Method for preparing polyhalide anion-exchange resin

FIELD: chemical technology, resins.

SUBSTANCE: invention relates to a method for preparing polyhalide strong-basic anion-exchange resins of gel and macroporous structure designated for disinfection of water in closed ecological objects, domestic drinking water and water from non-checked sources. Polyhalide anion-exchange resins is prepared from strong-basic quaternary ammonium anion-exchange resins in chloride form by their iodination with J2 solution in KJ at stirring, thermostatic control and washing out. Iodination is carried out with triiodide solution on conditioned strong-basic anion-exchange resins in chloride form in the content of strong-basic groups 80%, not less, in the mole ratio anion-exchange resin : triiodide = 1.0:(1.1-1.5). Ready product is kept at 20-55°C additionally. Invention provides preparing polyhalide anion-exchange resins characterizing by high resource in water disinfection and in simultaneous reducing iodine release in disinfecting water in retention of high disinfecting indices.

EFFECT: improved preparing method.

1 tbl, 8 ex

 

The invention relates to the production of Prigorodnyi strong-base anion exchange gel and macroporous structure intended for disinfection of water in closed ecological objects, household drinking water and water from unapproved sources.

In recent years, for these purposes widespread ion-exchange resin, containing in its composition anionic complexes of iodine and iodine-containing anions [Aksenenko, NV and other Chemistry and water technology, 1989, No. 2, s-182]

Known methods for producing Prigorodnyi resins [J.L. Lambert, Fina G.T. Ind. Eng. Chem. Prod. Res. Dev., 1980, 19, p.p.256-258; Hatch G.L., J.L. Lambert Ind. Eng. Chem. Prod. Res. Dev., 1980, 19, p.p.259-263; G.L. Hatch Ind. Eng. Chem. Prod. Res. Dev., 1981, 20, p.p.382-385], which include complex given the quaternization of the source of the anion by dimethylsulfate, washing unreacted reagent ethanol and deionized water. The resulting anion exchange resin coderoute solution of I2in KI at a molar ratio of 1:1-0,8 in the apparatus with a mechanical stirrer for 24 hours, then washed from the contact solution and then treated with resin in the fluidized bed circulating aqueous solution of I2at a temperature of 60-80°With not less than 24 hours. Received Prigorodny anion exchange resin contains a complex of iodine compounds of the following composition I3-, I5-, I7-and provides bessara is of considerable volumes of water.

However, these methods of obtaining have serious disadvantages. Preliminary preparation of the source of the anion complex and is accompanied by the formation of a large number of aggressive wastewater. Subsequent operation iodization multi-stage, time-consuming, requires special equipment.

A method of obtaining Prigorodnyi ion exchangers [US, 4594392, 08 F 8/22, 1986] by processing cybertechnologies of anion exchange resin with a solution of I2in KI with constant stirring for at least 24 hours. The ratio of anion exchange resin (based on total capacity):I2:KI is 1,0:1,0-1,2:0,7-1,0. The resulting anion exchange resin is washed from excess iodine 2-4 volumes of deionized water to one volume of the anion. Obtained in this way Prigorodny anion exchange resin contains various anionic form of iodine, including HIO, has high antibacterial properties.

The main disadvantage of this method is the high consumption (I2and KI and the duration of the process of iodization.

A method of obtaining polygaloides of the anion [RU, 2061703, 08 F 8/22, 1996] for water disinfection. The method involves cumbersome stage conditioning polymer, followed by iodination of the anion solution polyiodide a certain degree of saturation corresponding to the degree of saturation of the final product, while actionnow mixture of addition is maintained at normal temperature for 8-10 hours. The main disadvantages of this method are its duration, complexity and danger of working with solutions of iodine at a temperature of 80-85°With the specified degree of saturation jodorowski reagent. In addition, the high cost jodorowski reagent require additional washing of the final product from the excess of iodine 0.5 M KI solution and deionised water.

Used control method bactericidal material according to the wet density of the anion is not quite correct, because salt can go and on other (not only Quaternary) ammonium groups, increasing the density of the anion.

