AU2001281198A1 - Low energy method of pyrolysis of hydrocarbon materials such as rubber - Google Patents

Low energy method of pyrolysis of hydrocarbon materials such as rubber

Info

Publication number
AU2001281198A1
AU2001281198A1 AU2001281198A AU2001281198A AU2001281198A1 AU 2001281198 A1 AU2001281198 A1 AU 2001281198A1 AU 2001281198 A AU2001281198 A AU 2001281198A AU 2001281198 A AU2001281198 A AU 2001281198A AU 2001281198 A1 AU2001281198 A1 AU 2001281198A1
Authority
AU
Australia
Prior art keywords
reaction
pyrolysis
rubber
reactor
vacuum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
AU2001281198A
Other versions
AU2001281198B2 (en
Inventor
Jules E. Langlois III
Alan M. Levine
Ronald E. Nichols
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Delta Energy Holdings LLC
Original Assignee
Delta Energy Holdings LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Delta Energy Holdings LLC filed Critical Delta Energy Holdings LLC
Priority claimed from PCT/US2001/024899 external-priority patent/WO2002014742A1/en
Publication of AU2001281198A1 publication Critical patent/AU2001281198A1/en
Application granted granted Critical
Publication of AU2001281198B2 publication Critical patent/AU2001281198B2/en
Assigned to DELTA ENERGY HOLDINGS LLC reassignment DELTA ENERGY HOLDINGS LLC Request for Assignment Assignors: RJ LEEGROUP, INC.
Anticipated expiration legal-status Critical
Expired legal-status Critical Current

