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From waste to valuable fuel: How microwave-heated pyrolysis can recycle waste
automotive engine oil

Conference Paper · January 2011

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 FROM WASTE TO VALUABLE FUEL: HOW
MICROWAVE-HEATED PYROLYSIS CAN RECYCLE
WASTE AUTOMOTIVE ENGINE OIL
Su Shiung Lam 1,2, Alan D. Russell 1, Howard A. Chase 1
1
Department of Chemical Engineering and Biotechnology,
University of Cambridge, New Museums Site, Pembroke Street,
Cambridge CB2 3RA, United Kingdom
2
Department of Engineering Science, University Malaysia
Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia
Introduction
The production of waste automotive engine oil (WO) is
estimated at 24 million tons each year throughout the world, posing a
significant treatment and disposal problem for modern society. WO,
containing a mixture of low and high molecular weight aliphatic and
aromatic hydrocarbons, also represents a potential source of high-
value fuel and chemical feedstock. The preferred disposal option in
most countries is incineration and combustion for energy recovery,
though vacuum distillation and hydro-treatment have been researched
to recycle this waste [1]. However, these disposal routes are
becoming increasingly impracticable as concerns over environmental
pollution, and additional cost, sludge and wastewater disposal are
recognized due to the undesirable contaminants present in WO [1, 2].
As part of the growing interest in waste recycling, alternative
treatments have been investigated with the aim of recovering both the
energetic and chemical value of the WO. Pyrolysis techniques have
recently shown great promise as an economic and environmentally
disposal method for WO [3-5] – the waste material is thermally
cracked and decomposed in an inert atmosphere, with the resulting
pyrolysis oils and gases able to be used as a fuel or chemical
feedstock, and the char produced used as a substitute for activated
carbon, though the use of this technology is not widespread as yet.
The pyrolysis-oil is of particular interest due to its easy storage and
transportation as a liquid fuel or chemical feedstock. The oil can be
treated and catalytically upgraded to transport-grade fuels, or added
to petroleum refinery feedstocks for further processing and upgrading
[3]. While most WO pyrolysis studies have been focused on
conventional electric-resistance-heated and electric-arc-heated
pyrolysis [4, 6], there are very few studies about the pyrolysis oil
generated during microwave-heated pyrolysis of WO. Microwave-
heated pyrolysis has recently shown promise as a route for the
treatment and recycling of the WO [3]; the advantages of microwave-
heated-pyrolysis have been elaborated in previous work [5] and will
not be duplicated here. In this process, WO is mixed with a highly
microwave-absorbent material such as particulate carbon; as a result
of microwave heating the oil is thermally cracked in the absence of
oxygen into shorter hydrocarbon chains. The resulting gaseous
products are subsequently recondensed into pyrolysis oils of different
composition depending on the characteristics of the input substances
and reaction conditions.
This study investigates the characteristics of the pyrolysis oils
produced from microwave-heated-pyrolysis of WO collected from
different sources (unleaded gasoline and diesel automobile engines,
and mixtures from a service station), with a focus on their elemental
and hydrocarbon composition, and potential fuel properties. The
evaluation of the influence of the nature of the different waste oils is
important to assess the technical feasibility and applicability of using
the pyrolysis process as a route to energy recovery/feedstock
recycling from WO. There have been no reports on the composition
of oils resulting from microwave-heated pyrolysis of WO, although a
few studies have been performed on biomass pyrolysis [7, 8], and
conventional-electric-heated pyrolysis of WO [9, 10].
Prep. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2011, 56 (1), 19
Proceedings Published 2011 by the American Chemical Society
Experimental
Materials. Shell 10W/40 motor oil was used throughout the
experiments. The WO was collected from three sources: the
crankcase of both a gasoline and a diesel engine run on unleaded
fuel, and mixtures of used automotive oils sampled from a
garage/waste recycling centre. Before pyrolysis, the oil samples were
filtered such that the size of any remaining particulates (e.g. metal
particles, carbon soot, other impurities etc) was less than 0.45 µm;
volatiles and water were eliminated by heating at 110ºC; samples
were examined for hydrocarbon composition by Gas
Chromatography – Mass Spectrometry (GC-MS); the C, H, N, S, O
content were obtained by elemental analysis; calorific value was
determined by Differential Scanning Calorimeter (DSC). Particulate
carbon (TIMREX FC250 Coke, TIMCAL Ltd, Bodio, Switzerland)
was used as a microwave absorbent to heat the WO; this was pre-
heated to 800ºC for 50 minutes to remove any water and sulphur-
containing compounds).
Experimental details. The experimental apparatus and method
developed and used during this investigation have been described in
detail in previous work [5], though modifications were made to the
apparatus to enhance the collection and quality of pyrolysis-oils and
noncondensable-gases generated from the pyrolysis. Improvements
were achieved by installing a mixed-cellulose-ester-membrane filter
(ME-filter, 0.45 m ME25, Schlecher & Schuell, Germany) to
