Method of production of tow-, three-, quadrivalent manganese sulfates or their mixtures

FIELD: methods of production of manganese sulfates of different oxidation level.

SUBSTANCE: the invention is dealt with methods of production of manganese sulfates of different oxidation level. Two, three and quadrivalent manganese sulfates or their mixtures are produced by interaction of manganese oxides - MnO,Mn2O3,Mn3O4 and MnO2- of any origin with a concentrated sulfuric acid. The interaction is conducted in a vertical type beaded mill with glass beads of 1,5-2 mm diameter, in which in succession introduce a dissolvent non-reacting with a concentrated sulfuric acid, a manganous reagent and a sulfuric acid. They use the manganous reagent ground up to particle sizes of 1 mm and less and the 79.8-90 % sulfuric acid in a molar stoichiometrical surplus in respect to the manganous reagent of 1.20-1.72. Then engage the bead mill and conduct process at 5-25°C during 5-10 minutes at a ratio of masses of the dissolvent and the reagents of 2.33:1-10:1. The dissolvent is separated from the beads and the product by filtration. Manganese sulfate localized in the form of a film basically on the surface of beads and partially on the walls of the reactor manganese sulfate or a mix of manganese sulfates is dissolved in the sulfuric acid of a corresponding concentration or enter in the new process conducted in the same bead mill with a manganese sulfate (III) or (IV) in the capacity of an oxidizing agent. The technical effect is a fast and quantitative interaction of manganese oxides with a concentrated sulfuric acid at the room temperatures in conditions of a fine powdering of a solid phase in the bead mill.

EFFECT: the invention ensures the fast and quantitative interaction of manganese oxides with a concentrated sulfuric acid at the room temperatures and a fine powdering of a solid phase in the bead mill.

2 cl,30 ex, 2 tbl

 

The invention relates to the technology of sulfates of manganese in different oxidation States, including from natural materials, and can be used in the fields of application of these compounds as selective oxidants, catalysts, raw materials for other compounds, as well as primary processing of manganese ores.

It is known that sulfates two-, three -, and tetravalent manganese, receive as a result of exposure to sulfuric acid of various concentrations of certain compounds of manganese in the absence or in the presence of additional oxidants or reductants (Remy, the Rate of inorganic chemistry. Vol.2. M.: Mir, 1966, 836 S.).

The method for extracting manganese from the mn containing oxidized ores (A.S. USSR №1054302), including the processing of raw ore halogen acid in the mixture with sulfuric acid at molar ratio of the oxides of manganese of the higher oxidation States in terms of Mno2to the halogen acid 0,45-0,6, oxides of manganese of all forms in terms of manganese to sulfuric acid of 0.8-1.1 and ion concentration SO

2-
4
in the reaction mixture 6-17%. While reactions proceed

MPO+H2SO4MnSO4+H2O

MP3O4/sub> +NVG+3H2SO43MnSO4+Br2+4H2About

MP2O3+NVG+2H2SO42MnSO4+Br2+3H2O

MnO2+2HBr+H2SO4MnSO4+Br2+2H2O

i.e. Hydrobromic acid in this system acts as a reducing agent. Therefore, one purpose of this invention is to increase the output of the halogen.

A method of obtaining compounds of trivalent manganese (as the USSR №442150), under which the oxidation of compounds of divalent manganese is carried out by treatment with acidic extractant is a solution of an organic acid in kerosene followed by reextracting compounds of trivalent manganese in an aqueous solution of inorganic acid such as phosphoric, pyrophosphoric or sulfuric. At the same time as organic acids using fatty acids with the number of carbon atoms With7-C9, naphthenic or resin acids.

Closest to the claimed is a method of producing sulfates two-, three -, and tetravalent manganese or mixtures thereof by direct interaction of oxides of manganese, Mno, Mn2About3, MP3O4and MnO2any origin or mn containing minerals with concentrated sulfuric acid (lidin, R.A. and other Chemical properties of neolan the ical substances. M.: Chemistry, 1996, c.396-402).

The disadvantage of this method is that for turning each mn containing raw material in the corresponding manganese sulfate requires substantially different terms, this process is often carried out in varying degrees, accompanied by a change in valence state of manganese, which significantly reduces its selectivity. So, for example, manganese oxide (III) and Metagalaxy manganese converted into sulphate of manganese (III) in the processing of cold 50%sulfuric acid. To obtain the sulfate manganese (IV) in a similar way using a more concentrated sulfuric acid was not possible because of cold acid process does not occur, and when heated to 110° the main products are MP2(SO4)3and O2(gas). Mn(SO4)2manage to get the oxidation of sulphate of manganese (II) with potassium permanganate in an environment of concentrated sulfuric acid. In General, the partial or complete change of the valence state of manganese in the raw material during the formation of the mn containing products is a common phenomenon for this method.

