RU2184608C1 - Method of production of polymer sorbents - Google Patents

Abstract

FIELD: technology of production of polymer sorbent for environment control; localization and utilization of oil, petroleum products and liquid organic agents from contaminated areas of water surface and solid. SUBSTANCE: proposed method consists in injecting metered amount of homogeneous solution of carbamide resin at addition of 3 to 6% of finely-dispersed carbon of alkaline-earth metal at size of particles not exceeding 0/5 mm into foamed solution of inorganic acid with surfactant which was preliminarily heated to 40-50 C; this done, polymer mass is poured into mold. EFFECT: low-cost of rigid sorbent in form of mats, filters, granulated crumb. 3 cl, 1 dwg, 1 tbl

Description

 The invention relates to a technology for producing polymer sorbents used for environmental purposes to localize the collection and disposal of oil, oil products and liquid inorganic substances from contaminated sections of the surface of water, soil at emergency oilfield facilities, oil transportation pipelines, oil refineries, as well as scheduled cleaning of technological, circulating and sewage from heavy metal ions, gas emissions of harmful substances in chemical, metallurgical enterprises.

 A known method of producing urea-formaldehyde foam, including the preparation of a resin emulsion with waste production of ethyl sulfonates, followed by stirring in the reactor by supplying compressed air and curing the foamed mass with an acid hardener of hydrochloric acid of 6-8% concentration (patent RU 1807996 A3).

 The disadvantage of this method is that the resulting foam in its technical characteristics allows it to be used effectively mainly only as a heat-insulating material and less effective as a sorbent, due to its relatively low oil intensity.

Closest to the invention in technical essence is a method of producing a sorbent based on urea-formaldehyde resins, which includes the preparation of working solutions of the components, foaming them with compressed air, where liquid urea-formaldehyde foam with a multiplicity of 20-30 is kept until complete polymerization for 3-5 minutes, and then crushed in fraction fractions up to 2-20 mm, which are dried in a fluidized bed dryer at 30 ... 40 ^o C until a bulk density of 1.5 ... 3 kg / m ^{3 is} achieved (patent RU 2107543).

The main disadvantages of the polymer sorbent obtained by this method include: high dusting of the sorbent when applied to contaminated sites, its weathering, entrainment from contaminated sites and spreading to other places under the influence of wind loads. This is explained by the fact that this sorbent has an ultralight weight and low mechanical strength at a density of 1.5 .. .3 kg / m ³ . Having such a density and low strength, it is difficult to apply the sorbent mechanically to objects using various machines and mechanisms, such as air-pulse devices. The collection and disposal of such a sorbent also leads to technical difficulties.

 The more significant disadvantages of this sorbent include the fact that it has high sorption moisture. Therefore, the sorbent deposited on the water surface of the contaminated area additionally sorb water. In this case, the sorbate, impregnated with oil products and water, quickly loses its mechanical strength, therefore, it is automatically destroyed, i.e. breaks up into smaller fragments and fractions. As a result of this, the sorbate, not timely collected from the contaminated water surface, acquires a gel-like state and begins to partially lose its buoyancy, and, as a rule, sinks to the bottom. These circumstances further aggravate the ecological situation.

It should also be noted that this method of producing a sorbent by foaming compressed working solutions with compressed air and curing the foam with an acid catalyst includes subsequent forced drying of the foam, which requires high energy costs, since the moisture content of the sorbent before drying reaches 250-350%. Therefore, drying 1 m ^{3 of} sorbent to its normalized humidity, i.e. 6% and crushing into crumbs leads not only to significant energy consumption of 48-57 kW / h, but a long manufacturing process - more than 3 days. All these factors significantly determine the cost of the sorbent. The cost of 1 m ^{3 of} sorbent obtained by the above method is 870-930 rubles / m ³ . The high cost and low mechanical strength does not allow the use of this sorbent as long-term sorbent mats, booms, filters, etc., which significantly narrows the range of its functional technological capabilities of economic and environmental feasibility.

