RU147403U1 - FILTERING MATERIAL FOR PURIFICATION OF DRINKING WATER FROM IRON AND Manganese Ions - Google Patents

Abstract

1. Filter material for purifying drinking water from iron and manganese ions, containing a dispersed carrier, on the surface of which a catalytically active layer is formed, consisting of a mixture of oxide compounds of manganese of different valencies, characterized in that the dispersed carrier is made in the form of porous granules made of foamglassceramics.2 . The filter material according to claim 1, characterized in that the granules of foam glass ceramic have a diameter of from 0.8 to 2.0 mm, a pore size of from 0.036 to 0.135 mm, with an inter-pore wall thickness of 0.07-0.1 μm. The filter material according to claim 1 or 2, characterized in that the composition of the granules of foam glass includes clay, glass and an organic additive, in the following ratio, wt.%: 4. The filter material according to claim 1, characterized in that a catalytically active layer is formed on the surface of the glass-ceramic granules, consisting of a mixture of manganese oxides of different valencies: MnO, MnO and MnO with their mass ratio correspondingly equal to (0.5-1) :( 2-3 ) :( 5-6).

Description

The inventive utility model relates to the field of water treatment of drinking water, namely, filter materials used to purify water from manganese and iron.

Known inorganic sorbent used in water treatment [RU No. 2229336, IPC B01J 20/12, B01J 20/06, 2003]. The sorbent includes a carrier containing bentonite clay, subjected to successive thermal and acid activation, while the content of manganese dioxide in it is 10-14%.

The disadvantages of this sorbent include the fact that bentonite clay deoxidizes in water over time, which leads to its destruction.

Known sorption-filtering material for water treatment [RU No. 2483798, IPC B01J 20/06, B01J 20/16, B01J 20/32, 2011], used mainly for the purification of drinking water from manganese and iron. The material used is basalt fiber, which is pre-crushed in an aqueous medium to a size of 1 to 25 mm and chemically activated using one of a number of inorganic acids: hydrochloric, sulfuric or nitric.

The disadvantages of this material is the small size of basalt fiber (1 mm), which can lead to its slip into drinking water, which will make it unsuitable for drinking needs.

Known granular filter material intended for the purification of natural and waste water [RU No. 2162737, B01J 20/02, B01J 20/06, B01J 20/30, B01D 39/02, 2000]. The basis of the material used is a natural mineral - dolomite, which is crushed and treated at room temperature with a solution containing salts of divalent manganese ions.

The disadvantages of this material is that dolomite, even after firing, is a soft material, and in the process of its use as a filter material in the filters of water treatment plants, its abrasion occurs. As a result, water is contaminated with particles of dolomite, which increase its hardness.

Known sorption-filtering material for the purification of natural waters from compounds of iron and manganese [RU No. 2241535. IPC B01J 20/02, B01J 20/30, 2003]. As granular carbonate material, thermally untreated calcium carbonate is used, containing not more than 1% magnesium carbonate, chemically treated with manganese compounds.

Disadvantages - thermally untreated calcium carbonate, as a rule, softens in water over time, which leads to its destruction. In addition, abrasion will lead to the appearance of turbidity in the water and increase stiffness.

The prototype of the claimed utility model is a filter material for purifying water from manganese and iron [RU No. 2275335, IPC C02F 1/64, B01D 39/06, B01J 20/06, B01J 20/30, C02F 103/04, 2004]. In this filtering material, a particulate material of natural origin, burned rock, is used as a carrier, and a catalytically active layer consisting of a mixture of oxides MnO, Mn ₂ O ₃ and MnO _{2 is} formed on the surface of the burned rock.

The disadvantages of the prototype include the following:

- in a burnt rock there are a lot of dusty particles that are poorly washed out and form dirt after processing with reagents and a lengthy preliminary washing is required before use.

The objective of this utility model is to develop a filter material based on foam glass ceramic suitable for purifying water from iron and manganese.

The technical result is the creation of an effective material that allows you to purify water from iron and manganese, as well as the disposal of cullet.

This object is achieved in that, as a well-known, the proposed filter material for purifying drinking water from iron ions contains a dispersed carrier, on the surface of which a catalytically active layer consisting of a mixture of manganese oxide compounds is formed.

