Method of collecting oil or oil products from water surface (versions)

FIELD: chemistry.

SUBSTANCE: surface of a film of oil or oil products is treated with a reagent which contains a natural polymer and the reaction product is collected. The reagent used is polysaccharide microgel with mass of 20000-200000 Da and particle size of 50-600 nm in an aqueous solution with concentration of not less than 0.2 g/l. According to the first version of the method, before and after spraying the reagent, the periphery of the film of oil or oil products is treated with a biodegradable surfactant in the form of an aqueous solution with concentration of not less than 0.1 g/l. According to the second version of the method, the reagent is first mixed with a biodegradable surfactant in the form of an aqueous solution with concentration of not less than 0.1 g/l. Mixing is carried out until the ratio of the polysaccharide microgel to the biodegradable surfactant is 12:1-2:1.

EFFECT: high efficiency of the process of collecting oil or oil products from a water surface, low specific consumption of reagents and low residual content of said reagents in water.

2 cl, 6 ex

 

Group of inventions relates to methods of treatment of stains from oil or petroleum products and can be used to collect the film of oil, oils, oil, fuels and hydrocarbons for the purpose of cleaning the surface of the water, and for cleaning oil-contaminated or oil-water flows.

The known method of collecting oil from a water surface in case of emergency spills, including uniform spreading of the oil slick on sorbing means but the basis of waste of wood processing, the absorption of oil or oil products, followed by extraction of the obtained layer from the water surface by mechanical means, characterized in that for the purpose of increasing the efficiency of the collection process and reduce the cost of the way as sorbing means use of hydrolytic lignin with a moisture content of 8-15% with a volumetric flow of his 15-35% of the volume of spilled oil or oil products [patent RU 2033389, C02F 1/40, E02B 15/04, 1991].

The disadvantage of this method is the complexity of applying absorbing means on the surface of the oil slick, as well as high consumption of sorbent in the processing of thin films of oil.

The known method of collecting surface water oil spill, including spraying ferromagnetic absorbent and collect with absorbent oil, characterized in that collected from the surface of the mixture of water, oil and a�pumped through the sorbent magnetizer, includes magnetic plate with anti-friction coating, and then through the baffle, in which the coagulation of the ferromagnetic particles of absorbent material, and further enlarged absorbent agglomerates of oil separated from water [patent RU 2466238, E02B 15/04, C02F 1/48, 2011].

The disadvantage of this method is the complexity of the method, the use of special equipment for collecting oil from the water surface.

The closest in technical essence and the achieved result is a method of sorption of oil products from water surfaces and soil, including spraying sorbent on the basis of polyvinyl chloride with the subsequent recovery of oil. The method is characterized in that to increase the selectivity and efficiency of sorption as a sorbent use polystyrene, polypropylene, polyethylene, their copolymers in either the molecular ratio of the polydispersity of the particles 5-200 μm [application No. EN 94030825, IPC E02B 15/04, C02F 1/28, 18.08.1994]. This method is adopted for the prototype.

The disadvantage of this method is the entrainment of fine particles by air currents and the secondary pollution of their environment, since these polymers do not biodegrade in natural conditions and are a danger to living organisms.

A common disadvantage of known methods is the use of solid sorbents that are difficult n�wear on the surface of oil spills a large area without significant loss of reagent as well as that used in the process of gathering the reagents remain in the water column and harm the environment.

The objective of the claimed group of inventions is to improve the efficiency of the process of collecting oil from the water surface while increasing the environmental safety of this process.

The technical result, which directed the claimed group of inventions is to reduce the specific consumption of reagents used in the process of collecting oil from the water surface, as well as reducing the residual amounts of these reagents in water.

The technical result is achieved in that according to the first embodiment of the inventive method of collecting oil from the water surface comprises treating the surface of the film of oil or petroleum products with a reagent containing a natural polymer, with subsequent collection of the product of their interaction. Unlike the prototype in the inventive method the surface of a film of petroleum oil or oils treated with a reagent, which take microheli polysaccharides weight of from 20,000 to 200,000 daltons and a particle size of from 50 to 600 nm in aqueous solution with a concentration of at least 0.2 g/l, before or after spraying of the reagent to the contours of a film of petroleum oil or oils treated with a biodegradable surface-active�th substance in the form of an aqueous solution with a concentration of at least 0.1 g/L.

