RU2626207C1 - Composition for polymer sorbent and method for producing sorbent from composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: composition for polymer sorbent contains (wt %): urea-formaldehyde resin 25-30; emulsifying-stabilising additive 4-6; foaming agent 3-5; chloride sulfate sodium thiosulfate, which is a waste of the production of diaphene 10-13; dust of electrostatic precipitators of aluminium production 8-14; acid hardener 9-12; water - the rest.

EFFECT: invention allows to create a multifunctional composition and to produce a sorbent with improved physical-mechanical and operational properties.

5 cl,1 dwg, 4 tbl, 3 ex

Description

The present invention relates to the field of macromolecular compounds, in particular to a multi-purpose polymer composition for producing polymer sorbents, including combined, in the form of crumbs, mats, bonn, bioconveyors, ameliorants-aerants, fire-protective shielding-boomer oligomers used for localization, liquidation, collection, purification of polluted environment (soil, water, including radioactive, circulating and technological), rehabilitation and rehabilitation of disturbed lands from oil, oil products, toxic of radioactive isotopes, poisonous, aggressive, acid-base, ammonia compounds, including flammable liquids, and dissolved heavy metal ions at emergency facilities of oil transportation pipelines, oil fields, oil depots, oil pumping and filling stations at chemical and metallurgical enterprises, river and sea terminals, hydrostations , motor transport and railway enterprises, as well as other industrial facilities where emergency chronic leaks of oil products and toxic radioactive liquids are possible during industrial fire emergency situations accompanied by fires on the surface of soils and the hydrosphere.

Known polymer composition for producing a sorbent [RU No. 2186075, C08L 61/24, B01J 20/26, C08K 13/02, publ. 07.27.2002], including urea-formaldehyde resin, aniline hydrochloride, plasticizer - sulfonated naphthalene formaldehyde resin and graphite.

The low oil intensity of the sorbent and the high solidification time (polymer formation) of 40-60 minutes does not allow the use of this sorbent more efficiently, which significantly reduces the range of functional and technological capabilities. According to its operational characteristics, the resulting sorbent has a number of significant drawbacks - it requires mandatory disposal, has a low oil intensity and a multiplicity of the resulting sorbent, a long curing time and the release of formaldehyde, etc. Therefore, according to the significance of the criterion of this material as a sorbent with its oil capacity, low sorption rate and high emission, the equilibrium concentration of formaldehyde in air and the absence of biochemical oxidation of oil products, characterizes it as an ineffective sorbent.

The closest in technical essence and the achieved result, adopted as a prototype, is a multi-purpose foamed polymer composition to obtain a sorbent [RU No. 2186800, C08L 61/24, publ. 08/10/2002], including urea-formaldehyde resin, flame retardant, inert filler, foaming agent PO-1, hardener - inorganic acid and water.

The resulting sorbent has certain disadvantages, such as: a high percentage of urea resin, the release of free formaldehyde in excess of the MPC, as well as the presence in the composition of expensive starting ingredients, which greatly increases the cost of the sorbent and thereby inhibits its widespread adoption. In addition, the obligatory disposal of the sorbent is required, since it introduces secondary pollution.

A known method of producing a sorbent [RU No. 2197322, B01J 20/30, B01J 20/26, publ. January 27, 2003], including the preparation of two working solutions A and B, heated to 40-50 ° C, where solutions A of the emulsion and B of the foaming and curing agent require a strict preparation sequence.

The main disadvantage of the polymer sorbent obtained by this method is that it is adapted to only one brand of KFMT-15 resin and has a number of expensive components, requires large energy costs for heating the components, and labor costs for the production technology.

Closest to the invention in technical essence, adopted as a prototype, is a method for producing polymer sorbents [RU No. 2184608, B01J 20/30, B01J 20/26, publ. 07/10/2002] based on urea resins, including the preparation of working solutions of components heated to 40-50 ° C and foaming them with compressed air.

A significant disadvantage of this method is the high energy costs of production technology. In addition, this method of producing sorbents can be carried out using freshly synthesized resin of only one brand KFMT-15 (under the condition of guaranteed storage for 2 months). Also, this method limits the degree and possibility of using other polymer compositions to obtain sorbents. The use of expensive components to obtain sorbents according to this method determines its cost, therefore, according to the criteria “price - oil intensity, energy and labor costs” for the manufacture of 1 m ³ sorbent and its insufficiently high operational properties, the method for producing the sorbent becomes less effective and competitive.

The present invention is to develop a composition and method for producing a sorbent from a composition with improved physical, mechanical and operational properties of the sorbent.

The technical result of the invention is to expand the range and range of functional and technological capabilities of the sorbent based on the claimed composition, the possibility of using various brands of urea resins using waste products, increasing the shelf life of the composition, as well as improving the physical, mechanical, sorption and operational properties of the sorbent.

