Predictive models for a hydrocracking unit performance

Andreia Filipa Rijo Marianito

Instituto Superior Técnico
October 2015

Abstract: This work was carried out under a traineeship in Plant III in Sines refinery between March
and August 2015 with a view to development a semi-empirical kinetic model that was able to predict, with
reasonable confidence level, the catalytic reactor performance both 1st and 2nd stages of the commercial
unit of Hydrocracking of Sines refinery of Galp Energia. This is a unit with recent operation at the refinery
and high economic incentive, so it is important to understand how the main process variables influence the
different products yield. Ideally, the model should predict the conversion in each reaction stage as a fuction
of the operating conditions (LHSV, temperature, pressure, etc.), as well as of some relevant quality
characteristics of the charge, such as the organic nitrogen concentration, or aromatic content. The model
was validated with experimental data from the commercial unit. It is essential that it also includes a catalytic
deactivation term. It is intended that the model will improve the understanding of the influence of the VGO
physicochemical properties in the unit catalytic performance. Two different models have been developed,
the Model II is more elaborate and realistic, it provides results that describe reasonably the experimental
data and are strongly dependent on the physicochemical charge properties, so the primary purpose of this
work was achieved successfully.

Key-words: Refinery, Hydrocracking, kinetic model, catalytic deactivation, performance, charge

properties

1. Introduction
The hydrocracking unit is composed of with the same catalyst type, only for the catalytic
various sections, among which is the reaction cracking. The simplified scheme of the
section, which contains two reaction stages in a reaction/separation section is in figure 1.
high pressure circuit, the HC and HT reaction
sections occur at high temperature and pressure,
always in the presence of hydrogen, at elevated
partial pressure it is necessary to promote the HC
reactions and prevent formation of coke on the
catalyst, while hydrogen is recycled to the loop
reactor to promote a good contact.

The HC unit can operate at temperatures

between 300oC and 440oC and pressures
between 70 and 200 bar, the 1st stage operates
between 400-420oC, while the 2nd stage operates
at temperatures between 370-390oC. Both
reactors are heterogeneous fixed bed, and the
hydrocracking reactions are very exothermic, it is
therefore necessary constant cooling of both
reactors through the quench with hydrogen
streams between each bed. The reactor of first
the stage has six beds, with different catalysts,
while the reactor of the 2nd stage has four beds
Figure 1 - Simplistic scheme of the reaction/separation HC
unit
In this study, it is necessary to focus on
the importance of certain variables that affect
directly or indirectly the process yield. The
properties of the charge to the reactors have a
significant effect in various aspects of the
process, such as the catalyst life, the required
CAT, the hydrogen consumption, yields of

