Current Opinion in Solid State and Materials Science 8 (2004) 419425

Feedstock recycling of polymer wastes

Arthur A. Garforth
a

a,*

ndez-Mart nez a, Aaron Akah s Herna , Salmiaton Ali b, Jesu

Environmental Technology Centre, Department of Chemical Engineering, The University of Manchester, P.O. Box 88, Manchester M60 1QD, UK b Department of Chemical and Environmental Engineering, Faculty of Engineering, UNIPUTRA, 43400 UPM Serdang, Selangor, Malaysia

Abstract Current common polymer waste recycling methods, mechanical recycling and energy recovery, have drawbacks such as labour intensive sorting and atmospheric pollution. Feedstock recycling has emerged as an environmentally successful alternative for polymer waste management. 2005 Published by Elsevier Ltd.
Keywords: Plastics; Polymer recycling; Feedstock recycling; Tertiary recycling; Catalytic cracking

1. Polymer recycling Polymer waste might be regarded as a potentially cheap source of chemicals and energy, although its recycling varies widely across Europe [*1]. Disposing of the waste to landll is becoming undesirable due to legislative pressures (where waste to landll must be reduced by 35% over the period from 1995 to 2020) [2], rising costs, the generation of explosive greenhouse gases (such as methane) and the poor biodegradability of commonly used packaging polymers. The two main alternatives for treating municipal and industrial polymer wastes are energy recycling, where wastes are incinerated with some energy recovery and mechanical recycling. The incineration of polymer waste meets with strong societal opposition [3] and, there is the Kyoto Protocol to consider, as the UK moves towards its domestic goal of reducing carbon dioxide emissions by 20% by 2010 [2]. Mechanical recycling (the conversion of scrap polymer into new products) is a popular recovery path for manufacturers and is carried out on single-polymer waste streams as a market for recycled
Corresponding author. E-mail address: arthur.garforth@manchester.ac.uk (A.A. Garforth). 1359-0286/$ - see front matter 2005 Published by Elsevier Ltd. doi:10.1016/j.cossms.2005.04.003
*

products can only be found if the quality is close to that of the original. Unfortunately these products are often more expensive than virgin plastic [4,5]. In 2002 in the UK, only 17% of 3.8 million tonnes of polymer waste was recycled by these methods, the remainder was land-lled or incinerated (without energy recovery) [*1].

2. Feedstock recyclingcurrent state of the art Feedstock recycling, also known as chemical recycling or tertiary recycling, aims to convert waste polymer into original monomers or other valuable chemicals. These products are useful as feedstock for a variety of downstream industrial processes or as transportation fuels. There are three main approaches: depolymerisation, partial oxidation and cracking (thermal, catalytic and hydrocracking) [*6]. 2.1. Depolymerisation Polymers are divided into two groups: (i) condensation polymers and (ii) addition polymers. Condensation polymers which include materials such as polyamides, polyesters, nylons and polyethylene terephthalate (PET), can be depolymerised via reversible synthesis

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reactions to initial diacids and diols or diamines. Typical depolymerisation reactions such as alcoholysis, glycolysis and hydrolysis yield high conversion to their raw monomers [7]. In contrast, addition polymers which include materials such as polyolens, typically making up 6070% of municipal solid waste plastics [*1,3,4], cannot be easily depolymerised into the original monomers. However, the results obtained in the thermal depolymerisation of polymethylmethacrylate (PMMA) are noteworthy since at 723 K, a 98% yield to the monomer has been reported [*8]. 2.2. Partial oxidation The direct combustion of polymer waste, which has a good caloric value, may be detrimental to the environment because of the production of noxious substances such as light hydrocarbons, NOx, sulfur oxides and dioxins. Partial oxidation (using oxygen and/or steam), however, could generate a mixture of hydrocarbons and synthesis gas (CO and H2), the quantity and quality being dependent on the type of polymer used. Borgianni et al. [9] showed the possibilities of recovering energy from waste containing polyvinyl chloride (PVC) by a gasication process without additional dechlorination facilities. A new type of waste gasication and smelting system using iron-making and steel-making technologies has been described by Yamamoto et al. [10], reportedly to produce a dioxin-free and high-calorie puried gas. Hydrogen production eciency of 6070% from polymer waste has been reported for a two-stage pyrolysis and partial oxidation process [*11]. Co-gasication of biomass with polymer waste has also been shown to increase the amount of hydrogen produced while the CO content reduced [12]. The production of bulk chemicals, such as acetic acid, from polyolens via oxidation using NO and/or O2, is also possible [13,14]. 2.3. Cracking: hydro-, thermal- and catalytic Cracking processes break down polymer chains into useful lower molecular weight compounds. This can be achieved by reaction with hydrogen, known as hydrocracking or by reaction in an inert atmosphere (pyrolytic methods), which can be either thermal or catalytic cracking. Hydrocracking of polymer waste typically involves reaction with hydrogen over a catalyst in a stirred batch autoclave at moderate temperatures and pressures (typically 423673 K and 310 MPa hydrogen). The work reported, mainly focuses on obtaining a high quality gasoline starting from a wide range of feeds. Typical feeds include polyolens, PET, polystyrene (PS), polyvinyl chloride (PVC) and mixed polymers [15,*16,1721], polymer waste from municipal solid waste and other sources [17,18,2226], co-mixing of polymers with coal

