WO2003042289A1

WO2003042289A1 - Method and apparatus for the processing of carbon-containing polymeric materials

Info

Publication number: WO2003042289A1
Application number: PCT/AU2002/001543
Authority: WO
Inventors: Sergio Nusimovich
Original assignee: Tox Free Solutions Limited
Priority date: 2001-11-12
Filing date: 2002-11-12
Publication date: 2003-05-22
Also published as: US7188571B2; AUPR882601A0; US20040261672A1

Abstract

A method for the processing of carbon-containing polymeric material, the method comprising the steps of: Introducing the carbon-containing polymeric material into the retort of a retort assembly which includes a retort disposed at least partially within the combustion chamber, the retort containing an inert heat-transfer medium and an agitation means, wherein the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material, the combustion chamber having heating means to indirectly heat the rotatable retort; Heating the carbon-containing polymeric material and the inert heat transfer medium to cause such to at least partially decompose; Discharging processed carbon-containing polymeric material from the retort.

Description

"Method and Apparatus for the Processing of Carbon-Containing Polymeric

Materials"

Field of the Invention

The present invention relates to a method for the processing of carbon-containing materials and an apparatus when used for the processing of carbon-containing materials. More specifically, the method and apparatus of the present invention relate to the processing of carbon-containing polymeric materials, including tyres, plastics, and paper.

Background Art

Waste products comprising carbon-containing polymeric materials constitute one of the most significant environmental problems facing the world today. Polymeric materials make up a significant fraction of municipal solid waste, reaching up to 50 % of the total volume, as estimated by the U.S. Environmental Protection Agency. Recycling technologies, faced with difficulties such as having to segregate different types of plastics, poor economics and low quality final products, have failed to address the problem. The non-biodegradability of such polymeric waste material presents further problems.

Present methods and/or apparatus for the processing of carbon-containing polymeric materials have been directed to the processing of specific carbon- containing polymeric wastes. It is one object of the present invention to provide a method and apparatus for the processing of carbon-containing waste materials that is capable of processing a wide range of carbon-containing polymeric waste materials, including mixed products, such as different types of plastics.

The preceding discussion of the background to the invention is intended to facilitate an understanding of the present invention. However, it should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was part of the common general knowledge in Australia as at the priority date of the application. Throughout the specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

Disclosure of the Invention

In accordance with the present invention, there is provided an apparatus, when used for the processing of a carbon-containing polymeric material, the apparatus comprising a retort assembly which includes a retort disposed at least partially within a combustion chamber, the retort containing an inert heat-transfer medium, and an agitation means and the combustion chamber having heating means to indirectly heat the retort, wherein the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material.

Similar apparatus have been described for the separation of volatile materials from soils and the like. In such applications, the aim is to separate the volatile material from the medium with a minimum of chemical degradation of the volatile material. However, a primary aim of the treatment of carbon-containing polymeric materials involves chemical degradation of the polymeric materials by processes such as pyrolysis. It has been found that the enhanced heat transfer properties of the retort and the ability to control residence times afforded by the agitation means, are advantageous in applications requiring the breakdown of polymeric materials.

The application of apparatus for the processing of carbon-containing materials similar in design and operation to those described for the separation of volatile materials offers tremendous potential as it allows the user considerable flexibility. The dual application of the equipment of the present invention is counter-intuitive to its existing applications. Whilst the thermal desorption is a separation process that attempts to minimise breakdown of the products fed into the unit, pyrolysis is a physicochemical process that aims to synthesise new compounds by producing the breakdown, combination, and molecular rearrangement of the initial products. Commercial interest in the pyrolysis process is hence increased when pyrolysis is maximised and separation of the unreacted initial products is minimised. Moreover, the process offers a higher commercial potential when pyrolysis is carried out under controlled conditions, where the operator can control a set of variables that would allow him to selectively synthetise certain fractions.

Preferably, the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material to create a fluidised bed, or fluidised bed-like effect.

Preferably, the agitation means is controllable, whereby the residence time of the solid material in the retort may be controlled.

In one form of the invention, a longitudinal axis of the retort is inclined to the horizontal, and is bottom fed. Preferably, the longitudinal axis of the retort is substantially vertical and the retort is bottom fed. Preferably, where the retort is substantially vertical and the retort is bottom fed, the agitation means is further adapted to facilitate the transport of the polymeric material and the inert heat- transfer medium through the retort. In one form of the invention, the agitation means is provided in the form of an auger.

Preferably still, the retort is adapted to allow the exclusion of air or oxygen.

The apparatus and process object of the present invention offer the means to control key variables that affect the final composition and characteristics of the fractions obtained by pyrolysis, whilst allowing for the processing of a wide range of products. This is a distinctive difference with other pyrolysis processes that do not allow for the control of variables such as residence time.

The application of such technologies known for the treatment of contaminated soils to the processing of carbon-containing polymers is also hindered by a number of factors, due to their design and operation. Directly fired thermal desorbers are designed to process soil with volatile compounds. These apparatus produce the combustion of the polymers or hydrocarbons contained in the soil. Indirectly fired thermal desorbers, if operating in the presence of oxygen or air, do cause the degradation of compounds by oxidation or partial combustion, which also compromises their capabilities as controlled-pyrolysis apparatus. More important, all of these machines are designed to remove volatile or semi-volatile compounds from solids or sludge. Their use as pyrolysis reactors is impeded by their design and operation, mainly their heat transfer processes, fluid mechanics, the absence of a solid inert heat transfer medium inside the unit, and residence time, and more specifically, their inability to process pure polymers.

In one form of the invention, the retort comprises a substantially cylindrical body.

In one form of the invention, the substantially cylindrical body is mounted for rotation about its longitudinal axis.

The agitated retort allows for the control of the residence time, the retaining of the heat transfer medium, an intimate contact with said heat transfer medium, and the possibility to add other chemicals such as cracking catalysts to enhance the process.

