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Recycling polystyrene into fuels by means of FCC: performance of various acidic catalysts
Gabriela de la Puente, Ulises Sedran*
Â lisis y Petroquõ Âmica ± INCAPE (FIQ, UNL ± CONICET), Instituto de Investigaciones en Cata Santiago del Estero 2654, 3000 Santa Fe, Argentina Received 12 January 1998; received in revised form 30 July 1998; accepted 10 August 1998
Abstract In accordance with the option of recycling plastics into fuels by dissolving them in standard feedstocks for the process of catalytic cracking of hydrocarbons, FCC, various acidic catalysts (zeolites ZSM-5, mordenite, Y, and a sulfur-promoted zirconia) were tested in the conversion of polystyrene dissolved into inert benzene at 5508C in a ¯uidized-bed batch reactor. Experiments were performed with very short contact times of up to 12 s. Main products were in the gasoline range, including benzene, toluene, ethylbenzene, styrene, and minor amounts of C9±12 aromatics and light C5À compounds. Coke was always produced in very signi®cant amounts. All the products can be justi®ed with basis on the properties of each catalyst and the various possible catalytic reaction pathways: cracking after protolytic attack on the polymer fragments, styrene oligomerization and subsequent cracking, or hydrogen transfer to styrene. Styrene would be mainly produced in this system from thermal cracking of the polymer as the initial step. If present, shape selectivity effects due to catalyst structure can in¯uence signi®cantly the prevalence of the various reactions, because they would interfere with those undergoing bulky transition states, like styrene oligomerization or hydrogen transfer. Even though sulfur-promoted zirconia is highly acidic, the low proportion of Brùnsted-type acid sites does not allow the occurrence of secondary styrene reactions. It was shown that most favorable product distributions (higher yields of desirable products) are obtained on equilibrium commercial FCC catalysts. # 1998 Elsevier Science B.V. All rights reserved. Keywords: Polystyrene; Recycling; FCC; Zeolites
1. Introduction The disposal of waste plastic materials is an extreme problem which has a high environmental impact. In the last years, there has been increasing concern about the recycling of these waste materials, for which a number of different options exist . All
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the alternatives have some drawbacks: for example, direct reprocessing (primary recycling) can only be applied up to a certain limit; combustion (secondary recycling) may produce harmful gases, and land®lling has environmental risks due to the chemical inertness of these materials. The tertiary recycling implies the conversion of the polymers into more valuable chemicals or fuels, technological implementations depending on the type of polymers to be recycled . For example, condensation polymers can be
0926-3373/98/$ ± see front matter # 1998 Elsevier Science B.V. All rights reserved. PII: S0926-3373(98)00084-8
zeolite ZSM-5 (Mobil). Indeed.306 G. Chemical and physical properties of the catalysts used are summarized in Table 1. Norton. the main products under this methodology are in the gasoline range: ethylbenzene. It was shown that over commercial FCC equilibrium catalysts. it has 1. with important coke yields. the zeolite content is 9. Possible reaction mechanisms are considered to explain observed product distributions. de la Puente. it has been shown that for the particular case of polyethylene dissolved in VGO. it is possible to increase gasoline yields signi®cantly . However.3 wt% rare earth oxides. sulfur was incorporated by dipping the solid into a 1 N H2SO4 solution and ®nally the sample was calcined at 6008C for 3 h. Polyole®nic addition plastics with a massive production. studies were performed by using polystyrene dissolved in an inert solvent . Zeolon 900 H).1 wt% and the Ni and V contents are 300 and 1200 ppm. Sedran / Applied Catalysis B: Environmental 19 (1998) 305±311 