Composition for cleaning soil contaminated with oil and motor fuel

FIELD: chemistry.

SUBSTANCE: invention relates to environmental protection. The composition for cleaning soil contaminated with oil and motor fuel comprises peat filler, nitrogen and phosphorus fertiliser, used in ratio N:P2O5=1-10:1, zeolite-clay rock modified with a cationic surfactant, and cation-exchange minerals, with the following content of components, wt %: low- or high-moor peat 44.79-93.989; nitrogen fertiliser, N 0.01-0.15; phosphorus fertiliser, P2O5 0.001-0.06; zeolite-clay rock, modified with a cationic surfactant 1-15; cation-exchange minerals 5-40.

EFFECT: invention provides localisation and biodegradation of a hydrocarbon contaminant with high efficiency and prolonged effect.

6 cl, 4 ex

 

The invention relates to biotechnology, aimed at restoring the environment, subjected to air pollution, in particular to the cleaning of soil contaminated by oil and oil products.

Known composition (Patent RU №2238807 published 27.10.2004)designed for remediation of soils contaminated with oil. Composed of peat and nitrogen-phosphorus fertilizer at the following breakdown: nitrogen fertilizer - 24,25-44,10, phosphate fertilizer - 6,50-8,80, peat (dry substance) - 47,10-69,25 wt.%. This corresponds to the content of 12-15% nitrogen and 1.8-2.3% of phosphorus per 100 g of absolutely dry matter composition at a ratio of nitrogen and phosphorus of 1:0.15 in. Contained in the peat meteorologie microorganisms and included in the known composition of the fertilizers are designed to enhance the biodegradation of oil. The second purpose of the peat sorption holding oil and prevent its further spread in the soil. However, peat is amphiphilic sorbent with along with significant hydrophobic hydrophilic properties that are unfavorable for efficient binding of petroleum hydrocarbons in a wet environment.

Known composition (Patent RU №2422219, published on 27.06.2011) is also based on peat and nitrogen-phosphate fertilizers, which have been added to the zeolite. It is assumed that the zeolite increased the AET sorption activity of the composition of petroleum hydrocarbons. In fact, natural zeolite in a moist soil environment are much smaller than lowland and peat the peat by the ability to retain oil and fuel hydrocarbons and can only reduce the sorption activity of the composition in real soil conditions. In addition, according to research (A.Denisova et all. Soil and Sediment Contamination, 20:824-840, 2011; Khalilova A.F. other proc. XVII international. proc. "Lomonosov-2010", Moscow, 2010. - S), zeolites do not apply to soil additives that enhance the biodegradation of hydrocarbon contaminants.

The closest in technical essence and the achieved result is described composition (Patent RU No. 2450872, published on 20.05.2012), taken as a prototype, which contains non-sterile peat filler, nitrogen and phosphate fertilizer (at a ratio of N:P2O5=2,5-10:1), and zeolite-shale (CGP), the surface of which is repelling agent cationic surfactant (halide Tetra-substituted ammonium) in the following content, wt.%: lowland or intermediate peat - 98,989-84,79; nitrogen fertilizer, N - 0,01-0,15; phosphate fertilizer P2About5- 0,001-0,06; zeolite-clay rock, the modified cationic surfactant - 1-15. Contained in the composition of the organo-modified CGP has a high sorption activity against oil and fuel hydrocarbons. At the same time, when the long presence in the soil environment possible removal of part of the modifier from a modified CGP. The modifier has no toxic effect on humans and warm-blooded animals, however, as the connection relating to the type tetraalkylammonium ammonium cations, has a bactericidal effect, reducing the activity of soil microbiocoenosis, including hydrocarbon-oxidizing microorganisms. As a result, the proposed structure provides only short-bioremediate action on contaminated oil and petroleum products soil.

The claimed invention is an environmentally friendly composition intended for localization and biodegradation of hydrocarbon contaminant (oil and oil products) in soil with high efficiency and duration of action.