Links

Description

LOW ENERGY METHOD OF PYROLYSIS OF HYDROCARBON MATERIALS SUCH AS RUBBER
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Patent Application entitled "Low Energy Method of Pyrolysis of Hydrocarbon Materials such as Rubber", filed August 10, 2001, which claims priority under 35 U.S.C. §119(e) to provisional application Serial No. 60/224,405, filed August 10, 2000, and provisional application Serial No. 60/224,029, filed August 10, 2000.
FIELD OF THE INVENTION The present invention relates to a low energy method of pyrolysis of hydrocarbon materials such as rubber, coal, tar sands and the like. The method uses a clay catalyst and negative pressure to achieve lower energy input requirements, and produces improved solid carbonaceous material, oil, and combustible gas products. The system design profiles the energy input to take advantage of the exothermic reaction and optimize the required energy.
BACKGROUND INFORMATION In the United States, each resident discards approximately one waste tire annually. Discard of tires resulted in accumulation of approximately 242 million wasted tires nationwide in 1990 alone, exclusive of retreads. Waste tires are a minor portion of the solid waste stream yet represent a major disposal problem. While many waste tire incinerators have been designed, incineration may not maximize the potential economic recovery of energy and chemical materials from the tires.
Most tires are disposed of in landfills or in tire storage piles. However, whole waste tires are difficult to dispose of in landfills; they tend to collect gas, harbor rodents, snakes, and mosquitoes, pose a fire hazard, and drift upward in the landfill over time as other wastes consolidate and subside. Nonetheless, landfilling, stockpiling, or illegal disposal continue to be the primary methods of waste tire management.
Pyrolysis involves heating organic materials in the absence of oxygen to convert them to molecularly simpler and smaller organic compounds. When organic wastes such as waste tires are the feedstock, products of the process include char or carbon black, oil and gas. As early as 1830, a developer successfully commercialized an early application of pyrolysis involving the production of liquid products from wood. The production of coke from coal pyrolysis became the most common application of the technology; its use continues today. The use of wood pyrolysis to manufacture creosote oil expanded after the introduction of creosote as a wood preservative in 1838. Pyrolysis of coal and oil shales became common to produce oils in the United States and elsewhere in the mid-1800's. Pyrolysis plants to produce illuminating gas became common worldwide until the invention of the electric light bulb in 1879. Pyrolysis processes may operate either as batch feed or continuous feed systems. Batch feed systems process a single charge of feed stock at one time. After the required residence time in the batch thermoreactor, solid products and residue are removed. Alternatively, in continuous feed systems, feed stock is conveyed through the thermal reactor, and solid products and residue are continuously discharged.
Pyrolysis relies on the addition of heat to break chemical bonds, providing a mechanism by which organic compounds decompose and vaporize. Most systems for pyrolysis of waste rubber and other hydrocarbons report operating temperatures in the range of about 480°F to 1740°F. At temperatures above approximately 480°F, shredded tires release increasing amounts of liquid oil products and gases. Above 750°F, depending on the process employed, the yield of oil and solid tire derived char may decrease relative to gas production. Tires contain over 80% carbon and hydrogen, and these elements form the principle constituents of the solid, liquid and gaseous pyrolysis products. In addition to carbon-carbon bonds, decomposition of tires requires the breakage of sulfur-carbon and sulfur-sulfur bonds. The solid product produced by most pyrolysis processes that use tires or other solid organic feed stocks is termed "tire derived char", "tire derived carbon char", or carbon black. This solid product can be further processed and cleaned to produce a higher grade of carbon black, or it can be marketed directly. Carbon blacks differ in particle size, surface area, average aggregate mass, particle and aggregate mass distributions, structure and chemical composition, and are rated according to industry standards, based on these properties. Conformity with industry standards determines the marketability of the tire derived carbon black. For example, intermediate quality virgin (un-recycled) carbon black is usually used in rubber products, while lower grades are used in products such as hoses and solid (not steel- belted) rubber tires. High purity carbon blacks are used in toner and for electronic sensors.
The surface area of carbon black has a substantial impact on quality and applications; carbon blacks containing submicron particles have a high surface area to volume ratio. The average particle size of a commercial carbon black ranges from approximately 5000 A for a low cost thermocarbon to approximately 100 A for the most expensive high color paint carbon. Also important is structure, as measured by aggregate size and shape, the number of particles per aggregate, and their average mass. These characteristics affect aggregate packing and the volume of voids in the bulk material. Void volume is one of the standards by which carbon black grades are judged.
Typically, tire-derived carbon chars produce carbon blacks having particles in the size range of 10 to 100 microns. This particle size range limits the ability of the material to be substituted for standard, less variable, carbon blacks containing submicron particles. However, there are some applications which use carbon black grades containing larger particle sizes, for example, use in plastics to improve weathering resistance, or to impart antistatic and electrically conductive properties. Char or carbon char material generated from pyrolysis can also be used as a source of fuel.
Tire pyrolysis also produces a gas that contains combustible concentrations of butane, propane, methane and ethane. Due to large amounts of carbon monoxide and carbon dioxide in the gas, the gas cannot be blended with natural gas for sale. Tire pyrolysis systems can also generate an oil-based liquid similar to Number 6 grade fuel oil; the liquid constitutes approximately 30% to 50% of the product derived from the organic content of the tire feed stock. Due to the high temperature and absence of hydrogen in the reaction mixture, most rubber pyrolysis methods produce a liquid that is high in polyaromatic hydrocarbons (PAH); these compounds are detrimental when released in the environment.
Many methods of pyrolysis have been described in the art using clay as a catalyst or non-sticking agent. See, for example, U.S. Patent Nos. 1,680,908; 4,463,203; 4,300,009; 4,948,495; 5,114,541; 5,354,930; 5,233,109; and 5,114,541. These methods use high temperatures, in the range of 200° - 800° C (392°-1492° F), and do not use negative pressure/vacuum conditions. Other patents have attempted to fine tune the pyrolysis process to favor production of certain products over others; see, for example, U.S. Patent No. 5,359,061, which discloses pyrolysis of elastomers such as rubber tire scraps using molecular beam mass spectrometry techniques to detect decomposition products and to determine process parameters.
While some patents disclose the use of vacuum conditions, none disclose use of a vacuum in combination with the use of a catalyst. See, for example, U.S. Patent No. 5,720,230 which provides a method of pyrolysis for discarded rubber tires, using temperatures between about 350° F and 650° F, under slight vacuum conditions of one half to one inch mercury; and U.S. Patent No. 4,740,270, which discloses treatment of used rubber tires by vacuum pyrolysis, at a temperature range of about 360°C to 415°C (680 ° - 779° F) under subatmospheric pressure conditions. In most prior art methods the carbon black derived from pyrolysis of rubber tires does not meet the industry standards as to particle size, purity and the like. None of the above described methods of pyrolysis of rubber tires and hydrocarbons generally are accomplished at lower temperatures and yet able to produce a higher quality of carbon black and liquid oil low in polyaromatic hydrocarbons as reaction products. SUMMARY OF THE INVENTION
The present invention solves the above need by providing a low energy method of pyrolysis of hydrocarbon material, including rubber, in which the hydrocarbon material is heated under vacuum conditions, using a clay and metal catalyst. With the method of the present invention a higher quality of solid reaction products can be acliieved; carbon black is released from the rubber tires, rather than being created during the pyrolytic process. The liquid oil produced by the method of the present invention has reduced amounts of polyaromatic hydrocarbons and partially pyrolyzed rubber and hydrocarbon material as compared with other methods. The addition of a catalyst, in combination with negative pressure conditions, allows the process to proceed at a more rapid rate than other prior art methods. In addition, by drawing the oil and gases to the surface of the rubber during the course of the reaction, the oil and gases are more easily removed from the system. Use of a clay catalyst provides reactive sites within layers of the clay wherein the sites can share electrons with carbon and sulfur molecules in the rubber molecules. This sharing of electrons strains the adjacent carbon-carbon, carbon-sulfur, and/or sulfur-sulfur bonds, destabilizing them and decreasing the energy, and thus the temperature required to promote thermal cracking. The breakage of the bonds involves either free radical formation, ion formation or polarization or a combination of these. Additionally, the catalyst causes steric strain on the bonds which makes them more susceptible to cleavage. The use of metal dust in combination with clay further enhances the reaction.