The objective of the proposed solutions is to make possible rapid and quantitative conversion into the corresponding valence state of manganese in the raw material sulfates oxides and carbonates of manganese, h is the next natural origin, in cooperation with concentrated sulfuric acid at room temperature in thin milling of the solid phase in a bead mill.

This object is achieved in that in a bead mill, vertical type with glass driven in rotation or other movement of the paddle stirrer beads with a diameter of 1.5-2 mm impose nerealiausi with sulfuric acid solvent, the mn containing solid pre-crushed to particle sizes of 1 mm and less raw material and a concentrated (79,8%to 90%) sulfuric acid in a molar stoichiometric excess in relation to the mn containing reagent 1,20-1,72 include ball mill and lead the process at 5 -25°C for 5-10 min at an initial mass ratio of solvent and reagents of 2.33:1 to 10:1, after which the solvent is separated from the beads and the product by filtration, and localized in the form of a film mainly on the surface of the beads and partly the walls of the reactor manganese sulfate, or a mixture of sulphates dissolved in sulfuric acid of appropriate concentration, or introducing a new process carried out in the same bead mill with sulphate of manganese (III) or (IV) as an oxidant. As a solvent used boiling below 100° With low molecular weight paraffinic hydrocarbon or a mixture of these hydrocarbons.

Characteristics of the used materials is.

MnO2natural manganese oxide, water GOST 4470-70), technical (on THE 6-10-1808-81), reactive (TU 6-09-2962-78), vitamin waste industry (artificial pasta on THE 6-14-831-72).

MP2O3reactive (TU 6-09-3364-78) or obtained by combustion of manganese acetate (II) in a muffle furnace in the temperature range 600±20° C.

MP3O4obtained by burning artificial paste Mno2at a temperature of 960±15° With limited access of air.

The mn containing minerals such as rhodochrosite formula MPMs3; manganese formula IGOs; manganite formula Mno3·H2About; hausmannite formula MP3O4; Brunet formula 3MnO2·4MnO· SiO2(contents MP2O3- 78,3%; IGOs -11,7%; SiO2- 10%).

Sulfuric acid concentrated (GOST 14262-78)

Hexane MRTU 6-09-2937-66

Heptane reference (TU 6-09-4520-77)

Petroleum ether GOST 11992-66

Getting sulfates two-, three-, and tetravalent manganese or mixtures thereof is as follows. In ball mill vertical type with glass beads as pereirago agent sequentially load paraffin solvent, the mn containing raw material and sulfuric acid in the estimated quantities and ratios. Include ball mill and carry out the process within 5-10 minutes

On the East is within the specified time pereir stop and solvent is drained through the bottom drain pipe with a filter septum inlet, having a cell size of not more than 0.5-1 mm Remaining on the beads and the walls of the reactor manganese sulfate or a mixture of sulphates dissolved in sulfuric acid of appropriate concentration, or in a ball mill loaded with a reducing agent, a new reaction mixture for the targeted redox process with sulphate of manganese (III) or (IV) as an oxidant. If necessary, the remains of a paraffin solvent target process is removed by blowing through the bead mill air or other gas.

Example 1.

In a laboratory ball mill vertical type with 250 g of glass beads with a diameter of 1.5-2 mm as pereirago agent, driven in rotation or other movement of a blade stirrer (n=1440 rpm), enter 227 g of heptane, 4,48 g crushed to particle sizes of 1 mm and less reactive Mno2and 18,22 g 83%sulfuric acid at a temperature of 11.5° C. Include a ball mill and are tribochemical process for 5 minutes During this time the temperature in the reaction zone is practically unchanged and almost quantitative expenditure Mno2. Stop the stirring agitator bead mill, open the stop valve on the drain pipe at the entrance of which is located the filter baffle hole diameter 0.5-1 mm, and merge solution is tel in a specially designed container. Analysis of samples of the solvent shows the lack of a boot component, and transformation products. Almost no crushed solid phase, which has remained in the form of a film sulfate Mn(IV) on the surface of the beads and partly on the walls of a glass bead mill. The degree of conversion of Mno2exceeded 99%.