The technical result is achieved in that the composition for cleaning soil from oil and oil products contains lowland or peat, which is also the substrate carrier of hydrocarbon-oxidizing microorganisms (MSD), organic fertilizer and sorbent; mineral nitrogen and phosphate fertilizer (at a ratio of N:P2O5=1-10:1) to power the MSD; as an effective sorbent for oil and fuel hydrocarbons zeolite-clay rock, the surface of which is repelling agent cationic surfactant (halide tetraalkylammonium ammonium) (MCHP), and cation-exchange minerals, dedicated to superior quality products is obtained for binding washed out from MCHP modifier, in the following, wt.%:

Lowland or peat44,79-93,989
Nitrogen fertilizer N0,01-0,15
Phosphate fertilizer P2O50,001-0,06
Zeolite-clay rock, the modified cationic surfactants1-15
Cation-exchange minerals5-40

The main difference between the structure of the prototype is that it additionally contains a cation-exchange minerals, are able to bind cations of organic modifier (tetraalkylammonium ammonium). This property cation-exchange minerals eliminates bactericidal effect modifier selected from MCHP during his long stay in the soil. As the cation-exchange minerals in the inventive composition can be used: montmorillonite and clay based on them (bentonites), natural zeolites in the form of a zeolite-containing rocks, glauconites. In water and moist environments at temperatures from 0 to 50°C these minerals and rocks are actively bind all kinds of Tetra-substituted ammonium cations (R1R2R3R4 N+used when modifying CGP. To ensure complete binding of released modifier in the composition is introduced 2-40-fold excess of ion-exchange minerals relatively mcgp. Importantly, the interaction of the modifier and cation-exchange minerals formed product is not inferior or close mcgp on the effectiveness of retention of hydrocarbon pollutants and stimulate their biodegradation. Thus, under these conditions, which is typical for real soil environments, the additional introduction of the cheap cation-exchange minerals not only eliminates the disadvantage of the prototype caused by a partial loss of the modifier from MCHP, but the completion of the active sorbent in soil. Along with this, the constituent minerals are typical for a property - holding due to exchange interactions part nutrients, reducing their leaching from the soil into the groundwater and provides a prolonged effect of cation exchange minerals as stimulators of microorganisms.

In the composition used mcgp with the degree of modification, not exceeding 8% by weight of mineral medium, which contributes to the stability of organo-mineral sorbent. In accordance with this requirement, the interval of the change of the degree of modification mcgp is 1-8%. Upon receipt MCSP used cationic surfactant of the formula: R1R2R3R4N+Hal-. The substituents R1-R3- pyridine or alkyl groups with carbon chain length from 1 to 4 atoms, and/or benzyl; the substituents R4is an alkyl group with a carbon chain length from 1 to 18 atoms; a halogen anion Hal-is chloride or bromide.

Receiving a modified CHP is carried out in aqueous medium at low and medium temperatures (not higher than 50°C). Under these conditions, the hydrophilic centers located on the surface of minerals (zeolite and clay), the exchange interaction with tetraalkylammonium ammonium cations are blocked alkyl groups of the modifier, which gives mcgp hydrophobic properties. The resulting organo-mineral product has a high sorption activity against hydrophobic compounds, including hydrocarbons of oil and oil products, in any humidity conditions until fully hydrated.

Linking available (i.e., not adsorbed by soil and peat) molecules of petroleum hydrocarbons mcgp reduces the toxic effect on the microorganisms provided by the polluter, but also prevents migration of the hydrocarbon contaminant in the soil.

To stimulate the activity of hydrocarbon-oxidizing microorganisms in contaminated p is cue and an increase in the occurrence of biodegradation of crude oil and petroleum products use mineral nitrogen (urea, ammonium or potassium nitrate) and phosphorus (phosphates of alkali and alkaline earth metals) fertilizers, taken in the specified quantity and value.

The composition is prepared as follows: in a mixer put non-sterile lowland or peat, add nitrogen and phosphate fertilizer, then stir until smooth, then add the required amount of cation-exchange minerals and modified CGP, then stirring is continued until a uniform distribution of the components in the composition.

The application of the composition to the hydrocarbon-contaminated soil will be adjusted according to the level of contamination of the soil area to be processed. Regulation is carried out in two ways: by varying the content in the composition of the most expensive cost component - mcgp and/or the application dose of the composition into the soil. This is a good balance between the efficiency of biodegradation of the contaminant and the cost of implementation of environmental activities.

Example 1

The use of a composition with a low degree of contamination (1 g of petroleum hydrocarbons in 1 kg of soil). The application dose of 1 kg/m2.

The composition containing peat in the number 93,989 wt.%, the ammonium nitrate in an amount of 0.01 wt.% in terms of nitrogen, superphosphate in the amount of 0.001 wt.% in terms of R2About5the zeolite-clay is frequently breed Tatar-Strasunskas Deposit in the amount of 5.0 wt.%, and zeolite-shale of the same Deposit in the amount of 1.0 wt.%, gidrofobizirovannogo bromide of hexadecyltrimethylammonium in the amount of 1.0 wt.% from mass CGP, made in the upper (0-20 cm) layer of soil contaminated with diesel fuel. The top layer of soil was tilled and watered. After 3 months were determined by the residual content of diesel fuel in soil. The decrease in the concentration of the pollutant was not less than 93% of the original.

