WO2019147211A1

WO2019147211A1 - Method for producing a carbon adsorbent and method for regenerating same

Info

Publication number: WO2019147211A1
Application number: PCT/UA2018/000025
Authority: WO
Inventors: Мыхайло Сэргийовыч БОНДАРЭНКО
Original assignee: Мыхайло Сэргийовыч БОНДАРЭНКО
Priority date: 2018-01-26
Filing date: 2018-03-23
Publication date: 2019-08-01
Also published as: UA122415C2

Abstract

A carbon adsorbent is produced using a method which involves the following steps: pyrolysing tyre waste materials at 450-750°C in the presence of an inorganic carrier; separating out the metal particles of the cord using a magnetic separation technique; activating the solid carbon in an air stream at 150-400°C using water vapour at an elevated pressure; drying at 350°C; grinding the activated particles and mixing same with a secondary cellulose fibre. The sorption agent is a carbon adsorbent contained in a shell made of a non-woven textile material. Carbon adsorbent spent during an oil product sorption process is regenerated by heating the adsorbent to 750°C in a pyrolysis unit, causing the oil products to condense. Then, the solid carbon is activated, dried, ground and mixed with cellulose fibre.

Description

The method of obtaining carbon absorbent and method of its regeneration

5 The claimed group of inventions relates to the chemical industry and to the field of environmental protection, in particular, to a method for producing a universal hydrophobic carbon composite adsorbent obtained by processing rubber raw materials, to sorption means for eliminating oil spills, 10 oil products and other chemicals, and to a method of regeneration used carbon adsorbent, which is used to collect petroleum products, fuels, lubricants, natural and synthetic oils, fats, p stvoriteley, paint and other contaminants technical and chemical liquids.

15 From the prior art there are several ways to obtain solid carbon - the main component of the carbon adsorbent.

A known method of producing carbon and hydrocarbons from worn tires, which provides the ability to economically produce carbon, oil and fuel gas from used tires. Used 20 tires are crushed. The resulting solid rubber mixture is pyrolyzed at subatmospheric pressure in the reactor, while residues recycle to increase heat transfer and avoid sludge on the heat transfer surface. The prepared residues are separated from the products of the vapor phase of pyrolysis, and the products of the vapor phase of pyrolysis are then fractionated into oil and fuel gas (Patent US 4284616 A, IPC W29B 17/00, C09C 1/48, C10J 3/00, C01B 31/02, C10B 47 / 26, C01B 31/00, C10G 1/10, C09C 1/00, C 10B 53/07, published on 08/18/1981).

The disadvantages of this invention are: complex technical execution, multi-stage process and high ash content of the obtained carbon black.

The known method of thermal processing of worn tires, in which worn tires are loaded into the reactor, carry out the pyrolysis of the material at a temperature of 550-800 ° C in a reducing gas medium at a ratio of reducing gas to the material of 0.20-0.45: 1. Next, the pyrolysis products are separated and the solid residue is discharged. At the end of the pyrolysis, superheated steam is supplied at 250-300 ° C in an amount of 0.03-0.12: 1 to the loaded material. The reducing gas is obtained by the method of incomplete combustion of hydrocarbons with a = 0.4 - 0.085. The method reduces energy consumption, simplifies the process of recycling worn tires, allows you to get soot of improved quality for its reuse in the production of rubber compounds (Patent for the invention RU 2139187, IPC W29B 17/00, F23G 7/12, C08J 11/16, C08J 11/20 , published on 10.10.1999). The disadvantages, compared with the proposed method of obtaining, is to conduct pyrolysis at temperatures of 550 - 800 ° C and the use of a reducing gas.

A method of obtaining a sorbent of organic compounds, according to which the sorbent is obtained from carbon residue formed in the process of pyrolysis waste containing rubber, including worn car tires (patent for invention RU 2287484, IPC C01B 31/10, publ. 20.11.2006). The disadvantage of this method is multistage use of water and water vapor to activate the sorbent.

A known method of recycling worn tires, in which worn tires are pre-crushed and fed crushed mass in a screw pump, the method differs in that the screw tray is movable and vibration is transmitted in a horizontal plane, creating a forced movement of crushed and heated mass from worn tires tray (application for invention RU NQ2007144414, IPC HBB 17/00, publ. 10.06.2009). The disadvantages of this method is the use of complex equipment for grinding raw materials and the complex process of its submission to the pyrolysis reactor.

There is a method of processing waste tires, which includes the steps: sealing inside a pyrolysis furnace, into which tire waste is inserted and a carrier gas is introduced into it; pyrolizing worn tires by directly heating waste tires with a carrier gas introduced into a pyrolysis furnace; collecting oil by passing the vapor formed during the pyrolysis stage. The method of processing used tires allows pyrolysis of used tires through the circulation of the carrier gas and direct heating, and therefore prevents the danger of an explosion caused by conventional direct heating, ensures safety and improves the rate of oil collection using direct heating (Patent EP 2384872A2, MPK V29V17 / 00 , C08J11/00, published on 09.11.2011). The disadvantage of this method is the use of additional coolant - gas for heating the pyrolysis furnace.

