WO2006096085A1

WO2006096085A1 - Method for recycling rubber-containing and other industrial and domestic wastes into chemical raw material and engine fuel components

Info

Publication number: WO2006096085A1
Application number: PCT/RU2005/000173
Authority: WO
Inventors: Vladimir Vladimirovich Platonov
Original assignee: Obschestvo S Ogranichennoy Otvetstvennostu 'npk 'tekhnokhim'
Priority date: 2005-03-09
Filing date: 2005-04-06
Publication date: 2006-09-14
Also published as: RU2275397C1

Abstract

The invention relates to chemically recycling rubber-containing and other industrial and domestic wastes into motor fuel componenets and a raw material for base organic, petrochemical and biochemical synthesis, for producing anode masse for electrothermal and electrochemical factories, hydro-, heat- and sound-insulating materials and a road building asphalt concrete. The inventive method consists in thermocatalytically liquefying wastes at a temperature of 200-320 °C and a pressure ranging from 1 to 3 MPa in a hydrocarbon solvent, in subsequently separating liquid products and in carrying out the rectification thereof for obtaining target products. Said hydrocarbon solvent is embodied in the form of a mixture of alkylbenzene-containing hydrocarbons and a hydrocarbon hydrogen-dopant solvent having a lesser induction effect time, for example, tetralin or a paraffin-naphthenic oil fraction, whose boiling point ranges from 230 to 280 °C. Said invention makes it possible to substantially reduce the induction time of a thermolysis process by the greater hydrogen activity of the second solvent, to increase the atomic hydrogen or the liquid phase use factor for recombinating low-molecular radical thermolysis products of the waste organic materials, to increase the performance of a reaction device and to improve the process economic parameter.

Description

METHOD FOR PROCESSING RUBBER-CONTAINING AND OTHER INDUSTRIAL AND HOUSEHOLD ORGANIC WASTE IN CHEMICAL RAW MATERIALS AND MOTOR FUEL COMPONENTS

The invention relates to the chemical processing of rubber-containing, as well as industrial and domestic organic wastes (polyethylene, polystyrene, polyisobutylene, nylon, lavsan, enanth, nylon, polyvinyl chloride, various types of rubber, phenol-formaldehyde pillow resins, etc.) into motor fuel components and raw materials for the industry of basic organic, petrochemical and biochemical synthesis, the production of anode paste for electrothermal and electrochemical enterprises, hydro-, heat- and sound-proof materials, asphal concrete for road construction. The problem of chemical recycling of waste tires

(automobile, aviation, etc. transport), various industrial and domestic organic wastes is very relevant, due to the constant increase in the amount of these wastes and, at the same time, the lack of effective methods for their processing, taking into account the specifics of their chemical composition, to obtain a wide range of valuable products, raw materials for the industry of basic organic and petrochemical synthesis.

Given the complex chemical composition of various organic wastes and rubber-containing materials, the most promising methods are their integrated environmentally friendly chemical processing in order to obtain boiler fuel, components of high-octane motor fuels, raw materials for the petrochemical, organic and biochemical synthesis industries, production of hydro-, heat- and soundproof materials, asphalt concrete for road construction, carbon-graphite

SUBSTITUTE SHEET (RULE 26) materials, anode paste for electrothermal and electrochemical industries.

The solution to this problem will significantly expand the raw material base of hydrocarbon raw materials, in which, in connection with a significant reduction in the reserves of natural oil, the rate of its exploration, production and subsequent deep processing, there has been an acute shortage in recent years; solve the environmental problem of integrated and harmless disposal of rubber-containing and a wide range of industrial and domestic organic waste; significantly reduce the consumption of hydrocarbons produced on the basis of oil, brown and hard coal, oil shale, natural bitumen.

