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Polymer Degradation and Stability 92 (2007) 813e821 www.elsevier.com/locate/polydegstab

Y.-H. Lin*, M.-H. Yang

Department of Biochemical Engineering & Graduate Institute of Environmental Polymer Materials, Kao Yuan University, 821 Kaohsiung, Taiwan, ROC Received 27 October 2006; received in revised form 26 January 2007; accepted 31 January 2007 Available online 11 February 2007

Abstract

Keywords: Polymer; Fluidised-bed reactor; Pyrolysis; Catalyst; Selectivity

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Polypropylene (PP) was pyrolysed over spent FCC commercial catalyst (FCC-s1) using a laboratory uidised-bed reactor operating isothermally at ambient pressure. The inuence of reaction conditions including catalyst, temperature, and ratio of polymer to catalyst feed and ow rates of uidising gas was examined. The yield of gaseous and liquid hydrocarbon products at 390  C for spent FCC commercial catalyst (87.8 wt%) gave much higher yield than silicate (only 17.1 wt%). Greater product selectivity was observed with FCC-s1 as a post-use catalyst with about 61 wt% olens products in the C3eC7 range. The selectivity could be further inuenced by changes in reaction conditions. Valuable hydrocarbons of olens and iso-olens were produced by low temperatures and short contact times used in this study. It is also demonstrated that a post-use catalyst system under appropriate conditions the resource potential of polymer waste can be economically recovered and also can address the recycling desire to see an alternative to solve a major environment problem. 2007 Elsevier Ltd. All rights reserved.

1. Introduction

Polymer waste can be regarded as a potential source of chemicals and energy. Methods for recycling polymer waste have been developed and new recycling approaches are being investigated [1]. Chemical recycling, i.e., thermal and/or catalytic conversion of waste polymers into fuels or chemicals, has been recognised as an ideal approach and could signicantly reduce the net cost of disposal [2]. The most widely used conventional chemical methods for waste polymer treatment are pyrolysis and catalytic reforming. Since thermal degradation demands relatively high temperatures and its products require further processing for their quality to be upgraded, catalytic degradation of polymer waste offers considerable advantages.

* Corresponding author. Tel.: 886 7 6077777; fax: 886 7 6077788. E-mail address: lin@cc.kyu.edu.tw (Y.-H. Lin). 0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymdegradstab.2007.01.028

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Suitable catalysts have the ability to control both the product yield and product distribution from polymer degradation as well as to reduce signicantly the reaction temperature, potentially leading to a cheaper process with more valuable products [3e5]. Studies of the effects of catalysts on the catalytic degradation of polymer have been performed by (i) contacting melted polymer with catalyst in xed bed reactors [6e8], (ii) heating mixtures of polymer and catalyst powders in reaction vessels [9e11] and (iii) passing the products of polymer pyrolysis through xed bed reactors containing cracking catalysts [12e14]. However, the conguration of the pyrolysis-reforming reactors poses serious engineering and economics constraints. For the study of these pyrolysis-reforming reactions, it is difcult to measure the exact mass-ow rate of the reactant from the pyrolysis to catalytic zones, and consequently it is virtually impossible to identify and quantify the reactant and to control its quality. In addition, the use of xed

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Chemical catalysed recycling of waste polymers: Catalytic conversion of polypropylene into fuels and chemicals over spent FCC catalyst in a uidised-bed reactor

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Y.-H. Lin, M.-H. Yang / Polymer Degradation and Stability 92 (2007) 813e821

2. Experimental

The catalysts employed are described in Table 1. All the catalysts were pelleted, crushed and sieved to give particle sizes
Table 1 Catalysts used in the catalytic degradation of polypropylene

Au

Catalyst

Si/Al

th o

2.1. Materials and experimental procedures

Surface area (cm2/g) BETa 147 426 547 268 362 Micropore 103 263 429 21 297 External 44 128 118 247 65