The technical result is also achieved by the fact that according to the second embodiment of the inventive method of collecting oil from the water surface comprises treating the surface of the film of oil or petroleum products with a reagent containing a natural polymer, with subsequent collection of the product of their interaction. Unlike the prototype in the inventive method the surface of a film of petroleum oil or oils treated with a reagent, which take microheli polysaccharides weight of from 20,000 to 200,000 daltons and a particle size of from 50 to 600 nm in aqueous solution with a concentration of at least 0.2 g/l, the reagent is premixed with biodegradable surface-active substance in an aqueous solution with a concentration of at least 0.1 g/l, wherein the mixing is carried out until reaching the ratio of microgale polysaccharides to biodegradable surfactant equal to the ratio of 12:1 to 2:1.

Microheli represent a branched polymeric colloidal particles with a diameter of 0.01-1 μm, which are able to swell in solvents due to electrostatic or steric repulsion between the charged groups. They are formed as a result of the directed polymerization of monomers or pH-triggered neutralization of solutions of synthetic or natural polymers bearing carboxyl or amino group. To microllam policy�aridol, used in this invention are colloidal solutions of natural polysaccharides:

viscosimetry (<40%) carboxymethylcellulose and its salts with aliphatic amines (butylamine, benzylamine, Ethylenediamine, hexamethylenediamine); chitosan with degree of deacetylation 90-97%; pectin with a residual amount of methoxy groups <25%. The molecular weight of products may vary from 20 thousand to 200 thousand Yes, with high molecular weight (more than 200 thousand Da) and low molecular weight (less than 20 thousand Yes) derivatives of polysaccharides not applicable for this technology. Microheli polysaccharides used in this invention, can be obtained by physical Association or chemical crosslinking. For more sustainable for a long time microheli polysaccharides used chemical cross-linking of polymeric chains of polysaccharides with anhydrides and activated esters of dicarboxylic acids, diisocyanates, diisocyanates and other cross-linking agents. The diameter of the chemically cross-linked microgel particles of polysaccharides varies preferably in the range of 50-600 nm. Experimental data show that the minimum concentration of microgale polysaccharides in the reagent should be at least 0.2 g/L. the use of more concentrated solutions provides guaranteed e�effect, however, this leads to greater consumption of microgale polysaccharides.

As surfactants in the claimed group of inventions use biodegradable compound, which ensures the environmental safety of this technology. In combination with microheli on the basis of carboxymethyl cellulose is preferable to use a cationic surfactant, and in combination with microgame based on chitosan - anionic surfactants. Examples of biodegradable surfactants are derivatives of cyclic acetals, Alkylglucoside, esters of choline and fatty acids, esters of betaine, phosphate esters of fatty alcohols. The minimum concentration of surfactant in the aqueous solution should ensure the contraction of the oil film and reduce the spot area of petroleum or petroleum products. This property depends on the magnitude of the surface tension at the air - water. Experimental data show that for most surfactants contraction of the oil film is achieved when the concentration in the aqueous solution is not less than 0.1 g/L.

A mixture of microgale polysaccharides with surface-active substance forms a stable foam when applying the mixture on the surface film of oil or oil products at the same time the origin�odit contraction film which reduces its size, and encapsulation of oil or oil products, which prevents their spreading on the surface of the water. Thus, the use of microgel mixture of polysaccharides and surfactants provides a synergistic effect. Surfactants exhibit high affinity for the interface and lower the surface tension at the boundary of water and air, at the same time, microheli polysaccharides have a high affinity for oil and oil products, which is formed of a viscous film on the surface thereof. Together, these effects lead to the formation of stable droplets of oil or oil products and their agglomerates on the surface of the water, forming a jelly-like mass suitable for gathering and extraction from the water surface. The use of microgale polysaccharides and surfactants separately is less efficient as spraying microheli polysaccharides leads to the contraction of oil films, and the use of surfactants formed lenses and drops melt again on the surface of the water after 10-15 minutes because of the fall in the concentration of surfactants on the water surface and its interaction with the oil.