A known method of processing rubber-containing waste - waste tires, including grinding the latter to 4 - 0.75 mm, mixing with petroleum products, heating the resulting mass in a reactor at 65 - 37O ⁰ C for a time sufficient to dissolve the material, catalytic cracking of the resulting solution in the reactor at a temperature not lower than 450 ⁰ C and high pressure, unloading the product from the reactor and its subsequent distillation to obtain gaseous products, gasoline fraction, light and heavy oils

This method is characterized by multi-stage, the complexity of the technology associated with the need: grinding waste tires, which is very difficult, especially in the presence of steel cord; the use of a specific catalyst and its periodic regeneration; the use of high temperatures and pressures, causing the formation of significant quantities of low molecular weight gaseous products, as well as high molecular weight asphaltene hydrocarbons due to condensation reactions.

SUBSTITUTE SHEET (RULE 26) A known method of producing resin from rubber-containing waste, including heating it at a temperature above 200 ⁰ C in a hydrocarbon liquid with a duration that ensures the conversion of rubber into a viscous oil-like product, and contacting the latter with an alkylation catalyst (H ₂ SCb; S ₂ Cl ₂ ) after adding to it aliphatic aldehyde or ketone. The resulting resin is introduced into rubber compounds for tire production (US 3895059, 1975).

The specified method is also characterized by multi-stage, the need to use sulfuric acid, sulfur semi-chloride, capable of causing a condensation reaction, compaction, which complicates the preparation of low molecular weight liquid products. In addition, the use of the resulting product is limited and specific. A known method of processing rubber-containing waste, including mixing at a temperature of 290-380 ⁰ C solution of rubber-containing waste with a concentration of 10-80 wt.% In a hydrocarbon medium and distillation of low-boiling fractions. The hydrocarbon medium used is a product of deasphalting with propane of oil tar containing 2.4-5.9 wt.% Asphaltenes and a softening point of 34-45 ⁰ C. Low-boiling fractions with a boiling point of 230-310 ⁰ C are continuously distilled off during the entire mixing process (SU N ° 1613455, 1990).

The disadvantages of this method include, first of all, restrictions on the content of asphaltenes in the hydrocarbon medium. This condition is difficult to fulfill, since oil and oil products extracted in recent years are characterized by a high content of asphaltenes, resinous and organosulfur compounds, therefore, an increase in the number of extraction cycles is required

SUBSTITUTE SHEET (RULE 26) listed compounds. In addition, this method is characterized by insufficiently high yield of light fractions. The total amount of light fractions boiling in the temperature range up to 230 ⁰ C is 12.4-37.8 wt.%. A known method of processing rubber-containing waste, which consists in heat liquefying at 270-420 ⁰ C, pressure 1-6 MPa in a hydrocarbon solvent medium, which uses synthetic rubber waste, and in the presence of rare-earth metal (REM), or in the presence of intermetallic compounds REM-based, or in the presence of titanium hydride, taken in an amount of 0.5-10.0 wt.% from the reaction mixture. The method involves thermal liquefaction with a mass ratio of hydrocarbon solvent and waste of 2: 1-4: 1. The method is characterized by a low coefficient of use of the hydrogen donor potential of the solvent components, which requires its repeated use in the process, constant separation of the feedstock from liquid thermal fluid products, and also maintaining high pressure in the reaction apparatus (RU Ne2109770, 1998).

A significant disadvantage of this method is the use as a hydrocarbon solvent of synthetic rubber waste products that are not always available in the required quantity. In addition, quite scarce REMs, intermetallic compounds based on them, calcium hydrides, titanium hydrides are needed. A method is known for processing rubber-containing as well as organic industrial and household wastes into chemical raw materials and motor fuel components, carried out similarly to the above, in which one is used as a hydrogen donor solvent or a mixture of dkylbenzenes (toluene,

SUBSTITUTE SHEET (RULE 26) xylenes, ethylbenzenes, diethyl-, trimethyl- and tetramethylbenzenes), which are the basis of "crude benzene" - a product of high-temperature coking of coal. These hydrocarbons are effective hydrogen donors, are available in large quantities, their use in this technology allows us to solve both the technical, environmental and economic problems (RF patent N ° 2110535, 1998).