In an additional aspect of the invention, pyrolysis of the hydrocarbon material occurs under vacuum conditions in at least a first, a second and a third phase. By taking advantage of the exothermic nature of the reaction, only as much energy as is required is inputted into the system, preferably in the first and third phases. As the reaction progresses, and particularly during the middle phase of the reaction, less fuel is required to maintain the desired reaction temperature. Thus the fuel input is adjusted over time, providing at least three phases sequentially in time, or spatially inside the reaction chamber.
When a continuous pyrolytic process is used, the fuel input or temperature is varied spatially within the reaction chamber. The rubber or hydrocarbon material moves through the reaction chamber by means of a helicoid auger or other similar device. In the inlet portion of the reaction chamber, corresponding to the first phase of the reaction (the "activation phase"), higher heat input is required to initiate and overcome the activation energy of the reaction, and the inlet portion of the reaction chamber is heated accordingly. The rubber or hydrocarbon material is moved from a first location in the chamber to a second, intermediate location, corresponding to the second phase (the "decomposition phase") of the reaction, where the reaction is exothermic and less heat (fuel) input is required to ensure progress of the reaction. Finally, the rubber or hydrocarbon material is moved to a third location corresponding to the third phase (the "completion phase") of the reaction, where the reaction nears completion and slows, and fuel input is increased to complete the pyrolysis process.
It is an object of the present invention, therefore, to provide a low energy method of pyrolysis of rubber, tar sands, coal or other hydrocarbon materials. It is an additional object of the present invention to provide a low energy method of pyrolysis, using vacuum conditions and a catalyst.
It is an additional object of the present invention to provide a low energy method of pyrolysis which produces higher quality reaction products.
It is a further object of the invention to provide a low energy method of pyrolysis in which the fuel input is varied over time or spatially to take advantage of the exothermic nature of the reaction.
It is also an object of the present invention to provide an environmentally safe method of recycling rubber tires and other hydrocarbon materials.
These and other objects of the invention will be readily apparent from the following detailed description and appended claims.
BRIEF DESCRIPTION OF THE FIGURES The invention is further illustrated by the following non-limited drawings in which:
Figure 1 shows temperature profiles of the reaction using clay alone, clay in combination with metal dust, and pillared clay as catalysts.
Figure 2 shows a simple pyrolytic chamber and apparatus for drawing off liquid, solid and gaseous products of the reaction.
Figure 3 shows a continuous feed pyrolytic chamber and apparatus for drawing off liquid, solid and gaseous products of the reaction. Figure 4 shows the activation and reaction energies of the reaction with and without a catalyst. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides a low energy method of pyrolysis of hydrocarbon material comprising providing hydrocarbon material; loading the hydrocarbon material into a reaction chamber; adding a clay and metal dust catalyst to the reaction chamber; and heating the reaction chamber. This method occurs under vacuum conditions and yields reaction products comprising a substantially non- charred and non-oxidized solid residue having minimal unpyrolized material, a substantially non-oxidized and polyaromatic hydrocarbon-free liquid hydrocarbon product and a combustible gas. The catalyst in the present invention is a clay-metal dust combination which further reduces the amount of heat input required to complete the reaction, as compared with use of a clay catalyst alone. Aluminum (Al) and/or magnesium (Mg) metal dust are added to the clay to enhance the reaction. As used herein, "dust" refers to a particle size that is less than about 325 mesh for Mg and less than about 200 mesh for Al. While either metal can be used alone in combination with the clay, a preferred combination uses both metals. Typically, the metal dust will be added in a ratio of about [0.1 to 2]:[0.1 to 2]:[8] ([Al]:[Mg]:[Clay]). The preferred ratio is about 1:1:8. The metal is mixed with the clay prior to application to the hydrocarbon materials. Due to the similar densities of the three components, the mixture will not segregate during shipping and storage. Also, the dilution effected by the clay decreases any ignition hazard of the metal dusts. It is thought that the addition of metal dust enhances the reaction due to the metals scavenging the small amount of oxygen in the system and generating heat to promote the reaction, although the inventors do not wish to be bound by this. Additionally, the metals could be catalyzing the water-gas and other reactions to generate free hydrogen, which will be available to complete the cracking reaction. When metal dust is added the heat generated by the reaction occurs earlier in the process and is maintained for a longer time period and less heat input is required. The reaction proceeds further towards completion with less final phase heating required. Since the maximum temperature and pressure remain similar to the catalyst without the metals the products are not compromised by this catalyst-metal mixture. Figure 1 illustrates the temperature profiles in a batch system of the reaction using pillared clay, metals and clay (bentonite) and clay alone as catalysts. As can be seen in Figure 1, the reaction temperature of the hydrocarbon material increases with the use of pillared clay or metals and clay as catalysts, as compared with no catalyst or the use of clay alone. The energy optimization described can be applied in both batch and continuous reactor configurations.
As used herein, the term "clay" refers to the naturally occurring material comprising hydrated aluminum silicates in a layered structure and belonging to a general class of materials known as smectite. Smectite ores such as bentonite, and specific clay minerals such as montmorillonite and beidellite are included within the scope of the present invention. Also included are commercial products containing these clays such as cat litter or oil spill absorbent. These clays in combination with various counter ions, including hydrogen (H-form), sodium (Na-form), various metals (e.g. Al-form), and organic cations are also contemplated as being within the present invention.
Bentonite can also be modified by the introduction of metal hydroxide "pillars" between the layers. Pillaring clay is a process by which molecules are bound within the layers of clay to prop them open, making the clay more stable at higher temperatures and allowing interaction with larger molecules. Pillared clay is a more effective catalyst because the catalyst is stable over a larger temperature range. The term "clay" refers to any of the above materials, including those not specifically listed yet known to those skilled in the art. Preferred clays for use as a catalyst in the method of the present invention are smectites; most preferred is montmorillonite .
Typically, the clay and metal dust catalyst will be added in an amount of between about 0.01 to 3.0 wt%, based on the total weight of the rubber or hydrocarbon material. Preferably, the catalyst is added in an amount of between about 0.2 to 1.0 wt%.
As used herein, the terms "negative pressure conditions" or "vacuum conditions" refer to the use of a vacuum in which the pressure is below atmospheric. A preferred vacuum setting is about 2 to 16 inches mercury; most preferred is about 5 to 10 inches mercury. The non-charred carbonaceous residue containing little un-pyrolyzed rubber, produced by the methods of the present invention, is distinguishable from that produced in prior art methods. For example, the carbon black produced by the present methods has no detectable PAH's, less than about 15-20% unpyrolyzed rubber, and no oxidized organic contaminants as compared with significant levels of these contaminants in prior art products. An analysis of commercial standard black, IRB6, by Fourier Transform Infrared Spectroscopy (FTIR) confirmed the presence of more than 0.1% PAH's in such products. The current process, when operated without catalysts, produces product with over 70% un-pyrolyzed rubber and when operated at positive pressure generates product with significant amounts of oxidized organic contaminants, for example terephthalic acid. As used herein, the term " minimal un- pyrolyzed rubber" will refer to a solid residue having less than about 20% unpyrolyzed hydrocarbon material.