Preferably still, the retort is substantially surrounded by the combustion chamber to enable direct heating of the retort.

Preferably, the apparatus further comprises a high temperature filter through which the gaseous stream may pass after leaving the retort and prior to entering the afterburner.

In one form of the invention, the heat transfer medium is provided in the form of sodium silicate, or sand.

In another form of the invention, the heat transfer medium is provided in the form of alumina.

In one form of the invention, the retort contains one or more catalyst to improve the ratio of some of the fractions of the final products over the total of products obtained from the pyrolysis. These catalysts are of the type used in petroleum refining operations, in the cracking of hydrocarbons, obvious to those skilled in the art.

In a further form of the invention, the apparatus additionally comprises an afterburner, means to transfer a gaseous stream from the retort to the afterburner for combustion and means for passing the combustion gases from the afterburner to the retort assembly to provide heat for heating carbon-containing polymeric material in the retort.

In one form of the invention, the apparatus further comprises one or more condensers wherein each condenser is adapted to condense gaseous products produced by heating the polymeric material.

In one form of the invention, the apparatus further comprises a combustion engine, wherein the engine is adapted to receive and be fuelled by condensed gaseous products produced by heating the polymeric material until it decomposes, pyrolyses or desorbs. In one form of the invention, the engine is a gas turbine adapted to generate electricity from the gases produced from the decomposition of the polymeric materials, without prior condensation.

In accordance with the present invention, there is provided a method for the processing of carbon-containing polymeric material, the method comprising the steps of:

Introducing the carbon-containing polymeric material into the retort of a retort assembly which includes a retort disposed at least partially within the combustion chamber, the retort containing an inert heat-transfer medium and an agitation means, wherein the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material, the combustion chamber having heating means to indirectly heat the rotatable retort; Heating the carbon-containing polymeric material and the inert heat transfer medium to cause such to at least partially decompose;

Discharging processed carbon-containing polymeric material from the retort.

In one form of the invention, a longitudinal axis of the retort is inclined to the horizontal, and is bottom fed. Preferably, the longitudinal axis of the retort is substantially vertical and bottom fed. Preferably, where the retort is substantially vertical and bottom fed, the agitation means is further adapted to facilitate the transport of the polymeric material and the inert heat-transfer medium through the retort. In one form of the invention, the agitation means is provided in the form of an auger.

Preferably, the apparatus further comprises a high temperature filter through which the gaseous stream may pass after leaving the retort and prior to entering the afterburner. In one form of the invention, the heat transfer medium is provided in the form of sodium silicate, or sand.

In another form of the invention, the retort contains one or more catalyst to improve the ratio of some of the fractions of the final products over the total of products obtained from the pyrolysis. These catalysts are of the type used in petroleum refining operations, in the cracking of hydrocarbons, obvious to those skilled in the art.

Preferably, the steps of the method are performed concurrently.

In a preferred form of the invention, the method comprises the further step of:

Controlling the rate of passage of the carbon-containing polymeric material through the retort, such that the carbon-containing polymeric material is retained in the retort for a predetermined residence time.

Preferably, the step of heating the carbon-containing polymeric material to cause such to at least partially decompose is performed in a substantially oxygen-free atmosphere. In a specific form of the. invention, the step of heating the carbon- containing polymeric material to cause such to at least partially decompose is performed in an inert gas atmosphere. In a highly specific form of the invention, the step of heating the carbon-containing polymeric material to cause such to at least partially decompose is performed in an atmosphere substantially comprising nitrogen gas.

In a specific form of the invention, the carbon-containing polymeric material is provided in the form of one or more tyres.

In another form of the invention, the carbon-containing polymeric material is provided in the form of plastics. These plastics can be pure streams of waste polyethylene, polyethylene terphtalate, polypropylene, polystyrene, or PVC, or mixtures thereof. In the case of processing polymers containing halogens, such as PVC, the invention comprises the treatment of the gas stream produced from the pyrolysis to remove hydrogen chloride.

In another form of the invention, other carbon-containing polymers are fed into the unit, such as paper or wood, where the cellulosic fibres are pyrolysed to produce fractions of shorter molecules with properties consistent with those of liquid fuels obtained from biomass.

Where the carbon-containing polymeric material is provided in the form of tyres, the step of heating the carbon-containing polymeric material to cause such to at least partially decompose more specifically comprises the step of heating the tyres to between about 400-800°C. Preferably still, the tyres are heated to between about 450-600°C. In a specific form of the invention, the tyres are heated to 450°C . Where the carbon-containing polymeric material is provided in the form of tyres, the residence time of the tyres in the retort is preferably between about 30 and 240 minutes. Preferably still, the residence time is between about 45 and 180 minutes. In a specific form of the invention, the residence time is approximately 130 minutes.

Preferably, the method of the present invention takes place at atmospheric pressure or near atmospheric pressure. As would be understood by a person skilled in the art, increases in pressure reduce the temperature range.

Where the carbon-containing polymeric material is provided in the form of tyres, the step of introducing the carbon-containing polymeric material into the retort of a retort assembly more specifically comprises introducing the carbon-containing polymeric material into the retort at between approximately 200 kg per hour to 2000 kg per hour.

Preferably, where the carbon-containing polymeric material is provided in the form of tyres, before the step of introducing the carbon-containing polymeric material into the retort, the method of the present invention comprises the preliminary step of shredding the tyres.

Where the carbon-containing polymeric material is provided in the form of plastics, the step of heating the carbon-containing polymeric material to cause such to at least partially decompose more specifically comprises the steps of heating the carbon-containing polymeric material to melt such before heating the carbon- containing polymeric material to pyrolyse such.

Where the carbon-containing polymeric material is provided in the form of plastics, the step of heating the carbon-containing polymeric material to cause such to at least partially decompose more specifically comprises the step of heating the plastic to between about 300 and 1200°C. Preferably still, the plastics are heated to between about 450-1000°C. In a specific form of the invention, the plastics are heated to about 550°C.

