RU2132367C1 - Water-soluble detergent for cleansing surfaces from organic contaminations - Google Patents

Abstract

FIELD: water-soluble detergents. SUBSTANCE: water-soluble detergent containing nonionic surface-active substance and active additive has, additionally, polyelectrolyte at the following ratio of components, mas.%: nonionic surface-active substance, from 0.2 to 14.0; polyelectrolyte, 2,5-5.5; active additive, the balance. Used as active additive is sodium oxide or composition containing, mas.%: sodium oxide, 81.0-83.4; carbamide, 16.6-19.0; or composition containing, mas.%: sodium oxide, 40.0-46.0; sodium metasilicate of general formula Na₂O•nSiO₂, where n is I - 54.0-60.0; or composition including, mas. %: sodium oxide, 39.5-44.0; sodium metasilicate of general formula Na₂O•nSiO₂, where n = I - 55.0-59.2; carbamide, 0.8-1.5. EFFECT: improved efficiency of cleansing; increased rate of detergent reusing. 6 ex

Description

 The invention relates to the field of chemistry, namely to water-soluble alkaline detergents for cleaning metal, glass, ceramic surfaces, and also soil from hydrocarbon contaminants such as oil, oil products, lubricants, technical and household fats and oils.

 The invention can be used mainly for chemical-mechanized washing of technological and transporting containers, followed by separation of the contaminated phase and repeated use of a detergent solution.

 The invention can also be used in everyday life, as the proposed detergent does not contain toxic products and is environmentally friendly.

 Currently, a number of compositions of water-soluble detergents are known that are used to clean various surfaces from pollution of organic nature (oil, oil products, fats, oils, etc.).

 In the development of these compositions, along with ensuring a high washing action, it is very important from the point of view of environmental protection that the task of subsequent treatment of contaminated wash water with the possibility of reuse of the washing solution for the same purpose. At the same time, the most effective and economical way to clean aqueous-alkaline washing solutions contaminated with organic substances is to separate the emulsion formed during the cleaning process into the aqueous and organic phases. The implementation of this process is possible if the detergent, on the one hand, has a high emulsifying ability, and on the other hand, provides a quick and maximum complete separation of the spent emulsion.

 Despite the relevance of the problem, very few of the currently known water-soluble detergents satisfy the above requirements. This is explained by the fact that components of various functional purposes, introduced into the compositions to provide a complex complex of detergent properties, when combined in a solution often enter into antagonistic relations in terms of achieving an optimal balance of properties in emulsification-demulsification processes.

 It should be noted that the qualitative composition of the known detergents of the considered group is quite uniform and usually includes one or more surfactants, water-soluble inorganic salts of alkali metals and, in some cases, various organic additives. Strengthening one or more functions of the detergent is achieved, as a rule, by changing the balance of these components in the composition.

 Thus, water-soluble detergents containing surfactants of various types and an active alkaline additive, including soda ash, sodium silicate in the form of various modifications and sodium salts of phosphoric acid (SU 1824431, C 11 D 1/34, publ. 1993) are widely known.

 These compositions have a fairly high detergent effect, however, due to the formation of a stable emulsion of washed impurities in the volume of the spent solution, it is not possible to reuse the washing solution.

 Known water-soluble detergent TEMP-100 / SU, 644819 C 11 D 1/34, publ. 1979 /, intended for cleaning, in particular, metal surfaces from the remains of fuels and lubricants, oil and mud deposits and other types of pollution. The product contains a non-ionic surfactant, sodium metasilicate, di- or trisodium phosphate, soda ash, urea and a small amount of potassium salt of hydroxyethylated alkyl phenols of phosphoric acid or ethanolamine salt of alkyl esters of phosphoric acid.

 When using this detergent, a significantly less stable emulsion is formed with washed away impurities, however, their residual concentration in the aqueous phase of the spent solution after sludge is quite high, which limits the possibility of repeated use of the detergent solution.

