Chapter 27

Tyre Pyrolysis by Using Nano-catalyst

to Improve Energy Efficiency and Fuel
Quality

Chandresh Gabani, Yash Ranchh, Riddhi Barodia

and Pandian Sivakumar

Abstract Scrap tires are harmful waste because they are non-biodegradable, emit
toxins, create disposable problems and produces dioxines when burnt.
Technological conversion of scrap tires to fuel by pyrolysis exists. This study is
about taking it one step further by using nano Calcium Oxide (CaO) catalyst
derived from mineral industry waste. The nano-catalyst was synthesized from waste
and characterized by XRD, FTIR, TGA, BET analysis. From the laboratory studies
it was observed that this catalyst reduces the associated pollution problems and
increases the energy economy. The fuel thus produced had reduced sulphur due to
the formation of sulphated salts during pyrolysis. Further, it is intended towards
optimizing the process to produce quality fuel. The fuel produced was recovered in
three distinct product streams and characterized as per ASTM test methods. Thus,
this advanced process gives an integrated solution which is environmentally and
economically superior for conversion of waste tyres to fuel.

Keywords Nano-catalyst
Pyrolysis fuel
Characterization
Energy efficiency

27.1 Introduction

The disposal of solid waste is a major environmental pollution contributor across

the globe. This waste mainly includes non-biodegradable high-density materials
such as rubber and plastic waste, municipality solid waste, industrial waste, agri-
culture waste and their generation is increasing at higher rates day by day [1]. Waste
management codification demands an economical and environmental system that
can solve the waste disposal problem.
One of the major source of solid waste management problem is disposal of scrap
tyres because they are non biodegradable, artificial long chain hydrocarbon con-

C. Gabani
Y. Ranchh
R. Barodia
P. Sivakumar (&)

School of Petroleum Technology, Pandit Deendayal Petroleum University,
Gandhinagar 382007, India
e-mail: sivakumar.p@spt.pdpu.ac.in

© Springer International Publishing AG 2018 201

G. Anand et al. (eds.), Nanotechnology for Energy and Water,
Springer Proceedings in Energy, https://doi.org/10.1007/978-3-319-63085-4_27
202 C. Gabani et al.

taining polymer and can last for several decades when proper handling is not carried
out. Annually, about 1.6 billion scrap tyres are generated which is attributed to the
increase in global consumption of tyres for both public and commercial trans-
portation [2, 3]. To solve this problem there are various tyre disposal options such as
landfills, burning, open dumping, reclaiming, grinding, incineration, retreading etc.
But these processes have their setback and serve as a potential health and envi-
ronmental hazard. To curb this leading problem, it is essential to dispose it safely.
Recently, pyrolysis of waste tyres is becoming an important topic of research,
because it is a technically feasible and an eco friendly way to dispose and the
resultant energy recovery is an added advantage [4, 5]. Pyrolysis is a thermo
chemical process in which organic materials are thermally decomposed into simpler
constituent components when subjected to high heat and oxygen free atmosphere [2,
3]. The three basic products of pyrolysis are solid residue (char), liquid (crude oil)
and gases. Here, the gases having a mixture of H2, H2S, CO, CO2, CH4, C2H4, C3H6
etc. have high calorific value that can be recycled in the same process. The liquid can
be used as a substitute for diesel in internal combustion engine, fuel oil or petroleum
refinery feedstock whereas, the solid residue can be used as a low-grade activated
carbon, in cement manufacturing process and as an additive for road bitumen [6].
The main advantages of the pyrolysis process include simple equipment, ability
to handle any sort of rubber material and, low pressure operation. It has negligible
waste product, high energy conversion efficiency, neither toxic nor environmental
hazardous [7]. However, there is an existence of some problem related to the use of
liquid products due to their low quality, high sulfur content and variability of
properties [8]. So, catalysts were introduced into the process to reduce sulfur
content in the fuel and the extreme operating conditions. There are various catalysts
used for pyrolysis process. Among them, calcium oxide is an attractive option
because it produces low sulfur content liquid product when compared to other
catalysts. The calcium carbonate obtained from mining industries wastes is easily
available and cheaper. In this study, calcium carbonate was reduced to nano size
and converted into calcium oxide nano catalyst that was investigated for catalytic
pyrolysis of waste tyres.
The main objectives of this study are to solve the major environmental and
economic problem related to tyre pyrolysis, and to obtain high quality and low
sulfur fuel by using nano catalyst. This reduced the solid mass, sulfur content in
liquid fuel and operating temperature.