The liquid oil produced by the methods of the present invention also shows improved properties over oils produced in prior art methods. The oil produced by the present methods has decreased amounts of polyaromatic hydrocarbons and oxidized organic contaminants. It is also lighter in weight than oils generated by other prior art processes.
In one embodiment, when operation is in batch mode, the temperature of the reaction occurs between about 140°F and 850° F in the first or activation phase, preferably initiating below 155°F and peaking about 550° F. The temperature of the reaction is monitored by inserting a measuring device into the rubber or hydrocarbon material itself; constant energy is added to the system throughout the activation phase until oil condensation initiates at which time the heating is reduced or ceased. During the next (second) phase of the reaction, little or no fuel input is required due to the exothermic nature of the reaction., and the reaction temperature rises from about 550°F to 850°F or greater even in the absence of fuel input. Near the end of the decomposition phase of the reaction, the reaction slows and the temperature starts to decrease, during which time an increase in fuel is necessary to complete the pyrolytic process. Heating is resumed after the reaction temperature peaks and starts to decline and is continued until completion is noted by leveling of the temperature. In this configuration 25% less fuel is used with catalyst than without catalyst. An electronic feedback system or, in the case of a continuous helicoid reactor, a system that transfers heat from the exothermic region can be developed to automatically adjust the fuel input based on the reaction temperature. Figure 2 shows an embodiment of a pyrolytic reaction chamber and batch apparatus in which liquid, gaseous and solid reaction products are removed during the pyrolytic process, according to the methods of the present invention. Rubber tires 1 and a catalyst 3 are placed in the reactor chamber 5 and subjected to heat as measured by the temperature gauge 7, which monitors the heat of the reaction. A vacuum pump 9 maintains a negative pressure throughout the system, as measured by the vacuum gauge 11. Oil traps 13 collect oil produced by the reaction, while gases are vented off 15. A condenser coil 17 condenses the oil, and the flow valve regulator 19 controls the reactor atmosphere and vacuum level. Solid products remain in the reactor chamber 5 where they can be collected after completion of the reaction. In a further embodiment, in a continuous pyrolytic process, the temperature/fuel input can be varied spatially within the reaction chamber. First, the hydrocarbon material, at ambient temperature, moves from feeder bins into an initial temperature zone in the reactor that controls the heat input required to overcome the activation energy of the reaction. In the inlet portion of the reaction chamber, corresponding to the first phase of the reaction, higher heat input is required to initiate the reaction, and the inlet portion of the reaction chamber is heated accordingly, with heat input increasing until a reaction temperature of between about 450°-850° F is reached, more preferably a temperature of between about 500° - 600° F, most preferably about 550°F, for a period adequate to initiate a pyrolysis reaction as indicated by initiation of production of oil. The rubber or hydrocarbon material moves through the reaction chamber by means of a helicoid auger or other similar device, and is moved from the first location in the chamber to a second, intermediate location, corresponding to the second phase of the reaction, where lower fuel input is required to maintain the reaction temperature at between about 450°-850° F, more preferably a temperature of between about 500° - 600° F, most preferably about 550°F, and ensure progress of the reaction for a period adequate to continue the pyrolytic reaction, as indicated by the generation of heat. Finally, the rubber or hydrocarbon material is moved to a third location corresponding to the third phase of the reaction, and heat input is increased to maintain a reaction temperature of between about 450°-850° F, more preferably a temperature of between about 500° - 600° F, most preferably about 550°F, for a period adequate to complete the pyrolysis process, as indicated by a leveling of the temperature. The temperature of the reaction is measured at the center of the auger, and fuel input is adjusted to maintain the desired reaction temperatures and to take advantage of the exothermic nature of the reaction. A feeder and recovery system removes the gases from the controlled low temperature reactor chamber, yet allows it to continuously operate under a vacuum. As described above, an electronic feedback system can be developed to automatically adjust the fuel input based on the reaction temperature.
An example of a continuous feed system is shown in Figure 3. Shredded rubber 30 or other hydrocarbon material and a catalyst 35 are moved into inlet bins or feed hoppers 40 by means of a conveyor belt 45 or other similar apparatus. The elongated reaction chamber 50 is heated at both ends by gas burner 55 and gas burner 60. The hydrocarbon material is heated in the activation zone 65, and then moves by means of a helicoid auger 70 to the decomposition zone 73, where the exothermic portion of the reaction occurs. As the reaction slows, the hydrocarbon material is moved by means of the auger to the completion zone 75, after which solid residue moves into the outlet bins 80 to a solid material recovery system 85 to yield carbon black and steel, if initially present. Vapors 90 are continuously drawn off and condensed into oil 95 by a heat exchanger or oil condensers 100 or burned as fuel during the reaction. A vacuum pump 105 draws off the vapors and maintains a vacuum during the course of the reaction.
By knowing the energy requirements for activation of this reaction and the kinetics of energy production of this reaction (as shown in Figure 4), a spatially variable reactor which controls the energy added to the reactant materials as they move through the reactor can be designed, hi addition, since the gas produced contains manageable levels of contaminants, it is collected and added back to the system when needed. This design takes advantage of the thermodynamics of the reaction and is economical.
EXAMPLE The following example is intended to illustrate the invention and should not be construed as limiting the invention in any way.
Two pounds of rubber tires were loaded into a batch pyrolytic chamber having a 21 quart capacity, and 10 grams of a mixed metal catalyst consisting of aluminum, magnesium and bentonite in a mass ratio of 1 : 1 :8 was dispersed over the rubber. The reactor was heated with LPG fuel burned at a rate of 16 1/min until oil condensate was produced and the reaction temperature reached 550°F in the first phase, as determined by a thermocouple placed in a piece of rubber in the chamber. The LPG flow was turned off at this point. The temperature continued to rise through the heat generated by the exothermic reaction until the temperature reached 750°F in the second phase. During the process the combustible gas product was observed by flaring with a pilot light to be within ignitable levels for approximately 20 minutes. The carbon black produced composed greater than 74% of the solid product. The oil product was equivalent to number 6 grade fuel oil. Eighty such experimental tests were performed with similar results. Side-by-side comparative tests performed without catalyst produced little or no gas or oil and solid product consisting of less than 20% carbon black.
Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appending claims. What is Claimed Is:
1. A low energy method of pyrolysis of hydrocarbon material comprising: providing said hydrocarbon material; loading said hydrocarbon material into a reaction chamber; adding a clay and metal dust catalyst to said reaction chamber, and heating said reaction chamber for a sufficient time to provide substantially complete pyrolysis, said method occurring while maintaining a vacuum and yielding reaction products comprising a substantially non-charred and non-oxidized solid residue having minimal unpyrolyzed material, a substantially non-oxidized and polyaromatic hydrocarbon-free liquid hydrocarbon product and a combustible gas.
2. The method of Claim 1 , wherein said clay is selected from the group consisting of montmorillonite, bentonite, beidiUite and combinations thereof. 3. The method of Claim 1 , wherein said clay is pillared clay.
4. The method of Claim 1, wherein said clay is a natural ore.
5. The method of Claim 1, wherein said clay is a commercial clay containing product.
6. The method of Claim 5, wherein said commercial clay product is selected from the group consisting of cat litter and oil spill absorbent and combinations thereof.
7. The method of Claim 1 , wherein said clay and metal dust catalyst is added in an amount of about 0.01 wt.% to 3.0 wt.%, based on the total weight of said hydrocarbon material. 8. The method of Claim 1 , wherein the metal dust is added to the clay in a ratio of between about [0.1 to 2]:[0.1 to 2]:[8] of [Al] [Mg] [clay].
9. The method of Claim 1, wherein said metal dust is added in a ratio of between about [0.5 to 1]:[0.5 to 1]:[8] of [Al] [Mg] [clay].
10. The method of Claim 1 , wherein said metal dust is comprised of a mixture of aluminum and magnesium.