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beds or adiabatic batch where polymer and catalyst are contacted directly leads to problems of blockage and difculty in obtaining intimate contact over the whole reactor. Without good contact the formation of large amounts of residue are likely, and scale-up to industrial scale is not feasible. In order to compare the polymer cracking properties of different catalysts, it is preferable to examine the effects of catalysts without extensive complications due to reactions of primary cracking products, e.g. olens, with unconverted polymer by using techniques that minimise such interactions. For this purpose, a laboratory uidized-bed reactor has been used to study catalytic cracking of polymers by limiting the contact between primary volatile products and the catalyst/polymer mixture [15e18]. The catalyst increases signicantly the commercial potential of a recycling process based on catalytic degradation, as cracking catalysts could cope with the conversion of plastic waste co-fed into a renery FCC unit. It is certainly possible to develop commercial processes based on these approaches. Therefore, a more interesting approach is that of adding polymer waste into the FCC process, under suitable process conditions with the use of zero value of spent FCC catalysts, a large number of waste plastics can be economically converted into valuable hydrocarbons. However, much less is known about performance of uid catalytic cracking (FCC) commercial catalysts on the degradation of polymer waste. Although spent FCC catalysts have been investigated in some trials, the results for those studies are sketchy and were carried out by the use of batch or xed bed reactors [19,20]. Potential concepts has been investigated (Part I) using thermal analysis to estimate the kinetic behaviours and as a potential method to evaluate the effect of spent FCC catalysts on the catalytic degradation of polypropylene (PP). It is the objective of this work to investigate the product slate of the FCC process made by PP recycled into the usual chemicals and fuels, by means of its conversion over post-use FCC commercial catalysts in a catalytic uidised-bed reaction system, and specically for identication of suitable reaction conditions for enhancing the potential benets of catalytic polymer recycling.

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ranging from 75 to 180 mm. The catalyst was then dried by heating in owing nitrogen (50 ml min1) to 120  C at 60  C h1. After 2 h the temperature was increased to 520  C at a rate of 120  C h1 to active the catalyst for 5 h. In contrast with the micrometer size of the crystals in conventional zeolites [21], ZSM-5 and HUSY used in this work synthesised with smaller crystallite sizes [22,23] present a high proportion of external surface, which accounts for approximately 20e30% of the total zeolite surface area. The polymer used in this study was pure polypropylene (PP; isotactic, r 853.6 kg m3, MW z 332,000, Aldrich). High purity nitrogen was used as the uidising gas and the ow was controlled by a needle valve and pre-heated in the bottom section of the reactor tube. Flowmeters were used to measure the full range of gas velocities from the incipient to fast uidisation. Before catalytic pyrolysis experiments were started, several uidisation runs were performed at ambient temperature and pressure to select (i) suitable particle sizes (both catalyst and polymer waste) and (ii) optimise the uidising gas ow rates to be used in the reaction. The particle size of both catalyst (75e180 mm) and polymer (75e250 mm) were chosen to be large enough to avoid entrainment but not too large as to be inadequately uidised. High ow rates of uidising stream improve catalystepolymer mixing and external heat transfer between the hot bed and the cold catalyst. On the other hand, an excessive ow rate could cause imperfect uidisation and considerable entrainment of nes. 2.2. Experimental procedures and product analysis

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A process ow diagram of the experimental system is given elsewhere [15] and shown schematically in Fig. 1. A threezone heating furnace with digital controllers was used and the temperatures of the furnace in its upper, middle and bottom zones were measured using three thermocouples. By these means the temperature of the pre-heated nitrogen below the distributor and catalyst particles in the reaction volume could be effectively controlled to within 1  C. The polymer feed system was designed to avoid plugging the inlet tube with melted polymer and to eliminate air in the feeder. The feed system was connected to a nitrogen supply to evacuate polymer into the uidised catalyst bed. Thus, commingled polymer particles were purged under nitrogen into the top of the reactor

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Pore size (nm) eb 0.55 0.51 0.74 3.28e 0.55 0.51

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FCC-s1 ZSM-5 HUSY HAHA Silicalite

a b c d e

2.1 17.5 13.6 3.6 >1000

Total surface area (BET). The catalyst was a mixture of zeolite, a silicaealumina matrix and binder, not determined. Chinese Petroleum Corp., CPC, Taiwan, ROC. BP Chemicals, Sunbury-on-Thames, UK. Single-point BET determined.

