IL207140A - Production of light synthetic oil from scrap tires - Google Patents

Description

. 1 2 Baaley HaMelaha St., P.O. Box 1 1 47 Industrial Area K. Bialik 271 10, Israel Inventors: Mark LUBARSKY, 5A Marganit St., Rcchasim 20496 (IL); Alexander Glozman, 2d/3 Rabbi Yehuda Ha-Nassi St., Haifa (I L); Eduard ETHICSON, 10/3 Dan St., Qiriat Bialik 27000 (IL); Alex KATZ, 52/15 Haim St., Qiriat Bialik 27000 (IL); Assignee: Wastoil Eco Ltd., Kiryat Bialik (I L) PROD UCTION OF LIGHT SYNTHETIC OI L FROM SCRAP TI RE ABSTRACT A method and apparatus for thermal decomposition of scrap tires in order to produce light synthetic oil (hereinafter LSO) with low density and sul fur contamination, non- condensable hydrocarbon gas (hereinafter gas), pyrolytic carbon black (hereinafter Clip) and recovered metal (hereinafter steel wire). The described process is hermetic and ecologically friendly, and does not require shredding or cutting of scrap tires. Loading the whole scrap tires into processing unit and drawing them by gravity through the unit make the processing better than other existing solutions. The design of the processing unit yields high efficiency heat and mass exchange process and allows reliable control of product quality.

LIST OF REFERENCES The following references are considered to be pertinent for the purpose of understanding the background of the present invention: US 6,221 ,329 US 7, 101 ,463 US 4,740,270 US 4,250, 1 58 US 5,229,099 US 4,740,270 US 5,087.436 US 2006/01 63053 US 5,395,404 US 4,030,984 1 2 Baaley HaMelaha St., 1 2 rDN^an ^sn τη P.O. Box 1 147 Industrial Area 1 ! 47 ,7.n p^tcn rvnp.n .N K. Bialik 271 1 0, Israel Eco Ltd 7ΐρ·¾:27 1 1 0 BACKGROUND OF THE INVENTION The present invention relates to production of LSO, CBp and steel wire from scrap tires by a continuous process and without shredding. More specifically, the process according lo this invention enables to increase the yield of commercially valuable liquid hydrocarbons and CBp, Fraction with boiling point up to 360 °C consists of about 90% vol . of LSO or 70% vol . of gasoline and 1 0% of residue only. Valuable components of gasol ine or solvents can be easily produced from LSO. CBp can be used as modifying filler for paving grade asphalt, construction sealant and plastic resins. Further uses of CBp are colorants for construction materials such as concrete; and with recent development, it can be used as a feedstock for an 0 activated carbon product.

More than 1 0 million tons of scrap tires arc scrapped annually worldwide. About 80% of scrap tires end up in landfills. However, scrap tires' burning creates additional environmental problems, such as air pollution. Accumulation of large quantities of scrap tires having low degradation rates has become a major environmental problem for almost all developed countries. Because of their resistance to biodegradation, scrap tires provide a favorable environment for vermin, rodents and fire. Additionally, whole scrap tires are di fficult to store in landfills since they are bulky and cause damage to the landfill cap, as they tend to "float" their way to the top of the fill. In an attempt to prevent this migration, previous shredding of scrap tires is required. This process is energy intensive and wasteful as it does i0 not produce any useful product.

There are several additional methods of utilizing scrap tires, described in already existing patents. In general, two widely known technologies are liquefaction and pyrolysis. The first technology is used in an attempt to recycle the rubber in order to produce different rubber composites and the second - to produce hydrocarbons and fuel materials. These two !5 methods are subdivided into a lot of processes with various equipment usages. There are known pyrolysis processes in which scrap tires are destructively heated in the absence of oxygen to generate products such as synthetic oil, gas, CBp and steel wire. Quality and quantity of products depend on condition under which thermal decomposition processes take place. The most characteristic features of those processes will be outlined in the patents listed 50 below. 12 Baaley HaMelaha St., 12 riDS^an τη P.O. Box 1 147 Industrial Area 1 147 ,7.n n^ip.n.N K. Bialik 271 10, Israel Eco Ltd Tip¾:271 10 Metso Minerals Industries Inc. developed a commercial plant design with the capacity to process up to 100 tons per day and secured U.S. patents No. 6,221 ,329 and No. 7, 101 ,463 recognizing claims of process and design. These patents disclose a processing system for the reclamation and recovery of desirable materials from shredded vehicle tires (mean scrap tire) through pyrolysis. Vehicle tire pieces are fed into the feeding device end of the pyrolysis section by a rotatable feed cylinder that includes a screw-like flight extending from the inner wall of the feed cylinder. According to Metso Minerals, its 100-ton-per-day commercial plant should generate 32.4% of carbon black, 12% of steel wire, 28% of oil (mean synthetic oil) and 27.6% of non-condensable gas. The Metso Minerals pilot-plant oil product has a sulfur content of 1 .2%, specific gravity 0.95 and heating value 17,500 BTU's per pound (9722 kcal/kg). In this process shredded vehicle tires are exposed at the very beginning to a relatively high temperature (700 - 800 °C), which causes high yield of gas and decreases the yield of oil ( mean synthetic oil).

