WO2006096086A1

WO2006096086A1 - Method for recycling rubber-containing and other industrial and domestic wastes into chemical raw material and engine fuel components

Info

Publication number: WO2006096086A1
Application number: PCT/RU2005/000174
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: RU2272826C1

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. The inventive method consists in thermocatalytically liquefying wastes at a high temperature and pressure in a hydrocarbon hydrogen-dopant solvent, in subsequently separating liquid products and in carrying out the rectification thereof for obtaining target products, wherein the process is carried out in the presence of a mixture of hydrogen-dopant hydrocarbons, one of which is embodied in the form of alkyl benzenes and the second in the form of a hydrogen-dopant hydrocarbon, having a lesser induction effect time, at a temperature of 200-320 °C and a pressure of 1-3 MPa. Said process is also carried out in the presence of a catalyst in the form of a phthalocyanine or dimethylglyoxymates selected from a group containing copper, nickel, cobalt, molybdenum, titanium, manganese, iron and the mixture thereof. In the preferred embodiment, the process is carried out in a mixture of alkyl benzenes and tetralin at the mass ratio thereof ranging from 10:0.5 to 10:2.0 or in a mixture of alkyl benzenes and a paraffin-naphthenic oil fraction, whose boiling point ranges from 230 to 280 °C, at the same mass ratio. Said invention makes it possible to increase the hydrogen potential of the solvent by the more efficient use of a hydrogen thereof, the process selectivity for liquefying chemically complex wastes, to simplify the industrial process, and reduce temperature and pressure.

Description

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

5

The invention relates to the chemical processing of rubber-containing, as well as industrial and domestic organic waste (polyethylene, polystyrene, polyisobutylene, nylon, lavsan, enanth, nylon, polyvinyl chloride, various types of rubber, phenol-formaldehyde pillow resins, etc.) into motor components fuels 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, asf ltobetona for

15 road construction.

The problem of chemical recycling of used tires (automobile, aviation, etc. transport), various industrial and domestic organic waste is very urgent, due to the constant increase in the number of these

20 waste and, at the same time, the lack of effective methods for their processing, taking into account the specifics of their chemical composition, with the receipt of 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

25 waste and rubber-containing materials, the most promising are methods for 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, for the production of hydro-, heat- and sound-proof 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 - 370 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 elevated pressure, unloading the product from the reactor and its subsequent distillation to obtain gaseous products, gasoline fraction, light and heavy oils (US JVb 4175211, 1976).

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 liquid products from rubber waste, including heating them 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 SO ₄ , S ₂ Cl ₂ ) after adding to him an aliphatic aldehyde or ketone. The resulting resin is introduced into rubber compounds in the manufacture of tires (US JY <> 3895059, 1975).

The specified method is also characterized by multi-stage, the need to use sulfuric acid, sulfur semi-chloride, which can cause the occurrence of deep condensation reactions, compaction, which complicates the formation 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. As a hydrocarbon medium, a product of deasphalting with propane of oil tar containing 2.4-5.9 wt.% Asphaltenes and a softening point of 34-45 ° C is used. The distillation of low-boiling fractions with a boiling point of 230-310 ⁰ C is carried out continuously throughout 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, a pressure of 1 -6 MPa in a hydrocarbon solvent, 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 provides for thermal liquefaction with a mass ratio of hydrocarbon solvent and waste 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 from the liquid products of thermal fluidization of the feedstock, as well as maintaining high pressure in the reaction apparatus (RU N-> 2109770, 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 alkylbenzenes (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. The listed 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 No. 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 due to the low degree of hydrogen use from the composition of the gas phase resulting from the thermolysis of organic waste, the inability to simultaneously process ki of various chemical composition of raw materials.

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.

SUBSTITUTE SHEET (RULE 26) This drawback arises from the removal of a liquid fraction from the reaction mixture with a boiling point of less than 200 ⁰ C. The most 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. Removing this fraction from the reaction mixture and adding a high boiling point will not accelerate the transfer process hydrogen, 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 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).

A significant disadvantage of this method is the use of sufficiently scarce initiators, especially organic

SUBSTITUTE SHEET (RULE 26) iodine-containing compounds, the low degree of use of the hydrogen donor potential of the solvent components, the difficulty of separating the initiators and their conversion products from the surface of carbon black, as well as from liquid products, restrictions on the chemical composition of the processed raw materials, for example, polyvinyl chloride, acrylonitrile rubber, increased corrosion activity of the reaction mixture due to the presence of iodine-containing initiators, stringent requirements for storage and work with organic iodine-containing materials . The objective of the invention is to develop a method that allows you to abandon the scarce iodine-containing initiators, providing an increase in the hydrogen donor potential of the solvent, due to more efficient use of hydrogen of the latter, as well as the selectivity of the process when liquefying wastes with complex chemical composition, simplify the technology, reduce the energy consumption of the process, reduce temperature and pressure , increase the productivity of the process while increasing explosion and fire safety, environmental friendliness you increase the yield of fractions with a boiling point up to 200 ⁰ C, characterized by a low content of oxygen, nitrogen and organic sulfur, as well as unsaturated compounds, improve the quality of the carbon black filler in the rubber waste pyrolysis.