1
product as well as on the properties of these
products.
The system charge is a mixture of several
molecules of different sizes. The charge
composition is dependent on the crude oil used
and the operating conditions of upstream units.
The main charge properties analyzed in the
present study are the nitrogen concentration
and the paraffin/aromatic amount. The
compounds that contain nitrogen are viewed as
a temporary poison for the catalyst, and tend to
exist as basic compounds in the feedstock, which
can be adsorbed on the catalyst acid active sites,
neutralizing them and reducing the cracking
efficacy. On the other hand, polycyclic aromatic
compounds contribute to the formation of coke
on the catalyst surface, they are aromatic
compounds which can be up to several rings, and
tend to be dehydrogenated and make coke.
Therefore, the amount of these compounds in
the charge has a significant effect on the catalyst
activity and fouling rate. Because of the strong
effects of the charge properties in the HC unit
will be taken into account in the development of
the model. It should be noted that other
variables inherent to other procedural areas
influence, equally, the process yield, however,
for the purposes of this study, the emphasis is
placed only on the variables that have a direct
influence in the reaction section.
2. Results
The objective was to develop a robust
model that can predict the performance of both
stages, and to allow the establishment of their
operating conditions, taking into account the
different charge characteristics. The HC unit
receives charges from different sources, it is
necessary to compare the values obtained by
model with the values obtained in the unit in
operation, which constitutes the experimental
data. To do this, we used the data obtained from
analyzes carried out on the charges, VGO, OR and
effluent of both reaction stages.
Among the parameters analyzed to
obtain Model II, the distillation TBP values (°C),
density (kg/m3), and the nitrogen and sulfur
percentage (%) in the sample are used. The same
procedure is make for the Model I with the
addition of a parameter that give the charge
aromaticity account (UOPk).
The experimental data used begin to 23
May 2014, after the first planned stop, and cover
the period until 19 May 2015.
2.1. Procedure for sampling
With respect to the effluents samples of
the two reaction stages, there are two sample
collection panels, one for each stage. These are
high pressure sample points, and whenever it is
necessary to his collection, the operator follows
the procedure given by the licensor. Figure 2
illustrates a sampling panel.
The first step to be performed by the
operator is opening the valve V2 in order to
purge the system line with hydrogen for
cleaning, then to opening the valve V1 to the
reactors effluent entry. The sample is cooled in a
heat exchanger with cooling water at 25-30oC.
Ideally, the sample should be cooled to 50oC,
then it goes to a flash balloon, which
depressurizes, and gases are released into the
flare. The liquid sample is collected at the base
for a metallic container and removed for glass
bottle that is sent to the laboratory.
Figure 2 - Scheme for a sampling panel
However, throughout this study, we
detected some consistency problems with the
experimental data after laboratory analysis. The
amounts of TBP distillation, concluded that there
are deficiencies in the sample collection.
Sometimes the cooling water is not used, that is,
2
the valve V3 is not opened, so the sample can’t
has the recommended 50oC, however, the
problem may also be associated with any
deposits that may exist in the heat exchanger
which is in operation since the start of the unit
and which is isolated, that is, until now has never
been cleaned. Another hypothesis is that the
cooling water flow is not sufficient for cooling the
sample flow. Thus, it is concluded that the
sample analysis will tend to overestimate the
heavy ends at the expense of light.
With respect to the charges of both
stages, VGO and OR, are taken at strategic points
so that they can also be monitored. Both are
collected into panels similar to that shown in the
figure 2, but they are obtained in a low-pressure
panels.
2.2. Calculations
2.2.1. Mass balance
To obtain the mass balance, they are seen
as the Input the VGO flow and the make up H2,
and as output the remaining flows referring to
the products.
𝐼𝑛𝑝𝑢𝑡−𝑂𝑢𝑡𝑝𝑢𝑡
𝑀𝑎𝑠𝑠 𝐵𝑎𝑙𝑎𝑛𝑐𝑒(%) = × 100 (2.1)
𝐼𝑛𝑝𝑢𝑡
The mass balance is considered an
average in a 24 hour periods. The data
corresponding to days when the mass balance is
out of +/- 5% tolerance were discarded. It
redistributes the mass balance evenly between
the products through the expression 2.1.
100
𝑀. 𝐵. 𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑓𝑎𝑐𝑡𝑜𝑟 =
100−𝑀𝑎𝑠𝑠 𝐵𝑎𝑙𝑎𝑛𝑐𝑒
2.2.2. Yiels
Charge: Knowing the mass flow rates measured
in the unit and assuming a base of 100% for the