Claims (1)

  1. 11. The method of Claim 1 , wherein said metal dust is comprised of aluminum or magnesium.
    12. The method of Claim 1 , wherein said metal dust comprises Al particles of less than about 200 mesh size and Mg particles of less than about 325 mesh size.
    13. The method of Claim 1 , wherein said heating of said reaction chamber results in a reaction temperature of said hydrocarbon material of between about 150° to 850° F.
    14. The method of Claim 13, wherein said reaction temperature of said hydrocarbon material is maintained for a period of time sufficient to complete pyrolysis.
    15. The method of Claim 1 , wherein said heating occurs in at least a first, second and third phases and fuel input is adjusted to take advantage of the exothermic nature of the reaction. 16. The method of Claim 15, wherein said heating in said first phase maintains a reaction temperature of between about 450° - 850°F, for a period of time adequate to initiate pyrolysis.
    17. The method of Claim 15, wherein said heating in said second phase maintains a reaction temperature of between about 450° - 850°F, for a period of time adequate to provide continued pyrolysis.
    18. The method of Claim 15 , wherein said heating in said third phase maintains a reaction temperature of between about 450° - 850°F, for a period of time adequate to provide completion of pyrolysis.
    19. The method of Claim 15 , wherein said first, second and third phase occur sequentially over time.
    20. The method of Claim 15, wherein said first, second and third phase occur sequentially over space, as said hydrocarbon material moves through said reaction chamber.
    21. The method of Claim 1 , wherein said vacuum is maintained at a pressure of between about 2 inches to 16 inches mercury.
    22. The method of Claim 15, wherein said vacuum is maintained at pressure of between about 2 inches to 16 inches mercury.
    23. The method of Claim 1 , wherein said vacuum is maintained at a pressure of between about 5 inches to 10 inches mercury.
    24. The method of Claim 15, wherein said vacuum is maintained at pressure of between about 5 inches to 10 inches mercury.
    25. The method of Claim 1, wherein said hydrocarbon material is used rubber.
    26. The method of Claim 1, wherein said hydrocarbon material is tar sands.
    27. The method of Claim 1 , wherein said hydrocarbon material is coal.
    28. An apparatus for reclamation and recovery of constituents of discarded vehicle tires and other rubber based materials including organic and inorganic materials for reuse or environmentally safe disposal, said apparatus comprising: a feed system for transferring rubber products and a catalyst into an inlet of a low temperature reactor; one or more elongated reactor chambers having activation, decomposition, and completion zones, wherein said one or more reactor chambers each have a helicoid auger for transferring material from the inlet through said reactor and solid product from said reactor to an outlet; an inlet and an outlet bin positioned at each end of the reactor chambers for input, reaction initiation, product decomposition, reaction completion, and extraction of the into vapor and solid material; and a solid material recovery system.
    29. An apparatus according to Claim 41, further comprising a vapor recovery system for recovering vapors from a decomposition zone of said one or reactor chambers, wherein said vapor recovery system comprises: a heat exchanger for condensing vapors from said one or more reactor chambers; a liquid/gas separator for separating liquids condensed in said heat exchanger; and a vacuum pump for removing vapors from the decomposition chamber of said one or more low temperature reactor chambers through said heat exchanger and said liquid/gas separator, while maintaining a vacuum in said one or more low temperature reactor chambers.
    30. An apparatus of Claim 41 , wherein the feed system is a helicoid auger.
    31. An apparatus of Claim 41 , wherein an outlet conveyor is a helicoid auger.
    32. A process for reclamation and recovery of constituents of discarded vehicle tires and other rubber products cut into pieces for reuse or environmentally safe disposal, comprising: transferring tire pieces from a feed supply by a conveyor into a feeder bin; and transferring the tire pieces from the feeder bin to the inlet of a low temperature reactor chamber by a helicoid auger.
AU2001281198A 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber Expired AU2001281198B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US22402900P 2000-08-10 2000-08-10
US22440500P 2000-08-10 2000-08-10
US60/224,029 2000-08-10
US60/224,405 2000-08-10
PCT/US2001/024899 WO2002014742A1 (en) 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber

Publications (2)

Publication Number Publication Date
AU2001281198A1 true AU2001281198A1 (en) 2002-05-23
AU2001281198B2 AU2001281198B2 (en) 2006-08-17

Family

ID=26918360

Family Applications (3)

Application Number Title Priority Date Filing Date
AU2001281198A Expired AU2001281198B2 (en) 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber
AU8119801A Pending AU8119801A (en) 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber
AU2001283221A Abandoned AU2001283221A1 (en) 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber

Family Applications After (2)

Application Number Title Priority Date Filing Date
AU8119801A Pending AU8119801A (en) 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber
AU2001283221A Abandoned AU2001283221A1 (en) 2000-08-10 2001-08-09 Low energy method of pyrolysis of hydrocarbon materials such as rubber

Country Status (7)

Country Link
US (3) US6833485B2 (en)
JP (1) JP5057627B2 (en)
KR (1) KR100804158B1 (en)
CN (1) CN1179148C (en)
AU (3) AU2001281198B2 (en)
BR (1) BR0107096B1 (en)
WO (2) WO2002014040A1 (en)