The ratio of the reagent and biodegradable surfactants in the mixture d�should be in the range from 12:1 to 2:1. The upper bound of the range of the ratio of the reagent and biodegradable surfactants in the mixture is determined by the necessity of binding a surfactant reagent, if the ratio of the reagent and biodegradable surfactants in the mixture is above the ratio of 2:1, the excess surfactant will dissolve in water in the form of micelles and pollute the environment. The lower limit of the range of the ratio of the reagent and biodegradable surfactants in the mixture due to the need to pull the oil film on the water surface, if the ratio of the reagent and biodegradable surfactants in solution will be lower than the ratio of 12:1, the efficiency of the surfactant decreases, and the area of the oil film or oil is not reduced.

In all embodiments of the inventive method the reagent and the mixture with surface-active substance are sprayed with a special device (hose, spray gun) or applied in the form of foam directly on the surface film of oil or oil products.

After processing the film of oil or petroleum products with a reagent and surfactants, the boundaries of the film are shielded by means of nets or vouchers. In addition, fencing of a film of petroleum oil or oils can �to activates by contouring it with nets or booms, pre-treated microheli polysaccharides and/or surface-active substances, their properties can be measured directly with the introduction of mesh or Bon in the water. An additional advantage of the inventive method is that the use of surface-active substances protects the device used for collecting the oil boom, booms, etc.) from oil pollution. The claimed method allows to reduce the impact of petroleum or petroleum products on the environment, as adsorbed on surfaces, microheli polysaccharides and surfactants prevents the buildup of oil or oil products on these surfaces.

After processing the film of oil or petroleum products with microheli polysaccharides and biodegradable surfactants, collect oil or oil products with the help of pumps, nets or Kemerov. Using standard techniques of data collection, the effectiveness of which increases due to the fact that after interaction with microheli polysaccharides oil is encapsulated in the state, it does not spread and does not stick to the surface equipment for the collection.

The claimed method in comparison with the prototype is characterized by a number of new significant features, ensuring the achievement of the technical result - the use�s to collect from the water surface stains of oil or oil combination microheli polysaccharides with biodegradable surfactants in aqueous solutions.

A comparison of the proposed method with the known allows to make a conclusion on compliance of the claimed solution to the criterion "novelty".

Neither microheli polysaccharides or mixtures thereof with biodegradable surfactants has not previously been used for the collection of films of oil or oil products from the water surface. The use of biodegradable surfactants in combination with microheli polysaccharides helps to avoid breaking the oil into smaller particles and their distribution in the water column. In addition, the inventive method allows to significantly increase the collection efficiency of oil or oil products from the water surface due to the simultaneous decrease of the area of the film and transfer of crude oil in the encapsulated state.

The above allows to make a conclusion about conformity of the proposed technical solution the criterion of "inventive step".

The proposed method can be successfully used for the elimination of oil spills or oil on the surface of the water. Method feasible in real conditions, using known materials and substances. This allows us to conclude that the claimed solution to the criterion "industrial applicability".

The claimed group of inventions is characterized by two variants of the method of collecting oil from the surface �odes, which are United by one technical vision and help to achieve the same technical result - reduction of specific consumption of reagents used in the process of collecting oil from the water surface, and reducing the residual amount of these reagents in water.

The inventive method is characterized by the following examples of specific performance.

Example 1 (invention)

The collection of films of crude oil from the water surface using physically associated microgel based on chitosan and cationic surfactants in aqueous solutions.