It is known that when using polymer sorbents, the effect of open flame of burning oil and temperature leads to a large loss in the bulk density of the oligomer and, as a result, to a loss in oil consumption, decay, smoke, etc. Therefore, three main factors - the short shelf life of the resin as the main binder component for the production of sorbents, the narrow range of various brands of urea resins used in the technology, the environmental and fire safety of the operation of sorbents and their cost predetermined the technical solution task - to develop a technology for producing sorbents with the solution of existing factors adaptation in various applications using industrial waste.

It should also be noted that in the proposed sorbent composition and the method for its preparation, in view of the technical and economic feasibility, it is envisaged to use a wide range of different grades of urea resins with any content of free formaldehyde. For example, KFMT-15 resin has 0.15% free formaldehyde emission, 10.82% KF-Zh resin, M-1, M-2, M-3 resin more than 2%, i.e. in industrial batches of urea resin grades produced, the content of free formaldehyde ranges from the lowest 0.15% to the highest ≈14%. Therefore, it is necessary to reduce the environmental burden, i.e. emission of formaldehyde mg / m ³ in the air working zone, up to the maximum permissible concentration when using various grades of resins.

The problem is to achieve a technical result is solved by the fact that the composition and method of producing sorbents contains:

- urea resin of any trademarks, for example KFMT-15, KF-Zh, VPS-G, KFO, KF-B, KB-S, Fastener M-1, M-2, M-3, etc.,

- the foaming agent is sulfonol (alkylbenzenesulfonate, a mixture of isomers of sodium salts of alkylbenzenesulfonic acids, with the general formula RC ₆ H ₄ NaO ₃ S, where R is a radical corresponding to the general formula C _p H _{2p + 1} where n = 14-18), or SOFEX-PO-01A - a mixture of sodium salts of alkylbenzenesulfonic acids and alkylsulfonates of the linear structure of natural polymers,

- emulsifying-stabilizing water-soluble additive that allows you to bind the chemically free formaldehyde contained in the original resin, selected from the group of monomers or polymers, including polyvinyl alcohol with a molecular weight of 5000-6500 with a hydroxyl content of 35-40% by weight (according to the formula [-CH ₂ -CH (OH) -] _p , where p is the degree of polymerization), polyacrylamide, resorcinol, acrylamide, a synthetic linear polymer from the latex form (butyl acrylate rubber with acrylonitrile, hexyl acrylate rubber, diethyl hexyl acrylate rubber q), ethylene-propylene rubber, carboxymethylcellulose, polyethylene glycol, hydrogen peroxide, urea, a mixture of potassium and sodium salts of humic acids, particulate filler - Chloride Sulphate Sodium thiosulfate, which is a waste receiving diafen nitrogen production and consisting of the sodium salts of: sodium sulfate (Na ₂ SO ₄ ), sodium chloride (NaCl), sodium thiosulfate (Na ₂ S ₂ O ₃ ⋅ 5H ₂ O) and nitrosodiphenylamine, and fine chemical dust of electrostatic precipitators as a chemical-reactive filler (carbon-oxide compound), waste aluminum production, including a number of oxides Al ₂ O ₃ , F ₂ O ₃ , SiO ₂ , etc., sodium sulfate Na ₂ O ₃ , hydroaluminocarbonate NaAlCO ₃ (OH),

- as well as an acid hardener, which is used as an aqueous solution of a mineral acid selected from the series: phosphoric, hydrochloric, sulfuric, formic, oxalic, trichloroacetic, boric, organic potassium or sodium salts or their double or triple mixtures, ammonium hydroxide or its salts .

These ingredients introduced into the composition of the composition make it possible to obtain a multifunctional polymer sorbent effective in terms of performance, having sorption, heat-resistant, and shielding properties with a reduced formaldehyde emission index, regardless of the brands of urea resins used in the composition, and, if necessary, to obtain sorbents from urea resin by synthesis directly at the production site. And also in the process of technological production of the sorbent, it can increase not only the solubility and reactivity of the resin, and most importantly increase its shelf life up to 14 months, provided that there is no exposure to solar radiation on the composition. This makes it possible to use this composition in the harsh climatic conditions of Siberia and the Far North at any time of the year. This is especially true in the winter, during the operation of oil trunk pipelines and pumping stations, which is associated with great difficulties and economic costs for transportation, where this product is especially in demand taking into account environmental safety.