27.2 Experimental Section

27.2.1 Materials Preparation

The scrap tyres used in this experiment were collected from the Chiloda waste tyre
dump site, Gandhinagar district. They were cut into small pieces and the steel treads
were removed manually. Further, it was washed, dried and shredded to 3–5 mm.
27 Tyre Pyrolysis by Using Nano-catalyst to Improve Energy … 203

Calcium oxide nano catalyst was prepared by decomposing mineral rich in cal-
cium carbonate. This waste material was obtained from mineral processing industry.
Initially, it was crushed in a gyrated crusher and further it was reduced to nano size in
a high rate planetary mill. These nano sized particles were calcinated at high tem-
perature to get nano calcium oxide. The calcination temperature of the carbonate
mineral was determined by TGA thermogram (TA instruments SDT Q600, German).
FTIR spectrum of calcium carbonate mineral and calcium oxide were obtained from
Perkin Elmer, spectrum RX I (USA) using spectroscopically pure KBr.
For the synthesis of nano calcium oxide catalyst 100 g of calcium carbonate was
heated up to 800 °C and maintained for 30 min in a muffle furnace. The produced
calcium oxide was cooled in desiccators and sealed in polypropylene bags to
prevent from poisoning by CO2 and H2O.

27.2.2 Characterization

To get the desired efficiency of nano catalyst in pyrolysis process, the crystal
structure, shape, size and surface area of nano catalyst are more important and must
be specific. Thus nano calcium oxide catalyst was characterized by XRD, BET
analysis. Crystal structure and size of the nano catalyst was characterized using
Empyrean, PANalytical X-ray diffractometer. The total surface area was analyzed
by HORIBA SA-9600 series surface area analyzer (Japan).

27.2.3 Pyrolysis

Pyrolysis is the chemical decomposition of organic material at an elevated tem-

perature in the absence of oxygen. The main reaction was carried out with 100 g of
shredded scrap tyre and 1 g of nano calcium oxide as catalyst in a parr reactor up to
500 °C temperature heated at the rate of 15 °C min−1. The system was maintained
at this temperature for 30 min to ensure the complete conversion of tyres. To
validate the positive effects of nano-catalyst pyrolysis a controlled reaction was also
carried out without a catalyst under the same process condition.

27.3 Results and Discussion

27.3.1 Preparation and Characterization of Catalyst

The results of TGA showed the thermal decomposition pattern for CaCO3 rich mineral
in three steps. The initial decrease was observed at 80–173 °C. It was 2.3 wt% which
204 C. Gabani et al.

is due to the removal of bounded and unbounded moisture. The second small
decrease of 0.82 wt% at 470–546 °C was observed which is due to the removal of
hydrates and the final decomposition occured at 697–792 °C this was due to the
calcinations of calcium carbonate to calcium oxide. Even with a further increase in
temperature, the peak remained constant indicating that the conversion was com-
plete. According to stoichiometric proportion 56 wt% of CaO should be obtained
but 61.4 wt% was obtained due to the presence of 5.4 wt% of natural impurities
(Silica, Magnesium oxide etc.).
The FTIR spectrum clearly showed that the raw sample containing calcium
carbonate that resembled by the peak at 721, 883, 1495, 1801, 2535, 2909 and
2995 cm−1. The band at 1490 cm−1 is due to asymmetrical and symmetrical
lengthening of the O-C-O bond whereas, inplane and outplane bending modes of
carbonate anion bands were correspond to 715 and 880 cm−1 respectively.
Absorption bands at 715, 880 and 1490 cm−1 were assigned to calcite phase of
CaCO3. After calcinations, the broad bands obtained between 250 and 600 cm−1
indicate calcium oxide. Peaks at 1417 and 866 cm−1 were ascribed to C-O bond.
Thus, the FTIR spectrum conforms the formation and presence of calcium oxide.
In XRD, peaks appeared at 32.1, 37.2, 53.4, 64.8 and 67.9 associated with (111),
(200), (220), (311) and (222) cubic structure of calcium oxide. The crystal sizes
determined by Sherrer’s equation were between 40–89 nm. Surface area was analyzed
by BET. Surface area of CaCO3 and CaO were 5.25 and 435.54 m2g−1 respectively.
The pore volume and pore diameter of CaO were 0.467 cm3g−1 and 28 nm.