VGO, the make up of H2 is calculated by the
following expression.
𝑄𝑚𝑎𝑘𝑒 𝑢𝑝 𝐻2
𝜂𝑚𝑎𝑘𝑒 𝑢𝑝 𝐻2 (%) =
𝑄𝑉𝐺𝑂 ×100
Products: The yields of the various products are
calculated the same way, with the introduction
of the M.B. correction factor, expression 2.4.
𝑄𝑃𝑟𝑜𝑑𝑢𝑡𝑜𝑖 ×𝑀.𝐵.𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑓𝑎𝑐𝑡𝑜𝑟
𝜂𝑃𝑟𝑜𝑑𝑢𝑡𝑜𝑖 (%) =
𝑄𝑉𝐺𝑂×100
The mass balance considered all
products, but for the model the lighter products
are excluded, due to the low amount produced
when compared to other products; therefore, it
is necessary to normalize the yield values in
order to discard the lighter products, as the fuel
gas and LPG.
𝜂𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖 (%)×100
𝜂𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖,𝑛𝑜𝑟𝑚𝑎𝑙𝑖𝑧𝑒𝑑 (%) = (2.5)
100−∑ 𝜂𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑖 ,ℎ𝑖𝑔ℎ (%)
2.2.3. RCP
RCP is a Recycle Cut Point, it is the cut
point between the heavier product and the
charge of 2nd stage, OR. With the fixed cut point
value the composition of the VGO stream, OR
and effluents are estimated. With the
experimental TBP data and the recovery rates
(data obtained in laboratory), it is to interpolate
the value of the product cut point and is given
the sample composition. The required cut points
are the values shown in Table 1, it is according to
the experimental data.
Table 1 - Cut points for the different products
2.2.4. Conversions
The conversion to RCP x(RCP) measuring
(2.2)
the amount of charge that will give product in the
1st stage. The more feedstock is delivered to the
2nd stage, the greater their severity. For this
reason, x(RCP) is used to calculate the conversion
per pass in the 2nd stage. We only wish to
compute the overall conversion for the 1st stage,
i.e., they are considered all the reaction
products, this is considered a RCP of 371oC, and
(2.3)
the RCP established for diesel will therefore
cover all lighter products, excluding the UCO..
The PPC is the percentage of combined
charge, which is converted to products in the 2nd
stage reaction. The PPC is defined by the
(2.4)
expression 2.6.
3
 𝑄1 ×(1−𝑋(𝑅𝐶𝑃)−𝑄𝑈𝐶𝑂 )
𝑃𝑃𝐶, % = (2.6)
𝑄2
Q1 and Q2 are the mass flow rates to feed the 1st and
2nd stage, respectively. QUCO the purge mass flow and
x(RCP) is a 1st stage conversion for a RCP to 371oC.
2.2.5. CAT
CAT is the average operating temperature
for each reactor.
2.3. MODEL I
For the first case, some assumptions are
considered in order to describe the studied
system, it is necessary to make some approaches
to thereby simplify the model mathematically.
2.3.1. Assumptions
 Tubular and plug flow reactor
 Reactors in isothermal operation
 Homogeneous reactors
 Catalyst with similar characteristics on
all six beds, no difference between
HDM, HDS/HDN and HC – HC-R-01
 Apparent kinetic of 1st order – limiting
reagent – VGO
 Reaction order 0 relative to H2
 Deactivation rate of the catayst is
proportional to the catalytic activity
2.3.2. Kinetic Model
In order to model both reactors, based on
semi-empirical kinetic models considered an
ideal plug-flow tubular reactors in isothermal
operation. This is an approximation to the reality
that produces acceptable results and avoids a
large mathematical complexity which arises from
the fact that the concentration may not be
uniform, for example along the radial direction in
the reactor. So the concentration varies
throughout the reactor, it is necessary to select a
reactor volume element and make the mass
balance this 'slice' of the reactor shown in figure
3.
Figure 3 - Selection of a volume element in order to weigh
the plug flow tubular reactor
𝑄𝐶𝐴 |𝑥 − 𝑄𝐶𝐴 |𝑥+𝑑𝑥 = 𝑟 × 𝑑𝑉 (2.7)
To be r the reaction rate, given by:
𝑟 = 𝐾 × 𝐶𝐴 (1 − 𝑥) × 𝑒 −𝛼𝑡 . (2.8)
Integrating and replacing the expression 2.7, we
have the expression 2.9, assuming the Arrehnius
law for the pre-exponential factor.
𝑬𝒂⁄
−(𝒌𝟎 ×𝒆− 𝑹𝑻 ×
𝟏
×𝒆−𝜶𝒕 )
𝒙 = 𝟏 − (𝟏 − 𝒙𝟎 ) × 𝒆 𝑳𝑯𝑺𝑽 (2.9)
Expression 2.9 allows us to obtain the
conversion associated with the model, where k0
is the pre-exponential factor, Ea the activation
energy and LHSV space velocity (time-1). Knowing
that k0 depends of the charge properties and
temperature are taken into account two
possibilities for the value of the pre-exponential
factor, k0.
1st hypothesis: 𝑘0 = 𝑎 (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡) (2.10)
A first case in which k0 is just a constant
and is not affected by the different charge
properties, is not a realistic hypothesis and that
will not meet the required study.
2nd hypothesis: 𝑘0 =
𝑎0 ×𝑒 −𝑎1 ×𝑈𝑂𝑃𝑘
(2.11)
(1+𝑏×𝑁)𝑛
And a second case where k0 is affected by
the different charge properties such as nitrogen
percentage (%) and its aromaticity. Where a0, a1,
b and n are constant, C the nitrogen percentage
(%)in the charge and UOPk a parameter indicator
of the paraffins/aromatics in the charge.
4
 Figure 5 – Graphic comparison between experimental
apparent conversion and model conversion. 1st Hypothesis