U.S. patent No. 4,740,270 relates to vacuum pyrolysis of scrap tires and generating liquid, gaseous and carbonaceous solid products. As a result of the process synthetic oil is obtained with density 0.95 g/cm , calorific value 10,200 kcal/kg and dynamic viscosity 46 cP @ 49 °C. One can assume that high of density and viscosity has a negative effect on the subsequent water separation process.

U.S. patent No. 4,250,158 issued to Solbakken et al discloses a process for profitable recovering of carbon black, tar, oil (mean synthetic oil) and fuel gas ( mean gas) from used tires (mean scrap tire). Used tires are physically sliced and fragmented. The fragments are pyrolized in an oxygen-limited, hydrocarbon vapor at sub-atmospheric pressure while being relluxed with process tar condensate. The reactor temperature can be varied from 750 to 1800 °F, reaction time can be varied from 90 to 3 minutes, gas pressure over the reaction can vary from 1 to 20 PSIA, and the fed chip size can be of any size equal to or below 1 1/2 inches.

According to this patent, the synthetic oil has density 0.9447 g/cm3 @ 1 .5 °C, calorific value 10,521 kcal/kg and viscosity 1 1.4 cP @ 15.5 °C. This synthetic oil has relatively high viscosity and high final boiling point (90% @ 474 °C). Such properties of synthetic oil result in limited use in various applications. The process requires extra-hermetic system and shredding of scrap tire which increase capital and operational cost of equipment. 1 2 Baaley HaMelaha St., 1 2 riDN nn ^yn τη P.O. Box 1 147 Industrial Area 1 147 .7.n ^v i rrnp.n.x K. Bial ik 271 1 0, Israel EC Ltd np¾:271 10 U.S. patent No. 5,229,099, issued to Roy, describes a method for decomposing scrap tires under extreme vacuum. This method requires vacuum at 0.3kPa absolute pressure.

Synthetic oi l obtained by this method contains 0.8% sulfur, while its content in scrap tire is 1 .4%. According to this patent, the synthetic oils were subjected to fractional distillation which demonstrated 26.8 % wt. of gasoline fraction versus 67.2% wt, in current invention.

U.S. patents No. 4,740,270 and No. 5,087,436 describes similar decomposition processes under high vacuum. Disadvantages of these processes are scrap tire shredding, extreme vacuum, low content of the most valuable fraction IBP - 204 °C (26.4%>) and relatively high density 0.95 g/cnr\ U.S. patent application No. 2006/01 3053 A2 discloses a scalable pyrolysis system for batch processing of waste vehicle tires (mean scrap tire) to provide pyrolysis products.

Obtained pyrolysis products consist of approximately 20% synthetic oil, 25%» gas, 1 5% steel wire and other solid materials, together with approximately 40% carbon. Pyrolysis oil (mean synthetic oil) is similar in composition to light healing oil with slightly higher sulfur content 1 .5%. One of the disadvantages of this process is periodic operation.

U.S. patent No. 5,395,404 discloses a device into which whole tires (mean scrap tire) may be inserted. Tires inherently have a round void center for mounting to a wheel . The device has a healing tube which is inserted through this void center while tires are held within a vessel. Heat is applied to the heating tube. The tires are pyrolized at a temperature of 371 to 482° C. Obtained synthetic oil has sulfur content of 1 .04% and a heat value of about 1 7,668 ElTU 's per pound (9,81 6 kcal/kg). The process is carried out under overpressure 1 00 - 300 PS I. There is no control of product quality during the process. The solid and liquid products are withdrawn from the reactor without any separation. This kind of process is a typical periodic (batch) process.

