CN103145188B - A kind of purification process of manganese sulfate monohydrate - Google Patents
A kind of purification process of manganese sulfate monohydrate Download PDFInfo
- Publication number
- CN103145188B CN103145188B CN201310098140.2A CN201310098140A CN103145188B CN 103145188 B CN103145188 B CN 103145188B CN 201310098140 A CN201310098140 A CN 201310098140A CN 103145188 B CN103145188 B CN 103145188B
- Authority
- CN
- China
- Prior art keywords
- manganese sulfate
- sulfate monohydrate
- purification process
- high purity
- purity water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of purification process of manganese sulfate monohydrate, with industrial manganese sulfate monohydrate for raw material, add in high purity water and dissolve, starch sequestrant through organic amine modification adsorbs, acetyl cellulose membrane filtration, the filtrate obtained is through evaporation, concentrated, and the xln high purity water obtained after cooling crystallization carries out washing, dry, obtains the manganese sulfate monohydrate of purifying.Analyze after testing, the content of the manganese sulfate monohydrate foreign metal ion of purifying reaches food, medical required foreign metal ion lower than the desired value of 1ppm.The present invention adopts the starch sequestrant of organic amine modification cheap, and good impurity removing effect is biodegradable.The manganese sulfate monohydrate constant product quality obtained with purification process of the present invention, environmentally friendly, be suitable for suitability for industrialized 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 carry out adsorbing, the method for acetyl cellulose membrane filtration purifying manganese sulfate monohydrate.
Background technology
Manganese sulfate monohydrate is a kind of purposes inorganic salt widely, it is one of important trace element fertilizer, as fodder additives, its reagent specification often makes titrimetry ammonium, silver, tellurium, oxymuriate, bromate and periodate, in addition, scientific research, production are often made mordant, colored glaze manufacture and paint siccative etc.Manganese sulfate monohydrate heating removes crystal water and can obtain anhydrous manganous sulfate, anhydrous manganous sulfate is except such use, also can be used for the trace analysis mensuration reagent that more high analyte requires, not only for analysis, synthesis etc. in biological medicine, or excellent bulk drug, nutritional additive, and be the important component part of arginine kinase, prolinase, pyruvate carboxylase; Mn ion activates the effect of multiple enzyme in addition, be partial hydrolysis enzyme, the enzyme that washes away dike slopes, Starch phosphorylase, coring enzyme etc. activator, there is growth promoting effects, strengthen immunity and improve the effects such as animal reproduction performance.
In prior art, refine with the manganese sulfate monohydrate of technical grade, the content of its foreign metal ion is all at more than 3ppm, and the manganese sulfate monohydrate foreign metal ion being difficult to reach scientific research, medicine used need control the index request in 1ppm.As Chinese patent CN101875507A, CN1222486A individually disclose the method adopting chemical precipitation method to produce 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, cannot meet the requirement of environmental protection, in product simultaneously after process, 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 the purification process providing a kind of manganese sulfate monohydrate, to overcome the higher deficiency of foreign metal ion content in sulfuric acid monohydrate manganese product that prior art produces.
Technical conceive of the present invention is such:
With industrial manganese sulfate monohydrate for raw material, add in high purity water and dissolve, the starch sequestrant through organic amine modification adsorbs, acetyl cellulose membrane filtration, the filtrate obtained is through evaporation, concentrated, crystallization, xln high purity water is carried out wash, dry, namely obtain the manganese sulfate monohydrate of purifying.
Specifically, the purification process of manganese sulfate monohydrate of the present invention, comprises the steps:
Industrial manganese sulfate monohydrate is added in high purity water and dissolves, add the starch sequestrant of organic amine modification, stir 4 ~ 6 hours under normal temperature condition, filter and remove this sequestrant, filtrate, after acetyl cellulose filters, carries out evaporating, concentrating at 90 ~ 110 DEG C of temperature, suction filtration is carried out after cooling crystallization, the xln the obtained high purity water of 5 ~ 10 DEG C washs, dry under 100 ~ 120 DEG C of conditions, obtains the manganese sulfate monohydrate of purifying.