Where condensate is desired over gaseous products, lower temperatures in the range of approximately 400-500°C are used. Where gaseous products are desired over condensate, higher temperatures may be used.

Where the carbon-containing polymeric material is provided in the form of plastics, the residence time of the tyres in the retort is preferably between about 30 and 240 minutes. Preferably still, the residence time is between about 45 and 120 minutes. In a specific form of the invention, the residence time is approximately 80 minutes.

Where the carbon-containing polymeric material is provided in the form of a cellulosic material, such as paper or wood, the step of heating the carbon- containing polymeric material to cause such to at least partially decompose more specifically comprises the step of heating the cellulosic material to between about 400 and 800°C. Preferably still, the cellulosic material is heated to between about 450-800°C. In a specific form of the invention, the cellulosic material is heated to about 500°C. Where the carbon-containing polymeric material is provided in the form of cellulosic material, the residence time of the cellulosic material in the retort is preferably between about 30 and 240 minutes. Preferably still, the residence time is between about 45 and 120 minutes. In a specific form of the invention, the residence time is approximately 80 minutes.

The method of the present invention may further comprise the step of:

Reducing the pressure in the retort to enable lower temperatures to be used.

The step of discharging processed carbon-containing polymeric material from the retort may include:

Separating the heat transfer medium from the processed carbon-containing polymeric material

More specifically, the step of separating the heat transfer medium from the processed carbon-containing polymeric material comprises:

Separating the heat transfer medium from the processed carbon-containing polymeric material based on density differences.

In one form of the invention, the carbon-containing polymeric material decomposes into at least a gaseous stream.

Where the carbon-containing polymeric material decomposes into a gaseous stream, the method may comprise the step of:

Filtering the gaseous stream to remove particulate material therefrom.

Where the carbon-containing polymeric material decomposes into a gaseous stream, the method may comprise the step of: Condensing at least a portion of the gaseous stream to produce a condensate.

The step of condensing at least a portion of the gaseous stream, may more specifically comprise:

Fractionating at least a portion the gaseous stream to produce a range of condensate fractions.

Where the method comprises the step of condensing at least a portion of the gaseous stream to produce a condensate, the method may comprise the further step of:

Subjecting the condensate to flash distillation.

Combusting the gaseous stream to provide heat for heating the carbon- containing polymeric material.

Combusting the gaseous stream in a gas turbine to generate heat and electricity.

Combusting the gaseous stream in an afterburner or thermal oxidiser.

In one form of the invention, the carbon-containing polymeric material decomposes into at least a solid product. Where the carbon-containing polymeric material decomposes into a solid product, the method may comprise the step of:

Extracting the solid material from the retort.

The carbon-containing polymeric material may be provided in the form of a solid or a liquid.

Where the carbon-containing polymeric material is provided in the form of a solid, the carbon-containing polymeric material may be passed through a grizzly or sieve, to remove oversized material, prior to being introduced into the retort. In one form of the invention, where carbon-containing polymeric material may be provided in the form of a solid, in addition to or as an alternative to passing such through a grizzly or sieve, the carbon-containing polymeric material may be milled prior to being introduced into the retort.

Where the carbon-containing polymeric material is provided in the form of a solid, the carbon-containing polymeric material may be shredded or milled to reduce particle size and may include a separation stage. During this separation stage, metals or other material may be separated from the carbon-containing polymers.

Where the carbon-containing polymeric material is provided in the form of a liquid, the water content of the carbon-containing polymeric material is preferably minimised prior to introducing such into the retort. This may be achieved by preheating the liquid carbon-containing polymeric material to boil off any water.

In accordance with the present invention there is provided an apparatus, when used for the processing of a carbon-containing polymeric material, the apparatus being substantially as described in Australian patent 712838, the contents of which are hereby incorporated by reference. Brief Description of the Drawings

The present invention will now be described, by way of example only, with reference to seven embodiments thereof and the accompanying drawings, in which:

Figure 1 is a schematic representation of a portion of an apparatus for processing carbon-containing polymeric material;

Figure 2 is a schematic representation of a gas treatment portion of an apparatus for processing carbon-containing polymeric material in accordance with a first embodiment of the invention;

Figure 3 is a schematic representation of a gas treatment portion of an apparatus for processing carbon-containing polymeric material in accordance with a second embodiment of the invention;

Figure 4 is a schematic representation of a gas treatment portion of an apparatus for processing carbon-containing polymeric material in accordance with a third embodiment of the invention;

Figure 5 is a schematic representation of a gas treatment portion of an apparatus for processing carbon-containing polymeric material in accordance with a fourth embodiment of the invention

Figure 6 is a schematic representation of a solids treatment portion of an apparatus for processing carbon-containing polymeric material in accordance with a fifth embodiment of the invention;

Figure 7 is a schematic representation of a solids treatment portion of an apparatus for processing carbon-containing polymeric material in accordance with a sixth embodiment of the invention; Figure 8 is a schematic representation of a portion of an apparatus for processing carbon-containing polymeric material in accordance with a seventh embodiment of the present invention; and

Figure 9 is a schematic representation of two models developed to determine the feasibility of using a fraction of the recovered products as sources of energy.

It is to be understood that the embodiments are described by way of example only, and are not to be construed as in any way limited the scope of the invention as described. Further, it should be understood that the features described in two or more embodiments may be combined to produce an apparatus and/or method for processing carbon-containing polymeric material within the scope of the present invention.

Best Mode(s) for Carrying Out the Invention

In Figure 1 there is schematically shown a portion of an apparatus for processing a carbon-containing polymeric material, comprising a polymer feed assembly 10, and retort assembly 12. The retort assembly 12 in turn comprises a substantially cylindrical body 14 vertically disposed within a combustion chamber 16, the combustion chamber having heating means (not shown) to indirectly heat the cylindrical body 14.