Analysis of the current level of technology shows that closest to the proposed method of obtaining polygaloides of the anion exchange resin is a method for Prigorodnyi anion-exchange resins [EN, 2083604, 08 J 5/ 20, 1997]. The method consists in processing strong cybertechnologies anion exchanger, pre-translated in C1-shape and dried to a residual moisture content of 5-15% solution of I2in KI when the molar ratio of anion exchange resin:I2:KI, equal 1,0:0,8-1,2:0,7-1,0, the temperature in the same solution at a temperature of 45-55°and subsequent washing with 4 volumes of deionized water.

The main disadvantage of the prototype is high iodevicetree, especially in the earlier portions of disinfected water (17,0 is 13.0 mg/l)that buslaw which supports the need to develop the system further purification of water from iodine. In addition, the resulting product with a disinfecting efficiency, has a limited resource of water purification from bacteria (from 1000 to 3000 rpm/rpm), in addition, drying of the anion to a residual moisture content below 10% leads to serious destruction of the anion exchange resin granules.

In connection with the above experiencing technical task is to develop ways to obtain Prigorodnyi anion exchange resins characterized by high resource on disinfection of water while reducing iodobutane in disinfected water while maintaining a high disinfecting characteristics.

The problem is solved in that the receiving Prigorodnyi anion-exchange resin is carried out by the iodination under stirring solution of triiodide air-conditioned strong-base anion exchange resin in the chloride form with the contents of the strong-base groups is not less than 80% when the molar ratio of the anion to triiodide 1,0:1,1-1,5, followed by temperature and washing with water, and the finished product addition is maintained at 45-55°C.

The principal difference of the proposed method from the prototype and similar is primarily used as a source of resin air-conditioned strong base gel and macroporous anion exchange resin of industrial production with the contents of the strong-base groups is not less than 80%, and jodorowski reagent in the form of p is the target of triiodide at a certain ratio, as well as keeping the finished product at 45-55°C.

When using such resins do not require additional cleaning resin from organic impurities, additional the quaternization. The use of anion exchange resin with so many strong groups eliminates excessive formation Prigorodnyi forms of ionic groups of low and medium basicity, which does not have antibacterial properties. This leads to the production of bactericidal anion exchange resin with a stable disinfectant properties.

For the determination of strong-base groups in the original anion exchange resin using known testing methods. Full static exchange capacity (PSOY) is determined according to GOST 20255.1-84 0.1 N. hydrochloric acid solution.

The equilibrium of the static exchange capacity (ROE) is determined according to GOST 20255.1-84 0.1 N. sodium chloride solution.

The percentage of ROE and PARTICIPATED characterizes the contents of the strong-base groups in the anion exchange resin.

As the source of the anion used strong cybertechnologies anion exchange resin based on a styrene-divinylbenzene gel and macroporous structure type AB-17 (GOST 20301-74) or its chemical equivalents of foreign manufacture, for example the anion exchange resin grades NRW-400, NRW-505 (firm Pluralist, UK).

According to the proposed method Jodorowsky reagent, not only is no other solution triiodide, to simplify the process of its preparation (4-6 hours instead of several days on the prototype) and to reduce the temperature of the cooking jodorowski reagent to 45-50°With (instead of 80-85°With analogue). To obtain the proposed polygaloides anion exchange resin serves iodination carried out at a molar ratio of anion exchange resin : threadid equal to 1,0:1,1-1,5 on the anion exchange resin in the chloride form with known humidity.

Additional exposure contributes to the stability of iodine excretion throughout the work material.

The following examples illustrate the proposed method.

Example 1.

Preparation jodorowski reagent.

Weigh 500 g of iodine (GOST 4159-79), 327 g of potassium iodide (GOST 4232-74) and measure 490 ml of deionized water. Potassium iodide is dissolved in water at room temperature, add iodine, mixed and placed in a drying Cabinet at a temperature of (47±2)°C. For better dissolution of the iodine solution periodically stirred.

