the xln that filtration obtains washs with the high purity water 150ml of 5～10 ℃, then dry under 120 ℃, obtain the manganese sulfate monohydrate 92g of purifying.Detected result shows, this product meets food, medical standard, and the content of foreign metal ion all below 1ppm, specifically detects data referring to following table 1, and standard value is U.S. FCC(1996 version) the food chemistry standards of pharmacopoeia.
Table 1
| Test item | Standard value | Measured value |
| Manganous sulfate (MnSO 4·H 2O) content, % | 98.0～102.0 | 99.5 |
| Water-insoluble, % | ≤0.002 | 0.001 |
| Loss on heating, % | 10.0～13.0 | 10.2 |
| Heavy metal (in Pb), % | ≤0.002 | 0.001 |
| Plumbous (Pb), % | ≤0.001 | 0.0005 |
| Selenium (Se), % | ≤0.003 | 0.001 |
| Arsenic (As), % | ≤0.001 | 0.0003 |
Embodiment 2
in the reaction unit of agitator is housed, add than the high purity water 1000ml of anti-resistance greater than 17M Ω .cm, industry manganese sulfate monohydrate 100g, under room temperature after stirring and dissolving, the starch sequestrant 2g that adds the organic amine modification, stirring at normal temperature 8 hours, the filtering sequestrant, the acetyl cellulose film that gained liquid is 0.10 μ m with the aperture filters, filtrate is evaporated at the temperature of 90～110 ℃, concentrated, carry out suction filtration after cooling crystallization, the xln that filtration obtains washs with the high purity water 200ml of 5～10 ℃, then 100 ℃ of dryings, obtain the manganous sulfate 91g of purifying.Detected result shows, the complete food of this product, medical standard, and the content of foreign metal ion is all below 1ppm.The concrete data that detect are referring to following table 2, and standard value is U.S. FCC(1996 version) the food chemistry standards of pharmacopoeia.
Table 2
| Test item | Standard value | Measured value |
| Manganous sulfate (MnSO 4·H 2O) content, % | 98.0～102.0 | 99.8 |
| Water-insoluble, % | ≤0.002 | 0.001 |
| Loss on heating, % | 10.0～13.0 | 10.1 |
| Heavy metal (in Pb), % | ≤0.002 | 0.0009 |
| Plumbous (Pb), % | ≤0.001 | 0.0003 |
| Selenium (Se), % | ≤0.003 | 0.001 |
| Arsenic (As), % | ≤0.001 | 0.0005 |
Claims (6)
1. the purification process of a manganese sulfate monohydrate, is characterized in that, comprises the steps:
Industrial manganese sulfate monohydrate is added in high purity water dissolve, the starch sequestrant that adds the organic amine modification, stirred under normal temperature condition 4～6 hours, filter and remove sequestrant, filtrate is evaporated at 90～110 ℃ of temperature, is concentrated after acetyl cellulose filters, carry out suction filtration after cooling crystallization, the xln that obtains washs with the high purity water of 5～10 ℃, and is dry under 100～120 ℃ of conditions, obtains the manganese sulfate monohydrate of purifying.
2. purification process according to claim 1, is characterized in that, the anti-resistance of ratio of described high purity water is greater than 17M Ω .cm.
3. purification process according to claim 1, is characterized in that, the mass volume ratio of described industrial manganese sulfate monohydrate and high purity water is 1:5～10g/ml.
4. purification process according to claim 1, is characterized in that, the mass ratio of the starch sequestrant of described industrial manganese sulfate monohydrate and organic amine modification is 1:0.01～0.02, g/g.
5. purification process according to claim 1, is characterized in that, the aperture of described acetyl cellulose film is 0.10～0.22 μ m.
6. purification process according to claim 1, is characterized in that, the high purity water mass volume ratio of described xln and washing is 1:1～2, g/ml.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601220A (en) * | 2013-12-02 | 2014-02-26 | 国药集团化学试剂有限公司 | Preparation method for reagent-grade anhydrous sodium carbonate |
| CN103708507A (en) * | 2013-12-26 | 2014-04-09 | 国药集团化学试剂有限公司 | Preparation method of food-grade potassium carbonate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1204570A1 (en) * | 1983-06-15 | 1986-01-15 | Ленинградский Ордена Трудового Красного Знамени Технологический Институт Холодильной Промышленности | Method of producing manganese disulfate |
| JPH0431323A (en) * | 1990-05-24 | 1992-02-03 | Japan Metals & Chem Co Ltd | Purification of manganese sulfate solution |
| CN1222486A (en) * | 1998-01-08 | 1999-07-14 | 谢志强 | Production of manganese sulfate as food additive |
| WO2010096887A2 (en) * | 2009-02-26 | 2010-09-02 | Mineração Tabiporã Ltda | Process of production of manganese sulfate from the pirolusite chemical reaction |
| CN101875507A (en) * | 2010-08-04 | 2010-11-03 | 湖南汇通科技有限责任公司 | High purity manganese sulfate monohydrate and preparation method thereof |
| CN102849802A (en) * | 2012-10-08 | 2013-01-02 | 梧州三和新材料科技有限公司 | Preparation method of manganese sulfate solution with ultralow calcium and magnesium impurity concentration |
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2013
- 2013-03-25 CN CN201310098140.2A patent/CN103145188B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1204570A1 (en) * | 1983-06-15 | 1986-01-15 | Ленинградский Ордена Трудового Красного Знамени Технологический Институт Холодильной Промышленности | Method of producing manganese disulfate |
| JPH0431323A (en) * | 1990-05-24 | 1992-02-03 | Japan Metals & Chem Co Ltd | Purification of manganese sulfate solution |
| CN1222486A (en) * | 1998-01-08 | 1999-07-14 | 谢志强 | Production of manganese sulfate as food additive |
| WO2010096887A2 (en) * | 2009-02-26 | 2010-09-02 | Mineração Tabiporã Ltda | Process of production of manganese sulfate from the pirolusite chemical reaction |
| CN101875507A (en) * | 2010-08-04 | 2010-11-03 | 湖南汇通科技有限责任公司 | High purity manganese sulfate monohydrate and preparation method thereof |
| CN102849802A (en) * | 2012-10-08 | 2013-01-02 | 梧州三和新材料科技有限公司 | Preparation method of manganese sulfate solution with ultralow calcium and magnesium impurity concentration |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601220A (en) * | 2013-12-02 | 2014-02-26 | 国药集团化学试剂有限公司 | Preparation method for reagent-grade anhydrous sodium carbonate |
| CN103601220B (en) * | 2013-12-02 | 2016-01-27 | 国药集团化学试剂有限公司 | A kind of preparation method of SILVER REAGENT anhydrous sodium carbonate |
| CN103708507A (en) * | 2013-12-26 | 2014-04-09 | 国药集团化学试剂有限公司 | Preparation method of food-grade potassium carbonate |
| CN103708507B (en) * | 2013-12-26 | 2016-03-16 | 国药集团化学试剂有限公司 | A kind of preparation method of food-grade potassium carbonate |
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