Article

pubs.acs.org/EF

Kinetic Study of the Thermal and Catalytic Cracking of Waste Motor

Oil to Diesel-like Fuels
Diana C. Vargas,†,‡ María B. Alvarez,† Alexis Hidrobo Portilla,† Kevin M. Van Geem,‡
and Daniela Almeida Streitwieser*,†
†
Laboratory for Development of Alternative Energies (LaDEA), Department of Chemical Engineering, Universidad San Francisco de
Quito (USFQ), EC 170901 Quito, Ecuador
‡
Laboratory for Chemical Technology, Ghent University, B-9052 Ghent, Belgium

ABSTRACT: Considering the serious impact caused to the environment by the inappropriate disposal of waste motor oils, it is
essential to find alternative mechanisms to handle and dispose these wastes in a controlled process. The reuse of waste motor oil
as a resource for the synthesis of diesel-like fuels provides an alternative way for the disposal of this residue in a feasible,
sustainable, and environmentally responsible way. This work addresses the kinetic study of the catalytic cracking of waste motor
oil using mesoporous aluminum silicate materials impregnated with 1 and 2% zinc. Both the waste motor oil and liquid fuel
product were characterized according to ASTM standards to ensure an adequate characterization and to guarantee the proper
quality of the product. The results from the overall kinetic approach show that the cracking reaction can be described using a
first-order rate equation with respect to the concentration of the used motor oil. The activation energy for the thermal cracking
reaction is 370 kJ/mol. It is reduced by 22% to 287 kJ/mol when the alumina silicate catalysts are used. Also, during the reaction,
the overall yield of the reaction with respect to the liquid fuel is increased from 63% during the thermal reaction to 90% during
the catalytic reaction.

1. INTRODUCTION erated.12 Therefore, it is crucial to control and manage these

The continuous extraction of energetic resources has allowed
for the vast development of the current highly technology-
dependent society. However, the dilemma appears on how this
accelerated pace can be maintained without destroying the
environment.1,2 In this context, the need to find alternative
energy sources remains a continuous quest. One option is
focusing on renewable energy, which is regenerated naturally,
but typically, crops need to be cultivated for this purpose,3
which results in discussions on the use of land for food versus
energy. Another option is the utilization of wastes, such as a
selection of industrial, agricultural, or municipal waste streams.
These wastes need to undergo physical, chemical, or biological
processes to prepare them for their energetic utilization. This
approach has two advantages: the reduction of the use of fossil
resources but also the decrease of the amount of waste that
needs to be managed and will be send for landfill.4 Lubricating
motor oils are one of these potentially interesting waste
streams.
Annually, lubricating oils constitute 1% of the total oil
consumption, and approximately 50% of lubricant oils are used
for the automotive industry.5,6 The lubricating motor oils in
vehicles need to be changed regularly, because the high
temperatures and friction in the motor degrades and
contaminates the oil with heavy metals, soot, and aromatic
hydrocarbons.7−9 Worldwide in 2014, 67 million passenger cars
came into circulation, representing an increase of 16% in the
last 3 years. This growth is highest in the world’s emerging
economies.10 Overall, a total of 1236 million cars were
registered for circulation, with a total consumption of 4.5
million tons of lubricating oil.11 Waste motor oil is nowadays
the most abundant and dangerous pollutant residue gen-
residues. For years, incineration and combustion processes have
been used as the preferred disposal option for energy
recovery.13,14 However, these processes cannot be applied
everywhere as a result of the high investment cost for their
implementation and environmental pollution.13 This has
created growing interest in recycling and reutilization of
waste motor oil into lubricant base oil and the development
of new alternative methods, such as pyrolysis, to increase the
material and energetic recovery rates of these residues.9,12−17
The main investigations have been researching the different
pyrolysis techniques, such as pyrolytic distillation,16 micro-
wave,9 non-isothermal,15 and catalytic pyrolysis,9,14−16 or
kinetic studies of the pyrolysis reactions.12,15−17 Also “cracking”
techniques, including thermal and catalytic procedures, are
being investigated.9,13,18 Catalytic cracking allows for the
conversion of the lubricating motor oil into secondary diesel-
like fuel. Obviously, its use as a second-generation fuel reduces
the consumption of primary fuels, decreases greenhouse gas
(GHG) emissions, and contributes to climate change
mitigation.14,18 Catalytic cracking has the advantage that,
using aluminum silicate catalyst, the cracking temperatures
can be reduced in comparison to those in thermal
cracking.2,14,19
Aluminum silicates have been widely used to effectively
catalyze reactions, such as gas oil cracking, in fluid catalytic
cracking (FCC) processes as a matrix, in organic chemistry for
Diels−Alder reactions, and in selective ether cleavege.19−22 In
Received: August 1, 2016
Revised: October 14, 2016
Published: October 19, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.6b01868