The problem is solved due to the fact that when carrying out the method, thermocatalytic liquefaction of waste is carried out at elevated temperature and pressure in a hydrocarbon hydrogen donor solvent, followed by separation of liquid products and their rectification to obtain the desired products, while the process is carried out in the presence of a mixture of hydrogen donor hydrocarbons, as one of which alkylbenzenes are used,

SUBSTITUTE SHEET (RULE 26) and as the second, a hydrogen donor hydrocarbon having a shorter induction effect time, the process being carried out at a temperature of 200-320 ⁰ C and a pressure of 1-3 MPa in the presence of a catalyst, which is used phthalocyanines or dimethylglyoximes selected from the group consisting of copper, nickel, cobalt, molybdenum, titanium, manganese, iron and mixtures thereof.

Preferably, the method is carried out in a mixture of alkylbenzenes and tetralin, taken in a mass ratio of 10: 0.5-10: 2.0.

Preferably, the implementation of the method, the process is carried out in a mixture of alkylbenzenes and fractions with a boiling range of 230 - 280 ⁰ C paraffin-naphthenic oil, taken in a mass ratio of 10: 0.5-10: 2.0. It is preferable when using as a catalyst phthalocyanines selected from the group consisting of copper, nickel, cobalt, molybdenum, titanium, manganese, iron and mixtures thereof, a solvent: catalyst weight ratio of 1: 0.01 to 1: 0.05 is used. It is preferable to use a mass ratio of solvent: catalyst of 1: 0.01-1: 0.05 when using dimethylglyoximates selected from the group consisting of copper, nickel, cobalt, molybdenum, titanium, manganese, iron, or mixtures thereof, as a catalyst.

Preferably, the process is carried out in a weight ratio of waste: solvent equal to 1: 2 to 4.

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 are waste products

SUBSTITUTE SHEET (RULE 26) metallurgical coke. 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 - 280 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 to increase the hydrogen donor potential of the solvent, due to the more efficient use of hydrogen of the latter, as well as the selectivity of the process when liquefying wastes with a difficult chemical composition, simplifying the technology, reducing temperature and pressure, increasing the productivity of the process while increasing explosion and fire safety , ecological purity, increasing the yield of fractions with a boiling point up to 200 ⁰ C, characterized by a low content oxygen, nitrogen and organosulfur, as well as unsaturated compounds, improving the quality of carbon black, filler in rubber-containing waste, pyrogas.

The use of a mixture of alkylbenzenes, tetralin or a fraction with a boiling point of 230-280 ⁰ C of paraffin-naphthenic oil enriched in isoalkanes, cycloalkanes and hydroaromatic hydrocarbons, which are effective hydrogen donors, will significantly reduce the induction period of the thermolysis of organic material, waste due to higher hydrogen donor activity tetralin and fractions with a boiling range of 230-280 ⁰ C paraffin-naphthenic oil; raise

SUBSTITUTE SHEET (RULE 26) the utilization rate of atomic hydrogen or liquid phase for the recombination of low molecular weight radical products of thermolysis of organic waste material, increase the productivity of the reaction apparatus, improve 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 use of phthalocyanines or dimethylglyoximates as a catalyst makes it possible to abandon sufficiently deficient free iodine or iodine-containing compounds, most of which are thermally unstable, and working with some of them requires special conditions, for example, ethyl iodide, tert-butyl iodide, iodides of titanium, nickel; lower the temperature of the process, increase the yield of the boiling fraction to 200 ⁰ C, reduce the content of unsaturated, sulfur, nitrogen and oxygen-containing components in it, lower the pressure in the reaction apparatus due to more efficient transfer of molecular hydrogen from the gas fraction, as well as atomic hydrogen from the components hydrogen donor solvent with a radical product of thermolysis of organic waste material; significantly simplify the technology due to the rejection of thermodynamically unstable organic compounds of iodine, reduce the cost of the products, improve the economic performance of the process as a whole.

