PYROLYSIS OF HIGH DENSITY POLYETHYLENE (HDPE) WASTE PRODUCTS

INTO USEFUL FUELS

Abdulkareem S. A. 1 and Eleburuike N. A. 2+
1
Department of Chemical Engineering, University of Ilorin, P.M.B 1515, Ilorin, Nigeria;
2
Department of Chemical and Geological Sciences, Al-Hikmah University, P.M.B 1601,
Ilorin, Nigeria
E-mail: naeleburuike@gmail.com; TEL: +2348059569045
+ Corresponding author

ABSTRACT
High density polyethylene, HDPE was pyrolyzed in a self-designed stainless steel
laboratory reactor to produce useful fuel products. HDPE waste (discarded yoghurt bottles)
was completely pyrolyzed at 430-5200C for 21/2 hours, to obtain solid residue, liquid fuel oil,
and flammable gaseous hydrocarbon products. Presently, due to technical limitation, the
gaseous products (lower hydrocarbons, (C1 – C4) were eluted without collection. The resulting
liquid product was analyzed by gas chromatographic-mass spectrometric (GC-MS) analysis.
The GC-MS analysis result showed that the liquid product contained hydrocarbons in the
range of C8-C24 which were all distributed between paraffinic and olefinic hydrocarbons. The
most abundant compounds in the liquid product are the C16 – C25 hydrocarbons which falls
within the diesel (gas oil) range.
Keywords: Pyrolysis, High Density Polyethylene, Fuels

INTRODUCTION
Uncontrolled disposal of waste plastics in to the environment is becoming undesirable
due to population increase, increased use of polymeric materials for packaging and other
purposes, rising costs and the extremely poor biodegradability of commonly used polymers.
There is therefore a need for effective plastic waste management techniques that will convert
these discarded polymer waste products to economically useful and environmentally friendly
by-products. The approaches that have been proposed for recycling of waste plastics include:
(i)Primary recycling referring to the “in-plant” recycle of the scrap material. (ii)Mechanical
recycling which usually involves separating the thermoplastic wastes from its associated
contaminants and heating to their melting temperatures, usually around 1500C, followed by
injection and re-moulding of the recovered polymer (Achilias and Karayannidis, 2004 and
Association of Plastic Manufacturers in Europe, 2004). (iii)Chemical or feedstock recycling
which involves the transformation of plastic polymers by means of heat or chemical agents
leading to total depolymerization to the monomers, or partial degradation to other secondary
valuable materials like hydrocarbon products that may be used in the production of new
polymers, refined chemicals or fuels (Achilias and Karayannidis, 2004, Aguado and Serano,
1999 and Tukker, 2002). (iv) Energy recovery, which is an effective way to reduce the
volume of organic materials by incineration (Scheirs, 1998).
Among the recycling techniques, incineration meets with strong societal opposition
and mechanical recycling can be carried out only on single-polymer waste streams. However,
the most attractive method, in accordance also with the principles of sustainable development
is chemical recycling or tertiary recycling which converts waste polymers to either the
original monomers or other valuable chemicals. These products are useful as feedstock for a
variety of downstream industrial processes or as transportation fuel (Achilias et al., 2008).
 Pyrolysis, which is a chemical recycling method, involves the degradation of
polymeric materials by heating in the absence of oxygen to form short-chain compounds. The
process is usually conducted at temperatures between 500-8000C and results in the formation
of a carbonised char and a volatile fraction that may be separated into condensable
hydrocarbon oil and a non-condensable high calorific value gas (Aguado and Serano, 1999).
Among the different processes under study, those dealing with polyolefins are
predominant since this type of polymers account for more than 70% of the total plastic
content in the municipal solid waste stream (MSW) (Aguado et al., 2002). Therefore, this
study aimed at converting high density polyethylene waste (discarded yoghurt bottles) into
useful, added value, fuel oil products through pyrolysis.

EXPERIMENTAL
Sample Collection and Preparation
The polyalkene, HDPE, particularly discarded yoghurt bottles, were obtained from
household and municipal wastes. Then, they were washed, dried and shredded into small sizes
for easy handling and faster reaction.

Pyrolysis of HDPE
The pyrolysis reactions were carried out in an inert atmosphere of Nitrogen. 100g of
shredded HDPE was placed in a cylindrical stainless steel reactor (i.d. 12cm and length 22cm)
and the reactor was covered air tight. The reactor was purged with nitrogen gas for 20 minutes
and then heating commenced. The reaction temperature was measured and controlled by
means of a thermocouple. After 50 minutes and at about 4240C, evolution of gas started
slightly. At about 60 minutes, temperature increased to 4340C, evolution of vapour increased
largely and liquid products (the relatively higher molecular weight gases that had condensed
while passing through the pipe to the collection flask) started dropping. Liquid and gaseous
products leaving the reactor were separated using an ice trap which condensed all the
condensable hydrocarbon gases at its temperature (i.e. 40C) into liquids. The condensed
product that was retained in the ice trap was collected and weighed as the liquid product after
the reaction. Heating and product collection continued until at 2hr 30min and 5200C, after
which evolution of vapour effectively ceased. The residue solidified to grease and its weight
was obtained. The gaseous product that was non-condensing at 40C was eluted without
collection and its weight was found from the difference between the liquid and solid products
and the weight of HDPE feed (Uddin et al., 1997).