Close the valve discharge pipe, enter 7 g of salicylic aldehyde, 200 g of heptane and 0,075 mol Hydrobromic acid include mixing and lead a new redox process to practically complete consumption MP(SO4)2as oxidant. On the achievement of 97.8%spending sulfate manganese (IV) required in a given situation, with 17° C 54 minutes

Examples 2-15.

The equipment and procedure of a process similar to that described in example 1. Different nature used the mn containing reagent and solvent, the concentration of sulfuric acid and a molar excess, temperature and duration of the main process, the mass ratio of the loaded solvent and reagents, and the method of removing the resulting product from the bead mill. All these data are summarized in table 1.

Examples 16-30.

The mn containing reagent, equipment and verification procedure similar to that described in example 13. Vary the speed of the rotation mechanical stirrer, the bead sizes used, the mass ratio of beads and download and fractional composition of the mn containing reagent. The results obtained are summarized in table 2.

The positive effect of the proposed solution consists in the following:

1. The process is simple to perform and does not require any auxiliary and additional substances, in addition to presents a paraffin hydrocarbon liquid phase.

2. The process is fast and extremely mild temperature conditions. He does not need any additional supply or heat removal, which significantly simplifies the process flow and design of the reaction system.

3. The resulting products are solid and practically insoluble in the liquid phase system. But they can be easily localized on the solid surfaces (mainly pereirago agent) and is quite firmly held in this form. Moreover, on these surfaces without the involvement of the product is firmly held and excess sulfuric acid, and the reaction water. Therefore, in almost quantitative conversion of the mn containing reagent is salootdelenie liquid phase (solvent), which remains just drain and without any cleaning reusable.

4. The final state of the product provides the selection of its use in the new redox process without removal of the bead mill, or removal of the bead mill using a suitable solvent (sulphuric acid of a certain concentration of sulfates of manganese (III) and (IV) or dilute acid, and then just water for sulfate manganese (II)).

1. The method of producing sulfates two-, three -, and tetravalent manganese or mixtures thereof by direct interaction of oxides of manganese, Mno, Mn2About3, MP3O4and MnO2any origin or mn containing minerals with concentrated sulfuric acid, characterized in that the interaction is carried out in a bead mill, vertical type with glass beads with a diameter of 1.5-2 mm, driven in rotation and other movements paddle stirrer, which consistently give not react with concentrated sulfuric acid solvent, the mn containing pre-crushed to particle sizes of 1 mm or less reagent and 79.8÷90%sulfuric acid in a molar stoichiometric excess in relation to the mn containing reagent 1,20÷1,72 include ball mill and lead the process at 5-25°C for 5-10 min the mass ratio of solvent and reagents 2,33:1÷10:1, after which the solvent is separated from the beads and the product by filtration, and localized in the form of a film mainly on the surface of the beads and partly the walls of the reactor sulfate, Morgans is or mixture of sulphates dissolved in sulfuric acid of appropriate concentration or enter in a new process held in the same bead mill, with sulphate of manganese (III) or (IV) as an oxidant.

2. The method according to claim 1, characterized in that the solvent used boiling below 100°With low molecular weight paraffinic hydrocarbon or a mixture of these hydrocarbons.



 

Same patents:
The invention relates to the field of beneficiation of manganese ores, in particular, to methods for manganese concentrates chemical enrichment

The invention relates to the field of production of materials for electronic engineering, in particular to obtain powder of the oxide of the composition Pb(Mg1/3Nb2/3O3)
The invention relates to chemical processing of manganese ores, in particular the production of concentrates chemical enrichment for metallurgical industry

The invention relates to chemical technology compounds manganese and manganese concentrate low-phosphorus used in the production of high-grade manganese alloys and compounds, in direct alloying of steel, and the coating of welding electrodes

The invention relates to chemical technology compounds manganese and manganese concentrate low-phosphorus used in the production of high-grade manganese alloys and compounds, in direct alloying of steel, and the coating of welding electrodes

The invention relates to the production of nanostructured materials by chemical means

The invention relates to the field of production of manganese dioxide, in particular electrolytic synthesis methods
The invention relates to the production of inorganic compounds of manganese, used as catalysts, magnetic resistors and so on
The invention relates to inorganic chemistry, in particular to a technology for obtaining anhydrous manganese chloride

FIELD: methods of production of manganese sulfates of different oxidation level.

