Korean J. Chem. Eng.

, 20(4), 693-697 (2003)

Thermal and Catalytic Degradation of Waste High-density Polyethylene (HDPE)

Using Spent FCC Catalyst
Kyong-Hwan Lee†, Sang-Gu Jeon, Kwang-Ho Kim, Nam-Sun Noh, Dae-Hyun Shin, Jaehyeon Park,
Younghwa Seo*, Jurng-Jae Yee** and Geug-Tae Kim***

Clean Energy Research Department, Korea Institute of Energy Research, 71-2 Jang dong, Yusong ku, Daejeon 305-343, Korea
*Dept. of Environmental Engineering, Suwon Science College, Suwon 445-742, Korea
**Faculty of Architectural Design & Engineering, Dong-A University, Busan 604-714, Korea
***Dept. of Chemical and Polymer Engineering, Hannam University, Daejeon 306-791, Korea
(Received 27 November 2002 • accepted 28 February 2003)

Abstract−− Thermal and catalytic degradation using spent fluid catalytic cracking (FCC) catalyst of waste high-density
polyethylene (HDPE) at 430 oC into fuel oil were carried out with a stirred semi-batch operation. The product yield
and the recovery amount, molecular weight distribution and paraffin, olefin, naphthene and aromatic (PONA) distribu-
tion of liquid product by catalytic degradation using spent FCC catalyst were compared with those by thermal
degradation. The catalytic degradation had lower degradation temperature, faster liquid product rate and more olefin
products as well as shorter molecular weight distributions of gasoline range in the liquid product than thermal
degradation. These results confirmed that the catalytic degradation using spent FCC catalyst could be a better alternative
method to solve a major environmental problem of waste plastics.
Key words: Thermal & Catalytic Degradation, Spent FCC Catalyst, Waste HDPE, Liquid Product Distribution

INTRODUCTION cation processes, acidic catalysts such as zeolite Y, ZSM-5, silica-

alumina and mordenite mainly produce C5-C12 light hydrocarbon
The consumption of various plastic materials has been growing for the range of gasoline, whereas the thermal process with use of
continuously due to their versatility and low cost. Accordingly, the non-acidic catalysts produces C12-C22 compounds with the range of
waste arising from this expanding use of waste is enormous [Patel kerosene+diesel [Walendziewski, 2002; Buekens and Huang, 1998;
et al., 1998]. However, the recycling of waste plastics is a small per- Sakata et al., 1999; Park et al., 2002]. Also, the combination of py-
centage, whereas the large majority is landfilled or incinerated, caus- rolysis and catalytic reforming was known as a more efficient meth-
ing a severe environmental problem due to their chemical inert- od for processing large amounts of waste plastics [Songip et al.,
ness. Their impact on the environment needs to be mitigated. Ade- 1993].
quate alternative methods for recycling of waste plastics are needed In this study, thermal and catalytic degradations using spent FCC
for producing higher value products. The thermal and catalytic de- catalyst of waste HDPE, which can easily produce the low quality
gradation processes of waste plastics are accepted alternative meth- components, are compared. Spent FCC catalyst used in the cata-
ods, both economically and environmentally [Walendziewski, 2002; lytic degradation process is thrown away from the commercial FCC
Bockhorn et al., 1998]. process in Korea as a few ten thousand tons per year, although it
Pyrolysis of waste plastics could be proposed to produce the oil has high activity. It means that this catalyst can be reused in the liq-
feedstocks in the petroleum industry as a feed for a petroleum re- uid-phase cracking process. Accordingly, spent FCC catalyst with
finery catalytic cracker and steam cracker in the production of gaso- a low cost is utilized in the catalytic degradation process for waste
line and various alkenes. This method is a simple thermal process plastics into oil recovery. FCC catalyst, which is mainly composed
in which polymers at high temperature are melted and broken down of zeolite and matrix such as alumina and silica-alumina, is pre-
to smaller molecules as the mixture products of gaseous, liquid and pared by spray drier to make a strong fine powder type. Catalytic
solid hydrocarbons [Pinto et al., 1999]. However, these products degradation enables lowering of reaction temperature as well as boil-
are not good as fuels due to their low quality. Consequently, the in- ing temperature range, compared to thermal degradation. In the prod-
teresting method of polymer utilization is catalytic degradation. This uct distributions for the two processes, the yields, accumulative prod-
is to convert the melted polymer to light carbon derived materials, uct amount, PONA distribution and molecular weight distribution
constituting high quality components, in the presence of degrada- are discussed.
tion catalysts [Bagri and Williams, 2002; de la Puente et al., 2002;
Jeong et al., 2001; Lee and Shin, 2003; Park et al., 2002]. For appli- Table 1. Physical properties of waste HDPE
Items Mna Mwb Mw/Mn
†
To whom correspondence should be addressed.
Values 22550 367534 16.3
E-mail: [email protected]
a
‡
This paper is dedicated to Dr. Youn Yong Lee on the occasion of his Number average molecular weight.
b
retirement from Korea Institute of Science and Technology. Weight average molecular weight.
693
694 K.-H. Lee et al.

