LARGE-SCALE RECYCLING PROCESS FOR SCRAP TIRES AND RUBBER PRODUCTS R. E. Allred, N. C. Coons, D. J. Finley, and J. M.

Shoemaker Adherent Technologies, Inc. Albuquerque, NM 87123 www.adherent-tech.com and R. L. Wilder and J. D. Wilder Titan Technologies, Inc. Albuquerque, NM 87109 www.titantechnologiesinc.com ABSTRACT
A continuous tertiary recycling process has been developed for use on scrap tires and rubberbased materials. A standard size plant processes 100 tons per day of scrap tires into gaseous and liquid hydrocarbons, steel, and carbon black. The hydrocarbons are high-quality fuels, the steel is readiy resmelted, and the carbon black can be reused to reinforce rubbers and plastics. Additional uses for the carbon black are found in applications such as filters, inks, toners, and paints. By obtaining value from all the components in the scrap tires, the process is highly profitable and produces an attractive rate of return on investment while solving the waste tire disposal problem. KEY WORDS: Recycling, Scrap Tires, Rubber, Tertiary Recycling

1. INTRODUCTION
Scrap rubber tires have been accumulating for decades and are becoming an increasing problem throughout the US and the world. In the United States alone, where tire consumption is higher than in any other country, an estimated 250 million scrap tires are being generated annually with no indication of the wastestream slowing. This amounts to more than 1.5% of the municipal solid wastestream or roughly one scrap tire for each person in this country [1]. In addition, there are some three billion tires stockpiled in US landfills, collection sites, and illegal dumps that pose environmental problems and potential health and fire hazards.

In September of 1999, lightning ignited a pile of 5 million scrap tires near Westley, CA, and costs incurred in fighting and extinguishing the fire and for subsequent clean-up of the site are estimated at over $20 million [2]. In Stockport, England, at a plant that manufactures ground recycled rubber for use in manufacturing safety surfaces, several bags of ground rubber ignited during a shrink-wrap process. The blaze burned out of control and generated large amounts of black smoke killing one man and injuring others. Just recently, a blaze broke out at a storage facility in Holtsville, NY, where over 160,000 illegally stockpiled scrap tires ignited. It took nearly 24 hours and over 200 firefighters to put out the blaze [3]. These are only a few of several examples of the dangers of scrap tire stockpiles. Although local, state, and federal governments are desperately trying to battle the problem, current recycling methods for scrap rubber are not adequate for handling the volumes of scrap tires that are generated each year let alone the stockpiles that litter the world. Current options for the scrap tire wastestream include storing the scrap in piles at a specified location like the one pictured in Figure 1, sending the tires to landfills, retread, grinding into crumb rubber for constructional and engineering uses, and burning the tires for fuel (also referred to as tire-derived fuel or TDF) [4,5].

Figure 1. Tires are piling up worldwide In fact, the most practiced tire recycling methods are tire shredding to recover the steel cords and crumbing of the scrap rubber for use in asphalt and civil engineering projects. However, Civil engineering projects do not consume sufficient quantities of crumb rubber to significantly impact scrap tire stockpiles. Several companies and research and development firms are searching for new, innovative ways to use crumb rubber. Nonetheless, one of the major issues behind tire recycling and recycling in general is the economics of the process and the value of the products being produced [6]. Although it is technically feasible to manufacture and produce many of these new rubber products from recycled crumb rubber, several of these new products and processes have poor economic viability and have very small and limited markets.

The limited recycling of scrap tires dictates that new approaches are developed to reduce this wastestream and to reclaim value from this resource. Tertiary recycling (conversion of scrap rubber tires into hydrocarbons for reuse as oils and fuels), and recovery of steel and carbon black, is the most desirable means for economically reclaiming scrap tires.

2. TERTIARY RECYCLING PROCESS OVERVIEW

Research and development of the tertiary recycling process has been conducted jointly by Adherent Technologies, Inc. and Titan Technologies, Inc. (Albuquerque, NM) for a decade. The process has proven to be highly successful in recycling scrap tires. Three 100-ton per day commercial recycling plants using the technology have been conducting profitable operations in the Pacific Rim since construction in 1994. The appearance of the plant built in Taiwan in 1998 is shown in Figure 2.