SUBSTANCE: the invention is dealt with methods of production of manganese sulfates of different oxidation level. Two, three and quadrivalent manganese sulfates or their mixtures are produced by interaction of manganese oxides - MnO,Mn2O3,Mn3O4 and MnO2- of any origin with a concentrated sulfuric acid. The interaction is conducted in a vertical type beaded mill with glass beads of 1,5-2 mm diameter, in which in succession introduce a dissolvent non-reacting with a concentrated sulfuric acid, a manganous reagent and a sulfuric acid. They use the manganous reagent ground up to particle sizes of 1 mm and less and the 79.8-90 % sulfuric acid in a molar stoichiometrical surplus in respect to the manganous reagent of 1.20-1.72. Then engage the bead mill and conduct process at 5-25°C during 5-10 minutes at a ratio of masses of the dissolvent and the reagents of 2.33:1-10:1. The dissolvent is separated from the beads and the product by filtration. Manganese sulfate localized in the form of a film basically on the surface of beads and partially on the walls of the reactor manganese sulfate or a mix of manganese sulfates is dissolved in the sulfuric acid of a corresponding concentration or enter in the new process conducted in the same bead mill with a manganese sulfate (III) or (IV) in the capacity of an oxidizing agent. The technical effect is a fast and quantitative interaction of manganese oxides with a concentrated sulfuric acid at the room temperatures in conditions of a fine powdering of a solid phase in the bead mill.

EFFECT: the invention ensures the fast and quantitative interaction of manganese oxides with a concentrated sulfuric acid at the room temperatures and a fine powdering of a solid phase in the bead mill.

2 cl,30 ex, 2 tbl

FIELD: metal-protecting materials.

SUBSTANCE: invention relates to protection of metals against corrosion using paint and varnish coatings. Invention proposes using as anticorrosive pigments co-precipitated manganite-phosphates, manganite-silicates, manganite-sulfates of metals of the general formula: MMnOxnMZ wherein M means Ca2+, Zn2+, Fe2+, Sr2+ at Z - PO43-, SiO32-, and M means Ba2+ at Z - SO42-, PO43-, SiO32-; x = 2.5-3; n = 0.5-10 with the content of co-precipitated manganite of corresponding metal from 5 to 70 wt.-% as anticorrosive pigments. Proposed pigments by their anticorrosive properties exceed that of zinc tetraoxychromate. Invention provides applying low toxic anticorrosive pigment-inhibitors with protective properties comparable with that of chromate pigments.

EFFECT: expanded assortment of anticorrosive pigments.

1 tbl

FIELD: chemical industry branches, microelectronics.

SUBSTANCE: method comprises steps of placing finely divided powders of manganese, iron and sulfur into quartz ampoules; evacuating them and sealing; taking initial components in quantities corresponding to iron-manganese sulfide formula Fex Mn1-xS; heating ampoules in furnace at rate 40°C/h up to 960°C; soaking at such temperature for 10 days; cooling together with furnace; breaking produced ingots to finely dispersed powder; pressing bars; again placing them into quartz ampoules; evacuating; sealing and annealing at 1000°C for 1 day. Iron-manganese sulfides have giant magnetic resistance in wide range of concentration in temperature range 50 - 200 K.

EFFECT: possibility for producing small cost iron-manganese sulfides with giant magnetic resistance.

2 dwg, 2 tbl

FIELD: chemical industry; methods of the synthesis of the anhydrous manganese chloride.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the anhydrous manganese chloride. The method of production of the anhydrous manganese chloride includes the reaction of the powder of the metal with the hydrogen chloride under the anhydrous conditions. At least the part of the hydrogen chloride may be diluted in the dissolvent, which is selected from the group consisting of the ether, the dimethyl ether (DME), the butyl ether, the amyl ether, di-e-butyl ether, the glima polyesters, the diethylene glycol methyl ether (DEGME), triethylene glycol dimethyl ether (triglima), the diethylene glycol dimethyl ether (diglima), 1.2-dimethoxyethane(glima), cetaner (mixtures of 96 % glima and 4 % dimethoxymethane), mono-tret-butyl ether of ethylene glycol, mono-n-butyl ether of ethylene glycol, carbonates, dimethyl carbonate, diethyl carbonate, diacetates, ethylene glycol acetate, acetals, dimethoxymethane (DMM or the methylal), 2-ethylhexylacetate, the esters of vegetable oils, the esters of the animal fats, methylsoyate. The invention allows to eliminate the power-consuming stage of removal of the hydration water at production of the anhydrous manganese chloride.

EFFECT: the invention ensures elimination of the power-consuming stage of removal of the hydration water at production of the anhydrous manganese chloride.