subjected to solvolysis reactions to recover raw materials. This experimental tool has been used to study the conversion of polypropylene and polystyrene-based plastics dissolved into light cycle oil. following Breck's procedure . a more interesting approach for processing waste plastics and convert them into valuable fuels is to merge them into standard FCC feedstocks. Table 1 Catalyst properties Catalyst ZSM-5 MOR S-ZR E-CAT a b Since tertiary recycling of plastics through the FCC approach could be an interesting option to recover fuels. specially if it can be implemented with little technological developments. it is then necessary to determine the catalytic performance in the conversion of polystyrene of different. sulfur-promoted zirconia (S-ZR) and an equilibrium conventional FCC catalyst (E-CAT. Octydine BR 1160. Experimental Catalysts used were the following: mordenite (MOR. The amount of sulfur remaining on the catalyst after this treatment was 1.065 BET specific surface area (m2 gÀ1) 346 436 110 175 Chemical analysis. It has also been shown that polystyrene can be converted over other acidic catalysts when using combined thermal plus catalytic approaches in discontinuous or ¯ow reactors: the polymers can be either cracked thermally and then contacted with the catalysts . then. can be subjected to pyrolysis to produce a mixture of hydrocarbons that needs to be upgraded if they are to be used as fuels . potentially useful acidic catalysts. Si/Al ratio 174a 5.9b Acidityc (meq NH3 gÀ1) 0.152 0. It is the objective of this work to report the speci®c behaviors of the above-mentioned catalysts in the catalytic conversion of polystyrene following the FCC option. or sulfur-promoted zirconia. The sulfur-promoted zirconia was synthetized starting from a ZrOCl2Á8H2O solution . and the comparison against the performance of standard FCC catalysts. Engelhard. like zeolites mordenite and ZSM-5. Catalyst acidity was determined by means of the temperature programmed desorption of NH3 from 2008C to 6008C. or catalysts particles can be coated with the plastics and then heated [8. in the 450±5508C temperature range. that could be incorporated as additives to the catalyst in the FCC process. obtained from a sampling device in a running re®nery. 2. U. . In order to ascertain the speci®c contributions from plastics to the FCC product slate. to con®rm that this approach is feasible . the extension of the results to commercial applications has to be done with care. and for a given catalyst to oil ratio. since a ®xed-bed reactor was used.670 0. respectively). c Measured by NH3 temperature programmed desorption. Calculated from XRD data. A ¯uidized-bed batch reactor especially devoted to FCC studies (the so-called Riser Simulator ) may yield sounder results. benzene and styrene monomer. toluene.9 ± 12. like polyethylene or polypropylene.280 0. however.9].8 wt%.
involving certain mass of catalyst and gases and moving along it during a given residence time.15 0.00 12. as shown by scrupulous mass balance calculations. U.42 0.06 43. then. and reaction times were from 3 to 12 s. excluding coke.00 1.07 0.00 9. This is consistent with previous observations [5.54 2. some differences between catalysts are apparent.41 38.18 1. Sedran / Applied Catalysis B: Environmental 19 (1998) 305±311 307 The conversion of commercial polystyrene (average molecular weight: 312 000.59 0.00 2.90 7. however.00 4. the mass of catalyst was always 0.12] that also report that polystyrene can be completely cracked under milder conditions. toluene.00 0.06 0. It is to be noted that indane and indane-type compounds are predominant among C9±12 aromatics and that styrene dimers o trimers were not observed.00 9. most important products in all the cases when catalysts are present are benzene.00 No catalyst 0. and C9±12 aromatics. duplicate runs in which the plastic was dissolved in toluene at the same extension. with smaller amounts of cracking products C5À.85 0. as can be observed in the comparison of the evolution of the yields of most