RU2077504C1 - Disinfecting solution - Google Patents

Abstract

FIELD: inorganic chemistry, sanitary. SUBSTANCE: proposed solution comprises sodium hypochlorite, sodium hydroxide, sodium chloride and water. Solution comprises sodium hypochlorite with admixture of sodium chloride produced by direct reaction of chloric acid dissolved in mixture of tributyl phosphate with n-dodecane, with aqueous solution of sodium hydroxide, at following weight ratio of said components, wt.%: sodium hypochlorite 1.0-32.5; sodium hydroxide 0.1-2.2; sodium chloride 0.005-0.5, water being balance. EFFECT: effective and cheap disinfecting agent. 7 tbl

Description

 The invention relates to disinfecting aqueous solutions of inorganic salts of alkali metals containing active chlorine, having a strong disinfecting effect, and can be used for the treatment of drinking water, water purification of swimming pools, disinfection of wastewater, disinfection of rooms, livestock complexes, in medicine, in veterinary medicine , in the processing of agricultural products, etc.

Known use for disinfection of 0.5-10.0 wt. an aqueous suspension of bleach [1] and 1.0-2.0 wt. an aqueous solution of calcium hypochlorite [2]
The disadvantages of the known disinfectants are the need to use large doses of the active chlorine of these agents for disinfection, as well as the lack of a disinfecting effect against mycelia and spores of fungi, and calcium hypochlorite solution also to viruses and the causative agent of anthrax / bacillus anthracoid /.

 Known disinfectant solution containing sodium hypochlorite obtained by electrolysis of a solution of sodium chloride, sodium hydroxide, sodium chloride and water in the subsequent ratio of components, wt.

Sodium hypochlorite 1.0-2.0
Sodium hydroxide 1.0-2.0
Sodium Chloride 5.0-10.0
Water the rest [3]
The closest in composition to the proposed is a disinfectant solution, including sodium hypochlorite, containing the same amount of sodium chloride obtained by chlorination of a solution of sodium hydroxide, sodium hydroxide and water in the following ratio, wt.

Sodium hypochlorite 19.0-20.0
Sodium hydroxide 1.0-2.0
Sodium Chloride 19.0-20.0
Water the rest [4]
When disinfecting the above known solutions of sodium hypochlorite are diluted with water to a concentration of 0.1-0.4 wt. active chlorine.

 The disadvantages of the known disinfecting solutions are their low disinfecting activity, which necessitates the use of large doses of the active chlorine of these solutions for disinfection and the absence of a disinfecting effect on viiruses, anthrax pathogens / anthracoid bacillus /, as well as salinization of rooms and equipment during disinfection due to the large sodium chloride content.

 The objective of the present invention is to obtain a disinfectant solution having a high disinfecting activity and not causing salinization of rooms and equipment during disinfection.

 The problem is solved in that the known disinfecting solution, including sodium hypochlorite, sodium hydroxide, sodium chloride and water, contains sodium hypochlorite mixed with sodium chloride, obtained as a result of direct interaction of hypochlorous acid dissolved in a mixture of tributyl phosphate and n-dodecane with an aqueous solution of n -decane, in the following ratio, wt.

Sodium Hypochlorite 1.0-32.5
Sodium hydroxide 0.1-2.2
Sodium Chloride 0.005-0.5
Water is the rest.

 The proposed disinfecting solution has a high disinfecting activity, because it has a disinfecting effect on viruses, bacteria, mycelia and spores of fungi at significantly lower concentrations of active chlorine. When carrying out disinfection with the proposed solution, salinization of the disinfected surfaces is excluded due to the absence of sodium chloride in its composition.

 The indicated technical results are achieved due to the use of sodium hypochlorite in it, practically containing sodium chloride (only as an impurity), which is obtained by direct interaction of hypochlorous acid dissolved in a mixture of tributyl phosphate and n-dodecane with an aqueous solution of sodium hydroxide, as well as the ratio components in it, which allows you to maintain a high disinfectant activity of the solution for 2-8 months.

 The invention consists in the following.

 A disinfecting solution containing 1.0-32.5 wt. sodium hypochlorite with an admixture of 0.005-0.5 wt. sodium chloride, 0.1-2.2 wt. sodium hydroxide and the rest of the water.

 Sodium hypochlorite with an admixture of sodium chloride is obtained by direct interaction of dissolved in a mixture of TBP / 40 vol./ and n-dodecane hypochlorous acid with an aqueous solution of sodium hydroxide.