The retort assembly 12 is substantially similar to the retort assemblies described in Australian Patent 712838, the contents of which are hereby incorporated by reference.

The retort assembly 12 further comprises an auger or stirrer 18 to agitate the contents of the retort and drive the product from the feed point to the outlet and provide an adequate residence time. An extraction system 18b such as an auger is adapted to extract solid material from the cylindrical body 14. The cylindrical body 14 contains an inert heat transfer medium in the form of sand. Carbon-containing polymeric material is fed into the cylindrical body 14, which is heated by way of the combustion chamber 16 causing, depending on the conditions applied within the cylindrical body 14, the carbon containing polymeric material to thermally decompose into a gaseous phase 20, and/or a solid phase 22 in varying proportions. The decomposition of the carbon-containing polymer is achieved by both heat and residence time, with the residence time regulated by the movement of the stirrer or auger 18b that carries the carbon-containing polymer and the inert heat transfer medium in a resulting upward path from the inlet fed by the polymer feed assembly 10 to the outlet, thereby forming a fluidised bed-like arrangement. The gas stream 20, produced by the decomposition or desorption of the carbon-containing polymer subjected to indirect heat, is driven off the retort 14 by the effect of the vaporisation and the difference in pressure between the retort 14 and a filtration assembly 24. The solid phase 22 is removed from the cylindrical body 14 by way of the auger 18b, and separated from the heating medium based on differing densities. The gaseous phase 20 is then passed through the filtration assembly 24.

Referring now to Figure 2, in a first embodiment the gaseous phase 20 is then be passed to an afterburner or thermal oxidiser 26, where the gases are subjected to combustion. Gases produced by the afterburner may be subjected to further treatment.

Referring now to Figure 3, in a second embodiment, after passage through the filtration assembly 24, the gaseous stream is condensed, totally or partially, by way of a series of condensers 28 to produce one or more condensates 29. Uncondensed gases may be passed to an afterburner 26 as described in the first embodiment, or directly treated.

Referring now to Figure 4, in a third embodiment, after passage through the filtration assembly 24, the gaseous stream may be fed directly into a gas turbine 30, by which heat 32 and electricity 34 are generated. The electricity 34 is supplied to a power grid or used to supply power to the process. The heat 32 produced by the gas turbine 30 and may be used to heat the cylindrical body 14. At least a portion of the heat may also be used in other processes such as evaporation of water or pre-heating of the carbon-containing polymeric material. Referring now to Figure 5, in a fourth embodiment, the condensate 29 formed in the second embodiment is passed through a flash distillation assembly 36, to further fractionate such.

Referring now to Figure 6, in a fifth embodiment, the solid material 22 is heated in a further retort assembly 40 to produce a carbon product 42, and may be combined with one or more additives 38. The heat may be produced by the gas turbine 30 or an engine. The product 42 has applications in the processing of contaminated water or contaminated gas, in the removal of organic compounds and heavy metals.

Referring now to Figure 7, in a sixth embodiment, the solid material 22 may contain metals. For example, the carbon product 22, produced as a result of processing tyres, may contain zinc. The solid material 22 may then be processed in an agitated vessel 44. A leaching solution may be added to the agitated vessel 44 to extract the metal, producing a metal-rich leachate. The metal-rich leachate may be processed further by addition of other compounds or by crystallisation or evaporation, to produce a product 45. In one such application, product 45 can be sold as a liquid fertilizer. Referring finally to Figure 8 there is schematically shown a portion of an apparatus for processing a carbon-containing polymeric material, comprising a polymer feed assembly 46, a first retort assembly 48 and a second retort assembly 50. Each retort assembly 48 or 50 in turn comprises a substantially cylindrical body 52 vertically disposed within a combustion chamber 54. Each retort assembly 48 or 50 further comprises an auger or stirrer 56, to agitate the contents of the retort and drive the product from the feed ponit to the outlet and provide an adequate residence time. An extraction system 56b, such as an auger is adapted to extract solid material from the cylindrical body 52.

Carbon-containing polymeric material is fed into the cylindrical body 52 of the first retort assembly 48, and heated indirectly within the cylindrical body 52 by way of the combustion chamber 54 thereof. A gaseous stream 57, produced thereby is passed through a filtration assembly 58, with the remaining partially processed carbon-containing polymeric material is then passed to the second retort assembly 50 for further treatment. Remaining solid material 60 is processed as described in the context of Figures 6 and 7.

Having passed through the filtration assembly 58, two options are possible. In a first option, the gas stream 62 is directed to a gas turbine 64. Electricity produced by the gas turbine 64 may be used to power the plant 76 or fed into an electricity grid 78. Heat is also produced by the gas turbine 64. This heat can be used as part of the process to provide heat for the first and second retort assemblies 48 and 50. The second option involves the condensation of the gas stream 66, which is condensed by way of a series of condensers 68 to produce a condensate 70. The condensate is used to fuel a combustion engine 72, coupled to a generator 74. Heat produced by the combustion engine 74 is fed back to the first retort assembly 48, whilst the electricity produced by 74 may be used to power the plant or fed into an electricity grid.

Experimental Trials

Experimental trials were conducted in a unit comprising a vertical retort filled with sand as a heating medium, agitated with a helicoidal mixer. The mixer's speed could be regulated. The product is fed at the bottom of the vessel and is driven upwards in a fluidized bed regime, while it is subjected to heat supplied by two burners that heat the sand from an external combustion chamber. Products that are pyrolysed flow through the heat bed towards the gas treatment system. The pyrolysed solid is extracted from the top part of the vessel by a screw auger, whilst the gas is maintained at high temperature so it does not condense when it passes through the High Temperature Filter (HTF). The HTF removes particles from the gas stream, before this gas passes through a water-cooled condenser that separates condensable fractions. Two configurations were used. In the first one, an After Burner was used to destroy the non-condensed products, whilst in the second configuration a second condenser cooled with a glycol-water solution was used to increase recovery of hydrocarbons. The whole system is PLC-controlled, with temperature, pressure, oxygen content and flows regulated by the system. The plant is described in Figures 1 and 3 discussed above.