A known method for the production of carbon-containing sorbent materials, which discloses a method for the production of sorbent carbon of a new generation with an organized and repetitive internal structure (Patent EP 2578312 A2, IPC B01J 20/04, B01J 20/06, B01J 20/20, B01J 20/28, B01J 20 (30 April 10, 2013). Disadvantage This method is the use of additional activating reagents - hydroxides, which create the porous structure of solid carbon.

A method of obtaining activated carbon from worn tires, which relates to the field of heat treatment of materials with a carbon content and can be used to obtain active carbon from worn tires. The method includes a bar-disintegration grinding of worn tires at a pressure of 2000-4000 kg / cm ² , carbonization of the resulting crumb rubber in the medium of gases produced during carbonization, and steam-gas activation at a temperature of 750-800 ° C. The gases formed during carbonization are condensed, emitting a liquid fraction, and the uncondensed part of gases is returned to incineration into the furnace of the carbonization furnace (Application for invention RU 94029291, IPC SW 31/08, publ. 27.06.1996). The disadvantage of this method is the use of high pressure (2000-4000 kg / cm ² ) for grinding tires and high temperatures (750-800 ° C). In addition, this method is not intended to obtain a universal carbon composite adsorbent, which has high hydrophobic and oleophilic properties. This solution is chosen as the prototype of the claimed first object of the invention.

The objective of the proposed method of producing carbon adsorbent is to simplify the production technology of carbon adsorbent from secondary raw materials (waste rubber products) and to improve the quality characteristics of carbon adsorbent.

The technical result of the proposed method is to increase the stability of the carbon adsorbent, that is, to increase its ability to maintain high activity after regeneration, to increase the mechanical stability of the carbon adsorbent — it does not crumble or swell when used in water, increase the adsorption rate and the absorbing capacity of the carbon adsorbent. The task is solved by the fact that a method is proposed for obtaining carbon adsorbent, which includes grinding rubber raw materials, carrying out pyrolysis to obtain solid carbon black, mixing the obtained solid carbon with a hydrophobic material, in which, according to the invention, solid technical carbon is produced at a pyrolysis plant for processing rubber raw materials conditions of atmospheric pressure and temperature of 450-750 ° C in the presence of a modified catalyst supported by materials eolithic group, then from the obtained solid carbon with the help of a magnetic separator remove the metal parts of the cord, then perform thermal activation of solid carbon black in an air stream with the addition of superheated water vapor for 30 minutes at a temperature of 150-400 ° C in the pyrolysis chamber under conditions of elevated pressure, then the treated carbon is fed into the drying chamber, while the process of removing moisture is carried out at a temperature of 350 ° C for 1 hour, then prepared in the previous stages of the fabric Under high pressure conditions, carbon is fed to the sorbent production line, where, at ambient temperature, it is crushed and mixed simultaneously with a hydrophobic material, namely, a secondary cellulose fiber, the dosage of which is 20-30% of the total mass of the mixture, and the duration of mixing is 20-30 minutes.

The proposed method of obtaining the main component of the adsorbent, and the actual solid carbon:

does not require the use of complex equipment and additional energy, is simple in technical performance, all processes occur under atmospheric pressure, the pyrolysis itself takes place at temperatures up to 450-750 ° C, obtained solid carbon does not require additional treatment with chemical reagents, since it already has a developed porous structure.

In addition, the carbon adsorbent obtained is a product of a combination of the main component, carbon black, obtained in

5 as a result of catalytic pyrolysis and activation by steam, and secondary cellulose fiber.

A combination of two stages, namely, grinding the prepared solid carbon and mixing with a hydrophobic material, namely, the secondary cellulose fiber in the stated ratio leads to an improvement in the properties of the finished carbon adsorbent through the fact that its surface becomes more hydrophobic and reveals oleophilic properties, contributes to high sorption activity against a wide range of chemicals.

In the prior art, a known sorption material to remove oil contamination includes two layers, one of which is made of polypropylene fibers previously pre-fastened with needles and with a layer of polypropylene fibers made more dense than a layer of hollow siliconized polyester fibers (Patent for invention RU 2210644, IPC D04H0 1/46, B01D 39/16, published on 08/20/2003). The disadvantage of this tool is the low hydrophilicity of the material and the low absorption rate of petroleum products. In addition, the material used can not be further regenerated.

A well-known sorbent for cleaning the surface of water from oil and oil products containing activated carbon, which is characterized in that it additionally contains granulated polystyrene foam and cold hardening glue (Patent for invention UA 95035, IPC B01J 20/20, C02F 1/28, publ June 25, 2011). Disadvantage sorbent there are difficulties in collecting oil and oil products from the surface of the water (low hydrophilicity).