U.S. patent No. 4,030,984 discloses a method and apparatus by which the whole tires (mean scrap tire) are suspended in hot Hue gases and then the scrap tires are melted and converted into pyrolysis products. The process is performed at the presence of 02, CO, C02, N2 and H20, which negatively affects the quality of products and creates the conditions for contamination by dioxins. In spite of the continuous loading of scrap tire, this process still belongs to the batch type of pyrolysis. Obtained synthetic oil has 8.1 % wt boiling up to 1 90°C only. 1 2 Baaley HaMelaha St., P.O. Box 1 147 Industrial Area . Bialik 271 1 0, Israel Various methods and apparatuses are found in the prior art for scrap tires pyrolysis. These devices use heat and relatively high pressure, or sub-atmospheric pressures. Some of the devices require introduction of hydrogen or other supplemental materials. In addition, some of the reactors have a moving part providing drive force to pyrolized material. Most 5 existing patents, intended to util ization of whole scrap tires, are based on batch process principle. This approach reduces process capacity and possibility to control quality of products. Those features of prior art processes are problematic and don't provide reliable operation. Synthetic oil obtained from processes mentioned above has a high final boiling point (90% boi ling up to 474°C, low content of fraction boiling up to 200°C), density of 10 more than 0.92 - 0.97 g/cm3, is extremely contaminated by sul ur ( 1 .0 - 1.5 %) and is not stable under long term storage conditions. This is the reason for the l imited commercial usage of this product. Additional labor-intensive techniques are required in order to achieve the desired quality of synthetic oil or derived products.

SUM MARY OF THE I NVENTION The invented process is a continuous pyrolysis of whole scrap tire in order to produce LSO, gas, CBp and recovered metal. Current invention represents a solution for producing LSO with low content of sulfur and evaporation of 90% vol. up to 300°C. According to the present invention, whole scrap tires are exposed to thermal decomposition under various kinetic and thermodynamic conditions. The process is carried out in a single apparatus (hereinafter Processing Unit or PU) where liquefaction, thermal decomposition and coking take place. The PU may virtually be divided into 5 zones: Feeding, Soaking, Reaction, Annealing and Upper. The fed scrap tires are degassed by the loading device in order to prevent penetration of oxygen into the PU and then fall down into the soaking zone. This zone provides high efficiency heat and mass transfer process by contact of scrap lires with downstream heavy condensate and overhead vapor stream. The treated scrap tires are heated at this stage to 350 - 450°C, lose their initial shape and are exposed to primary decomposition. From this point the decomposed material are drawn by gravity to the reaction and annealing zones, where the temperature rises to 450 - 550°C and 550 - 700°C 'it) correspondingly. CBp is withdrawn from annealing zone by discharging device. The overhead vapor is formed during the process, passes from anneal ing zone to reaction, soaking , . , 12 Baaley HaMelaha St., 12 ΓΠΝ^ΏΠ ^vn τη P.O. Box 1 147 Industrial Area Wastoil 1 147 .T.ri p^N1:. mnp.n.K . Bial ik 271 10, Israel ECO Ltd 7ip¾:27 l 10 and upper zones, where it is partially condensed to downstream heavy condensate. The overhead vapor leaving the upper zone is exposed to the next condensation to form LSO, trace water and gas. Preferable retention limes and temperature ranges for the processed material in various zones are indicated in Table 1 .

Table 1.

The invented process has several advantages: a) Reduced operation cost due to elimination of shredding/cutting processes. b) Favorable conditions for thermal decomposition of scrap tire due to improved mass and heat transfer processes. c) Returning the downstream heavy condensate to the process in order to produce more LSO and CBp with low ash content. d) LSO with low speci fic gravity facilitates separation of water-oi l emulsion. e ) The invented process is operated continuously. f) PU has two independent spiral furnaces that signi ficantly increase heat transfer surfaces. g) The invented technology assumes usage of al l l iquid and gaseous products as energy sources for technological needs. Excess amount for these products can be used for commercial energy production. Thus, such process organization ensures flexibility and energy self-sufficiency. 12 Baaley HaMelaha St., P.O. Box 1147 Industrial Area Wastoil 12 n^N^ttn ΊΠ ΤΠ 1147.Ί.η Ρ^ΚΊ mp.n.K K. Bialik 27110, Israel Eco Ltd ηρτ.:27110 BRIEF DESCRIPTION OF DRAWING Figure 1. Principal scheme of the process 12 Baaley HaMelaha St., P.O. Box 1147 Industrial Area Wastoil 1147.i.n Ρ^ΚΌ rr p . Bialik 27110, Israel Eco Ltd 7TO27110 Figure 2. Spiral Furnace , . 12 Baaley HaMelaha Si., P.O. Box 1147 Industrial Area . Bialik 27110, Israel fable 2 lists the positions and part descriptions regarding the principal scheme in Figure 1. , . 12 Baaley HaMe!aha St., 12 VV2 'm P.O. Box 1 147 Industrial Area 1 147 .τ.η ^w2 rvnp.n.K . Bialik 271 1 0, Israel CO Ltd 7lp¾:27 l 1 0 Table 2. Conti nued DETAI LED DESCRIPTION OF THE PREFERRED EMBODIMENT Process unit (PU) 32 and supplemental systems, which, according to the current invention, are intended for thermal decomposition of scrap tires in order to produce LSO.