Chitosan (1 g) with degree of deacetylation of 95% and a molecular weight of from 60 to 200 thousand Yes was dissolved in 1 l of 0.01 M hydrochloric acid. To this solution was added a solution of sodium hydroxide 0.05 M to pH 7.5. The resulting suspension of chitosan microgel centrifuged for more concentrated suspensions (5 g/l), which was used to process the oil film. A film of oil in the pool contribut solution palmitoylation by spraying an aqueous solution with a concentration of 0.1 g/l on the perimeter of the oil film. While there is a shrinking of the film with the formation of lenses and large drops in the center, which is treated with a suspension of chitosan microgel (0.2 g/l). While there was the appearance of gel formations on the surface of oil droplets and the formation of AGL�of Muratov, which were collected using fine-meshed network.

Example 2 (invention)

The collection of films of crude oil from the water surface using physically associated microgel based on salts of carboxymethyl cellulose and anionic surfactants in aqueous solutions.

Sodium salt of carboxymethyl cellulose (20 g) with degree of substitution by carboxymethyl groups in the range of 15-50% and a molecular weight of from 30 to 120 thousand Yes was dissolved in 1 l of water. To this solution was added concentrated hydrochloric acid until acidic pH=3-4 reactions. The resulting microgel solution of carboxymethyl cellulose with a concentration of 2 wt.% was diluted with water ten times and used to contain the spill. For this film of oil in the pool first contribut solution of phosphoric ester of catelouge alcohol by spraying of a solution with a concentration of 3 g/l on the perimeter of the film. While there is a shrinking of the film with the formation of lenses and large drops in the center of that process microgel suspension of carboxymethyl cellulose (0.2 g/l). This has resulted in gel formation on the surface of oil droplets and the formation of agglomerates with sizes of 2-3 cm, which were collected using fine-meshed network.

Example 3 (invention)

The collection of films of crude oil from the water surface using chemically linked microgel �and the basis of pectin and nonionic surfactants in aqueous solutions.

Pectin (5 g) with a degree of methoxylation 1-25% and a molecular weight of from 20 to 100 thousand Yes was dissolved in 1 l of a solution of sodium hydroxide (2 g/l). To this solution was added 2 g of benzylamine hydrochloride and 200 mg diisocyanatobutane. After complete dissolution the solution was added 3 ml of formalin and left for 2 h under vigorous stirring. The resulting solution with a concentration of 0.5% was acidified using and centrifuged to obtain a more concentrated suspensions (5 g/l), which is then again podslushivaet sodium hydroxide and used for collecting the oil film. The microgel suspension of pectin (5 g/l) was sprayed over the film of oil in the pool. While there was the appearance of gel formations on the surface of oil droplets, which led to the formation of clots. For more dense agglomerates on the oil spill dealt a solution steelsecurity (2 g/l). While there was a decrease in the area of the stain with the formation of lenses and large clots in the heart, which was collected using a fine-meshed network.

Example 4

The collection of films of crude oil from the water surface using a mixture of aqueous solutions of physically associated microgel based on chitosan and anionic surfactants

Chitosan (1 g) with degree of deacetylation of 95% and a molecular weight of from 60 to 200 thousand Yes was dissolved in 1 l of 0.01 M hydrochloric acid. To this solution add�backed by the sodium hydroxide solution 0.05 M to pH 7.5. To the resulting suspension of chitosan microgel (1.2 g/l) was added a solution of anionic surfactant (cetilistat) with a concentration of 0.1 g/l and the resulting mixture was used for film processing oil, wherein the ratio of microgale polysaccharides and surfactants in the final mixture was 12:1. The mixture was sprayed over the film of oil in the pool. While there was a contraction of the oil film and the appearance of the gel formations on the surface of oil droplets, which led to the formation of agglomerates, which were collected using fine-meshed network.