Figure 4 – Calculation scheme. Model I

To better understand the mechanism

developed to obtain the following results, it is
observed in Figure 4, in which each block
represents the steps followed and the respective
input and output parameters.

The kinetic parameters (model output

parameters) are optimized using the Excel Solver
tool with the GRC linear non method based on
the minimization of the difference squared
between the conversion given by the model and
experimental conversion, using a least squares
method.
2.3.3. 1st stage results
Figure 6 – Graphic comparison between experimental
apparent conversion and model conversion. 2 nd Hypothesis
In the last figures are represented the
experimental data and the final result obtained
by the model, using the two different hypothesis
for the pre-exponential factor described above.

In the following figures are plotted the
experimental results and the apparent
conversion computed using the model. By
expression 2.9 the apparent conversion was
calculated by the model, values which were
subsequently compared with the apparent
conversions calculated from the experimental
data.
A graphical analysis of the residuals
against the expected values (conversion model)
can also be interesting, as it allows us to observe
if there is any trend or pattern associated with
the errors, or if they are simply randomly
distributed.

Figure 7 - Residue vs expected value. 1st stage

5
 From the analysis of the previous figure it
is concluded that the errors associated with the
model are scattered, and there isn’t any
tendency for the residual values. The results
showed the same type behavior for both
hypothesis.
Figure 8 - Comparison of model and experimental apparent
conversion apparent conversion. 1st stage
From the analysis of the previous figure, it
follows that once again, both accepted
hypotheses have the same behavior. Table 2
presents the kinetic parameters for the 1st and
2nd hypothesis, for the 1st stage.
Table 2 - Model Kinetic parameters associated with the 1st
stage
The value of the cumulative residuals,
corresponding to the 2nd hypothesis, presents a
slight improvement when compared to the 1st
hypothesis, however, it can not be considered a
significant improvement and it does not justify
the use of more parameters, so with a simple
model and with less parameters the same quality
of results can be obtained.
2.3.4. 2nd Stage Results
The conversion is calculated by
expression 2.6, however for the 2nd stage isn’t
subtracted from the product in the charge,
calculate the PPC conversion and the conversion
by the model, not by subtracting the product
"transported" in the charge. The results exhibit
the same behavior observed in 1st stage,
considering the two assumptions the expressions
2.10 and 2.11.
2.4. MODEL II
The model I described above is a simple
model that seeks to describe the conversion at
each stage from an elementary kinetic, when you
consider that the conversion of VGO is the
limiting step. Even introducing some charge
quality parameters, this model fails in general to
describe accurately conversions measures in the
effluent. In addition, there is an evident
dispersion in the experimental points, resulting
from sampling technique the reaction effluent,
making it difficult to develop an accurate model.
The Model II is more elaborate, already
considering a reaction network across product
lumps. Is removed, so the assumption of limiting
step and, more importantly, it is possible to
obtain the overall yield of the various products,
experimental measurement which is more
accurate.
2.4.1. Assumptions
 Tubular and plug flow reactor
 Reactors in isothermal operation
 Homogeneous reactors
 Catalyst with similar characteristics on
all six beds, no difference between
HDM, HDS/HDN and HC – HC-R-01
 Reaction order 0 relative to H2
 Langmuir-Hinshelwood kinetics with
VGO adsorption term
 cumulative Deactivation
 Law of conservation of mass
(Contribution quench gas (H2)
negligible)
For the possible deployment of the
model, it is necessary to define the cracking
reactions occurring inside the reactor, as is
known to occur numerous reactions it is
impossible to define precisely all of them.
However, we can define a kinetic model in which
the molecules are grouped by lumps. It was,
therefore, a kinetic model involving four lumps:
VGO, diesel, kerosene and naphtha.
6
 Taking lim 𝑑𝑉 → 0, it has:

−𝑑(𝑚̇𝑥𝑖 ) + ∑ 𝑟𝑖 𝑑𝑉 = 0 (2.13)

Taking 𝑑𝑚̇ = 0. It has:

𝑚̇𝑑𝑥𝑖 = ∑ 𝑟𝑖 𝑑𝑉 (2.14)

𝑑𝑥𝑖
𝑚̇ = ∑ 𝑟𝑖 (2.15)
𝑑𝑉

As 𝑑(𝜌𝑉)̇ = 0 (2.16)
Figure 9 - Yield vs. Conversion of various products in pilot
plant
We have 𝑑𝜌𝑉̇ + 𝑉̇ 𝑑𝜌 = 0 (2.17)
The reactions considered for the model
As 𝑉̇ e ρ are constants, was replace 𝑚̇ by
development are shown in Figure 10, the choice
expression 2.14 for 𝜌𝑉̇ and we have:
of the following reactions is supported by Figure
9. 𝜌𝑉̇ 𝑑𝑥 = ∑ 𝑟 𝑑𝑉 (2.18)