The closest analogue of the sorption means, which is claimed, is a means for cleaning the surface of water from oil and petroleum products, containing a reservoir of porous sorbent, and the reservoir is made in the form of a two-layer plate, which consists of a layer of porous material based on the composition of crumb rubber from 0.2 to 2, 5 mm and powdered polyethylene, at a ratio of May. h .: Rubber crumb - 100, Polyethylene - 5-20 and polyethylene film connected to a porous material when heated (Patent for utility model RU 6165, IPC В32В 25/00, publ. 16.03.1998). The disadvantage of this tool is the low degree of absorption of oil and oil products, the two-layer design of the tool, which complicates its production, as well as the use of synthetic materials, the burning of which after use can cause additional environmental pollution.

The task of the second object of the invention is the creation of a sorption agent produced from a material, the raw material for which is spent rubber products, which would provide increased sorption capacity and absorption rate of petroleum products and other chemical and organic substances.

The technical result of the second object of the invention is to increase the sorption capacity and the rate of absorption of petroleum products and other chemical and organic substances while reducing the geometrical dimensions of the sorption agent itself and the amount of carbon adsorbent in its composition, enabling the sorption agent to be used in any media, including water and on land while ensuring consistently high sorption capacity under various conditions of its use and increase the time of retention of accumulated substances inside the sorption means without their leakage to the outside.

The problem is solved in that the proposed sorption tool consisting of a shell and a filler, in which the shell is made of nonwoven material, and as the filler used carbon adsorbent, manufactured according to claim 1 of the claims. In the proposed sorption tool, nonwoven fabric is secondary textile, with a density of 50-75 microns, and carbon adsorbent is a hydrophobic composite material that contains in% May: secondary cellulose fiber - 20-30% and carbon black - 70-80%, which is obtained from secondary rubber raw materials by the method of low-temperature catalytic pyrolysis and activated using superheated water vapor. In addition, under the shell contains a liner of recovered organic material.

Due to the new properties of the filler, namely the carbon adsorbent, the proposed tool has a high degree of absorption, increases the rate of sorption of pollutants;

- increases the convenience of sorption means;

- expanding the list of chemicals that can be absorbed (more than 100 liquids);

- carbon adsorbent, which is contained in the used sorption tool (with absorbed substance), can be regenerated for reuse.

It is known that the used carbon adsorbent (sorption means based on it) with the substance absorbed by it can be disposed of in the traditional way - by transferring it to the appropriate enterprises. Disposal of the carbon adsorbent is carried out according to the method of disposal, which is applied to the material collected by the adsorbent. In addition, it is possible to use the adsorbent used to collect petroleum products, as a filler in the production of asphalt bitumen, or as a solid fuel for industrial boilers or its component. The carbon adsorbent material allows it to be utilized by burning in industrial boilers to produce thermal energy, which makes its use cost-effective and at the same time prevents secondary pollution of the natural environment. The carbon in the composition of the adsorbent makes it a mixture with oil valuable energy product, and does not require, as is the case with other sorbents, the addition of coal to intensify the combustion process.

In the case when the adsorbed material is oil and oil products, it is possible to recycle the used carbon adsorbent, with simultaneous desorption of the collected oil product to produce hydrocarbon condensate.

In the prior art, a method for utilization of activated carbon by an oxidizing agent is known by low-temperature oxidative-destructive regeneration, including catalytic conversion of sorbed substances on the surface and in the pores of the carbon matrix with the formation of oxygen-containing functional groups and obtaining an ion exchanger in which the regeneration is carried out by demineralization with partial oxidation of the matrix surface, an aqueous solution of nitric acid or alkaline and / or hydrochloric acid is used as an oxidizing agent. solutions (Patent for invention UA N ° 77564, IPC B01J 20/34, C01B 31/08, publ. 5.12.2006). The disadvantage of this method is the use of various chemical substances (for example, a solution of nitric acid, alkali). In addition, the disadvantage of this method is the lack of commercial products, as a result of the application of the method, as well as the release of hazardous chemicals into the atmosphere. The closest to the method of regeneration of the used carbon adsorbent is the method of regeneration of sorbents for the removal of oil and oil products (SU 1453672, IPC WOY 15/00, publ. 10.11.1996), including the processing of the sorbent with organic, water-immiscible low-boiling and easy to mix with water vapor solvents that are supplied from below and discharged from above, with the removal of residual solvents from the sorbent with live steam or heated inert gas. In the method to reduce the consumption of solvent and energy costs for the regeneration of sorbents in the form of foamed polymeric materials of open-porous structure, the regeneration of sorbents is carried out with a mixture of water and solvent at the boiling point of the mixture, and water is removed above the sorbent layer below the zone of separation of water and solvent with oil , and the solvent with oil divert from the water surface on top of the zone of separation. The disadvantages of this method are the use of solvents in the regeneration process, which leads to the formation of toxic gaseous products, long processing time, high energy costs and the impossibility of multiple recovery of the sorbent by this method.