The use of tetralin as an initiator, and phthalocyanines

SUBSTITUTE SHEET (RULE 26) or dimethylglyoximates as catalysts for the thermolysis of organic waste material, increasing the efficiency of hydrogen transfer from the hydrogen donor components of the solvent and molecular hydrogen from the gas phase, makes the process of thermocatalytic liquefaction of rubber-containing materials, as well as a wide range of industrial and household organic waste, more selective, operating at low pressure and lower temperature there is no need to separate iodine and its compounds from liquefaction products, since their quantities are extremely small, they are very volatile and will easily pass into gaseous products. At the same time, manganese, iron, nickel, vanadium, cobalt, molybdenum phthalocyanines or dimethylglyoximates are easily removed by magnetic separation.

The method is as follows: Rubber-containing, other industrial and household organic waste (waste tires, chambers, conveyor belts, rubberized shaft shafts, polyethylene, polystyrene, polypropylene, polyisobutylene, synthetic rubber, polyvinyl chloride, nylon, are loaded into a rotating autoclave (2 l), nylon, enanth, lavsan and others). Then add a hydrogen donor hydrocarbon solvent in a weight ratio of alkylbenzenes: tetraline / or a fraction with a boiling point of 230 - 28O ⁰ C paraffin-naphthenic oil equal to 10: 0.5 - 10: 2.0; catalyst phthalocyanines / or dimethylglyoximates in an amount of 0.01 - 0.05 (May.% of solvent).

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.

Phthalocyanines or dimethylglyoximes containing metals

SUBSTITUTE SHEET (RULE 26) with a variable oxidation state, atomic hydrogen is easily cleaved from the components of a hydrogen donor hydrocarbon solvent, especially tetralin, as well as cyclohexanes and hydroaromatic hydrocarbons of the oil fraction and transfers it to radical products formed during the thermolysis of organic waste material. Hydrogen transfer is also 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.

Liquid products are separated from solids (metal cord, carbon black and others), and then they are subjected to rectification to obtain the desired products - fractions with a boiling point up to 200 ⁰ C, 200-280 ⁰ C and above 280 ° C.

Examples of the proposed method are shown in the table. Examples JSe 1 through N »5 inclusive relate to the nearest

SUBSTITUTE SHEET (RULE 26) analogue of the invention and are given to confirm the advantages of the claimed method.

Description of an example illustrating the claimed invention (JVe 9 in the table). 150 g of waste (waste rubber, tire, polyethylene, polystyrene, polyisobutylene, synthetic rubber, polyvinyl chloride and others), 450 g of a hydrogen donor solvent containing 400 g of toluene and 20 g of tetralin / or fraction with a boiling point of 230 are loaded into a rotating autoclave (2 l). - 280 ⁰ C paraffin-naphthenic oil, 4.5 g of phthalocyanines / or dimethylglyoximes of nickel, cobalt, manganese, iron. 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 May 95. % of the organic waste material, the content of the fraction boiling in the temperature range up to 200 ⁰ C is 83.2 May. % of liquid products, up to 32O ⁰ C - 95.5 may. % 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 - 28O ⁰ C paraffin-naphthenic oil), catalysts - phthalocyanines / or dimethylglyoximes can increase the yield of liquid products and the content of fractions with a boiling point to 200 ⁰ C, enriched in isoalkanes, cycloalkanes, hydroaromatic and aromatic hydrocarbons, lower temperature, pressure, reduce the process time.

SUBSTITUTE SHEET (RULE 26)

In about

H

Claims

.15 SUMMARY OF THE INVENTION

1. A method of processing rubber-containing, as well as 5 industrial and domestic 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 the fact that the process is carried out in the presence of a mixture of hydrogen donor hydrocarbons, one of which is used alkylbenzenes, and as a second o - hydrogen donor hydrocarbon having a shorter induction effect time, while the process is carried out at a temperature

15 200-320 ⁰ C and a pressure of 1-3 MPa in the presence of a catalyst, which is used phthalocyanines or dimethylglyoximes selected from the group consisting of copper, nickel, cobalt, molybdenum, titanium, manganese, iron and mixtures thereof.

2. The method according to p. 1, characterized in that the process is carried out in a 20 mixture of alkylbenzenes and tetralin, taken in a mass ratio

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 range of 230 - 280 ⁰ C paraffin-naphthenic oil, taken in a mass ratio,

25 is equal to 10: 0.5-10: 2.0.

4. The method according to p. 1, characterized in that when using phthalocyanines as a catalyst selected from the group consisting of copper, nickel, cobalt, molybdenum, titanium, manganese, iron and mixtures thereof, the mass ratio solvent: zo catalyst equal to 1: 0.01 to 1: 0.05.

SUBSTITUTE SHEET (RULE 26)

5. The method according to p. 1, characterized in that when using dimethylglyoximates as a catalyst selected from the group consisting of copper, nickel, cobalt, molybdenum, titanium, manganese, iron or mixtures thereof, mass

> solvent: catalyst ratio of 1: 0.01-l: 0.05.

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

SUBSTITUTE SHEET (RULE 26)