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INVENTION
Russian Federation Patent RU2220986

METHOD FOR RECYCLING RUBBER WASTES

METHOD FOR RECYCLING RUBBER WASTES

Name of the inventor: Bochaver KZ
The name of the patentee: Limited Liability Company "N.T.D Tama"
Address for correspondence: 125009, Moscow, p / 184, for the PPF "JUS" V.V.Kuryanovu (for LLC "N.T.D. Tama")
Starting date of the patent: 2003.04.24

The invention relates to the utilization of chemical waste - organic industrial and household waste in the engine fuel and chemical raw materials, which can be used as a boiler fuel, bitumopodobnogo binder or the raw material to produce it, carbon, or raw materials for its production for electric arc furnaces, electrolytic baths carbon-carbon steel materials, etc., and a small amount of hydrocarbon gas, which can be used as fuel. Waste thermal liquefaction process is carried out at startup in an organic solvent at a temperature of 280-435 o C and a pressure of not less than 2.9 MPa, separating the liquid fraction into a fraction boiling above 220 o C in a weight ratio of solvent to waste more than 1.0 at start. In this case the liquid fraction with a boiling point up to 220 o subjected to catalytic reforming, and a portion of the liquid fraction is then used as the desired product and part is used as the solvent with a new portion of waste at a weight ratio of more than 1.0 but not more than 3.0 and this return is carried out repeatedly. The technical result is to accelerate the method and its simplification, increasing productivity to overcome the high-octane fractions obtained carbon black as a commercial product

DESCRIPTION OF THE INVENTION

The invention relates to the utilization of chemical waste - organic industrial and household waste rubber in the engine fuel and chemical raw materials, which can later be used as a boiler fuel, bitumopodobnogo binder or the raw material to produce it, carbon, or raw materials for their production, to electric furnaces, electrolytic baths, carbon-carbon material (SMM) for metallurgy, etc., but also a small amount of hydrocarbon gas, which can be used as fuel.

The problem of chemical processing of various organic industrial and household polymeric wastes is very urgent because of the steady increase in their number, littering nature.

Solving this problem allows us to solve the environmental problem of complex and harmless disposal of rubber industrial and household waste, to broaden the base of hydrocarbons produced from petroleum, coal, oil shale, natural bitumen.

A method of processing rubber waste into motor fuel and chemical raw materials, including thermal liquefaction (thermolysis) of wastes at an elevated pressure in a hydrocarbon solvent (WO 95/20007 International Application, C 08 J 11/20, publ. 07.27.95).

In this method, as the hydrocarbon solvent used is synthetic rubber waste, combined in a weight ratio to the starting rubber waste is 2 ÷ 4: 1, respectively, and thermal liquefaction process is carried out at a temperature of 270-420 o C and a pressure of 1.6 MPa.

In addition, in one embodiment of the method, obtained after distillation liquid fraction boiling above 200 o C is partly returned into the process as an additive in the hydrocarbon solvent in a weight ratio of 1 ÷ 5: 10, respectively, and the remaining part of this fraction was isolated as desired product.

The advantage of this method is to simplify the technology and increase the yield of light fractions having a boiling point up to 200 o C.

A limitation of the method is to use a solvent as waste from the synthetic rubber production, and waste is not always available in the required quantities.

A method of processing organic polymeric wastes, including thermal liquefaction of waste at a temperature above 270 o C at an elevated pressure in at least one solvent - alkylbenzene, separation of the liquid fraction and its distillation (RF patent 2167168, C 08 J 11/04, publ. 20.05. 2001).

In this process, waste thermal liquefaction when using high pressure of at least 6.1 MPa, and after distilling the liquid fraction with a boiling point of not less than 210 o C are introduced again in the processed waste thermal liquefaction as an additional component to the solvent in a weight ratio of the additional component to the solvent is not less than 1: 1.

In embodiments of this method, when the weight ratio of thermal liquefaction of waste solvent and waste is selected from 1: 1 to 4.2: 1. Also, after distilling the liquid fraction with a boiling point of not less than 210 o C is introduced at a weight ratio of the additional component to the solvent is not less than 5: 1.

The advantage of this method is the use of alkylbenzene as the organic solvent.

A limitation of this method - the need to work at high pressures not less than 6.1 MPa.