The technical result is achieved in that the composition for a polymeric sorbent containing urea-formaldehyde resin, a foaming agent, hardener and water additionally contains an emulsifying-stabilizing additive, sodium thiosulfate chloride, which is a waste product of diaphene, dust from aluminum electrostatic precipitators in the following ratio of components, wt.% Wt. :

urea-formaldehyde resin 25-30 emulsifying stabilizing additive 4-6 foaming agent 3-5 sodium sulfate thiosulfate chloride, diaphene waste 10-13 dust aluminum electrostatic precipitators 8-14 acid hardener 9-12 water rest

As an emulsifying-stabilizing additive, a substance selected from the group is used: polyvinyl alcohol, polyacrylamide, acrylamide, resorcinol, synthetic latex, carboxymethyl cellulose, polyethylene glycol, hydrogen peroxide, urea, a mixture of potassium and sodium salts of humic acids.

Sulfonol is used as a foaming agent - a mixture containing sodium salts of alkylbenzenesulfonic acids and non-sulfonated hydrocarbons with existing isomers of sodium dodecylbenzenesulfonate or SOFEX-PO-01A - a mixture of sodium salts of alkylbenzenesulfonic acids and linear alkyl sulfonates of natural polymers.

An acidic hardener is an aqueous solution of a mineral acid selected from the series: phosphoric, hydrochloric, sulfuric, formic, oxalic, trichloroacetic, boric, organic potassium or sodium salts or their double or triple mixtures, ammonium hydroxide or its salts.

A method of producing a polymer sorbent from a composition based on a urea-formaldehyde resin, comprising preparing an emulsion, foaming it with compressed air and subsequent curing, is mixed in the first stage by weight. %: urea-formaldehyde resin 25-30 emulsifying-stabilizing additive 4-6, sodium thiosulfate chloride, which is a waste product of diaphene 10-13, dust from aluminum electrostatic precipitators 8-14, foaming agent 3-5, for 15-20 minutes to a homogeneous mass , processed in an ultrasonic field with a frequency of 1.5⋅10 ⁵ -10 ⁷ hertz in the cavitation mode in the presence of compressed air at an excess pressure of 0.25 ÷ 0.3 MPa and a working air flow rate of 0.7 ÷ 5 m ³ / min, the second stage, the polymer mass is subjected to curing with the addition of acid hardening Itel in the amount of 9-12 weight. % to obtain the sorbent, then carry out exposure for 0.7-1.6 hours at a temperature of 15-30 ° C.

The essence of the invention lies in the fact that the composition and the method for producing the sorbent use the full chemical and technological compatibility of the ingredients with the urea resin, regardless of its brand, therefore, using a foaming agent - sulfonol or SOFEX-PO-01A, and - sodium sulfate thiosulfate, which is a waste product of the production of diaphen of nitrogen production, which, in combination with a foaming agent, as a result of a chemical reaction, additionally functionally initiate and increase the activity and solubility of the resin (at the same time, its solubility is almost unlimited), its activity, reactivity increases, and the foam formed from it has a high foaming ratio, aggregate resistance to destruction, time resistance and foam stability.

It was found that in the technological process for the production of sorbents, regardless of the composition in the curing stage, formaldehyde is released. Therefore, the present invention proposes to eliminate this drawback by introducing into the composition, for example, polyvinyl alcohol, which allows you to bind the chemically free formaldehyde contained in the original urea resin and formaldehyde released during the curing of the composition, and at the same time increase the physicomechanical and operational characteristics (tensile strength, flexibility, elasticity), reduce dusting and cracking, due to optimal crosslinking, while preserving the open-mesh mesop the porous structure of the sorbent, which determines sorption, and protective properties. At the same time, it is possible to reduce the toxicity index within the MPC, not exceeding the hygienic requirements for the safety of the substance and its biodegradability.

The main requirement for the choice of an emulsifying-stabilizing additive is not only its high reactivity with respect to formaldehyde under the conditions of sorbent production (without additional technological operations, so as not to complicate the production process), but also the fast and good solubility of the substance in the reaction aqueous medium, which is essential increases the efficiency of its interaction with formaldehyde over the entire volume of the reaction mass. In this case, the reactivity of polyvinyl alcohol interacts with formaldehyde, forming methylol derivatives, where the alcohol binds formaldehyde, forming polyvinyl acetal fragments in the polymer chain according to the optimal scheme corresponding to:

In addition, polyvinyl alcohol is additionally involved in the formation of transverse stitched bridges when stitching a urea resin, which leads to a significant increase in the strength and elasticity of sorbents.

During the technological stage of manufacturing a polymer sorbent, a chemical reaction filler is additionally introduced into the composition of the emulsion solution in the form of finely dispersed dust of electrostatic precipitators, waste aluminum production, which has high temperature and fire resistance, low density, etc. It should be specially noted that the fine dust of electrostatic precipitators used in the resin emulsion as a chemical-reaction filler is a waste from the KrAZ plant aluminum production, where the phase composition of electrostatic dust consists of a number of oxides, while electrostatic dust is a complex carbon-containing sodium oxide complexonate compound character. The data are shown in table 1.

