Universidad San Francisco de Quito Usfq

UNIVERSIDAD SAN FRANCISCO DE QUITO USFQ
Colegio de Ciencias e Ingenierías
Evaluation of thermal and catalytic cracking with aluminosilicates of

lubricant motor oil in a Plug Flow Tubular Reactor (PFTR)
Proyecto de investigación
José Fernando Noboa Guerrón
Ingeniería Química
Trabajo de titulación presentado como requisito

para la obtención del título de
Ingeniero Químico
Quito, 19 de julio de 2019

2
Universidad San Francisco de Quito USFQ

Colegio de Ciencias e Ingenierías
HOJA DE CALIFICACIÓN
DE TRABAJO DE TITULACIÓN

José Fernando Noboa Guerrón
Calificación:
Nombre del profesor, Título académico

Daniela Almeida Streitwieser, Dr. Ing.
Firma del profesor
Quito, 19 de julio de 2019

3
Derechos de Autor
Por medio del presente documento certifico que he leído todas las Políticas y Manuales
de la Universidad San Francisco de Quito USFQ, incluyendo la Política de Propiedad
Intelectual USFQ, y estoy de acuerdo con su contenido, por lo que los derechos de propiedad
intelectual del presente trabajo quedan sujetos a lo dispuesto en esas Políticas.
Asimismo, autorizo a la USFQ para que realice la digitalización y publicación de este
trabajo en el repositorio virtual, de conformidad a lo dispuesto en el Art. 144 de la Ley Orgánica
de Educación Superior.
Firma del estudiante: _______________________________________
Nombres y apellidos: José Fernando Noboa Guerrón
Código: 124940
Cédula de Identidad: 1722816145
Lugar y fecha: Quito, 19 de julio de 2019

4
Resumen
Mundialmente el mercado automovilístico está en constante crecimiento, aumentando la

demanda de aceite lubricante de motor (ALM) y, consecuentemente, generando mayor
cantidad de residuos y contaminación derivada del ALM. Una alternativa para tartar con este
contaminante es mediante el rompimiento de largas cadenas de hidrocarburos con tecnologías
de craqueo en procesos térmicos y catalíticos. Este estudio analiza el craqueo térmico y
catalítico de ALM, utilizando un Reactor Tubular De Flujo Pistón (PFTR) para la obtención
de combustibles similares al diésel entre otros productos. Los productos fuero separados en
gases, líquidos y residuos en una columna de destilación flash. El catalizador utilizado fue un
aluminosilicato mesoporoso preparado en un medio ácido mediante la condensación de un
xerogel formado a partir de tetraetil ortosilicato (TEOS) y tris-sec-butilato de aluminio (TBA),
utilizando Triton X-114 como agente porogénico. Se evaluó el craqueo térmico en un PFTR
con temperaturas de reacción entre 340°C y 400°C, con los rendimientos más altos a 360°C y
400°C respectivamente. Sin embargo, en las reacciones a 400°C se observaron considerables
pérdidas de masa a través de vapores y humo generado. En el craqueo catalítico, los
aluminosilicatos mostraron un aumento en el rendimiento de la reacción a 360°C de 7.44% a
9.02%, indicando un efecto positivo al utilizar aluminosilicatos mesoporosos en un reactor de
lecho empacado para el proceso de craqueo.
Palabras clave: aceite lubricante de motor (ALM), craqueo térmico, craqueo catalítico, reactor
tubular de flujo pistón (PFTR), reactor de lecho empacado.
5
Abstract
The worldwide automobile market is constantly growing, increasing the demand of lubricant
motor oil (LMO) and, in consequence, generating more LMO waste and contamination. An
alternative for dealing with this contaminant is by breaking the long hydrocarbon chains of
LMO with cracking technologies in thermal or catalytic processes. In this study, thermal and
catalytic cracking of LMO were analyzed using a Plug Flow Tubular Reactor (PFTR) to obtain
diesel-like fuels among other products. The products were separated into gases, liquids and
residues in a flash distillation column. The catalyst used was a mesoporous aluminosilicate
prepared on an acidic medium by condensation of a xerogel prepared from tetraethyl
orthosilicate (TEOS) and aluminum tri-sec-butylate (TBA) using Triton X-114 as a porogen
agent. Thermal cracking was evaluated at a PFTR with reaction temperatures between 340°C
and 400°C with the highest yields of 7.44% and 8.02% at 360°C and 400°C, respectively.
However, in reactions at 400°C high losses of gaseous products as fumes were observed. For
the catalytic cracking, the aluminosilicates showed an increase in yield at 360°C from 7.44%
to 9.02%, showing the positive effect of using mesoporous aluminosilicates as catalysts in a
packed bed reactor for the cracking process.
Keywords: lubricant motor oil (LMO), thermal cracking, catalytic cracking, plug flow
tubular reactor (PFTR), packed bed reactor.
6
Contents
List of figures ............................................................................................................................. 8
List of tables ............................................................................................................................... 8
Abstract ...................................................................................................................................... 9
1. Introduction .......................................................................................................................... 10
2. Methods and Materials ......................................................................................................... 13
2.1. Raw material pretreatment ............................................................................................ 13
2.2. Experimental equipment ............................................................................................... 13
2.2. Catalyst preparation ...................................................................................................... 15
2.3. Preparation of the packed bed for the cracking reaction ............................................... 16
2.4. Characterization of raw materials and products............................................................ 17
2.4.1. Specific gravity and API density ........................................................................... 17
2.4.2. Kinematic Viscosity ............................................................................................... 17
2.4.3. Determination of fire point .................................................................................... 18
2.4.4. Distillation of products .......................................................................................... 18
3. Results and discussions ........................................................................................................ 19
3.1. Thermal cracking in a plug flow reactor ................................................................... 19
3.2. Catalyst preparation and packed bed cracking.......................................................... 22
3.3. Characterization of raw materials and products........................................................ 25
4. Conclusions and recommendations...................................................................................... 26
5. References and cited articles ................................................................................................ 26

7
6. Annexes................................................................................................................................ 30
6.1. PID controller code ....................................................................................................... 30
6.2. Temperature profiles ..................................................................................................... 42
6.3. Mass Balance tables ...................................................................................................... 43

8
List of figures
Figure 1. Simplified diagram of PFR used for cracking LMO ................................................ 13
Figure 2. Block diagram for cracking reaction. ....................................................................... 15
Figure 3. a) Diagram of equipment used in hydrocarbon distillation presented on the standard
ASTM D-86 30. b) 90% Distillation temperatures of hydrocarbons as a function of carbon
number31................................................................................................................................... 19
Figure 5. Mass balance in thermal cracking reactions at temperatures: a)340°C, b)360°C,
c)380°C and d)400°C. .............................................................................................................. 21
Figure 6. Mesoporous aluminosilicate prepared on an acidic medium. .................................. 22
Figure 7. Packing configuration of the cracking reactor.......................................................... 23
Figure 8. a) Temperature profile for the catalytic cracking reaction in a packed bed reactor. b)
Mass balance for catalytic cracking reaction using a mesoporous aluminosilicate as a catalyst
in a packed bed reactor. ........................................................................................................... 23
List of tables
Table 1. Mass balance for thermal cracking reactions at different temperatures. ................... 21
Table 2. Volume and porosity results from reactor packing. ................................................... 23
Table 3. Cracking mass balance results for thermal and catalytic cracking at 360°C. ............ 24
Table 4. Characterization of cracking raw materials and distilled products. ........................... 25