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Commercial Name Equilibrium catalystsc ZSM-5 zeolited Ultrastabilised Y zeolitec Amorphous silica aluminac Synthesized in-house

Y.-H. Lin, M.-H. Yang / Polymer Degradation and Stability 92 (2007) 813e821

815

N2

V1

2 4

TC1

TC2

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V4

Fig. 1. Schematic diagram of a catalytic uidised-bed reactor system: (1) Feeder, (2) furnace, (3) sintered distributor, (4) uidised catalyst, (5) reactor, (6) condenser, (7) ow meter, (8) 16-loop automated sample system, (9) gas bag, (10) GC, and (11) digital controller for three-zone furnace.

Rgp hydrocarbon production rate of gaseous products in each spot rung=min 100=total hydrocarbon production of gaseous products over the whole spot runsg Gaseous hydrocarbon products were analysed using a gas chromatograph equipped with (i) a thermal conductivity detector (TCD) tted with a 1.5 m 0.2 mm i.d. molecular sieve 13X packed column and (ii) a ame ionisation detector (FID) tted with a 50 m 0.32 mm i.d. PLOT Al2O3/KCl capillary column. A calibration cylinder containing 1% C1eC5 hydrocarbons was used to help identify and quantify the gaseous products. The remaining solid deposited on the catalyst yieldwt% Pg 100=polymer fedg Mass balances of 90 5% were obtained for all experiments. Due to the high nitrogen ow rates used in this study, it is difcult to completely recover all the lower molecular weight material, and this results in some loss in the mass balance.

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and allowed to drop freely into the uidised-bed at t 0 min. At sufciently low polymer/catalyst ratios (as used in this study) the outside of the catalyst particles are not wet with polymer, so the catalyst particles move freely. Volatile products leaving the reactor were passed through a glass-bre lter to capture catalyst nes, followed by an iceacetone condenser to collect any condensable liquid product. A three-way valve was used after the condenser to route product either into a sample gas bag or to an automated sample valve system with 16 loops. The Tedlar bags, 15 L capacity, were used to collect time-averaged gaseous samples. The bags were replaced at intervals of 10 min throughout the course of reaction. The multiport sampling valve allowed frequent, rapid sampling of the product stream when required. Spot samples were collected and analysed at various reaction times (t 1, 2, 3, 5, 8, 12, 15, and 20 min). The rate (Rgp, wt% min1) of hydrocarbon production of gaseous products collected by automated sample system in each run was dened by the relationship:

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V2

TC3

after the polymer degradation was deemed residues and contained involatile products and coke. The amount and nature of the residues were determined by thermogravimetric analysis (TGA).

3. Results and discussion The reactor and various units of the collection system were weighted before and after the runs to determine the mass balance. Catalytic pyrolysis products (P) are grouped together as hydrocarbon gaseous (<C5), liquids (gasoline (C5eC9), condensate in condenser and captured in lter and BTX) and residues (coke and products, involatile at reaction temperature, deposited on catalyst) to enable the overall pyrolysis processes to be described more easily. A number of runs were repeated in order to check their reproducibility. The term yield as used in this paper is dened by the relationship:

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11

py
10

V3

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Y.-H. Lin, M.-H. Yang / Polymer Degradation and Stability 92 (2007) 813e821 Table 3 Summary of products of PP degradation over FCC-s1 catalyst (uidising N2 rate 600 ml min1, catalyst particle size 75e180 mm, polymer to catalyst ratio 30 wt%, and total time of collection 30 min) Degradation results Temperature ( C) 330 360 390 26.9 60.9 54.3 5.4 1.2 12.2 9.9 2.3 91.8 feed) ed ed 0.1 1.7 8.8 2.2 14.1 2.7 16.5 3.5 14.2 4.5 7.4 1.5 2.8 1.2 420 31.2 58.2 52.7 3.9 2.0 10.2 7.6 2.6 92.7 ed ed 0.3 2.3 10.3 2.9 15.4 3.3 16.2 3.2 11.9 3.8 8.0 1.8 2.8 1.7 450 34.2 56.7 50.9 3.3 2.5 9.1 6.0 3.1 93.2 ed 0.2 0.4 2.7 11.2 3.2 16.5 3.4 13.7 4.6 10.3 3.3 8.7 2.1 3.2 1.6