In this case, the average particle size of the dust of electrostatic precipitators is 22.9 μm, where the particle size distribution of dust is in the micron fineness class with the grade content,% weight. presented in table 2.

The particle size of the dust of electrostatic precipitators is close to nanoparticles in the state of aggregation (specific surface ≈ 110.000-135.000 cm ² / g), which makes it possible to efficiently introduce a chemically reactive finely divided filler, which includes a number of oxides in the emulsion, consisting of an aqueous solution of urea resin and a foaming agent. Moreover, studies have shown that the possibility of introducing various fillers into the composition, including inert ones, without significantly reducing the expansion rate and foam stability should be no more than 20 parts by weight. The principle of producing polymer sorbents is based on the fact that the initially formed polyhedral foam containing a foaming agent, a resin, an emulsifying-stabilizing additive, a chemical-reactive filler, etc., is cured by quickly introducing an aqueous hardener solution into the foam.

The features of the urea-formaldehyde polycondensation mechanism and the spatial structure of the cured resin determine some properties of the urea-formaldehyde resin-based polymer binder. With an increase in the content of methylol and ether groups in the initial resin, the release of formaldehyde and water during the curing of polymer binders increases. If a significant amount of free methyl groups is retained in the cured resin, the strength and water resistance of the polymer are reduced. These and other features must be taken into account in the process of applying urea-formaldehyde binders for various purposes, for example: foamed urea-formaldehyde fertilizers, poroplasts, polymer sorbents, etc.

H ₂ N-CO-NH ₂ + CH ₂ O↔H ₂ N-CO-NHCH ₂ OH

It was found that the optimal cure of urea-formaldehyde resins occurs upon heating or at room temperature in the presence of compounds of predominantly acidic nature, for example: hydrochloric, phosphoric, oxalic, phthalic acids, their salts (AlCl ₃ , ZnCl ₂ ). The net polymers obtained as a result of curing are colorless, lightfast, stable in organic solvents and oils, are easily painted, however, they have a number of drawbacks - reduced water resistance, brittleness, low resistance to destructive effects, emission of free formaldehyde, etc.

Therefore, in the manufacture of the sorbent, the introduction technology and the amount of fillers and other additives in the composition are determined during the reaction of the interaction of reactive components, the chosen curing catalyst - urea-formaldehyde resin, in particular with hydrochloric acid, depending on the type of fillers, since the composition of the composition is chemically fine-dispersed dust of electrostatic precipitators consisting of various chemical elements, then as a result of chemical reactions from interaction of the filler with the curing catalyst - hydrochloric acid and urea resin during the manufacture of the sorbent occurs following chemical reaction between:

Al ₂ O ₃ + 6HCl → 2AlCl ₃ + 2H ₂ ONaF + HCl → NaCl + HF ↑

AlF ₃ + 3HCl → AlCl ₃ + 3HF ↑ CaF ₂ + 2HCl → CaCl ₂ + 2HF ↑

Fe ₂ O ₃ + 6HCl → 2FeCl ₃ + 3H ₂ OFeO + 2HCl → FeCl ₂ + H ₂ O, etc.

As can be seen from the course of chemical reactions, a variety of gases are released, which are combined with forced air-mechanical foaming with simultaneous gas formation resulting from the interaction with hydrochloric acid in the course of an intense polycondensation reaction, i.e. curing leads to a decrease in the process of sedimentation, i.e. sedimentation and residual shrink stress at the phase boundary of the polymer oligomer, while reducing linear shrinkage, and precipitated salts, including fluorine salts of NaF, AlF ₃ , CaF ₂ during foaming, i.e. the contact of particles of salts, water and resin on the contact surface increases the saturation coefficient, as a result of which reactions of dissolution of salt crystals, including anhydrous minerals, immediately begin to occur and the result of their flow is the saturation of water with Ca + and Na + ions and others. Foamed composition after pouring it in the form or formwork at a high curing rate has a high aggregate stability and coalescing elements, i.e. no precipitation is observed.

The ions Ca + and Na + are the initiators of the condensation process, intensify and facilitate the rapid flow of the main technological indicators, the rate of foaming of the foam mass, the gelation time, while optimizing the interstructural polymer-crystalline framework of the hardening foamed high-mass oligomer and, as a whole, reinforcing the structure of the sorbent, giving when fully cured and dried, increased density, naturally mechanical strength, heat resistance and, as a result, low shrinkage value Oh deformation and sorption moisture.

During chemical reactions, foaming of the evolved gases additionally occurs, while the foam cells grow and come into contact, resulting in their mutual compression and deformation of the surface, where the evolved gases located at the points of contact of the cells form the so-called triangles and Gibbs capillaries. These capillaries have a size less than 0.035 microns and occupy up to 3 ÷ 5% of the volume. Their presence determines a high specific surface area of 5000 cm ² / cm ³ with a pycnometric density ranging from 0.6 cm ³ , while the porous structure is caused by the perforation of the so-called core and film formations during curing. The number of open pores in the oligomer-sorbent ranges from 85.8-91.4%, while the number of dead-end non-absorbing closed pores does not exceed 7.2-11.8%.