The objective of the method of regeneration of the used carbon adsorbent is to simplify the process of processing the used carbon adsorbent into a conditioned product with high sorption characteristics.

The technical result of the method of regeneration of the used carbon adsorbent is to simplify the process of processing the used carbon adsorbent into a conditioned product, ensuring high stability of the carbon adsorbent after its repeated regeneration, which is to maximize the retention of its activity when reused.

The problem is solved by the fact that the proposed method of regeneration of the used carbon adsorbent, including desorption of the collected oil from the surface of the used carbon adsorbent and obtaining solid carbon black, which is then subjected to heating, grinding and mixing with cellulose impurity, in which the desorption of the collected oil from the surface of the used carbon adsorbent is carried out in a pyrolysis unit by heating the specified carbon adsorbent to a temperature of 750 ° C and condensation of oil product vapors under atmospheric pressure for 4 hours, then obtained regenerated solid carbon black is fed to the thermal activation stage, which is carried out in an air stream with the addition of superheated water vapor for 30 minutes at a temperature of 150-400 ° C in a pyrolysis chamber under pressurized conditions, then solid carbon black is fed to a drum-type convection dryer where at a temperature of up to 200 ° C, moisture is removed from it for 1 hour, then the obtained solid carbon is fed to the adsorbent production line, where it is ground and mixed simultaneously together with recycled cellulose fiber, the dosage of which is 20-30% of the total mass of the mixture at ambient temperature, the mixing time is at least 20-30 minutes, and after that, the finished carbon adsorbent is packed in plastic bags with a capacity of 10-20 kg or in another container.

In addition, in the process of desorption in the pyrolysis unit reactor, a vapor-gas mixture and a solid regenerated carbon adsorbent is formed.

In addition, the gas-vapor mixture is divided into a mixture of non-condensed combustible gases used to operate the pyrolysis unit, and condensed liquid petroleum products suitable for further processing. The proposed invention is illustrated in Figure 1, which schematically shows a longitudinal section of the tool according to claim 5 and Figure 2, where the proposed sorption means according to claim 8 of the formula are schematically depicted.

In the proposed method of producing carbon adsorbent, which includes grinding rubber raw materials, carrying out pyrolysis to produce solid carbon black, mixing the obtained solid carbon with a hydrophobic material, solid carbon black is produced at a pyrolysis unit for processing rubber raw materials at atmospheric pressure and temperature 450-750 ° C in the presence of a modified catalyst, the carrier of which are the materials of the zeolite group. Such a catalyst, for example, can be a modified mineral palygorskite, which add 3-5% of the mass of tires that are processed. This catalyst intensifies the release of hydrocarbons in the processing of tires, helps to remove the greatest amount of hydrocarbons from carbon. Also, due to the fact that the catalyst absorbs such harmful substances as sulfur oxide, mercaptan, polycyclic aromatic hydrocarbons, asphaltene residues, emissions to the atmosphere are reduced.

Made by the proposed method, the carbon adsorbent is the product of a combination of carbon black obtained from the pyrolysis of polymer waste (used tires and other rubber and plastics waste) with recycled cellulose fiber. The combination of these components occurs mechanically under conditions of high pressure (for example, at a pressure of 2-2.5 bar) and simultaneous grinding. In the proposed method, 20-30% recycled cellulose fiber based on the total weight of the mixture (adsorbent) is used, as a result, the surface of the resulting adsorbent becomes hydrophobic and detects oleophilic properties that contribute to the high sorption activity of the carbon adsorbent with respect to a wide range of chemicals. The composition of the carbon adsorbent obtained by the proposed method is shown in Table 1.

Table 1

Carbon black is produced at the pyrolysis plant for processing used tires in atmospheric pressure and at a temperature of 450-750 ° C.

The principle of operation of the pyrolysis unit is to use the method of thermal decomposition of raw materials - semi-coking. The use of a catalyst in the process of pyrolysis of rubber products helps to eliminate pollutants from the vapor-gas mixture, the hydrocarbon fraction and helps reduce the presence of undesirable compounds in the solid residue. The catalyst also blocks the catalytic capabilities of metal oxides, which are an integral part of the composition of the metal cord that is in the rubber goods. It also contributes to the standardization of source products.

Coking is the decomposition of organic substances under the action of temperature without access to air, as a result of which destructive transformations of the feedstock take place with the formation of a solid residue and a vapor-gas mixture. The steam-gas mixture consists of vapors of flammable liquid and non-condensed flammable gases. The gas fraction is a mixture of various types of gases released during the heat treatment of raw materials. The technological cycle from the preparation of raw materials (input control, removal of metal cord and grinding) to the shipment of pyrolysis products lasts for 10 hours, the capacity of the installation of technical carbon is 1.5-3 tons per day (depending on the feedstock). In the production process, solid carbon is obtained, which is less active, with a low dispersion index and an average structural index.