 The invention solves the problem of creating a cheap, highly efficient with a wide range of functional, technological and technical capabilities, environmentally friendly, multi-purpose polymer sorbent.

 The use of such a sorbent is possible in various industries: fuel and energy, oil and gas industrial complexes, oil transportation and processing companies, chemical, metallurgical enterprises and other organizations involved in rail, river and sea transportation, storage, warehousing and sale of oil products at oil depots and gas stations.

 The technical result consists in obtaining a cheap, tough, universal, non-dusting, polymer sorbent in the form of mats, booms, filters, granular chips.

 Mandatory requirements for the preparation and use of these “Unipolymer-M” sorbents are specially designed and approved by regulatory authorities and the technical specifications TU 2223-001-02067907-96 “Polymeric sorbents” were first introduced in Russia.

The technical result is achieved by the fact that in the claimed method for producing a polymeric sorbent based on urea resins, which includes preparing working solutions of components, foaming them with compressed air, according to the invention, to a solution heated up to 40-50 ^° C and foamed inorganic acid with a surfactant having an acidic environment, A urea resin solution with 3-6% alkaline earth metal carbonate added in an amount of not more than 0.5 mm in particle size is injected dosed, then the polymer mass is poured into the shape of the product.

 As surfactants, alkylbenzenesulfonic acid is used.

 Orthophosphoric acid is used as the inorganic acid.

 The method of foaming and subsequent curing of the polymer composition is based on the reaction of the interaction of acid with carbonates. Carbonates for uniform distribution in a urea-formaldehyde resin by mechanical stirring are pre-sieved and a fraction is selected with a particle size of not more than 0.5 mm. Inorganic acid is used as a blowing agent, which is also a catalyst for the curing of the urea resin. Additionally, to increase the multiplicity of the foam, a surfactant (foaming agent) having an acidic medium is introduced into the inorganic acid. The interaction of the catalyst, an inorganic acid, with a foaming agent and carbonates occurs almost instantly (within 5-12 seconds), which leads to the peculiarities of the manufacture of urea poroplasts-sorbents. The interaction of carbonate, evenly distributed throughout the volume of the resin with partially foamed inorganic acid, produces carbon dioxide, which further foams the resin composition. The foaming process begins in the mixing chamber (head) and ends after 6-9 seconds in the filled form in the form of a mat, boom, sheet or other structure, where the foam mass is fed with the help of a foam conduit. The polycondensation process, i.e. full cure of the foam ends after 12-15 minutes.

 The resulting material is a rigid and durable white foam with open porosity. It should be especially noted that the humidity of the freshly prepared sorbent is 25-30%, which is an order of magnitude lower than the humidity of the freshly prepared sorbent obtained in a known manner, and this, in turn, reduces the energy costs of drying the polymer mass and obtaining the Unipolymer-M marketable sorbent " In addition, the sorbent obtained by the proposed method has high strength, does not dust and when sorbing oil products on the water surface, does not acquire a gel state and does not degrade into small fragments and fractions, and has 100% buoyancy. If it is necessary to create hydrophobic, fire-retardant and heat-resistant, for example, booms, mats, crumbs, various modifying additives, for example polyvinyl alcohol, technical glycerin, latex, urea-methyl cellulose and fillers, for example, thermally split graphite (TRG or STG) can be added to the urea resin. TU 2164-001-05015070-97). For the regeneration of sorbing booms, mats or their biological disposal, microorganism strains can be added, for example, Destroil TU 9291-00605803071-96, Putidoyl, etc.

 The analysis of the prior art by the applicant, including searches by patents and scientific and technical sources of information, and the identification of sources containing information about analogues of the claimed invention made it possible to establish that the applicant did not find a source characterized by features identical to all the essential features of the claimed invention. The definition from the list of identified analogues of the prototype, as the closest in the totality of the features of the analogue, allowed us to establish a set of essential distinguishing features in relation to the applicant's technical result, in the claimed method, set forth in the claims.