9

José Noboa1, Andrés Torres1, Alexis Hidrobo1, Daniela Almeida Streitwieser1
1
Instituto de Energías y Materiales Alternativos, Departamento de Ingeniería Química, Universidad San Francisco de Quito
USFQ, Av. Diego de Robles y Vía Interoceánica ,Quito, Ecuador
Abstract
The worldwide automobile market is constantly growing, increasing the demand of lubricant
motor oil (LMO) and, in consequence, generating more LMO waste and contamination. An
alternative for dealing with this contaminant is by breaking the long hydrocarbon chains of
LMO with cracking technologies in thermal or catalytic processes. In this study, thermal and
catalytic cracking of LMO were analyzed using a Plug Flow Tubular Reactor (PFTR) to obtain
diesel-like fuels among other products. The products were separated into gases, liquids and
residues in a flash distillation column. The catalyst used was a mesoporous aluminosilicate
prepared on an acidic medium by condensation of a xerogel prepared from tetraethyl
orthosilicate (TEOS) and aluminum tri-sec-butylate (TBA) using Triton X-114 as a porogen
agent. Thermal cracking was evaluated at a PFTR with reaction temperatures between 340°C
and 400°C with the highest yields of 7.44% and 8.02% at 360°C and 400°C, respectively.
However, in reactions at 400°C high losses of gaseous products as fumes were observed. For
the catalytic cracking, the aluminosilicates showed an increase in yield at 360°C from 7.44%
to 9.02%, showing the positive effect of using mesoporous aluminosilicates as catalysts in a
packed bed reactor for the cracking process.
Keywords: lubricant motor oil (LMO), thermal cracking, catalytic cracking, plug flow tubular
reactor (PFTR), packed bed reactor.

10
1. Introduction
In the last decades, world development has become petroleum-dependent; consequently, the
amount of waste and residues from it has become a major environmental threat. Refined oil
products are obtained through different separation processes and reactions, producing a high
versatility of materials and compounds. These derivatives are used to synthesize different
chemical precursors, raw materials or fuels1. One of the distillation fractions obtained from
crude oil is lubricant motor oil (LMO), used to lubricate the mobile parts in machines and most
commonly used by the automotive industry. New developments in LMO tend to improve fuel
economy in new cars2. LMO is a mixture composed of base lubricant oil, which makes up
3,4
about 95% of long hydrocarbon chains between C18 to C44 . Among these chains, some
components can be naphthenic, paraffinic or aromatic compounds5, the remaining 5% is made
from additives. The latter are added to improve the resistance to wear, to improve oxidation
resistance, to control corrosion and contamination from reaction and wear products, to reduce
the effect of temperature over LMO’s viscosity, and to enhance the lubricant characteristics by
inhibiting foam generation and reducing pour point5.
Due to the increase in the demand of LMO and the lack of mineral hydrocarbon sources 6, three
types of LMO are produced: mineral, synthetic or semisynthetic (mixture of both). Mineral
LMO is extracted directly from the distillation of crude oil, and its molecules contain
approximately 30 carbon atoms arranged in aliphatic and cyclic chains5. Synthetic LMO is
prepared by chemical reactions for carbon bonds formation by adding different organic
compounds like esters, olefins, glycol and aliphatic hydrocarbons. Synthetic LMO is preferred
in some cases over mineral LMO since high temperatures have a mild effect over its properties,
and it does not combust or explode when exposed to oxidizing agents, however, this type of
synthetic oil is less available and more expensive5.

11
The LMO consumption growth is a potential environmental problem since used LMO contains
heavy metals from the motor wear added to the oil hydrocarbons, out of which some may be
carcinogens7. Considering the high number of cars and trucks in circulation, and that the useful
life of LMO for gasoline and diesel engines is of 5 000 to 15 000 km8, used LMO can be
considered a major contaminant. This residue is one of the most problematic soil and water
contaminants. In fact the United States Environmental Protection Agency (EPA) has reported
that one gallon of used LMO can pollute up to one million gallons of water, which are
challenging to treat in traditional water treatment plants9. Used LMO must be collected by
environmental managers, who can treat the used oil to reuse or recycle it. The recycle process
consists of filtration to prepare lubricating base oil and reusing involves thermal processes, like
pyrolysis or cracking. Nevertheless, the most common treatment is incineration, if possible
with energy recovery10.
Current investigations are converging towards non-petroleum dependent energies and
generally green technologies. One of these investigation branches is the search for alternative
energies, sources and technologies. Producing energy and fuels from residues and second-
generation raw materials, such as used LMO, is an alternative for energy production and a way
of dealing with the contamination problem11–15. In this study, an alternative proposal for
treating used LMO residues is presented, which consists of cracking the LMO into shorter
molecules, conserving the high energetic potential of the used LMO. Hydrocarbon cracking is
the breaking of long chains of molecules into smaller ones, producing lighter compounds which
can be given different uses 16.
There are two types of cracking technologies: thermal and catalytic. Thermal cracking consists
of subjecting the sample under high temperatures and pressures, to break it down physically
into smaller molecules. These molecules are in consequence lighter and can be separated by
17
distillation processes . The cracking products are not necessarily homogeneous since they
12
could be gaseous, liquid or even solid. Coke generation is not a desirable byproduct, but an
unavoidable one in this process18. Catalytic cracking is similar to thermal cracking, but the
mechanism is slightly different. The reaction requires lower activation energy for the reaction,
and the yield of the desired product can be improved. The catalyst speeds up the process and
increases the selectivity of the reaction, thereby increasing the quality and the quantity of the
desired fraction (e.g. gasolines)19.
Many catalysts have been tested to evaluate their effect on the reaction kinetics, and the yield
in continuous reactors. In previous investigations, mesoporous aluminosilicates have shown
effective catalytic activity in batch systems11,20. These catalysts are used in heterogeneous
processes where the reactants are adsorbed on the catalysts surface, the reaction occurs, and
the products are desorbed. For this reason, catalysts need a high surface area, and thus
mesoporous materials (e.g. aluminosilicates or silicoaluminophosphates) are used, since they
allow diffusion of long chain molecules as found in used LMO with diameters between 20°A
and 200 A°. On the other hand, zeolites are microporous and do not allow the diffusion of big
molecules20–22.
One of the most common arrangements to perform a catalytic reaction is using a packed bed
reactor. This setup does not suspend the catalyst in the reactants flow, but rather has it fixed to
the reactor; thus, it is simpler to recover the catalysts. It is easier to scale up than Batch reactors
and simpler to operate than other catalytic reactors (e.g. fluidized catalytic reactors). This
research evaluates the thermal and catalytic cracking of new mineral LMO using a continuous
stainless-steel Plug Flow Tubular Reactor (PFTR) to produce lighter hydrocarbon fractions that
can be used as fuels. The products will be separated in a distillation column and stored to be
characterized using laboratory equipment to measure density, viscosity, fire point and
distillation point.
13
2. Methods and Materials
2.1. Raw material pretreatment
For this process, new mineral 15W40 LMO has been used, to avoid the side effects of metals,
emulsions formed by the contact of LMO with water and fuels and other contaminants that
come from motor wear23. Therefore, the feed does not need any thermal pre-treatment process,
since it will not have water content that need to be removed, as it is done in previous and similar
investigations 12,13
. However, the LMO was passed through a 200 μm stainless steel mesh to
prevent any possible solid contamination from entering the system.
2.2. Experimental equipment
The equipment used for thermal and catalytic cracking is a continuous PFTR. It consists of a
5.5-liter storage tank (T-1) where the new LMO was stored before it was pumped by P-1 at a
flow rate of 60 mL/min to a tubular heating zone (HZ-1). HZ-1 is a 2.50 m long ½” stainless
steel tube where the temperature of the LMO is increased up to the desired reaction temperature
by using an external electrical resistance of nickel-chromium, which supplies around 2000 W
power to the system. The residence time in HZ-1 was close to 4.70 minutes. The heated LMO
entered the reactor (R-1) and remained in the reaction zone for about 0.40 minutes. R-1 is a
0.18 m long ½” stainless steel tube where the cracking reaction takes place. A diagram of the
equipment is shown in Figure 1.
Figure 1. Simplified diagram of PFR used for cracking LMO