Table 2. Physical properties of spent FCC catalyst

Surface area (m2/g) Pore volume (cm3/g) BJH* desorption average
Items
Total Micro- Meso- Total Micro- Meso- pore diameter (Å)
Values 151 76 75 0.2533 0.0303 0.2230 39.95
*BJH means the Barrett, Joyner and Halenda method.

EXPERIMENTAL uct, as a function of lapse time, for thermal and catalytic degrada-
tion of waste HDPE at 430 oC. In the case of thermal degradation, the
Waste HDPE used as raw material was palletized 1/8 inch (O.D.) liquid product did not appear until the reaction temperature reached
X a few cm (L) and its physical properties are presented in Table 1. 430 oC. After the lapsed time passed 30 min at constant tempera-
Spent FCC catalyst of a few ten-micrometer sizes was treated with ture of 430 oC, the initial liquid product appeared. On the other hand,
air stream during 4 h at 400 oC, before being used in this experi- the catalytic degradation produced initial liquid product at a reac-
ment. The surface area and pore volume of this catalyst were ob- tion temperature of about 350 oC. From these results, an applica-
tained from nitrogen adsorption isotherms measured at liquid-nitro- tion of spent FCC catalyst for the degradation of waste plastic shows
gen temperature (Micromeritics, ASAP-2000). Total surface areas much faster liquid products in comparison with the thermal degra-
were determined by using the BET equation within a relative pres- dation in the absence of catalyst, due to more degradation of heavy
sure of 0.2, and a distinction between micropores and mesopores molecules by the active sites of catalyst. In addition, the catalytic
was made using the T-plot method. Its physical properties are pres- degradation showed much higher rate of oil product than thermal
ented in Table 2. degradation. If waste plastic in the degradation process is conducted
The degradation experiment of waste HDPE was carried out in with short residence time in a continuous stirred tank reactor, more
a stirred semi-batch reactor at 430 oC under atmospheric pressure partial degradation of plastic can occur by thermal degradation, while
[Lee et al., 2001]. Waste HDPE of 200 g and catalyst of 10 g were the rest of the feed can be built heavy oil like wax. It is necessary
charged in the reactor. After charging, it was purged with a nitro- to notice that the heavy oil obtained by the partial degradation of
gen flow of 20 cc/min. The temperature of the reactor increased up plastic is similar to coke.
to 430 oC with a heating rate of about 7 oC/min and maintained at 3. PONA Distribution for Liquid Product
430 oC for 4 h. The impeller speed was 200 RPM. Gas products The PONA distribution of liquid product obtained from thermal
were vented after cooling by condenser to 7 oC. Liquid products, and catalytic degradation of waste HDPE at 430 oC is shown in Figs.
as a function of lapse time, were measured by weight. Each liquid 2 and Fig. 3, respectively. In Figs. 2, 3, 4 and 5, the fraction in the
product was quantified and qualified by gas chromatography, using Y-axis means the fraction of weight percentage. In the case of ther-
FID and MS detectors [Lee et al., 2002]. Residue yield was deter- mal degradation, paraffins and olefins as the main products con-
mined after the reaction was finished and defined as the ratio of the sisted of around 40%, both, and naphthenes show around 15%, and
solid amount produced to the initial reactant amount. Gas yield was also aromatic compounds hardly appeared in the liquid product.
calculated from the difference between 100 and total yield of liquid This tendency is not changed, although the lapse time of reaction is
and solid products.

RESULTS AND DISCUSSION

1. Product Yield
Table 3 shows the product yields obtained from thermal and cat-
alytic degradation using spent FCC catalyst of waste HDPE at 430
o
C. In the case of product distribution of catalytic degradation, the
yield of gaseous products did not differ from that of thermal degra-
dation, but the yield of oil products was increased to about 80%
whereas that of residue was reduced to about 1%. These results in-
dicate that the heavier residues were decomposed into lighter oil prod-
uct by catalytic degradation.
2. Accumulative Amount of Liquid Product
Fig. 1 shows the accumulative amount distribution of liquid prod-

Table 3. Yields of gas, liquid and residue obtained from thermal

and catalytic degradation of waste HDPE at 430 oC
Gas (%) Liquid (%) Residue (%)
Fig. 1. Accumulative amount of liquid products obtained from
Thermal degradation 20.0 75.5 4.5 thermal and catalytic degradation using spent FCC cata-
Catalytic degradation 19.4 79.7 0.9 lyst of waste HDPE at 430 oC.
July, 2003
 Catalytic Degradation of Waste HDPE Using Spent FCC Catalyst 695

