RU2123978C1 - Charge for treating drinking water and method of treating drinking water - Google Patents

Abstract

FIELD: water treatment. SUBSTANCE: method consists in adding to water physiologically essential minerals and trace minerals. Charge contains 1-70 wt % of carbon sorbent and 30-99 wt % of material consisting of organic ionite with porous structure in air- dry state and inorganic sparingly soluble compounds at ratio 35:90:(10-65). Additionally, charge can contain 0.5-5% of bactericide ionite. Drinking water or softened water is saturated with physiologically essential additives when being passed through the charge. Application of method not only allows saturating water with common minerals but also with trace minerals, not only allows sorbing injurious organic impurities but also heavy metal, aluminum, and iron ions. When saturating water with, for instance, fluoride ions, specific output can be raised to 10 min^-1. EFFECT: enhanced water treatment efficiency. 4 cl, 2 tbl

Description

 The invention relates to the field of water treatment and, in particular, to the field of drinking water treatment by introducing physiologically necessary macro- and microelements into it.

 A known method of processing drinking water by passing it through a dolomite-containing rock of the following composition, wt. %: calcium - 20, magnesium - 11, iron - 0.002, copper - 0.01, cobalt - 0.001, nickel - 0.002, zinc - 0.01, chromium - 0.002, vanadium - 0.001. When water is passed through a filling in the form of granules of this mineral with a size of 1-5 mm, macrocells (calcium, magnesium) and trace elements (iron, copper, zinc) physiologically necessary for humans are introduced into it (RF Patent N 2056358, MKI C 02 F 1 / 18, publ. 20.03.96).

 The disadvantages of this method, as well as filling, include the impossibility of adjusting the content of specific types of macro- and microelements in the treated water, the impossibility of introducing microelements not contained in the dolomite-containing mineral into the water. The rate of transmission of water through such a filling is low (1-2 l / h).

 A known method and filling for conditioning desalinated water. The method consists in filtering water to saturate it with physiologically necessary calcium and magnesium ions through filling in the form of granules of activated carbon, on the pore surface of which are inorganic sparingly soluble compounds containing ions released into the water (AS USSR N 1608138, MKI C 02 F 1/68, published 23.11.90). The known method and filling make it possible to maintain concentrations of calcium and magnesium ions in filtered water at a physiologically necessary level for 30 liters of skipped water with a filling mass of 100 g and a flow rate of 50 ml / min, and 1 liter of filling can saturate with salts about 500 liters of desalinated water.

 The disadvantages of this method and the filling for processing include their use exclusively for the introduction of macronutrients such as magnesium, calcium, potassium. The filling has a low capacity during sorption of heavy metal ions. In addition, the rate of transmission of water through such a backfill and its salt saturation resource are low.

An analysis of the current state of the art shows that the closest technical solution to the proposed one is the method of fluorination (conditioning) of drinking water by passing it through a filling consisting of granules 0.3-1.5 mm in size, including cellulose ester (mainly cellulose acetate ) and an inorganic compound containing fluorine ion (mainly calcium fluoride is a sparingly soluble compound), as well as activated carbon granules with a size of 0.01-0.5 mm. The ratio of components in the filling is, wt. %: 1-50: 10-90: 1-85. (RF patent N 2092451, MKI C 02 F 1/68, publ. 10.10.97). Such a method and filling for its implementation allow saturating water with fluorine ions in an amount of 0.5-1.5 mg / l at a specific rate of water passage through the filling of 0.5-5 min ^-1 . In addition to introducing fluoride ions into drinking water, a filling volume of 100-120 ml is capable of removing organic impurities from water over a period of 350-400 liters.

 The main disadvantage of this method and filling is their use solely for introducing fluoride ions into drinking water. The weakly expressed ion-exchange properties of the granules of the composite material do not allow backfilling and the described method for actively removing such harmful impurities as heavy metal ions. In addition, the absence of disinfecting materials in the backfill composition contributes to its fouling by bacteria.

 In connection with these, a technical problem arose - the development of a filling for the treatment of drinking water, as well as the method of introducing physiologically necessary micro and macro elements into the water with simultaneous sorption of impurities of heavy metal ions and organic compounds from it, increasing the reliability of protecting the filling from biofouling.