[24,25,2731], co-mixing of polymers with dierent renery oils such as vacuum gasoil [3236] and scrap tyres alone or co-processed with coal [3741]. To aid mixing and reaction, solvents such as 1-methyl naphthalene, tetralin and decalin have been used with some success [25,28,41]. Several catalysts, classically used in renery hydrocracking reactions, have been evaluated and include transition metals (e.g., Pt, Ni, Mo, Fe) supported on acid solids (such as alumina, amorphous silicaalumina, zeolites and sulphated zirconia). These catalysts incorporate both cracking and hydrogenation activities and although gasoline product range streams have been obtained, little information on metal and catalyst surface areas, Si/Al ratio or sensitivity to deactivation is quoted. In thermal degradation, the process produces a broad product range and requires high operating temperatures, typically more than 773 K and even up to 1173 K [*8,4249]. On the other hand, catalytic degradation might provide a solution to these problems by allowing control of the product distribution and reducing the reaction temperature [48,5053]. Catalytic cracking studies have been mainly limited to pure polymers (predominantly using polyolens and PS) and fresh, pure acid catalysts (zeolites predominating). Zeolites are crystalline, porous aluminosilicates [5456] characterised by channel networks and pore openings of molecular dimensions (see Fig. 1, [57]) leading to increased shape selectivity in petrochemical

Fig. 1. Typical zeolites used in polymer cracking [57]: (a) H-ZSM-5, (b) H-Mor (Mordenite), (c) H-Y or HUS-Y and (d) H-Beta.

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reactions [5456,58]. PVC is problematic because HCl strips from the polymer at relatively low temperatures [59,60]. In Japan, a low temperature thermal cracking stage is employed prior to catalytic cracking, however, co-mingling with other polymer waste is required to boost the H content of the residual partially cracked polymer waste. Typically iron-based catalysts have been employed to dechlorinate the PVC/mixed polymer-derived oil [52,6163]. The catalytic cracking of PS to benzene, toluene and xylene (BTX), as well as styrene monomer, has been carried out by a number of researchers at operating temperatures from 623823 K over acid catalysts such as zeolites (HMOR HZSM-5, HY), amorphous SiO2Al2O3, BaO powder and a sulfur-promoted zirconia [6467]. Predominantly, catalytic cracking research has focussed on the degradation of polyolens to gas, liquid and waxy products using a range of acid catalysts (typically, amorphous silica alumina and zeolites). For example, in Japan, legislative pressures have resulted in research targeting a stable liquid product. Other researchers have targeted an end use, such as, gasoline-range hydrocarbons and others the production of ethene and propene [15,48,6874]. A variety of reactor types has been used including batch [53,70,75] and xed bed [52,68,69,71,7679], or non-catalytically using thermal degradation in a uidised bed reactor or kiln [59,80,*81]. With batch reactors, secondary cracking reactions predominate, yielding a broad range of products including heavy aromatics, coke and saturated hydrocarbons. Fixed bed reactors are prone to blocking due to the viscous nature of melted polymer presenting problems when scaling-up [82]. Non-catalytic thermal cracking using a uidised bed reactor with sand as a uidising agent or kiln requires a higher operating temperature and produces products in a very broad range [*81]. On the other hand, the use of a uidised bed reactor has advantages in terms of heat and mass transfer, as well as constant temperatures throughout the reactor [48,82,83]. Recent work has logically extended studies to uid catalytic cracking (FCC) catalysts with comparisons to pure zeolites and silica alumina [74,84,*85]. Before design predictions can be made for a pyrolysis process on an industrial scale, an understanding of the interface between the polymer and the catalyst must be developed. The mechanism of interaction is highly complex, with three phases (liquid polymer, solid catalyst and gaseous products), mass transfer by diusion, convection and bulk ow as well as cracking-type reactions with a large number of products. Fig. 2 shows a scanning electron micrograph (SEM) of a nely blended mixture of high density polyethylene (HDPE) and ZSM-5 after heating from room temperature to 478 K. The polymer particles have melted and owed but individual catalyst and polymer particles were still noticeable. On increasing the temperature to 573 K, the