 The insufficient complete separation of the spent emulsion can be explained by the antaganism in the stabilization ability between nonionic surfactants and salts of phosphoric acid alkyl esters, as well as by the blocking of the demulsifying properties of urea due to the possible reaction of urea with acidic phosphate residues.

The detergent TEMP-100D / SU 973607, C 11 D 1/835, publ. 1982 /, which differs from the aforementioned TEMP-100 agent in that instead of urea, an additive inert with respect to the acid residues of phosphates is introduced - a polymer of the quaternary salt of N, N ¹ -dialkyl-N, N-diallylamonium with m.m. 30000 - 700000.

 TEMP-100D detergent has a rather high detergent effect and provides the possibility of a 3-fold use of a detergent solution separated from the contaminated phase after sludge.

 However, a significant drawback of the detergent in question (as well as all the detergents described above) is the use of relatively large amounts of phosphate-containing compounds in them, the ingress of which into wastewaters leads, as you know, to eutrophication of water and thereby harm the environment. Therefore, when developing detergents, they are currently trying, if possible, not to introduce phosphate-containing compounds into the composition, despite their high washing activity.

 Of the known phosphate-free water-soluble detergents intended for cleaning surfaces from organic contaminants, the closest to the claimed composition and the achieved effect is a water-soluble detergent / RU 2010845, C 11 D 3/04, publ. 1994 /, containing a nonionic surfactant in an amount of 5 to 10 wt.%, As well as an active additive, including (calculated on the composition) from 15 to 25 wt.% Sodium sulfate, from 15 to 25 wt.% Sodium silicate, from 0 , 05 to 5.00 wt.% Bischofite (magnesium chloride obtained by crystallization of sea water) and from 35 to 65 wt.% Soda ash (sodium carbonate).

 The specified tool has a high detergent effect against various organic contaminants. When using it, a relatively quick and complete separation of the spent emulsion is achieved (the residual concentration of oil contaminants emulsified in the aqueous phase is up to 20 mg / l according to published data), which allows the use of a washing solution for cleaning repeatedly (5-8 times).

 The objective of the present invention is to provide a water-soluble detergent capable of quickly and efficiently cleaning various surfaces from a wide range of hydrocarbon contaminants, as well as providing the possibility of significantly increasing the frequency of reuse of the detergent solution due to a more complete phase separation of the emulsion formed during the cleaning process.

The problem is solved in that in a water-soluble alkaline detergent containing a nonionic surfactant and an active additive, according to the invention, a polyelectrolyte is additionally included, and sodium carbonate, or a composition including, wt.%, Is used as an additive in the agent:
Sodium carbonate - 81.0 - 83.4
Urea - 16.6 - 19.0,
or composition comprising, wt.%:
Sodium carbonate - 40.0 - 46.0
Sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1 - 54.0 - 60.0,
or composition comprising, wt.%:
Sodium carbonate - 39.5 - 44.0
Sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1, - 55.0 - 59.2
Urea - 0.8 - 1.5,
in the following ratio of components in the tool, wt.%:
Nonionic surfactant - 0.2 - 14.0
Polyelectrolyte - 2.5 - 5.5
Active Supplement - Else
Thus, the task is solved by introducing a polyelectrolyte into a detergent and using sodium carbonate, or a composition, including, wt.%: As an active additive:
Sodium carbonate - 81.0 - 83.4
Urea - 16.6 - 19.0,
or composition comprising, wt.%:
Sodium carbonate - 40.0 - 46.0
Sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1 - 54.0 - 60.0,
or composition comprising, wt.%:
Sodium carbonate - 39.5 - 44.0
Sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1, - 55.0 - 59.2
Urea - 0.8 - 1.5,
in the following ratio of components in the tool, wt.%:
Nonionic surfactant - 0.2 - 14.0
Polyelectrolyte - 2.5 - 5.5
Active Supplement - Else
In the course of experimental studies, the inventors were able to create a composition of water-soluble alkaline detergent, which, due to the optimally balanced composition of the components, successfully solves the problem.