3.1. Degradation of PP over silicalite and spent FCC commercial catalyst Product distributions for PP degradation over silicalite (Si/ Al > 1000) in the 330e450  C range are summarised in Table 2. At temperatures below 390  C, a large amount of solid residue, presumably unconverted commingled polymer and high molecular weight degradation products, remained on the silicalite catalyst. The yield of gaseous and liquid hydrocarbon products at 390  C was only 17.1 wt% (Table 2) compared with 87.8 wt% (Table 3) when spent FCC commercial equilibrium catalyst (FCC-s1) was used. Typically thermal degradation productions were observed with silicalite showing primary cracking products and an even spread of carbon numbers consisting of C3eC6 olens products with some isomerisation of BTX. At higher temperatures, product streams containing C1eC9 hydrocarbons were produced with gaseous yield 21.2 wt% and liquid range yield 18.7 wt% of polymer converted at 450  C. Some similar trends in product yields were observed with spent FCC catalyst (FCC-s1) as the reaction temperature was increased. Gaseous and coke yields increased and involatile residues (unreacted or partially reacted PP) and liquids decreased. Product distributions with FCC-s1 catalyst contained more olenic materials in the range of C3eC7 (about 61 wt%

Table 2 Summary of products of PP degradation over silicalite catalyst Degradation results Temperature ( C) 330 360 390 10.2 6.9 5.1 1.6 0.2 82.9 feed) n.d n.d 0.2 0.3 4.2 0.6 4.9 n.d 3.1 ed 1.4 0.2 0.3 n.d 0.1 ed

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450 21.2 18.7 13.4 2.8 0.4 60.1 0.1 0.1 0.5 0.9 6.8 1.3 11.5 0.5 5.2 0.2 4.1 0.5 1.8 0.2 0.6 0.3

420

Yield (wt% feed) P Gaseous ( C1eC4) 3.5 7.1 Liquid 2.5 4.3 P Gasoline ( C5eC9) 1.7 2.8 Condensate liquida 0.7 1.4 0.1 0.1 BTXb Residuec 94.0 88.6 Distribution of C1eC9 hydrocarbon products (wt% C1 n.d n.d n.d n.d C2 C] n.d 0.2 2 C3 n.d 0.1 1.8 2.8 C] 3 C4 n.d 0.4 C] 1.6 3.6 4 C5 n.d n.d 0.9 1.8 C] 5 C6 n.d ed ] C6 0.5 0.7 C7 n.d n.d 0.1 0.3 C] 7 C8 n.d n.d C] ed ed 8 P C9 n.d n.d

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15.9 13.0 8.9 2.1 0.2 72.9 ed 0.1 0.3 0.8 5.6 0.9 8.2 0.3 3.8 0.1 2.6 0.3 1.4 ed 0.3 0.1

Fluidising N2 rate 600 ml min1, catalyst particle size 75e180 mm, polymer to catalyst ratio 30 wt% and total time of collection 60 min. a Condensate liquid: condensate in condenser and captured in lter. b BTX: benzene, toluene and xylene. c Residue: coke and involatile products. d e: less than 0.01 (wt%); n.d: not detectable.

rs
a b c d

Yield (wt% feed) P Gaseous ( C1eC4) 20.8 22.3 Liquid 64.4 64.5 P Gasoline ( C5eC9) 57.4 56.9 Condensate liquida 6.6 6.9 0.4 0.7 BTXb Residuec 14.8 13.2 Involatile residue 13.2 11.3 Coke 1.6 1.9 Mass balance (%) 88.2 89.3 Distribution of C1eC9 hydrocarbon products (wt% C1 n.d n.d C2 n.d n.d C] ed 0.1 2 C3 1.1 1.5 C] 5.6 6.6 3 1.9 1.6 C4 C] 12.2 12.6 4 C5 1.8 2.4 C] 19.8 18.9 5 3.4 3.5 C6 C] 17.5 16.2 6 C7 3.7 4.6 6.6 6.2 C] 7 C8 1.2 1.2 C] 2.8 3.1 8 P C9 0.6 0.8