27.3.2 Thermal and Catalytic Pyrolysis

Pyrolysis was performed in parr reactor with 100 g of different tyre samples loaded
without and with 1 wt% of nano calcium oxide catalyst. The results obtained are
listed in Table 27.1. It is clear that the use of nano catalyst increased the yield of

Table 27.1 Physiochemical characterization of tyre pyrolysis product

Characteristics Thermal pyrolysis Catalytic pyrolysis
Weight of tyre charged 100 g 100 g
Max. temp 500 °C 500 °C
Holding time at 500 °C 30 min 30 min
95% oil recovery temp 496 °C 454 °C
Catalyst (wt%) 0% 0.5%
Liquid (wt%) 34% 46%
Residue (wt%) 38% 19%
Gas product (wt%) 28% 35%
Sulfur (Gas) 4.2% 5.1%
Sulfur (Liquid) 1.6% 0.2%
Sulfur (Solid) 1.2% 1.4%
27 Tyre Pyrolysis by Using Nano-catalyst to Improve Energy … 205

liquid and gaseous product. The catalyst, being in nano size, it mixes thoroughly
with the reactant at transition temperature of rubber to make the reaction efficient.
While comparing the sulphur content, it was found that the sulfur in gaseous and
solid products was high. This is due to the cracking of organic sulfur compounds
into smaller non condensable gases whereas the fixing of sulfur takes place in
residue to form of elemental sulfur and sulfates in solid.

27.4 Conclusion

In this study, the conversion of waste tyres into valuable liquid hydrocarbons by
catalytic pyrolysis was investigated. The effects of nano catalyst on maximum
recovery temperature of the product and quality of oil from catalytic pyrolysis were
investigated. The main conclusions obtained by applying nano catalyst in pyrolysis
are as follows:
1. The main problem preventing the use of waste tires as an alternative fuel is due
to the high levels of sulfur compounds in the pyrolysis product which is solved
by nano catalyst. The nano calcium oxide catalyst increases the concentration of
sulfur in gaseous and solid phases to reduce the percentage of sulfur in liquid
yield.
2. The process became economically viable owing to moderate temperature
requirement. Reduction of above 50 °C was observed to yield maximum oil (95
wt%) was obtained in catalytic pyrolysis. The uncondensed gaseous product has
high calorific value which is enough to be reused for heating purpose in the
pyrolysis reaction after scrubbing.
3. Lesser amount of solid residue remained in catalytic pyrolysis than thermal
pyrolysis resulting in increased quantity liquid and gas phase.
Thus, the eco-friendly technique of tyre pyrolysis was optimized and the nano
catalyst solves the main problem of environment pollution by existing tyre pyrol-
ysis plant. With further studies can result into commercially profitable business.

References

1. S.T. Kumaravel, A. Murugesan, A. Kumaravel, Tyre pyrolysis oil as an alternative fuel for
diesel engines—A review. Renew Sust Energy Rev 60, 1678–1685 (2016). doi:10.1016/j.rser.
2016.03.035
2. D. Bunthid, P. Prasassarakich, N. Hinchiranan, Oxidative desulfurization of tire pyrolysis
naphtha in formic acid/H2O2/pyrolysis char system. Fuel 89, 2617–2622 (2010). doi:10.1016/j.
fuel.2010.04.026
3. P.T. Williams, Pyrolysis of waste tyres: a review. Waste Manag. 33, 1714–1728 (2013).
doi:10.1016/j.wasman.2013.05.003
206 C. Gabani et al.

4. A. Quek, R. Balasubramanian, Liquefaction of waste tires by pyrolysis for oil and chemicals-A
review. J. Anal. Appl. Pyrol. 101, 1–16 (2013). doi:10.1016/j.jaap.2013.02.016
5. J.I. Osayi, S. Iyuke, S.E. Ogbeide, Biocrude production through pyrolysis of used tyres.
J. Catal. 1, 1–9 (2014). doi:10.1155/2014/386371
6. M.R. Islama, M.N. Islama, N.N. Mustafia, M.A. Rahima, H. Haniub, Thermal recycling of
solid tire wastes for alternative liquid fuel: the first commercial step in Bangladesh. Procedia
Eng 56, 573–582 (2013). doi:10.1016/j.proeng.2013.03.162
7. K. Tudu, S. Murugan, S.K. Patel, Light oil fractions from a pyrolysis plant-an option for energy
use. Energy Procedia 54, 615–626 (2014). doi:10.1016/j.egypro.2014.07.303
8. S. Boxiong, W. Chunfei, I. Cai, G. Binbin, W. Rui, Pyrolysis of waste tyres: the influence of
USY catalyst/tyre ratio on products. J. Anal. Appl. Pyrol. 78, 243–249 (2007). doi:10.1016/j.
jaap.2006.07.004