Figure 2. 100-ton per day Titan tertiary tire recycling plant in Taiwan The term tertiary recycling has been adopted from the American Plastics Council; by definition, it is the processing of plastics back to valuable chemicals or fuels for reuse [7]. When applied to complex mixtures such as scrap tires, the tertiary recycling process converts polymeric waste into reusable hydrocarbon fractions for reincarnation as polymers, monomers, fuels, or chemicals, automatically separating the steel, fiberglass, and carbon black with little manpower. 2.1 Description of System A block flow diagram for the tertiary recycling process is given in Figure 3. The system is a fully automated process for the conversion of scrap tire chips into the saleable commodities of

scrap steel, carbon black, and refined oil. This process is accomplished in a reactor unit using a process-specific catalyst and temperature to break down the polymeric network structure of the scrap rubber tire chips.

Figure 3. Schematic of tertiary tire recycling process The scrap tires are shredded into approximately 2 x 2 in. chips and continuously weighed and delivered to the inlet hopper of the oil-sealed screw conveyor. Materials transport through the process reactor is accomplished using 40-ft long horizontal stainless steel screw conveyors to agitate the material along while transporting it through the six stages of the heated zone. The conveyors have top inlets and discharge chutes at each end. Individual hydraulic drives and a central hydraulic pumping system power the reactor s horizontal screw conveyors. The inlet and outlet connections to the screw conveyors of the reactor have liquid oil seals. In addition, the outlet connection to the carbon black screw conveyor for the carbon black product has a dry carbon seal to prevent oxygen from entering the process. As the material passes through the heated zone, organics are cracked and gasified and drawn off the reactor into an offgas system by a turbine pump. Each reactor conveyor has a perforated top in order to vent the gases off the process. A vertical stainless steel plenum welded to each conveyor provides a means to collect these process gases. The gas is then filtered to remove the carbon black carried over from the heated zone. The gases (consisting mostly of vaporized fuel oils) are then pumped through two separate condensing stages, each of which is water cooled. Cooling is provided through an air-cooled process chiller with a circulating pump system. Noncondensable gases are collected and recycled as the fuel medium for the burners, which maintain the temperature in the reactor unit. Excess non-condensable gases are discharged to a flare and burned.

The reactor unit is constructed with a 3/16-in. thick carbon steel liner on 6 x 6 x 0.5-in. tube steel frame. The interior is insulated with 6-in. thermal Ceramics Pyro-Bloc E-Module (or equal) with a 316SS (stainless steel) internal support system for operating ranges up to 1200 F. The exterior is jacketed with 14-gauge aluminized steel. The heating chamber is constructed of 3/16-in. stainless steel ducts with six dual-fuel-fired burners/heaters, a recirculating fan, a combustion air blower, and an auxiliary matching burner/heater for redundancy. The heaters are designed to burn either oil or gas recovered from the recycling process. The burners discharge into a 10-ft carbon steel combustion air chamber. The combustion chamber includes a 316SS flame guard to withstand the high firing temperature of the fuel oil. A recirculating blower in the heating chamber is connected to the reactor unit with six automatic adjustable inlet ducts, one for each screw conveyor level, to force the heating air evenly through the reactor to heat the process. The circulating blower is also used for cool down when the process is shut down for maintenance. A combustion air blower is installed in the combustion air stack. Combustion air is provided with a make-up air damper tee in the recirculated return air before the burner. A screw conveyor is mounted at the discharge from the reactor unit to remove the carbon black and scrap steel. This conveyor is cooled with a water jacket to reduce the product temperature for separation. The product then enters a drum magnet to separate the scrap steel and carbon black. These products are delivered to the scrap steel conveyor inlet with an open tank water seal, the carbon plug seal conveyor and then to the outlet pick-up points for collection of the solid products.