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Condensate liquid: condensate in condenser and captured in lter. BTX: benzene, toluene and xylene. Residue: coke and involatile products. e: less than 0.01 (wt%); n.d: not detectable.

at 390  C) with minor products, methane and ethane, only detectable at the higher reaction temperatures. The rate of hydrocarbon production as a function of time for PP degradation over FCC-s1 catalyst at different reaction temperatures is compared in Fig. 2 and, as expected, faster rates were observed at higher temperatures. At 450  C, the maximum rate of hydrocarbon production was 36 wt% min1 after only 2 min with all the polymer degraded after approximately 11 min. As the temperature of reaction was decreased, the initial rate of hydrocarbon production dropped and the time for PP to be degraded lengthened. At 330  C the rate of hydrocarbon production was signicantly lower with the polymer being degraded more slowly over 20 min. 3.2. Effect of reaction conditions on PP degradation over spent FCC catalyst The effect of reaction conditions including ow rates of uidising gas (270e900 ml min1), ratios of polymer to catalyst feed (1:1e1:6) and catalyst type (FCC-s1) has been investigated. The results shown in Fig. 3 illustrate that for efcient PP degradation good mixing is required, with a dramatic drop-off in the rate of degradation observed only at the lowest

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Y.-H. Lin, M.-H. Yang / Polymer Degradation and Stability 92 (2007) 813e821
40 35 30 330C 360C 390C 420C 450C

817

Table 4 Product distributions shown from FCC-s1 catalysed degradation of PP at different uidising N2 rates Degradation results uidising N2 rates (mL/min) 900 Yield (wt% feed) P Gaseous ( C1eC4) Liquid P Gasoline ( C5eC9) Condensate liquida BTXb Residuec Involatile residue Coke Mass balance (%) 29.6 60.5 55.1 4.9 0.5 9.9 7.7 2.2 89.2 750 28.8 60.4 54.7 4.9 0.8 10.8 8.5 2.3 89.6 600 26.9 60.9 54.3 5.4 1.2 12.2 9.9 2.3 91.8 450 26.3 60.7 54.6 4.5 1.6 13.0 10.5 2.5 90.3 300 26.1 60.1 53.7 4.3 2.1 13.8 11.2 2.6 94.1

Rgp (wt%/min)

25 20 15 10 5 0 0 2 4 6 8 10 12 14 16

18

20

Time (min)
Fig. 2. Comparison of hydrocarbon yields as a function of time at different reaction temperatures for the catalytic degradation of PP over spent FCC commercial catalyst (FCC-s1) (rate of uidisation gas 600 ml min1, catalyst particle size 75e180 mm, polymer to catalyst ratio 30 wt%).

Reaction temperature 390  C, catalyst particle size 75e180 mm, polymer to catalyst ratio 30 wt%, and total time of collection 30 min. a Condensate liquid: condensate in condenser and captured in lter. b BTX: benzene, toluene and xylene. c Residue: coke and involatile products.

35 30 25

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uidising ow used (300 ml min1). Furthermore, changing the uidising ow rate inuences the product distribution. At low ow rates (high contact times for primary products), secondary products are observed with increased amounts of coke precursors (BTX) although the overall degradation rate is slower as shown by increasing amounts of partially depolymerised products (Table 4). The amount of FCC-s1 used in the degradation of PP polymer remained constant and, therefore, as more waste polymers were added to the reactor then fewer catalytic sites per unit weight of catalyst were available for cracking. The overall effect of increasing the polymer to catalyst ratio from 0.1:1 to 0.6:1 on the rate of hydrocarbon generation was small but predictable (Fig. 4). As the polymer to catalyst ratio increases, the possibility of PP polymer adhesion to the reactor wall

increases as the amount of unreacted polymer waste in the reactor rises. The total product yield after 20 min showed only a slight downward trend even after a 6-fold increase in added polymer waste. This can be attributed to the sufcient cracking ability of FCC-s1 and excellent contact between PP polymer and catalyst particles. As more PP was added, lower C5eC9 gasoline yields but higher liquid yields and involatile products were observed (Table 5). More BTX (coke precursor) was produced but increasing the polymer to catalyst ratio had only virtually no effect on C1eC4 hydrocarbon gases production. Both the carbon number distribution of the products of PP polymer cracking at 390  C over FCC-s1 catalyst, zeolitic catalysts (ZSM-5 and HUSY) and non-zeolitic amorphous silica alumina (SAHA) used in this study and the nature of the product distribution were found to vary with the catalyst used. As shown in Table 6, the yield of volatile hydrocarbons for