The closest is the method for recycling organic polymer, including rubber waste, comprising at startup of the reactor thermal liquefaction of waste in an organic solvent - alkinbenzole at a temperature above 270 o C and a pressure of 6 MPa, separating a liquid fraction from the undissolved product, distilling the liquid fraction into a fraction with a boiling point up to 220 o C and a fraction with a boiling point above 220 o C (Russian patent 2110535, C 08 J 11/04, publ. 10.05.98 city).

In this process, waste thermal liquefaction is performed at a temperature of 270-420 o C and a pressure of 1.6 MPa at a weight ratio of solvent and waste 2 ÷ 4: 1, respectively, in the presence of a rare earth metal or intermetallic compounds based on rare earth metals in the presence or, taken in the amount of titanium hydride 0.5-10% by weight of the reaction mixture used as solvent alkylbenzene such as toluene, xylene, trimethyl-dimethyl-tetramethylbenzene, or mixtures thereof, or used as a solvent distillate "crude benzene", the resulting high-temperature coking coals that accelerates the recycling process and improve the yield of liquid products and in the past and the content of fractions with a boiling point of 200 o C. Thus, the method allows to increase the degree of conversion of rubber and other organic wastes.

The limitations of this method are:

- For efficient thermal liquefaction (thermolysis), the process is carried out in the presence of a rare earth metal or intermetallic rare earth metal or in the presence of titanium hydride taken in an amount of 0.5-10% by weight of the reaction mixture, which complicates the manufacturing process and removal of these and other catalysts additives in the processing of the resulting valuable target product - carbon black - is very complex;

- Poor quality of the carbon black due to the large amount of ash materials - a consequence of Solvent additives;

- High consumption of solvents in the preparation of high-quality gasoline fraction.

Problem solved by the invention - technology simplification, reduction of energy consumption, lower operating costs, increased functionality and improving the quality of the products.

The technical result, which may be obtained by carrying out the claimed method, - speeding up the process and simplify the technology, performance improvement process to yield high-octane gasoline fraction, obtaining technical carbon as a commodity product.

To solve this task with achieving said technical result in the known method for recycling rubber wastes comprising thermal liquefaction waste during startup of the reactor in an organic solvent at a temperature above 270 o C and a pressure of 6 MPa, separating a liquid fraction from the undissolved product, distillation (under thermal liquefaction ) of the liquid fraction into a fraction with a boiling point up to 220 o C and a fraction boiling above 220 o C, thermal liquefaction according to the invention when run in batch reactor waste in an organic solvent is carried out at a temperature of 280 ÷ 435 o C and a pressure of at least 2.9 MPa at a weight ratio of organic solvent to waste more than 1.0, the liquid fraction with a boiling point up to 220 o C is subjected to catalytic reforming, subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 o C is used as the target product, and subjected to another catalytic reforming part of the liquid fraction with a boiling point up to 220 o C is used as the solvent (without the addition of new thermal liquefaction at another portion of the organic solvent: alkinbenzola, gasoline fraction, and the mixture alkinbenzolov etc., as occurs in prior art) and recycled to a new batch of thermal liquefaction waste at a temperature of 280-435 o C and a pressure of at least 2.9 MPa at a weight ratio of solvent to waste more than 1.0, obtained for the new batch of waste liquid fraction having a boiling temperature below 220 o C is subjected to catalytic reforming, catalytic reforming subjected to new waste load of the liquid fraction with the boiling temperature up to 220 o C is used as the target product, and the other subjected to catalytic reforming of the liquid fraction with the boiling temperature up to 220 o C returns to the thermal liquefaction of the next batch of waste, the process in these conditions of thermal liquefaction and catalytic reforming continue for the next and subsequent batches of waste, with the return portion subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 o C in the thermal liquefaction of waste for subsequent batches.

Additional embodiments of the claimed method, where appropriate, to:

- The organic solvent (actuator) used alkylbenzene and / or a gasoline fraction with boiling points up to 220 o C;

- Subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 o C returned to the new batch of waste thermal liquefaction at a pressure in the range of not less than 2.9 MPa ÷ not more than 5 MPa at a weight ratio of solvent to waste in a range of not more than 1.0 ÷ 3.0.

As a result, thermal liquefaction process rubber waste according to the proposed method as target products prepared:

- A small amount of hydrocarbon gases (2,0-5,3 wt.%);

- Fraction of light hydrocarbons boiling at a temperature of 60-220 o C;

- The heavy fraction of hydrocarbons boiling at a temperature above 220 o C;

- Carbon black in powder form.