The solution to the problem is that the backfill for the treatment of drinking and desalinated water includes a carbon sorbent and a material containing physiologically necessary additives for humans in the form of sparingly soluble inorganic compounds on a carrier, which are used as organic ion exchangers having a porous structure in an air-dry state, with their mass ratio of 10-65: 35-90, respectively, with the ratio of the components of the filling, wt.%:
Carbon sorbent - 1 - 70
Organic ion exchangers with sparingly soluble compounds - 30 - 99
In addition, the backfill may additionally contain a bactericidal ion exchanger containing silver in its composition, with a ratio of backfill components, wt.%:
Carbon sorbent - 1 - 70
Organic ion exchangers with sparingly soluble compounds - 30 - 99
Bactericidal action ionite - 0.5 - 5.0
A method of treating potable or desalinated water with physiologically necessary additives is to pass water through the described filling.

Organic macroporous or macrocellular strongly and / or weakly acidic cation exchangers with a polystyrene, polyacrylic and polymethacrylic matrix, as well as organic macroporous or macrocellular high and / or low basic anion exchangers, are used as organic ion exchangers with a porous structure in an air-dry state. polystyrene and polyacrylic matrix or other cation exchangers and anion exchangers, similar in structure and properties, having a total pore volume of 0.1 - 1.0 cm ³ / g and a grain size of 0.3-1.5 mm

 As inorganic sparingly soluble compounds (MPC), the material contains inorganic salts, oxides, hydroxides, acids having a solubility lower than 8 g / l and containing elements physiologically necessary for human life, such as Ca, Mg, F, Se, Zn, Cu, Fe, Mn, Cr and others. MRS, including physiologically necessary elements, are formed as a result of exchange and redox reactions.

 Inorganic sparingly soluble compounds are precipitated in the pores of the organic ion exchanger by successive treatments with solutions of substances that enter into exchange or redox reactions with the precipitation of one or more reaction products.

As a carbon sorbent, carbon fiber materials such as AMN, KMN, AUT-M, PCM are used, which have the ability to sorb organic impurities and heavy metal compounds from water or activated carbons with a total pore volume of 0.6-1.8 cm ³ / g . To achieve a disinfecting and / or sterilizing effect, hydrocarbon sorbents containing silver can be used, for example, AG-3C, AG-8C and others.

 As the ion exchanger of bactericidal action, cation exchangers in silver form can be used, for example, KU-23CM, C-150AC, or similar properties.

 Analysis of the claimed fillings for the treatment of drinking water and a method for the treatment of drinking water and known technical solutions shows that there is no combination of features that are identical in technical essence to the claimed ones. A comparative analysis of the proposed solutions with the prototype shows that the claimed solutions differ from the prototype using a new carrier for sparingly soluble compounds with a certain ratio of the components included in the filling composition.

 Thus, the claimed "backfill" and "method" meet the criteria of the invention of "novelty." In the literature and practice there is no information about the method and backfill identical to those proposed and this does not follow explicitly from the prior art. This allows us to conclude that the claimed solutions meet the criterion of "inventive step". The proposed solutions ensure the achievement of a technical result, can be implemented during water treatment, enriching it with physiologically necessary elements for a person and provide the possibility of their multiple reproduction, which allows us to conclude that the claimed technical solutions of the criterion of "industrial applicability" are satisfied.

Example 1. Anion exchange resin AB-17-10P (GOST 20301) in an amount of 10 ml is treated with a solution of Na ₂ SO ₄ until completely converted to sulfate form. Then the anion exchange resin is treated with a solution of CaCl ₂ . The resulting material contains a sparingly soluble compound (MPC) CaSO ₄ at a mass ratio of MPC: ion exchanger (MPC: I) 65:35. Getting backfill is that the material is placed in a column with an inner diameter of 11 mm A carbon sorbent KNM is placed above it with a mass ratio of sorbent: ion exchanger (C: I) of 1:99.

The implementation of the method consists in passing low-saline water (total hardness (coolant) - 0.5 mEq / l) through the filling described in the example from top to bottom. To test the ability to sorb heavy metal ions, lead (II) ions are introduced into the source water in an amount of 3 MAC (0.3 mg / l). At the column outlet, the content of lead ions in water is determined by the plumbon method (GOST 18293) and the content of calcium ions (GOST 1451) after passing 30 l of water at a rate of 50 ml / min. Specific productivity (UP) in this case is 5 min ^-1 . The content of calcium ions in the filtrate is 1.6 mEq / L, the content of lead ions is 0.002 mg / L. The resource is 3000 volumes of water per volume of backfill. The material and backfill parameters are presented in Table 1. Table 2 presents the analysis results and physiological norms (FN) for the content of elements in water.