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900 ml/min 750 ml/min 600 ml/min 450 ml/min

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35

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0 2 4

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6 8

py
10 12

10% wt/wt 30 25 20% wt/wt 30% wt/wt 40% wt/wt 60% wt/wt

Rgp (wt%/min)

th o Au

20 15 10 5 0

Rgp (wt%/min)

300 ml/min

20 15 10 5 0

10

12

14

16

18

20

14

16

18

20

Time (min)
Fig. 3. Comparison of hydrocarbon yields as a function of time at different uidisation gas for the degradation of PP over FCC-s1 catalyst (reaction temperature 390  C, catalyst particle size 75e180 mm, polymer to catalyst ratio 30 wt%).

Time (min)
Fig. 4. Comparison of hydrocarbon yields as a function of time at different ratios of polymer to catalyst for the degradation of PP over FCC-s1 catalyst (reaction temperature 390  C, catalyst particle size 75e180 mm, rate of uidisation gas 600 ml min1).

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Y.-H. Lin, M.-H. Yang / Polymer Degradation and Stability 92 (2007) 813e821
35 FCC-s1 30 25 20 15 10 5 0 HUSY ZSM-5 SAHA Silicalite

Table 5 Product distributions shown from FCC-s1 catalysed degradation of PP at different ratios of polymer to catalyst (reaction temperature 390  C, catalyst particle size 75e180 mm, uidising N2 rate 600 ml min1, and total time of collection 30 min) Degradation results Ratio of polymer to catalyst (% wt) 10 Yield (wt% feed) P Gaseous ( C1eC4) Liquid P Gasoline ( C5eC9) Condensate liquida BTXb Residuec Involatile residue Coke Mass balance (%)
a b c

20 27.8 61.7 55.4 5.3 1.0 10.5 8.3 2.2 90.6

30 26.9 60.9 54.3 5.4 1.2 12.2 9.9 2.3 91.8

40 27.6 60.3 52.9 5.8 1.6 12.1 10.4 1.7 92.5

60 28.2 59.2 51.4 6.0 1.8 12.6 10.7 1.9 90.4

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6 8 10

26.7 63.2 57.4 4.9 0.9 10.1 7.6 2.5 89.5

Rgp (wt%/min)

py
12 14 16 18 20

Time (min)

Condensate liquid: condensate in condenser and captured in lter. BTX: benzene, toluene and xylene. Residue: coke and involatile products.

Fig. 5. Comparison of hydrocarbon yields as a function of time for the catalytic degradation of PP at 390  C over different catalysts (waste polymer to catalyst ratio 30 wt%, rate of uidisation gas 600 ml min1).

Table 6 Summary of products of PP degradation over various commercial catalysts Degradation results Catalyst type FCC-s1 Yield (wt% feed) P Gaseous ( C1eC4) Liquid P Gasoline ( C5eC9) Condensate liquida BTXb Residuec Involatile residue Coke Mass balance (%) 26.9 60.9 54.3 5.4 1.2 12.2 9.9 2.3 91.8

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ZSM-5

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HUSY 33.5 58.7 54.8 3.4 0.5 7.8 2.9 4.9 92.4 30.2 56.9 52.9 3.7 0.3 12.9 10.5 2.4 90.5

zeolitic catalysts (ZSM-5 z HUSY) gave higher yield than spent FCC commercial catalyst (FCC-s1) and non-zeolitic catalysts (FCC-s1 z SAHA) and the highest was obtained for ZSM-5 (nearly 90 wt%). Overall, the bulk of the products observed with these acidic cracking catalysts (FCC-s1, ZSM-5, HUSY and SAHA) were in the gaseous and liquid phase with less than 13 wt% solid residues of involatile residue and coke collected. The differences in the product distributions between those catalysts can be seen with ZSM-5 producing a much more C1eC4 hydrocarbon gases (56 wt%) than FCC-s1, HUSY and SAHA catalysts. Some similarities were observed between FCC-s1 and SAHA with C1eC4 and C5eC9 yields, which were approximately 27e30 wt% and 53e54 wt%, respectively. The highest level of unconverted polymer was observed with silicalite, while the highest coke yields were observed with HUSY. The rate of gaseous hydrocarbon evolution further highlights the slower rate of degradation over silicalite catalyst as shown in Fig. 5 when comparing all catalysts under identical conditions. The results