The light fraction of liquid hydrocarbons having a boiling temperature below 220 o C is a mixture of a solvent of hydrocarbons and hydrocarbons derived from rubber, as a result of thermolysis and is a low viscosity (from petrol viscosity) liquid of light yellow color, having the smell of aromatics and unsaturated hydrocarbons, distilled usually within 60-220 o C. The concentration of aromatics - benzene and alkylbenzenes about 60% by weight (see table 1, column 2)...

The heavy fraction of liquid hydrocarbons resulting from thermal liquefaction (thermolysis) of rubber, has a small (less than 5 wt.%) Admixture of the light fraction of hydrocarbons is a black and viscous (consistency light oil) liquid solidifies in the range of 0 ÷ +5 o C.

Carbon black - the product of rubber thermolysis - easy pulverized powder, black color, free-flowing.

As we know from analogue acting part of thermal liquefaction (thermolysis thermal dissolution) is alkyl benzene (or a mixture of alkyl benzenes). Therefore to activate thermolysis process appropriate to increase the concentration of aromatics in the solvent.

This is achieved by reforming the vapors of thermolysis light fraction with a boiling point up to 220 o C, after separation from the insoluble liquid fraction and distilling the product directly when termooozhizhenii liquid fraction.

For this purpose, a light fraction of liquid hydrocarbons (product of thermal liquefaction) is subjected to reforming, for example, fixed bed vysokokremnezemnyh zeolite catalyst (ZSM-5 type promoted with 2% ZnO), at a temperature of 440-520 o C (see., E.g., RF Patent 2130960) . Reformate can be used, and various other known methods for producing gasoline fractions vysokoaromatizirovannyh (see., E.g., RF Patent 2039790).

Thus, in contrast to the known methods the process of thermal liquefaction subsequent waste batches carried neprosredstvenno only solvent, obtained by the process of thermal liquefaction, and in order to activate the thermal liquefaction of subsequent batches of waste resulting from distillation reactor thermal liquefaction light fraction with a boiling point up to 220 o C before using it as a solvent for thermal liquefaction of subsequent batches of wastes is reformed. There is no need to completely deficient thermal liquefaction organic solvent for subsequent batches of waste and the thermolysis and other activators, such rare earth metals, intermetallics, titanium hydride and other substances.

Balance liquid product accumulates in the circulation of the light fraction of liquid hydrocarbons through processes of reforming and thermal liquefaction is a vysokoaromatizirovannuyu, isomerized so sweet high-octane gasoline component. Part of the desired product were collected and used for its intended purpose as the accumulation of surpluses. Subjected to catalytic reforming the remainder of the liquid fraction with the boiling temperature up to 220 o C is returned to the thermal liquefaction of the next batch of waste.

METHOD FOR RECYCLING RUBBER WASTES

FIG. 1 shows a flow diagram of implementing the proposed method

METHOD FOR RECYCLING RUBBER WASTES

FIG. 2 - functional diagram of a pilot plant that has been used to determine the modes

FIG. 1 schematically shows: a thermolysis reactor 1, unit 2 preparation and submission of rubber waste, reforming reactor 3, refrigerator-condenser 4, the gas-liquid separator 5, the pump 6, tube furnace 7, the dispenser 9, distillation column 10.

Depending on the kind of raw material supplied may perform preliminary preparing raw materials (e.g., grinding, separation of sludge, etc.).

The technological process of thermal liquefaction (thermolysis) of rubber waste starts with the preparation of raw materials, such as used tires. Rubber-containing wastes are washed, crushed and separated from the slurry I (steel cord, textiles and dirt) at node 2 and is supplied to the reactor 1 (conical), a fluidized bed of rubber crumb and industrial carbon, in a solvent in a state close to Pseudocritical.

In the fluidized bed occurs solvent rubber thermal liquefaction and turning it into products thermolysis:

II - liquid heavy hydrocarbons having a boiling point above 220 o C,

III - industrial carbon powder withdrawn from the reactor 1 pneumatically,

IV - gas-steam fraction of light hydrocarbons with a boiling point up to 220 o C.

IV stream is cooled and partially condensed in cooler-condenser 4 is subjected to separation in the gas-liquid separator 5. The fraction of liquid light hydrocarbons V (FLU) pump 6 is fed into a tube furnace 7 (with flame heating) where it is heated to the temperature required for reforming 3. If the reactor, for example, using a fixed bed of reforming catalyst comprising zeolite ZSM-5 type promoted with 2% ZnO (see. for example, Russian patent 2130960), the tube furnace is heated FLU 7 V to temperatures of about 500 o C. and the temperature after reforming FLU V is approximately 450 o C.