A significant disadvantage of this method is the use of rare-earth metals, intermetallic compounds based on neodymium, lanthanum, cerium, aluminum, as well as titanium and calcium hydrides, which are relatively deficient materials, the difficulty of their subsequent extraction from the mass of carbon black and highly resinous heavy hydrocarbon residues, high pressure in the reaction apparatus due to the low degree of use of hydrogen from the composition of the gas phase resulting from the thermolysis of organic waste.

A known method of processing organic polymer waste, including heat liquefaction of waste at a temperature above 27O ⁰ C at elevated pressure in at least one solvent - alkylbenzene, separation of the liquid fraction and its distillation, while using heat liquefaction of wastes using an increased pressure of at least 6.1 MPa, and after distillation, a liquid fraction with a boiling point of at least 21O ⁰ C is introduced during thermal liquefaction of the newly processed waste as an additional component to the solvent in a mass ratio of additional component and solvent not less than 1: 1 (RF patent N ° 2167168, 2001).

A significant disadvantage of this method is its inefficiency in obtaining high-octane gasoline fraction. This disadvantage arises due to the removal of the liquid fraction from the reaction mixture with a boiling point of less than 200 ⁰ C. Most

SUBSTITUTE SHEET (RULE 26) active initiators of the continuation of the chain of radical reactions are low molecular weight alkylbenzenes with a boiling point of up to 200 ⁰ C. The removal of this fraction from the reaction mixture and the addition of a high boiling point will not accelerate the process of hydrogen transfer, and generally speed up the process. A high boiling fraction is added for subsequent thermocracking to obtain kerosene and solar fractions, but not a high octane gasoline fraction.

The closest in technical essence to the proposed method is a method in which the waste is subjected to thermocatalytic liquefaction at 220-360 ⁰ C, pressure 1-3 MPa in a hydrocarbon hydrogen donor solvent in the presence of an initiator - free iodine and / or iodine-containing compounds, taken in an amount of 0.01 -0.50 wt.% Of solvent to obtain the desired products. Inorganic and organic iodine compounds are used selected from the group consisting of iodides of potassium, titanium, cobalt, nickel, ethyl iodide, tert-butyl iodide and others, or mixtures thereof. The solvent used is alkylbenzene, a mixture of alkylbenzenes, alkylbenzene-containing hydrocarbon mixtures. Preferably, the method is carried out in a weight ratio of waste: solvent 1: 2-4. The method allows to simplify the process technology, to increase the yield of liquid products of better quality, which can be used as components of motor fuel and chemical raw materials (RF patent N ° 2156270, C 1, 2000).

The disadvantages of this method include the low degree of use of the hydrogen donor potential of the solvent components, a sufficiently high energy intensity of the process,

SUBSTITUTE SHEET (RULE 26) due to the temperature of the process not less

22O ⁰ C, as well as its duration.

The objective of the invention is to develop a method to increase the hydrogen donor potential of the solvent, due to more efficient use of hydrogen of the latter, simplify the technology, reduce temperature and pressure, increase process productivity while increasing explosion and fire safety, increase the yield of fractions with a boiling point up to 200 ⁰ C, characterized by a low content of oxygen, nitrogen and organosulfur, as well as unsaturated compounds, to improve the quality of carbon black, fill calves in rubber waste, pyrogas.

The problem is solved due to the fact that during the processing of rubber-containing and organic industrial and household wastes into chemical raw materials and motor fuel components, thermocatalytic liquefaction of wastes is carried out at elevated temperatures and pressures in a hydrocarbon solvent, followed by separation of liquid products and their rectification to obtain target products, of this, according to the invention, a mixture of alkylbenzene-containing hydrocarbons with hydrocarbon water is used as a hydrocarbon solvent orododonornym solvent having minimal induction effect, and the process is carried out at a temperature of 200-320 ⁰ C, a pressure of 1-3 MPa.

In a preferred embodiment, tetralin or fractions of paraffin-naphthenic oil with a boiling point of 230-280 ⁰ C are used as a hydrocarbon solvent having a shorter induction time than alkylbenzene-containing hydrocarbons.