SAHA

56.2 38.8 33.5 3.5 1.8 5.0 3.1 1.9 94.5

Reaction temperature 390  C, uidising N2 rate 600 ml min1, polymer to catalyst ratio 30 wt%, and total time of collection 30 min. a Condensate liquid: condensate in condenser and captured in lter. b BTX: benzene, toluene and xylene. c Residue: coke and involatile products.

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Silicalite 10.2 6.9 5.1 1.6 0.2 82.9 80.3 2.6 94.1

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of the products of PP degradation reect the differing cracking effect of FCC-s1 catalyst compared with the zeolite and nonzeolitic materials. The maximum rate of generation was observed after 2 min with the zeolite catalysts whereas the maximum was observed after 3 min with FCC-s1 and SAHA.

3.3. Variation of product stream with catalytic selectivity and catalyst deactivation

P P Equilibrium ratios of i-butene/ butenes (i-C]/ C]) and 4 4 i-butane/n-butane (i-C4/n-C4) were predicted using Gibbs free energy minimisation on the PRO/II package for the temperatures used experimentally and are presented alongside the corresponding experimental results in Table 6. The i-butene/ P butenes ratio is very close to the predicted equilibrium values and thus the reactions involved in the production and interconversion of butenes are very fast over FCC-s1, and their ratio is primarily equilibrium controlled. The i-butane/n-butane ratio reects the involvement of tertiary C4 carbenium ions in bimolecular hydrogen transfer reactions and since tertiary carbenium ions are more stable than primary ions, a higher yield of iso-butane would be expected. As can be seen in Table 7, the observed i-butane/n-butane ratios at 390  C are well above calculated equilibrium values consistent with the cracking of long chain hydrocarbon molecules to yield iso-butylcarbenium ions which provide a source for i-butane, via hydrogen transfer, or i-butene. The selectivity could be varied by changes in different operating conditions used in this study. Further evidence of the increase in secondary reactions, for example, bimolecular hydrogen transfer, was seen P P in the lowering of the olen/ parafn (o/p 4.52 at 330  C versus o/p 2.86 at 450  C) and i-butane/n-butane (i-C4/n-C4 3.23 at 330  C versus i-C4/n-C4 1.83 at 450  C) ratios as temperature increases, in the experimental range. At fast ow rates, primary cracking products are favoured as evidenced by the increasing ratios of i-butene/ P P butenes (i-C]/ C] 2.12 in 300 ml min1 N2 uidising 4 4

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Y.-H. Lin, M.-H. Yang / Polymer Degradation and Stability 92 (2007) 813e821

819

Table 7 Inuence of reaction conditions on product selectivity for the catalysed degradation of PP over FCC-s1 catalyst: experimental and predicted equilibrium results Ratio Reaction conditiona Temperatureb ( C) 330 P i-Butene/ butenes P i-Butene/ butenese i-Butane/n-butane i-Butane/n-butanee P SOlens/ parafnsf
a b c d e f

P/C ratioc (wt%) 450 0.43 0.45 1.83 0.77 2.86 10 0.57 3.46 3.61 30 0.52 2.47 3.91 60 0.54 2.29 3.43

N2 rated (ml min1) 300 0.46 600 0.51 2.47 3.91 900 0.59 3.53 4.28

390 0.49 0.50 2.47 0.89 3.91

30 20 10 0

FCC-s1

rs
3

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4 5 6

Wt %

Wt %

20 10 0

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30

HUSY

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4 4 4

P rate versus i-C]/ P ] 3.53 in 900 ml min1 N2 uidising C4 P 4 rate) and olen/ parafn (o/p 3.65 in 300 ml min1 N2 uidising rate versus o/p 4.28 in 900 ml min1 N2 uidising rate).