In aforesaid method, the specific impedance value of described high purity water is greater than 17M Ω cm, and described industrial manganese sulfate monohydrate and the mass volume ratio of high purity water are 1:5 ~ 10g/ml.
The preparation method of the starch sequestrant of described organic amine modification is referring to the report of the M Sc thesis " the preparation and property research of natural polymeric chelant " of Tianjin University of Technology Hu Chunhong, and the present invention repeats no more.The mass ratio of described industrial manganese sulfate monohydrate and the starch sequestrant of organic amine modification is 1:0.01 ~ 0.02g/g.
The aperture of described acetyl cellulose film is 0.10 ~ 0.22 μm.
The high purity water mass volume ratio of described xln and washing is 1:1 ~ 2g/ml.
With the manganese sulfate monohydrate that the above-mentioned purification process of the present invention obtains, 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 Chemicals Codex proposes manganese sulfate as food additive.
Beneficial effect of the present invention:
1, the present invention adopts through the starch sequestrant of organic amine modification as the agent of foreign metal ion remaval, the toxicological harmless process problem of the manganese sulfate solution containing complex compound and foreign metal ion can be solved, utilize the starch sequestrant of organic amine modification can react rapidly with the foreign metal ion in manganese sulfate solution at normal temperatures and generate water-fast chelating precipitation, thus reach the object removing foreign metal ion.
2, after the present invention carries out toxicological harmless process under plurality of impurities metal ion Coexistence Situation, can 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 nontoxic, without features such as secondary public hazards, manganous sulfate toxicological harmless processing links can be widely used in.
3, the present invention adopts the starch sequestrant of organic amine modification cheap, and good impurity removing effect is biodegradable.
4, by the manganese sulfate monohydrate constant product quality that purification process of the present invention obtains, environmentally friendly, be suitable for suitability for industrialized production.
Embodiment
Below by specific embodiment, the present invention is described further, but embodiment does not limit the scope of the invention.It should be noted that, following examples are only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Embodiment 1
In the reaction unit that agitator is housed, add the high purity water 500ml that specific impedance value is greater than 17M Ω cm, industry manganese sulfate monohydrate 100g, after stirred at ambient temperature dissolves, add the starch sequestrant 1g through organic amine modification, stirring at normal temperature 6 hours, filtering sequestrant, gained liquid via hole diameter is that the acetyl cellulose film of 0.22 μm filters, filtrate is evaporated at the temperature of 90 ~ 110 DEG C, concentrated, suction filtration is carried out after cooling crystallization, the xln that filtration the obtains high purity water 150ml of 5 ~ 10 DEG C washs, then dry at 120 DEG C, obtain the manganese sulfate monohydrate 92g of purifying.Detected result shows, this product meets food, medical standards, and the content of foreign metal ion is all at below 1ppm, and the concrete data that detect are referring to following table 1, and standard value is U.S. FCC (version in 1996) Food Chemicals Codex standard.
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 that agitator is housed, add the high purity water 1000ml that specific impedance value is greater than 17M Ω cm, industry manganese sulfate monohydrate 100g, after stirred at ambient temperature dissolves, add the starch sequestrant 2g of organic amine modification, stirring at normal temperature 8 hours, filtering sequestrant, gained liquid aperture is that the acetyl cellulose film of 0.10 μm filters, filtrate is evaporated at the temperature of 90 ~ 110 DEG C, concentrated, suction filtration is carried out after cooling crystallization, the xln that filtration the obtains high purity water 200ml of 5 ~ 10 DEG C washs, then 100 DEG C of dryings, obtain the manganous sulfate 91g of purifying.Detected result shows, the complete food of this product, medical standards, and the content of foreign metal ion is all at below 1ppm.Concrete detection data are referring to following table 2, and standard value is U.S. FCC (version in 1996) Food Chemicals Codex standard.