Fig. 2. Fractions of paraffin, olefin, naphthene and aromatic prod- Fig. 4. PONA distributions of liquid products obtained from ther-
ucts obtained from thermal degradation of waste HDPE mal degradation of waste HDPE at 430 oC (lapse time=102
at 430 oC. min).

matic compound fraction was increased to about 5% by the arom-

atization of olefin in the cracked product. The spent FCC catalyst
used as a degradation catalyst of waste HDPE markedly increased
the fraction of olefin and aromatic components with comparatively
high octane number in the liquid products, due to the olefin prod-
uct from the primary cracking of high molecular weight polyethyl-
ene and the aromatic product from the cyclization of olefin inter-
mediates within pores of catalyst as shape selectivity [Lee et al.,
1998].
4. Molecular Weight Distribution for Liquid Product
Characteristics of molecular weight distribution of liquid prod-
uct obtained by the thermal degradation of waste HDPE at a lapse
time of 102 min are presented in Fig. 4. Both paraffin and olefin,
as a main liquid product, were distributed in a wide range of mo-
lecular weight ranging between 80 and 400, due to the random-chain
scission of long hydrocarbon molecules. They showed a similar
type of molecular weight distribution with bimodal structure. On
the contrary, naphthene products that were obtained by the cycliza-
tion of carbonium ion intermediates from paraffin and olefin com-
ponents showed a narrow molecular weight distribution and one
Fig. 3. Fractions of paraffin, olefin, naphthene and aromatic prod- modal structure, which are the light oil products below 150 of mo-
ucts obtained from catalytic degradation of waste HDPE lecular weight with the single ring derivatives.
on spent FCC catalyst at 430 oC. Molecular weight distributions of liquid product obtained from
the catalytic degradation of waste HDPE at a lapse time of 82 min
are shown in Fig. 5. For each product group, molecular weight dis-
increased to about 240 min. On the other hand, the catalytic degra- tributions clearly show a different tendency with those of thermal
dation as shown in Fig. 3 produced much more olefins, which con- degradation process as shown in Fig. 4. More light oil products in
sisted of around 80% as a main product. For the catalytic reaction the range of gasoline were obtained by the catalytic degradation.
mechanism, the interaction between the active sites of acidic cata- Spent FCC catalyst as a cracking catalyst improved the conversion
lyst and the hydrogen atoms from linear polyethylene makes the of heavy reactant to obtain the light oil with high quality product.
carbenium ions and then undergoes β-scission to form the olefin This means that the molecular weight distribution of liquid product
products [Seddegi et al., 2002]. The paraffin fraction in the cata- can be easily controlled by pore size distribution in the spent FCC
lytic degradation process was decreased to about 15%, whereas aro- catalyst, including the micropore of zeolite and the mesopore of
Korean J. Chem. Eng.(Vol. 20, No. 4)
696 K.-H. Lee et al.

tion with about 80%, while the thermal degradation process showed
the bimodal product distribution and also higher paraffin as well as
olefin fraction.

ACKNOWLEDGMENTS

This work was performed with the financial assistance of Indus-

trial Waste Recycling R & D Center (Project No. A-A-1), which is
21 C Frontier Projects of Korea Ministry of Science and Technology.

REFERENCES

Bagri, R. and Williams, P. T., “Catalytic Pyrolysis of Polyethylene,” J.

