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    Tire Pyrolysis Chemtech PDF

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    Huỳnh TG

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    © All Rights Reserved
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    of 6
    ARKETPLACE Pyrolysis of scrap tires: Can it be profitable? Processing them into higher value-added, marketable products — activated carbon and carbon black—may be the answer to the question of what to do with all of our used tires. Marek A. Wéjtowicz Michael A. Serio posal problems. The same prop- erties that make them desirable as tires—most notably, durability — also make their disposal and repro- cessing difficult, Tires are almost immune to biological degradation ‘Dumping the 280 million tres that are ‘generated each year in the United States into landfills is becoming an ‘unacceptable solution (J). In addition to the continuous flow of waste tres, approximately 2-3 billion tires are already stored in piles throughout the United States; illegal dumping is also becoming a serious problem. Tires take up large amounts of valuable landfill space, provide breeding sites for mosquitoes and rodents, and present fire and health hazards. Recently, a large mountain of tires in Canada caught fire, and widespread environmental consequences resulted because of the oils and gases gener- ated from the decomposing. rubber. Such fires are difficult to contain because of the ties’ high flammabil- ity and because of the pockets of air present in the piles. One fire in Hun- tington, VA, bumed for nine months. Large-scale efforts use tires either as a fuel (Oxford Energy Corp.) or as 4 filler for asphalt (Rubber Asphalt Producers). These two technologies consume about 28 million tires anau- ally (2). However, feeding the ties and slagging are problems when the tires are burned, and the rubber asphalt filler costs 40% more than conventional material. RW Technol- ‘ogy has also tried to convert tres into S crap tires present formidable dis- The authors are with Advanced Fuel Research Inc. ‘ther plastic products, but the market riche seems to be small Pyrolysis—the thermal degradation fn the absence of oxygen—is another way to reprocess scrap tires. The prod- cts are fuel gas, ols, and a solid resi- due (char), which contains appreciable {quantities of mineral matter and low- ‘grade carbon black. The three products have comparable yields by weight. ‘More than 30 major pyrolysis projects have been proposed, designed, pat- ented, licensed, or built over the past decade, but none has been commer- cially successful (3). The success of any tire-processing technology depends fon environmental performance (emis- sions) and process economics. Almost no emissions are produced by tire pyrolysis except for minor fugitive sources and equipment leaks (3. 4). The two most important factors affecting process economics are the tipping fees charged for tre disposal and the selling prices of the products (). Tipping fees have been steadily increasing over years, and this trend is expected to continue. Depending on the region, fees vary from $35 to {$108 per ton of whole tres delivered in mass quantities (3). Selling prices of the products yield low returns because of the low market value of the fuels and the low quality of the recovered char of carbon black (carbon black extracted from the pyrolysis char is of very low purity and cannot be used in tire manufacturing) There- fore, 0 obtain a positive cash flow, it ‘would be desirable to develop a pro- cess based on the recovery of value- added products such as high-grade carbon black, activated carbon, or valuable chemicals (e.g, benzene, tol- vene, and xylene). We believe that significant improvement in the eco: nomics can be accomplished by ‘upgrading the primary pyrolysis prod: ucts to secondary products of higher value. Process description ‘The concept of pyrolytic reprocess- ing of waste tires into value-added products is presented in Figure 1 Characteristics of the reactants and products, the process conditions, and the yields of pyrolytic products are based on an extensive literature review and on the data collected in ‘our laboratory (5, 6). The primary products of tire pyrolysis are pyro lytic gas (also known as pyro-gas), oils, and char. This process yields substantial quantities of oils and char, which can undergo additional pro- cessing to secondary, value-added products. According to the proposed Scheme, char upgrading is imple- mented in a closed-loop activation step that yields an activated carbon and climinates undesirable byproducts and emissions. A stream of CO, is used for high-temperature char activ tion, which is followed by CO, recov- ery through the reverse Boudouard reaction. The latter step is an optional Feature of the proposed process. Upgrading the char produces high- surface-area activated carbon and finely divided carbon, which we refer to as the Boudouard carbon. Ash-free oils are turned into high-quality carbon black by using the furmace process. As an alternative, ols can be separated into valuable chemical feedstocks by distillation. Product upgrading is expected 10 greatly Serap tres Primary products Furor ‘Secondary, acess * | value aed produ 20-85% 58a eye, Bude atte