The unit had a nominal capacity of two tonnes per hour. Throughput of the unit depends on a number of variables and the physicochemical characteristics of the feed. Moisture content, density, viscosity, calorific capacity, and composition have an effect on heat requirements, processing rates, and end products.

Two variables are important in the process: temperature and residence time. Operating temperature in the retort is the key variable that affects pyrolysis and thermal decomposition, with the quality and composition of the final products being in direct relationship to the operating temperature. Residence time is the other important variable, which affects composition of the final products and feed rates. The degree of cracking and decomposition is directly proportional to residence time. The unit further comprised a feeding hopper and screw conveyor to be able to feed granulated tyres into the retort.

1. Tyres

The trials consisted of the thermal pyrolysis of granulated tyres, with a particle size of 5 mm, screened of metal and fluff. Tests 0014, 0015, and 0016 were carried out using a TDPP configuration (see Figure 1 and 3). Analysis of the granulate tyres is presented in Table I:

Table I - Analysis of granulated tyres

(*) On a dry basis

(1) Test 0014 and 0015

(2) Test 0016, samples 020417-01-S-Feed-1020 and 020417-02-S-Feed-1020

The first set of trials, called for the running of two trials at two feed rates, to test the capabilities of the unit to process the feed material and handle the produced gases. The process conditions are summarized in Table II.

Table II - Process conditions

Nitrogen was used as a blanketing inert gas to inhibit both oxidation and combustion during the process. Condensing of the generated gas was achieved by means of the on-line condenser, with cooling water circulated from the cooling tower.

The second set of trials was designed to prove the limits of the plant in terms of heat transfer and capacity. Sampling of the gas before and after the After Burner was also to be completed by a third party, with the samples analyzed for VOCs, SVOCs, PAHs, Dioxins and Furans, particulates, SOx, and heavy metals. The process conditions are summarized in Table V.

Table V - Process conditions

Table VI - Process variables

*) The feed rate varied from 12 to 20 % (**) This is an estimated average (***) The feed rate varied from 15 to 23 %

Pyrolysis of tyres produces three streams: a hydrocarbon-rich oil, a solid char, and gas. The condensed oil was evaluated as a fuel substitute, or as a raw material for the separation of valuable fractions. The results are summarized in Table VI. Table VI - Analysis of condensed oil

Table VII - Analysis of hydrocarbons in condensed oil by GC/MS

An analysis by GC/MS was also performed for a composite sample of the condensed product C-10. The scan indicated presence of a large number of compounds. Table VIII presents the twenty most abundant compounds. Table VIII - The 20 most abundant compounds identified by GC/MS in sample C- 10, with relative abundance indicated in parenthesis

• Toluene (4.56) • Trimethyl Benzene (1.52)

• p-Xylene (3.64) • 2-Mehtylindene (1.44)

• Ethyl Benzene (3.27) • 1 ,3-bis (3-phenoxyphenoxy) Benzene (1.31)

• 1 -methyl-4-(1 -methylethyl) Benzene • 2-ethenyl Naphtalene (1.09) (2.76)

• 2-methyl Naphtalene (2.44) • 1 -methyl-4-(1 -methylenethen) Benzene (0.95)

• Naphtalene (2.37) • 2,6-dιmethyl Naphtalene (0.97)

• Trimethyl Benzene (2.36) • 1 ,5-dimethyl Naphtalene (0.95)

• o-Xylene (2.22) • Fluorene (0.91)

• (1-methyl-2-cycloprepen-1 ) Benzene • Indane (0.90) (1.75)

• 2-methyl Naphtalene (1.64) • 1 ,3-dimethyl 1H-lndene (0.87)

Analysis of the data indicates that the following families of compounds are present: Benzene and Alkyl Benzenes, Naphtalene and Alkyl Naphtalenes, Fluorenes and Indenes, Anthracenes, Phenantrenes, Pyrenes, Biphenyls, and some Phenols. Some Sulfur compounds have been identified, such as Benzothiazole, and Dibenzothiophene.

Table IX - Estimated Average Composition for Condensed Oil

In Test 0016 liquid samples were collected from two points: Tank 305, receiving the fraction condensed by HX03, and Tank 306, receiving the fraction condensed by HX04 (Figure 1b). These two condensers operated under the following conditions: Table XI - Operating conditions of condensers in Test 0016

A sample of condensate was analyzed before and after separation of water (L305- BP and L305D-BP, respectively), to assess it as a fuel. Two separate samples from Tank 305 and 306, respectively, were analyzed by a second independent laboratory. The analysis results are presented in Table XII.

Table XII - Analysis of condensed oil Test 0016

(1) Sample taken on April 18 2002 from Tank 305, analyzed by BP Refinery (Kwinana) Australia, after water setting and decanting

(2) Analysis of sample L-305-BP before water setting and decanting

(3) Sample taken on April 182002 from Tank 305, at 1 P , analyzed by Geotech Australia (4) Sample taken on April 182002 from Tank 306, at 1 PM, analyzed by Geotech Australia

(5) By method AS 1036.6.3.3

(6) By method IP 190

(7) Based on method ASTM D5452

(8) By method ASTM D5185

Distillation of the lighter fraction was used to increase the flash point of the condensate from Test 0016, in order to conduct corrosion tests. The results are presented in Table XIV.