In addition, the total porosity (V _Σ ) and the limiting sorption volume (W _s ) with the use of an organo modifier, depending on the difference between V _Σ cm ³ / g and W _s cm ³ / g, allows to determine the total volume of macropores V _ma (cm ³ / g ), which vary in the ranges of 0.33-0.76 cm ³ / g for V _Σ and 0.02-0.05 cm ³ / g for W _s , which allows one to obtain a sorbent, regardless of the order of application of the components, with a more developed surface structure and low bulk density from 6 to 35 kg / m ³ and high porosity (P%) in the range from 85.8 to 91.4% with a low sedimentation coefficient.

The involvement in the composition for the production of polymeric vinyl alcohol sorbents, nitrogen production diaphene wastes and fine dust of electrostatic precipitators allows using these ingredients to increase the shelf life of the compositions, increase the stability and activity of the polycondensation chemical process using various grades of urea resins, the solubility of the resin, its reaction ability, strength, elasticity, heat resistance of polymer sorbents and, at the same time, significantly reduce shrinkage ku, brittleness, moisture and vapor permeability and emission of formaldehyde emissions into the environment during production and operation, as well as increase the activity of the curing of the foamed polymer mass, taking into account aggregative stability.

As a result of this, a reduction in the cost of the sorbent is achieved with an increase in its competitiveness in the market of polymer materials and products, as the functionality is expanded and it becomes possible to obtain sorbents of various grades, modifications and structural products (mats, booms, etc.).

By the method of regression analysis, the equation of dependence of oil intensity (HE, g / g), oil intensity (ME, g / g) and water absorption (VP, g / g) of a poroplast (for example, a sorbent) obtained from a reactive organo modifier, sodium sulfate thiosulfate chloride, foaming agent, polyvinyl alcohol and resin depends primarily on the volume of macropores (Vma) and other significant factors, while:

NOT = 3.415⋅Vma-0.405, where R ² is the reliability of the approximation R ² = 0.97.

Additionally, equations describing the dependence (NOT, g / g) and compressive strength (σ _pr M _pa ) on the amount of filler (C) were obtained by the method of mathematical analysis:

NOT = 59.337-0.614 ° C at R ² = 0.996- (1)

= σ _pr 0,1991-0,0123⋅S 0,0005⋅S + ^2, with R ² = 0,937- ⁽²⁾

Assessment of the significance of the coefficient of the regression levels (1) and (2) at a significance level of g = 0.05 showed that all the coefficients are significant. The result of mathematical processing showed that the regression equations adequately reflect the synthesis process of obtaining polymer materials for a given composition composition.

Consequently, polyvinyl alcohol introduced into the composition of the resin emulsion in a predetermined ratio, nitrogen production diaphene wastes, fine dust of electrostatic precipitators can simultaneously improve both the physical, mechanical and operational properties of the resulting polymer sorbent with wide functional capabilities.

The technology for producing polymer sorbents based on the proposed composition of the composition and the method for producing the sorbent allows non-waste technology of a two-component scheme in accordance with the technological production schedule, TU 2254-001-02067879-2009 and guidelines using the PGUM foam-generating unit or the gas-liquid mobile unit GZhU-M modular type. Equipment for the production of PGUM sorbents includes: an emulsion tank and a hardener tank, containers for modifiers and fillers, a first stage reactor for air-mechanical foaming of the emulsion, a second stage reactor with double-circuit foaming of the air mass and its stabilization, a pump with an electric motor, a remote control control units for optimization and temperature control of components with instrumentation with shut-off and control equipment, mixer for supplying an aqueous solution of hydrochloric acid to a foaming mass, a foam pipe for forming a partially cured polymer mass and pouring it into cassettes, where the design of molding cartridges can be different in the form of sheets, rugs, bonnets and other products according to TU 20.60.21-001-90375318-2017. If it is necessary to obtain a polymer sorbent in the form of crumbs, the sorbent is crushed, modified with additional immobilization of associated biocultures and oil-oxidizing strains and packaged in plastic containers (bags), followed by vacuum. Foaming reactor of the first stage with mass transfer turbulizing device, reactor for additional foaming, stabilization and maturation of the foam of the second stage, with built-in ultrasonic disperser of ultrasonic ultrasound. The process of regulating the technological parameters upon receipt of the polymeric material is carried out using control and locking and regulating devices in manual or automatic modes.