Anal. Appl. Pyrol., 63, 29 (2002).
Bockhorn, H., Hornung, A. and Hornung, U., “Stepwise Pyrolysis for
Raw Material Recovery from Plastic Waste,” J. Anal. Appl. Pyrol.,
46, 1 (1998).
Buekens, A. G. and Huang, H., “Catalytic Plastics Cracking for Recov-
ery of Gasoline-range Hydrocarbons from Municipal Plastic Wastes,”
Res. Con. Recycl., 23, 163 (1998).
Fig. 5. PONA distributions of liquid products obtained from cat- de la Puente, G., Klocker, C. and Sedran, U., “Conversion of Waste Plas-
alytic degradation of waste HDPE at 430 oC (lapse time= tics into Fuels: Recycling Polyethylene in FCC,” Appl. Catal. B, 36,
82 min). 279 (2002).
Jeong, S.-W., Kim, J.-H. and Seo, G., “Liquid-phase Degradation of
silica-alumina [Lee et al., 1998]. Accordingly, the improved acces- HDPE over Alkali-treated Natural Zeolite Catalysts,” Korean J.
sibility of the heavy reactant into the mesopore and also that of the Chem. Eng., 18, 848 (2001).
cracked intermediates into the micropore may increase the reaction Lee, K.-H., Ha, B. H. and Lee, Y. W., “Catalytic Cracking of Vacuum
rate. This result suggests that the large molecule reactants were firstly Gas Oil on the Dealuminated Mordenites,” J. Catal., 178, 328 (1998).
cracked to small intermediates on external surface of catalyst or with- Lee, K.-H., Ha, B. H. and Lee, Y. W., “Catalytic Cracking of Vacuum
in mesopores of silica-alumina and then the cracked intermediates Gas Oil over the Modified Mordenites and Y-type Zeolites Mixed
were broken down to smaller product in micropore of zeolite. The with Alumina,” Ind. Eng. Chem. Research, 37, 1761 (1998).
main product was olefin components, which is the light oil product Lee, K.-H., Kim, S.-K. and Shin, D.-H., “Catalytic Decomposition of
with molecular weight below 200 in the range of gasoline. Among Waste HDPE over Zeolite, in a Semi-batch Reactor,” J. Korean Solid
the olefin products, the C7 components showed a maximum frac- Wastes Eng. Soc., 18(5), 442 (2001).
tion of above 20%. The fraction of olefin products sharply decreased Lee, K.-H., Noh, N.-S., Shin, D.-H. and Seo, Y. H., “Comparison of Plas-
with the increase of the molecular weight. Other components pro- tic Types for Catalytic Degradation of Waste Plastics into Liquid
duced a little fraction. This result led to the conclusion that the cat- Product with Spent FCC Catalyst,” Polym. Degrad. Stab., 78, 539
alytic degradation using spent FCC catalyst showed a better result (2002).
on the production of light oil from waste plastic. Lee, K.-H. and Shin, D.-H., “Catalytic Degradation of Waste Polyolefinic
Polymers Using Spent FCC Catalyst with Various Experimental Var-
CONCLUSIONS iables,” Korean J. Chem. Eng., 20, 89 (2003).
Patel, M. K., Jochem, E., Radgen, P. and Worrell, E., “Plastics Streams
Both thermal and catalytic degradation using spent FCC catalyst in Germany-an Analysis of Production, Consumption and Waste
were compared for the liquid-phase reaction of waste HDPE in a Generation,” Res. Con. Recycl., 24, 191 (1998).
stirred semi-batch reactor at 430 oC. Park, J. J., Park, K. N., Park, J.-W. and Kim, D. C., “Characteristics of
1. Thermal and catalytic degradation of waste HDPE convert it LDPE Pyrolysis,” Korean J. Chem. Eng., 19, 658 (2002).
to fuel oil with over 75% yield. However, the catalytic degradation Park, J. R., Yoon, J. H. and Park, D. W., “Catalytic Recycling of the Mix-
process produces much less residue content than that from thermal ture of Polypropylene and Polystyrene,” Polym. Degrad. Stab., 76,
degradation. 61 (2002).
2. In comparison to the thermal degradation process, the cata- Pinto, F., Costa, P., Gulyurtlu, I. and Cabrita, I., “Pyrolysis of Plastic
lytic degradation process results in lowering of the degradation tem- Wastes. 1. Effect of Plastic Waste Composition on Product Yield,” J.
perature of waste HDPE as well as the boiling temperature in the Anal. Appl. Pyrol., 51, 39 (1999).
liquid product. Furthermore, the faster rate of oil product is obtained Sakata, Y., Uddin, M. A. and Muto, A., “Degradation of Polyethylene
from the catalytic degradation process. and Polypropylene into Fuel Oil by Using Solid Acid and Non-acid
3. In the liquid product distribution, the catalytic degradation pro- Catalysts,” J. Anal. Appl. Pyrol., 51, 135 (1999).
cess produced mostly the products below 150 of molecular weight Seddegi, Z. S., Budrthumal, U., Al-Arfaj, A. A., Al-Amer, A. M. and
like the components of gasoline range and much higher olefin frac- Barri, S. A. I., “Catalytic Cracking of Polyethylene over All-silica
July, 2003
 Catalytic Degradation of Waste HDPE Using Spent FCC Catalyst 697

MCM-41 Molecular Sieve,” Appl. Catal. A, 225, 167 (2002). 153 (1993).
Songip, A. R., Masuda, T. and Kuwahara, H., “Test to Screen Catalysts Walendziewski, J., “Engine Fuel Derived from Waste Plastics by Ther-
for Reforming Heavy Oil from Waste Plastics,” Appl. Catal. B, 2, mal Treatment,” Fuel, 81, 473 (2002).

Korean J. Chem. Eng.(Vol. 20, No. 4)