 Despite the fact that the invention is based on knowledge and well-known ideas about the functional role of each of the components of the product, when solving the problem, the authors had to deal with difficulties due to the complexity of the relationships between components of different chemical nature both in a single-phase aqueous solution and in a two-phase system formed in the volume of the solution in the process of cleaning surfaces from hydrocarbon contamination.

 The use of nonionic surfactants in the composition provides good surface wettability and a high solubilizing effect in relation to water-insoluble hydrocarbon contaminants with moderate foaming.

 The introduction of less than 0.2 wt.% The specified component negatively affects the washing ability of the product, and use in the tool more than 14.0 wt. % Surfactant leads to the formation of a hard-to-destroy detergent emulsion in the product to be washed (reverse emulsion).

 At the same time, a nonionic surfactant in the claimed concentration range ensures the universality of the action of the detergent with respect to a wide range of washed hydrocarbons (from light oil products to heavy oil residues).

 As a nonionic surfactant, compounds containing an organic hydrophobic group of one hydrophilic residue can be used, for example, condensation products of alkyl phenols or higher fatty alcohols from ethylene oxide, condensation products of propylene glycol and ethylene oxide or propylene oxide and other similar compounds. It is preferable to use nonionic surfactants that are biodegradable, such as, for example, nonyl phenylethylene oxide with the number of oxide groups from 9 to 12 (neonol) or ethylene propylene glycol esters (syntanol).

 The introduction of a polyelectrolyte in the amount of from 2.5 to 5.5 wt.% Provides, on the one hand, a high emulsifying effect and prevents the absorption of contaminants on the surface being washed at the cleaning stage, and on the other hand, does not adversely affect the speed and the completeness of the separation of the aqueous and organic phases during the sedimentation of the spent emulsion.

 Of the currently known polyelectrolytes, i.e. substances of polymer nature, capable of forming polymer-colloidal complexes in solutions, for example, polymers of acrylic acid or sodium salts of polyacrylic acid with m.m can be used as a detergent. 50,000 - 120,000, as well as the sodium salt of carboxymethyl cellulose (Na - CMC).

 It should be noted that recently the above compounds are increasingly used in detergents mainly to prevent the resorption of organic contaminants on the washed surface. However, the behavior of polyelectrolytes in complex multicomponent systems containing, among other components, inorganic salts prone to hydrolysis in aqueous solutions, has not been studied much, therefore, only as a result of lengthy experiments, the inventors were able to find the optimal concentration limits of the polyelectrolyte content in the composition, in which, along with achieving the goal The invention ensures the stability of aqueous solutions of detergent by preventing precipitation of hydrolysis products.

 The introduction of an active additive into the detergent composition provides, first of all, the required detergency of the solution due to the alkaline properties of the additive. Moreover, as shown by experiments, the task of the invention is equally successfully solved when using the above described types of additives, which expands the possibilities of raw materials in the production of detergent.

 The use of an active additive in the claimed range (80.5 - 97.3 wt.%) Provides, along with high detergency, a balance of emulsifying-demulsifying properties of the detergent.

 Each of the active additives used in the product exhibits additional useful properties in various applications of the detergent.

 So, the use of sodium carbonate as an active additive provides a stronger detergent effect, which is especially important in the case of cleaning surfaces from heavy petroleum products such as fuel oil.

The use as an additive of a mixture of sodium metasilicate with sodium carbonate in the claimed quantitative ratio of these components determines good anticorrosive properties of the detergent, which is relevant in the case of using the product for cleaning metal surfaces. Moreover, it was experimentally established that in the composition of the additive it is necessary to use sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1.

 The introduction of urea in the composition of the active additive increases the cloud point of the detergent solution, which expands the technological capabilities of the surface cleaning process. In addition, urea enhances the demulsifying effect, which is especially important when cleaning surfaces from light oil products.