The sorbent is obtained by mixing in the first container with a volume of 1.5–3 m ³ an emulsion solution (urea resin, a foaming agent, a water-soluble additive, sodium thiosulfate sulfate chloride and a chemical-reactive filler of fine dust of electrostatic precipitators - industrial wastes in appropriate proportions) and by air-mechanical sparging using a special ultrasonic dispersant - an ultrasound disperser installed inside the reactor, mix these ingredients for 15-20 minutes until a homogeneous, homogeneous stable strength solution to yield good resin flowable emulsion-suspension. At the same time, an ultrasonic dispersion ultrasonic disperser integrated in the reactor allows the emulsion to be additionally processed in an ultrasonic field, forming a nonlinear ultrasound effect with a frequency of 1.5⋅10 ⁵ -10 ⁷ hertz, which leads to cavitation of particles in a liquid medium, and not only does the air contact surface with an emulsion, but high turbulence is also created, thereby the entire foaming process is finally intensified and stabilized. In the second tank with a volume of 0.3 ÷ 0.6 m ³ prepare an aqueous solution of mineral acid of 10% concentration. After refueling the installation with components and their preliminary preparation, these components are fed to the first stage reactor for foaming the emulsion using shut-off and control equipment and a pump system in manual or automatic modes. Compressed air supplied to the reactor with a pressure of 2-3 kg / cm ² , where the air flow rate Q = 0.7-5 m ³ / min (determined depending on the productivity and design features of the PGUM, GZhU-M foam generating unit). Entering the second-stage reactor, a partially foamed emulsion is foamed instantly by the method of air-mechanical, aerodynamic mixing, creating a turbulent regime under the Reynolz criterion of 4500 or more, where the intensity, resistance, and the rate of foaming are calculated to a calculated value using the sensors installed in the reactor the ability to control the start time of polycondensation, i.e. curing mechanism process. Next, the resulting air-foam mixture, passing through the foam, stabilizes the maturation of the foam and increases the starting time threshold by 1.5-2 times, is fed to the mixer, in which a special on-off nozzle is installed, which allows the optimal hardener consumption to be injected in the form of fog, as a result of which the air-foam mixture mixes evenly and partially hardens, forming a jelly. The final polycondensation reaction is carried out in a conveying-forming foam conduit, where the polymer mass is transformed within a few minutes into a foam-polymer, quick-hardening oligomer-sorbent, poured into special forms (cartridges). After that, the foam placed in the molds is subjected to isothermal exposure for 0.7-1.6 hours at a temperature of 15-30 ° C until stripping strength is reached, after stripping, the wet sorbent fragments are finally dried in a batch drying chamber to a standard humidity of 8-12 % and crushed (crushed) into granules in the range of 0.8-3 mm, followed by packaging, in accordance with TU and work regulations.

In the process of acid curing, the foamed mass solution goes through three stages of transformation:

- in the first stage, a viscous liquid such as a colloidal solution is formed,

- in the second stage passes into a loose elastic mass containing 40-60% water and a jelly-like jelly,

- in the third stage, the foamed mass is completely cured, resulting in the formation of a solid insoluble oligomer - a polymer sorbent of high multiplicity, porosity, developed structure and low density.

An important step in obtaining a high-quality polymer sorbent is the transition time from the first stage to the second, i.e. the appearance of the first flakes of cured resin in the solution (τ ₁ ) and the formation of a dense lump of polymer (τ ₂ ). The most optimal polycondensation process when producing sorbents takes place only at τ ₁ = 10 ÷ 60 s and τ ₂ = 100 ÷ 300 s, which allows to obtain a polymer sorbent with the most improved physicomechanical, sorption and operational properties with a significant reduction in its cost.

Moreover, in continuous production modes - stationary conditions - a workshop or cyclic production, i.e. Directly on oil-contaminated sites in the field, according to the developed PLARN (oil spill response plan), the technological process of obtaining and applying the sorbent is carried out.

A comparative analysis of the claimed technical solution with prototypes shows that the claimed composition and the method of its production meets the criterion of "novelty" and meets the improved physical, mechanical and operational properties of the sorbent, including its multifunctional significance, versatility, competitiveness and high efficiency:

- in the prototypes of the method and composition for producing a sorbent, there is a narrow range of technical capabilities where the issue of disposal is not resolved, and in the claimed technical solution, the resulting sorbent has a wide range of functional and technological capabilities (such as a sorbent, ameliorant arant, heat-resistant shielding oligomer, etc. .), which makes it possible to apply this composition technologically as a multifunctional dual-triple purpose;

- in the prototypes of the method and composition for producing the sorbent, only one brand of urea resin KFMT-15 is used. Therefore, the possibility of using a wide range of other cheaper and more affordable urea resins, such as KF-Zh, VPS-G, KFO, KF-B, KB-S, Fastener M-1, resin M-70, etc., in this composition and method is not possible, which is one of the significant disadvantages, and in the claimed technical solution it is possible to use various grades of commercial urea resins using industrial wastes;

