Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09C—RECLAMATION OF CONTAMINATED SOIL
  • B09C1/00—Reclamation of contaminated soil
  • B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09C—RECLAMATION OF CONTAMINATED SOIL
  • B09C1/00—Reclamation of contaminated soil
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09C—RECLAMATION OF CONTAMINATED SOIL
  • B09C1/00—Reclamation of contaminated soil
  • B09C1/08—Reclamation of contaminated soil chemically
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K17/00—Soil-conditioning materials or soil-stabilising materials
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/044—Hydroxides or bases
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring

Definitions

• the claimed group of inventions relates to the field of organic chemistry and can be used to clean the soil of oils, including oil, fuel oil, fuels, hydrocarbons, liquid fuels, as well as for the processing and collection of oil, oils, fuel oil, fuels, hydrocarbons and other oil products from hard surfaces, for example, from the inner surfaces of tanks for storing oil or oil products, equipment used in the extraction, refining, transportation of oil, equipment used to produce oil products, drill cuttings a, gravel, sand in storage facilities or from other hard surfaces.
• molasses and surfactants in a concentration range of 10-40 mg / kg of soil, and molasses contribute up to final sugar concentration of 3-10 g / kg of soil [Patent for invention RU2301258, MP C12N1 / 26, B09C 1/10, 04/01/2005].
• a substance for cleaning solid surfaces from oil and oil products which includes an aqueous acidic solution containing a polymer substituted by an amino group, a halogenating agent, and one or more surfactants.
• Chitosan is preferably used as the polymer substituted by an amino group
• the halogenating agent is preferably a sodium hypochlorite solution [US Patent No. 7229952B2. IPC CI 1D3 / 30, C02F1 / 52, C02F1 / 56, E21 B43 / 22, 19-Dec-2002].
• the disadvantage of the prototype is the use of polysaccharides that do not have surface-active properties, which significantly increases their consumption in the process of cleaning the soil and hard surfaces, and also reduces their oil-washing properties.
• a known method of cleaning the soil from oil pollution which consists in introducing into the soil a nutritional supplement, including molasses, stimulating the growth of oil-oxidizing microorganisms contained in the soil, the additive additionally containing surfactants in a concentration range of 10-40 mg / kg of soil, and molasses is added to a final sugar concentration 3-10 g / kg of soil [Patent for invention RU2301258, IPC C12N1 / 26, B09C 1/10, 04/01/2005].
• a known method of removing hydrocarbon materials from solid soil which involves the preparation of an aqueous suspension from a mixture of a hydrophobic adsorbent selected from foamed synthetic materials, and said soil in the presence of water, the adsorbent having a density lower than the density of water, mixing said suspension and performing gravitational adsorbent separation from thus obtained aqueous mixture
• Patent for invention US6153017A. IPC B09C1 / 02, C10G1 / 00, 29-Jan-1998].
• a known method of sorption of oil, oil products from water and soil surfaces comprising spraying a sorbent based on polyvinyl chloride followed by oil collection, and in order to increase the selectivity and efficiency of sorption, polystyrene, polypropylene, polyethylene, their copolymers in any molecular ratio with polydispersity are used particles of 5-200 microns.
• a known method of cleaning surfaces from oil and oil products including surface treatment with a dispersed polymer-containing composite material, followed by regeneration or disposal of the spent product, in which the polymer is natural rubber latex or styrene butadiene rubber deposited on an inert filler, characterized in that as filler use a material with a developed specific surface obtained by foaming the starting component immediately before application Niemi him polymer and filler polymer processing performed under reduced pressure in the range from 0.9 atm to 1 * 10-4 atm.
• Addplication for invention RU201 1 108189. IPC ⁇ 02 ⁇ 15 / 04, C02F1 / 28, ⁇ 09 ⁇ / 32, B01J20 / 32, 03/02/2011 1].
• a known method of cleaning solid surfaces from oil pollution including jet washing of solid surfaces in a stream of washing liquid and subsequent phase separation of the contaminated washing liquid, and as a washing liquid using 1-15% aqueous dispersion of monodisperse solid particles, which are polystyrene microspheres or mineral particles having a size selected from the range of 0.2-6.0 ⁇ m, a surface modified with an organosilicon surfactant, and a maximum two-dimensional
• the pressure 2D films formed from them, from 12 to 18 mN / m, the phase separation of the contaminated washing liquid is carried out by adding an aqueous electrolyte solution [Invention patent RU2500490, IPC V08VZ / 08, 29.06.2012].