14
The products were separated in a flash distillation column (DC-1) heated with three 60 Ω
resistances and filled with 1” diameter and 1 cm length stainless steel rings; this is equivalent
to six theorical plates24. Finally, the liquid products were collected and stored in amber flasks
for posterior analyses.
The reaction was performed at steady state conditions during 65 minutes after the desired
temperature is reached. Equation 1 was used to keep track of the process’ mass balance.
𝑚𝐹 − 𝑚𝐵 − 𝑚𝐷 = 𝑚𝐿 [𝑔] (1)
Where mF is the mass fed by P-1, mB is the unreacted LMO that could be reused and was
collected at the bottom of the distillation column from L-10, mD refers to the liquid obtained
from the distilled products from L-8, and mL is the amount of mass lost in the process, mainly
in non-condensable gases from L-8.
The electrical resistances were controlled using a PID system that kept the process’ temperature
steady. The thermal cracking in the PFR was evaluated for initial reaction temperatures
between 340°C and 400°C in 20°C steps. The cracking process was evaluated by measuring
the yield of the liquid and gaseous products as function of the reaction temperature.
The temperature at the head of the distillation column was kept at 70°C. The column was kept
10% flooded and the condensate liquid at the top was collected at a temperature of 30°C, while
the residues at the bottom of the column were collected at 120°C. A simplified block diagram
of the process is presented in Figure 2.

15
Figure 2. Block diagram for cracking reaction.
The light fraction products obtained from the top of the column at L-8, in the diagram presented
in Figure 1, were both liquid and non-condensable gases. Since the fractions of interest are to
be used as fuels, the liquid was collected in a graduated cylinder, and the non-condensable
gases in a polyethylene sealed Tedlar bag.
After the reaction ended, yield of liquids, YLiq, and gases, YGas, were calculated using equations
2 and 3 respectively.
𝑚𝐷
𝑌𝐿𝑖𝑞 = × 100 (%) (2)
𝑚𝐹
𝑚𝐿
𝑌𝐺𝑎𝑠 = × 100 (%) (3)
𝑚𝐹
2.2. Catalyst preparation
The catalysts used in this study are mesoporous aluminosilicates with high surface area, that
have shown an effective catalytic activity in previous investigations 11. Also, their properties
can be modified in order to fulfill the industrial needs; thus, they are commonly used in the
hydrocarbon industry.
To prepare these aluminosilicates, tetraethyl orthosilicate, 𝐶8𝐻2𝑂4𝑆i (TEOS), was used as a
silicon source, aluminum tri-sec-butylate, 𝐴𝑙[𝑂𝐶𝐻(𝐶𝐻3)𝐶2𝐻5]3 (TBA), was the aluminium

16
source and the porogen agent was Triton X-114. The aluminosilicate was formed by
condensation of the xerogel formed by the reactants as described by Hidrobo et al.25.
First, 4.5211 g of Triton X-114 were mixed with 60 mL of water in a 250 mL Erlenmeyer and
stirred at 8 000 rpm for 15 minutes until a thick foam was formed. After that, 5 drops of nitric
acid were added until the pH of the solution was 1. When the desired pH was reached, 23.1049
g of TEOS were added to the solution by dripping it from a separating funnel, and then it was
stirred for two hours. Meanwhile, in another 250 mL Erlenmeyer 3.7707 g of TBA were
weighed. The previous mixture was transferred to the Erlenmeyer with TBA, and this new
mixture was stirred at 8 000 rpm for 24 hours. The thick mixture was transferred to a
hydrothermal PTFE reactor and left hermetically closed in an oven for 24 hours at 150°C. After
this hydrothermal treatment, the solid product was washed with a 50/50 water/ethanol solution
using a Büchner flask. The solids were transferred to a porcelain capsule and calcinated in a
muffle furnace at 550°C for 24 hours.
2.3. Preparation of the packed bed for the cracking reaction
To pack the reactor with the catalysts, a 200 μm stainless steel mesh was placed on one edge
of the 0.18 m stainless steel reactor, followed by approximately 1.5 g of glass wool. The reactor
was then filled with the catalyst and pumice rock at a ratio of 0.49 (volume of catalyst by
volume of pumice rock). Pumice was used to fill the reactor and to avoid the catalysts from
being suspended in the LMO. The reactor was filled until it had a total porosity (ƐT) around 0.2
(80% packed) according to the equation:
𝑉𝑜𝑖𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑜𝑙𝑢𝑚𝑛

Ɛ𝑇 = (4)
𝐸𝑚𝑝𝑡𝑦 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑐𝑜𝑙𝑢𝑚𝑛
Where the void and empty volumes were measured experimentally by filling the reactor with
distilled water and measuring the capacity with a graduated cylinder. For the actual cracking
reaction, the procedure was the same as the one described in section 2.1. The cracking
17
temperature was chosen as the one that showed the highest yield when thermal cracking was
evaluated.
2.4. Characterization of raw materials and products
To identify the raw material and the distilled products, different characterization processes had
to be done.
2.4.1. Specific gravity and API density
Specific gravity of LMO and cracking products was measured at 15°C to compare this density
to the values that are reported using the standard ASTM D-129826. This was used to determine
density and API density gravity at 15°C (60°F) and these results were compared with the values
reported by the Ecuadorian Normalization Institute (INEN)27 for diesel and gasoline fuels. To
determine the specific gravity (ɣ), a hydrometer was used keeping the sample cool in a water
bath at 15°C for 45 minutes. To calculate density (ρ), and API density equations 5 and 6 were
used.
𝜌𝑠𝑎𝑚𝑝𝑙𝑒
ɣ= (5)
𝜌𝑤𝑎𝑡𝑒𝑟
141.5
𝐴𝑃𝐼 = − 131.5 (6)
ɣ
All this information and the water density were taken at 15°C.
2.4.2. Kinematic Viscosity
Viscosity was measured with a Cannon-Fenske size 25 viscometer with a 0.002 cSt/s constant
(cv). Just like the density, the sample and the instrument were placed on a water bath to keep
the temperature at 40°C for more than 45 minutes according to the standard ASTM D-445,
Standard Method of Test for Viscosity of Transparent and Opaque Liquids 28. The water bath
was used in order to make the sample more fluid, and, therefore, take less time to move between
18
the calibrated marks of the viscometer. The time was taken in seconds to use the constant and
find the kinematic viscosity (υ) knowing the time (t) using equation 7.
𝜐 = 𝑐𝑣 × 𝑡 (𝑐𝑆𝑡) (7)
2.4.3. Determination of fire point
To determine the fire point, the procedure followed was based on the standard ASTM D-9229,
with small variations for availability purposes. First, 80 mL of the samples were placed on 100
mL beakers, the samples were heated using a Bunsen burner. To record the temperature a
thermometer is placed so the end of the sensor is approximately 1.25 cm from the bottom of
the beaker, when the samples were hot, approximately 30°C colder than the expected fire point
a flame is slowly put in contact with the surface of the sample. The fire point is the temperature
when the surface of the sample catches on fire and the flame lasts for more than five seconds.
2.4.4. Distillation of products
The light fractions were distilled to record the gas temperature when 90% of the samples had
been evaporated and recovered. The equipment used was a Precision Scientific Petroleum
Herzog with a maximum power of 1100 W, normalized according to the ASTM D-86: Standard
Test Method for Distillation of Petroleum Products at Atmospheric Pressure30. The equipment
is presented in Figure 3.a); it includes a distilling flask were 100 mL of the sample were poured;
the thermometer was placed in line with the glass connection to the condenser. The condenser
was submerged in a cool bath with temperatures between 0°C and 5°C, the distilled product
was collected in a closed graduated cylinder at 18°C approximately.