 A detergent is prepared by simply mixing the components.

 To prepare a detergent solution, a dry detergent is dissolved in water in a ratio of 1:24. The pH of the solution is 13.0 - 13.5.

 Examples of the invention.

 Example 1

A detergent of the following composition was prepared, wt.%:
Neonol AF9-12 - 3.8
Sodium polyacrylate with m.m. 50,000 - 120,000 - 2.7
Soda ash (sodium carbonate) according to GOST 5100-85 - 93.5
Tested an aqueous solution of detergent.

 The washing ability of the solution was determined by the following method.

где α - степень очистки,%,
P₀ - начальная масса пластины, г,
P₁ - масса пластины с загрязнениями, г,
P₂ - масса пластины после обработки моющим раствором, г.0.03-0.06 g of hydrocarbon contamination was applied to the surface of a pre-defatted and suspended metal plate measuring 40 x 27 x 2 mm in size. The plates were held for 2-4 days. The contaminated surface was cleaned by immersion in a washing solution and mechanical stirring of the solution with a stirrer. After cleaning, the samples were washed with water, dried and weighed. The percentage of removed contaminants from the surface of the plate was determined by the formula

where α is the degree of purification,%,
P ₀ - the initial mass of the plate, g,
P ₁ - the mass of the plate with dirt, g,
P ₂ - the mass of the plate after treatment with a washing solution,

 In this example, heating oil was applied to metal plates.

Cleaning was carried out with a washing solution with t = 10 ^o C.

 The degree of purification was 98%.

 The emulsion formed during the cleaning process was poured into a measuring cylinder and left until the organic and aqueous phases were completely separated. After 60 seconds, complete separation of the emulsion was visually observed. To control the completeness of phase separation, the residual concentration of pollution in the aqueous phase was determined according to the industry standard OST 38013-78-85 "Determination of the content of oil products in wastewater".

 The residual concentration was 0.2 mg / L.

 50 cleaning cycles were carried out, in each of which a washing solution separated from the organic phase was used from the previous cycle, while the above indicators of the properties of the solution remained practically unchanged.

 Example 2

A detergent of the following composition was prepared, wt.%:
Syntanol ALM-10 - 3.9
Na-CMC with a degree of polymerization of 400 - 1.5
Soda ash in accordance with GOST 5100-85 - 94.6
Tested detergent solution, as described in example 1.

Crude oil was used as laundered contamination. Cleaning was carried out with a washing solution with t = 20 ^o C. The time of separation of the emulsion is 10 minutes

 The degree of purification was 98%.

 The residual concentration of petroleum products is 0.2 mg / l.

 The frequency of use of the washing solution without deterioration of performance was 30 times.

 Example 3

A detergent of the following composition was prepared, wt.%:
Neonol AF9-12 - 14.0
Sodium polyacrylate with m.m. 50,000 - 120,000 - 5.3
Soda ash in accordance with GOST 5100-85 - 35.1
Sodium Metasilicate - 45.6
The amount of soda ash and sodium metasilicate calculated on the composition of the active additive was 43.5% and 56.5%, respectively.

 Tested detergent solution, as described in example 1.

 As the object of cleaning used carbon steel plates (Art. 3), contaminated with industrial oil "30".

Cleaning was carried out with a washing solution with t = 18 ^o C. The time of separation of the emulsion was 30 minutes

 The degree of purification was 98.5%.

 The residual concentration of petroleum products is 0.2 mg / l.

 The frequency of use of the washing solution without deterioration of performance was 25 times.

 Example 4

A detergent of the following composition was prepared, wt.%:
Neonol AF9-12 - 14.0
Sodium polyacrylate with a degree of polymerization of 400 - 5.0
Soda ash in accordance with GOST 5100-85 - 35.0
Sodium Metasilicate - 45.0
Urea - 1.0
The amount of soda ash, sodium metasilicate and urea in terms of the composition of the active additive is 43.2%, 55.6%, 1.2%, respectively.