A disinfectant solution is prepared as follows. A solution of hypochlorous acid in a mixture of TBP / TU 6-09-1443-76 / and n-dodecane / TU 6-09-3730-74 / is brought into contact with an aqueous solution of sodium hydroxide / water GOST 2874-82 for 3-10 minutes , sodium hydroxide GOST 2263-79 / with a concentration of sodium hydroxide of 1.0-12.0 mol / dm ³ with vigorous stirring. After delamination of the resulting emulsion, the aqueous phase having a pH of 11-12 and representing a disinfecting solution is separated from the organic phase.

To prepare the disinfecting solution, an organic solution of hypochlorous acid is used, obtained by extraction with a mixture of TBP and n-dodecane from an electrolysis solution of sodium chloride at pH 4-6.8, or from its aqueous solution obtained after passing gaseous chlorine through water or chlorinating an aqueous solution sodium hydroxide at a temperature of -25 -33 ^o C.

 In the resulting disinfectant solution, to characterize its composition, the content of sodium hypochlorite, sodium chloride, sodium hydroxide, TBP and n-dodecane is determined.

The mass content of sodium hypochlorite is determined as follows: 10 cm ^{3 of the} obtained disinfectant solution are pipetted into a volumetric flask with a capacity of 100 cm ³ / pipette 2-2-10 according to GOST 20292-74, flask 2-100-2 according to GOST 1770-74 /, brought the volume of the solution with distilled water according to GOST 6709-72 to the mark and mixes thoroughly. 10 cm ^{3 of the} resulting solution is pipetted into a conical flask / Kn-2-250-34 according to GOST 25336-82 /, 10 cm ^{3 of an} aqueous solution of potassium iodide with a mass fraction of 10% / potassium iodide according to GOST 4232-74 / is added, mixed, added 20 cm ³ sulfuric acid solution at a concentration of 1 mol / dm ^3/98 g / dm ³ / / sulfuric acid in accordance with GOST 4232-74 /, again stirred, the flask was stoppered and placed in a dark place. After 5 minutes, the iodine released is titrated with a solution of sodium sulfate / GOST 27068-86 / with a concentration of 0.1 mol / dm ³ until the solution is light yellow, 2-3 cm ^{3 of an} aqueous starch solution with a mass fraction of 1% / soluble starch is added according to GOST 10163-76 /, and continue to titrate until the solution becomes discolored.

,
где V объем раствора серноватистокислого натрия концентрации точно 0,1 моль/дм³, израсходованный на титрование, см³;
0,003723 масса гипохлорита натрия, соответствующая 1 см³ раствора серноватистокислого натрия концентрации точно 0,1 моль/дм³.The mass content of sodium hypochlorite / x, wt. / Is calculated by the formula

,
where V is the volume of a solution of sodium sulfate concentration exactly 0.1 mol / dm ³ spent on titration, cm ³ ;
0.003723 mass of sodium hypochlorite, corresponding to 1 cm ³ solution of sodium sulfate, concentration exactly 0.1 mol / dm ³ .

The result of the analysis is the arithmetic mean of the results of two parallel determinations, the allowable discrepancy between them with a confidence level of 0.95 is not more than 2 g / dm ³ .

,
где V объем раствора нитрата серебра концентрации точно 0,1 моль/дм³, израсходованный на титрование.The determination of sodium chloride content was carried out as follows: 10 cm ^{3 of the} obtained disinfectant solution were transferred by pipette / 2-2-10 according to GOST 20292-74 / into a volumetric flask with a capacity of 100 cm ³ / flask 2-100-2 according to GOST 1770-74 /, distilled water / according to GOST 6709-72 / the volume of the solution is brought to the mark and thoroughly mixed. 10 cm ^{3 of the} resulting solution is pipetted into a conical flask / Kn 2-250-34 according to GOST 25336-82 /, 2-3 drops of a potassium chromate solution with a mass fraction of 1% / potassium chromate according to GOST 4459-75 / are added and titrated with a nitrate solution silver / silver nitrate according to GOST 1277-75 / with a concentration of 0.1 mol / dm ³ to orange-yellow color. Then the mass content of sodium chloride / wt. / Is calculated by the formula:

,
where V is the volume of a solution of silver nitrate concentration exactly 0.1 mol / DM ³ used for titration.

The result of the analysis is the arithmetic average of the results of two parallel determinations, the allowable discrepancy between them with a confidence level of 0.95 is not more than 0.01 g / dm ³ .

 The mass content of sodium hydroxide is determined by the method of quenching with hydrochloric acid / GOST 11086-76. Sodium hypochlorite. Technical conditions, p. 6-7 /.

 The content of TBP and n-dodecane was controlled by known methods / Lurie, Yu.Yu. Analytical chemistry of industrial wastewater. M. Chemistry, 1984, v. 1, p. 214 for TBF, etc. 2, p. 314 for n-dodecane / and did not exceed 0.001 wt.