• a method for cleaning hard surfaces from oil and oil products by treating them with additives which includes an aqueous acidic solution containing a polymer substituted by an amino group, a halogenating agent, and one or more surfactants.
• Chitosan is preferably used as the polymer substituted by an amino group
• the halogenating agent is preferably sodium hypochlorite solution [US Patent No. 7229952B2, IPC C 1 1 D3 / 30, C02F1 / 52, C02F1 / 56. E21 B43 / 22, 19-Dec-2002].
• the method is selected as a prototype.
• the disadvantage of the prototype is the use of polysaccharides, which do not have surface-active properties, which significantly increases their consumption in the process of cleaning solid surfaces from oils, and also reduces their oil-washing properties.
• the technical problem to which the claimed substance is directed is to increase the efficiency of cleaning the soil and solid surfaces from oils, including oil and oil products, while improving the environmental safety of the process of cleaning the soil and solid surfaces from oils and making it possible to reuse those removed from the soil and from hard surfaces of oils, as well as surfactants.
• the technical result to which the claimed substance is directed is to increase oil washing properties, reduce the specific consumption of reagents used in the process of cleaning the soil and solid surfaces from oil and oil products, while improving the environmental safety of the process of cleaning the soil and solid surfaces from oils, including oil or petroleum products, and ensuring the possibility of reuse of oils removed from the soil and from hard surfaces, as well as surfactants.
• the technical problem to be solved by the claimed method of cleaning the soil from oils, including oil and oil products is to increase the efficiency of cleaning the soil from oils, including oil and oil products, while improving the environmental safety of the process of cleaning the soil from oils and making it possible reuse of oils removed from the soil, as well as surfactants.
• the claimed method of cleaning the soil from oils is aimed at increasing the efficiency of cleaning the soil from oils, including oil and oil products, reducing the specific consumption of reagents used in the process of cleaning the soil from oils, while improving the environmental safety of the process of cleaning the soil from oils and making it possible to reuse oils removed from the soil, as well as surfactants.
• a method for cleaning the soil of oils, including oil and oil products involves treating the soil particles with a reagent in the form of an aqueous solution of a natural polysaccharide and a surfactant, followed by collecting the product of the interaction of the reagent with oil.
• the soil is initially collected by immersing it in a reagent, polysaccharide microgels with a molecular weight of 20,000 to 200,000 daltons and a particle size of 10 to 1,000 nm are used as a natural polysaccharide, while the total concentration of polysaccharide microgels and surface active substance in an aqueous solution is not less than 0.05 g / l, and the ratio of polysaccharide microgels to surfactant is in the range from 100: 1 to 1: 100.
• the soil can be ground, preferably mechanically, to form soil particles no larger than 50 mm in size.
• the soil is ground, for example, using a screw, crusher, screen, mill or other means for grinding.
• the soil is crushed, for example, using a mixer, screw, mill or other means for grinding.
• the technical problem which is aimed by the claimed method of cleaning solid surfaces from oils, including oil and oil products - increase the effectiveness of cleaning solid surfaces from oils, including oil and oil products, while improving the environmental safety of the process of cleaning solid surfaces from oils and making it possible to reuse oils removed from solid surfaces, as well as surfactants.
• a method for cleaning solid surfaces from oils, including oil and oil products involves treating a solid surface with a reagent in the form of an aqueous solution of a natural polysaccharide and a surfactant, followed by collecting the reaction product of the reagent with oil.
• a reagent in the form of an aqueous solution of a natural polysaccharide and a surfactant, followed by collecting the reaction product of the reagent with oil.
• polysaccharide microgels with a molecular weight of 20,000 to 200,000 daltons and a particle size of 10 to 1,000 nm are used as a natural polysaccharide, while the total concentration of microgels of polysaccharides and surfactant in an aqueous solution is at least 0, 05 g / l, and the ratio of microgels of polysaccharides to surfactant is in the range from 100: 1 to 1: 100.
• Polysaccharide microgels are branched polymer colloidal particles with a diameter of 0.01 - 1 ⁇ m, which are able to swell in solvents due to electrostatic or steric repulsion between charged groups. They are formed as a result of directed polymerization of monomers or pH-initiated neutralization of solutions of synthetic or natural polymers bearing carboxyl or amino groups.
• the polysaccharide microgels used in this group of inventions may include colloidal solutions of natural polysaccharides: low-substituted ( ⁇ 40%) carboxymethyl cellulose and its salts with aliphatic amines (butylamine, benzylamine. Ethylenediamine.