Example 5

The collection of films of crude oil from the water surface using a mixture of aqueous solutions of physically associated microgel based on salts of carboxymethyl cellulose and cationic surfactants

Sodium salt of carboxymethyl cellulose (20 g) with degree of substitution by carboxymethyl groups in the range of 15-50% and a molecular weight of from 30 to 120 thousand Yes was dissolved in 1 l of water. To this solution was added concentrated hydrochloric acid until acidic pH=3-4 reactions. The resulting solution of carboxymethyl cellulose microgel was diluted with water to obtain a concentration of 0.6 g/l To microgel suspensions of carboxymethyl cellulose was added an aqueous solution of a cationic surfactant (palmitoylation) with a concentration of 0.1 g/l and the resulting mixture was used for processing film of oil, when it� the ratio of microgale polysaccharides and surfactants in the final mixture was 6:1. The finished mixture is sprayed over the film of oil in the pool. While there was a contraction of the oil film and the appearance of the gel formations on the surface of oil droplets, which led to the formation of agglomerates with sizes of 2-3 cm, which were collected using fine-meshed network.

Example 6

The gathering film of crude oil on the water surface using a mixture of aqueous solutions of physically associated microgel based on salts of carboxymethyl cellulose and cationic surfactants applied in the form of foam.

Sodium salt of carboxymethyl cellulose (20 g) with degree of substitution by carboxymethyl groups in the range of 15-50% and a molecular weight of from 30 to 120 thousand Yes was dissolved in 1 l of water. To this solution was added concentrated hydrochloric acid until acidic pH=3-4 reactions. The resulting solution of carboxymethyl cellulose microgel was diluted with water to obtain a concentration of 0.4 g/l To microgel suspensions of carboxymethyl cellulose was added cationic surfactant (palmitoylation) to a concentration of 0.2 g/l and the resulting mixture was used for film processing oil, wherein the ratio of microgale polysaccharides and surfactants in the final mixture was 2:1. The mixture was applied in the form of foam around the edge of the oil slick in the pool. While there was a contraction of the oil film and the appearance of gel formation on the surface�ness oil droplets, which led to the formation of agglomerates with sizes of 2-3 cm, which were collected using fine-meshed network.

The claimed group of inventions allows to solve the task and provides the technical result - reduction of specific consumption of reagents to 1-5 ml solution of 1 m (10-25 times lower than the nearest analogues), and also reduces the residual amount of the reagents used in water up to the minimum concentration at which the reagents has no adverse impact on the environment.

1. Method of collecting oil from a water surface, comprising treating the surface of the film of oil or petroleum products with a reagent containing a natural polymer, with subsequent collection of the product of their interaction, characterized in that the surface film of oil or oil products is treated with a reagent, which take microheli polysaccharides weight of from 20,000 to 200,000 daltons and a particle size of from 50 to 600 nm in aqueous solution with a concentration of at least 0.2 g/l, in this case, before or after spraying of the reagent to the contours of a film of petroleum oil or oils treated with a biodegradable surface-active substance in an aqueous solution with a concentration of at least 0.1 g/L.

2. Method of collecting oil from a water surface, comprising treating the surface of the film of oil sludge� oil reagent, contains natural polymer, with subsequent collection of the product of their interaction, characterized in that the surface film of oil or oil products is treated with a reagent, which take microheli polysaccharides weight of from 20,000 to 200,000 daltons and a particle size of from 50 to 600 nm in aqueous solution with a concentration of at least 0.2 g/l, the reagent is premixed with biodegradable surface-active substance in an aqueous solution with a concentration of at least 0.1 g/l, wherein the mixing is carried out until reaching the ratio of microgale polysaccharides to biodegradable surfactant equal to the ratio 12:1 ÷ 2:1.



 

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3 dwg

FIELD: chemistry.

SUBSTANCE: method consists in mixing cyano-containing solutions and pulps with hydrogen peroxide and a gas ozone-oxygen mixture with the ozone concentration of more than 160 g/m3, in the ozone/hydrogen peroxide ratio of 1.5:1, pH 11-12, temperature of 45-50°C in the presence of copper ions. The cyano-containing solutions and pulps are deactivated in the copper ion concentration of not less than 1:8 to the cyanide and rhodanide concentration.

EFFECT: higher rate and effectiveness of deactivating the cyano-containing solutions and pulps, lower consumption of agents and power costs, improved economical efficiency of the process.

2 cl, 2 ex

FIELD: biotechnology.