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Table 1. Characterization Methods

norm method equipment
ASTM D5623 Standard Test Method for Flash Point by Tag Closed Cup Tester Herzog HFP 380 Pensky
Martens
ASTM D8624 Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure Precision Scientific Petroleum
Instrument Herzog
25
ASTM D1298 Standard Test Method for Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum Hydrometer Precision API
and Liquid Petroleum Products by Hydrometer Method
ASTM D227026 Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100 °C Viscometer CANNON 100 T642
Kohler bath KV3000
ASTM D429427 Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy-Dispersive X-ray HORIBA SLFA 2800
Fluorescence

this work, the aluminum silicates are investigated for the first average mesopore diameter (DBJH) was calculated as 4 VBJH/
time for the catalytic cracking of waste motor oil in a batch SBJH.21,22
reactor. These experimental data have been used to determine a 2.3. Cracking Process. The cracking process includes three steps:
pretreatment of the waste motor oil, catalytic cracking of the treated
simple kinetic model for the catalytic cracking reaction. The
material, and post-treatment. Figure 1 shows a block diagram of the
waste motor oil and obtained products from the cracking
reaction have been characterized according to ASTM norms to
meet all quality control standards and regulations to be used as
diesel fuel in Ecuador.

2. EXPERIMENTAL SECTION
2.1. Reagents. The waste motor oil was supplied by a collection
station in Quito, Ecuador, where the oil is received on a daily basis. Figure 1. Block diagram of the catalytic process.
The reagents used for the synthesis of the aluminum silicate catalysts
employed in the Experimental Section are tetraethyl orthosilicate general process. The waste motor oil has to undergo a pretreatment
(TEOS, 98% purity) and Triton X-114 (laboratory grade) by Sigma- prior to the cracking process to eliminate any water residues or solids
Aldrich Chemicals, aluminum tri-sec-butylate (TBA, 97% purity) and by heating the sample at 100 °C for at least 24 h and then filtering the
hydrochloric acid fuming 37% [guaranteed reagent (GR) for analysis] sample.
by Merck Chemicals, and zinc chloride (97.1% purity) by J.T. Baker. The equipment used for the thermal and catalytic cracking of the
All reagents were bought from Laboratorio de Reactivos H.V.O. waste motor oil is a 250 mL high-temperature-resistant borosilicate
(Quito, Ecuador). All of the chemicals were used in the conditions that glass batch reactor (Figure 2) placed in the Precision Scientific
they were received.
2.2. Characterization Methods. The characterization methods
used to analyze the waste motor oil and the final product of the
cracking reactions are based on different ASTM methods. The
standards, methods, and equipment for the characterization are given
in Table 1.
The used lubricating motor oil and the obtained product of the
cracking process at the best condition have been characterized using a
Shimadzu gas chromatography−mass spectroscopy (GC−MS) model
QP2010 Ultra Plus (Shimadzu, Japan) equipped with an autosampler/
autoinjector AOC 20i-s and operated with the GCMS Solution
software (version 4.11 SU2). A Restek silica column model SH-Rxi-
5Sil MS has been used. Prior to the injection into GC−MS, 1 μL of
sample needed to be filtered with a syringe polytetrafluoroethylene
(PTFE) 0.45 μm filter and diluted in 1 mL of hexane. The GC oven
temperature program began at 40 °C with an equilibration time of 0.5
min, followed by a 10 °C/min ramp up to 320 °C, where the
temperature was kept for 2.75 min. A He carrier gas flow velocity of Figure 2. Schematic of the experimental apparatus: (a) glass batch
42.7 cm/s, an injector temperature of 150 °C, a purge flow of 1.5 mL/ reactor, (b) heater section of the Precision Scientific Petroleum
min, and a split ratio of 100:1 were used with an automatic injection of Herzog equipment, and (c) graduated cylinder for the collection of the
0.2 μL. The mass spectra were recorded with the system equipped product.
with an electron ionization (EI) source operating at 70 eV in the range
from m/z 35 to 800. The ion source was kept at 280 °C, while the
interface was at 320 °C. The method included a solvent cut time of Petroleum Herzog silt with a maximum power of 1100 W, which is
2.00 min. used as the reaction system, heating the reactor and condensing the
The aluminosilicates were characterized using nitrogen adsorption/ vapor obtained by the cracking reactions. For the thermal cracking
desorption isotherms at −196 °C obtained on a Micromeritics ASAP experiments, 100 g of the pretreated waste motor oil is placed in the
2010 apparatus. The specific surface area of the aluminosilicates was batch reactor without any catalysts, while for the catalytic cracking
determined from the linear part of the Brunauer−Emmett−Teller experiments, the same amount of sample is introduced in the reactor
(BET) equation (p/p0 = 0.05−0.15). The mesopore size distribution but also 1 g of catalyst is added.
was calculated from the desorption branch of the nitrogen adsorption/ The flask with the sample is agitated and placed in the cracking
desorption isotherms and the Barrett−Joyner−Halenda (BJH) equipment (Precision Scientific Petroleum Herzog). During the first
formula. The mesopore surface area (SBJH) and mesopore volume 20 min, the power of the equipment is set to 50% of its full power and
(VBJH) were obtained from the pore size distribution curves. The then increased with a ramp of 10 W/h until the desired temperature is