Table XIV - Flash point and corrosion test before and after distillation, Test 0016

(1 ) Sample taken on April 182002 from Tank 305, at 1 PM, analyzed by Geotech Australia

(2) Sample taken after distillation of 20 % of L-305-1300, analyzed by Geotech Australia

In order to study the composition of the product and characterize the different fractions, the two samples from Tanks 305 and 306 respectively, were analyzed using Methods USEPA 8260, 8270, and 8015B to quantify volatile and semivolatile organic compounds and establish total hydrocarbons and their fractions. These results are presented in Table XV.

Table XV - Analysis of condensed oil Test 0016 (mg/L)

(1) Sample taken on April 182002 from Tank 305, at 1 PM, analyzed by Geotech Australia

(2) Sample taken on April 182002 from Tank 306, at 1 PM, analyzed by Geotech Australia No chlorinated compounds, ethers, and chlorophenols were detected. The composition of the condensed oil is presented in Table XVI:

Table XVI - Average Composition for Condensed Oil from Test 0016

The results from all trials indicate that the majority of the hydrocarbons are aromatic in nature, predominantly alkyl Benzenes. The composition of the condensate in Test 0016 is consistent with Test 0014 and 0015, but has improved considerably. The condensate contains 92 % of hydrocarbons, of which over 92 % are C29 or below. The high calorific value and low metal content are also important features of the product. Compatibility tests indicate that the product is suitable as a fuel oil blending component.

Gas is produced during the process, in the form of hydrogen, methane, and light hydrocarbons. Gas sampling and analysis was undertaken to establish composition of the gas, determine the efficiency of the pollution control devices, and demonstrate the compliance of the plant with stringent environmental standards. The results of the analysis of the gas samples are presented in the table below:

Table XVIII - Emissions to atmosphere as detected in Test 0016 in mg/Nnr

(1) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Method 6C (2) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Method 18 and Method 0030 (3) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Modified Method 5 (4) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Method 23 (5) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Method 5 (6) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Method 7E (7) Sampling method USEPA Method 1 and Method 2, Analysis method USEPA Method 29 Table XIX - Composition of hydrocarbons C1 to C6 before and after the afterburner in mg/Nm³

The gas has high concentrations of hydrocarbons with high calorific values,

The third stream produced from the pyrolysis process is char. Potential uses of the char obtained from the pyrolysis of tyres include its reuse as carbon black, its use as a solid fuel, and applications as adsorbents. The char was analyzed to determine Sulphur and hydrocarbon fractions. The results are presented in Table XXI.

Table XXI - Analysis of hydrocarbons and Sulphur in char samples

The changes in the design of TDPP-III compared to TDPP-II produced a char with only traces of Toluene and Xylene, whilst no other organic compounds were detected. The reduced level of hydrocarbons produced a reduction in the calorific value and a decrease in the ratio of mass of char produced per mass of tire. This supports a model where gas and condensate are maximized in detriment of the mass of char produced, resulting in an improved model for energy production based on use of gas and liquid only. The distribution of compounds between char and oil is shown in Table XXIII. Table XXIII - Analysis of char and oil from Test 0016

(1) Sample taken on April 182002 from out feed bin, at 1 PM, analyzed by Geotech Australia

(2) Sample taken on April 182002 from Tank 305, at 1 PM, analyzed by Geotech Australia

The mass balance has been estimated based on field measurements taken during Test 0014, 0015, and 0016. The gas produced from the pyrolysis of the tyres was destroyed by combustion in the After Burner. A balance of mass and an estimate of the elemental composition of the initial product and the produced char and oil is presented in Table XXVIII.

Table XXVIII - Estimated balance of mass from elemental composition of tyres, char, and condensed oil

Per kg of tyres Sourc e Carbon Hydrogen Oxygen Nitrogen Sulfur Other Total

Tyres % w/w (1) 78.38% 6.48% 3.86% 0.18% 1.84% 9.26% 100.00% kg/kg tyres 1 0.784 0.065 0.039 0.002 0.018 0.093 1.000

Char % w/w (2) 35.54% 0.00% 14.78% 0.00% 0.57% 49.11% 100.00% kg/kg tyres 0.322 0.114 - 0.048 - 0.002 0.158 0.322

Oil % w/w (3) 90.92% 7.58% 0.00% 0.00% 1.34% 1.50% 101.34% kg/kg tyres 0.394 0.358 0.030 0.000 0.000 0.005 0.006 0.399

Gas % w/w (4) 87.06% 9.78% 0.00% 0.00% 3.16% 0.00% 100.00% kg/kg tyres 0.36 0.31 0.03 - - 0.01 - 0.36

Estimated molar ratios Carbon to hydrogen

Tyres 1.0

Oil 1.0

Gas 0.7

(1) Elemental analysis performed by Geotech Australia (2) Elemental analysis performed by Geotech Australia, sulfur analysis by Geotech Australia, and "other" includes adjusted ash content

(3) Estimated from fractions for total petroleum hydrocarbons, as analysed by Geotech Australia. A weighted average molecular weight has been calculated from each hydrocarbon fraction, allowing for double bonds (4) Estimated from balance of mass for carbon, hydrogen, and sulfur

Table XXVIII has been used to estimate the composition of the gas. The model simplifies the composition to Methane, Ethylene, Carbon Monoxide and Dioxide, and Hydrogen Sulfide, as these five gases account to over 96 % of the gases, although other gases are present. The data is presented in Table XXVIIIb.

Table XXVIIIb - Estimated composition of pyrolysis gas

The results of gas analysis confirm that Methane is the most abundant gas, with ethane and ethylene also present in significant quantities. The percentages of the gas mix are presented in Table XXVIIIc, based on results presented in Table XIX.

Table XXVIIIc Composition of hydrocarbons C1 to C6 before the afterburner in mg/Nm³

In order to provide an estimate of calorific value from the gas, an average calorific value was calculated using 50 MJ/kg as a conservative value. The estimates are presented in Table XXIX.

Table XXIX - Energy and generation estimate for pyrolysis gas

2. Plastics

Process conditions for the pyrolysis of plastics are presented in Table XXX.