The relation in catalytic activity to catalyst deactivation was examined by the transient change in the amount of gaseous compounds produced. Rapid variation in the product stream of FCC-s1 and HUSY catalysts was observed (Fig. 6)

co
5 5 5

Represents a series of runs with different reaction temperature, polymer to catalyst ratio and N2 uidising rate. Polymer to catalyst ratio 30 wt% and 600 ml min1 N2 uidising rate. Reaction temperature 390  C and uidising N2 600 ml min1. Polymer to catalyst ratio 30 wt% and reaction temperature 390  C. Predicted equilibrium data. Denotes the ratio of the sum all olenic to parafnic products.

30 20 10 0

ZSM-5

th o

Wt %

Au

30 20 10 0

SAHA

Wt %

Time (min)
i-C4 tot C4= tot C5=

Fig. 6. Some of hydrocarbon products of isobutene (i-C4), catalysts.

P butanes (tot C4]) and pentanes (tot C5]) as a function of time for PP degradation over different

py
3.65
6 6 6

0.55 0.54 3.23 1.04 4.52

2.12

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when the spot samples, taken during the course of the reaction, were analysed. The deactivation is reected in the decrease of the amount of iso-butane (i-C4) produced (product of bimolecular reaction) and the relative increase in olens (product of monomolecular reaction), exemplied by, C] and C]. The 4 5 spent FCC-s1 catalyst with bimodal pore structures, which is composed of both the micropore of zeolite and the mesopore of silicaealumina, may allow bulky reactions to occur, ultimately leading to the generation of coke and subsequently deactivation of the catalyst. The deactivation was more exaggerated in the case of HUSY with its large pore openings and internal supercages. In contrast, ZSM-5 is resistant to coking when coke builds up on outer surface and the product stream remains essentially unchanged, whereas the weakness and lower density of the acid sites in SAHA along with the increased tolerance to coke in the amorphous structure is most likely the reason for the lack of variation in the product stream over this catalyst.

Acknowledgements The authors would like to thank the National Science Council (NSC) of the Republic of China (ROC) for nancial support (NSC 95-2211-E-244-013). Thanks also are due to Professor M.D. Ger and Dr. C.-M. Chiu for samples of ASA, spent FCC commercial catalyst and surface area/pore size measurements.

References

4. Conclusions A laboratory catalytic uidised-bed reactor has been used to obtain a range of volatile hydrocarbons by catalytic degradation of polypropylene in the temperature range of 330e450  C. The catalytic degradation of PP over spent FCC catalyst performed in uidised-bed reactor was shown to be a useful method for the production of potentially valuable hydrocarbons. In the presence of the spent FCC commercial catalyst at 390  C used in this work, conversion of PP polymer to volatile hydrocarbons in the catalytic uidised-bed reactor was more than 87 wt% of feed in 20 min, while silicalite yielded less than 18 wt% of feed after 60 min. The use of uidised-bed reaction system coped with a spent FCC equilibrium catalyst can be a better option from economical point of view since it can gives a good conversion with comparable short reaction time, and even its activity is lower than that of the zeolites (ZSM-5 and HUSY) and silicaealuminas (SAHA), this can be compensated by increasing the catalyst to PP ratio. Product distributions with FCC-s1 catalyst contained more olenic materials in the range of C3eC7 (about 56 wt% at 390  C). Experiments carried out with FCC-s1 catalyst gave good yields of volatile hydrocarbons with differing selectivity in the nal products dependent on reaction conditions. However, silicalite give very low conversions of polymer waste to volatile hydrocarbons compared with spent FCC catalyst (FCC-s1) under the same reaction conditions. The selectivity could be further inuenced by changes in operating conditions; in particular, olens and iso-olens were produced by low temperatures and short contact times. From a practical point of view, the use spent equilibrium catalyst from FCC units can be the most adequate solution. It is concluded that the use of spent FCC commercial catalyst and under appropriate reaction conditions can have the ability to control both the product yield and product distribution from polymer degradation, potentially leading to a cheaper process with more valuable products.

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