The method of obtaining carbon adsorbent includes the following operations:

Collection of secondary raw materials (waste rubber products).

Since the retort in which the pyrolysis process is carried out can hold up to 1 ton of crushed rubber-technical products, such a mass of secondary raw materials is optimal. Next, carry out the grinding of the collected raw materials into parts ranging in size from 2 to 10 centimeters by loading waste rubber products on the machine for grinding. Grinding does not lead to loss of substance mass.

Crushed rubber products are loaded into retorts in order to carry out the pyrolysis process.

The process of pyrolysis occurs at a temperature of from 450 ° to 750 ° C for 8 hours. The pyrolysis process is carried out by gradual heating, with an increase in temperature every 5 minutes at 5-10 ° C and in the absence of air. To improve the characteristics of the original substance in the process of pyrolysis, a catalyst is added, namely a modified mineral palygorskite, with a total mass of from 3 to 5% of the incoming substance, depending on the characteristics of rubber products. The process results in a mixture of carbon black and metal cord parts with a total mass of up to 50% of the original substance, which is about 500 kg. The resulting solid carbon enters the magnetic separator, where the additional removal of metal parts of the cord from it is carried out. As a result of this process, parts of the metal cord, which was in rubber-technical products (20% by weight of the mixture loaded into the separator), and carbon black (80% by weight of the mixture loaded into the separator — 400 kg) are obtained.

In order to improve the quality of carbon black, namely, increase the porosity of its structure, then it is activated by superheated water vapor in the pyrolysis chamber at a temperature of 150-400 ° C.

Next, activated solid carbon is fed to a drum-type convection dryer for the purpose of dehydration, where at a temperature of up to 350 ° C for 1 hour moisture and residual aromatic hydrocarbons are removed. During this process, carbon black can lose up to 3% of its mass.

Dehydrated carbon at elevated pressure (2-2.5 bar) is fed to the sorbent production line, where at ambient temperature it is crushed and mixed simultaneously with a hydrophobic material, namely, the secondary cellulose fiber, the dosage of which is 20-30% from the total mass of the mixture, while the duration of mixing is 20-30 minutes.

A mixture of activated carbon and recycled cellulose fiber forms a carbon adsorbent with a total weight of 480-500 kg per 1 ton of waste rubber products. Next, the finished product is Packed in plastic bags with a capacity of 10-20 kg or in another container (polypropylene bags or big bags).

A sample of the carbon adsorbent obtained by this technology has the physicochemical parameters indicated in Table 2 and the particle size characteristics indicated in Table 3. table 2

Table 3

The resulting carbon adsorbent does not contain harmful substances, does not enter into chemical reactions with sorbed substances, does not emit heat, is not combustible and explosion-proof, safe for the environment and does not require special storage and transportation conditions.

Thus, the novelty of the method for producing a carbon adsorbent as a product of production consists of the following factors: - use as a basic sorbent material of secondary raw materials - carbon black obtained in the process of pyrolysis of polymeric waste;

- use of the method of hydrophobization of carbon black - by adding secondary cellulose fiber and the technology of mixing and grinding;

- selection of the optimum ratio of the constituent parts of the material of the adsorbent (70-80% carbon, 20-30% recycled cellulose fiber).

Advantages and characteristics of the carbon adsorbent obtained by the proposed method are: high adsorption capacity and absorption rate, hydrophobicity, high ability to retain the absorbed substance, buoyancy even in the state of full saturation, absorption capacity of various substances, the possibility of forced desorption and environmental friendliness.

In addition, the carbon adsorbent obtained has a high sorption capacity - 1 kg of sorbent absorbs 3-5 kg of oil, also has good performance relative to other liquids.

The resulting carbon adsorbent can be applied to a wide range of liquid substances (more than 100), which allows the use of a single product to solve many problems. The carbon adsorbent has a high rate of sorption. The fine-grained structure allows the carbon adsorbent to absorb spilled substances almost instantly (up to 1 minute). This is of great importance in response to accidental spills, which should be eliminated as soon as possible, especially on the surface of water bodies.

Hydrophobicity provides a high buoyancy rate of the carbon adsorbent (98%), so that it does not sink even in a state of complete saturation with the absorbed substance for a long time (up to 21 days). The high retention capacity of the adsorbent prevents the adsorbed substances from entering the environment, hydrophobicity provides protection against leaching of absorbed substances. Due to this, there is no threat of secondary pollution.

These properties are a significant advantage of the carbon adsorbent, manufactured according to the proposed method, when collecting oil and oil spills of a large area from the water surface, because they prevent precipitation of the sorbent, the ingress of harmful substances into the water and its secondary pollution, as well as pollution of the reservoir by the sorbent itself. This makes it possible, if necessary, to increase or postpone for a while the work on the elimination of spills on the water surface. Due to its fine-grained structure, carbon adsorbent is also effective in collecting thin oily films from the water surface.