Fig. 2. Mixture of HDPE/ZSM-5 at 478 K, 200 times magnication. Reprinted from Garforth and co-workers [*85].

melted polymer has completely wetted the zeolite particles (Fig. 3). The catalytic degradation of HDPE has been carried out in a laboratory uidised bed reactor using pure zeolites and fresh, steam deactivated and equilibrium catalysts (E-Cats) with dierent rare earth oxides and Ni and V loadings (listed in Table 1) [48,83,8688]. At 723 K, the products from polymer cracking were mostly gases in the range C1C9 (determined by GC analysis), and coke and unreacted polymer (determined by thermogravimetric analysis) [48,89]. As expected, trends in polymer cracking (Table 3) reected the dierent nature of catalysts, with fresh commercial FCC catalysts and pure ZSM-5 catalyst converting 8590% of their feeds to gaseous, liquid and carbonaceous products. The lower activity of pure US-Y (ex Croseld Chemical) was expected due to its rapid deactivation. On the other hand, the less active steamed and equilibrium catalysts showed only 6070% conversion to the volatile products. The E-Cats showed negligible loss in overall conversion of HDPE due to metal contamination, although the products of polymer degradation were olen-rich compared with steam deactivated Cat-1S and -7S. Figs. 4 and 5 show selected olen and paran products in the carbon range of C3C6, respectively, for the catalysts. US-Y is the major active component in commercial FCC catalysts and therefore the product yields compared favourably. The level of activity of the various catalysts was reected in the amount of primary (olen) versus secondary (paran) products observed. With high acidities of both fresh catalysts (Cat-1 and -7,

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Fig. 3. Mixture of HDPE/ZSM-5 at 573 K, 200 times magnication. Reprinted from Garforth and co-workers [*85].

Table 1 Catalyst details (supplied by Engelhard Corporation, USA) [88] Catalyst Cat-1 Cat-7 Cat-1S Cat-7S E-Cat 1 E-Cat 2
a

Commercial name Fresh commercial FCC catalyst Fresh commercial FCC catalyst a Steam deactivated FCC catalyst a Steam deactivated FCC catalyst Equilibrium FCC catalysts Equilibrium FCC catalysts

REO (wt%) 0.8 9.6 0.8 9.6 1.3 1.6

) UCS (A 24.4 24.7 24.3 24.5 24.3 24.3

MSA (m2/g) 112 90 90 72 76 32

ZSA (m2/g) 264 331 198 241 99 95

Ni (ppm) 171 5400

V (ppm) 217 6580

Steaming conditions: 4 h/1061 K/100% steam.

Table 2 Weight% of product distributions at T = 723 K; C/P = 6:1 [88] ZSM-5 Gaseous Liquid Coke Involatile Total 83.7 2.0 2.4 11.9 100.0 US-Y 55.9 0.5 4.5 39.1 100.0 36.6 60.2 3.2 100.0 48.8 47.8 Cat-1 75.0 9.0 6.5 9.5 100.0 44.4 52.2 3.4 100.0 53.7 42.5 Cat-7 71.8 6.8 7.2 14.2 100.0 47.4 48.8 3.8 100.0 60.0 35.7 Cat-1S 50.4 7.2 3.0 39.4 100.0 38.4 60.2 1.4 100.0 31.4 67.1 Cat-7S 55.8 7.8 4.9 31.5 100.0 44.4 52.8 2.8 100.0 48.7 48.6 E-Cat1 64.5 1.4 1.5 32.6 100.0 35.2 63.4 1.4 100.0 23.6 74.9 E-Cat2 65.8 1.4 1.2 31.6 100.0 37.1 62.6 0.3 100.0 23.0 76.6

Gaseous product distribution C1C4 68.6 C5C9 23.1 BTX 8.3 Total 100.0

Total gaseous product Parans 27.0 Olens 64.7

Yield (wt%) = (P(g)/Polymer feed (g)) 100.