Families Citing this family (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5057627B2 (en) * 2000-08-10 2012-10-24 デルタ エナジー ホールディングス エルエルシー Low energy pyrolysis method for hydrocarbon materials such as rubber
KR100526017B1 (en) * 2002-11-25 2005-11-08 한국에너지기술연구원 Apparatus and method for recovery of non-condensing pyrolysis gas
US7824523B2 (en) 2005-05-17 2010-11-02 Earthfirst Technologies, Inc. Catalytically activated vacuum distillation system
WO2007040381A1 (en) * 2005-10-05 2007-04-12 Agustin Javier Pretelin Nova System for recycling used tyres and rubber derivatives
CA2642617A1 (en) 2005-10-06 2007-04-19 Swaminathan Ramesh Method of recycling a plastic
DE102005057653A1 (en) * 2005-11-21 2007-09-06 Winkelkötter, Peter Process for conversion of organic secondary raw materials to oil mist and process for carrying out the process
CN1326974C (en) * 2005-11-30 2007-07-18 曹志德 Catalyst for producing light fuel oil using oily rock as raw material and its method
US20070289720A1 (en) * 2005-12-13 2007-12-20 University Of South Florida Self-Heating Chemical System for Sustained Modulation of Temperature
CN2878390Y (en) * 2006-04-07 2007-03-14 王新明 Multi-functional full automatic remote constant temperature heat supply cracking device for waste and old tyre
US8263038B2 (en) 2006-04-18 2012-09-11 Delta-Energy Holdings, Llc Method of devolatilizing recycled carbon black and associated method
WO2007128798A1 (en) * 2006-05-05 2007-11-15 Bioecon International Holding N.V. Improved process for converting carbon-based energy carrier material
EP1970425A1 (en) * 2007-02-20 2008-09-17 BIOeCON International Holding N.V. Improved process for converting carbon-based energy carrier material
RU2008147901A (en) 2006-05-05 2010-06-10 БИОеКОН Интернэшнл Холдинг Н.В. (NL) POLYMERIC MATERIAL OF PHOTOSYNTHETIC ORIGIN, INCLUDING DISPERSED INORGANIC MATERIAL
MY160001A (en) * 2006-11-07 2017-02-15 Cabot Corp Carbon blacks having low pah amounts and methods of making same
US7947248B2 (en) * 2007-05-17 2011-05-24 Tellus Technology, Llc Pyrolyzed rubber products and processes
US20100312037A1 (en) * 2008-01-31 2010-12-09 M-I L.L.C. Total containment tank cleaning system
DE102008010758A1 (en) * 2008-02-23 2009-09-10 SWU Gesellschaft für Umwelttechnik mbH Process for pyrolysis of organic waste and biomaterials
US7825213B2 (en) * 2008-04-11 2010-11-02 Chem Engineering Energy, Llc Method of making a metal terephthalate polymer
US20090295509A1 (en) * 2008-05-28 2009-12-03 Universal Phase, Inc. Apparatus and method for reaction of materials using electromagnetic resonators
US8288599B2 (en) 2008-06-30 2012-10-16 Kior, Inc. Co-processing solid biomass in a conventional petroleum refining process unit
US20100065411A1 (en) * 2008-09-17 2010-03-18 Jianguo Li Revolving waste plastic-oil converting equipment and method of using the same
US8317980B2 (en) * 2008-09-17 2012-11-27 Nantong Tianyi Environment And Energy Technology Limited Corporation Reactor for converting waste materials into fuel, a feeding system for feeding waste materials into the reactor, and methods for converting waste materials into fuel
US8524959B1 (en) 2009-02-18 2013-09-03 Kior, Inc. Biomass catalytic conversion process and apparatus for use therein
US8558043B2 (en) 2009-03-04 2013-10-15 Kior, Inc. Modular biomass treatment unit
EP3568451A4 (en) 2009-05-22 2019-11-20 KiOR, Inc. Processing biomass with a hydrogen source
US8623634B2 (en) 2009-06-23 2014-01-07 Kior, Inc. Growing aquatic biomass, and producing biomass feedstock and biocrude therefrom
CN101935540A (en) * 2009-06-30 2011-01-05 上海绿人生态经济环境保护研究所 Innocuous treatment technology for waste rubber by adding catalyst comprising steel wire
EP2449057B1 (en) * 2009-07-01 2021-08-11 Circa Group PTY Ltd Method for converting lignocellulosic materials into useful chemicals
WO2011009074A2 (en) * 2009-07-16 2011-01-20 Champagne Gary E Vacuum pyrolytic gasification and liquefaction to produce liquid and gaseous fuels from biomass
JP5755652B2 (en) * 2009-09-25 2015-07-29 ピロリクス・アー・ゲーPyrolyx Ag Method and apparatus for multistage heat treatment of rubber waste, especially scrap tires
ES2362781B2 (en) * 2009-12-30 2012-09-28 Pirorec, S.L PROCEDURE AND INSTALLATION FOR INTEGRATED RECYCLING BY DEPOLIMERIZATION.
US8057641B2 (en) 2010-07-19 2011-11-15 Kior Inc. Method and apparatus for pyrolysis of a biomass
US8772556B2 (en) 2010-09-22 2014-07-08 Kior, Inc. Bio-oil production with optimal byproduct processing
US9017428B2 (en) 2010-11-16 2015-04-28 Kior, Inc. Two-stage reactor and process for conversion of solid biomass material
US8507644B2 (en) 2011-03-29 2013-08-13 Chem Engineering Energy Method of making a metal terephthalate polymer
SG195053A1 (en) * 2011-05-20 2013-12-30 Raghavendra Rao Turlapati Catalysts for production of combustible fuel and fixed carbons from homogeneous and heterogeneous waste
CN102504857B (en) * 2011-11-07 2013-11-06 李昊民 Intermittent type waste rubber cracking device
RU2014131227A (en) 2012-01-06 2016-02-20 Киор, Инк. TWO-STAGE REACTOR AND METHOD FOR CONVERSION OF SOLID BIOMASS
CA2870183A1 (en) * 2012-04-10 2013-10-17 Earl R. Beaver Device and process for the recovery of increased volumes of pure terpenes and terpenoids from scrap polymers and elastomers
US9453130B2 (en) 2012-05-17 2016-09-27 Wing-Yam Wong Pyrolytic oil for the manufacturing of carbon black
US9365777B2 (en) * 2012-06-13 2016-06-14 Red Leaf Resources, Inc. Methods of operation for reduced residual hydrocarbon accumulation in oil shale processing
US8801904B2 (en) 2012-07-03 2014-08-12 Aemerge, LLC Chain drag system for treatment of carbaneous waste feedstock and method for the use thereof
CN103047645B (en) * 2012-12-25 2017-02-08 管理 Mg catalysis water-based combustion-supporting coal, gas and oil low-carbon sulfur nitrate discharge frying-pan kiln
US9920262B1 (en) 2016-11-22 2018-03-20 Rj Lee Group, Inc. Methods of separation of pyrolysis oils
CN107267206B (en) * 2017-08-08 2019-05-24 台州市绿保物资回收有限公司 A kind of hydrogenation modification method of waste tire cracking vapour bavin wax oil mixed fraction
CN107267205B (en) * 2017-08-08 2019-11-05 浙江绿保再生资源科技有限公司 A kind of tire pyrolysis oil distillate fixed bed hydrogenation modification Catalytic processes
US10767115B2 (en) 2017-09-27 2020-09-08 Rj Lee Group, Inc. Methods and apparatus for clarification of pyrolysis oils
US10596487B2 (en) 2017-09-27 2020-03-24 Rj Lee Group, Inc. Methods and apparatus for clarification of pyrolysis oils
AU2018375218A1 (en) 2017-12-01 2020-07-02 Ergon, Inc. Method for modifying asphalt using oil having reduced polycyclic aromatic hydrocarbon (PAH) content obtained from the pyrolysis of waste tires
US10577540B2 (en) 2018-06-06 2020-03-03 Rj Lee Group, Inc. Method and apparatus for steam separation of pyrolysis oils
RU2712616C1 (en) * 2019-01-09 2020-01-29 Федеральное государственное казённое военное образовательное учреждение высшего образования "Военная академия радиационной, химической и биологической защиты имени Маршала Советского Союза С.К. Тимошенко" Министерства обороны Российской Федерации Recycling of released personal protective means by the method of oxygen free thermal pyrolysis
WO2021204818A1 (en) 2020-04-07 2021-10-14 Total Research & Technology Feluy Waste plastic based oil upgrading into high value chemicals via direct catalytic cracking
CN114317010B (en) * 2022-01-10 2023-04-14 安徽科技学院 Biochar preparation carbonization furnace capable of carrying out agricultural waste resource classification
WO2023208892A1 (en) 2022-04-29 2023-11-02 Orion Engineered Carbons Gmbh Gas black derived from rubber-derived pyrolysis oil
WO2023208654A1 (en) 2022-04-29 2023-11-02 Orion Engineered Carbons Gmbh Carbon blacks based on renewable carbon black feedstocks