B DOI: 10.1021/acs.energyfuels.6b01868
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reached. The condensate from the cracking reaction is collected in the
receiver cylinder and weighted. The condensate volume is registered as
a function of the temperature, and these values are later used to
calculate the concentration of waste motor oil as a function of time. A
residue conformed of heavy hydrocarbons with the catalyst and
impurities are settled at the bottom of the reactor. The experimental
design is presented in Table 2.
Table 2. Experimental Design for This Study
components cannot be well separated as a result of its complexity.32 In
this study, a simplified cracking reaction is assumed and presented in
terms of an average oil molecule of hydrocarbon of C30, as described in
eq 2, and with the symbols defined in eq 3. The used motor oil (A)
cracks to the desired products (P), which are the intermediate
hydrocarbons with a number of carbon atoms between C8 and C20,
and lighter fractions (B) up to C7 have a low boiling point and are not
suitable as liquid fuels, although they could be used as steam cracker
feed or internally in the process.33

percentage of C30H62 → C5H10 + C13H 24 + C12H 24 (2)

impregnated metal in temperature
experiment catalyst metal catalyst (%) (°C)
A → B + 2P (3)
thermal 300, 310, 320,
cracking 330, 340 350, The model used for the kinetics study of the cracking reactions of
and 360
waste motor oil is a global potential law model, where the reaction rate
catalytic aluminum Zn 300, 310, 320,
cracking silicate and 330 is a function of the concentration. The rate of consumption of the
Al/Si waste motor oil, RA, represented by the potential law expression is
catalytic aluminum 1 300, 310, 320, presented in eq 4; by applying the logarithm, it can be linearized to
cracking silicate and 330 obtain the kinetic parameters
Al/Si Zn 1%
catalytic aluminum Zn 2 300, 310, 320, RA = − kCA n (4)
cracking silicate and 330
Al/Si Zn 2% where k and n are the kinetic constant and the reaction order,
respectively.
The Arrhenius law was used to determine the temperature
The concentration of waste motor oil is calculated on the basis of dependency. The linear expression of the Arrhenius law is used to
the amount of oil that remains in the reactor over time. The following obtain the activation energy (EA) and pre-exponential factor (k), as
volumetric relation is used: presented in eq 5.
CA = (m0 − mR )/(MoilVoil) (1)
ln(k) = ln(k 0) − EA /RT (5)
where the concentration of the waste motor oil, CA, in g/g, is obtained
by subtracting the mass of product recovered (mR) from the starting 2.5. Catalyst Preparation. The materials used for catalytic
mass of raw material (m0) divided by the molecular weight of the cracking of the used motor oil consist of mesoporous aluminum
model molecule used to represent waste motor oil (Moil) and the silicates produced in-house. The material structure frame is
volume of oil remaining in the reactor Voil. synthesized with TEOS as the silicon organic−inorganic precursor
The cracking reaction is completed when all of the liquid and TBA as the aluminum precursor.19 The molar relation between
constituents of the used motor oil have been volatilized and only a silicon and aluminum (Si/Al) is 7.5. Triton X-114 is used as a pore
solid residue remains in the flask. After the cracking reaction, the modulator agent. The metallic salt used to generate the catalytic active
condensate undergoes a rectification process that yields three different sites is zinc chloride.
fractions: the light or gaseous fraction, the intermediate fraction, and To synthesize the catalysts, 4.5 g of Triton X-114 is vigorously
the heavy product. The intermediate fraction is the desired final agitated with 30 mL of deionized water and the metallic salt according
product. These fractions are separated according to their bubble point to the defined relation. In this case, 1 and 2% of zinc is added. The
temperature range. The desired product is collected at a bubble aluminum silicates can be synthesized by either a basic or an acidic
temperature between 149 and 288 °C. This temperature range is method.
chosen because diesel is made of saturated hydrocarbons (paraffin) For the acid method, the pH of the mixture must be decreased to 1,
and unsaturated (olefin) and aromatic chains that contain 10−19 which is accomplished by adding concentrated hydrochloric acid. After
carbon atoms.28 the pH reaches a value of 1, 11.5 g of TEOS is added during vigorous
2.4. Kinetic Study. The difficulty in defining a simplified cracking agitation for 2 h. Afterward, 1.9 g of TBA is added to the mixture and
reaction of the used motor oil is due to the nature of motor oil itself. the agitation continues for 24 h. The resulting mixture is transferred to
The Material Safety Data Sheet (MSDS) of lubricant motor oil defines a hydrothermal Teflon reactor, where it is heated to 150 °C for 24 h.
its molecular weight or chemical formula as not available or as a The solid product is then washed with a water−ethanol solution in a
mixture between C15 and C50.29,30 Motor oil is a blend of various Büchner fennel and dried at atmospheric temperature. Finally, the dry
hydrocarbons and additives, where around 80% are alkanes in the product must be calcined at 550 °C for 24 h with a heating ramp of 3
C15−C40 range.31 Its characterization is very difficult because its °C/min.19

Table 3. Characterization of Waste Motor Oil and Products from the Cracking Process
flash pointa distillationb API gravityc kinematic sulfur contente norm
material process (°C) (°C) (deg) viscosityd (cSt) (%, p/p) fulfilled
desired product diesel #2f min 51 max 288 32−39 2.5−6 max 0.7
raw material waste motor oil 69 380 29.6 113.14 0.364 no
final product of different cracking thermal cracking 65 354 37.4 4.65 0.1614 yes
processes catalytic cracking Al/Si 68 342 38.9 4.67 0.1403 yes
catalytic cracking 69 343 38.5 4.78 0.1305 yes
Al/Si Zn 1%
catalytic cracking 70 345 39.0 4.72 0.1264 yes
Al/Si Zn 2%