Table XXX - Process conditions

The process' temperature can be regulated to increase the production of pyrolysis gas. The gas stream can be used directly as fuel for a gas turbine, with solids removed in the HTF. The composition of the gas and oil varies with the fed plastic mix. Likely compositions are as follows:

Table XXXI - Process outputs

Solids extracted from the retort contain carbon, silicates, metal oxides, sulfates, alumina, and other compounds.

3. Grease

Tests were conducted to demonstrate the applicability of the apparatus to the processing of waste hydrocarbon grease, using a configuration that included a water-cooled condenser and the After Burner. Feeding of the grease was achieved using a positive displacement pump. Process conditions are summarized in Table XXXII.

Table XXXII - Process conditions

The trial was run at temperatures of 400-430°C.

Analysis of the condensed oil was performed, with the objective of evaluating the pyrolysis oil as a fuel. The results are summarized in Table XXXIII.

Table XXXIII - Analysis of condensed oil

The sample was subjected to flash distillation producing a final product with a flash point of 71 °C that met specifications as a fuel for combustion engines, similar in properties to marine diesel fuel, based on CIMAC standards.

Modifications and variation such as would be apparent to the skilled addressee are considered to fall within the scope of the present invention.

Claims

The Claims Defining the Invention are as Follows

1. An apparatus, when used for the processing of a carbon-containing polymeric material, the apparatus comprising a retort assembly which includes a retort disposed at least partially within a combustion chamber, the retort containing an inert heat-transfer medium, and an agitation means and the combustion chamber having heating means to indirectly heat the retort, wherein the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material.

2. An apparatus as claimed in claim 1 characterised in that the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material to create a fluidised bed, or fluidised bed-like effect.

3. An apparatus as claimed in claim 1 or 2 characterised in that the agitation means is controllable, whereby the residence time of the solid material in the retort may be controlled.

4. An apparatus as claimed in any one of the preceding claims characterised in that a longitudinal axis of the retort is inclined to the horizontal, and the retort is bottom fed.

5. An apparatus as claimed in claim 4 characterised in that a longitudinal axis of the retort is inclined to the horizontal, and the retort is bottom fed.

6. An apparatus as claimed in any one of the preceding claims characterised in that the agitation means is further adapted to facilitate the transport of the polymeric material and the inert heat-transfer medium through the retort.

7. An apparatus as claimed in claim 6 characterised in that the agitation means is provided in the form of an auger.

8. An apparatus as claimed in any one of the preceding claims characterised in that the retort is adapted to allow the exclusion of air or oxygen.

9. An apparatus as claimed in any one of the preceding claims characterised in that the retort comprises a substantially cylindrical body.

10. An apparatus as claimed in claim 9 characterised in that the substantially cylindrical body is mounted for rotation about its longitudinal axis.

11. An apparatus as claimed in any one of the preceding claims characterised in that the retort is substantially surrounded by the combustion chamber to enable direct heating of the retort.

12. An apparatus as claimed in any one of the preceding claims characterised in that the apparatus further comprises a high temperature filter through which the gaseous stream may pass after leaving the retort and prior to entering an afterburner.

13. An apparatus as claimed in any one of the preceding claims characterised in that the heat transfer medium is provided in the form of sodium silicate, or sand.

14. An apparatus as claimed in any one of the preceding claims characterised in that the heat transfer medium is provided in the form of alumina.

15. An apparatus as claimed in any one of the preceding claims characterised in that the retort contains one or more catalysts.

16. An apparatus as claimed in any one of the preceding claims characterised in that the apparatus additionally comprises an afterburner, means to transfer a gaseous stream from the retort to the afterburner for combustion and means for passing the combustion gases from the afterburner to the retort assembly to provide heat for heating carbon-containing polymeric material in the retort.

17. An apparatus as claimed in any one of the preceding claims characterised in that the apparatus further comprises one or more condensers wherein each condenser is adapted to condense gaseous products produced by heating the polymeric material.

18. An apparatus as claimed in any one of the preceding claims characterised in that the apparatus further comprises a combustion engine, wherein the engine is adapted to receive and be fuelled by condensed gaseous products produced by heating the polymeric material until it decomposes, pyrolyses or desorbs.

19. An apparatus as claimed in claim 18 characterised in that the engine is a gas turbine adapted to generate electricity from the gases produced from the decomposition of the polymeric materials, without prior condensation.

20. A method for the processing of carbon-containing polymeric material, the method comprising the steps of:

Introducing the carbon-containing polymeric material into the retort of a retort assembly which includes a retort disposed at least partially within the combustion chamber, the retort containing an inert heat-transfer medium and an agitation means, wherein the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material, the combustion chamber having heating means to indirectly heat the rotatable retort;

Heating the carbon-containing polymeric material and the inert heat transfer medium to cause such to at least partially decompose;

Discharging processed carbon-containing polymeric material from the retort.

21. A method according to claim 20 characterised in that the agitation means is adapted to agitate the inert heat transfer medium and the carbon containing polymeric material to create a fluidised bed, or fluidised bed-like effect, and the method includes the step of agitating the inert heat transfer medium and the carbon containing polymeric material to produce a fluidised bed or fluidised bed effect.

22. A method according to claim 20 or 21 characterised in that the agitation means is controllable, whereby the residence time of the solid material in the retort may be controlled.

23. A method according to any one of claims 20 to 22 characterised in that the steps of the method are performed concurrently.

24. A method according to any one of claims 20 to 23 characterised in that the method comprises the further step of:

25. A method as claimed in any one of claims 20 to 24 characterised in that the step of heating the carbon-containing polymeric material to cause such to at least partially decompose is performed in a substantially oxygen-free atmosphere.

26. A method according to claim 25 characterised in that the step of heating the carbon-containing polymeric material to cause such to at least partially decompose is performed in an inert gas atmosphere.