remove any metallic solid residues trapped in the pyrolysis-volatiles
before they pass through the condensation system. The refined
experimental apparatus is shown in Figure 1.
1) Microwave oven
2) Reactor
3) Motor stirring system
4) Injecting vessel and pump
5) ME filter
6) Condenser (60ºC)
7) Condenser (25ºC)
8) Condenser (0ºC)
9) Cold trap (about -70ºC)
10) Main collecting vessel
11) 2nd collecting vessel
12) Cotton wool filter
13) Milipore 7015 pump
14) Gas bag
15) Pressure gauge
16) Pressure relief valve.
Figure 1. Schematic layout of microwave-heated pyrolysis system
Briefly, microwave-heated pyrolysis of WO was performed in a
bell-shaped quartz reactor (180x180x180 mm) filled with 1 kg of
particulate carbon, which is stirred and heated by a 5 kW microwave
oven over a range of pyrolysis temperatures (250 to 700ºC) and purge
gas flows (0.1 to 0.75 L/min) to understand the influence of these
process conditions on the final pyrolysis oils obtained; N2 purge-gas
was vented through the system to maintain the apparatus in an inert
nitrogen atmosphere. WO sample was continuously added to the
reactor at a constant feeding rate of about 1 kg/h over a period of
about 2 hours as soon as the target pyrolysis temperature was
achieved. Gases, solids, and vapors generated in the pyrolysis
reaction, termed generally as pyrolysis volatiles (consisting of a
hydrocarbon mixture of gases, liquids, and solids existing in a vapor
phase), leave the reactor, and either condense into pyrolysis oil or are
sampled as noncondensable-gases before vented from the system.
The yield of residue material, pyrolysis oil, and noncondensable
gases were determined and analyzed by GC-MS (liquid and gas
fractions only), elemental analyzer (liquid only), and DSC (liquid
only) to identify their chemical composition. The data recorded is the
average of the results obtained from three valid repeated runs
performed under identical conditions.
Temperature measurement and analytical methods. The
temperature measurement and its limitations, and the relevant
 1
analytical methods are not the main focus of this preprint and will be Alkylbenzenes – ethylbenzene, propylbenzene, methylethybenzene. 2 The
presented if required later. The detailed descriptions of some of the density of gasoline lies between 720 and 775 kg/m3 [11, 12] 3 CV – Calorific
analytical methods have been reported in previous work [3]. value, also regarded as higher heating value (HHV) in literature. 4 The
calorific value of fossil fuels (i.e. kerosene, fuel oil, gasoline, diesel) lies
Selected Results and Discussion
between 45.5 and 47.8 MJ/kg [6, 13]
GC-MS analysis revealed that linear and branched paraffins with
Table 2 and Table 3 show the liquid yield, elemental
carbon chain length in the C20 to C40 range were the predominant
composition, content of valuable hydrocarbons, density and calorific
hydrocarbon structures in the composition of the waste oils collected
value (CV) of the pyrolysis oils obtained. The microwave-heated
from different sources (Table 1).
pyrolysis generated a 85-88 wt% yield of a condensable pyrolysis oil
with a low sulphur and oxygen content, and a density and calorific
Table 1. Main Compounds Identified for Waste Oils (%)
value comparable to traditional liquid fuels derived from fossil fuel.
Gasoline Diesel Recycling
engine engine centre Examination of the composition of the oils showed the formation of
Linear (<C20) 8.2 10.1 8.7 light paraffins and aromatic hydrocarbons that could also be used as a
Linear and branched paraffins 90.2 87.9 89.4 chemical feedstock. The nature and the source of collected waste oils
(C20-40) seemed to have little influence on the chemical composition and fuel
Double bonds 0.1 0.1 0.1 properties of the pyrolysis oils, indicating the potential of this
Cyclics 0.3 0.5 0.5 pyrolysis process in treating ‘real-world’ mixtures of waste oils
Aromatics 1.2 1.4 1.3 collected from different sources.

The waste oil produced a fairly pale yellowish-gold oil Conclusions

hydrocarbon product with small amounts of a black phase (Figure 2).
It is thought that the light black phase was formed from the minor
quantities of very fine carbon particles originally present in the
pyrolysis reactor; they are likely to escape from the reactor and co-
migrate with the pyrolysis oil. These carbon particles can be easily
removed by filtration.
Microwave-heated pyrolysis of waste automotive engine oils
produces significant amounts of liquid hydrocarbon oils containing
BTX and benzene derivatives; these products can be treated and used
as either an energy source or industrial feedstock. It is evident that
microwave-induced pyrolysis has huge potential as a means of
recovering commercially valuable products from problematic waste
oil, in addition to diverting waste streams from current yet
environmentally-harmful disposal techniques such as landfilling and
incineration.
Acknowledgement. We thank Enval Ltd, the Public-Service-
Department of Malaysia Government, and University Malaysia
Terengganu for the advice, material, and financial support of this
project.

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Prep. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2011, 56 (1), 20

Proceedings Published 2011 by the American Chemical Society
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Prep. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2011, 56 (1), 21

Proceedings Published 2011 by the American Chemical Society
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