a
ASTM D56.23 bASTM D86.24 cASTM D1298.25 dASTM D2270.26 eASTM D4294.27 fINEN 1489.34

C DOI: 10.1021/acs.energyfuels.6b01868
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Figure 3. Chromatograms by GC−MS of (a) commercial diesel, (b) jet fuel, (c) gasoline, (d) untreated used motor oil, (e) product of thermal
cracking, and (f) product of catalytic cracking with Al/Si Zn 1%.
3. RESULTS AND DISCUSSION
3.1. Characterization of Raw Material and Cracking
Products. Before the kinetic analysis of the cracking reaction is
performed, the waste motor oil is pretreated and characterized.
The standard methods and equipment used are described in
Table 3. The characterization is made to compare it to the final
product to identify its potential use as raw material to obtain
commercial diesel-like fuel. The results of the analyses of the
waste motor oil as well as the acceptable ranges for diesel-like
fuels are presented in Table 3. The characterization analyses are
performed to the intermediate fractions obtained from the
cracking reaction of all experiments of each catalytic system
combined, after a rectification process at boiling points between
149 and 288 °C of the raw cracking products. The obtained
results show that all values for the waste motor oil are out of
range for the requirements for diesel #2 as expected. Diesel #2
corresponds to a liquid diesel fuel with a reduced sulfur content
used for combustion engines according to the Ecuadorian
technical norm NTE INEN 1489.34
The distillation products from the cracking processes present
boiling point values that are above the maximum permitted
D DOI: 10.1021/acs.energyfuels.6b01868
Article
range for diesel #2. For this reason, all of the final products
from the cracking experiments require an additional rectifica-
tion process to acquire only the diesel cut. The other
characterization analyses for the final products showed values
within the diesel #2 ranges given by INEN 1489 norm.34
Also, the used motor oil and product of the catalytic cracking
reaction with the Al/Si catalysts have been analyzed by GC−
MS and compared to chromatograms of commercial diesel, jet
fuel, and gasoline fuels. The chromatograms of the commercial
products are presented in panels a−c of Figure 3. In Figure 3d,
the chromatogram of the untreated used motor oil is shown. As
seen in the chromatogram and from previous investigations,
conventional GC techniques cannot separate motor oil
fractions clearly as a result of its complex composition, resulting
in a hump of the unresolved complex mixture,32 even though a
variety of hydrocarbons, ranging between C12 and C60, can be
identified, resulting in an average molecular weight in the range
of a C30 paraffin. In Figure 3e, the product of the thermal
cracking is analyzed, presenting a broad spectrum of
compounds between C11 and C30 in a similar range as in the
chromatogram of diesel but with a higher fraction of heavy
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Figure 4. Characterization of the catalysts: (a) nitrogen adsorption/desorption isotherms and (b) pore size distribution determined from the N2
desorption isotherms, for aluminosilicates (Al/Si) and aluminosilicates with 1% Zn (Al/Si Zn 1%).

Figure 5. Concentration of used motor oil during the reaction for thermal cracking: (a) thermal cracking reaction at 300−330 °C and (b) thermal
cracking reaction at 340−360 °C.