- in the prototypes of the composition and method for producing polymer sorbents, they are carried out only when using fresh synthesized resins, and since all urea resins have, according to GOST and TU, a limited shelf life of 2-3 months, in the claimed technical solution as a result of the chemical reaction of the interaction of chloride sulfate thiosulfate sodium with a urea resin additionally initiate and increase the solubility of the resin, while its solubility is almost unlimited, its reactivity increases, and the resulting of foam it has a high multiplicity of foaming, the shelf life of urea resin increases to 14 months or more;

- in the prototypes of the composition and method for producing polymer sorbents during operation, high fragility, dusting intensity, low elasticity and elasticity were revealed, and in the claimed technical solution using emulsifying-stabilizing water-soluble additives it is possible to completely eliminate these disadvantages and give the sorbent new operational and environmental properties.

The analysis of the claimed composition composition shows that it meets the criterion of "inventive step". The technical solution for obtaining the sorbent from the claimed composition, according to the developed regulations, the algorithm of actions and the technical specifications, allows for the production in stand-alone conditions at any enterprises.

The composition for the polymer sorbent and the method for its preparation are illustrated by the following examples.

Example 1

Two solutions are prepared at the same time in two different containers: in the first container, an aqueous resin solution of the emulsion suspension, and in the second container of a given concentration, a solution of inhibited hydrochloric acid. Then, by air-mechanical mixing of the components using an ultrasonic dispersant - ultrasound, for 15-20 minutes, 25 masses are brought to a homogeneous homogeneous mixture. % urea resin KFMT-15, 4 wt. % emulsifying-stabilizing water-soluble additives - polyvinyl alcohol, 3 wt. % foaming agent, 10 mass. % sodium thiosulfate sulfate chloride, 8 wt. % of a chemically reactive fine filler (dust of electrostatic precipitators), while the material balance, i.e. the ratio of the composition of the emulsion to the hardener corresponds to within 91 ÷ 9%, the polyvinyl alcohol introduced into the composition completely binds formaldehyde, forming polyvinyl acetal fragments in the polymer chain according to the scheme:

Next, the emulsion solution of the mixture-suspension is pumped into the first-stage reactor with a mass-heat exchange device and foamed using additional compressed air, processed in an ultrasonic field with a frequency of 1.5 × 10 ⁵ -10 ⁷ hertz in the cavitation mode in the presence of compressed air at overpressure 0.25 ÷ 0.3 MPa and a working air flow rate of 0.7 ÷ 5 m ³ / min; in the second stage, the polymer mass is subjected to curing with the addition of an acid hardener in an amount of 9-12 wt.% to obtain a sorbent, then the exposure is carried out in t cross-section 0.7-1.6 hours at a temperature of 15-30 ° C.

Example 2

Obtaining a sorbent is carried out analogously to example 1, by mixing 28 mass. % urea-formaldehyde resin KF-J, 5 wt. % emulsifying-stabilizing water-soluble additives - polyacrylamide, 4 wt. % foaming agent, 12 mass. % sodium thiosulfate sulfate chloride, 11 wt. % chemical-reactive fine filler (dust of electrostatic precipitators), 10 mass. % phosphoric acid of 10% concentration, where the composition of the emulsion and hardener in a mass ratio correspond within 90% ÷ 10%. Taking into account the use of polyacrylamide, instead of polyvinyl alcohol, formaldehyde is bound to form methylol derivatives of polyacrylamide, which is confirmed by experimental data on the reduction of formaldehyde content in the cured sorbent, where the chemical reaction proceeds according to the scheme:

Example 3

Obtaining a sorbent is carried out analogously to example 1, by mixing 30 mass. % urea-formaldehyde resin VPS-G, 6 wt. % emulsifying-stabilizing water-soluble additives - acrylamide 5 wt. % foaming agent, 13 mass. % sodium thiosulfate sulfate chloride, 14 wt. % chemical-reactive fine filler (dust of electrostatic precipitators), 12 mass. % oxalic acid of 10% concentration, while the composition of the emulsion and hardener in a mass ratio correspond within the range of 88% ÷ 12%. In the case of the use of acrylamide, formaldehyde is also bound to form methylol derivatives of acrylamide, where the reaction proceeds according to the following scheme:

Introduction to the composition of the urea-formaldehyde resin is less than 25 mass. % is insufficient for the polycondensation reaction, i.e. polymer curing slows down, and linear and volumetric shrinkage occurs, therefore, the porosity multiplicity decreases sharply and, as a result, porosity, including macro-micropores, mesopores. And the introduction of urea-formaldehyde resin more than 30 mass. % leads to cost overruns of resin and, consequently, to the cost of the sorbent. When introduced into the composition of the chloride chloride of sodium thiosulfate less than 10 mass. % leads to insufficient reactivity (solubility of the resin), thereby reducing not only the solubility coefficient of the resin, but also the shelf life, and more than 13 mass. % leads to a change in the viscosity of the emulsion and a violation of the balance of foaming. Introduction to the composition of the chemical-reactive fine filler (industrial waste dust) in the range from 8 to 14 mass. % is the most optimal, since less than 8 mass. % leads to insufficient physical and mechanical properties of the sorbent, and more than 14 mass. % leads to the need to increase the concentration of hydrochloric acid in the composition, and also increases the shrinkage of the sorbent and reduces its multiplicity and aggregative stability.