3. TERTIARY RECYCLING CONVERSION PRODUCTS

3.1 Hydrocarbons After the tires undergo catalytic conversion in the reactor, the liquid fraction is removed from the unit and analyzed for fuel value. The hydrocarbons formed from the process are distilled to determine their fuel composition. The distillation results from a typical reactor run are given in Table 1. As can be seen from the low percentage of residue (bottoms) present in the liquid hydrocarbon fraction, the rubber from the tires is almost completely converted into high-quality fuels. Gas chromatography/mass spectroscopy (GC/MS) analysis of the liquid conversion products showed them to be primarily aliphatic hydrocarbons. Due to the very low concentration of contaminants in the liquid stream, the hydrocarbons can either be upgraded into higher quality fuels or used immediately as a valuable fuel source for ships, heating systems, consumer items, or generators. 3.2 Gaseous Products The non-condensable gas stream can be collected in gas cells and analyzed by GC/MS to determine the composition and content of combustible hydrocarbons. Past tire recycling runs were analyzed to determine composition of the gas stream. Approximately 65% of the gas stream was composed of low molecular weight alkanes and alkenes with a typical heating value of 20,000 BTUs/lb. Other gases included nitrogen, oxygen, carbon monoxide, and carbon dioxide.

Table 1. Composition of Reclaimed Oil from Tertiary Tire Recycling Initial Boiling Point (F) 5% recovered (F) 10% recovered (F) 20% recovered (F) 30% recovered (F) 40% recovered (F) 50% recovered (F) 60% recovered (F) 70% recovered (F) 80% recovered (F) 90% recovered (F) 95% recovered (F) End Point (F) Percent Recovery Percent Residue Percent Lost 82 96 124 188 246 290 318 376 392 420 466 494 545 99 1 0 bottoms kerosene naptha gasoline

3.3 Carbon Black Carbon black, when combined with rubber, substantially increases the hardness and durability of the product. The wear characteristic of carbon black reinforced rubber is a function of the particle size, and the ability to resist wear varies inversely with the particle size (i.e., the finer the particles, the better the rubber-reinforcing properties). Particle size is measured by numerical grade, in nanometers (nm). The highest grade of carbon black has a particle size under 20 nm and is designated as super abrasion furnace. The lowest grades are the semi-reinforcing furnace blacks with particle sizes from 50 to 500 nm. The rubber industry is the major consumer of carbon black while the greatest quantity of carbon black is used in automotive tires. Therefore, the tire industry s requirements and specifications for carbon black are a major focus for the research team. Tire manufacturers traditionally use ASTM grades N220 (20-25 nm; 110-140 m2/g) and N330 (26-30 nm; 70-90 m2/g). However, semi-reinforcing carbon black (ASTM grade N770) with a typical diameter range of 61-100 nm and surface area of 17-35 m2/g has been used for tire carcasses. The carbon black recovered from the tire recycling plant is consistently free of hydrocarbons. No residual odor or oily appearance indicative of hydrocarbon residue has been apparent in the recovered samples. The carbon black tends to be very granular and has a high bulk density. In addition, no residual polymer was present in the carbon black recovered. The average BET

surface area of the carbon black was measured to be 25.31 m2/g as noted in Table 2. A sample of the carbon black was analyzed by inductively coupled plasma (ICP) to determine the percent ash/contaminant content (ASTM D 482) and to identify the contaminants (Table 2). Table 2. Composition of Carbon Black Metals by ICP Aluminum Antimony Arsenic Barium Beryllium Bismuth Boron Cadmium Calcium Chromium Cobalt Copper Iron Lead Magnesium ppm 205 <1.0 <1.0 16 <1.0 <1.0 16 <1.0 9333 40 <1.0 44 1600 69 533 Nickel Phosphorus Potassium Selenium Silicon Silver Sodium Strontium Thallium Tin Titanium Vanadium Zinc Ash Content, ASTM D 482, wt % Metals by ICP Molybdenum ppm 6 56 210 301 <1.0 1960 <1.0 330 <1.0 <1.0 2 962 26 45,866 8.12

The ash content in the carbon black was higher than desired (8.12 wt%). Tire manufacturers prefer carbon black that contains less than 5 wt% impurities. However, the carbon black can be treated to remove ash or can be activated, which would improve both its quality and its value. Activated carbon is the generic term used to describe a family of carbonaceous adsorbents with a highly crystalline form and extensively developed internal pore structure. A wide variety of activated carbon products are produced exhibiting markedly different characteristics depending upon the raw material and the activation technique used in their production. Activated carbon is tested for several of the same properties as those for carbon black including surface area, pore size distribution, iodine absorption, and bulk density. Porosity is what distinguishes activated carbon from carbon blacks.