𝑉̇
As 𝐿𝐻𝑆𝑉 = (2.19)
𝑉𝑐𝑎𝑡

𝑑𝑉 = 𝑉̇ 𝑑𝜏 (2.20)
Figure 10 - Cracking reactions considered to model
development Replacing the expression 2.20 in expression 2.18,
we have: 𝜌𝑉̇𝑑𝑥 = ∑ 𝑟 𝑉̇𝑑𝜏 (2.21)
It was concluded that diesel and kerosene
are primary products, while naphtha is a So, 𝜌𝑑𝑥 = ∑ 𝑟 𝑑𝜏 (2.22)

secondary product, as the slope at the origin is

𝑑𝑥 ∑ 𝑟⁄
practically nil, therefore, initially there will be no Diferencial equation: 𝑑𝜏
= 𝜌 (2.23)
naphtha formation, just don’t admit the reaction
For the calculation of the reaction rate
𝑉𝐺𝑂 → 𝑁𝑎𝑝ℎ𝑡𝑎, but only the reactions 4 and 5
Langmuir-Hinshelwood type kinetic is assumed.
of the previous figure, wherein the formation of
𝐸𝑎⁄
primary products stems from naphtha. In figure 𝑘0 ×𝑒 − 𝑅𝑇 ×𝐶𝑖
𝑟𝑛 = × ∅𝑛 (2.24)
11 is shown the calculation scheme followed for 1+𝐾𝑎𝑑𝑠 ×𝐶𝑖 +𝑘𝑁 ×𝐶𝑁

Model II, where they observe the Input and Where k0 is the pre-exponential factor
Output parameters of the model applied to both and Ea the activation energy, R is the gas
stages. constant, T is the operating temperature (in this
case, is used the CAT considering the isothermal
reactor) Ci reagent composition, CN is the
nitrogen concentration in the charge (VGO)
constant for each day. KADS is a constant
associated to the reagent adsorption on to the
catalyst active sites and KN is a constant
associated with the nitrogen concentration in
the charge. Ø is the activity of the catalyst, is a
cumulative factor that decreases over the unity
of the time working, then Ø is calculated
recursively by the expression 2.25, and τ is the
reactor residence time.
Figure 11- Calculation Scheme. Model II
∅𝑛 = ∅𝑛−1 −∝× 𝑟𝑛−1 × ∆𝑡 (2.25)
2.4.2. Kinetic Model

𝑚̇𝑥𝑖 |𝑉 − 𝑚̇𝑥𝑖 |𝑉+𝑑𝑉 + ∑ 𝑟𝑖 𝑑𝑉 = 0 (2.12)