• Hexamethylenediamine Hexamethylenediamine
• chitosan with a degree of deacetylation of 90-97%
• pectin substances containing carboxyl and / or amino groups with a residual amount of methoxy groups ⁇ 25%, as well as other polysaccharide microgels.
• the molecular weight of the products can vary from 20 thousand to 200 thousand D. while high molecular weight (more than 200 thousand D) and low molecular weight (less than 20 thousand D) derivatives of polysaccharides are not applicable for the claimed inventions.
• polysaccharide microgels that are more stable for a long time, chemical crosslinking of the polymer chains of polysaccharides is carried out using anhydrides and activated esters of dicarboxylic acids, diisocyanides, diisocyanates, and other crosslinking agents.
• the diameter of the chemically cross-linked particles of the polysaccharide microgel preferably varies between 50-600 nm.
• the polysaccharide microgels used in this group of inventions can be obtained by physical association or chemical crosslinking.
• the experimental data show that the minimum concentration of polysaccharide microgels in an aqueous solution should be at least 0.025 g / l, preferably at least 0.1 g / l.
• the concentration of polysaccharide microgels in an aqueous solution is less than 10 g / l, which is due to an increase in the viscosity of the working solutions, which negatively affects the penetration of the solution into the pores of the material and, thus, reduces its washing ability.
• polysaccharide microgels have a pronounced affinity for interfaces, which is the basis for their practical application. They form monolayers on the surface of solids, such as soil particles, metals, silicates, plastics and other materials, and are also able to encapsulate organic solvents (benzene, toluene, chlorohydrocarbons), oil, oil products, and vegetable oils.
• organic solvents benzene, toluene, chlorohydrocarbons
• surfactants in the claimed group of inventions can be used various (used in industry) nonionic. anionic and cationic surfactants.
• the surfactants used are selected in such a way that, when interacting with polysaccharide microgels, no water-insoluble precipitates form.
• Anionic surfactants are preferably used in combination with carboxymethyl cellulose-based microgels and carboxyl group-based microgels, while cationic surfactants are used in combination with chitosan-based microgels and amino-based pectin microgels.
• Minimum surfactant concentration substances in the working solution should provide an effective reduction in surface tension at the phase boundary on the treated surface or soil particle.
• the concentration in the solution is not less than 0.025 g / l, while the concentration of surfactants in the aqueous solution is preferably not less than 0.1 g / l.
• the concentration of surfactants in the aqueous solution is less than 50 g / l, due to the fact that the use of more concentrated solutions leads to an unreasonably high consumption of surfactants.
• Sodium lauryl sulfate and other sulfonated fatty alcohols, sodium stearate and other salts of fatty acids, cetylpyridinium chloride and other quaternary salts, ethoxylated alcohols, sugars and phenols can be used as surfactants.
• the total concentration of microgels of polysaccharides and surfactant in an aqueous solution is at least 0.2 g / l, which increases the efficiency of oil removal.
• the ratio of microgels of polysaccharides and surfactants in the solution should be in the range from 100: 1 to 1: 100.
• the lower boundary of the ratio of microgels of polysaccharides and surfactants is due to the fact that an excess of microgel leads to a decrease in the mobility of oil droplets, which in turn makes it impossible to extract them from porous bodies, such as, for example, soil particles.
• the upper limit of the ratio of microgels of polysaccharides to surfactants is due to the fact that an excess of surfactant leads to a pronounced effect of secondary contamination of a solid surface or soil particles.
• the ratio of microgels of polysaccharides to surfactants in the solution is in the range of 10: 1 to 1: 10.
• microgels of polysaccharides allows to minimize the secondary deposition of oils on the surface due to surface hydrophilization and encapsulation of oil droplets.
• Surface hydrophilization is achieved by the formation of a monolayer of polysaccharide microgel particles on the surface being cleaned.
• the encapsulation of oil droplets occurs due to the deposition of the microgel of polysaccharides at the oil-water interface.
• a mixture of polysaccharide microgels with a surfactant forms a stable foam, which makes it possible to apply it to the processed hard surface or surface of soil particles.
• the droplets of oil are washed out while the surface is hydrophilized.
• surfactants exhibit a high affinity for the interface and reduce surface tension at the water-oil interface, while polysaccharide microgels have a high affinity for oils, forming a viscous film on their surface. Together, these effects lead to the formation of stable oil droplets that separate from solid surfaces and the surfaces of soil particles.
• microgels of polysaccharides and surfactants separately are less effective, since the application of microgels of polysaccharides leads to the formation of films that reduce the mobility of oil droplets, especially in porous substrates. At the same time, the use of surfactants without polysaccharide microgels leads to their increased consumption due to the secondary deposition of oil on the substrate.