19
Figure 3. a) Diagram of equipment used in hydrocarbon distillation presented on the

standard ASTM D-86 30. b) 90% Distillation temperatures of hydrocarbons as a function of
carbon number31.
From this distillation test, the temperature was recorded when 90% of the sample is distilled
so it can be compared to the relationship between the temperature and the carbon number of
the hydrocarbon, presented in Figure 3.b). The relationship is presented in: Properties,
Specifications, and Quality of Crude Oil and Petroleum Products and published by ASTM 31.
3. Results and discussions
3.1. Thermal cracking in a plug flow reactor
First, to study LMO cracking using a PFR, steady temperature profiles of the reactor at different
temperatures had to be assured. To see how controllers kept a steady temperature over time,
Figure 4 is presented.
20
a) 400 b) 400
350 350
300 300
Temperature [°C]
Temperature [°C]
250 250
T_in [°C] T_in [°C]
200 200
T_out [°C] T_out [°C]
150 150
T_col [°C] T_col [°C]
100 100
50 50
0 0
0 20 40 60 80 0 20 40 60 80
Time [min] Time [min]
c) 400 d) 400
350 350
300 300
Temperature [°C]
Temperature [°C]
250 250
T_in [°C] T_in [°C]
200 200
T_out [°C] T_out [°C]
150 150
T_col [°C] T_col [°C]
100 100
50 50
0 0
0 20 40 60 80 0 20 40 60 80
Figure 4. Temperature profiles for thermal cracking at temperatures: a)340°C, b)360°C,
c)380°C and d)400°C.
Figure 4 shows that, during the reaction, the temperatures at the exit of the heating zone HZ-1
and entering the reactor R-1 (T_in), the temperature at the exit of the reactor R-1 (T_out), and
the gas temperature at the top of the distillation column (T_col) are kept constant over time,
showing steady state conditions. Also, the graphs evidence that there is a slight systematic
error, since the temperature at the start of the reactor was around 10°C less than the set
temperature.
To compare the cracking reactions at different temperatures, the mass balance presented in
equation 1 was used. The process was carried out with an inlet flow rate of 60 mL/min, and the
output streams at the exit of the column were measured continuously. The results from the
mass balance over time for different reaction temperatures are presented in Figure 5.
21
a) 4000 b) 4000
mF [g] mF [g]
3500 3500
mB [g] mB [g]
3000 3000
mD [g] mD [g]
2500 2500
Mass [g]
Mass [g]
mL [g] mL [g]
2000 2000
1500 1500
1000 1000
500 500
0 0
0 20 40 60 80 0 20 40 60 80
c) 4000 d) 4000
mF [g] mF [g]
3500 3500
mB [g] mB [g]
3000 3000
mD [g] mD [g]
2500 2500
Mass [g]
Mass [g]
mL [g] mL [g]
2000 2000
1500 1500
1000 1000
500 500
0 0
0 20 40 60 80 0 20 40 60 80
Figure 4. Mass balance in thermal cracking reactions at temperatures: a)340°C, b)360°C,
c)380°C and d)400°C.
From Figure 5 it is evident that more distilled mass was recovered at 360 and 400°C cracking
temperatures. The overall mass balance and yield calculations are presented in Table 1. The
residence time in the reactor (τ) was 0.40 minutes. The experiments were carried out twice and
the results presented are the mean of the data obtained.
Table 1. Mass balance for thermal cracking reactions at different temperatures.
Cracking
mB mD mL YLIQ Unreacted
Temp mF [g] YGAS [%]
[g] [g] [g] [%] [%]
[°C]
340 3432 3089 195 148 5.69 89.99 4.32
360 3432 3119 255 58 7.44 90.88 1.68
380 3432 3153 195 84 5.67 91.87 2.46
400 3432 2736 275 421 8.02 79.72 12.26
22
The results show that at 360°C and 400°C the highest liquid yields of 7.44% and 8.02% are
reached, respectively. However, at 400°C the mass losses, as a gas yield, of 12.26% are higher
than the desired product yield of 8.02%. These experiments become difficult to handle, because
the mass loss comes from non-condensable products which are exiting through the bottom of
the column at high temperatures without being cooled down in the condenser. The cracking
process at 400°C was also more difficult to handle, as the distilled and bottom products left the
distillation column at a high temperature at 60°C and 215°C, respectively, whereas at a reaction
temperature of 360°C the products exit at about 30°C and 120°C respectively. Therefore,
according to the results from Table 1 and the fact that the 360°C cracking reaction was easier
to operate and the yield was higher than other cracking temperatures (with the exception of the
reaction at 400°C), 360°C was chosen as the reaction temperature for the catalytic process.
3.2. Catalyst preparation and packed bed cracking
The aluminosilicates used for this process as catalysts were prepared following the procedure
presented in section 2.2. For the catalysts, the particles with diameters greater than 2 mm were
chosen since they are not suspended in the oil and therefore are ideal for packing the reactor.
Figure 6 shows the aluminosilicates obtained.
Figure 5. Mesoporous aluminosilicate prepared on an acidic medium.

23
The packing configuration of the catalyst into the reactor is shown in Figure 7. This
configuration allows the LMO to flow smoothly and kept the catalyst from being suspended in
the liquid and carried out of the reactor.
LMO
FLOW
Figure 6. Packing configuration of the cracking reactor.