8 cl, 3, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention can be used for preparation of manganese fluoride used in the production of gaseous fluorine. The method of manganese fluoride preparation includes the stage (1) of the manganese interreaction with fluorinating agent in temperature range from 50 to 250 °C and the stage (2) of the further interreaction of the product obtained at stage (1) with fluorinating agent in temperature range from 250 to 450 °C. The manganese compound is at least one compound selected from the group consisting of MnF2, MnCO3, MnO and their hydrates. The fluorinating agent is at least one compound selected from the group consisting of F2, ClF and ClF3. The manganese fluoride obtained in the aforesaid process is MnFx (x = 3 ÷ 4).

EFFECT: invention allows to simplify the manganese fluoride preparation, to decrease the temperature of the process and to exclude the stages of sublimation and solidification.

11 cl, 7 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention can be used for producing manganese tetrafluoride, which is used as an oxidising agent and a source for production of pure fluorine. To obtain manganese tetrafluoride, a manganese compound and a fluorinating agent are reacted at temperature ranging from 250 to 350°C and pressure ranging from 1.0 to 10.0 MPa, while continuously or intermittently grinding the initial manganese compound and the reaction product. The initial manganese compound used can be MnF2, hydrate of MnF2, MnCl2, MnCO3 and MnO, and the fluorinating agent used can be F2, ClF and ClF3.

EFFECT: invention simplifies industrial production of manganese tetrafluoride due to prevention of its sublimation at high temperature and subsequent condensation when cooling and provides for more complete fluorination of the manganese compound.

8 cl, 4 dwg, 5 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: method of producing potassium permanganate involves reacting potassium superoxide (KO2) and manganese dioxide (MnO2) in the presence of fuel in form of carbon, with the following ratio of components (wt %): potassium superoxide (KO2) 46.9-52.7; manganese dioxide (MnO2) 45.3-52.6; carbon (C) 0.5-2.0. The initial components are mixed in two steps, where manganese dioxide and fuel are mixed at the first step, and potassium superoxide is added to the obtained mixture at the second step. The process is initiated through local heating the obtained mixture at temperature of about 500°C.

EFFECT: reduced power input in synthesis of potassium permanganate and increased content of the basic substance in the synthesis product.

3 ex

FIELD: process engineering.

SUBSTANCE: invention relates can be used in metallurgy, electronics and in production of pigments and welding electrodes. Wastes of production of ferrous alloys containing, mainly, manganese represent slimes of fume gases washing from furnaces producing ferromanganese and silicon manganese. Said wastes are directed for thermal sulphating 1 that comprises furnace processing of material fed from mixer wherein said wastes have been subjected to treatment by acid with flow rate approximating to stoichiometric. Teflon chutes are used inside the furnace to produce SO2. Then hydrometallurgical phase is performed consisting of vatting stage 2, primary 3 and secondary 4 washing stages and that of conditioning. Vatting is carried out at intensive mixing in reactor with coating that regulates acidity using anolyte of electolyser or synthetic anolyte. Primary washing stage 3 is carried out in the same reactor till pH increases to values approximating to neutral one by removing, mainly, iron and aluminium. Produced fine pulp is filtered in pressure filter, flushed by water, preferably, in the same pressure filter, to produce inert wastes. Fine pulp flushing water is added into the mixer or used again to concentrate manganese therein. At secondary flushing stage 4, zinc impurity is removed by settling ZnS. Solution obtained after conditioning 5, is directed to electrolysis 6 to produce electrolytic manganese.

EFFECT: possibility to recover wastes to produce 99,9%-pure manganese.

5 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: magnetic cobalt-manganese sulphide with giant magnetoresistance contains manganese, sulphur and cobalt in the following ratio, wt %: cobalt 10-20, manganese 40-30, sulphur 50.

EFFECT: invention enables to design microelectronic elements based on the giant magnetoresistance effect for a wide range of temperature and magnetic fields, cuts expenses on manufacturing materials with giant magnetoresistance.

2 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: absorbent thermostabilising material based on manganites of rare-earth elements is obtained in fine powder state. Manganites having phase transition dependency of radiation capacity on temperature and general formula A(1-X)BxMnO3 are used, where A is a rare-earth element, B is a substituting element, x ranges from 0.1 to 0.3. Compounds of corresponding elements are selected. Their concentration is selected to create the required composition. The compounds are mixed and heated until formation of a solid solution which is ground. Binder and solvent are added to the obtained material in the require proportion. The obtained mixture is stirred until obtaining a homogeneous mass and the applied onto the surface to be coated in a thin layer.

EFFECT: obtaining the desired product with high output.

3 cl, 1 dwg, 1 tbl

Up!