Clip, gas and recovered steel wire, are shown in Figure 1 . Operational pressure of PU is slightly above the atmospheric pressure, by 1 0 kPa to 30 kPa, but preferably by 1 0 kPa to 15 kPa. The scrap tires to be utilized are located in the accumulation bin 12, from which they are entrained by conveyor and delivered to unscrambler 13 of loading chamber 14. Loading chamber 14 is equipped with piston 18 for receiving and degassing the whole scrap tire.

Piston 18 provides tightness and air pressing-out by scrap tire pressuring. Piston 1 serves for transportation of degassed scrap tire to the PU. This way the scrap tire is introduced into the process in the absence of air. Pistons 18, 19 have hydraulic actuators 18/19 for moving and pressuring the scrap tires. These hydraulic actuators 18/19 are connected by lines 21 to the hydraul ic unit 20 forming the hydraulic system of loading device. Once the scrap tire is placed in the loading chamber 14, actuator 18/1 moves the piston 18 forward in order to press the scrap tire and press-out the air. The pressed-out air leaves the loading chamber 14 through 3-way valve 23 via prcssed-out air relieving l ine 103. Piston 18 reaches the stop point at the same moment at which the 3-way valve 23 is switched to the position of delivering inert gas to the loading chamber 14 through inert gas line 106. The inert gas is applied for displacing the air residue from pressured scrap tire. The displaced air residue is leaved the loading chamber 14 via air residue evacuation valve 23a and air residue relieving l ine 1 12.

The scrap tire captured between two pistons, 18 and 19, is introduced into the feeding zone of PU 32. Actuator 18/19 moves piston 19 forward, thus increasing the gap between the two pistons 18, 19 and releasing the scrap tire. Released scrap lire falls down into the ramp 19a. Ramp 19a with the scrap tire turns right in order to put scrap tire on the scrap tire stack in the 1 2 Baaley HaMelaha St., 12 riDN^n ^ n 'm P.O. Box 1 147 Industrial Area 1 147 .7,n p^s^ mp.n.N . Bialik 271 10, Israel Eco Ltd np¾:271 10 soaking zone. Since the scrap tire has been put on the stack of thermally decomposed scrap tires, ramp 19a follows this stack unti l the ramp reaches horizontal position. When the horizontal position has been reached due to squeezing of scrap tire stack, control system 22 returns the ramp to its previous position. In this way measuring of stack level in the PU is carried out by ramp 19a. Control and synchronization of pistons 18, 1 , ramp 1 a and of 3 -way valve 23 are performed by controller 22.

PU 32 shown on Figure 1 is divided into 5 zones: feeding zone 31 , soaking zone 52, reaction zone 51 , annealing zone 50 and upper zone 53. PU is a cylindrical apparatus resembling a column where decomposed scrap tires are moved down by gravity and pass soaking 52, reaction 51 and annealing 50 zones at 350 - 450°C, 450 - 550°C and 550 - 700°C correspondingly. The moving bed of whole scrap tires is heated beginning from feeding temperature to the said pyrolysing temperature by conductive, convective and radiant heat transfer processes.