material. This can be due to carriage of unreacted oil through
the distillation step, while the chromatograms of the catalytic
cracking reactions in Figure 3f show a very narrow range of
peaks between C8 and C13, resulting in light hydrocarbons, in a
range very similar to the chromatogram of gasoline.
3.2. Characterization of Aluminosilicates. The alumi-
nosilicates prepared for the catalytic reaction have been
characterized as previously described. Figure 4 illustrates the
N2 adsorption/desorption isotherms for the synthesized
materials with and without the addition of a metal as well as
the pore size distribution.
The calcined Al/Si sample presents a well-defined step in the
adsorption isotherm at relative pressures p/p0 = 0.45−0.7 and a
hysteresis loop in the desorption isotherm over the same
relative pressure range. This feature results from the
condensation of the adsorbate within the framework-confined
mesopores. This hysteresis loop is indicative of mesoporos-
ity.21,22 Because the hysteresis loop at high partial pressure (p/
p0 > 0.8) is associated with textural mesoporosity or
macroporosity, it can be concluded that the Al/Si sample
lacks textural mesoporosity, as indicated by the absence of a
hysteresis loop at p/p0 > 0.8. However, when the sample is
subjected to the addition of Zn, the material presents a type IV
isotherm. The isotherms for the Al/Si Zn 1% sample show large
type H1 hysteresis with ink-bottle-type connected pores, and a
development of some macroporosity occurs. This is in
E DOI: 10.1021/acs.energyfuels.6b01868
agreement with the hysteresis loop at medium and high partial
pressure and suggests a shift of pore size to higher values.
In Figure 4b, it can be observed that the materials undergo an
important increase in the pore diameter, starting at 44 Å when
Al/Si is calcined directly and going to 203 Å when it is
subjected to the addition of zinc. The opposite conclusion is
observed with respect to the surface area, where the addition of
Zn sharply decreases the surface area of Al/Si. Thus, Al/Si has a
surface area close to 600 m2/g, while Al/Si Zn 1% barely
reaches 100 m2/g.
3.3. Cracking Reaction of Waste Motor Oil. The time
dependence of the unreacted waste motor oil concentration at
different reaction temperatures for thermal cracking is
presented in Figure 5. The time axis for both thermal cracking
figures is different. In Figure 5a, the experimental time was 250
min for the experiments at 300−330 °C, while for the
experiments with cracking temperatures of 340−360 °C
(Figure 5), the time was 60 min.
In Figure 6a, it can be observed that, for cracking
temperatures of 300−320 °C, the reaction rate is small,
because no significant reaction of the oil can be observed, while
at a cracking temperature of 330 °C, the concentration of oil,
CA, decreases substantially with time. Nonetheless, as shown in
Figure 6b, the required reaction temperature is ideally between
340 and 360 °C to obtain a high conversion of the waste motor
oil in the desired product. These curves can be fitted as a
function of time using an exponential regression model with
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Figure 6. Concentration of used oil during the reaction for catalytic cracking: (a) catalytic cracking using the Al/Si matrix, (b) catalytic cracking
using the Al/Si matrix impregnated with 1% zinc, and (c) catalytic cracking using the Al/Si matrix impregnated with 2% zinc.

equations of the form y = −aebx. The value for the parameters a Table 4. Mass Balance Obtained for the Cracking Reactions