7
 ØN is the catalytic activity of the day n (day
study), Øn-1 is the catalytic activity from the
previous day, α is the catalyst deactivation factor,
rn-1 at the previous day's reaction rate, given by
the expression 2.24 and Δt is the interval in days.
Thus, it integrates along the reactor using the
Euler method. The desired result is the effluent
composition at the reactor outlet, to that
integrates to the residence time of each stage,
variable for each day, given by the inverse of
LHSV. It was also studied the integration step,
and it follows that the best was 0.002 hours.
2.4.3. Calculations
After numerical integration by Euler's
method, the compositions of the effluent have
been computed. It was then made a mass
balance to the system of Figure 12, in order to
obtain the mass flow rate of each product outlet,
to thereby calculate the yield by the expression
2.26.
𝑄𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑌𝑖𝑒𝑙𝑑 (%) = × 100 (2.26)
𝑄𝑉𝐺𝑂
Figure 12 - Scheme system considered for the model.
Reaction zone / separation
 NAPHTAS Balance
𝑥𝑁,1 × 𝑄1 + 𝑥𝑁,2 × 𝑄2 = 𝑄𝑁 (2.27)
 KEROSENE Balance
𝑥𝐾,1 × 𝑄1 + 𝑥𝐾,2 × 𝑄2 = 𝑄𝐾 (2.28)
 DIESEL Balance
𝑥𝐷,1 × 𝑄1 + 𝑥𝐷,2 × 𝑄2 − 𝑥𝐷,𝑈𝐶𝑂 × 𝑄𝑈𝐶𝑂 = 𝑄𝐷 (2.29)
 UCO Balance
𝑥𝑈𝐶𝑂,1 × 𝑄1 + 𝑥𝑈𝐶𝑂,2 × 𝑄2 − 𝑥𝑈𝐶𝑂,𝑂𝑅 × 𝑄𝑂𝑅 =
𝑥𝑈𝐶𝑂,𝑈𝐶𝑂 × 𝑄𝑈𝐶𝑂 (2.30)
Q1 and Q2 are the mass flow of stream 1 and 2,
respectively, and xi,1 and xi,2 are the compositions of
the different products in respective streams (model
data).
While the composition and amount of
VGO are model inputs, the quantity and OR
composition is determined by the model through
a separation factor in a fractionating column.
However, this separation factor isn’t constant
over the period under study, because it is known
that on the 5 August 2014, due to a reaction
upset the fractionating column, the bottom
plates were damaged and the column lost
separation efficiency of the recycle oil and diesel,
of around 3%. Figure 13 is a graphical
comparison of the experimental composition
and the composition achieved by using the
separation factors mentioned above, which is
visible to the proximity of values.
Figure 13 - Composition of comparison in diesel UCO
(experimental) and composition in diesel obtained by model
After optimization of kinetic parameters,
a model sensitivity analysis is done in relation to
the nitrogen values in the charge, that is, the
intention was to confront the data supplied by
the licensor relative to the influence of nitrogen
in the charge, with the values obtained during
the the model application, as shown in the
following figure. It is known from the design
conditions, and what is the expected influence of
the nitrogen concentration in the expected
variation on the CAT value.
8
 Figure 14 - Operative curve vs. model curve

Figure 17 - Experimental yield vs Model yield - NAPHTAS

It was concluded that in addition the
model developed to capture the variations of
nitrogen in charge, meets with the overall trend
indicated by licensor, which allows us to state
that one of the major objectives is accomplished,
that is, the variation is well described by the
constant inhibition nitrogen adjusted by the
model.

It is now graphically compared the

experimental performance against the yield
calculated by the model data. The following Figure 18 - Experimental yield vs Model yield - UCO
figures illustrate the yield of each product, such
For the above figures, the data points
as diesel, kerosene, naphtha and UCO.
(days) in which the mass balance didn’t close, or
introduce an error greater than +/- 5%. In the
previous figures, two important periods for the
unit are represented, the first period to 6 August
2014, the incident that occurred in fractionating
column and that meant a loss of yiel of this,
clearly visible for diesel. And a second period to
15 September 2014, when there was a decrease
in 1st stage conversion, increasing by
consequent, the conversion in the 2nd stage, due
Figure 15 – Experimental yield vs Model yield - DIESEL
to accelerated catalyst deactivation which was
felt in the 1st reaction stage. In the following
tables the kinetic parameters are optimized for
the 1st and 2nd reaction stage.