Example 2. Similar to example 1, except that the material used as a carrier cation exchanger KU-23 (GOST 20298) containing CaF ₂ as MPC. The activated carbon BAU-A (GOST 6217) located after the material was used as a carbon sorbent. The ability to sorb aluminum ions was investigated. For this, aluminum ions with a concentration of 1.2 mg / L were introduced into the source water. At the exit from the column, the content of aluminum ions is also determined (GOST 18165). The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

Example 3. Similar to example 1, except that the material used as a carrier cation exchange resin C-106 (PUROLITE) containing Cu (OH) ₂ as MPC. Activated carbon AC-20G (PUROLITE) located in front of the material was used as a carbon sorbent. A study of the sorption of heavy metals is not carried out. At the outlet of the column, the content of copper (II) ions is determined (GOST 4388). The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

Example 4. Similar to example 1, except that in the material as the carrier used A-835 (PUROLITE), containing as MPC Ag ₂ SeO ₃ . As a carbon sorbent used activated carbon AGM (TU 6-16-2589-82), located after the material. A study of the sorption of heavy metals is not carried out. At the column outlet, the selenium content is determined by spectrophotometric method with a 3.3 '' reagent - diaminobenzidine. The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

Example 5. Similar to example 1, except that the material contains MPC Mg (OH) ₂ . As the carbon sorbent, the fibrous sorbent ANM (TU 6-16-3091-89) used after the material was used. The ability to sorb barium ions was investigated. The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

Example 6. Similar to example 1, except that the material used as a carrier cation exchanger C-150 (PUROLITE) containing MPC ZnCO ₃ . Activated carbon FAS (TU 6-16-3096-89) mixed with material is used as a carbon sorbent. A study of the sorption of heavy metals is not carried out. At the outlet of the column, the content of zinc (II) ions is determined (GOST 18293). The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

Example 7. Anion exchange resin AN-511 (TU 6-05-211-1311-85) in an amount of 10 ml is treated with a NaOH solution until completely converted to the hydroxyl form. Then the anion exchange resin is treated with a solution of KMnO ₄ . The material contains MPC Mn (OH) ₂ and MnO ₂ in an amount of 25 wt.% In terms of manganese. To establish the content of MPC in the material, the material is burned and the manganese content is determined in the residue (GOST 4974). The carbon sorbent used is activated carbon SKT (TU 6-16-2477-88), which is mixed with the material. Further, similarly to example 1, except that in the filtrate determine the content of manganese and examine the sorption of iron (III). The iron content in the initial solution and the filtrate is determined according to GOST 4011. The material and filling parameters are presented in table 1. The analysis results are presented in table 2.

Example 8. In a column with an inner diameter of 25 mm, a carbon sorbent KNM (TU 6-16-28-1561-93) is placed sequentially (along the water); material containing 10 ml of CaSO ₄ (from example 1); material containing 10 ml of Mg (OH) ₂ (from example 5); material containing 3 ml of CaF ₂ (from example 2); material containing 5 ml of Cu (OH) ₂ (from example 3) with a ratio of C: And 10:90 wt.%.

The implementation of the method consists in passing distilled water through the filling described in the example. At the column outlet, the content of calcium, magnesium, fluorine and copper ions in water is determined after passing 30 l of water with a specific productivity of 3.0 min ^-1 . The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

Example 9. Cation exchanger KU-23 (GOST 20298) is treated with a solution of CaCl ₂ . Then the cation exchange resin is treated with a solution of MgSO ₄ . After that, the cation exchange resin is treated with a solution of Na ₂ CO ₃ . The content of MPC CaSO ₄ and MgCO ₃ in the material is 45 wt. % In a column with an inner diameter of 46 mm, silver-plated activated carbon AG-3C (GOST 20464) and 10 ml of material are placed sequentially (along the water) with a mass ratio of C: And 70:30 wt.%.