 The resulting disinfectant solution is characterized by disinfecting activity, for which it is diluted with water according to GOST 2874-82 to a concentration of 0.1-0.5 wt. active chlorine, the content of which is controlled by the iodometric method / GOST 11086-76. Sodium hypochlorite. Technical conditions, p. 5-6 /.

Disinfecting activity was determined by known methods / Instruction for determining the bactericidal properties of new disinfectants N 739-68. Approved by the USSR Ministry of Health, 1968. Methodological recommendations for determining the virucidal activity of drugs N 1119-78. Approved by the USSR Ministry of Health, 1978. On the procedure for testing and introducing disinfectants into practice. Order of the Ministry of Health of the USSR N 1239, 1978 /. The following set of microorganisms was used:
E. coli strain 1256,
Staphylococcus aureus strain 906,
anthracoid bacillus strain 1955, the latter in the form of daily and 21-day culture,
vaccinia virus
trichophyton gypsum.

 To determine the disinfecting activity, both batiste test objects containing the above microorganisms and various objects infected with these microorganisms were used.

Example 1. In 1 DM ³ acidified to a pH of 5.4 electrolysis solution of sodium chloride / concentration of NaCl 4 wt. /, Containing 8.7 g / DM ³ sodium hypochlorite, add 0.3 DM ³ mixture TBP / 40 vol. / And n-dodecane / 60 vol. / and stirred for 4 minutes. Then the resulting emulsion is defended, and after separation, the organic phase containing hypochlorous acid in a solution of a mixture of TBP and n-dodecane is separated. The aqueous phase after separation contains 0.42 g / DM ³ sodium hypochlorite and has a pH of 6.6. To a solution of hypochlorous acid add 0,065 DM ³ 40 wt. an aqueous solution of sodium hydroxide / concentration of sodium hydroxide 10 mol / DM ³ / and stirred for 4 minutes. The emulsion obtained is defended, and after delamination, the aqueous phase with a pH of 11.5 is separated, which is a disinfecting solution. The resulting solution has the following composition, wt. sodium hypochlorite 12.7; sodium chloride 0.05; sodium hydroxide 0.1; water the rest. No traces of TBP and n-dodecane were detected.

The resulting disinfectant solution is diluted with water to a concentration of active chlorine, respectively 1 g / DM ³ / 0.1 wt. /, 2 g / DM ³ / 0.2 wt. /, 3 g / DM ³ / 0.3 wt. /, 4 g / dm ³ / 0.4 wt. / And 5 g / dm ³ / 0.5 wt. /. The resulting solutions treated various surfaces infected with Escherichia coli and Staphylococcus aureus by wiping with a rag soaked in the solution. For each microorganism, a minimum killing dose was established at an exposure of 10 and 15 minutes. The results are shown in table 1.

 After drying, no traces of sodium chloride were observed on the treated surface.

Example 2. 10 dm ^{3 of} water for 120 minutes is chlorinated with gaseous chlorine at 18 ^o C. The resulting weak solution of hypochlorous acid is contacted with constant stirring with 4 dm ^{3 of a} mixture of TBP / 40 vol./ and n-dodecane / 60 vol. /. After separation of the emulsion, the organic phase containing a solution of hypochlorous acid in a mixture of TBP and n-dodecane is separated. To the resulting solution was added 1.2 dm ^{3 of a} 4% aqueous sodium hydroxide solution (sodium hydroxide concentration 1.0 mol / dm ³ ) and stirred for 10 minutes. After delamination of the resulting emulsion, the aqueous phase is separated, containing a disinfecting solution with a pH of 11.2 of the following composition, wt. sodium hypochlorite 1.0; sodium chloride 0.005; sodium hydroxide 0.1; water the rest. No traces of TBP and n-dodecane were detected. The resulting disinfectant solution is diluted with water to a concentration of active chlorine of 1, 2, 3, 4, 5, 6, 7, 8, 9 g / dm ³ / from 0.1 to 0.9 wt./respectively.

 The disinfecting activity of the solution is determined using test objects infected with various microorganisms. At the same time, for each microorganism, the minimum killing dose is set at an exposure of 10, 15, 30 and 45 minutes. The results are shown in table 2.

Example 3. In the reactor load 5 dm ^{3 of} water, 2 kg of sodium hydroxide and 1.8 dm ^{3 of a} mixture of TBP / 40 vol. / And n-dodecane / 60 vol. /. Upon cooling to -33 ^o C and constant stirring, the resulting mixture is chlorinated. Hypochlorous acid resulting from this is immediately extracted with a mixture of TBP and n-dodecane. After settling, the organic phase containing a solution of hypochlorous acid in a mixture of TBP and n-dodecane is separated. To the resulting solution was added 0.3 dm ^{3 of a} 48% aqueous sodium hydroxide solution / sodium hydroxide concentration of 12 mol / dm ³ / and stirred for 10 minutes. After delamination of the resulting emulsion, the aqueous phase is separated containing a disinfecting solution with a pH of 11.8 of the following composition wt. sodium hypochlorite 32.5; sodium chloride 0.5; sodium hydroxide 2.0; water is the rest. No traces of TBP and n-dodecane were detected.