Empty and void volumes were measured to calculate porosity with equation 4. The results for
volume and porosity for two configurations are shown in Error! Reference source not found..
Table 2. Volume and porosity results from reactor packing.
Type Void Volume [mL] Mass [g] Total Porosity

Empty Reactor (E.R.) 16.9 - -
E.R. + Glass Wool + Pumice 1.4991
7.2 0.43
Rock (P.R) (P.R.)
E.R. + G.W. + P.R. + 1.7644
3.1 0.18
Catalyst (Cat.) (Cat.)
The total porosity after the reactor was packed was 0.18 which means that it was 82% full of
glass wool, pumice rock and catalyst. The LMO inlet flow was kept constant at 60 mL/min and
τ was 0.40 minutes. The temperature profile for this reaction is shown in Figure 7a), showing
a steady temperature profile during the cracking reaction and the same systematic deviation of
-10°C from the set temperature.
a) 400 b) 4000
mF [g]
350 3500
mB [g]
300 3000
Temperature [°C]
mD [g]
250 2500
Mass [g]
T_in [°C] mL [g]

200 2000
T_out [°C]
150 1500
T_col [°C]
100 1000
50 500
0 0
0 20 40 60 80 0 20 40 60 80
Figure 7. a) Temperature profile for the catalytic cracking reaction in a packed bed reactor.
b) Mass balance for catalytic cracking reaction using a mesoporous aluminosilicate as a
catalyst in a packed bed reactor.
24
The mass balance for the catalytic reaction is shown in figure 8 b). This figure shows that this
catalytic reaction was more stable than some thermal cracking mass balances and the mass loss
is very small. Table 3 shows a comparison between thermal cracking at 360°C and catalytic
cracking at the same temperature.
Table 3. Cracking mass balance results for thermal and catalytic cracking at 360°C.
Cracking
Cracking mB mD mL YLIQ Unreacted YGAS
Temp. mF [g]
Type [g] [g] [g] [%] [%] [%]
[°C]
Thermal 360 3432 3119 255 58 7.44 90.88 1.68
Catalytic 360 3432 3084 309 39 9.02 89.86 1.12
Table 3 summarizes the yield, the lost mass and the unreacted percentage. These results show
an improvement with the catalytic cracking over the thermal cracking in the liquid yield from
7.44% to 9.02% at a 360°C. Also, the lost mass percentage lowered from 1.68% to 1.12% in
the catalytic process, so the unreacted LMO is not being degraded, thus allowing it to be reused.
This improvement is due to the increase in selectivity in catalytic reactions, where the desired
reaction is favored. However, for a more precise analysis of the selectivity improvement,
experiments on the reaction mechanisms and on parallel reactions should be carried out. These
experiments were carried out twice with very similar results and the data presented in Table 3
is the average of the results.
The results from the thermal and catalytic cracking agree with the results presented by Molina
et al. since the highest yield was achieved with a reaction carried out at 360°C24. These results
show great improvement from previous investigations 12,13,24, where the yield was lower than
4% (whereas in this study the lowest yield was 5.67%) and the minimum lost mass was around
1.65%.
25
3.3. Characterization of raw materials and products
Since one of the goals of this study was to produce Diesel like fuels, the characterization results
were compared to the results from Diesel type II reported by INEN in the INEN 1489:2012
standard27. The results from the characterization are presented in Table 4.
Table 4. Characterization of cracking raw materials and distilled products.

INEN Thermal Catalytic
Raw
Property 1489:2012 Cracking Cracking
LMO
Diesel II at 360°C at 360°C
Kin. Viscosity
2.0 - 5.0 102.7 3.1 3.7
@40°C [cSt]
Density @15°C
~ 0.87 0.88 0.86 0.86
[g/mL]
API Grade
̴ 33.00 29.82 33.56 33.88
@15°C
90% Distillation
< 360 - 220 225
Temperature [°C]
Fire Point [°C] > 51 - 51 52
From this table, it is safe to assume that the distilled products from the cracking process have
very similar properties to the ones presented for Diesel type II according to INEN 1489:2012.
The results for Raw LMO agree with the properties given by the supplier of this LMO with
SAE:15W40. The fire points of both samples were close to the minimum of 51°C reported by
INEN and the distillation temperature was low in comparison. This means that the products are
a light version of Diesel with a low carbon number, between C12 and C15.
Both thermal and catalytic cracking products are like Diesel type II, also by analyzing the 90%
distillation temperature using the graph presented by M. R. Riazi and S. Eser (Figure 3.b)31 it
is possible to get an approximation of the carbon number of the products. From the graph it
can be determined that the products have a carbon number between to C12 and C15
approximately, which agrees with the composition of Diesel-like fuels11,32.

26
4. Conclusions and recommendations
This study has shown that thermal and catalytic cracking of lubricant motor oil (LMO) in a
continuous Plug Flow Tubular Reactor (PFTR) are alternative processes for dealing with this
harsh contaminant, producing fuels similar to Diesel type II. Experiments of thermal cracking
using a PFTR have shown that the reaction temperature plays an important role on the yield of
the process, with the highest values of 7.44% and 8.02%, obtained with reactions at 360 and
400°, respectively. However, the reaction at 400°C showed a high mass loss (12.26%) given
by a higher gas product yield, which could be problematic to handle. Catalytic cracking
reaction showed an increase in the reaction yield at 360°C from 7.44% to 9.02%. The catalysts
were mesoporous aluminosilicates prepared by condensation in an acidic medium. The
catalytic cracking also showed less mass lost than all the other cracking scenarios of only
1.12%. This means that the selectivity of the desired cracking reaction is increased, and
therefore, LMO was not degraded into volatile gases. These results show a considerable
improvement in yield compared to previous investigations. For future studies, the samples need
to be analyzed with gas chromatography to see how the fractions are distributed and thereby
allow a better comparison with other fuels, lighter than diesel.
5. References and cited articles
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Unused and Used Motor Oils. Sci. Total Environ. 1983, 32, 55–64.
(8) Marcheva, M.; Droppa, P.; Marko, M. The Degradation of Engine Oil O-239, SAE
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Reacción de Craqueo Térmico de Aceites Lubricantes Nuevos y Usados En Un
Reactor de Lecho Fijo., Universidad San Francisco de Quito, 2017.
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(PFTR) by Catalytic Cracking of Used Motor Oil, Universidad San Francisco, 2018.
(14) Meier, H. F.; Wiggers, V. R.; Zonta, G. R.; Scharf, D. R.; Simionatto, E. L.; Ender, L.
A Kinetic Model for Thermal Cracking of Waste Cooking Oil Based on Chemical
Lumps. Fuel 2015, 144, 50–59. https://doi.org/10.1016/j.fuel.2014.12.020.
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A. A Study of the Catalytic Steam Cracking of Heavy Crude Oil in the Presence of a
Dispersed Molybdenum-Containing Catalyst. Pet. Chem. 2017, 57 (7), 618–629.
https://doi.org/10.1134/S0965544117070088.
(16) Kunwar, B.; Chandrasekaran, S. R.; Moser, B. R.; Deluhery, J.; Kim, P.; Rajagopalan,
N.; Sharma, B. K. Catalytic Thermal Cracking of Postconsumer Waste Plastics to
Fuels. 2. Pilot-Scale Thermochemical Conversion. Energy and Fuels 2017, 31 (3),
2705–2715. https://doi.org/10.1021/acs.energyfuels.6b02996.
(17) Demirbas, A. Gasoline-like Fuel from Waste Engine Oil via Catalytic Pyrolysis.
Energy Sources, Part A Recover. Util. Environ. Eff. 2008, 30 (16), 1433–1441.
https://doi.org/10.1080/15567030701258469.
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(18) Jambor, B.; Hájeková, E. Formation of Coke Deposits and Coke Inhibition Methods
during Steam Cracking. Pet. Coal 2015, 57 (2), 143–153.
(19) Speight, J. G. The Chemistry and Technology of Petroleum, Fourth.; Heinemann, H.,
Ed.; CRC Press: Boca Ranton, 2006.
(20) Hidrobo, A.; Retuert, J.; Araya, P. Aluminosilicatos Mesoporosos Catalíticamente
Activos Obtenidos Usando El Biopolímero Quitosano Como Agente Formador de
Poros. Av. en Ciencias e Ing. 2016, 1 (1), 1–5. https://doi.org/10.18272/aci.v1i1.8.
(21) Araujo, A. S.; Domingos, T. B.; Souza, M. J. B.; Silva, A. O. S. Xylene Isomerization
in SAPO-11/HZSM-5 Mixed Catalyst. React. Kinet. Catal. Lett. 2001, 73 (2), 283–
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(22) Csicsery, S. M. Shape-Selective Catalysis in Zeolites. Zeolites 1984, 4 (2), 116–126.
(23) Uthman, H. Recycling and Characterisation of Spent Lubricating Oil. Int. J. Environ.
Waste Manag. 2017, 19 (2), 181. https://doi.org/10.1504/IJEWM.2017.10004681.
(24) Molina Barrera, C. Diseño, Construcción y Puesta En Marcha de Un Reactor de Lecho
Fijo En Acero Inoxidable Para El Craqueo Catalítico de Aceites Lubricantes Usados,
Universidad San Francisco de Quito, 2015.
(25) Hidrobo, A.; Retuert, J.; Araya, P. Aluminosilicatos Mesoporosos Obtenidos
Utilizando Tritón X. - SíNtesis, Caracterización Textural y
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Ecuatoriana INEN 1 48999 6ta rev. 2012, i, 1–6.
(28) ASTM. Standard Test Method for Kinematic Viscosity of Transparent and Opaque
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6. Annexes
6.1. PID controller code
#include <Key.h>
#include <Keypad.h>
//////////////////////////////////////////////////////////////////////////
// PROYECTO REACTOR DE CRACKEO //
//FIRMWARE: CRAKEO versiÃ³n: V1 solo para arduino MEGA //
// no funciona para arduino uno //
// //
//////////////////////////////////////////////////////////////////////////
// TECLADO 4X4 //
// modo de conectar: //
31
// teclado pin8 a arduino pin2 //