Then reformate is sent to the distribution device 9 of the reactor 1 as a solvent.

LFU carrying part is withdrawn from the circulating flow and fed to distillation column 10 for the purpose of obtaining stabilized gasoline fraction VI, VII and gas separation stabilization VIII (used as a fuel in a tube furnace 7). At the II liquid heavy hydrocarbons having a boiling point above 220 o C is removed from the reactor 1 remains of steel cord IX.

FIG. 2 schematically shows: a thermolysis reactor 1 (electrically heated, sealed) with a bag of glass or carbon fabric for rubber crumb or bigger fragments of tires, the reactor 3 with a zeolite-containing reforming catalyst, refrigerator-condenser 4 vapor thermolysis products (water), gas-liquid separator 5, gas meter 16, 17 thermometers, pressure gauges 18, 19 for measuring the capacity of the light fraction of liquid hydrocarbons, measuring capacity 20 for the heavy fraction of the products, the sampler 21, an adjustable valve 22, the shut-off valves 23, 24 electric heaters.

The experiments were conducted in the following sequence.

In reactor 1 bag of 12 liters placed fragments of tires or crumb rubber waste. Poured into the reactor 1 solvent. Produce internal heating volume of the reactor 1 to a temperature of 280 ÷ 350 o C, while maintaining the pressure at 2.5 ÷ 5.0 MPa. Further temperature rise is continued by the exothermic reaction of thermal liquefaction (thermolysis). Depending on the weight ratio of organic solvent to waste (trigger) (or the solvent by using the light fraction of the liquid hydrocarbons as the solvent further), the temperature rises to the level 330 ÷ 500 o C. The expansion and evaporation of the solvent and formation of hydrocarbon gas pressure rises to 2.5 ÷ 5.0 MPa and maintained at a predetermined level 2.5 ÷ 5.0 MPa by resetting of the organic solvent vapor and gas through the reforming reactor 3, a capacitor 4, a refrigerator, a gas-liquid separator 5 and the valve 22. The amount of hydrocarbon gas is recorded the gas meter 16. The temperature and pressure in the reactors 1 and 3 are recorded thermometers 17 and 18 gauges.

Termination temperature increase in the reactor is one end of thermal liquefaction process (thermolysis). After fifteen minutes of holding pressure in the installation is reduced to atmospheric system. At the same throughout the test gas meter 16 registering the number of uncondensed gas - thermolysis product. The liquid product (light liquid fraction of NK - 220 o C) of the gas-liquid separator 5 is poured into a measuring cup 19. After cooling the reactor 1 it vented, take out and weighed carbon black in the bag. Fused the heavy fraction of liquid hydrocarbons in the volumetric capacity of the reaction products 20. dimensional tanks 19 and 20 and the probe 21 is analyzed to determine their composition. Part of fraction PC - 220 o C and subjected to reforming, is used as the solvent for the next experiment. Thus, the subsequent thermal liquefaction produced by the resulting solvent previous experiment (light fraction subjected to reforming). The results of reforming the solvent are summarized in Table 1, third column.

The results of experiments to determine the thermal liquefaction modes are summarized in Table 2.

Table 2 provides the opportunity to evaluate the effect of the weight ratio of solvent: rubber, temperature, process pressure and solvent composition on the quality and yield of products:

- The ratio of solvent: tires equal to 0.774 resulted in clumping of the carbon black due to a high temperature due to the acceleration of the process exothermic reaction heat at a low heat capacity shortage of thermolysis products and a solvent for the subsequent thermal liquefaction operation (Table 2, Experiment 1);

- The ratio of solvent: tire equal to 0.93 (Table 2, Experiment 2), given the output of high-quality end products, but little light fraction is only enough for a solvent for reuse thermal liquefaction, and turns a very small part of the desired product - gasoline fraction with a boiling point up to 220 o C. Experience shows that there is no opportunity to get at least a significant share of the target product - high-octane gasoline fraction, therefore it is advisable to use a ratio of solvent: tires more than 1.0;

- Increase in the ratio solvent: tires to 3.0 (Table 2, experiment 8) results in increased energy consumption for maintaining the circulation of large amounts of solvent, the volume increase of 1.3 units of reactors, both of the thermolysis and the reforming process, so that the ratio whiter 3 unprofitable;

- At a temperature of 260 o C or below (Run 12) and at a pressure of 2.5 MPa and below (Table 2, experiment 5, 11) is not thermal liquefaction reaction, rubber swells in the solvent but not soluble;

- Using a solvent not subjected to reforming, in the step of return to the light fraction thermal liquefaction dramatically increasing loss (Table 2, Experiment 13).