important products for all the catalyst samples.88 68.00 0. reaction time: 9 s) Catalyst C1 C2 C3 C4 C5 C6 Benzene Toluene Ethylbenzene Styrene Xylenes C9 aromatics C10 aromatics ZSM-5 0.12 0.16 0. It can be seen that according to the catalyst properties.91 10. ethylbenzene and styrene.52 0.00 0. the conversion of polystyrene is complete over all the catalysts and contact times used.00 10.88 0.81 10. that were determined by a conventional burning-off gravimetric method.00 0.54 0.00 0.27 S-ZR 0.84 75.79 0. The basic design concept of this unit considers that a slice of the environment of an ideal riser reactor.00 0. with and without catalysts. ethylbenzene and C9±12 aromatics.39 MOR 1. is located into this batch reactor.5 wt%) was conducted at 5508C in a riser simulator reactor . and even under different contact regimes.16 0. reaction time evolved in the riser simulator is equivalent to contact time and motion along the ideal riser.G.00 0.98 4.9.15 ml.22 2. Coke yields from the solvent itself were assessed separately by means of experiments in which only the solvent was injected.10 36. The product distributions on the various catalysts used in this work. were estimated from separate. Results and discussion The conversion of polystyrene dissolved into benzene was performed at 5508C.32 3. which are presented in Table 2 Conversion of polystyrene dissolved in benzene (yields of most important products at 5508C (coke excluded).20 5. toluene.97 2.61 5. with internal recirculation and ¯uidized-bed regime. polydispersity: 2. The total volumes injected into the reactor were 0.86 8.16 5.8 g.55 0. The yields of benzene.17 0.07 0.86 32.4) dissolved in benzene (6. Nevertheless. like 4508C.59 0. which is a product from the reaction.05 1.46 0.00 0.76 0. and an example of thermal cracking  under the same conditions is also included for comparison: the thermal conversion of polystyrene at this high temperature of 5508C and short contact times under 12 s yields mainly styrene monomer and minor amounts of benzene.65 64. de la Puente.96 E-CAT 0. Experiments showed that benzene does not yield products in the gas phase under these conditions.00 0.85 13.34 0. Under the experimental conditions used. 3. Duplicate runs were performed under identical conditions to measure coke yields. Reaction products were analyzed by gas chromatography. products range from C1 to C12 compounds. a temperature that is used in FCC units when they are operated in the more severe ``light ole®ns mode''.00 0.52 .00 3. aimed at maximizing their production . are presented in Table 2 for a particular contact time (9 s).
Yields of main products in the conversion of polystyrene (6.5 wt% in benzene) over catalyst MOR as a function of contact time. 1. 1. 1. styrene is the most important product in the ®rst steps of reaction (short contact times) with a decreasing yield pro®le showing further reaction. T5508C. (&) toluene. de la Puente. T5508C. (}) styrene. Sedran / Applied Catalysis B: Environmental 19 (1998) 305±311 Fig. 1). T5508C. 2.5 wt% in benzene) over catalyst S-ZR as a function of contact time. 3. (~) ethylbenzene. Symbols: (*) benzene. where styrene has a steep decreasing pro®le. Yields of main products in the conversion of polystyrene (6. Figs. Fig. . U. It can be seen that for the catalyst ZSM-5 (refer to Fig. 1±4 as a function of reaction time.5 wt% in benzene) over catalyst E-CAT as a function of contact time. while benzene Fig. Symbols as in Fig. In all the catalysts. benzene is the second more important gas phase product. The product distribution is quite different on mordenite (refer to Fig. while ethylbenzene and toluene have similar low yields. Yields of main products in the conversion of polystyrene (6. and (5) coke. 2).5 wt% in benzene) over catalyst ZSM-5 as a function of contact time. T5508C. 1. Yields of main products in the conversion of polystyrene (6. Fig. Symbols as in Fig. Symbols as in Fig. toluene is the most important product at longer reaction times (over 8 s). 4. having an increasing yield pro®le.308 G.