so-cry Futon duce ads Bo. Haas Situ, fa Bann ot cal aves, me gee, | eo ro 05% coon 55m Sut my . Wweanzet other |_se-ss | (agra) Akane Tygon pope on Mae Be S Gate merotte Ban > ethane ‘nydrocarbons Seiten SS ty aoe Ronan. Oy tN oae kanes | a 00 poo Kee on sik ote ‘Aldehydes. Lees sats ater 15% ah (most 200) sere) oar oso) (Gait) gee outourcarbon ‘Figura 1. The pyrolyie reprocessing of sera irs yields substantial quantities of ols and char, which can undergo further processing to secondary, value-added products, Char upgrading results in producing high-surface-area activated carbon and Boudouard carbo. Ast- {tee ols are tured into high-quality carbon bk improve the economics of scrap tire pytolysis. ‘Our proposed process is shown in Figure 2 (p. 50). A stream of scrap tires centers the pyrolyzer, where it comes t0 contact with a recycle stream of product gas, which acts as a carrier as for pyrolysis, Mixing used tires with other waste material and solid- ‘waste pretreatment are optional fea- tures of the process. Another option is. to recycle part of the pyrolysis oil from the condenser into the pyro- lyzer; this option is represented by a dotted line in Figure 2. It is expected thatthe recycled oil will undergo par- tial cracking, leading to an altered gas ‘composition at the reactor outlet. System flexibility allows for wide variations in the ratio of gas to oil recycling, depending on product char- acteristics and requirements, The pyrolyzer operates at ~1173.K, and the product streams are fuel gas (which also contains pyrolysis lig- lids) and char. The pyrolysis liquids are separated from the volatiles in a Condenser and then subjected to par- tial combustion in an oil furnace t0 produce carbon black. The latter step is almost identical to the commercial carbon black manufacturing, except that the feedstock is pyrolysis oil rather than a petroleum product. The high-BTU gas is combusted to supply the process heat requirements, The solid product does not have sufficient surface area to make it commercially attractive, and thus, an activation step is needed. Char activation uses CO, at the same temperature as the pyrolyzer (©1173 K), which reduces the CO, to €O. The consumed CO, is regenerated in @ Boudouard reactor with simulta neous formation of finely divided carbon. ‘The net result of this process is the ‘conversion of used tires into three mar- ketable products: activated carbon, carbon black, and Boudouard carbon ‘The production of carbon black and Boudouard carbon is a novelty in the proposed scheme, yet it may be inte- rated into the process by adapting existing technologies. The elements of the process are described here. Feed stream preparation. The tres fare shredded and possibly combined with another waste stream. The use of mixed wastes would improve the appeal and the numberof sites where a plant could be installed. This feature, lac, or the ols can be separated into valuable chemical feedstocks by dstilation, however, increases the complexity of the design as well as the operating costs. The size reduction required for scrap ties does not appear to be exces sive. Infact, higher char activation eff- ciencies were reported for coarse waste ‘material (~ 170 mg) than for fine parti- cles (<50 mesh) (5). The optimal size ‘of scrap tire material for the process has not been determined. Because the cost of shredding increases with decreasing particle size, there isan eco- ‘nomic incentive to make the tre pieces as large as possible. For smaller parti- cles, pretreatment with O increases char yields and surface areas (5). It is rot clear, however, whether these ben efits justify the added cost of oxygen prevreatment Pyrolysis and char activation units. Although a rotary kiln reactor has been successfully used for pyroly- sis of tires itis not necessarily the best solution for a high-throughput system (7). A kinetic analysis of tie pyrolysis indicates that the process is relatively fast and can be completed in <1 at 873K. This speed allows the use of fan entrained-flow reactor, which is appropriate for high-throughput appli- cations, Unfortunately, only relatively tite) . me : Fr] To lM it oan ; Fea Ht ‘inst cutcet ig- isan als Ga Are comimmret ety — esnips Ee ae ue gas esto ss Tees i (Tame) 48 Gas) | sur Ss fa Gente > co ae rime) et oer - ar = {is Oe ‘Boudouard | CO ‘Figur 4. Co-separaton process. One dlsadvarage ofthe single-reactor scheme that, Bovdouard carbon is produced fay com lex separation step i required to recover pure CO from the pyrolysis gas is required. diesel engine (16). Boudouard carbon | commercially viable. In particular, the '= Use as transportation fuel would | is similar to carbon black (except for | following topics must be addressed: require upgrading because of the rela- | having a zero-hydrogen content), and | product quality, the determination of tively high aromatic content of the oil. | in some cases can be substituted for | reaction rates at various CO-10-CO; '= Because carbon black is required to | carbon black. The potential applica- | ratios in the feed gas, reactorype ‘make tires, the production of carbon | tions of this product include the man- | selection and design, separation of black from the oil is a form of tire | ufscture of colorants and lubricants. | Boudovaed