Physico-mechanical characteristics and operational properties of the resulting sorbent based on the proposed composition and method of preparation are shown in tables 3 and 4.

* Note: the physicochemical, mechanical and operational properties of sorbents with differentiated oil capacity were determined according to standard certified methods, according to the accreditation certificate, and also according to the main methods of polymer sorbents of the Unipolymer-M, Mesorb series that were additionally developed and approved by the Institute of Oil and Gas of SFU ”,“ Unipolymer-Agro ”,“ Menom ”,“ Unipolymer-BOS ”,“ Unipolymer-Bio ”, tested in Russia, the CIS and the USA.

The cost of sorbents in comparison with the prototype is reduced, this is due to the fact that the expensive components used in the prototype are replaced with the full market value of the waste from aluminum and nitrogen production enterprises in Krasnoyarsk. In addition, the proposed composition allows you to widely vary the algorithm of technological functionally dependent parameters (oil capacity, porosity, strength, heat resistance, etc.), which, depending on the purpose of the use of sorbents, allows you to classify them as sorption, agro-reclamation and fire-retardant materials of the Unipolymer- M ”,“ Unipolymer-Bio ”,“ Unipolymer-Ferro ”,“ Unipolymer-BOS ”,“ Unipolymer-Agro ”for environmental, fire and other purposes, which allows us to expand the range of functional and technical iCal tasks with maximum transformation and optimization of technological processes of sorbents and their use in Siberia and Far East import substitution without environmental technologies. The developed method for producing sorbents is basic and can be integrated with any known polymer compositions and newly developed, including foreign analogues.

Claims (7)

1. Composition for a polymer sorbent containing urea-formaldehyde resin, a foaming agent, hardener and water, characterized in that it additionally contains an emulsifying-stabilizing additive, sodium thiosulfate chloride, which is a waste product of diaphene, and dust from aluminum electrostatic precipitators in the following ratio of components, wt.%: urea-formaldehyde resin                       25-30 emulsifying stabilizing additive              4-6 foaming agent                                                              3-5 sodium sulfate thiosulfate chloride, diaphene waste 10-13 dust aluminum electrostatic precipitators       8-14 acid hardener                                                9-12 water                                                                           rest 2. The composition according to p. 1, characterized in that as an emulsifying-stabilizing additive, a substance selected from the group is used: polyvinyl alcohol, polyacrylamide, acrylamide, resorcinol, synthetic latex, carboxymethyl cellulose, polyethylene glycol, hydrogen peroxide, urea, a mixture of potassium and sodium salts of humic acids. 3. The composition according to p. 1, characterized in that sulfonol is used as a foaming agent - a mixture containing sodium salts of alkylbenzenesulfonic acids and non-sulfonated hydrocarbons with existing isomers of sodium dodecylbenzenesulfonate or SOFEX-PO-01A is a mixture of sodium salts of alkylbenzenesulfonates of natural polymers of alkyl sulfonates and alkylsulfonates. 4. The composition according to p. 1, characterized in that as an acid hardener use an aqueous solution of a mineral acid selected from the series: phosphoric, hydrochloric, sulfuric, formic, oxalic, trichloroacetic, boric, organic potassium or sodium salts or their double or triple mixtures of ammonium hydroxide or its salts. 5. A method of obtaining a polymer sorbent from a composition based on a urea-formaldehyde resin, comprising preparing an emulsion, foaming it with compressed air and subsequent curing, characterized in that at the first stage they are mixed (wt.%): Urea-formaldehyde resin 25-30, emulsifying-stabilizing additive 4 -6, sodium sulfate thiosulfate chloride, which is a waste product of diaphene 10-13, dust from aluminum electrostatic precipitators 8-14, blowing agent 3-5, mixing is carried out for 15-20 minutes to a homogeneous mass in ultrasound ov field with a frequency of 1.5 510 ⁵ -10 ⁷ Hz in the cavitation mode in the presence of compressed air at an excess pressure of 0.25 ÷ 0.3 MPa and a working air flow rate of 0.7 ÷ 5 m ³ / min, in the second stage polymer the mass is subjected to curing with the addition of an acid hardener in an amount of 9-12 wt.% to obtain a sorbent, then hold for 0.7-1.6 hours at a temperature of 15-30 ° C.

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