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1680908A (en) 1925-12-24 1928-08-14 Nishida Hirotaro Method of preparing artificial petroleum from rubber scrap or vulcanized-rubber waste
JPS5222671B2 (en) * 1973-07-30 1977-06-18
US4038152A (en) * 1975-04-11 1977-07-26 Wallace-Atkins Oil Corporation Process and apparatus for the destructive distillation of waste material
US4250158A (en) * 1978-02-15 1981-02-10 Intenco, Inc. Process for recovering carbon black and hydrocarbons from used tires
US4300009A (en) 1978-12-28 1981-11-10 Mobil Oil Corporation Conversion of biological material to liquid fuels
US4308103A (en) * 1980-06-02 1981-12-29 Energy Recovery Research Group, Inc. Apparatus for the pyrolysis of comminuted solid carbonizable materials
DE3042964A1 (en) 1980-11-14 1982-07-01 Ernst Prof. Dr. 7400 Tübingen Bayer METHOD FOR ELIMINATING HETEROATOMES FROM BIOLOGICAL MATERIAL AND ORGANIC SEDIMENTS FOR CONVERTING TO SOLID AND LIQUID FUELS
US4432890A (en) * 1981-03-30 1984-02-21 Ashland Oil, Inc. Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion
US5209169A (en) * 1982-03-29 1993-05-11 Basic J N Sen Incinerator improvements
JPS5851114A (en) * 1981-09-21 1983-03-25 Polymer Processing Res Inst Method of scoring thermoplastic film
US4463203A (en) 1981-11-13 1984-07-31 Gi Kim D Process for the preparation of fuel oil, fuel gas and pyrolysis coke by pyrolysis
US4740270A (en) 1986-06-19 1988-04-26 Universite Laval Vacuum pyrolysis of scrap tires
US5087375A (en) * 1987-10-21 1992-02-11 Aggio Recovery Method for producing insoluble industrial raw material from waste
US4759300A (en) * 1987-10-22 1988-07-26 Balboa Pacific Corporation Method and apparatus for the pyrolysis of waste products
US4977839A (en) * 1988-01-14 1990-12-18 Chemical Waste Management, Inc. Process and apparatus for separating organic contaminants from contaminated inert materials
US4948495A (en) 1988-07-26 1990-08-14 The United States Of America As Represented By The United States Department Of Energy High liquid yield process for retorting various organic materials including oil shale
JPH073093Y2 (en) * 1989-06-15 1995-01-30 日本ピラー工業株式会社 Floating ring for shaft sealing equipment
GB2237815B (en) 1989-11-06 1994-01-05 Univ Singapore Production of synthetic crude petroleum
JP3204664B2 (en) * 1990-09-17 2001-09-04 オリンパス光学工業株式会社 Motor drive control device
US5216149A (en) 1991-06-07 1993-06-01 Midwest Research Institute Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products
US5230777A (en) * 1991-12-13 1993-07-27 James Jarrell Apparatus for producing fuel and carbon black from rubber tires
US5411714A (en) 1992-04-06 1995-05-02 Wu; Arthur C. Thermal conversion pyrolysis reactor system
US5369215A (en) * 1992-04-06 1994-11-29 S-P Reclamation, Inc. Depolymerization method for resource recovery from polymeric wastes
US5354930A (en) 1992-06-29 1994-10-11 Bp Chemicals Limited Process for converting polymers by contacting same with particulate material suspended in a toroidal shape
JPH06228568A (en) * 1993-01-29 1994-08-16 Mazda Motor Corp Method and equipment for obtaining hydrocarbon oil from waste plastic or rubber material
DE4327633A1 (en) 1993-08-17 1995-02-23 Siemens Ag Transport device for waste
US5894012A (en) 1993-08-19 1999-04-13 Gilbert W. Denison Method and system for recovering marketable end products from waste rubber
US5389691A (en) * 1993-09-07 1995-02-14 Univ. Of Wyoming Process for co-recycling tires and oils
JP3265411B2 (en) * 1993-10-12 2002-03-11 エムエヌエンジニアリング株式会社 How to oil waste plastic
US5437237A (en) * 1994-03-24 1995-08-01 Digre; John L. Continuous pyrolysis system
US5589599A (en) * 1994-06-07 1996-12-31 Mcmullen; Frederick G. Pyrolytic conversion of organic feedstock and waste
US5555823A (en) * 1994-09-02 1996-09-17 Davenport; Ricky W. Method and apparatus for feeding waste material to a dry kiln
US5653183A (en) * 1994-09-22 1997-08-05 Balboa Pacific Corporation Pyrolytic waste treatment system
US5783046A (en) 1994-11-28 1998-07-21 Gentech, Inc. Process and apparatus for the destructive distillation of rubber
JPH08159430A (en) * 1994-12-02 1996-06-21 Kobe Steel Ltd Method of combustion treatment for rubber waste
US5618407A (en) * 1995-07-18 1997-04-08 Phillips Petroleum Company Catalytic cracking process utilizing a catalyst comprising aluminum borate and zirconium borate
CN1145395A (en) 1995-08-08 1997-03-19 周鼎力 Method and appts. for prodn. gasoline, diesel oil and carbon black by utilizing wasted rubber
US5662052A (en) 1995-11-13 1997-09-02 United States Department Of Energy Method and system including a double rotary kiln pyrolysis or gasification of waste material
US5900224A (en) 1996-04-23 1999-05-04 Ebara Corporation Method for treating wastes by gasification
US5720232A (en) 1996-07-10 1998-02-24 Meador; William R. Method and apparatus for recovering constituents from discarded tires
US5720230A (en) * 1996-08-19 1998-02-24 Mansfield; Shane Sliding pull-out shelf
US5820736A (en) 1996-12-23 1998-10-13 Bouziane; Richard Pyrolysing apparatus
KR100253723B1 (en) * 1997-07-03 2000-04-15 지종기 High temperature dc-plasma torch of enhanced electrode persistence by fomring vacuum
EP0908673B1 (en) * 1997-10-13 2002-05-15 Alstom Method for processing residues and/or ash from thermal treatment of refuse
US6210562B1 (en) * 1997-10-15 2001-04-03 China Petrochemical Corporation Process for production of ethylene and propylene by catalytic pyrolysis of heavy hydrocarbons
US6226889B1 (en) * 1998-03-19 2001-05-08 Sepradyne Corporation Continuous rotary vacuum retort apparatus and method of use
US5993751A (en) * 1998-06-02 1999-11-30 Moriarty; Jack Pyrolizer
US6221329B1 (en) 1999-03-09 2001-04-24 Svedala Industries, Inc. Pyrolysis process for reclaiming desirable materials from vehicle tires
US6170411B1 (en) 1999-11-01 2001-01-09 Byung Kyu An Waste tire incinerating and post-treating system
WO2001044405A1 (en) * 1999-12-14 2001-06-21 Tirenergy Corporation Processes for pyrolyzing tire shreds and tire pyrolysis systems
JP5057627B2 (en) * 2000-08-10 2012-10-24 デルタ エナジー ホールディングス エルエルシー Low energy pyrolysis method for hydrocarbon materials such as rubber
US6835861B2 (en) * 2000-08-10 2004-12-28 Rj Lee Group, Inc. Low energy method of pyrolysis of hydrocarbon materials such as rubber
US6619214B2 (en) * 2001-06-20 2003-09-16 Karen Meyer Bertram Method and apparatus for treatment of waste