carbon from the iron cata- recycling and seems to be more prac- | The production of finely divided | lyst, and exploration of noncatalytic tical than trying to recover the origi- | carbon from CO has never been com- | reaction pathways. ral carbon black from the char. ‘merealized, presumably because of | Energy and mass balances. The Boudouard carbon production | the relatively high value of CO and | fuel gases produced during pyrolysis, from CO. This process step was dis- | uncertainties associated with market- | can be used to provide process heat ccussed by Walker (9) as part of his | ing Boudouard carbon. During World | for the pyrolysis and activation coal-processing scheme. The tempera- | War TI, however, the reaction was | stages. Some heat can also be recov- ture of the Boudouard reactor is main- | used in Germany fo produce a substi | ered from the manufacturing of tained at 773-800 K, and the carbon | tute for carbon black (17). Although | carbon black by partial combustion of product is ash free and has a panicle | some information on the reaction | the oil and from the production of Size significantly smaller than can be | Kinetics and product characteristics | Boudouard carbon. Preliminary esti- obtained by grinding (15). In fact the | has been available for a long time | mates show that the process outlined Particle size of Boudouard carbon is | (18, 19), more research and develop- | in Figure 2 will be self-sufficient Small enough to burn completely in a | ment are needed to make the process | from an energy standpoint. Existing Figure 2. Tira pyrolyss process proposal. ‘The nt results tree marketable products: activated carton, carbon black, and Bovd- ‘ua carbon The production of carbon back {nd Boudouard carton s very much a nov fy, athough it may be integrated ito the process by adapting existing technologies. small particles ean be fed into such a reactor, mainly because of heat transfer limitations, For the larger pieces of tire material, & fluidized-bed reactor ‘could be used. In either case, a hot cyclone is desirable to separate char particles from the volatiles. In this scene, char evan by CO tes e in a separate reactor, allowing the oxides of carbon to be cyeled between the activation step (produc: ing CO) and a disproportionation step (producing CO; and carbon). In this way, CO is periodically consumed (activation) and regenerated (dispro- portionation), and CO and CO, say relatively pure ‘Another possibility is to use a moving-bed countercurrent system. Although the solids throughput would necessarily be lower, this disadvan- tage would be offset by combining the pyrolysis and char activation stages ina single reactor. In this Scheme, tire pieces would be fed into the reactor atthe top and CO, at the bottom (Figure 3). A temperature of ~1173 K would prevail at the boom ‘of the reactor so that the char would bbe progressively pyrolyzed and then activated as it moves through the reactor. This design simplifies the process of feeding the tire pieces and climinates the need for a hot cyclone because the volatiles and char come ‘out of opposite ends of the reactor ‘The moving-bed concept has been used in a large-scale coal gasification plant in Beulah, ND, that produces synthetic pipeline gas (8). ‘There are some liferences between the two processes, however. The tie- processing unit would operate under atmospheric pressure because there is gwar [tr proces eat reece lo, me i carn from] Ecce. Achat crbon——Bouteuard carton litle ono advantage in producing act- vated carbon at an elevated pressure. ‘The coal gasification system is inter. nally heated by introducing O, at the bottom and partially combusting a por tion of the coal. in the tie-processing reactor, the pyrolysis gases that come off the top ofthe unit would be com- ‘usted externally, and the hot exhaust ‘gases (moslly CO, and HO) would be introduced intothe botiom of the reactor for char activation. The reac- tor would be insulated to prevent heat Teses. ‘The single-eactor scheme (Figure 3) for processing tres has two disadvan- tages: The pyrolysis gas has a lower heating value because it is diluted with the flue gas, and if Boudouard carbon is to be produced, a fairly complex separation step is required t0 recover pure CO from the pyrolysis gas (Figure 4). Previous work has Shown thatthe final activated carbon product is not very sensitive to the Conditions under which pyrolysis is cartied out (5), thus allowing for greater design flexibility. ‘We have shown that activation using an 8% COyHe mixture at 1173 K for 3-10 his sufficient to obtain chars with high surface area (5). The residence time canbe reduced by raising the tem- perature, increasing the CO, partial Pressure, or by using steam instead of ‘CO,. The cha activation chemistry can be represented by the following two (C0, activation CO, +C72C0 (Ghe Boudouard reaction ‘Steam activation HO +C + CO+H, Both reactions are endothermic, and the equilibrium reaction becomes more favorable as the temperature increases. The use of steam produces a higher reaction rate and a higher surface area product, and the use of CO; increases the production of CO from the activation step. The CO can then be subjected to the reverse Bou-

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