4. MARKETS
Carbon black is an essential chemical in many industries throughout the world and has applications in rubber, plastics, coating, inks, and toners. The rubber industry consumes approximately 90% of the $4.5 billion carbon black market; approximately 66% of all carbon

black is consumed by tires while another 9.5% of carbon black is used in other automotive applications. Carbon black production is typically located in geographical areas where it is used. The projected demand for these products is shown in Figure 4.
P rojected C Y 2001 D em an d for C arb on B lack 7.8 M illio n M etric Tons

O ther R egions 15% O ther A sia/P acific 19%

N orth A m erica 26%

Japan 11%

C hina 12%

W estern E urope 17%

Figure 4. Carbon black demand for tire applications The current applications for activated carbon are overwhelming, and there is high demand for the material in various industries. In fact, activated carbon is commonly used in many domestic and industrial applications ranging from simple shoe insole deodorizers to the manufacturing of complex industrial chemicals. Examples are given in Tables 3 and 4 for its different applications in various industries as well as its suitability for an assortment of vapor phase and liquid phase applications. 4.1 Economic Analysis A detailed economic model has been developed to fully understand and analyze the economics of the tire recycling process and business requirements for collecting and processing scrap tires. The model is based upon a single-site processing facility with a capacity of 100-tons/day and operating 330 days per year. The model allows for varying the number of collection sites, transportation, equipment, site development, operation and maintenance (O&M) expenses, and other associated costs. Varying the sale price of the reclaimed carbon black is also possible. In the model, no value is given to gaseous hydrocarbons produced in the tertiary recycling process; rather, it is assumed that all gases would be used as fuel for cogeneration equipment to offset process utility costs. Liquid products would be sold on the commodities market. The model was developed using a Microsoft Excel Ver. 5.0TM workbook format. The model allows the user to change a variety of input variables and observe the sensitivity of the economic projections to the selected changes. Inputs to the economic model include amounts paid for scrap tires (positive or negative), amount of scrap collected, transportation costs, specific O&M costs, capital costs, size-reduction costs, waste disposal costs, inflation rate, interest rate, minimum attractive rate of return (MARR), percent investment borrowed, income tax rate, and process products and their market value. Also, one can vary the number of processing facilities. Model outputs include initial investment

Table 3. Vapor Phase Applications of Activated Carbon Industry Solvent Recovery Description Recovery of organic solvents to optimize economics and control vapor emissions Typical Use Acetate fibers (acetone), pharmaceuticals (methylene chloride), film coating and printing (ethyl acetate), magnetic tape (MEK) Adsorption of alcohols and amines To meet CEN 141 standards- Type A respirators Removal of heavy metals and dioxins from flue gas Extraction of some harmful elements of cigarette smoke Airports (partially combusted fuel odors), offices, fume cupboards Air treatment for face masks and respirators, shoe insole deodorizers and water treatment Removal of food odors

Carbon Dioxide Industrial Respirators Waste Disposal

Purification of carbon dioxide from fermentation processes Adsorption of organic vapors Disposal of domestic, chemical and clinical waste by hightemperature incineration Incorporation as powder or granule in filter tips HVAC Impregnation of powdered activated carbon into foam/ fiber/non-woven substances In-situ filter units

Cigarettes Air Conditioning Composite Fibers

Refrigerator Deodorizers

costs; annual O&M, transportation, and processing expenses; revenues and gross profit; margin on annual revenue (MAR); and internal rate of return (IRR ). Also, output information, such as present worth (PW), future worth (FW), and annual worth (AW based upon the MARR) are provided by the model. The economic model provides an accurate estimate of the economic feasibility of the tertiary tire recycling process. If an investor were to commit funds today toward a proposed recycling business, a return on those funds would be expected. The future return is in the form of income generated by the sale of the output products recovered from the recycling process as determined from the characterization and market analysis work. These cash flows (e.g., capital costs, O&M expenses, revenues), which we call incremental cash flows, represent the change in the investors total cash flow that occurs as a direct result of the investment in the tertiary recycling process.