13]. styrene is reacted signi®cantly on this catalyst. would be cracked. not included in the ®gures). which would produce ethylbenzene. 1±4 show that the catalytic action is unambiguous and depends on catalyst properties. They were assessed after deducting the coke formed by the solvent. As can be seen in Fig. As can be deduced from the yield curves (refer to Figs. or alkylaromatics. product distributions result different. 1±4). The reaction of hydrogen transfer to styrene. Fig.8. This same group of main products can be also the result of another reaction pathway : the direct electrophilic proton attack on the aromatic rings of the polymer chains. 4). that allowed to con®rm that they follow the same reaction pathways. it is expected that shape selectivity effects will be less manifest and the resulting reaction products will also re¯ect the subsequent transformation of styrene from the initial thermal conversion of the polymer. consequently. MOR is the largest coke producer. some routes can be favored relatively and. some of the main reaction products (benzene. about 30 wt%. However.12].6. Sedran / Applied Catalysis B: Environmental 19 (1998) 305±311 309 is produced in smaller amounts and ethylbenzene yield is very low. and catalytic conversion of styrene monomer . and its eventual in¯uence on coke formation is completely masked by the inherently high coke yield in this reacting system . Ni and V loadings are relatively low. with yields as high as 87 wt%. toluene. which has a stronger dependency. styrene. styrene would be preserved. The rate of decrease of styrene yield is pronounced on the FCC equilibrium catalyst (refer to Fig. 1). U. (b) Styrene molecules could also be subjected to direct hydrogen transfer to yield ethyl- benzene. Then. indane and derivatives) can be justi®ed [6. Then. in turn.12. like acid function. the main steps in the conversion of polystyrene could be outlined as follows. the oligomers produced in the zeolite channels should be restricted to a few units. while benzene could be the result of the attack on whichever ``internal'' rings of the fragments of the chains. Therefore. the incidence of external sites would be relatively more important through the interaction with polymer chain fragments: toluene. since. to proceed. 3 shows that on sulfur-promoted zirconia styrene has a ¯atter pro®le. Following this judgment. and also from experiments of thermal and catalytic conversion of polystyrene-based polymers [5. oligomerization. benzene and ethylbenzene are produced in similar amounts with increasing yield pro®les. which have bulky intermediate states. as suggested by results in Fig. less than 2 wt%. essentially. or two fragments of the polymer (an end protonated cation and a shorter polymer chain). the ®rst main step would be the thermal cracking of polystyrene to yield styrene monomer units. depending on the relative importance of the various alternatives of the catalytic cracking pathways. also has a bulky bimolecular transition state which would not be favored in the shape selective structure of this zeolite. 2. Results presented so far can be rationalized in terms of an expected overall reaction mechanism  and the particular properties of each catalyst. it is expected that benzene yields be relatively important. then. All the samples produce small amounts of cracking products (C5À compounds. The comparisons of product distributions in Table 2 and yield curves in Figs. The other catalysts produce coke at approximately the same rate. two alternative pathways are possible: (a) Styrene molecules could be subjected to oligomerization reactions and the resulting oligomeric cations. which would yield benzene and a macrocation. thus. As a result. 2. The yields of coke in the cracking of polystyrene over the various catalysts are also included in the ®gures. de la Puente. the only acting mechanism would be the one on the polymer fragments as con®rmed in the product distribution (refer to Table 2 and Fig. would be selectively favored against hydrogen transfer due to the high density of acid sites in this catalyst (see Table 1). It can be seen that among the zeolite catalysts. As a consequence. and corresponding to the catalysts' role. the trend to crack them to yield toluene is higher than for the other . could be formed from protonation in the endmost rings of the polymer chains. while ethylbenzene yield is very signi®cant.G. while toluene is formed in a smaller extension. Consequently. According to the properties of the catalysts. and even though both oligomerization  and hydrogen transfer  reactions depend on site density. more than two fold the combined yields of benzene and toluene. The zeolite mordenite (MOR) has a pore system which behaves essentially as a one-dimensional system. with pore openings de®ned by 12-member rings. In the particular case of the E-CAT. the fact that ZSM-5 produces mainly styrene could be reasoned as the result of steric hindrances in the small pores and cavities of the zeolite that do not allow the oligomerization reactions.