Table 1 shows the results of chromatographic analysis of light fraction products obtained by thermal liquefaction rubber before reforming (Table 1, column 2) and after (Table 1, column 3). Alkylbenzenes active content in 60 and 80 wt.%. Reforming converts paraffin, naitenovye and unsaturated hydrocarbons to aromatics (alkinbenzoly).

Shown in Table 2 the results of experiments confirm the high efficiency of thermal liquefaction (thermolysis) of rubber at a temperature of 280 to 435 o C and a pressure of at least 2.9 to 5 MPa, which corresponds to parameters close to pseudocritical for a mixture of hydrocarbons of the thermolysis light liquid fraction at intervals boiling from NC to 220 o C. It can be seen from table 2, to raise the pressure higher than 5 MPa is inappropriate, since it does not increase the yield of target product and leads to unnecessary energy costs.

For reference: the critical parameters of the LAB:

- Toluene R cr = 4.0 MPa, t cr= 320,8 o C,

- Meta-xylene P cr = 3.5 MPa, t cr= 346,0 o C,

- Ethylbenzene P cr = 3.7 MPa, t cr = 346.4 o C, etc.

Starting thermal liquefaction process is carried out with an organic solvent such as alkylbenzene or any alkylbenzene technical and fractions with a boiling point mixture to 220 o C. In the absence of alkylbenzenes may use any of the gasoline fraction having a boiling temperature below 220 o C, or other organic solvents capable of dissolving in the process thermolysis of rubber. Spend a few thermal liquefaction cycles, so that the composition of the solvent for subsequent operations have stabilized due to the formation of new portions rastvoritelyai gradual transfer of the initial organic solvent in the A part of (over) the light fraction.

With a limited amount of alkyl benzene and the lack of it for the starting amount of the organic solvent, as studies have shown, can be added to it any straight-run gasoline. Thus, to start the process naphtha was used containing 14% of aromatic hydrocarbons. By repeated circulation in its installation (1) alkylbenzenes content increased and stabilized at 80%. In another case, to start the process, toluene was used in a mixture with straight run gasoline. As a result of repeated circulation of alkyl benzenes content and increased to 80%.

The most successful application of a method for processing waste rubber is industrially applicable in the chemical processing into motor fuel and chemical raw materials various rubber materials, primarily tires.

CLAIM

1. Method for processing rubber waste, comprising a waste thermal liquefaction when run in an organic solvent at a temperature above 270 ° C and a pressure of 6 MPa, separating the insoluble liquid fraction from the product distillation of the liquid fraction, characterized in that the distillation is carried out at a liquid fraction of a fraction with the temperature boiling up to 220 ° C and a fraction boiling above 220 ° C, thermal liquefaction launch waste batch in an organic solvent is carried out at a temperature of 280 - 435 ° C and a pressure of at least 2.9 MPa at a weight ratio of organic solvent to waste more than 1, 0, a liquid fraction with a boiling point up to 220 ° C is subjected to catalytic reforming, subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 ° C is used as the target product, and the other subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 ° C is used as solvent and is recycled to a new batch of waste thermal liquefaction at a temperature of 280 - 435 ° C and a pressure of at least 2.9 MPa at a weight ratio of solvent to waste more than 1.0 - less than 3.0, obtained for the new batch of waste to the liquid fraction boiling temperature below 220 ° C is subjected to catalytic reforming, subjected to catalytic reforming for a new batch of waste of the liquid fraction with a boiling point up to 220 ° C is used as the target product, and the other subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 ° C again used as the solvent and recycled to the next batch of waste thermal liquefaction process at these conditions and catalytic reforming thermal liquefaction continued for the next and subsequent batches of waste, with the return portion subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 ° C, respectively, again for thermal liquefaction of waste for subsequent batches.

2. A method according to claim 1, characterized in that when run in an organic solvent is alkylbenzene and / or a gasoline fraction with boiling points up to 220 ° C.

3. The method of claim 1, wherein the portion subjected to catalytic reforming of the liquid fraction with a boiling point up to 220 ° C is recycled to a new batch of waste thermal liquefaction at a pressure in the range of not less than 2.9 - less than 5 MPa.

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Publication date 16.01.2007gg