// teclado pin1 no coneccion HABILITA LA COLUMNA DE LETRAS //
//////////////////////////////////////////////////////////////////////////
// modo de conectar LCD //
//LCD es I2C, pin SDA de LCD a pin SDA en RTC del lado de + pines //
//LCD es I2C, pin SCL de LCD a pin SCL EN RTC del lado de + pines //
//////////////////////////////////////////////////////////////////////////
// modo de conectar RTC DS1307 //
//RTC es I2C, pin SDA de RTC del lado de - pines a pin Arduino mega 20 //
//RTC es I2C, pin SCL de RTC del lado de - pines a pin Arduino mega 21 //
// V de RTC es a 5V talvez no haga falta el GND //
// GND del RTC del lado de - pines se conecta a GND del arduino //
//////////////////////////////////////////////////////////////////////////
// thermoCS es pin 25 del arduino y es para todos los chips MAX6675
// thermoCLK (SCK) es pin 26 del arduino es para todos los chips MAX6675
// thermoDO es el pin 22 del arduino, es datos DO del sensor No. 1
// thermoDO2 es el pin 23 del arduino, es datos DO del sensor No. 2
// thermoDO3 es el pin 24 del arduino, es datos DO del sensor No. 3
//
//
// Reset por software de arduino pin9 a arduino reset pero con TBJ //
// salida PWM es arduino pin11 //
//////////////////////////////////////////////////////////////////////////
#include <Wire.h>
#include "RTClib.h";
#include <LiquidCrystal_I2C.h> // libreria para la pantalla
#include <Key.h>
#include <Keypad.h> //libreria para el teclado
#include <Time.h>
#include "max6675.h"
#include <SPI.h>
#include <EEPROM.h>
#define address 0
struct DATOS{
float temperatura;
float proporcional;
float integral;
//boolean usable;
int tiempo_grabar;
};
union MEMORIA{
DATOS dato;
byte b[sizeof(DATOS)];
}
32
miMemoria;
int thermoDO = 22;
int thermoCS = 25;
int thermoCLK = 26;
int thermoDO2= 23;
int thermoDO3= 24;
MAX6675 thermocouple(thermoCLK, thermoCS, thermoDO);
MAX6675 thermocouple2(thermoCLK, thermoCS, thermoDO2);
MAX6675 thermocouple3(thermoCLK, thermoCS, thermoDO3);
RTC_DS1307 RTC;
#define reset 9
#define PIN_OUTPUT 11 //salidoa PWM para rele SSD
float Setpoint, Input, Output, error;
float Input2, Input3;
float Kp=12, Ki=0.8, Kd=0;
const byte rows = 4;
const byte cols = 3;
char keys[rows][cols] = {
{'1','2','3'},
{'4','5','6'},
{'7','8','9'},
{'*','0','#'}
};
//////////////////////////////////////////////////////////////////////////
byte rowPins[rows] = {2, 3, 4, 5}; //connect to the row pinouts of the keypad en orden F1,
F2...
byte colPins[cols] = {6, 7, 8}; //connect to the column pinouts of the keypad en orden C1,
C2..
Keypad keypad = Keypad(makeKeymap(keys), rowPins, colPins, rows, cols ); //inicializa el
teclado echo por una libreria en arduino
LiquidCrystal_I2C lcd(0x27, 16, 2);
int calentador = 9; //reset
int cal=0;
int temp=0;
int temp0=0;
unsigned int n = 1;//contador de loop
unsigned int m=1;
float tempF=2.5;
int tiempo;
float temporal;
int tiempog=2;
////////////////////////////////////////
void setup() {
Wire.begin();
RTC.begin();
Wire.begin();
RTC.begin();
RTC.adjust(DateTime(__DATE__, __TIME__)); // descomentar para igualar el reloj
Serial.begin(9600); // inicializa el monitor serial
lcd.init(); //inicializa la lcd
33
lcd.backlight(); //inicializa el contraste de la lcd