In order to localize and eliminate accidental contamination, the carbon adsorbent is used by direct application (spraying) to the spill stain using a portable spray device of a knapsack type or manually, using improvised means (shovel, etc.) or directly spilling out of the bag. Adsorbent spraying on the surface of open or closed water bodies also occurs with the help of a stationary spraying device located on the deck of the vessel, directly on the spill spot, with its preliminary localization by barrier sorption means (sorbent booms or pillows).

It is also possible to use carbon adsorbent as a filler for filters of cassette-type wastewater treatment plants (similar to activated carbon), placing it in a sheath of nonwoven material (secondary textiles). Hydrophobic carbon adsorbent creates a selective barrier that allows water to pass through and retains contamination. In combination with high sorption This ability allows using carbon adsorbent for purification of large volumes of water from suspended particles in sewage treatment plants - industrial septic tanks and systems for pre-treatment of industrial and storm sewage.

On the basis of the carbon adsorbent, sorption products are produced. As shown in Fig.1-2, the proposed sorption tool contains the shell 1, the liner 2 from the recovered organic material, for example, from the secondary cellulose fiber, and the filler 3. The shell 1 is made of non-woven material such as secondary textiles, with a density of 50-75 microns. In the proposed technical solution, the carbon adsorbent containing in% May is used as a filler:

Secondary cellulose fiber 20-30;

Technical carbon 70-80.

In one of the embodiments of the invention, on the basis of the proposed carbon adsorbent composition, a sorption agent is made in the form of sorption booms (as shown in FIG. 1), which consist of a nonwoven fabric wrapper 1, which is made in the form of a sleeve and filled with filler 3, namely carbon adsorbent. Under the shell 1 contains the liner 2, made of recovered organic material, such as recycled cellulose fiber, which envelops the filler 3. The sleeve shell 1, protected by durable textile mesh 4 and equipped with a cable 5, two carbines 6 and loops 7 for connecting sorption booms - boom sections among themselves.

The design characteristics of the boom section are mainly as follows:

- diameter - 0.13-0.15 m;

- length - 3.0-3, 5 m;

- weight - 10-12 kg. Sorption booms are used to limit spills of oil, petroleum products, technical liquids, edible oils and other substances, for example, on the surface of a reservoir, and its localization, preventing spreading of the spill beyond the sorption barrier. To do this, the boom sections, interconnected by carbines 6, are placed in a tight closed ring on the border of the spill spot and a clean surface. A carbon adsorbent is applied inside the ring to bind the spilled substance.

Sorption booms are collected after collecting the pollutant and sent to a specially equipped place of storage, and then for recycling or regeneration of the used carbon absorbent.

Also based on the carbon adsorbent, which is made according to the method stated in claim 1 of the formula, make sorption means in the form of a pillow according to claim 9 (as shown in Figure 2), which are used to absorb petroleum products, oils and other chemicals from solid surface, from water, wastewater, indoors and in open areas. The hydrophobic material of the pillow filler does not absorb water, the pillow remains on the surface after complete saturation with the collected substance, and its filler does not release the collected material.

The cushion is used in areas of spills and leaks, in wells and septic tanks with oily waste, or where oil needs to be separated from water, in industrial plants with constantly leaking equipment.

Structurally, the pillow consists of a shell 1 of nonwoven material (secondary textile), a liner 2 of recovered organic material, for example, recycled cellulose fiber, and filler 3 of a carbon adsorbent. The design parameters of the cushion are mainly as follows:

- length - 0.38-0.42 m;

- width - 0.38-0.42 m;

- height - 0.06-0.08 m.

Additionally, there is the possibility of making a pillow with a one-sided (inner layer) plastic wrap, which is designed to prevent the flow of a substance collected under the equipment that constantly leaks.

The amount of sorption booms and pillows required depends on the nature, location and amount of chemical fluid that is absorbed.

Since the filler, namely, carbon adsorbent, has a fine-grained structure, the proposed sorption means almost instantly absorbs the spilled substances (up to 1 minute). This is essential for the response to accidental spills, which should be eliminated as soon as possible, especially on the surface of water bodies. Due to the fine-grained structure of the carbon adsorbent, the proposed sorption tools are also effective in collecting thin oily films from the water surface.

The hydrophobicity of the carbon adsorbent (98%) provides a high rate of buoyancy of sorption means, so that they do not sink even in a state of complete saturation with the absorbed substance for a long time (up to 21 days).

The high retention capacity of the adsorbent (99%) does not allow adsorbed substances to be released into the environment, hydrophobicity provides protection against leaching of absorbed substances. Due to this, there is no threat of secondary pollution.

Regarding the consumer qualities of the sorption agent based on carbon adsorbent, the new one is the expansion of the possibilities and methods of handling the used sorbent - use as fuel and regeneration of the adsorbent with simultaneous desorption of oily substances.