The implementation of the method consists in passing distilled water into which cadmium ions in an amount of 0.1 mg / l are previously introduced. Water transmission is carried out with a specific productivity of 1.0 min ^-1 . At the outlet of the column, the content of calcium, magnesium, cadmium ions in the water is determined. The material and backfill parameters are presented in table 1. The analysis results are presented in table 2.

 Example 10. Analogously to example 2, except that aluminum compounds are not introduced into the source water. The bactericidal action ion exchanger KU-23SM (TU 6-06-10-88) is introduced into the composition of the backfill, which is placed between the layers of the material and the carbon sorbent, with a ratio of C: I: KU-23CM 40: 59.5: 0.5 wt. % At the column outlet, the content of silver ions (GOST 18293) and fluorine ions in the water is determined. The concentration of fluorine ions is 0.8 mg / l, silver ions - 0.01 mg / l.

 Example 11. Analogously to example 10, except that the introduced bactericidal ion exchanger is mixed with the material at a ratio of C: I: KU-23CM 40: 55: 5 wt.%. The concentration of fluorine ions is 0.7 mg / l, silver ions - 0.04 mg / l.

 The above examples do not limit the location of the components of the backfill, the number and type of materials used in them containing organic ion exchangers and inorganic sparingly soluble compounds.

The use of poorly soluble ion-exchange compounds having a porous structure in an air-dry state in the amount of 35-90 wt.% As a carrier is due to the fact that other porous carriers do not provide uniform release of micro and macro elements into water at a specific productivity (transmission rate water) more than 1 min ^-1 .

 The content of poorly soluble inorganic compounds in the amount of 10-65 wt.% Is due to the fact that with a smaller amount of MPC on the ion exchanger, a sufficient amount of physiologically necessary ions does not get into the water. With an increase in the content of MGS on the ion exchanger over 65 wt.%, The number of necessary treatments of the ion exchangers with highly soluble compounds sharply increases, which complicates the method of obtaining the material.

 The amount of carbon sorbent (1-70 wt.%) Is due to the fact that a smaller amount does not allow sorbing organic impurities and heavy metal ions to a sufficient degree, and a larger amount does not allow maintaining the release of physiologically necessary substances at the required level.

 As can be seen from the presented examples and tables 1 and 2, the use of the proposed backfill and the method of introducing physiologically necessary additives allows you to enter macro- and microelements in water both individually and in any necessary combination, sorb not only harmful organic impurities, but also heavy ions metals, aluminum and iron, which is almost impossible using a well-known technical solution. The specific productivity at saturation of water, for example, with fluorine ions, can be increased by 2 times in comparison with the known technical solution. The use of bactericidal action ion exchange resin or silver-containing activated carbon in the proposed backfill prevents their biofouling.

Claims (1)

1. A filling for the treatment of drinking water, including a carbon sorbent and a material containing an organic compound and inorganic sparingly soluble compounds, characterized in that, as an organic compound, the material contains organic ion exchangers having a porous structure in an air-dry state, and sparingly soluble inorganic compounds when they are the mass ratio of 35 - 90: 10 - 65, respectively, with the ratio of the components of the filling, wt.%:
Carbon sorbent - 1 - 70
Organic ion exchangers with sparingly soluble compounds - 30 - 99
2. The filling according to claim 1, characterized in that it contains a bactericidal ion exchanger with a ratio of the components of the filling, wt.%:
Carbon sorbent - 1 - 70
Organic ion exchangers with sparingly soluble compounds - 30 - 99
Bactericidal action ionite - 0.5 - 5.0
3. A method of treating drinking water by introducing physiologically necessary inorganic ions by passing water through a bed containing a carbon sorbent and a material containing an organic compound and inorganic sparingly soluble compounds, characterized in that the material as an organic compound contains organic ion exchangers having a porous structure in air dry state, and sparingly soluble inorganic compounds with their mass ratio of 35 - 90: 10 - 65, respectively, with the ratio of components asypki, wt.%:
Carbon sorbent - 1 - 70
Organic ion exchangers with sparingly soluble compounds - 30 - 99
4. The method according to claim 3, characterized in that the backfill further comprises a bactericidal ion exchanger with a ratio of backfill components, wt.%:
Carbon sorbent - 1 - 70
Organic ion exchangers with sparingly soluble compounds - 30 - 99
Bactericidal action ionite - 0.5 - 5.0L

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