 Therefore, the claimed invention meets the condition of "novelty."

 To verify the compliance of the claimed invention with the condition "inventive step", the applicant conducted an additional search for known solutions in order to identify features that match the distinctive features of the claimed method from the prototype. The results showed that the claimed invention does not follow explicitly from the prior art for the specialist, since the influence of the transformations provided for by the essential features of the claimed invention is not revealed from the prior art determined by the applicant to achieve a technical result.

 This allows us to conclude that the condition "inventive step".

 The drawing shows a block diagram of the sorbent for the proposed method, where 1 is a container for kabamide resin and carbonate, 2 is a container for acid and a foaming agent, 3 is a tank-hopper for modifying additives, 4 is a reactor for foaming acid and a foaming agent, 5 - mixing chamber, 6 - output foam, 7 - cassette forming mats (mold), 8 - device for forming bon.

 The method of producing polymer sorbents is as follows. On the site provided for the production of sorbent, a stationary or mobile specialized installation PGUM operating in the air-mechanical foaming of components is located. The installation is additionally aggregated by a mixing chamber 5, a foam conduit 6, a compressor (not shown in the diagram). The installation consists of a tank 1 with a high-speed mixer for resin and chalk, a tank with an acid solution and a foaming agent 2, metering pumps, an acid foaming reactor, foaming 4, a piping system, shut-off and control valves and a mixing chamber 5 with an outlet foam 6. Additionally, on the site equipment is installed: a hopper for modifying additives 3, a container for the starting components, a hopper for carbonates (chalk, limestone, etc.), a disintegrator-grinder, a ball mill for grinding carbate materials s, a granulator (not shown in the drawing) and fixtures - cassettes 7 forming mats and sheets or molds 8 for bon. According to the formulations of the polymer compositions, the installation is charged with consumable components.

Carbonate, for example, chalk or ground limestone CaCO ₃ (particle size not more than 0.5 mm) in an amount of 3 to 6%, is mixed with urea-formaldehyde resin, for example KFMT-15 GOST 14231-88 or TU 6-06-12-88 (without adding water) in the tank 1. Separately mix a solution of an inorganic acid and a foaming agent, previously heated to a temperature of 40-50 ^o C, in the tank 2. At the same time, an inorganic acid, for example, technical orthophosphoric acid GOST 10678-76 or TU 2142-002- 00209450-96, used simultaneously as a blowing agent and a cured catalyst Ia urea resin. A surfactant (foaming agent), for example, ABSFK grade alkylbenzenesulfonic acid (TU 2481-003-0029906-93), which has an acidic environment, is used additionally to increase the multiplicity of the foam. In the foaming reactor 4 serves an acid solution with a foaming agent and compressed air pressure P = 2-3 kg / cm ² . Next, the solution foamed in the first stage is fed into the mixing chamber (head) 5, into which a homogeneous portion is dosed by the pump, which is a mixture of resin with carbonate. The foaming process of the second stage begins in the mixing chamber (head) 5 and ends in 5-10 seconds in the filled molds 7 or 8, where the finally formed foamed polymer mass is fed with the help of the foam sleeve 6. The process of a complete chemical polycondensation reaction, i.e. curing, ends after 12-15 minutes in products, such as booms, mats or sheets. The resulting sorbent is a hard, non-shrink, thermosetting and durable white foam with an open cellular structure and porosity. Depending on the technical requirements and application conditions, the obtained products from the polymer sorbent are additionally painted in any color with the help of acidic dyes, for example, booms, mats, filters, and the sheets, if necessary, are granulated by crushing into fine fractions, dried to a normalized humidity of about 6% and packed according to assortment in containers.