The soaking zone provides wetting of scrap tires by spraying downstream heavy condensate, as well as their partial l iquefaction and initial decomposition. Wet rubber is a better heat conductor than dry rubber. Short distance 1 - 1 0 cm from PU wall and low thickness I - 2 cm of decomposed scrap tire ensure effective heat transfer to the thread (outer) surface of scrap tire. Hot process vapor is a source of heat for the inner surface of scrap tire. Thereby the heat energy required for the process is provided from two sources. One source is the radiation of PU walls and the second source is the recovered heat from formed products. The stack of scrap tires forms moving bed with a hollow center for escaping of process vapor from decomposed material . This hollow center has a physical extension in form of central opening 54 of drain plate 65. Thus, the stack of scrap tires is a moving bed with countereurrent direction relatively to process vapor motion. This countercurrent movement provides perfect conditions not only for heat, but also for mass transferring process. The same method is kept in soaking 52, reaction 51 and annealing zones 50 of PU. As the decomposed material is moved towards the annealing zone 50, the temperature rises and reaches 550 - 700 °C. Under these conditions the decomposed product releases traces of hydrocarbons and forms CBp with volatility content of less than 4% according to AST D3 1 75. In predefined time the solid products at 550 - 700°C arc discharged from the annealing zone 50 by solids discharging device 71 through the opening 70 with their subsequent separation to pyrolytic . 1 2 Baaley HaMelaha St., 1 2 nDn^an ^yn η P.O. Box 1 147 Industrial Area 1 147 .i.n ^κ-α jvnp.n.N K. Bialik 271 10, Israel ECO Ltd W 27 \ 10 carbon and steel wire by engaging claw (not shown in Figure 1 ). The engaging claw catches steel wi re and draws through a specific gap (not shown in Figure 1 ) into steel wire chamber 73. while pyrolytic carbon falls through the grate into pyrolytic carbon chamber 74.

Subsequent withdrawal of steel wire and CHp from chambers 74 and 73 is performed through the hermetic sluice blanked by an inert gas (not shown in the Figure 1 ) via steel wire and pyrolytic carbon discharging lines 75, 76 correspondingly. The inert gas is delivered to the solids discharging device through control valves 77, 78 and via inert gas line 1 6.

Experimental work has indicated that the reaction time of 25 to 40 minutes is required to achieve optimal destruction. This optimal reaction time is a function of feed rate, retention time, reactor temperature, partial pressure of gas over the decomposed material, the rate at which the vapor phase leave the processing unit and the amount of liquid process condensate present with the solid phase in the processing unit.

During the thermal decomposition of scrap tire the generated hydrocarbons and traces of water form a process vapor. This process vapor entrains particles of carbon. Elimination of this particle contamination is achieved in two steps. Both steps operate l ike scrubber. The first step occurs in soaking zone 52 by means of downstream heavy condensate and the second step occurs in direct condenser 57. Wetted particles are entrained by downstream heavy condensate and returned to the soaking zone 52.

Processing unit 32 should be made of thermo- and corrosion resistant material, preferably stainless steel. Inner and outer surfaces of oven 47 should be made of the same material. These surfaces have to stand in severe temperature conditions mostly in annealing zone 50. Annealing 50 and reaction 51 zones are equipped with at least two independent ovens 47. Number of ovens may be increased in order to enlarge the capacity of PU. Each burner is installed tangentially to the wall of the anneal ing zone. Air-fuel mixture burning occurs in furnaces 44 by means of by minimum two burners 45, and hot Hue gas goes via two separate spiral ducts 49 surrounding the annealing 50 and reaction 51 zones. The flue gas escapes from ovens 47 through two chimneys 46 at the temperature range of 350 - 400 °C. This leaving Hue gas may be used for preheating of air to be directed to combusting area.

Shell 48 covers the ovens and is equipped with thermo insulation.