 Tests of the washing solution were carried out as described in Example 3. The time for separation of the emulsion was 15 minutes. The remaining indicators coincided with the results of example 3.

 Example 5

A detergent of the following composition was prepared, wt.%:
Neonol AF9-12 - 0.2
Na-CMC with a degree of polymerization of 400 - 2.4
Soda ash in accordance with GOST 5100-85 - 81.2
Urea - 16.2
The amount of soda ash and urea in terms of the composition of the active additive was 83.2% and 16.8%, respectively.

 Tested detergent solution, as described in example 1.

 They cleaned metal plates contaminated with diesel fuel and lighting kerosene.

Cleaning was carried out with a washing solution with t = 23 ^o C.

 The emulsion separation time was 5 minutes for diesel fuel and 20 minutes for kerosene.

 The degree of purification in both the 1st and 2nd cases was 98%.

 The frequency of use of the washing solution without deterioration was 50 times.

 Example 6

 A detergent of the same composition as in Example 1 was prepared.

The washing solution was used to wash the soil contaminated with oil products, for which 4 parts of the washing solution were loaded onto 1 weight part of the soil into the treatment tank and the contents of the container were mixed for 10 min at t = 20 ^o C. Then the contents of the container were defended and after emulsion separation layers of organic and aqueous phases were poured from the tank. The soil remaining in the tank was washed with water to more completely remove surfactants. The washed soil was investigated for the content of oil products and surfactants. The results of the analysis showed that the content of the above substances in the soil does not exceed the level of maximum permissible concentrations (MPC). Detergent solution separated from contaminants was used to wash the soil in 10 washing cycles without deteriorating the results.

 The inventive detergent was pilot-tested in the Wagon Depot of the Bologoe station, the Wagon Depot of the Kemerovo station, as well as at TPP-15 in St. Petersburg.

 Detergent solutions were used to clean tanks of various hydrocarbon contaminants: crude oil, fuel oil, bitumen, diesel fuel, kerosene, and fuel oil sludge.

Used jet processing method at a temperature of the washing solution of 20 - 45 ^o C.

 Using the washing solution returned to the cycle after sedimentation, 120 tanks were washed to the standard degree of purification.

 In addition, a detergent solution was used to clean soil contaminated with heavy oil products in the Bugry village of the Leningrad Region, as well as oil-contaminated soils from Kuwait and Vietnam. Analysis of samples of cleaned soils and soils showed that the concentration of the above contaminants in them is significantly lower than the MPC.

 Thus, the inventive detergent has a number of positive properties. It provides quick and effective cleaning of surfaces from hydrocarbon contamination, quick and complete separation of the emulsion formed during the cleaning process and, accordingly, the possibility of reuse of the detergent solution.

 In addition, the proposed tool has a simple component composition, which makes it economical and technologically advanced in manufacture. The tool is not corrosive to surfaces made of carbon steel, alloy steel, aluminum alloys. The components used are environmentally friendly.

Claims (1)

A water-soluble detergent for cleaning the surface from organic contaminants, containing a nonionic surfactant and an active additive, characterized in that the agent further comprises a polyelectrolyte in the following ratio, wt.%:
Nonionic surfactant - 0.2 - 14.0
Polyelectrolyte - 2.5 - 5.5
Active Supplement - Else,
moreover, as an active additive, the product contains sodium carbonate or composition, including, wt.%:
Sodium carbonate - 81.0 - 83.4
Urea - 16.6 - 19.0,
or composition comprising, wt.%:
Sodium carbonate - 40.0 - 46.0
Sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1, - 54.0 - 60.0,
or composition comprising, wt.%:
Sodium carbonate - 39.5 - 44.0
Sodium metasilicate of the general formula Na ₂ O • nSiO ₂ , where n = 1, - 55.0 - 59.2
Urea - 0.8 - 1.5