Table 2), high reactivity was expected and a high yield of secondary products, parans, was observed. By contrast, the used catalysts with lower acidities and poisoned with heavy metals yielded predominantly ole-

nic products mostly in the carbon range of C3C6. Evidence of high REO stabilisation of steam deactivated catalyst, Cat-7S, was noted with a yield of balanced primary and secondary products (Figs. 4 and 5). During the

A.A. Garforth et al. / Current Opinion in Solid State and Materials Science 8 (2004) 419425 Table 3 Total plastic waste generated and recovered in Western Europe (kt) [*1] 1993 Total plastics waste Total plastics waste recovered Mechanical recycling Feedstock recycling Energy recovery %Total plastics waste recovered 16,211 3340 915 0 2425 21 1995 16,056 4019 1222 99 2698 26 1997 16,975 4364 1455 334 2575 26 1999 19,166 6183 1888 346 3949 32 2001 19,980 7357 2521 298 4538 37 2003 21,150 8230 3130 350 4750 39

423

25
C3= C4= C6=

20
C5=

15 10 5 0 ZSM5 USY Cat1 Cat7 Cat1S Cat7S ECat1 ECat2

Fig. 4. Selected olen products (wt%) at T = 450 C; C/P = 6:1.

25 C3 20 C5 15 10 5 0 ZSM5 USY Cat1 Cat7 Cat1S Cat7S ECat1 ECat2 C6 C4

dot) have addressed this issue but there remains the high energy and process costs of the feedstock recycling technology. Thermal and catalytic cracking although eective require signicant operating temperatures and are strongly endothermic, leading to large adiabatic temperature falls across reactors. However, improving the economics of the process itself by using exhausted zero-cost catalysts to produce a tailored product will help to make the process viable [83]. Oxidation methods, energetically more favourable, are at high temperature and have associated diculties such as dangerous emissions, product quality and expensive materials of construction. Hydrocracking studies have been limited to date and merit further study since the process is exothermic and can be carried out at signicantly lower temperatures. Another strategy worth considering is the targeting of large volume guaranteed waste streams, such as, from paper recycling plants to reduce collections costs. If this is linked with careful characterisation of this type of waste stream, the supply of a quality controlled polymer waste should be possible. Acknowledgements This work was performed with the nancial support of the University Putra Malaysia. Thank you to Dr. D.H. Harris (Engelhard Corporation) for catalysts and technical advice. Thanks also to Miss S. Maegaard for her contribution on thermal analysis and microscopy and also Mr. R.J. Plaisted of the Centre of Microporous Materials. Special thanks to Dr. D.L. Cresswell for useful discussion during the preparation of this review. References The papers of particular interest have been highlighted as: * of special interest.
[*1] Plastics Europe (Association of Plastic Manufacturers). An analysis of plastics consumption and recovery in Europe (20022003). Published in 2004.

Fig. 5. Selected paran products (wt%) at T = 723 K; C/P = 6:1.

steaming process in the FCC regenerator, catalysts will lose some of framework aluminium ions, creating defects in the crystals and leading to decreased catalyst acidities [87]. Nevertheless, with the presence of RE in the FCC catalysts, the steam dealumination is hindered. Therefore, with RE, the catalyst activities are maintained by reducing the amount of crystal destruction as seen here. 3. Conclusions Although feedstock recycling has been heralded as having great potential, polymer waste recycling levels have remained virtually unchanged at 350 kt since 1997 (see Table 3, [*1]). High costs associated with collection, sorting and transportation to provide a guaranteed supply of low chlorine-containing polymer waste to recycling sites remain signicant. Schemes such as Duales System Deutschland [*90] in Germany (green

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[70]

[71]

[72]

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[74]

[75] [76]

[77]

[78]

[79]

[80] [*81]

[82]

[83]

[84]

[*85]

[86] [87]

[88]

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