The walls between the spiral ducts 49 increase the heal transfer area. The heat energy is transferred to the decomposed material mostly by radiation in anneal ing zone 50 and , . 1 2 Baaley Ha e!aha St., 12 mx^n ^vi τη P.O. Box 1 1 47 Industrial Area 1 147 .i.n rvnp.n.K . Bial ik 27 1 1 0, Israel ECO ltd 7VO:27 l 10 convection in reaction zone 51. Working temperature range of the furnaces 44 is 1200 - 1 3 0°C, which is enough to maintain the temperature in the annealing zone 50 in the range of 550 - 70O°C The upper zone 53 of PU 32 is the extension of process section 36 and includes distribution heads 58, drain plate 65 and direct condenser 57. Overhead vapor leaving the upper zone 53 vie vapor line 60 is partly condensed in condensers 80 and 81 forming mixture of LSO/water. The mixture of LSO, water and gas Hows to three phase separator 82. Part of LSO after separation is directed by pump 105 from separator to condenser 57 of Upper section 53 through LSO return line 63 and sprayed by distribution heads 58 on the packing bed 59 in order to provide cooling and partial condensing of hot process vapor incoming from soaking zone via central opening 54 of drain plate 65 and packing bed 59. The packing bed 59 of condenser 57 consists of an ordinary packing material such as Raschig or Pall rings. The measuring temperature of overhead vapor is performed by sensor 69 and controlled by control valve 68. Partial ly condensed process vapor forms downstream heavy condensate which is accumulated on the drain plate 65 and overflows via drainage tubes 64 to the soaking zone 52. The working temperature range of drain plate 65 and incoming process vapor is 350 - 400°C. Overhead vapor of the upper zone has the temperature of 1 70 - 220 °C. The temperature of gas-condensate mixture at the outlet of condenser 81 is in the range of 40 - 50°C. This mixture enters three phase separator 82, where LSO separates from gas and water. Separated water is discharged through water drainage line 94 and directed to treatment. LSO is pumped out from separator 82 by pump 105 and is divided into three streams. The first stream flows through strainer 107 and control valve 68 to distribution heads 58, the second stream Hows through liquid fuel line 102, strainer 707 and filtered liquid fuel line 1 05 to the burners 45 and the third stream is pumped to the next treatment or storage - LSO line 66 to storage. Gas from three phase separator 82 is sucked by compressor 1 0 through line 92 in order to maintain the constant pressure in PU 32, condensers 80 and 81 and three phase separator 82. Compressed gas is del ivered at 20 - 30 bar to liquid/dry gas separator 101 where il is separated to liquid (C3 - C5) and dry gas (C02, CO, H2, C ] - C2) Part of dry gas may be used as fuel and directed through l ine 109 to the burners 45. 1 2 Baaley HaMelaha St., P.O. Box 1 147 Industrial Area Wae-fcoi! 1 147 .T.n p^ff π'ηρ.η.κ K. Bialik 271 10, Israel ECO Ltd ■ηρ¾:27 Ι 1 0 EXAMPLE 1 The whole scrap tires were fed into the processing unit 32 at the rate of 60 Kg per hour through loading chamber 14. The rubber decomposed into pyrolytic products while the processing unit 32 was heated by heating ovens 47 to keep the temperature of materials in the reaction zone at about 350 - 550 °C and in the annealing zone at about 600 - 700 °C. Process vapor from the soaking zone 52 entered the upper zone 53 where it was separated into downstream aromatic condensate and overhead vapor. The downstream aromatic condensate was returned from the drain plate 65 of the upper zone into the soaking zone 52. The temperature at the top of the upper zone 53 was about 1 70 - 180 °C. The overhead vapor which left the upper zone 53 via process vapor fine 60 was condensed and separated in the three phase separator 82 into LSO, water and gas. The yields of LSO, Clip, gas and steel wire are shown in fable 2, LSO properties are shown in Table 3. Pyrolytic C p in Example 1 has an ash content of 1 1 .7%, sul fur content of 1 .43%. heating gross value 7,31 kcal/kg ( 1 3, 167 Btu/lb) and is obtained in a form of very line powder.

The part of LSO from Example 1 was fractionated under atmospheric pressure into two fractions. Each of those fractions was tested in accordance to ASTM D86 (Engler disti llation). For each of these fractions specific gravity and sulfur content were determined. In addition, the octane number in accordance with ASTM D2699 and aromatic content were determined for gasoline fraction. Combined results of lest performed on distilled products are listed in Table 5.

EXAMPLE 2 (Comparative ) This experiment was carried out in the previously described processing unit and under the same temperature conditions, without returning the downstream aromatic condensate to soaking zone, in order to illustrate the undesired effect on Light synthetic oil and CBp quality. Under these conditions the obtained LSO is heavier and contains less gasol ine fraction.