Similar Documents

Publication Publication Date Title
AU2001281198B2 (en) Low energy method of pyrolysis of hydrocarbon materials such as rubber
US6835861B2 (en) Low energy method of pyrolysis of hydrocarbon materials such as rubber
AU2001281198A1 (en) Low energy method of pyrolysis of hydrocarbon materials such as rubber
Martínez et al. Waste tyre pyrolysis–A review
Osayi et al. Biocrude production through pyrolysis of used tyres
EP0588814B1 (en) Treatment of automobile shredder residue by vacuum pyrolysis
US5095040A (en) Process for conveying old rubber tires into oil and a useful residue
US4588477A (en) Traveling fluidized bed distillation of scrap tires and rubber vulcanizate
US20120289753A1 (en) Method and installation for complete recycling through depolymerisation
US7188571B2 (en) Method and apparatus for the processing of carbon-containing polymeric materials
US20060004236A1 (en) Method of separating and converting hydrocarbon composites and polymer materials
JP2019504156A (en) Method for producing wax and liquid fuel from waste plastic
WO2006123970A2 (en) Method for recycling rubber- or rubber and polymer mixture-containing wastes and a plant for carrying out said method (variants)
US20220098045A1 (en) Pyrolysis method and reactor for recovering silica from polymer waste material
JP2024502067A (en) Carbon black manufacturing method
Williams Pyrolysis; an environmentally attractive recycling route for used tyres
AU2002339240A1 (en) Method and apparatus for the processing of carbon-containing polymeric materials
Udayanga et al. Turning tire green: examine waste tire pyrolysis as a green solution.
Kaminsky Pyrolysis of Mixed Plastics
US20060247127A1 (en) Process for converting a carbonaceous source into an adsorption material
WO2002072731A1 (en) An apparatus and process for recovery of oil from used tyres or wastes of elastomeric products
Nkosi et al. A review of waste tyre pyrolysis: a discussion and analysis