and b and the coefficient of determination R2 are shown in for the Different Processes at the Best Temperature
Table 5. Conditions
As presented in Table 2, the catalytic cracking has been
light heavy
investigated with three different catalysts. These catalysts fraction intermediate fraction residue losses
decrease the reaction temperature and increase the selectivity process (%) fraction (%) (%) (%) (%)
of the desired product. Panels a−c of Figure 6 show the results thermal cracking 4.8 61.6 15.4 14.2 4.0
of the decrease of the waste motor oil concentration versus catalytic cracking 5.0 86.5 4.5 2.5 1.5
time for the catalytic cracking reactions at different temper- Al/Si
atures. All of them show a reduction in the concentration of catalytic cracking 5.2 89.5 1.5 2.0 1.8
Al/Si Zn 1%
waste motor oil, CA, at shorter periods of time compared to that catalytic cracking 4.0 91.5 1.5 2.0 1.0
obtained for the thermal cracking reaction. In panels a and b of Al/Si Zn 2%
Figure 6 at 330 °C, the lowest CA point is reached already after
approximately 80 min of reaction. In Figure 6c, the lowest obtained. For the catalytic cracking reaction (Figure 7b) with
reaction time at 330 °C is already reached after 50 min of an Al/Si matrix as the catalyst, a mean reaction order of 1.0 ±
reaction. 0.12 was also obtained. In the case of the cracking reaction with
The mass balance for the different cracking processes as a an Al/Si matrix impregnated with zinc at 1% (Figure 7c), the
weight percentage is shown in Table 4. It can be observed that mean reaction order is 0.8 ± 0.13, and finally, for the reaction
the catalytic cracking with the catalyst that formed an Al/Si using an Al/Si matrix impregnated with zinc at 2%, a reaction
matrix with 1% zinc shows the highest yield for the desired order value of 0.9 ± 0.20 was obtained.
intermediate fraction. With the results obtained from the differential analysis, the
3.4. Kinetic Analysis. The differential analysis method is values of the kinetic constants are determined for the
used to obtain the kinetic rate law of the cracking reactions. In experiments at different temperatures. These results are used
Figure 7, the linearized form of the potential law model is for the application of the linearized Arrhenius equation to
presented for the different experiments, which can be modeled obtain the pre-exponential factor, k0, and the activation energy,
with equations of the form y = mx + b, where m represents the EA. By applying the Arrhenius law model, the kinetic constants
reaction order and b represents the y-axis intercept. obtained for every temperature were investigated for the
In Table 5, the values for the parameters of the linear different cracking reactions, as shown in Figure 8.
equations m, b, and R2 are presented. The value b is the log base The results presented in Figure 8 show lower activation
10 value of the kinetic constant. As presented in Table 5 for the energy values for the catalytic cracking experiments compared
thermal cracking, a mean reaction order of 1.0 ± 0.18 was to the thermal cracking. In the case of the thermal cracking, the
F DOI: 10.1021/acs.energyfuels.6b01868
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Figure 7. Differential analyses for experimental data: (a) thermal cracking reaction, (b) catalytic cracking using the Al/S matrix, (c) catalytic cracking
using the Al/Si matrix impregnated with 1% zinc, and (d) catalytic cracking using the Al/Si matrix impregnated with 2% zinc.