The yields of LSO, CBp, gas and steel wire are shown in Table 3, and LSO properties are shown in Table 4. . 12 Π3Ν7ΰΠ ^ΙΠ ΤΠ 1 47.i.n p^N^ rvnp ECO Ltd 71p¾:27110 Table 3. The yield of LSO, CBp, gas and steel wire in Example 1 and Example 2 Mass Balance of the Products Wt. % Wt. % Example 1 Example 2 LSO 36.0 41.0 Gas 12.2 9.0 CBp 39.0 37.1 Steel Wire 12.0 12.0 Water 0.8 0.9 Total 100.0 100.0 Table 4. The LSO Properties of Example 1 and Example 2 Example 1 Example 2 * Distillation range, "C : Start point (IBP) 46.7 72.9 % point 111.2 142.7 50% point 160.4 269.1 70% point 192.3 345.5 90% point 261.2 - End point (FBP) 346.0 345.5 Percentage of distillation, vol. % 95.4 71.3 Residue, vol. %, 2.3 26.7 Loss 2.3 2.0 Specific Gravity, 15 °C 0.8738 0.9520 Sulfur content, mass. % 0.73 1.19 Q„ (Net heat of combustion), Btu/lb 1 ,010 - Ash, mass. % 0.003 0.011 Viscosity, 38 °C, cSt 0.92 2.87 performed in accordance with ASTM D86. , . 12 Baaley HaMelaha St., P.O. Box 1147 Industrial Area Wastoil 12 ΓΟΝ^ΏΠ ' m τπ 1147.i.n rmp.n.K . Bialik 27110, Israel ECO Ltd τιρ¾:27110 Table 5. Properties of Gasoline and Fuel Oil Fractions (Example 1).

Gasoline fraction Gasoil fraction Distillation range, °C : Start point (IBP) 45,6 171.4 % point 82,5 178.6 50% point 118,8 243,3 70% point 135,4 283,7 90% point 166,5 352,2 IZnd point (FBP) 1942 370.2 Percentage of distillation, vol. % 97.7 95.3 Residue, vol. % 1.4 3.7 Specific Gravity 0.8101 0.9263 Sulfur content, mass. % 0.53 0.93 *Octane Number 97.8 - Aromatics, vol. % 52 - Olefins, vol. % 41 - Ash, mass. % 0.005 performed in accordance with AST D2699.

Claims (1)