What is new is that the dispersed carrier is made in the form of porous granules of foam glass ceramic.

It is preferable that the granules of foam glass ceramic have a diameter of from 0.8 to 2.0 mm, a pore size of from 0.036 to 0.135 mm, with an inter-pore wall thickness of 0.07-0.1 microns.

In addition, the composition of foam glass ceramic includes clay, glass and an organic additive, in the following ratio of components, wt.%:

Clay 8-25

Organic additives 3-10

Glass is the rest.

It is preferable that a catalytically active layer consisting of a mixture of manganese oxides: MnO, Mn ₂ O ₃ and MnO _{2 is} formed on the surface of the foamglass-ceramic granules with a mass ratio of respectively (0.5-1) :( 2-3) :( 5 -6).

To obtain a filter material capable of purifying water from iron and manganese, glass-ceramic granules were subjected to sequential treatment with solutions of modifying reagents containing, including manganese compounds.

When processing foam-glass-ceramic granules with modifying reagents, on its surface a complex of not only oxide compounds of manganese was obtained: Mn ₂ O ₃ , MnO ₂ . but also hydroxide: Mn (OH) ₂ , which was confirmed by X-ray diffraction studies using a DRON-UM1 diffractometer. Subsequently, after drying on the surface of the granules, a complex of oxide compounds MnO, Mn ₂ O ₃ , MnO _{2 was} obtained.

It was experimentally established that a mixture of manganese compounds: MnO, Mn ₂ O ₃ , MnO ₂ deposited on porous glass-ceramic granules causes a high catalytic activity of the loading of the claimed material in relation to various salts of iron and manganese dissolved in water.

The nuclei of the formation of Mn ₂ O ₃ , MnO ₂ on the surface of granules of foam glass ceramic are Mn ^{2+ ions} that neutralize ≡Si-O centers. During the formation of MnO ₂ particles on the surface of the glass-ceramic granules, doubly charged Mn ²⁺ cations serve as a kind of chemical bridges between the aluminosilicate framework and manganese dioxide particles: ≡Si-O-Mn ²⁺ -O ₂ Mn. The bridge cations Mn ²⁺ enter the outer lining of its double electric layer. Thus, aluminosilicate - oxide interaction (the so-called SVAO effect) is provided through the Mn ²⁺ bridge cations. This effect leads to the stabilization of higher forms of manganese oxidation.

Highly active manganese dioxide deposited on the surface of granules of foam glass ceramic forms an intermediate complex MnO ₂ -O ₂ with water-soluble oxygen. The oxidation of ions by sorbed manganese dioxide can be represented as the following general scheme:

Mn ²⁺ + O = O → Mn ³⁺ , Mn ⁴⁺

An active “player” in the oxidation reaction of Mn ^{2+ ions with} insoluble manganese oxides is O ^2– oxygen radical anions formed on the surface of the foamglass ceramic granules during the sorption of oxygen molecules.

In the work [Gubaidulina T.Α., Melnikov A.G. Granular catalytically active material for the purification of drinking water from iron and manganese. // Chemistry - XXI century: new technologies, new products: Proceedings of the IX International scientific-practical conference. - Kemerovo, May 16-17, 2006. - S. 204-206.] it was indicated that manganese dioxide adsorbed on the surface of the loading granules also acts as an oxidizing agent, converting soluble Mn ^{2+ ions} to insoluble oxides:

Mn ²⁺ + MnO ₂ C → Mn ₃ O ₄ , Mn ₂ O ₃ C,

where C - granules of foamglass ceramics (aluminosilicates).

Mn ₂ O ₃ oxide also has oxidizing properties, and it is possible that its role is significant in the oxidation of Mn ²⁺ .

The utility model is illustrated with graphic materials.

In FIG. 1 a) presents granules made of foam glass ceramic with a diameter of 0.8-2.0 mm

In FIG. 1 b) granules are presented in a section with a thickness between inter-pore walls of 0.07-0.1 μm.

The utility model is further illustrated by specific examples of material manufacturing.

In the claimed utility model, it is proposed to use foamglass ceramic granules as a carrier, with the characteristics shown in Table 1, granule diameters from 0.8 to 2.0 mm, having a pore size of 0.036-0.135 mm, with a pore wall thickness of 0.07-0 , 1 μm (Fig. 1).