SUBSTANCE: biohybrid composite material for sorption and degradation of crude oil and petroleum products is proposed. The material is a thermoplastic polymer with fibre-forming properties - acrylonitrile copolymer with methyl acrylate. It comprises incorporated phosphorus-containing cationites and/or nitrogen-containing anionites, the cell walls of aquatic plants of the family Lemnaceae (Lemnaceae) and immobilized cells of bacteria-oil destructors.

EFFECT: composite material has high adsorption capacity and a higher degree of biodegradation of petroleum hydrocarbons.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the field of natural water purification for economic-drinking and industrial water supply, including slightly muddy coloured low-temperature water. The method includes the reagent processing of water with a coagulant and a flocculant, carrying out volume coagulation under the conditions of mechanical mixing, clarification in horizontal settling tanks, equipped with floatation chambers at the output, filtration, decontamination of the purified water, collection of washing water into a balancing reservoir with its further mixing with initial water.

EFFECT: provision of the drinking water quality independent on seasonal fluctuations of the initial water quality and temperature conditions, increased degree of clarification of water to be coagulated before filtration, reduction of the washing water consumption.

1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: inventions can be used for processing sewage waters and conditioning sludge before its dehydration. A lime-based composition for processing waters and sludge contains, at least, one mineral agent, which contains at least lime and at least one linear, branched and/or transversely cross-linked hydrophilic organic polymer of a non-ionic, anionic, cationic or amphoteric origin. The mineral agent contains slaked lime in the solid phase, with the organic polymer being includes on the surface and inside the said solid phase of slaked lime, where the said lime-based composition represents a solid composition. The method of preparing the composition for processing waters and sludge includes the introduction of the mineral agent and a water solution, dispersion or an inverse emulsion, which contains the organic polymer and water, in contact. The method includes the realisation of a partial reaction of quicklime with all or a part of water, which contains the organic polymer, obtaining slaked lime in the solid phase, including the organic polymer.

EFFECT: inventions provide the effective conditioning of sludge to be dehydrated due to the distribution of the polymer in a smaller amount relative to the mineral agent.

15 cl, 7 tbl, 5 ex

FIELD: machine building.

SUBSTANCE: device makes it possible to treat not only water but other liquids close in viscosity to water, for instance, benzenes, diesel fuel, sunflower seed oil, wine material, etc. The water treatment device comprises chambers installed at the distance from each other that are open from top with a layer of filtering material, pipelines with hydraulic locks, supply and drain nozzles. Supply nozzles are installed under the layer of filtering material. Chambers are divided into filtering elements with multi-layer filtering materials, which are retained tightly along the perimeter with multi-section frames. Each chamber for effective operation in regeneration mode is provided at least by one vibrator with parameters, which are determined by formulas, and a radiator for ultrasonic frequency for disinfection at impact capacity of at least 2 W/cm.

EFFECT: invention makes it possible to improve ten times and more the main process characteristics of a filter and perform simple regeneration of filtering material and its disinfection.

FIELD: machine building.

SUBSTANCE: water treatment device includes settling tanks with thin synthetic nets for levelling of speeds of treated water, in the whole clear section of the settling tank, and also with the help of filtering chambers with substantially improved structure, with new filtering materials from polypropylene, with the possibility of performance of simple regeneration, disinfection.

EFFECT: device provides for improvement of main process characteristics ten and more times.

FIELD: devices for purification of household and industrial sewage.

SUBSTANCE: the invention is dealt with devices for purification of household and industrial sewage and intended for electrical and cavitational treatment of sewage containing a large quantity of organic compounds. The device for purification of sewage consists of a body made out of a dielectric material partitioned by diaphragms for two electrode chambers and one working chamber, that contains a filtering material. The electrode chambers have cavitational field sources installed and the working chamber is supplied with a the bubbler installed in it. The technical result consists in an increase of recuperation of the filtering material at the expense of application of a cavitational field to it, decrease of the microbiological semination, and an increase of cavitational effect on particles.

EFFECT: the invention ensures an increase of the filtering material recuperation, decreased microbiological semination and increased the cavitational effect on particles.

1 dwg

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