400 g strong-base anion-exchange gel structure brand AV-17-cs with the contents of the strong-base groups 95% in the chloride form and with a residual humidity of 15%.

The molar ratio of anion exchange resin : threadid 1,0:1,1.

Salt of the anion exchange resin is carried out in a reactor with a volume of 2 l, in which pre-placed Jodorowsky reagent, then add the above to the number of the prepared resin, mix and thermostatic in the same capacity at the temperature of (50±2)°C for 2 hours. The resulting product is washed with three volumes of deionized water, wring out the filter, transferred into a Bank of yellow glass and the finished product is maintained at a temperature of 55°C for 6 hours.

The parameters of the process of obtaining polygaloides anion-exchange resin and quality of product produced in example 1 are presented in the table.

Examples 2-7. The parameters of the processing stages of the source of the anion and the results of the finished product is presented in the table.

Examples 2-4 - a method of obtaining analogous to example 1.

Example 5 is an extract of the finished product is not performed.

Example 6 is less than 80% of the strong-base groups.

Example 7 is the ratio of the anion and triiodide less less.

Example 8. An example of the prototype.

Table

Indicators of process parameters and properties Prigorodnyi anion exchange resins.
# exampleThe original strong-base anion exchange resin (C1-form)The contents of the strong-base groups %The molar ratio of anion exchange resin : threadidExtract of the finished productThe oxygen is the radio-iodine in water, mg/l *)Resource for disinfecting ability, about/about **)
1 liter30th liter60th liter100th liter
Temperature,°Time, h
1AV-17-cs gel951,0:1,15566,04,34,03,16000
2AV-17-PC macroporous891,0:1,25566,26,55,3the 4.710000
3AV-17-cs gel951,0:1,5506,510,08,86,24,57000
4AV-17-PC macroporous851.0:1,24577,06,66,04,29600
5AV-17-PC macroporous851,0:1,2Not done11,26,35,5TracesNot defined
6AB-17-10 the h macroporous 771,0:1,55562,32,21,9NoNot defined
7AV-17-cs gel951,0:1,05064,21,9<1,0No1000
8AV-17-10P macroporous (prototype)851,0:1,0 (corresponds to value in the prototype anion exchange resin:J2:KJ 1,0:1,0:1,0)Not done17,111,0None (does not work)Not defined1000

*) In the column with a diameter of 12 mm was loaded with 10 ml polygaloides anion-exchange resin and was passed deionized water with speed (90±10) ml/min Mass concentration of iodine in the water was determined by the photometric method in the extract (Dean) when λ=540 nm.

**) Disinfecting effect was tested for cleaning model solutions prepared with water containing Escherichia coli Escherichia coli, the concentration of which was 1.2×10/8M.L./DM3. The model solution was passed through a 10 ml polygaloides anion-exchange resin. The analysis was carried out according to GOST 2874-82 and pain 4.2.1018-2001.

In R. the result of the conducted tests, the water passed through the loading polygaloides anion exchange resin meets the requirements of SanPiN 2.1.4.559-96 on microbiological indicators.

Thus, the presented results show that obtained by the proposed method Prigorodnaya anion-exchange resin provides a good resource for water disinfection (3-10 times more compared to the prototype) with a significant reduction of residual iodine in the treated water.

The introduction of an additional stage - exposure of the finished product - contributes to the uniformity of iodobutane throughout the resource.

The original strong-base anion exchanger with the contents of the strong-base groups is not less than 80% leads to a significant reduction of the required amount of iodine to ensure the disinfecting ability of the final product.

The method of obtaining Prigorodnyi anion exchange resins of the strong cybertechnologies anion exchange resin in the chloride form by the iodination them with a solution of I2in KI with stirring, the temperature and washing with water, characterized in that the iodination is conducted with a solution of triiodide air-conditioned and strong-base anion exchange resin in the chloride form with the contents of the strong-base groups is not less than 80% when the molar ratio of anion exchange resin:triode, equal to 1.0:1.1 to 1.5, and the finished product is optionally maintained at 45-55° C.



 

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