1. Wastoil Eco, Ltd. 12 Baaley HaMelaha St., 1 2 ΠΝ^ 1Ί P.O. Box 1 1 47 Industrial Area Wastoil ΰΠ ,l?m Τ 1 147 .n p^wn rrnp.n.N . Biahk 271 1 0, Israel ECO Ltd 7ip¾:271 10 AI MS at is claimed is: A method of manufacturing LSO and CBp from scrap tires with steel wire, comprising of the following steps: a. feeding the whole scrap tires under inert gas or steam, without previous shredding, into the processing unit in continuous and uninterruptible manner; and b. keeping the whole scrap tires in contact with the downstream aromatic condensate (hereinafter wetted stack) having a boiling temperature greater than 300° C; and c. wetting the stack in soaking zone in order to improve heat conductivity of rubber d. decomposing this wetted slack by indirect heating and by upstream process vapor; and e. healing the tread scrap tires by radiation from process unit wall.. f. healing the inner surface of scrap lires by hot upstream process vapor. g. moving the wetted stack down toward the annealing zone by gravity; and h. moving the wetted stack down in the processing unit with the temperature within the processing unit gradually increasing up to the values of annealing temperature; and i . moving the wetted stack down within a processing unit to produce a process vapor, and sol ids comprising of CBp and steel wire; and j . moving the process vapor to the upper section of processing unit; and k. separating the process vapor within the upper section to downstream aromatic condensate and overhead vapor; and I. returning the downstream aromatic condensate from the drain plate of the upper zone into the soaking zone of processing unit as a wetting agent for the scrap tire stack; and in. eliminating particle contamination of process vapor by downstream aromatic condensate; and n. coking the downstream aromatic condensate on CBp surfaces in the annealing zone to increase yield of CBp; and o, reducing the density of LSO as a result of generating additional light products in this coking process; and Wastoil Eco, Ltd. 1 2 Baaley HaMelaha St., 1 2 ΓΠΝ^Π ^ιο τη P.O. Box 1 147 industrial Area 1 147 ,7.n ^x1:. mp K. Bialik 27 10, Israel ECO Ltd Tii?¾:271 10 p. spraying a portion of LSO on the packing bed of the upper zone in the downward direction to provide additional purification of process vapor from particle contamination; and q. separating CBp from steel wire at the bottom of processing unit at the temperature of 550 - 700 °C; and A method according to claim 1 , for producing the LSO having a low sulfur content, specific gravity less than 0.88, initial boiling point of 40 - 60 °C, and 90% vol. boiling up to 300 °C. 3. A method according to claim 1 , wherein scrap tires are processed without being cut into pieces / shredding. 4. A method according to claim 1 , wherein scrap tires contain steel wire. 5. A method according to claim 1 , wherein scrap tires are continuously fed into the processing unit and thermal decomposition process is continuously operated. 6. A method according to claim 1 , wherein whole tires are moved down by gravitational force within the processing unit while the temperature in annealing zone gradually increases to 550 - 700 °C. 7. A method according to claim 1 , wherein scrap tires are thermally decomposed within the processing unit to produce process vapor and a solid consisting of CBp and steel wire. 8. A method according to claim 1 , wherein soaking, thermal decomposition and coking processes take place in a sequential manner in one processing unit. 9. A method according to claim I , wherein process vapor moves from the annealing zone into the upper zone and solids residue is directed to the annealing zone of processing unit. A method according to claim 1 , wherein process vapor is separated in the upper zone into downstream aromatic condensate and overhead vapor. A method according to claim 9, wherein downstream aromatic condensate with sol id particles are returned from the drain plate of the upper zone to soaking zone. A method according to claim 9, wherein downstream aromatic condensate is used as the wetting agent (surfactant) for soaking the scrap tire. A method according to claim 9, wherein downstream aromatic condensate is the heating media for the scrap tires. Wastoil Eco, Ltd. 1 2 Baaley Ha elaha Si.. V2 ΤΠ P.O. Box 1 147 Industrial Area W st oil 1 2 -DtODrt ^ 1 147 .i.n ^x rmp . Bialik 271 1 0, Israel Eco Ltd τρτ.:271 1 0 14. A method according to claim 9, wherein downsti cam aromatic condensate is deslrucled in the process section into additional LSO, Clip gas. 15. A method according to claim 9, wherein the upper zone overhead vapor is condensed and separated to give LSO. 1 . A method according to claim 14, wherein overhead vapor alter condensation is divided to LSO, water and gas. 17. A method according to claim 1 , wherein part of said LSO is sprayed on the packing bed of the upper section in a downward direction lo provide additional puri fication from particle contamination and control the quality of LSO. I S. A method according to claim 1 . wherein sol id residue in the bottom of processing unit is annealed at the temperature of 550 - 700 °C to reduce the content of hydrocarbons in the C p 1 . A method according to claim I , wherein steel wire is separated from CBp after thermal decomposition of scrap t ires. 20. A method according to claim I , wherein the CBp product is substantially metal free. 21. A method according to claim 1 , wherein a solid residue is divided to steel wire and Clip after the annealing zone of processing unit. 22. A method according to claim 1 , wherein steel wire and CBp arc discharged from the processing uni t. 23. A method according to claim 1 , wherein the LSO has low density, which facilitates rapid separation of water-oil emulsion. 24. A method according to claim 1 . wherein the LSO does not form stable emulsion with water. 25. The apparatus for thermal decomposition of whole scrap tires which comprises: a. processing unit and separation system according to Figure 1 ; processing unit as a vertical cylindrical vessel having a process section and upper zone; c. Process section of processing unit includes a soaking zone, reaction zone and annealing zone with opening for removal solid product. Wastoil Eco, Ltd. 1 2 Baaley Ha elaha St.. P.O. Box 1 147 Industrial Area Was-toil 12 nDf ttn V2 τπ 1 147 .i.n v sri rrnp K. Bialik 271 10, Israel ECO Ltd ρ¾:271 10 26. The apparatus according to claim 25, wherein the scrap tires within said processing unit are transported by means of gravity to minimize the energy required for transportation of raw materials into processing unit. 27. The apparatus according to claim 25, with a whole scrap tire feeding mechanism which is connected to the processing unit. 28. The apparatus according to claim 25. wherein the annealing zone of the process section has two or more burners mounted in the furnace tangentially to the annealing zone wall. 29. The apparatus according to claim 25, wherein annealing zone of process unit is heated by the radiation of burners flame. 31). The apparatus according to claim 25, wherein each burner or group of burners is mounted in its own furnace and the furnace is constructed in form of spiral ducts around the wall of annealing and reaction zones. 31. The apparatus according to claims 25, 30 wherein Hue gas from each furnace Hows by its own spiral track around the reaction zone wall . 32. The apparatus according to claim 25, wherein the reaction zone of the processing unit is heated by Hue gas which Hows spiral ly from furnaces to heating jacket of reaction zone. 33. The apparatus according to claim 25, wherein the upper zone serves for heat-mass exchange process between the process vapor and LSO. 34. The apparatus according to claim 25, wherein the upper zone includes a condenser for separating downstream aromatic condensate from the process vapor.