Table 4. Liquid Phase Applications of Activated Carbon Industry Potable Water Treatment Description Granular activated carbons installed in rapid gravity filters Sterilization with chlorine Potable water treatment Ultra-high-purity water Operation of carbon in leach, carbon in pulp and heap leach circuits Recycling of steam condensate for boiler feed water Industrial contamination of groundwater reserves Process effluent treatment to meet environmental legislation Ozone injection for removal of organic contaminants Typical Use Removal of dissolved organic contaminants, control of odor and taste problems Chlorine removal and adsorption of dissolved organic contaminants Removal of trihalomethanes and phenolics Total organic carbon reduction Recovery of gold from tailings dissolved in sodium cyanide Removal of oil and hydrocarbon contamination Reduction of total organic halogens and adsorbable organic halogens Reduction of total organic halogens, biological oxygen and chemical oxygen demand Removal of residual ozone and control of chloramines levels

Soft Drinks Brewing Semi-conductors Gold Recovery

Petrochemical

Groundwater

Industrial Wastewater

Swimming Pools

A recycling facility with an input of 100 tons of scrap tires per day would produce gaseous and liquid hydrocarbons and metals and activated carbon which, when separated, would have a commercial value of about $361/ton. The economics of such a recycling plant operating 330 days annually are projected in Table 5. Table 5. Economic Projections for a 100-Ton/Day Processing Plant Revenue Operating Expense Gross Profit Depreciation Expense (10-year straight line) Net Profit Before Taxes $ $ $ $ $ 11,917,125 3,450,670 8,467,455 782,652 7,684,803

5. CONCLUSIONS
Tertiary recycling of scrap tires has proven to be an economical solution to the waste tire disposal problem. In this process, hydrocarbon gases and liquids, steel, and high-value carbon black are recovered for reuse. The gaseous hydrocarbons are used to generate heat and electricity for the recycling process. Liquid hydrocarbons are a high-quality fuel oil that can be used directly or further refined to improve value. Reclaimed steel is readily recycled and is desired by steel mills because of its high surface-to-volume ratio. As produced, the carbon black has ready markets for reinforcing rubbers and plastics, or as an active ingredient in inks, toners, or paints. The carbon black may be further increased in value by chemical treatment to either remove ash content or activate it for use in filtration applications. The keys to process economics are obtaining value from all the components in the scrap and using a high volume (100-ton/day) continuous process. Eighty such plants would be needed in the US alone to process the scrap tires generated annually without processing any of the three billion tires already present in dumps throughout the country.

6. REFERENCES
1. 2. 3. 4. J. R. Serumgard, A. L. Eastman, Scrap Tire Recycling: Regulatory and Market Development Progress, ACS Symposium Series 1995, 609, pp. 237-244. Scrap Tire News, , 14 (5), 4 (May 2000). Scrap Tire News, 14 (7), 8 (July 2000). U.S. Environmental Protection Agency, (Region 5), Scrap Tire Handbook: Effective Management Alternatives to Scrap Tire Disposal in Illinois, Indiana, Michigan, Minnesota, Ohio, and Wisconsin, 1994. M. Farrell and D. Block, Funding Innovative Uses for Scrap Tires, BioCycle, March 1999, pp. 61-63. C. P. Rader and M. A. Lemieux, The Recycle of Plastics and Rubber- A Contrast, Rubber World, May 1997. G.A. Mackey, Thermolysis, Chemolysis, and Gasification as Advanced Recycling Technology for Waste Plastic, 208th Amn Chem Soc Mtg, Washington, DC, Aug 1994.

5. 6. 7.