The resulting disinfectant solution is used to disinfect natural and waste water and linen. For the disinfection of linen, a portion of / 0.06 dm ³ / of the obtained disinfectant solution is diluted with water to an active chlorine concentration of 0.2 wt. / 2 g / dm ³ / and soaked in it linen infected with bacterial, including tuberculosis / mako-bacteria /, and viral etiology. Table 3 shows the data on the total time of disinfection required during the processing of linen.

The second part of the obtained disinfectant solution is used to disinfect water from the Neva River and wastewater. When treating water from the Neva River with a disinfecting solution for 15 minutes already at a dose of 0.2-0.5 mg of active chlorine per 1 dm ^{3 of} water, its disinfection is achieved at the initial BGKP index (BGKP the number of bacteria of the Escherichia coli group is 1 dm ³ ) 1-15 million 0.01 dm ^{3 of the} resulting solution is sufficient for disinfection of up to 6 m ^{3 of} water.

When treating wastewater having an initial titer of BGKP (BGKP is the smallest volume of water in dm ³ , which contains 1 bacterium of the group of Escherichia coli) less than 10 ^-6 , the amount of disinfecting solution at which disinfection is achieved is 2.0-10 mg dm ³ for active chlorine, i.e. 0.01 dm ^{3 of the} obtained disinfectant solution is sufficient for disinfection of 0.3-1.5 m ^{3 of} water.

Example 4. A disinfecting solution with a pH of 10.4 of the following composition, wt. sodium hypochlorite 12.7; sodium chloride 0.05; sodium hydroxide 2.2; water - the rest is prepared in the same way as described in example 1. The resulting disinfectant solution is diluted with water to a concentration of active chlorine, respectively 1 g / DM ³ / 0.1 wt. /, 2 g / DM ³ / 0.2 wt. / 3 g / dm ³ / 0.3 wt. / And 5 g / dm ³ / 0.5 wt. /. The disinfectant activity of the solution is determined using test objects in the same way as described in example 2. The results obtained are shown in table 4, the same results are given for comparison for a disinfectant solution containing sodium hypochlorite obtained by electrolysis / Methodological instructions for the use of sodium hypochlorite produced at the Saner-5-30, Saner-5-120, Saner-5-240, Saner-5-400 units for disinfection in medical institutions. M. GK sanitary and epidemiological surveillance of the Russian Federation, 1993, p. 5-8 /.

 Example 5. Disinfectant solution with a pH of 9.3, containing, by weight. sodium hypochlorite 12.7; sodium chloride 0.05; sodium hydroxide 1.0 in water, prepared in the same manner as described in example 1.

 The obtained disinfectant solution is used for disinfecting linen in the same way as described in Example 3. The results are shown in table 5. The same results are given for comparison with a disinfectant solution of sodium hypochlorite obtained by electrochemical methodology / Methodological instructions for the use of sodium hypochlorite produced in plants Saner-5-30, Saner-5-120, Saner-5-240, Saner-5-400, for disinfection in medical institutions. M. GK sanitary and epidemiological surveillance of the Russian Federation, 1993, p. 5-8 /.

 Example 6 / control /. Check the disinfectant activity of a sodium hypochlorite solution having a composition in accordance with GOST 11086-76 obtained by chemical means using test objects, as described in example 2, with an exposure of 60 minutes. The results are shown in table 6.

 The gypsum test solution of sodium hypochlorite does not disinfect the bacillus of anthracoid and trichophytone.

 Example 7 / control /. A disinfecting solution of sodium hypochlorite having a composition in accordance with GOST 11086-76, obtained by chemical means, is used for disinfection of linen, which is carried out as described in example 3. The results are shown in table 7.

 The test solution of sodium hypochlorite does not have a disinfecting effect on linen contaminated with tuberculosis bacteria.

Claims (1)

1 Disinfecting solution, including sodium hypochlorite, sodium hydroxide, sodium chloride and water, characterized in that it contains sodium hypochlorite mixed with sodium chloride, obtained by direct exposure to hypochlorous acid, dissolved in a mixture of tributyl phosphate and n-dodecane, with an aqueous solution of hydroxide sodium in the following ratio of components, wt. 3 Sodium hypochlorite7 1.0 32.53 Sodium hydroxide7 0.1 2.23 Sodium chloride7 0.0005 0.53 Water7 Else

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