Example 1. In the tank load 90 vol.h. urea resin KFMT-15 (without adding water) add 3% chalk grade MO, previously sieved through a sieve with a mesh of not more than 0.5 mm. For uniform distribution of chalk over the entire volume, a high-speed mechanical mixer is included, where the resin and chalk are mixed for 10-12 minutes until a homogeneous mass is obtained. In the tank with a solution of phosphoric acid - 17 vol.h. add 2 parts Foaming agent alkylbenzenesulfonic acid brand ABSFK TU 2481-036-04689375-95 and heated to a temperature of 40-50 ^o C. Using a sparging device, the solution is stirred for 8-10 minutes.

 A phosphoric acid solution with a foaming agent and compressed air are fed into the foaming reactor. As a result, foaming occurs in the reactor, i.e. an increase in the volume of phosphoric acid solution. The rate of foaming reaches 70-80 rpm./unit Then, the orthophosphoric acid solution foamed in the first stage is fed into a mixing chamber (head), into which a homogeneous portion is injected at the same time as a mixture of KFMT-15 urea resin with chalk. In the interaction of carbonate, i.e. chalk distributed over the entire volume of the resin with a solution of phosphoric acid pre-foamed to a high multiplicity, carbon dioxide is released, which additionally foams the resin, thereby forming a finely dispersed stable, resistant, highly multiple, partially cured polymer foam.

 The foaming process of the second stage begins in the mixing chamber (head) and ends after 5-10 seconds in the filled form or design of the product, such as a boom, mat or sheet, where a finally formed foamed polymer mass is fed using a foam sleeve. In this case, the compaction of the wet polymer mass in the filled form does not occur, since the residual carbon dioxide emission during the chemical reaction of the interaction of carbonate with acid does not allow the polymer sorbent to condense. The process of a complete chemical polycondensation reaction, i.e. curing ends in 12-15 minutes. The resulting sorbent is a hard, non-shrinking and durable porous plastic of white color with open porosity, where the number of open pores reaches 83-91%.

Example 2. To increase the fire resistance of the sorbent in the tank load 100 m.h. urea resin KFMT-15, add 4 m.h. carbonate - ground limestone CaCO ₃ and liquid glass 2.0 m.h. and according to example 1, mix thoroughly. In the tank with a solution of phosphoric acid 20 vol.h. add 3 parts Foaming agent alkylbenzenesulfonic acid brand ABSFK and heated to a temperature of 40-50 ^o C and sparged, i.e. mix for 8-10 minutes with compressed air. Next, the process of obtaining the sorbent is carried out analogously to example 1.

 Physico-mechanical and technical and economic indicators of sorbents are given in the table.

 As can be seen from the table, the polymer sorbents obtained by the known and proposed methods have significant operational differences, which indicates the advantage of the proposed sorbent.

 Using the proposed method for producing a polymer sorbent allows you to get cheap, tough, durable and dust-free porous plastics with a wide range of functional technological and technical capabilities, environmentally friendly.

 For the inventive method in the form as described in the independent paragraph of the claims, the possibility of its implementation using the means described in the application is confirmed. Therefore, the claimed invention meets the condition of "industrial applicability".

 The proposed method for producing a polymer sorbent meets all sanitary and hygienic standards and is an environmentally friendly material. This sorbent passed industrial tests in the Omsk, Irkutsk, Novosibirsk regions, Krasnoyarsk Territory, in the joint stock companies Transsibneft OJSC and Sibnefteprovod OJSC, Uraltransnefteprodukt OJSC (Bashkortostan).

Claims (3)

1. A process for preparing a polymeric sorbent on the basis of carbamide resins comprising preparing working solutions components, foaming with compressed air, characterized in that the preheated up to 40-50 ^o C, and foamed inorganic acid solution with a surfactant with an acidic medium dosed urea resin injected homogeneous solution with added, in an amount of 3-6% finely divided alkaline earth metal carbonate with a particle size of not more than 0.5 mm, then the polymer mass is poured into the shape of the product.  2. The method according to p. 1, characterized in that as surfactants use alkylbenzenesulfonic acid.  3. The method according to p. 1, characterized in that as inorganic acid use orthophosphoric acid.

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