Table 5. Parameters Obtained for the Experimental Data

exponential regression differential analysis kinetic parameters
temperature
experiment (°C) a b R2 ma b R2 kb ma k0b EAc
−2
thermal 300 211.65 −0.002 0.9814 1.0038 −2.7098 0.9751 2.668 × 10 1.0 ± 0.18 3.01 × 10 30
370.39
310 200.7 −0.002 0.9751 1.2310 −3.2380 0.9814
320 199.59 −0.002 0.9913 0.8022 −2.2447 0.9913
330 224.5 −0.026 0.9677 0.9859 −1.5738 0.9677
340 224.48 −0.055 0.9823 1.0256 −1.2257 0.9823
350 287.57 −0.066 0.977 0.9777 −0.5417 0.9777
360 224.59 −0.077 0.9677 0.9815 −0.0423 0.9828
Al/Si 300 204.02 −0.001 0.8951 0.8876 −2.7453 0.8951 3.390 × 10−2 1.0 ± 0.12 7.44 × 1024 304.39
310 207.51 −0.001 0.9935 0.8188 −2.5823 0.9935
320 202.66 −0.003 0.947 0.7154 −2.3449 0.9962
330 201.29 −0.033 0.9828 0.9906 −1.4698 0.9828
Al/Si Zn 1% 300 200.7 −0.0005 0.904 0.7333 2.6937 0.9821 4.123 × 10−2 0.8 ± 0.13 1.11 × 1023 280.71
310 199.78 −0.004 0.9865 0.8405 −2.1516 0.9819
320 188.31 −0.008 0.9837 0.9946 −2.0923 0.9837
330 237.88 −0.033 0.9914 0.9876 −1.4325 0.9914
Al/Si Zn 2% 300 201.00 −0.0006 0.9452 0.7077 2.5536 0.9773 6.22 × 10−2 0.9 ± 0.20 6.09 × 1022 278.37
310 209.36 −0.003 0.9989 0.8848 −2.2557 0.9989
320 179.54 −0.014 0.9449 1.1992 −2.1346 0.9449
330 230.27 −0.047 0.9936 0.9139 −1.2060 0.9936
a
Reaction order. bExponential factor at 330 °C and pre-exponential factor [(mol/L)1 − m min−1]. cActivation energy (kJ/mol).