SUBSTITUTE SHEET (RULE 26) Preferably, the method is carried out at a weight ratio of alkylbenzene containing hydrocarbons: tetralin / or a fraction of paraffin-naphthenic oil with a boiling point of 230-280 ⁰ C equal to 10: 0.5 to 10: 2.0. Preferably, the method is carried out in a weight ratio of waste: solvent (solvent mixture) of 1: 2-4.

In the implementation of the method, initiators can be used, for example, free iodine and / or iodine-containing compounds taken in an amount of 0.01-0.50 wt.% Of the solvent can be used as initiator.

Rare-earth metals, or rare-earth-based intermetallic compounds, or titanium hydride, taken in an amount of 0.5-10.0 wt.% Of the reaction mixture, or other known initiators can also be used as initiators. As a source of alkylbenzenes, it is advisable to use

"crude benzene" or its individual components (toluene, xylenes, solvent fraction) obtained by high-temperature coking of fossil fuels and which is a waste product of metallurgical coke production. Amounts of "crude benzene" are quite large, but it still does not find rational use. It is advisable to use tetralin or fractions with a boiling point of 230 - 28O ⁰ C paraffin-naphthenic oil as additional hydrogen donors that significantly reduce the induction period of the thermolysis of organic waste material. Tetralin is a product of the catalytic hydrogenation of coke chemical naphthalene, its quantities are significant, but has not yet been rationally applied.

The technical result from the use of the invention is achieved by introducing a new feature - the use of a mixture of alkylbenzenes and

SUBSTITUTE SHEET (RULE 26) a hydrogen donor hydrocarbon having a shorter induction effect than alkylbenzenes, for example, tetralin or a fraction with a boiling point of 230-280 ^° C of paraffin-naphthenic oil enriched in isoalkanes, cycloalkanes and hydroaromatic hydrocarbons (effective hydrogen donors). The technical result consists in a significant reduction in the induction period of the process of thermolysis of the organic waste material due to the higher hydrogen donor activity of tetralin and a fraction of paraffin-naphthenic oil with a boiling point of 230-280 ⁰ C; in increasing the utilization of atomic hydrogen or liquid phase for the recombination of low molecular weight radical products of thermolysis of organic waste material, increasing the productivity of the reaction apparatus, improving the economic performance of the process as a whole. In tetraline and fractions with a boiling point of 230-280 ^° C of paraffin-naphthenic oil, which act as initiators of the reaction, the energy for breaking the C - H bond with the formation of atomic hydrogen is less important than the energy for breaking similar bonds in alkylbenzenes. Due to this, a decrease in the temperature of the onset of the reaction and a decrease in pressure, as well as the reaction time, are possible.

The method is as follows. Rubber-containing, other industrial and household organic waste (waste tires, chambers, conveyor belts, rubberized ventilation shaft hoses, polyethylene, polystyrene, polypropylene, polyisobutylene, synthetic rubber, polyvinyl chloride, nylon, nylon, enanth, lavsan is loaded into a rotating autoclave (2 l) and others). Then add a hydrogen donor hydrocarbon solvent in a weight ratio of alkylbenzenes:

SUBSTITUTE SHEET (RULE 26) tetralin / or fraction with a boiling point of 230 - 280 ⁰ C of paraffin-naphthenic oil equal to 10: 0.5 - 10: 2.0 and the initiator in the required amount.

The process of thermocatalytic liquefaction of waste is carried out at a temperature of 200 - 320 ⁰ C and a pressure of 1-3 MPa; mass ratio of waste: solvent 1 -.2-4.