lcd.setCursor(0,0);
lcd.print("CRACKE0 V1 ");
lcd.setCursor(0,1);
lcd.print("Calentador 1 ");
delay(1000);
lcd.clear();
//analogReference(INTERNAL1V1);
}
////////////////////////////////////////
void loop() {
// Input = thermocouple.readCelsius();
// Input2 = thermocouple2.readCelsius();
// Input3 = thermocouple3.readCelsius();
// recuperar datos de la memoria EEPROM:
for( int i=0 ; i<sizeof(DATOS) ; i++ )
miMemoria.b[i] = EEPROM.read( address+i );
tempF=miMemoria.dato.temperatura;
Kp=miMemoria.dato.proporcional;
Ki=miMemoria.dato.integral;
tiempog=miMemoria.dato.tiempo_grabar;
char tecla=keypad.getKey();
if (tecla != NO_KEY){
switch (tecla) {
case '*': // entrar en modo calibracion
Serial.println("modo calibracion");
cal=1;
menu();
break;
case '#':
// entrar en modo informacion
Serial.println("modo informacion");
cal=1;
presentarPID();
break;
}
}
// Temp_inicial = (analogRead(A0)*0.1)-1; //temperatura del rio
//Serial.println(Temp_inicial);
// Setpoint=(Temp_inicial+tempF); //descomentar para cargar
Input2 = thermocouple2.readCelsius();
Input3 = thermocouple3.readCelsius();
Setpoint=tempF; //coemntar para cargar
//while(lazo<=100){
float ahora=micros();
Input = thermocouple.readCelsius();
// Input = (analogRead(A8)*0.1); //temperatura salida del calentador
delay(500);
float error=Setpoint-Input;
float P=Kp*error;
34
float despues=micros();
float tiempo=despues-ahora;
float I=Ki*error*tiempo;
Output=P+I;
if(Output<0){Output=0;}
if(Output>254){Output=255;}
analogWrite(PIN_OUTPUT, Output);
//lazo++;
//}
//lazo=0;
n++;
//Serial.println(n);
if(n==3){ lcd.clear(); actualizar_lcd();m++;}
if(m==tiempog){ archivo();}
} //fin del programa principal
///////////////////////////////////////////
void menu(){
m=0;
while(cal==1){
lcd.setCursor(0,0); //columna 0 linea 0
lcd.print("MODO CALIBRACION ");
lcd.setCursor(0,1);
lcd.print("1TEM 2INF 3SALIR");
delay (1);
m++;
if(m==1000){ lcd.clear(); informe_config(); cal=0; m=1;digitalWrite(9, HIGH);return; }
char teclas=keypad.getKey();
if (teclas != NO_KEY){
switch (teclas) {
case '1': // modo calibarcion de temperatura
temp=1;
n=1;
temperatura();
break;
case '2': // entrar en modo informacion
Serial.println("modo informacion");
cal=1;
presentarPID();
break;
//////////////llamado menu calibracion///
case '8': // modo calibarcion de PID
cal=1;
n=1;
clave();
break;
//////////////////////////////////////////
case '3': // finalizar y enter
lcd.clear();
miMemoria.dato.temperatura = tempF;
miMemoria.dato.proporcional = Kp;
35
miMemoria.dato.integral = Ki;
miMemoria.dato.tiempo_grabar=tiempog;
for( int i=0 ; i<sizeof(DATOS) ; i++ )
EEPROM.write( address+i , miMemoria.b[i] );
Setpoint=tempF;
informe_config();
// analogWrite(9, 1);
digitalWrite(9, HIGH);
delay(100);
// digitalWrite(9, LOW);
// delay(100);
cal=0;
break;
}
delay(1);
}
}
return;
}
/////////////ACTUALIZA LCD /////////////////////////
void actualizar_lcd(){
// n=0;
// return;
///////////
// lcd.clear();
lcd.setCursor(0,0);
lcd.print("T1 T2 T3[oC]"); // print a simple message
lcd.setCursor(0,1); // move to the begining of the second line
// lcd.setCursor(3,1);
lcd.print(Input,0);
lcd.setCursor(5,1);
lcd.print(Input2,0);
lcd.setCursor(10,1);
lcd.print(Input3,0);
n=1;
return;
}
/////////////LEE TEMPERATURA PARA ARCHIVO /////////////////////////
void archivo(){
DateTime now = RTC.now();
Serial.print(now.day(), DEC);
Serial.print('/');
Serial.print(now.month(), DEC);
Serial.print('/');
Serial.print(now.year(), DEC);
Serial.print(';');
Serial.print(now.hour(), DEC);
Serial.print(':');
Serial.print(now.minute(), DEC);
Serial.print(':');
36
Serial.print(now.second(), DEC);
Serial.print(';');
Serial.print(Input);
Serial.print(';');
Serial.print(Input2);
Serial.print(';');
Serial.print(Input3);
Serial.print(';');
Serial.println(Output);
m=1;
return;
}
/////////////////////////////////////
void pid(){
m=0;
while(cal==1){
lcd.setCursor(0,0);
lcd.print("PID CALIBRACION ");
lcd.setCursor(0,1);
lcd.print("1KP 2KI 3SALIR");
delay (1);
m++;
char teclas=keypad.getKey();
if (teclas != NO_KEY){
switch (teclas) {
case '1': // modo calibracion de constante proporcional
temp=1;
n=1;
KP();
break;
case '2': // modo calibracion de constante integral
temp=1;
n=1;
KI();
break;
case '3': // terminar y enter
Setpoint=tempF;
lcd.clear();
menu();
cal=1;
break;
case '4': // menu escondido para ajustar tiempo de grabacion
temp=1;
n=1;
tiempo_grabacion();
break;
}
delay(1);
} }
37
return;
}
///////////////////////
void tiempo_grabacion(){
lcd.clear();
lcd.print("Antes tg:");
//lcd.print(" tg:");
lcd.print(tiempog);
teclado();
if(temporal<0){temporal=0;}
tiempog=temporal;
miMemoria.dato.tiempo_grabar=tiempog;
menu();
}
///////////////////////
void KI(){
lcd.clear();
lcd.print("Antes ");
lcd.setCursor(7,0);
lcd.print(" Ki:");
lcd.print(Ki,1);
teclado();
Ki=temporal*0.1;
miMemoria.dato.integral = Ki;
menu();
}
//////////////////////
void KP(){
lcd.clear();
lcd.print("Antes ");
lcd.setCursor(7,0);
lcd.print(" Kp:");
lcd.print(Kp,1);
teclado();
Kp=temporal;
miMemoria.dato.proporcional = Kp;
menu();
}
////////////////////////////
void temperatura(){
lcd.clear();
lcd.print("Antes Temp=");
// lcd.print("T:");
lcd.print(tempF,1);
teclado();
38
tempF=temporal;
miMemoria.dato.temperatura = tempF;
Setpoint=(tempF);
menu();
}
///////////////////////
void teclado(){
m=0;
int numero1=0;
int numero2=0;
int numero3=0;
while(temp==1){
char tecla=keypad.getKey(); //Lee tecla presionada por usuario
m++;
delay (5);
if (tecla != NO_KEY){ //verifica si una tecla esta presionada o no
if (n == 4 ){ //obtiene el numero de las decimas
numero3 = tecla - '0';
lcd.print(numero3);
n=5;
}
if (n == 2 && tecla =='*'){ //separdor de fraccion nuemro menores a 10
numero2=numero1;
numero1=0;
lcd.setCursor(9,1);
lcd.print(".");
n=4;
}
if (n == 3 && tecla =='*' ){ //separdor de fraccion
lcd.setCursor(9,1);
lcd.print(".");
n=4;
}
if (n == 2 ){ //obtiene el numero de las unidades
lcd.setCursor(8,1);
lcd.print(numero2);
n=3;
}
if ( n == 1 ){ //obtiene el numero de las decena
lcd.setCursor(0,0);
lcd.setCursor(7,1);
lcd.print(numero1);
n=2;
}
if ( tecla == '#'){ //tecla de enter
temporal=10*numero1 + numero2 + 0.1*numero3;
39
Setpoint=(tempF); //descomentar para cargar

//Serial.println(tempF);
lcd.setCursor(7,1);
lcd.println(tempF);
n=1;
cal=1;
temp=0;
numero1=0;
numero2=0;
numero3=0;
return;
// menu();
}
}
}
}
///////////////////////////////
void presentarPID(){
lcd.clear();
lcd.setCursor(0,0);
lcd.print(" CRACKEO V1 ");
delay (500);
lcd.clear();
lcd.setCursor(0,0);
lcd.print("Controlador 1");
lcd.setCursor(0,1);
lcd.print("Set:");
lcd.print(tempF);
lcd.setCursor(7,1);
lcd.print("Tmax:");
lcd.print(Setpoint);
delay (500);
lcd.clear();
lcd.setCursor(0,0);
lcd.print(" Datos PID ");
lcd.setCursor(0,1);
lcd.print("Kp:");
lcd.print(Kp);
lcd.setCursor(7,1);
lcd.print(" Ki:");
lcd.print(Ki);
delay (500);
informe_config();
}
///////////Informe configuracion/////
void informe_config(){
Serial.println("CRACKEO V1");
Serial.println("Calentador 1");
Serial.print("Setpoint: ");
Serial.println(tempF);
40
Serial.print("Parametros de PID: ");