Table 3 – kinetic parameters for the 1st stage model

Figure 16 - Experimental yield vs Model yield - KEROSENE

Table 4 - kinetic parameters for the 2nd stage model

9
 This model is sensitive to nitrogen
variations in the charge (load property
considered for the model development), for the
five reactions considered was obtained values for
the pre-exponential factor and the activation
energy, Ea. The activation energy lies within the
range of expected values, as well as pre-
exponential factors have all the same order of
magnitude. The parameter related to the
catalytic deactivation, α, is much higher in the 1st
stage in Model II, it is considered as a whole, and
as such, the deactivation factor fulfils this entire
period, and it is concluded that the catalytic
deactivation observed in the 1st stage is more
severe than that in the 2nd stage.
It was also considered the 1st stage
effluent compositions (single stage with frequent
samplings) for obtaining the optimum values of
the kinetic parameters. The only effluent for
which analysis is available, is used for
optimization of kinetic parameters, so to "force"
the model to represent what is produced in the
1st stage, and not to be completely randomly.
3. Conclusion
Model I is a relatively simple model and
does not show any significant difference in the
results, when the charges properties change. In
fact the model fits to the experimental data, but
not have in attention the physical and chemical
properties of the charge.
So, it was necessary to develop a more
complex but also more realistic model, which
although essentially become under the same
assumptions, and considering a network reaction
between products lumps. The assumption of
limiting step was removed and it was possible to
obtain the overall yield of the various products,
the products yield is a more correct experimental
measurement. It is an elaborate and realistic
model whose results are to conform to the
experimental data and are strongly dependent
on the physicochemical properties of the charge,
thus fulfilling the fundamental objective of this
work, figure 14 checks that the model captures
the nitrogen charge variations, following the
trend predicted by the licensor. The charge
composition (% diesel and VGO) is also given as
Input to the system, so the model can take into
account that the composition charge and the
nitrogen percentage present in the charge.
References
Site Oficial Galp Energia
http://www.galpenergia.com
Data Book de Segurança, Saúde e Ambiente
2013, Refinaria de Sines, Galp Energia.
Direcção Geral de Energia e Geologia, DGEG;
Ministério do Ambiente, Ordenamento do
Território e Energia; Governo de Portugal.
http://www.dgeg.pt/ Consultado a 14/05/2015
Informação Estatística; Associação Portuguesa
de Empresas Petrolíferas, APETRO.
http://www.apetro.pt/ Consultado a 16/07/2015
Secção Energia, Jornal Expresso Online, noticia
referente a 16 de Janeiro de 2013 às 17h23min.
http://expresso.sapo.pt/economia/economina_
energia/nova-unidade-da-refinaria-de-sines-ja-
produz-gasoleo=f779915
ISOCRACKING, CBI/Lummus Global
http://www.cbi.com/images/uploads/tech_shee
ts/Isocracking-12.pdf
Chevron Lummus Global LLC, “Process Manual,
Chevron Isocracking Unit, Galp Refinery, Sines,
Portugal”, December 2007
Chevron Lummus Global LLC, “Operations
Training Workbook - Chevron ISOCRACKING
Unit”, Galp Refinery; Sines, Portugal; October
2010
www.famousscientists.com.org/rudolf-christian-
karl-diesel/
Consultado a 15/09/2015
www.webserver.dmt.upm.es
Consultado a 15/09/2015
Lemos, Francisco; M. Lopes, José; Ramôa Ribeiro,
Fernando; “Reactores Químicos”, IST PRESS,
Novembro 2002, ISBN: 972-8469-09-8
10
www.earthobservatory.nasa.gov Mark Harmon, “Step-by-Step Optimization with
Solver Excel, The Excel Statistical Master”, Excel
Consultado a 1/09/2015
Master Series, 2011. ISBN: 987-1-937159-11-5.
www.astm.org
Costa, Fernando Pestana, “Equações diferenciais
Consultado a 1/09/2015 ordinárias”, Março 2001, IST Press. ISBN: 972-
8469-00-4.
Nunes dos Santos, A. M., “Reactores Químicos”,
Vol 1, Fundação Calouste Gulbenkian, 1990,
ISBN: 972-31-0519-5

Kayode Coker, A., “Modeling f Chemical Kinetics

and Reactor Design”, Gulf Publishing Company,
Texas, 2001. ISBN: 0-88415-481-5

Cooper, Alfred Ronald, Jeffreys, Godfrey

Vaughan, “Chemical Kinetics and reactor
design”, Oliver and Boyd, 1971, Universidade de
Califórnia. ISBN: 0050021141

Harriott, Peter, “Chemical Reactor Design”, CRC

Press, 2002. ISBN: 0203910230

“Technical Data Book – Petroleum Refining”,

American Petroleum Institute (API), Sixth Edition,
April 1997.

Azita Barkhordari, Shohred Fatemi, Mahdi

Daneshpayeh, Hossain Zamani; “Development of
a discrete kinetic model for modeling of industrial
hydrocracking reaction accompanied with
catalyst deactivation”, School of Chemical
Engineering, Faculty of Engineering, University of
Theran, Iran.

M. Rashidzadeh, A. Ahmad, S. Sadighi; “Studying

of Catalyst Deactivation in a Commercial
Hydrocracking Process (ISOMAX)”, Journal of
Petroleum Science and Technology, Vol.1, No 1,
2011, 46-54.

Couch, Keith A.; Glavin, James P.; Johnson, Aaron

O.; “The Impact of Bitumen-Derived Feeds on the
FCC Unit”, UOP LLC, a Honeywell Company; Des
Plaines, Illinois, USA.

Esteves, Eduardo, “Regressão não-linear

utilizando a ferramenta Solver do Microsoft
Excel”, Instituto Superior de Engenharia,
Universidade do Algarve; 10 de Janeiro de 2011.

https://support.microsoft.com (Solver uses

generalized reduced gradient algorithm)

11