GC-MS Analysis of Liquid Products

The liquid product of pyrolysis of HDPE was characterized using Gas
chromatographic – Mass spectrometric (GC-MS) analysis which produced chromatogram that
contain about 29 peaks and each of these peaks represents an identified compound.

RESULTS AND DISCUSSION

Products of Thermal Cracking of HDPE
The percentage yield of liquid, gaseous and solid products obtained from the thermal
cracking of HDPE is given in Table 1.
Table 1. Yield of Products of Thermal Cracking, Wt(%)
Products Yield Wt(%)
Liquid 50.64±0.35
Gas 15.74±0.40
Solid 33.62±0.31

Three products were obtained from the cracking reactions and were classified as: gas
products (high calorific value gas, combustible when contacted with flame), liquid products,
and solid-like products in form of grease. The products above are similar to the products
earlier reported in the literature (Ortega et al., 2006 and Gorka et al., 2007).
The liquid product obtained was very light and oily. It had the appearance of common
fuels such as kerosene and petrol, but it had a characteristic smell that is different from either
petrol or kerosene. The solid residue product of thermal cracking was very soft and grease-
like. The gaseous products obtained from this reaction consisted of light gases that were non-
condensing at 40C, and they could be assigned to lower hydrocarbons in the range of C 1-C4
(boiling point: <200C) which normally exist in the gaseous form at the collection and room
temperature (Wittcoff and Reuben, 1996).

Result of GC-MS Analysis of Liquid Products

Fig.1 below presents the chromatogram obtained from the GC-MS analysis of the
liquid product of pyrolysis of HDPE.

Fig. 1: GC-MS Chromatogram of the Liquid Product of Pyrolysis of HDPE

 The percentage yield of each of the identified compounds was calculated by measuring the
height (cm) of the line under which they appear as a percentage of the total height of the peaks. The
percentage abundance of the identified compounds is reported in Tables 2 and 3.

Table 2. Hydrocarbons and their Relative Abundance in the Liquid Product

Suggested Petroleum
Hydrocarbons Relative Abundance (%) Fraction
C8-C9 6.46 Petrol (Gasoline)
C10-C15 32.62 Kerosene
C16-C25 60.92 Diesel (Gas Oil)

Table 3. Percentage Abundance of Paraffins and Olefins in the Liquid Product

C8-C9 C10-C15 C16-C24
Paraffins 3.62 16.7 41.48
Olefins 2.84 15.92 19.44

The GC-MS analysis result characterized the liquid product of pyrolysis by peaks in
the chromatogram which were assigned to paraffinic and olefinic hydrocarbons in the carbon
number range of C8-C24. More parraffins were produced than olefins as shown in table 3 and
they were mostly straight chain. Only a few branched-chain hydrocarbons were produced.
Also, the most abundant compounds are those in the C16-C25 range which correspond to gas
oil (diesel) fraction. In a previous study reported in the literature (Ortega et al., 2006), liquid
products obtained were classified as: gasoline (C5-C12), turbosine (C13-C14), kerosene (C15-
C17), gas oil (C18-C28), and fuel oil (C29-C44). Also, in another report, product in the C9-C25
range obtained was analyzed into fractions and a conclusion was made that the products
conform to the hydrocarbon products from refineries which include: petrol, C4 to C12;
kerosene, C10 to C18; diesel, C15 to C25; fuel oils, C20 to C50 (Low et al., 2001). Therefore,
from the GC-MS analysis results, we can infer that the liquid products obtained in this work
will also conform to those in the main hydrocarbon products from refineries and are a blend
of petrol (gasoline), C5 to C9, boiling point range: 20-1750C; kerosene, C9 to C16, 175--2750C;
and diesel (gas oil), C15 to C25, 200-4000C (Wittcoff and Reuben, 1996). This suggested that
the liquid products produced in this work could be suitable either for adding to the existing
fuels or as intermediate feedstock in a refinery.

CONCLUSION
Recycling of HDPE into useful added value fuel products has been achieved through
pyrolysis in a self-designed stainless steel laboratory reactor. Liquid products obtained have a
mainly aliphatic composition consisting of a series of paraffins and olefins of different carbon
numbers. They have compositions overlapping those of existing hydrocarbon fuels such as
petrol (gasoline), diesel (gas oil) and kerosene and hence, possess a great potential to be
recycled back into the petrochemical industry as a feedstock for the production of new
plastics or refined fuels.

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