Composition 1 was obtained in the following weight ratio of the components of the mixture, wt.%:

Clay 8,

Coke 5.

Sawdust 3

Glass (cullet) - the rest.

Composition 2 was obtained in the following ratio of components, wt.%:

Clay 10,

Coke 5.

Sawdust 3.

Glass (cullet) - the rest.

Composition 3 was obtained in the following ratio of components, wt.%:

Clay 25,

Coke 5,

Sawdust 3

Glass (cullet) - the rest.

Subsequently, foam-glass ceramic granules obtained from composition 2 were used to modify the surface of the granules with modifying reagents.

The granules were poured with a solution of manganese dichloride and kept with stirring for 15-20 minutes. Then the solution of manganese dichloride was drained until the droplets disappeared. The potassium permanganate solution was made alkaline with sodium hydroxide and granules were poured with it. To obtain an oxide film, the final processing was performed with sodium sulfate.

Table 2 presents experimental data on the intensity of staining to obtain a filter material with the claimed composition of the catalytically active layer depending on the concentration of the reagents.

Table 2. Name of material Concentration, g / l Experiment 1 Experiment 2 Manganese Dichloride 25 thirty Potassium permanganate thirty 35 Sodium sulfate 25 thirty Caustic soda 5 6 Staining intensity beige brown

Results:

When using concentrations of reagents:

- experiment 1 — a layer was obtained consisting of a mixture of manganese hydroxide: Mn (OH) ₂ and manganese oxides: Mn ₂ O ₃ , MnO ₂ with a mass ratio of components (0.5: 2: 5).

- experiment 2 — a layer was obtained consisting of a mixture of manganese hydroxide: Mn (OH) ₂ and manganese oxides: Mn ₂ O ₃ , MnO ₂ with a mass ratio of components (0.7: 2.5: 5.5).

After drying on the surface of the samples obtained in examples 1 and 2, a catalytically active layer consisting of a mixture of manganese oxide compounds: MnO, Mn ₂ O ₃ , MnO _{2 was} obtained on the surface of granules made of foam glass ceramic.

The characteristics of the inventive filter material for the purification of drinking water from iron and manganese ions are shown in table 3.

Table 3. The characteristics of the inventive filter material Name of indicator Material properties Determination method Appearance foamglass granules GOST R 51641-2000 Color Light beige to brown Smell Without smell Bulk bulk mass (bulk density), kg / m ³ 200 ... 290 GOST 8735-88

Testing of well water samples for purification from iron and manganese ions was carried out using filter material based on foamglass ceramic granules obtained in accordance with experiment 2.

Table 4 shows the test results of the inventive filter material.

The obtained oxide manganese compounds on the surface of foam-glass ceramic granules interact with manganese and iron compounds dissolved in water to form insoluble compounds that precipitate on the surface of the granules.

As can be seen from the results of operational tests, the complex of oxide compounds: Mn ₂ O ₃ , MnO ₂ and MnO, obtained on the surface of the glass-ceramic, can reduce the content of iron and manganese dissolved in water by 10-15 times.

Claims (4)

1. Filter material for purifying drinking water from iron and manganese ions, containing a dispersed carrier, on the surface of which a catalytically active layer is formed, consisting of a mixture of oxide compounds of manganese of different valencies, characterized in that the dispersed carrier is made in the form of porous granules made of foam-glass ceramic. 2. The filter material according to claim 1, characterized in that the granules of foam glass ceramic have a diameter of from 0.8 to 2.0 mm, pore size from 0.036 to 0.135 mm, with a thickness of inter-pore walls of 0.07-0.1 microns. 3. The filter material according to claim 1 or 2, characterized in that the composition of the granules of foam glass includes clay, glass and an organic additive, in the following ratio, wt.%: Clay 8-25 Organic supplements 3-10 Glass rest 4. The filtering material according to claim 1, characterized in that a catalytically active layer consisting of a mixture of manganese oxides of different valencies: MnO, Mn ₂ O ₃ and MnO _{2 is} formed on the surface of the glass-ceramic-granule granules, respectively, equal to (0.5 -1) :( 2-3) :( 5-6).

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