Example 2

The use composition when the average degree of pollution (30 g of petroleum hydrocarbons in 1 kg of soil). The ava - 2 kg/m2.

The composition containing peat in the number 74,88 wt.%, the ammonium nitrate in an amount of 0.1 wt.% in terms of nitrogen, superphosphate in the amount of 0.02 wt.% in terms of P2O5the zeolite-shale Tatar-Strasunskas Deposit in the amount of 20.0 wt.%, and zeolite-shale of the same Deposit in the amount of 5.0 wt.%, gidrofobizirovannogo bromide of hexadecyltrimethylammonium in the amount of 5.0 wt.% from mass CGP, made in the upper (0-20 cm) soil layer. The top layer of soil was tilled and watered. After 3 months were determined by the residual content of diesel fuel in soil. The decrease in the concentration of the pollutant was not less than 96% of the original.

Example 3

The use of the composition at high polluted the I (100 g of petroleum hydrocarbons in 1 kg of soil). The ava - 3 kg/m2.

The composition containing peat in the number 44,79 wt.%, the ammonium nitrate in the amount of 0.15 wt.% in terms of nitrogen, superphosphate in the amount of 0.06 wt.% in terms of R2About5the zeolite-shale Tatar-Strasunskas Deposit in the amount of 40.0 wt.%, and zeolite-shale of the same Deposit in the amount of 15.0 wt.%, gidrofobizirovannogo bromide of benzylhydroxylamine in the amount of 8.0 wt.% from mass CGP, made in the upper (0-20 cm) soil layer. The top layer of soil was tilled and watered. After 3 months were determined by the residual content of diesel fuel in soil. The decrease in the concentration of the pollutant was not less than 98% of the original.

Example 4

The use composition when the average degree of pollution (30 g of petroleum hydrocarbons in 1 kg of soil). The ava - 2 kg/m2.

The composition containing peat in the number 74,88 wt.%, the ammonium nitrate in an amount of 0.1 wt.% in terms of nitrogen, superphosphate in the amount of 0.02 wt.% in terms of P2O5bentonite clay Beslanskogo Deposit in the amount of 10.0 wt.%, and zeolite-shale Tatar-Strasunskas Deposit in the amount of 5.0 wt.%, gidrofobizirovannogo bromide of hexadecyltrimethylammonium in the amount of 6.0 wt.% from mass CGP, made in the upper (0-20 cm) layer of soil is s. The top layer of soil was tilled and watered. After 3 months were determined by the residual content of diesel fuel in soil. The decrease in the concentration of the pollutant was not less than 96% of the original.

1. Composition for treatment of soils contaminated with oil and motor fuel containing peat filler, nitrogen and phosphate fertilizer with a ratio of N:P2O5=1-10:1, zeolite-shale, modified cationic surfactant, characterized in that it further comprises a cation-exchange minerals in the following ratio, wt.%:

Peat filler44,79-93,989
Nitrogen fertilizer N0,01-0,15
Phosphate fertilizer P2O50,001-0,06
Zeolite-clay rock, the modified cationic surfactants1-15
Cation-exchange minerals5-40

2. The composition according to claim 1, characterized in that as peat filler use non-sterile lowland or peat.

3. The composition according to claim 1, characterized in that as a nitrogen fertilizer use urea, ammonia, or to linwu nitrate, as phosphorus - phosphates of alkali and alkaline earth metals.

4. The composition according to claim 1, characterized in that the cationic surfactant use of Quaternary ammonium salts having the formula R1R2R3R4N+Hal-where the substituents R1-R3- pyridine or alkyl groups with carbon chain length from 1 to 4 atoms, and/or benzyl; the substituents R4is an alkyl group with a carbon chain length from 1 to 18 atoms; a halogen anion Hal-is chloride or bromide.

5. The composition according to claim 4, characterized in that the cationic surfactant is 1-8% by weight of the zeolite-clay rocks.

6. The composition according to claim 1, characterized in that as the cation-exchange minerals use montmorillonite and clay based on them (bentonites), natural zeolites in the form of a zeolite-containing rocks, glauconites.



 

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2 tbl

FIELD: chemistry.

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1 ex

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2 dwg, 1 tbl

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5 cl, 2 dwg, 1 tbl

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2 ex

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22 cl, 1 dwg

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2 tbl

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FIELD: environmental protection.

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6 ex

FIELD: disposal of solid waste.

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2 cl, 5 dwg

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EFFECT: increased degree of separation of oil sludge into cleaned oil sludge, water, refuse and mechanical admixtures.

3 dwg

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