activation energy value is 370.39 kJ/mol, as shown in Figure 8a. for the catalyst with an Al/Si matrix with 2% zinc, as shown in
On the other side, the catalytic cracking reactions present lower Figure 8d.
activation energies, EA. The obtained values are 304.39 kJ/mol The two main differences between thermal and catalytic
for the catalyst with an Al/Si matrix (Figure 8b) and 280.71 kJ/ cracking are the reaction yields and the decrease on the
mol for the catalyst with an Al/Si matrix with 1% zinc (Figure activation energies. By comparison of the activation energies
8c). The lowest activation energy of 278.37 kJ/mol is obtained presented in Table 5, the reaction catalyzed by the Al/Si matrix
G DOI: 10.1021/acs.energyfuels.6b01868
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Figure 8. Graphic method for the determination of the activation energy of the cracking reactions using the Arrhenius law for (a) thermal cracking
reaction, (b) catalytic cracking reaction using Al/Si, (c) catalytic cracking reaction using Al/Si Zn 1%, and (d) catalytic cracking reaction using Al/Si
Zn 2%.
shows a decrease of 17.8% with respect to thermal cracking,
while the Al/Si matrix impregnated with 1% Zn shows a
decrease of 24.2% and the Al/Si matrix impregnated with 2%
Zn shows the highest decrease, with a value of 24.8%.
The reaction yield, defined as the amount of intermediate
product obtained over the amount of used motor oil at the
beginning of the experiment, is also enhanced by the catalyzed
cracking reaction. The value obtained for thermal cracking is
63%, while for the Al/Si matrix, it increases to 86%. It increases
further for the Al/Si matrices impregnated with 1 and 2% Zn to
89 and 90%, respectively.
Furthermore, the final conversion is presented as a function
of the reaction temperature in Figure 9. Three different stages
Figure 9. Conversion of the waste motor oil as a function of the
temperature for the different reactions.
H DOI: 10.1021/acs.energyfuels.6b01868
Article
of the conversion of waste motor oil can be observed: stage 1
from 290 to 310 °C, stage 2 from 310 to 330 °C, and stage 3
from 330 to 350 °C. For the first stage, no significant reaction is
observed; at 290 °C, the conversion for thermal and catalytic
cracking is zero, showing that the cracking process has not
started at that reaction temperature. At 300 °C, below 10% of
the waste motor oil is cracked. At stage 2, the conversion of the
process starts to increase for all cracking experiments. The
difference between the thermal and catalytic cracking can be
clearly observed for the conversion at 320 °C, where the
highest conversion is found for the catalytic cracking with the
Al/Si matrix with 2% zinc. At stage 3, the maximum conversion
for the catalytic route is reached at 330 °C, while the maximum
conversion for thermal cracking is reached at 340 °C. In
summary of the overall catalyst performance regarding the
grades of conversion values, it can be inferred that the catalyzed
reactions using the Al/Si matrix with 2% Zn showed the highest
activity for all cracking conditions.
4. CONCLUSION
In this investigation, the thermal and catalytic cracking of waste
motor oil was studied. During the experiments, the reaction
temperature was varied for the different reaction processes:
thermal cracking and catalytic cracking with three different
catalysts.
The results show that the use of catalysts enables higher
conversion rates at moderate reaction conditions. Also, the
overall yield of the reaction is increased from 63% with the
thermal cracking to 90% with the Al/Si matrix with 2% zinc.
The kinetic study showed that lower activation energies were
obtained for the catalytic conversion, with the lowest activation
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
energy of 278.37 kJ/mol for the Al/Si matrix with 2% zinc,
clearly illustrating the potential of these catalysts for this
process.
The analysis of the final products obtained by all of the
different cracking processes shows that they can meet the
necessary requirements for diesel #2 after a final rectification
step.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: dalmeida@usfq.edu.ec.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors thank Universidad San Francisco de Quito for the
financial support through the Chancellor Grants 2009 and 2012
and for the continuous support to the investigations performed
at LaDEA. The authors also thank the Laboratory for Quality
Control of Clean Products Terminal “El Beaterio” EP
PetroEcuador for all of the support during the characterization
analyses conducted.The authors wish to acknowledge David
Alexis Egas Proaño PhD, from the Department of Chemical
Engineering - USFQ, for the help provided during the
chromatographic characterization and interpretation of the
samples. This research has been supported by the Belgian
Development Cooperation through VLIR-UOS. VLIR-UOS
supports partnerships between universities and university
colleges in Flanders (Belgium) and the South looking for
innovative responses to global and local challenges at www.
vliruos.be.
■
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