As explained above. FCC units. The cracking of these short oligomers also yields C9 aromatics. associated to the lack of severe steric hindrances. are produced on this catalyst. coke yields similar to those observed in resid cracking were measured. the fact that if the technology is to be implemented on existing. as can be seen in Table 2. U. which in turn (if being a C9 aromatic) can be cracked into benzene and C3. are preserved in this catalyst. It can be seen in Figs. ZSM-5 is the one yielding the lowest amounts. according to the mechanism described above. higher unit cell size sample of the same FCC catalyst. which produces more benzene and toluene. and less benzene. the high activity of MOR. It can be seen in Fig. no effect of shape selectivity is expected on the pore structure of the SZR catalyst. The higher relative yield of ethylbenzene from hydrogen transfer to styrene over E-CAT could be explained as the consequence of the lower acid site density. de la Puente. Moreover.and Lewis-type. which is kept by coke combustion in the regenerator. C9 aromatics. present technology is facing the demand for processing heavier feedstocks. E-CAT. and second. 1±4 that all the catalysts yield high amounts of coke. sulfur-promoted zirconia and an equilibrium FCC catalyst) are able to convert polystyrene into fuel products that are mainly in the range of gasoline when it is reacted at the high temperature of 5508C . is very reduced . like isomerization  and MTBE synthesis . For some of them. or modi®ed. due to two facts: ®rst. Coke production has a signi®cant importance in this polymer recycling option. Sedran / Applied Catalysis B: Environmental 19 (1998) 305±311 possibilities (e. or the alkyl chain cycled to form C9 indane-type compounds that would react preferentially to coke since they are very important coke precursors . the comparison of the yields of the most important products over the various catalysts used allows to state that the E-CAT is more convenient: in general terms. instead. The product distribution on the commercial equilibrium FCC catalyst E-CAT is justi®ed based on the proposed mechanism. However. and less ethylbenzene  than the E-CAT. which affects oligomerization reactions more signi®cantly than those of hydrogen transfer.g. From the gasoline composition standpoint. the presence of Brùnsted sites. due to the low activity. Sulfur-promoted zirconia has been studied extensively in the last years as a potentially useful catalyst for acid catalyzed reactions . SZR also shows similar coke yields and relatively high C9 proportions. then the heat balance. originates similar amounts of coke. then. the production of precursors from cracking of styrene oligomeric cations being not favored against the hydrogen transfer. Conclusions Acidic catalysts of different types (ZSM-5. coke precursors. in similar magnitudes. were introduced to give proper response to the increased coking rates .310 G. a fact that can be ascribed to its shape selectivity effects interfering with the coking process. In that sense. leads to this high coke production. It is to be noted that when high amounts of polystyrene (25%) dissolved into LCO were converted on an equilibrium FCC catalyst. The high yields of styrene (which means that it is not extensively converted after the initial thermal cracking of the polymer). the similar yields of toluene and ethylbenzene. 3 that the yield curves are similar to those of ZSM-5. mordenite. The same discussion basis could also be applied to the comparison against a fresh. with the exception of catalyst MOR. styrene and coke. the production of benzene as the next most important gas phase product. could all be explained as occurring on the reduced fraction of Brùnsted-type sites on the catalyst's low speci®c surface area according to the reaction mechanisms that were described above. their relative amounts depending on the pretreatment calcination conditions. the high yields observed. which has an average pore diameter of Ê . the yield curve of styrene has a steeper decreasing pro®le. it has been shown that the maximum in catalytic activity is reached when the catalyst is calcined at around 6008C. has to be preserved into ranges that are controllable technically. Similarly to MOR. like catalyst coolers. it has to be considered that the acidic properties of sulfur-promoted zirconia depend strongly on the pretreatment calcination temperature : acidic sites are both of Brùnsted. 4. particularities in observed products about 50 A should be the result of the various reaction pathways and catalyst acidic properties. Among the other catalysts. and the presence of C9 aromatics in considerable yields (refer to Table 2). ring protonations in the oligomers to yield benzene). if any. When calcination temperature is higher than 6008C. and new devices. more ethylbenzene and toluene.