• the reagents are applied to the surface of the soil particles or solid surfaces in the form of a solution or foam manually or using a special device (hose, spray). Drops of oil float to the surface of the solution and are carried away by its stream. The separation of the oil emulsion and water is carried out using any known method, for example, sedimentation or centrifugation. The oil is regenerated by breaking the emulsion by adding an opposite polymer, for example, polyamines in the case of microgels containing a carboxyl group, or polyacids in the case of microgels containing an amino group. In some cases, precipitation is achieved by adding opposite polycations, such as aluminum or calcium salts.
• an opposite polymer for example, polyamines in the case of microgels containing a carboxyl group, or polyacids in the case of microgels containing an amino group.
• precipitation is achieved by adding opposite polycations, such as aluminum or calcium salts.
• the oil phase is separated by sedimentation, centrifugation or mechanical extraction of the gel films, depending on the ratio of reagent-oil in the emulsion.
• microgels of polysaccharides, nor mixtures thereof with surfactants have previously been used to clean solid surfaces and soil from oils.
• the use of surfactants in combination with polysaccharide microgels improves the cleaning efficiency due to the simultaneous hydrophobization of the surface and the transfer of oil to the encapsulated state.
• inventive substance can be produced in real conditions using known means and operations.
• inventive methods are feasible in real conditions, using known materials and substances. This allows us to conclude that the claimed facilities meet the criterion of "industrial applicability".
• inventive substance and the claimed methods are characterized by the following examples of specific performance.
• Chitosan (1 g) with a degree of deacetylation of 95% and a molecular weight of 60 to 100 thousand D is dissolved in 1 l of 0.01 M hydrochloric acid.
• a sodium hydroxide solution of 0.05 M to pH 7.5 was added to the obtained suspension of chitosan microgel and the resulting solution is used to remove fuel oil from the inner surface of the steel tank.
• a 25 liter steel tank is used to store petroleum products.
• 0.5 L of the resulting solution is poured into a steel container and mixed vigorously.
• a monolayer of polysaccharide microgel particles is formed on the surface to be cleaned and the polysaccharide microgel is deposited at the oil-water interface, and oil droplets float to the surface of the solution and are carried away by its flow.
• a 5% solution of polyacrylic acid is added to it, the precipitate formed is filtered off. and squeezed on a mechanical press to extract fuel oil, while in the tank remains an aqueous solution of a surfactant.
• the fuel oil extraction efficiency (the ratio of the amount of the obtained product to the initial product deposited on a solid surface) was 98%.
• the sodium salt of carboxymethyl cellulose (20 g) with a degree of substitution on carboxymethyl groups in the range of 25-30% and a molecular weight of 30 to 50 thousand D is dissolved in 1 liter of water.
• the resulting solution of the carboxymethyl cellulose microgel with a concentration of 2% of the mass is diluted ten times with water, 50 g of anionic surfactant - sodium lauryl sulfate are added and used to clean the soil from oil. To do this, the soil removed from the surface is crushed to a size of less than 5 mm and poured with the resulting solution, previously heated to 80 ° C.
• Pectin (5 g) with a degree of methoxylation of 1-5% and a molecular weight of from 40 to
• the resulting solution is used to clean sand from toluene.
• sand contaminated with toluene is poured with the resulting solution, incubated for 5 minutes with vigorous stirring, filtered and sent for regeneration.
• the formation of a monolayer of polysaccharide microgel particles on the surface to be cleaned and subsequent deposition of polysaccharide microgel at the oil-water interface are observed. Drops of oil float to the surface of the solution, after which they are removed from the surface with a fine mesh sieve.
• the claimed group of inventions allows to increase the efficiency of cleaning solid surfaces or soil from oils, including oil and oil products. reducing the specific consumption of reagents while improving the environmental safety of the process of cleaning solid surfaces or soil from oils and making it possible to reuse oils removed from the soil and from solid surfaces, as well as surfactants.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Environmental & Geological Engineering (AREA)
• Materials Engineering (AREA)
• Soil Sciences (AREA)
• Health & Medical Sciences (AREA)
• Nanotechnology (AREA)
• Public Health (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Emergency Medicine (AREA)
• Dispersion Chemistry (AREA)
• Molecular Biology (AREA)
• Physics & Mathematics (AREA)
• Composite Materials (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Processing Of Solid Wastes (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Water Treatment By Sorption (AREA)

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