At the initial stage of the reaction, first of all, atomic hydrogen, under the influence of iodine or iodine-containing products, is split off from tetralin, then from the other components, hydrogen is a donor hydrocarbon solvent, as well as cyclohexanes and hydroaromatic hydrocarbons, of the oil fraction and is transferred to radical products formed during the thermolysis of organic waste material . Hydrogen transfer is additionally intensified by naphthalene structures formed during tetralin dehydrogenation. This explains the high speed of the liquefaction process, low temperatures and pressures, a high degree of use of hydrogen components of the solvent and the gas phase, deep thermolysis of waste compounds, low oxygen, nitrogen and sulfur content, as well as unsaturated compounds in the resulting liquid products, high yield the latter; increasing the selectivity of the reactions of isomerization, cyclization, hydrogenation and dehydrogenation, hydrodealkylation, hydrogenation of polyamide, disulfide, polyester bonds, heterocycles with their subsequent destruction, responsible for the formation of significant quantities of cycloalkanes, isoalkanes, hydroaromatic and aromatic hydrocarbons characterized by high octane numbers; a decrease in the content of oxygen, nitrogen, and organosulfur, as well as unsaturated compounds in liquid products.

SUBSTITUTE SHEET (RULE 26) Liquid products are separated from solids.

(metal cord, carbon black and others), after which they are subjected to rectification to obtain the target products - fractions with a boiling point up to 200 ⁰ C, 200-280 ⁰ C and above 280 ⁰ C. Examples of the proposed method are shown in the table. Description of the example (N ° 4 in the table): 150 g of waste (recycled rubber, tire, polyethylene, polystyrene, polyisobutylene, synthetic rubber, polyvinyl chloride and others), 450 g of hydrogen donor solvent containing 430 g of toluene are loaded into a rotating autoclave (2 l), 20 g of tetralin / or a fraction with a boiling point of 230 - 280 ⁰ C paraffin-naphthenic oil, 0.90 g of free iodine and / or its inorganic, organic compounds (potassium, titanium, cobalt iodides, ethyl iodide, tert-butyl iodide, etc.).

The process is carried out at a temperature of 300 ⁰ C, a pressure of 2.5 MPa for 30 minutes. The yield of liquid products is 95.0 may. % of the organic material of the waste, the content of the fraction boiling in the temperature range up to 200 ⁰ C is 83.0 May. % of liquid products, up to 32O ⁰ C - 95.5 wt.%. The obtained fractions can be used as high-octane components of motor fuel and chemical raw materials for the production of basic organic, biochemical and petrochemical synthesis. Carbon black can be recommended as a filler in rubber products, production of anode paste for electrothermal and electrochemical industries. From the table it follows that the use of a mixture of hydrocarbon donors of hydrogen (alkylbenzenes, tetralin or a fraction with a boiling point of 230-280 ⁰ C paraffin-naphthenic oil) can increase the yield of liquid products and the content of fractions with a boiling point up to 200 ⁰ C enriched in isoalkanes ,

SUBSTITUTE SHEET (RULE 26) cycloalkanes, hydroaromatic and aromatic hydrocarbons, lower temperature, pressure, reduce process time.

SUBSTITUTE SHEET (RULE 26) W n

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ABOUT

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Claims

CLAIM

1. A method of processing rubber-containing and industrial and household organic wastes into chemical raw materials and motor fuel components, including thermocatalytic liquefaction of wastes at elevated temperature and pressure in a hydrocarbon hydrogen donor solvent, followed by separation of liquid products and their rectification to obtain target products, characterized in that the process carried out in the presence of a mixture of hydrogen donor hydrocarbons, one of which is used alkylbenzenes, and the second is hydrogen a donor hydrocarbon having a shorter induction effect time, while the process is carried out at a temperature of 200-320 ⁰ C and a pressure of 1-3 MPa.

2. The method according to p. 1, characterized in that the process is carried out in a mixture of alkylbenzenes and tetralin, taken in a mass ratio of 10: 0.5 - 10: 2.0.

3. The method according to p. 1, characterized in that the process is carried out in a mixture of alkylbenzenes and fractions with a boiling point of 230 - 280 ⁰ C paraffin-naphthenic oil, taken in a mass ratio of 10: 0.5 - 10: 2.0.

4. The method according to p. 1 or 2, characterized in that as the initiator use free iodine and / or iodine-containing compounds, taken in an amount of 0.01 - 0.50 wt.% From the solvent.

5. The method according to any one of paragraphs. 1-3, characterized in that the process is carried out with a mass ratio of waste: solvent, equal to 1: 2-4.

SUBSTITUTE SHEET (RULE 26)