Serial.print("Temperatura entrada: ");
Serial.print(Input);
Serial.print(" Kp: ");
Serial.print(Kp);
Serial.print(" ;Ki: ");
Serial.print(Ki);
Serial.print(" PWM:");
Serial.println(Output);
Serial.print("Intervalo de grabacion: ");
Serial.println(tiempog);
Serial.println("fecha;hora;T1;T2;T3");
lcd.clear();
m=0;
//temp0=1;
loop();
}
//////////////////////////////////////////
void clave(){
float abrir=328;
m=0;
lcd.clear();
lcd.print("*INGRESE CLAVE*");
m++;
temp=1;
teclado_abrir();
if (abrir==temporal*10){
lcd.clear();
lcd.setCursor(0,0);
delay(1000);
pid();
}else{
lcd.clear();
lcd.print("NO MOLESTES");
cal=0;
m=1;
delay(1000);
loop();
};
}
/////////teclado clave////////
void teclado_abrir(){
m=0;
int numero1=0;
int numero2=0;
int numero3=0;
while(temp==1){
char tecla=keypad.getKey(); //Lee tecla presionada por usuario
41
m++;
if(m==1000){ lcd.clear(); informe_config(); cal=0; m=1;return; }
delay (5);
if (tecla != NO_KEY){ //verifica si una tecla esta presionada o no
if (n == 4 ){ //obtiene el numero de las decimas

lcd.print("*");
n=5;
}
if (n == 2 && tecla =='*'){ //separdor de fraccion nuemro menores a 10
numero2=numero1;
numero1=0;
lcd.setCursor(9,1);
lcd.print("*");
n=4;
}
if (n == 3 && tecla =='*' ){ //separdor de fraccion
lcd.setCursor(9,1);
lcd.print("*");
n=4;
}
if (n == 2 ){ //obtiene el numero de las unidades

lcd.setCursor(8,1);
lcd.print("*");
n=3;
}
if ( n == 1 ){ //obtiene el numero de las decena
lcd.setCursor(0,0);
lcd.setCursor(7,1);
lcd.print("*");
n=2;
}
if ( tecla == '#'){ //tecla de enter
temporal=10*numero1 + numero2 + 0.1*numero3;
Setpoint=(tempF); //descomentar para cargar

//Serial.println(tempF);
lcd.setCursor(7,1);
lcd.println(tempF);
n=1;
cal=1;
temp=0;
numero1=0;
numero2=0;
numero3=0;
42
return;
// menu();
}
}
}
}
///// END /////////////
6.2. Temperature profiles
340
Time T_in St. Dv. T_out St. Dv. T_col St. Dv.
[min] [°C] Tin [°C] Tout [°C] Tcol
0 333 4 260 2 73 0
10 329 5 266 1 68 4
20 331 2 265 2 70 3
30 336 4 265 0 65 4
40 335 1 266 0 70 0
50 335 1 268 1 65 8
60 334 1 267 1 64 2
65 334 1 266 1 69 3
360
0 354 1 282 1 69 3
10 350 4 280 3 71 0
20 351 3 283 1 69 2
30 353 4 282 1 71 1
40 352 2 284 3 70 2
50 353 2 283 3 73 1
60 353 0 284 2 68 3
65 350 4 283 2 67 2
380
0 370 1 290 3 65 3
10 377 0 274 0 71 1
20 367 2 292 1 71 1
30 362 0 285 5 73 0
40 370 0 293 1 70 1
43
50 372 9 290 7 65 5
60 374 7 285 1 63 3
65 365 2 275 0 68 3
400
0 392 1 302 0 66 3
10 392 1 307 0 68 3
20 390 0 308 2 65 1
30 393 0 306 1 67 2
40 392 1 306 1 65 5
50 393 1 308 2 68 2
60 394 1 308 2 71 1
65 394 1 306 0 69 2
360 cat
0 349 5 278 1 72 2
10 350 1 272 4 62 2
20 351 1 278 1 67 1
30 349 1 278 1 67 1
40 351 2 277 1 70 4
50 351 3 276 4 67 7
60 353 1 277 1 61 0
65 352 3 275 2 63 2
6.3. Mass Balance tables
340
Time
[min] mF [g] mB [g] mD [g] mL [g]
0 0 0 6 0
10 528 475 15 38
20 1056 871 59 126
30 1584 1366 73 145
40 2112 1821 115 176
50 2640 2376 141 123
60 3168 2851 180 137
65 3432 3089 195 148
360
44
Time Mass in Lost Mass

[min] [g] Bottom Mass [g] Distillate Mass [g] [g]
0 0 0 0 0
10 528 494 27 8
20 1056 987 60 9
30 1584 1461 110 13
40 2112 1935 148 30
50 2640 2408 188 43
60 3168 2882 233 53
65 3432 3119 255 58
380

0 0 0 0 0
10 528 498 26 4
20 1056 996 55 5
30 1584 1494 85 5
40 2112 1971 119 22
50 2640 2448 137 56
60 3168 2904 165 99
65 3432 3153 195 84
400

0 0 0 0 0
10 528 397 63 69
20 1056 793 96 167
30 1584 1269 142 174
40 2112 1665 184 262
50 2640 2062 229 349
60 3168 2538 254 376
65 3432 2736 275 421
360 cat

45
0 0 0 0 0
10 528 495 28 5
20 1056 968 80 8
30 1584 1463 101 20
40 2112 1936 149 27
50 2640 2409 199 32
60 3168 2881 251 35
65 3432 3084 309 39
6.4. Characterization
Picnometer 25 mL @ 15°C
Sample Weight [g] Density [g/mL]
Calibrating
Picnometer 26.0305 -
water density
Pic. + water 50.8548 -
Water 24.8243 0.993
S.G. S.G. S.G. S.G. Std. Dev. Density Std. Dev. Dens
Sample 1 2 3 a S.G. [g/mL] [g/mL] API
0.87 0.89 0.88 0.88 29.8
LMO 5 0 5 3 0.006 0.88 0.006 2 Densit
0.86 0.86 0.86 0.86 33.5 y
360/70 5 0 5 3 0.002 0.86 0.002 6
360/70/ 0.86 0.86 0.86 0.86 33.8
C 0 0 5 2 0.002 0.86 0.002 8
Visc. Const. 0.002 cSt/s
Time 1 Time 2 Time 1 Time 2 Time a Viscosity

Sample [hh:mm:ss] [hh:mm:ss] [s] [s] [s] [cSt]
51332.0 51332.0 51332.0
Viscosit
LMO 14:15:32 14:15:32 0 0 0 102.66
y
360/70 0:26:17 0:25:15 1577.00 1515.00 1546.00 3.09
360/70/
C 0:30:27 0:31:15 1827.00 1875.00 1851.00 3.70
Sample IDP [°C] T at 90% [°C]

360/70 65 220 Distillation
360/70/C 63 230

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UNIVERSIDAD SAN FRANCISCO DE QUITO USFQ

Colegio de Ciencias e Ingenierías

Evaluation of thermal and catalytic cracking with aluminosilicates of

José Fernando Noboa Guerrón

Trabajo de titulación presentado como requisito

Quito, 19 de julio de 2019