The proposed method of regeneration of the used carbon adsorbent, which is the third object of the present invention, is carried out using an installation for processing the spent carbon adsorbent, which consists of the following sections (process units):

- desorption site of sorbed oil, oil sludge and / or mixtures of waste oil products;

- site of final regeneration and preparation of carbon adsorbent;

- the site of thermal activation of solid carbon black in the air stream with the addition of superheated steam;

- reservoir park for hydrocarbon condensate;

- a warehouse of finished solid products.

The main technical and economic indicators of the regeneration process of the used carbon adsorbent:

- the estimated annual capacity of the site with desorption of sorbed oil from the surface of the adsorbent is 6,600 tons per year;

- the estimated operating time of the reactor - 330 working days per year;

- daily output of carbon adsorbent feedstock with sorbed oil or oil products - 20 tons per day;

- daily capacity of the plant for output:

- for desorbed oil or oil products - at least 5 tons;

- carbon adsorbent - not more than 2.0 tons

The recycling process begins with the shipment of the used carbon adsorbent from the temporary waste storage site to the pyrolysis unit. As an input to the process regeneration uses a carbon adsorbent containing a sorbed substance that has been removed from the sorption agent, for example sorption booms after their use.

1 ton of the mixture is loaded into the retort, which is placed in the pyrolysis unit and heated to a temperature of 750 degrees. In the process of pyrolysis, desorption of the absorbed substances occurs in the form of a hydrocarbon fraction, which after condensation acquires a liquid state with a total mass of up to 800 kg, and which can be reused. In the pyrolysis unit, desorption of the sorbed oil product from the surface of the carbon adsorbent occurs by heating the latter to a temperature of 400 ° C and condensing the oil product vapor under atmospheric pressure for 4 hours.

As a result of the process of processing a mixture of used adsorbent with oil by pyrolysis, the following is obtained:

- steam-gas mixture, which after condensation is divided into liquid petroleum products, suitable for further processing and a mixture of non-condensed combustible gases used to operate the pyrolysis unit;

- hydrocarbon gas fraction C2-C4, formed from petroleum product absorbed by the sorbent when heated in a pyrolysis unit. The resulting gas through the gas distribution system enters the furnace installation, where it is burned to maintain its temperature, providing energy efficiency of the regeneration process;

- desorbed oil product from the gas-vapor phase, which is condensed in the gas distribution system, consisting of a refrigerator and a pipeline system; - regenerated solid carbon, which remains in the retort of the installation and after the termination of condensation of the oil product is fed further for processing.

In order to improve the quality of carbon black, namely to increase the porosity of its structure, then it is activated by superheated water vapor in the pyrolysis chamber.

Next, the regenerated solid carbon black is fed to the thermal activation stage, which is carried out in an air stream with the addition of superheated water vapor for 30 minutes. at a temperature of 150-400 ° C in a pyrolysis chamber under conditions of high pressure (for example, 2-2.5 bar).

Next, solid carbon is fed to a drum-type convection dryer for the purpose of dehydration, where at a temperature of up to 200 ° C for 1 hour moisture and residual aromatic hydrocarbons are removed.

Dehydrated carbon at elevated pressure (2-2.5 bar) is fed to the sorbent production line, where it is crushed at ambient temperature and mixed simultaneously with a cellulosic impurity, which is a secondary cellulose fiber, the dosage of which is 20-30% May from the total mass of the mixture (adsorbent) at ambient temperature; mixing time is 20-30 minutes. After that, the ready-made carbon adsorbent is packed in plastic bags with a capacity of 10-20 kg or in another container (polypropylene bags or big bags).

As a result of the processing of the mixture of the used adsorbent with oil by pyrolysis, the following is obtained: gas that is burned in the furnace of the installation to maintain its temperature, solid carbon and desorbed oil from the gas vapor phase. Depending on the state of the mixture (soil contamination, humidity, length of storage time after collection, and other factors) it is possible to return up to 70% of petroleum products relative to the amount of oil that was collected by the sorbent and was in the soil at the spill site. The oil product obtained in this process is a distillate of a wide fractional composition (synthetic oil).

The oil product obtained as a result of condensation is shipped to the tank farm, from where it is shipped to the consumer. The obtained desorbed distillate oil is used as a hydrocarbon feedstock for further processing at refineries.

After regeneration, an adsorbent of carbon and petroleum desorbed distillate is obtained with the indices that are listed in Table 1.

Table 1. Physico-chemical characteristics of the products of regeneration of the used carbon adsorbent

The proposed method for producing a carbon adsorbent allows to obtain a product that is the main adsorbent material of a highly efficient, environmentally friendly carbon adsorbent, and obtained as a result of the utilization of used tire covers. In addition, the use in its manufacture of secondary raw materials (tires) makes the method of obtaining carbon adsorbent more environmentally and economically viable.