27. A method according to claim 26 characterised in that the step of heating the carbon-containing polymeric material to cause such to at least partially decompose is performed in an atmosphere substantially comprising nitrogen gas.

28. A method according to any one of claims 20 to 28 characterised in that the carbon-containing polymeric material is provided in the form of one or more tyres.

29. A method according to claim 28 characterised in that the step of heating the carbon-containing polymeric material to cause such to at least partially decompose more specifically comprises the step of heating the tyres to between about 400-800°C.

30. A method according to claim 29 characterised in that the tyres are heated to between about 450-600°C.

31. A method according to claim 30 characterised in that the tyres are heated to 450°C .

32. A method according to any one of claims 28 to 31 characterised in that the residence time of the tyres in the retort is preferably between about 30 and

240 minutes.

33. A method according to claim 32 characterised in that the residence time is between about 45 and 180 minutes.

34. A method according to claim 33 characterised in that the residence time is approximately 130 minutes.

35. A method according to any one of claims 28 to 34 characterised in that, before the step of introducing the tyres into the retort, the method of the present invention comprises the preliminary step of shredding the tyres.

36. A method according to any one of claims 20 to 27 characterised in that the carbon-containing polymeric material is provided in the form of one or more plastics.

37. A method according to claim 36 characterised in that the plastics include one or more halogen containing polymers, and the method comprises the step of treating a gas stream produced from the pyrolysis to remove hydrogen chloride.

38. A method according to claim 36 or 37 characterised in that the step of heating the plastics material to cause such to at least partially decompose more specifically comprises the steps of heating the carbon-containing polymeric material to melt such before heating the carbon-containing polymeric material to pyrolyse such.

39. A method according to any one of claims 36 to 38 characterised in that the plastics are heated to between about 300 and 1200°C.

40. A method according to claim 39 characterised in that the plastics are heated to between about 450-1000°C.

41. A method according to claim 40 characterised in that the plastics are heated to about 550°C.

42. A method according to any one of claims 36 to 41 characterised in that the residence time of the plastics in the retort is between about 30 and 240 minutes.

43. A method according to claim 42 characterised in that the residence time is between about 45 and 120 minutes.

44. A method according to claim 43 characterised in that the residence time is approximately 80 minutes.

45. A method according to any one of claims 20 to 27 characterised in that the carbon containing polymeric material is provided in the form of a cellulosic material, the cellulosic fibres thereof being pyrolysed to produce fractions of shorter molecules with properties consistent with those of liquid fuels obtained from biomass.

46. A method according to claim 45 characterised in that the step of heating the cellulosic material to cause such to at least partially decompose more specifically comprises the step of heating the cellulosic material to between about 400 and 800°C.

47. A method according to claim 46 characterised in that the cellulosic material is heated to between about 450 and 800°C.

48. A method according to claim 47 characterised in that the cellulosic material is heated to about 500°C.

49. A method according to any one of claims 45 to 48 characterised in that the residence time of the cellulosic material in the retort is preferably between about 30 and 240 minutes.

50. A method according to claim 49 characterised in that the residence time is between about 45 and 120 minutes.

51. A method according to claim 50 characterised in that the residence time is approximately 80 minutes.

52. A method according to any one of claims 20 to 51 characterised in that the method further comprises the step of:

Reducing the pressure in the retort to enable lower temperatures to be used.

53. A method according to any one of claims 20 to 52 characterised in that The step of discharging processed carbon-containing polymeric material from the retort includes

Separating the heat transfer medium from the processed carbon-containing polymeric material.

54. A method according to claim 53 characterised in that the step of separating the heat transfer medium from the processed carbon-containing polymeric material more specifically comprises: Separating the heat transfer medium from the processed carbon-containing polymeric material based on density differences.

55. A method according to any one of claims 20 to 54 characterised in that, where the carbon-containing polymeric material decomposes into a gaseous stream, the method comprises the step of:

Filtering the gaseous stream to remove particulate material therefrom.

56. A method according to any one of claims 20 to 55 characterised in that, where the carbon-containing polymeric material decomposes into a gaseous stream, the method comprises the step of:

Condensing at least a portion of the gaseous stream to produce a condensate.

57. A method according to claim 56 characterised in that the step of condensing at least a portion of the gaseous stream more specifically comprises:

58. A method according to claim 57 characterised in that the method comprises the further step of:

Subjecting the condensate to flash distillation.

59. A method according to any one of claims 55 to 58 characterised in that the method comprises the further step of:

60. A method according to any one of claims 55 to 58 characterised in that the method comprises the further step of:

61. A method according to any one of claims 55 to 58 characterised in that the method comprises the further step of:

Combusting the gaseous stream in an afterburner or thermal oxidiser.

62. A method according to any one of claims 20 to 61 characterised in that, where the carbon-containing polymeric material is provided in the form of a solid, the carbon-containing polymeric material may be passed through a grizzly or sieve, to remove oversized material, prior to being introduced into the retort.

63. A method according to any one of claims 20 to 62 characterised in that, where the carbon-containing polymeric material is provided in the form of a solid, the carbon-containing polymeric material may be shredded or milled to reduce particle size and may include a separation stage, during which metals or other material may be separated from the carbon-containing polymers.

64. A method according to any one of claims 20 to 63 characterised in that, where the carbon-containing polymeric material is provided in the form of a liquid, the water content of the carbon-containing polymeric material is minimised prior to introducing such into the retort, optionally by preheating the liquid carbon- containing polymeric material to boil off any water.

65. An apparatus, when used for the processing of a carbon-containing polymeric material, the apparatus being substantially as described in Australian patent 712838, the contents of which are hereby incorporated by reference.

66. An apparatus substantially as described herein with reference to Figures 1 and 2, 1 and 3, 1 and 4, 1 and 5, 1 and 6, 1 and 7, or 8.