References  K. J. vol. Eng.J. thus giving an extra support to this recycling option since minor technological modi®cations would be needed. Srinivasan. Tochihara.M. G. King. Kuroki. shape selectivity effects can in¯uence signi®cantly the prevalence of reactions. S. Eng.  B. Kluwer Academic Publishers. Very important amounts of coke are formed. Abajo. Dordrecht. Fõ (1997) 199. Breck.E. US Patent 5 102 628 (1992). Catal. Wiley.  S. Emanuel. J. Lo Azkoiti. 192 (1993) 349. Carniti. Zhibo.  D.). Bilbao. Sedran. 17. R. Ng. J. 1984. P. I. Styrene would be mainly produced from thermal cracking of the polymer as the ®rst step. p. Âgoli. E. Ueno. Proceedings of the Eighth International Congress on Catalysis. Parera.  S.L. Ind. M.I. MOR. Beltrame. the low proportion of Brùnsted-type acid sites does not allow for the occurrence of secondary styrene reactions. J. R. Even though sulfur-promoted zirconia is highly acidic. Arandes. K. Keogh. Argentina). Cerrato.  C. Resulting product distributions can be explained considering the particular properties of each catalyst and the various possible catalytic reaction pathways: cracking after protolytic attack on the polymer fragments.G. vol. Bertini.  R. Wiley. Kakuta.L. NATO ASI Series E: Chemical Reactor Technology for Environmentally Safe Reactors and Products. is the one showing the best product distribution in terms of gasoline composition when yields are compared. 36 (1997) 4530. Catal. I. Berlin. Catal. Bolis.I. ZSM-5 and S-ZR could only be considered as catalyst additives in FCC process. both undergoing bulky transition states.  G. Proj. New York. Verlag Chemie. 36 (1994) 405. Sommer. . J. de la Puente. U.N. Sedran.H. G.A.A. Fõ Cabrol. Poly. Polym. S. Acknowledgements This work was performed with the ®nancial assistance of University of Litoral. R. Appl. p. E. Beltramini. Res. H. Comelli. Â pez-Valerio. A. If present. Energy & Fuels 9 (1995) 216.M. N. Appl.  J. Ohkita. Arandes. N.  R. ACS Symp. Sedran / Applied Catalysis B: Environmental 19 (1998) 305±311 311 under the approach of ¯uidized catalytic cracking. Chem. C.S. Chem. P. Ferna Â ndez. 1985. styrene oligomerization and subsequent cracking. July (1992) 30. D. Shelley. Dogu.  U.M. Depending on the catalyst properties and the contact time. Today 20 (1994) 219. New York. Eng. 1992. Davis.S. M. Ikemura.  G. December (1993) 30.A. Secretary of Science and Technology (Santa Fe. T. J. 593. R. II. Chem. Moore. Churõ Ân. Parera. Morterra. de Lasa. J. Chem.  Z.  S. U. Res. T. Fouhy. Today 29 (1996) 303. 12H/163. V. in: H. 67  M. Catal. U. Audisio. Rev.J. G. de la Puente. Meeting Abs. White. R. Eng. J. or hydrogen transfer to styrene. S. Superacids. C. Prakash. 36 (1997) 4523. Ogawa.  R. because they would interfere with styrene oligomerization or hydrogen transfer. Stab. Deg. Vera.A. Polym. Kim. T. Morioka. Sci.  G. Washington. Sci. vol. Ide. Mizushima. 1974. Eng. toluene. Zeolites Molecular Sieves.K. Y. 29 (1984) 2561. 1996. 29 (1990) 191. A. J. 151 (1995) 96. I. Chem. Lin. P.S. Moore. White. Y. Âgoli. 63 (1997) 1287.. F. ethylbenzene and styrene.-Sci. the major products are benzene. Revella (Eds. de Lasa.A.L. Sedran. 1165.  J. Olazar. Culp.  D. 41. Olah. 225. ACS.A. Nishio. J. DC. Fouhy.W. Quiroga. Ind. The ®nancial assistance of Antorchas Foundation (Argentina) is gratefully acknowledged. The comparison of performances of the different catalysts reveals that E-CAT. p. N.  H. besides being the base catalyst for FCC. Eng. Lin.M. Catal.
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