The proposed sorption tools can be successfully applied by oil producing organizations and oil refineries, at industrial enterprises, car services, gas stations, tank farms, in air and sea ports, sea and river vessels, at bulk stations of oil and oil products and other enterprises. The advantages and characteristics of the proposed means are: high adsorption capacity and absorption rate, hydrophobicity, high ability to retain the absorbed substance, buoyancy even in a state of full saturation, the ability to absorb a wide range of substances, the possibility of forced desorption and environmental friendliness.

The proposed method of regeneration of the used carbon adsorbent with the release of the liquid hydrocarbon fraction brings the user economic benefits, and creates the prerequisites for the environmental management of economic activity - the preservation of natural energy resources through the use of processed products.

Despite the fact that the present invention is described in detail, including some variants of its implementation, it is obvious to a person skilled in the art that changes in form and detail can be made without departing from the scope and scope of this invention.

Claims

Formula

1. A method of producing a carbon adsorbent, which includes grinding rubber raw materials, carrying out pyrolysis to produce solid carbon black, mixing the obtained solid carbon with a hydrophobic material, characterized in that solid carbon black is produced at a pyrolysis unit for processing rubber raw materials at atmospheric pressure and temperature 450-750 ° C in the presence of a modified catalyst, the carrier of which are materials of the zeolite group, then from the obtained solid carbon with using a magnetic separator, the metal parts of the cord are removed, after which thermal activation of solid carbon black is carried out in an air stream with the addition of superheated water vapor for 30 minutes at a temperature of 150-400 ° C in a pyrolysis chamber under pressurized conditions, then the treated carbon is fed into a drying chamber , while the process of removing moisture is carried out at a temperature of up to 350 ° C for 1 hour, after which solid carbon prepared in the previous stages is fed under high pressure to l In the production of the sorbent, where at ambient temperature, it is crushed and simultaneously mixed with a hydrophobic material, namely, a secondary cellulose fiber, the dosage of which is 20-30% of the total mass of the mixture, while the duration of mixing is 20-30 minutes.

2. A sorption agent consisting of a shell and a filler, characterized in that the shell is made of nonwoven material, and the carbon adsorbent used in the method, which is made by the method according to claim 1, of the formula.

3. Sorption tool according to claim 2, characterized in that the nonwoven fabric is a secondary textile, density of 50-75 microns.

4. Sorption agent according to claim 2, characterized in that the carbon adsorbent is a hydrophobic composite material, which contains in% May .:

Secondary cellulose fiber 20-30;

Technical carbon 70-80.

5. Sorption tool according to claims 3-4, characterized in that the shell is made in the form of a sleeve, around which an additional protective sheath is made of textile mesh, and the ends of the said sleeve are equipped with a cable and at least one connecting element.

6. Sorption tool according to claim 5, characterized in that the connecting element is a carbine.

7. Sorption tool according to claim 5, characterized in that the sleeve is made with a diameter of 0.13-0.15 m and a length of 3.0-3, 5 m.

8. Sorption tool according to claim 5, characterized in that in addition under the shell contains a liner of recovered organic material.

9. Sorption tool for PP.3-4, characterized in that it is made 0.38-0.42 m long, 0.38-0.42 m wide and 0.06-0.08 m high.

10. Sorption tool according to claim 9, characterized in that in addition under the shell contains a liner of recovered organic material.

11. The method of regeneration of the used carbon adsorbent, including desorption of the collected oil from the surface of the used carbon adsorbent and obtaining solid carbon black, which is then subjected to heating, grinding and mixing with cellulosic impurity at the stage, wherein desorption of the collected oil from the surface of the used carbon adsorbent is carried out in the pyrolysis installation by heating the specified carbon adsorbent to a temperature of 750 ° C and condensation oil product vapor at atmospheric pressure for 4 hours, next, the obtained regenerated solid carbon black is fed to the thermal activation stage, which is carried out in an air stream with the addition of superheated water vapor for 30 minutes at a temperature of 150-400 ° C in a pyrolysis chamber under pressurized conditions, then solid carbon black is fed to a convection dryer drum type, where at a temperature of up to 200 ° C, moisture is removed from it for 1 hour, then the solid carbon obtained is fed to the adsorbent production line, where it is ground and one temporary mixing together with recycled cellulose fiber, the dosage of which is 20-30% of the total mass of the mixture at ambient temperature, and the duration of mixing is at least 20-30 minutes, and after that, the finished carbon adsorbent is packaged in plastic bags with a capacity of 10-20 kg or other container.

12. The method according to claim 11, characterized in that during the desorption process in the pyrolysis reactor installation, a vapor-gas mixture and a solid regenerated carbon adsorbent is formed.

13. The method according to p. 12, characterized in that the gas-vapor mixture is divided into a mixture of non-condensed combustible gases used for the operation of the pyrolysis unit, and condensed liquid petroleum products, which are suitable for further processing.