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. a purification process for manganese sulfate monohydrate, is characterized in that, comprises the steps:
Industrial manganese sulfate monohydrate is added in high purity water and dissolves, add the starch sequestrant of organic amine modification, stir 4 ~ 6 hours under normal temperature condition, filter and remove sequestrant, filtrate, after acetyl cellulose filters, carries out evaporating, concentrating at 90 ~ 110 DEG C of temperature, suction filtration is carried out after cooling crystallization, the xln the obtained high purity water of 5 ~ 10 DEG C washs, dry under 100 ~ 120 DEG C of conditions, obtains the manganese sulfate monohydrate of purifying.
2. purification process according to claim 1, is characterized in that, described dissolving is used and the specific impedance value of washing high purity water is greater than 17M Ω cm.
3. purification process according to claim 1, is characterized in that, described industrial manganese sulfate monohydrate and the mass volume ratio of dissolving high purity water are 1:5 ~ 10g/ml.
4. purification process according to claim 1, is characterized in that, the mass ratio of described industrial manganese sulfate monohydrate and the starch sequestrant of organic amine modification is 1:0.01 ~ 0.02g/g.
5. purification process according to claim 1, is characterized in that, the aperture of described acetyl cellulose film is 0.10 ~ 0.22 μm.
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 ~ 2g/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310098140.2A CN103145188B (en) | 2013-03-25 | 2013-03-25 | A kind of purification process of manganese sulfate monohydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310098140.2A CN103145188B (en) | 2013-03-25 | 2013-03-25 | A kind of purification process of manganese sulfate monohydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145188A CN103145188A (en) | 2013-06-12 |
| CN103145188B true CN103145188B (en) | 2015-07-29 |
Family
ID=48543576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310098140.2A Active CN103145188B (en) | 2013-03-25 | 2013-03-25 | A kind of purification process of manganese sulfate monohydrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103145188B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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 |
-
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103145188A (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106673840B (en) | Clear liquid type high-potassium liquid fertilizer and special potassium solution thereof | |
| Shen et al. | The effects of humic acid urea and polyaspartic acid urea on reducing nitrogen loss compared with urea | |
| CN102603028B (en) | Application of palygorskite clay serving as adsorbent in treatment of picric acid waste water | |
| CN102390844B (en) | Preparation process of large-grain ammonium sulfate crystals | |
| CN101787040A (en) | Method for preparing cefmetazole sodium | |
| CN103145188B (en) | A kind of purification process of manganese sulfate monohydrate | |
| CN111825501A (en) | Preparation method of water-soluble humic acid fertilizer | |
| CN107321325A (en) | A kind of nano material of absorption effluent heavy metal and preparation method thereof | |
| CN106800506A (en) | A kind of preparation method of anhydrous sodium acetate | |
| CN109867687B (en) | High water-soluble amoxicillin and preparation method thereof | |
| CN104386664B (en) | The method of ammonium potassium dihydrogen phosphate produced by fertilizer grade primary ammonium phosphate | |
| CN101423231A (en) | Purification method of solid cyanamide | |
| CN101906109B (en) | Method for preparing cefuroxime sodium | |
| CN103333081A (en) | Preparation method of 1,1-cyclohexanediacetic acid mono amide | |
| CN102303854B (en) | Purification method of monopotassium phosphate | |
| CN101987747A (en) | Preparation method of reagent-grade ammonium molybdate | |
| CN104843649A (en) | Preparation method for calcium peroxide | |
| JP2010059090A (en) | Method for producing glucosamine derivative | |
| CN102491910B (en) | Method for synthesizing 2,6-dibromo-4-(trifluoromethoxy) aniline by water-phase method | |
| CN103739475B (en) | Method for preparing battery grade anhydrous lithium acetate | |
| CN104163439A (en) | Synthetic method of cyanamide aqueous solution by using sodium hydroxide | |
| CN101186277A (en) | Method for preparing calcium peroxide from calcium chloride | |
| CN101153006A (en) | Gluconic acid cobalt and method of preparing the same | |
| CN111440012A (en) | Preparation method of low-chlorine amino acid fertilizer | |
| CN102639468B (en) | A plant nutrient obtained from the rice husk and a process of preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |