Fuel 212 (2018) 61–76

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Fuel
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Predictive modeling and optimization for an industrial Coker Complex MARK

Hydrotreating unit – development and a case study
⁎
Eslam S. Sbaaei, Tamer S. Ahmed
Chemical Engineering Department, Faculty of Engineering, Cairo University, Giza 12613, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: This work presents a model for UOP Coker Complex Hydrotreating Process using Aspen HYSYS Petroleum
Coker Complex Refining module. The model depends on routinely taken industrial data of process streams during normal op-
Hydrotreating reactor erating conditions. Acquired data sets have been tested and screened in order to ensure data validity for building
Model calibration the model and avoiding erroneous results. A detailed kinetic model of hydrotreating reactions in the reactor has
Process optimization
been applied. The trickle bed reactor (TBR) model has been validated using 3 months of industrial plant data. In
addition, rigorous tray-by-tray simulations for hydrogen sulfide absorption tower and TBR effluent fractionation
tower have been utilized to match the performance of the plant’s towers. The model has been used then for
studying the effects of different process variables on the plant performance. In addition, the model has been used
in optimizing the operating conditions of the process. This optimization showed a potential for notable savings of
fuel and energy consumption in the process, while increasing the process productivity.

1. Introduction reactors are highly desirable with respect to environmental regulations

In the recent decades, petroleum refiners’ interests have trended
toward obtaining a fuel with low environmental pollutants such as
sulfur, nitrogen and aromatics instead of maximizing conversion of
heavy oil to liquid fuels. World regulations have imposed legislations in
order to minimize SOx and NOx emissions as well as soot particles from
both refiners’ flares and their products after burning. Therefore, recent
environmental regulations take strict decisions towards refiners that
contravene the allowable proportions of these pollutants in their pro-
ducts. For example, U.S. Environmental Protection Agency has begun
enforcing deterrent rules that determine the maximum quantities of
sulfur compounds in diesel fuel since mid-2006 [1].
Quality of extracted crude oils has diminished over the last two
decades as a result of ongoing efforts to discover new oil fields in order
to fulfill the global fuel demand. Therefore, environmental pollutants
already exist in the current crudes in large quantities, adversely af-
fecting the human and ecosystem. Hydrotreating is thought to be one of
the effective solutions to generate a fuel compatible with environmental
regulations. Therefore, refiners now increase hydrotreating severity in
order to make their products identical to the standard specifications
[2]. In general, hydrotreating is designed primarily to remove the sulfur
and nitrogen. In addition, this process performs an excellent job of
saturating olefinic and aromatic compounds for producing a commer-
cial jet and diesel fuel. Liquid fuels produced from hydrotreating
due to their few pollutants content and high performance inside the
engines.
Trickle bed reactor (TBR) is widely used in hydrotreating. TBR is
three phases, trickle flow regime, fixed bed reactor where hydrogen and
hydrocarbons concurrently flow downward over a fixed bed of catalyst
particles while hydrotreating reactions occur. Liquid hydrocarbons
travel down as a laminar film and/or in rivulets over the solid particles,
whereas hydrogen passes through the remaining void space. Dissolved
hydrogen and hydrocarbons molecules diffuse through the catalyst
surface in order to find the distributed active sites. Therefore, the ele-
vated pressures are preferred inside TBRs to improve the gas solubility
and molecular diffusivity during hydrotreating. Usually, TBRs operate
adiabatically at high temperatures to promote hydrotreating, inasmuch
as the kinetics and thermodynamics of most reactions improve when
the temperatures of TBRs are raised [3–5].
Hydrotreating TBR catalysts consist of promoted MoS2 or WS2
particles uniformly distributed on supports with high surface area such
as macro porous alumina or zeolite. Co, Ni, or both are added as pro-
moters to bridge with Mo or W atoms in order to provide the active sites
required for hydrotreating reactions. The selectivity of Co and Ni to-
wards these reactions differs. CoMo catalysts have a higher HDS per-
formance at low operating pressures compared to NiMo catalysts.
However, CoMo catalysts have a lower HDN performance. NiCoMo
catalysts combine between CoMo and NiMo catalysts benefits.

⁎
Corresponding author.
E-mail address: Tamer.S.Ahmed@cu.edu.eg (T.S. Ahmed).

http://dx.doi.org/10.1016/j.fuel.2017.10.032
Received 30 May 2017; Received in revised form 18 July 2017; Accepted 5 October 2017
0016-2361/ © 2017 Published by Elsevier Ltd.
E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Nomenclature LNi Light nitrogen compounds

LP Light paraffinic compounds
CCR Conradon Carbon Residue LS Light sulfur compounds
DEA Di ethanolamine MA Medium aromatic compounds
EOR End of Run MN Medium naphthenic compounds
FBP Final boiling point MNA Medium naphthenic aromatic
HA Heavy aromatic compounds MNi Medium nitrogen compounds
HDA Hydrodeasphaltenization MP Medium paraffinic compounds
HDM Hydrodemetallization MS Medium sulfur compounds
HDN Hydrodenitrogenation TBR Trickle bed reactor
HDO Hydrodeoxygenation VA Vacuum aromatic compounds
HDS Hydro desulfurization VN Vacuum naphthenic compounds
HN Heavy naphthenic compounds VNA Vacuum naphthenic aromatic
HNA Heavy naphthenic aromatic compounds VNi Vacuum nitrogen compounds
HNi Heavy nitrogen compounds VP Vacuum paraffinic compounds
HP Heavy paraffinic compounds VS Vacuum sulfur compounds
HS Heavy sulfur compounds WABT Weight average bed temperature
IBP Initial boiling point ψ Property of a petroleum fraction
L Light compounds θ Known property of a petroleum fraction
LA Light aromatic compounds wi Weighting factor of process variable i
LN Light naphthenic compounds Xi Process variable i

Industrially, more than one type of these catalysts is used inside TBR.
NiMo catalysts are often put as a protective layer to the main catalyst
against deactivation by olefins and gum precursors [6–11]. On the other
hand, physical characteristics of TBR catalysts such as pore volume,
bulk density, shape and size influence catalyst effectiveness factors and
thus heat and mass transfer rates [12–14]. Catalysts with large pores
are preferred for demetallization, whereas catalysts with small pores
are favored for desulfurization. Therefore, catalyst characteristics be-
side reactions kinetics should be considered during TBR modeling.
Modeling of an industrial hydrotreating unit generally requires
process identification. An industrial data is usually utilized in order to
recognize the relations between the real system variables due to the
nonlinearity of these relations as well as the complexity of process
chemistry. However, several published researches developed a kinetic
model for HDS and HDN reactions based on experimental data in order
to predict the behavior of industrial catalysts inside TBRs during hy-
drotreating of oil fractions. Mederos and Ancheyta [15–17] developed a
kinetic model considering the main reactions present in hydrotreating
process in order to compare between co-current and counter-current
operation modes of TBRs. They utilized the kinetic parameters obtained
from experimental data to predict the dynamic behavior of industrial
hydrotreating TBRs. Rodríguez et al. [18] modeled kinetics of HDS with
power law approaches and Langmuir-Hinshelwood approach using the
data reported by Mederos and Ancheyta [15–17] in order to compare
between the results of different kinetic models. Alvarez et al. [19,20]
developed a kinetic model to investigate the hydroprocessing behavior
with both gas and liquid quenching in a multi-fixed-bed reactor. In
addition, they used kinetic and aging data obtained from hydro-
processing experiments to study the effect of reactor configuration on
the cycle length of heavy oil fixed-bed hydroprocessing unit [21].
In order to develop a validated TBR model, kinetic models for all
hydrotreating reactions should be developed. However, in the previous
models hydrodeasphaltenization reactions (HDA) were excluded.
Therefore, Jarullah et al. [22] developed a kinetic model for HDA re-
actions in TBR. Elizalde and Ancheyta [23] used a three stage deacti-
vation model for simulating the complete period of catalyst deactiva-
tion during heavy oil hydrotreating. In addition, they employed a pore
plugging model to investigate the deactivation of heavy oil hydro-
treating catalysts. Because of the prevalent current trend of oil refiners
toward production of diesel fuel with ultra low pollutants, Paz-zavala
et al. [24] developed a kinetic model for HDS process to obtain ultra
low sulfur diesel in order to be applied to commercial units proving
their capability.
Due to the complexity of modeling the kinetics for some reactions,
several studies executed modeling of hydrotreating and different pet-
roleum processing units based on industrial data using commercial si-
mulators such as Aspen HYSYS. Remesat et al. [25] evolved a lumped
parameter dynamic model using both Excel and HYSYS for industrial
VGO hydrotreater. Du et al. [26] proposed a real component based
method for simulation of a diesel hydrotreating process using the
software of Unisim Design, which is similar to HYSYS. Said et al. [27]
modeled an industrial Penex isomerization unit using Aspen HYSYS
Petroleum Refining isomerization reactor model. On the other hand,
many studies utilized the commercial software for optimizing the op-
erating conditions of industrial units. Weifeng et al. [28] optimized the
catalytic reforming process for an industrial unit using Aspen Plus
platform. Al-Lagtah et al. [29] proposed some modifications to an ex-
isting plant for gas sweetening process in order to increase its profit-
ability and sustainability using an optimization tool in Aspen HYSYS.
Finally, Taqvi et al. [30] enhanced the performance of distillation
column for acetone production unit by applying optimization techni-
ques provided in Aspen Plus simulator.
Very little attention was paid in the literature to the application of
kinetic modeling and optimization to an existing industrial hydro-
treating unit. In this context, we present here a process kinetic model
for an existing industrial UOP Coker Distillates Hydrotreating unit using
Aspen HYSYS Petroleum Refining Hydroprocessing Bed® module. In
addition, the model has been utilized for investigating the effect of
different process variables on process performance and for process
optimization.
2. Process description
The hydrotreating unit under investigation is designed to treat
several petroleum fractions produced by distillation or thermal cracking
including straight run and cracked gas oil cuts in order to meet the
marketing specifications. This unit is a part of Coker Complex units that
consist of two-stage distillation unit where long residue of Land
Belayim crude oil is distillated in an atmospheric and vacuum distilla-
tion towers to separate all fractions as possible. In addition, short re-
sidue is sent to delayed coking unit to generate gas, wild naphtha,
cracked middle distillates and coke. All middle distillates are charged to
hydrotreating unit, where olefins and aromatics are saturated, and
sulfur and nitrogen compounds are eliminated. Hydrotreating units in

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E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Coker complex play an essential role in raising the marketing value of encourage the acid gases removal by diethanolamine (DEA) absorption.
delayed Coker product. Hydrotreating unit under investigation consists On the other hand, in the fractionation section, atmospheric pressure is
of two sections: a high-pressure (reaction) section (Fig. 1A) and a low- required in order to separate the treated effluent into desirable and
pressure (fractionation) section (Fig. 1B). In the reaction section, pre- more valuable products.
heated charged feed (distillates) is brought up to reactions temperature
through a fired heater, followed by mixing with rich-hydrogen gases.
This mixture enters to TBR where hydrotreating reactions take place. 3. Process chemistry
The heat regenerated from exothermic reactions is used in feed-pre-
heating by heat exchangers train. High pressure is required in this Hydrotreating reactions can be classified into hydrogenolysis reac-
section to increase the distillates purification by hydrotreating and to tions and hydrogenation reactions. Hydrogenolysis reactions are hy-
drodesulfurization (HDS), hydrodenitrogenation (HDN),

Fig. 1. Process Flow Diagram of Coker Complex Hydrotreating Unit.

63
E.S. Sbaaei, T.S. Ahmed
hydrodeoygenation (HDO) and hydrodemetallization (HDM). On the
other hand, hydrogenation reactions are olefins saturation and aromatic
saturation. Due to low oxygen compounds and metals content of pet-
roleum crudes, HDO and HDM scarcely occur during hydrotreating.
Since the acidity of hydrotreating catalysts and hydrogen partial pres-
sure inside hydrotreating reactors are lower compared to hydrocracking
catalysts and reactors. Some cracking reactions can occur during hy-
drotreating; however, their extent is normally low. Therefore, cracking
function of standard hydrotreating catalysts is low, whereas other re-
actions, depending on impurities present, prevail inside TBR. All hy-
drotreating reactions are irreversible except aromatic hydrogenation
that becomes equilibrium-limited at high temperatures when naph-
thenes dehydrogenation is encouraged. The optimum temperature for
maximizing aromatic saturation depends generally on liquid hours’
space velocity (LHSV), hydrogen partial pressure and catalyst; never-
theless, it typically lies in range 320–350 °C [6,7].
4. Reactor model
Aspen HYSYS v.8.6 Petroleum Refinery Hydroprocessor Bed®
module was employed in creating a rigorous model of an existing hy-
drotreating TBR. According to Aspen HYSYS manual v.8.6, the module
contains a detailed kinetics model of hydroprocessing reactions that
occur in either hydrotreating or hydrocracking. TBR model contains
rate equations for HDS, HDN, saturation, cracking and ring opening.
The rate expression for each reaction is coded in order to match lit-
erature data. All reactions are irreversible except aromatic saturation.
Typically, the reaction network consists of 97 kinetic lumps and 177
reactions. The details and the interactions of the reactions are illu-
strated in Fig. 2. Each reaction class is first order reaction with respect
to the primary reactant. In addition, each reaction-class rate equation
has a denominator term following typical Langmiur-Hinshelwood-
Hougen-Watson mechanism. Reaction rate equations are expressed in
the model as
Reaction Rate = Global Activity × Reaction Class Activity
× Heterogenous Reaction Rate
(1)
TBR model can be adjusted in order to match plant TBR perfor-
mance via two schemes: basic tuning and advanced tuning schemes.
Basic tuning includes the tuning of the activity parameter of TBR such
as global activity (overall TBR activity) and specific reaction-class
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Fuel 212 (2018) 61–76
activity parameters (activity of each type of reactions, e.g.: HDS class
reactions). Global activity parameter influences the rate of all reactions.
On the other hand, the activity of each specific reaction-class can be set
via the specific reaction-class activity parameter (e.g., HDS activity
parameter for HDS-class reactions). If basic tuning is scanty, kinetic
parameters of each individual reaction may be adjusted to match the
plant performance utilizing advanced tuning.
The process flow diagram of the unit under investigation is identical
to that shown in Fig. 1. The current work is only interested in the hy-
drotreating TBR, DEA contactor and fractionator. No changes or special
procedures were implemented for building TBR model and the model
was calibrated according to samples that are routinely taken during
normal operation of the industrial unit.
4.1. Industrial data
Data from the industrial hydrotreating unit under investigation
were collected and were organized into data sets. Each data set re-
presents an operating day of the unit. Each data set includes an analysis
of all input and output streams (make-up hydrogen, recycle gases and
distillates feed), and products’ properties such as specific gravity, sulfur
weight percentage, …,etc. In addition, each data set includes the op-
erating conditions of TBR, fractionator and DEA contactor. Typically,
industrial data gathered and arranged into data sets were taken during
steady state operation period in order to avoid incorrect results for the
model.
4.2. Data screening
Model quality relies mainly on the data used in model building. As
mentioned before, data sets utilized for developing this process model
were obtained during normal operation. Acquiring consistent data from
industrial units may occasionally be a quite difficult task due to fre-
quent variations in feed and process conditions. Data sets gathered in
days that witnessed any abnormal changes in process operation were
excluded. In addition, an overall mass balance test was applied to all
data sets and any data sets having a mass balance error exceeding 2%
were excluded [27,31]. In order to guarantee data verification, a sulfur
balance was also applied to data sets by calculating the sulfur weight in
each stream and any sets having an error exceeding 3% were excluded
[27]. Except for days that witnessed abnormal changes, most data sets
Fig. 2. Aspen HYSYS Hydroprocessor Bed model reaction network.
E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Table 1 under investigation. Using this principle, an optimization algorithm

Difference between Aspen HYSYS model identified feed and TBR under investigation feed. was applied in order to estimate the composition of these petroleum
fractions by minimizing the error between the known (actual) proper-
Property Analysis of Aspen Analysis of feed of TBR Under
HYSYS Model feed Investigation ties of these fractions and the calculated Aspen HYSYS properties. In
this work, the following objective function was minimized.
Specific gravity 0.878 0.879 m
ASTM Distillation: ∥θ−ψ∥
I. B. P. [°C] 175 175
φ= ∑ θ
× 100
70% vol. dist. [°C] 367 367
j=1 (2)
Sulfur content [wt%] 2.47 2.50
Suitable boiling range (initial boiling point (IBP) and final boiling
Nitrogen content 1655 1650
[ppm]
point (FBP)) was used to create a model stream identical to the actual
Cetane number 49 49 feed stream. Table 1 shows that properties of the model and the actual
C to H Ratio [wt%] 6.99 7 stream were approximately similar at IBP = 268 °C and FBP = 390 °C.
It is noted that the feed Conradson Carbon Residue (CCR) and metals
content are not present in these properties, since the model excludes
Table 2 both properties from the feed properties (equal to zero). Catalyst de-
Adjustable factors used for TBR model calibration.
activation rate in this model depends mainly on paraffins, olefins,
Parameter Range of deviation from the base naphthenes and aromatics quantities in the feed (PONA analysis) and
on hydrogen partial pressure.
Global Activity 11–15
Saturation Activity 20–25
HDS Activity 0.01–0.04
4.4. Model calibration and parameters estimation
HDN Activity 0.095–0.22
Bromide No. 8–15 Parameters estimation is the most critical step in model develop-
ment. A well-calibrated model generates significant and repeatable
forecasts over a wide range of operating conditions. Inappropriate ca-
Table 3 libration of TBR model may result in an over calibrated model with a
Terms included in objective function for reactor model calibration and applied
poor predictive power. Aspen HYSYS Hydroprocessor Bed model au-
weighing factors.
thorizes user to match plant performance through basic tuning and
Term Applied Weighting Factor advanced tuning by setting kinetic parameters for each reaction. Model
developers allege that basic tuning of TBR model is enough to corre-
Temperature Rise [°C] 1
spond with plant data. In this work, a basic tuning scheme was im-
Nitrogen content [ppm] 1
Sulfur content [wt%] 100 plemented in order to avoid over calibration of the model. Advanced
Specific gravity 10000 tuning may require extremely precise plant data that were not practical
in our case. For rigorous representation of plant TBR, the next steps
were pursued:
Table 4
Estimated average activity parameters for TBR.
4.4.1. Generating streams
Parameter Aspen HYSYS model adjustable values Each data set was utilized to produce a stream representing TBR
charge at the operating day that each data set represents.
Global Activity 12.482
Saturation Activity 23.252
4.4.2. Running the model
HDS Activity 0.0244
HDN Activity 0.1481 Reactor model requires some mechanical data of TBR and some
Cracking Activity 0.001 deactivation characteristics of catalyst to run. The mechanical data
Ring-Opening Activity 0 include TBR dimensions and catalyst properties (catalyst bed porosity
Bromide No. 9.656 and bulk density). These data are required for predicting amount of
catalyst loaded in TBR and also for estimating pressure drop through
TBR catalyst bed during the operation. On the other hand, the deacti-
were extremely consistent having an average mass balance and sulfur
vation characteristics include weight average bed temperature (WABT)
balance error of 0.0866% and −0.3858%, respectively.
at start of run (SOR) and at end of run (EOR), TBR on-stream days and
catalyst deactivation parameters (initial and long-term deactivation
4.3. Crude oil assay definition constants and the activation energy for deactivation). These char-
acteristics are necessary for predicting the remaining lifetime of TBR
Aspen HYSYS Petroleum Refining ships with over 200 pre-char- catalyst. After identifying these properties, the model was allowed to
acterized assays that can be copied and edited to match user’s needs. run generating an output stream.
These assays are arranged by region of origin, country, and oil char-
acteristics (sweet or sour, heavy, medium, light, …etc.). The Belayim 4.4.3. Model calibration
land-2013 assay utilized in this model is one of these assays. Since the Reactor model calibration is a manual adjustment of the activity
petroleum assay becomes invalid after delayed Coker, the model stream parameters in order to match plant data. In this work, TBR model was
was considered to represent the actual feed only in terms of quantities calibrated with the aid of Aspen HYSYS Optimizer® by minimizing the
of impurities introduced to the reactor. Therefore, major properties of following objective function
the actual feed such as S%, N%, Cetane number and Bromide number n

were used as an alternative to PONA analysis for model stream. In this f (x) = ∑ (wi × (Xmodel−Xplant)2)
i=1 (3)
step, Petroleum Feeder® in Aspen HYSYS was used to cut the middle
distillates required to be treated from the whole crude oil by identifying Reactions activity parameters were adjustable variables normalized
initial and final boiling point of these fractions. In addition, these cuts by specified lower and upper bounds as shown in Table 2. Exceeding
were calibrated according to samples actually obtained from the unit the range between lower and upper bounds leads to numerical

65
E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Fig. 3. Plant versus model with model calibration data sets.

Fig. 4. Plant versus model for the 3 months after calibration.

Table 5 industrial naphtha reforming unit and they cautioned that including all
Fractionator specifications. measurements in reactor calibration may result in a poor calibrated
model that responds violently even to small changes to input variables.
Specification Value
Only sulfur, nitrogen content and specific gravity were the reactor
Condenser Temperature [ C] o
40 measurements utilized in this model. In addition, temperature rise
Gas Oil Draw tray Temperature [oC] 295 through the catalytic bed was used as an indicator to quantities of
Kerosene Draw Temperature [oC] 230
olefins saturated inside TBR because olefins saturation is the most
Gas Oil Draw Flow Rate [kg/h] 10,356
Diesel Oil Draw Flow Rate [kg/h] 18,607 exothermic hydrotreating reactions. Routine sampling in the industrial
unit under investigation does not include a sample for olefins content.
Thus, olefins content expressed by Bromide number was also con-
problems during model calibration. It is important not to include all sidered as an adjustable variable with reactions activity parameters as
measurements of plant TBR in reactor model calibration. Pashikanti exhibited in Table 2. Temperature rise through the catalytic bed and
and Liu [32] have utilized HYSYS reformer model for simulating an sulfur, nitrogen and specific gravity of the TBR feed and effluent were

66
E.S. Sbaaei, T.S. Ahmed
Fig. 5. Coker Complex Hydrotreating unit model.
included as process variables in the optimization function.
Weighting factors were utilized to give more importance to certain
variable in a group of variables. Moreover, these factors could be used
in order to adjust the difference in variables measurement units. For
example, sulfur content is measured in weight percentage, nitrogen
content in part per million and temperature rise in Celsius, whereas
specific gravity is dimensionless. On the other hand, large weighting
factors were applied for terms where a closer fit is required. On the
contrary, lowest weighting factors were applied for less important
terms. Although all terms have the same degree of importance,
weighting factors were applied in this model for adjusting the variables
measurement units. Table 3 shows the reactor measurements that were
included in optimization function and weighting factors used with
them.
The three previous steps were iterated for each data set and activity
parameters were calculated individually for each data set. Roughly all
activity parameters were found to vary within a narrow range for dif-
ferent data sets. Consequently, the average values of calculated activity
parameters are expected to be extremely acceptable for model cali-
bration. Table 4 shows the average activity parameters estimated
through calibration process for TBR.
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Fuel 212 (2018) 61–76
4.5. Model validation and testing
Fig. 3 exhibits the model performance versus plant yields for the 26
data sets utilized in the TBR model calibration process. The model
forecasts are satisfactory for hydrotreating TBR. It should be observed
that a closer fit might be achieved with advanced tuning of kinetic
parameters (especially the rate constants of HDS, HDN, cracking and
saturation reactions). Nevertheless, advanced tuning requires quite
accurate plant measurements, which were unavailable.
In order to ensure the model prediction power, this model yields
were compared with the plant yields for the next 3 months after cali-
bration. The catalyst of TBR under investigation has been loaded since
mid-2011. On-stream days of hydrotreating unit under investigation
before this study were 450 days. In this step, 90 days on operation of
TBR after calibration would be added to the days of catalyst on-stream
in the model. Fig. 4 shows that the model was quite useful in tracking
the plant performance for the 3 months after the calibration. It is also
observed in Figs. 3 and 4 that HDN, aromatic saturation and cracking
reactions are strongly affected by the catalyst deactivation more than
other hydrotreating reactions.
E.S. Sbaaei, T.S. Ahmed
4.6. DEA contactor model and fractionator model
Even though this study is interested in the optimization of process
variables of reaction section only, a rigorous DEA contactor model and
fractionator model are also required for precise prediction of hydro-
treating TBR yield. The standard inside-out method was applied for
both models because of its quick convergence with a vast variety of
specifications [33]. For DEA contactor (absorber) model no specifica-
tions were required, since DEA contactor's function is to eliminate hy-
drogen sulfide and this function can be enhanced by increasing strength
(concentration) or flow rate of the absorption solution. Data provided
by Kaes [34] shows that an overall efficiency of plant DEA contactor
about 20–25%. Since the plant absorber has 21 valve trays, the absorber
model should contain about 4 theoretical trays. On the other hand, for
the fractionator (atmospheric distillation) model, number of specifica-
tions is required. Since fractionator’s function is to distillate the pro-
ducts with identical specifications from TBR effluent according to their
boiling ranges. Hence, products flow rate and draw-trays temperature
shown in Table 5 were used to specify the fractionator model. Data
provided by Kaes [34] mention that an overall efficiency of plant
fractionator about 50–60% divided into 30% of stripping zone effi-
ciency, 30% of flash to first-draw zone efficiency, 40–50% of first-draw
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Fuel 212 (2018) 61–76
Fig. 6. Effect of TBR inlet temperature on: A- hydrogen
consumption inside TBR; B- sulfur content difference be-
tween TBR inlet and outlet liquid streams; C- nitrogen
content difference between TBR inlet and outlet liquid
streams; D- Cetane number difference between TBR inlet
and outlet liquid streams; E- Catalyst remaining lifetime
during the study period. TBR pressure = 35 bar, H2:HC
mass ratio = 0.0326, LHSV = 0.8752 h−1, H2S concentra-
tion in recycle gases = 464 ppm, TBR feed
IBP:FBP = 268:390 °C.
to second-draw efficiency and 60–70% second-draw zone to reflux zone
efficiency. Since the plant fractionator has 31 valve trays, divided into 6
trays in stripping zone, 6 trays in flash to first-draw zone, 9 trays in
first-draw to second-draw and 10 trays in second-draw zone to reflux
zone. Hence, the fractionator model should contain 14 theoretical trays
divided to 2, 2, 4 and 6 trays, respectively. It should be noted that fluid
package of DEA contactor model (Acid Gas-Chemical Solvent) is dif-
ferent from what was used in the reactor and fractionator model
(HCRSRK). Therefore, Stream Cutter in Aspen HYSYS was utilized for
performing this transition. Fig. 5 shows a complete process flow dia-
gram of the process model.
5. Process variables
Having built a process model for Coker Complex Hydrotreating unit,
the following step is to investigate the effects of each process variable in
order to predict the process performance for a given variation in a
process variable. Investigating the effects of each process variable is
essential for process optimization. The following study was performed
utilizing the average composition of industrial unit feed during the
study period.
E.S. Sbaaei, T.S. Ahmed
5.1. Reactor inlet temperature
Hydrotreating reactions are exothermic; hence, a rise in tempera-
tures inside TBRs is observed. All hydrotreating reactions are irrever-
sible except aromatic saturation. Hydrodearomatizaion is still far from
equilibrium at operating temperatures allowed to be used inside an
industrial TBR. However, an increase in TBR temperatures reduces the
equilibrium constant of aromatic saturation. In general, high TBR
temperatures are favored during hydrotreating for increasing the ve-
locity of reactions. Nevertheless, once equilibrium temperature is
reached, the processing pathway begins to drift toward undesirable
backward reactions. Therefore, the rate of hydrotreating reactions,
away from the thermodynamic equilibrium, boosts with the tempera-
ture, causing more hydrogen consumption inside the TBR (Fig. 6A).
Consequently, the TBR product specifications get better with the aug-
mentation in the inlet temperature because HDS, HDN and saturation
activity enhance at higher temperatures. This is reflected in Fig. 6B–D
that show the effect of TBR inlet temperature on sulfur, nitrogen con-
tent and Cetane number of TBR product, respectively. Since the TBR
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Fuel 212 (2018) 61–76
Fig. 7. Effect of hydrogen to hydrocarbons ratio on: A- hy-
drotreating severity inside TBR; B- sulfur content difference
between TBR inlet and outlet liquid streams; C- nitrogen
content difference between TBR inlet and outlet liquid
streams; D- Cetane number difference between TBR inlet
and outlet liquid streams; E- Catalyst remaining lifetime
during the study period. TBR inlet temperature = 290.4 °C,
TBR pressure = 35 bar, LHSV = 0.8752 h−1, H2S con-
centration in recycle gases = 464 ppm, TBR feed
IBP:FBP = 268:390 °C.
operation is still far from equilibrium, hydrotreating selectivity towards
HDN is enhanced by the increase in the TBR inlet temperature
(Fig. 6B and C), inasmuch as higher temperatures increase the activity
of hydrogenation and thermal decomposition reactions. However, the
equilibrium constant of reversible reactions decreases at higher tem-
peratures. Therefore, an increase in the processing severity for the TBR
above 310 °C becomes less (Fig. 6A). In general, an increase in TBR
temperatures is not preferred, inasmuch as this increase promotes coke
formation on the catalyst surface. Thus, this leads to deactivation fol-
lowed by shortness in the lifetime of the TBR catalyst (Fig. 6E). Actu-
ally, TBR operators sometimes can resort to increase the inlet tem-
perature, especially at end of run in order to compensate the loss in the
catalyst activity. This increase in TBR temperatures should be per-
formed without exceeding the maximum allowable bed temperature
(400 °C) as recommended in the operating manual. Above this tem-
perature, the rate of coke formation becomes very rapid, and a little
improvement in the process performance is obtained. However, Fig. 6E
shows that the catalyst lifetime will run out and the TBR operators will
be forced to introduce the hydrotreating bed to the regeneration step as
E.S. Sbaaei, T.S. Ahmed
soon as the TBR inlet temperature approaches to 310 °C.
5.2. Hydrogen to hydrocarbons ratio
Hydrogen is necessary for completing hydrotreating reactions and
decreasing coke deposition on the catalyst surface. Generally, in-
creasing the inlet hydrogen flow leads to higher hydrogen partial
pressure inside the TBR that enhances the processing severity and
consequently further improvement in the TBR product specifications
(Fig. 7A–D). Hydrogen acts as a reduction agent for sulfur and nitrogen
impurities by converting them to H2S and NH3, and as a saturation
agent for unsaturated hydrocarbons and gum precursors that deactivate
TBR catalyst by converting them to stable paraffinic compounds. Hy-
drogen to hydrocarbons weight ratio (H2:HC) must exceed 0.025 in
order to improve the TBR product specifications such as nitrogen con-
tent and Cetane number (Fig. 7C and D), as well as to extend the cat-
alyst lifetime (Fig. 7E). This ratio also provides enough heat sink to
absorb continuously the heat of reactions. Furthermore, hydrogen de-
ficient atmosphere inside an industrial TBR creates a greater tendency
to form coke. However, in Fig. 7E, a slight decrease in the TBR catalyst
lifetime was observed at higher H2:HC ratios. This decrease happens
because some highly exothermic reactions begin to occur inside the
TBR at higher hydrogen partial pressures, causing the catalyst deacti-
vation by thermal effects. Virtually, the selection of optimal H2:HC
ratio during hydrotreating depends mainly on hydrogen consumption
and feedstock quality, as well as economic criteria.
5.3. Liquid hours’ space velocity
Contact time between the three phases: gas (hydrogen), liquid
(hydrocarbons), and solid (catalyst) must be sufficient for accom-
plishing hydrotreating reactions. Therefore, an increase in liquid hours’
space velocity (LHSV) results in reducing the rate of hydrotreating re-
actions, causing a depression in the processing severity inside the TBR
(Fig. 8A). Hence, a decrease in the TBR product quality will occur. In
addition, an increase in LHSV leads to more hydrogen consumption
70
Fuel 212 (2018) 61–76
Fig. 8. Effect of liquid hours’ space velocity (LHSV) on: A-
hydrotreating severity inside TBR; B- hydrogen consump-
tion inside TBR; C- Catalyst remaining lifetime during the
study period. TBR inlet temperature = 290.4 °C, TBR pres-
sure = 35 bar, H2:HC mass ratio = 0.0326, H2S concentra-
tion in recycle gases = 464 ppm, TBR feed
IBP:FBP = 268:390 °C.
inside the TBR (Fig. 8B), since higher quantities of contaminants are
introduced to the TBR. Indeed, this parameter relies mainly on the
upstream units’ capacity. However, the TBR cannot operate at LHSV
higher than 1.2 h−1 under the current operating conditions because of
catalyst deactivation as shown in Fig. 8C.
5.4. Reactor pressure
Higher pressures inside the TBR augment the concentration of hy-
drogen molecules in the liquid hydrocarbons. Consequently, the
number of hydrogen and hydrocarbon molecules will rise inside the
catalyst pores. This leads to increase the processing severity, thereby
improving the TBR product quality (Fig. 9A–D). Higher TBR pressures
increase the activity of HDN on HDS (Fig. 9B and C) because hydro-
genation reactions are promoted at higher pressures. Therefore, the
TBR pressure should exceed 35 bar in order to guarantee more im-
provements to the TBR product (Fig. 9C and D) and longer life to the
TBR catalyst (Fig. 9E). Actually, this parameter relies mainly on plant
design. Higher TBR pressures require a larger compressor and huge
equipment’s metal thickness in order to withstand the pressure effect.
5.5. Hydrogen sulfide and ammonia in recycle gases
Hydrogen sulfide and ammonia, produced from HDS and HDN, have
an inhibition effect on hydrotreating reactions. Hydrogen sulfide and
ammonia cover the active sites that normally adsorb hydrogen, creating
a relative poor surface of hydrogen. This leads to a decrease in the
processing severity (Fig. 10A), thereby decreasing the product quality.
It is observed that the inhibition effect of hydrogen sulfide is higher
compared to ammonia. A poisoning tendency of these compounds is
related not only to their basicity, but also to their structure [35].
Nevertheless, hydrogen sulfide does not decrease the catalyst lifetime as
ammonia (Fig. 10C). Ammonia exposed to the supported catalyst en-
courages to form cobalt support compounds, which have higher oxi-
dation state than cobalt metal [36]. Therefore, presence of ammonia
inside the TBR increases the cracking activity as shown in Fig. 10B. The
E.S. Sbaaei, T.S. Ahmed
formation of cobalt support compounds causes structural changes of the
catalyst. Thus, existence of ammonia in the recycle gases shortens the
catalyst remaining time (Fig. 10C) and its removal is necessary. Actu-
ally, hydrogen sulfide concentration in recycle gases is diluted by DEA
contactor. On the other hand, ammonia reacts with hydrogen sulfide,
forming ammonia salts that can be easily eliminated by demineralized
water injected into TBR effluent.
5.6. Feed composition
Because of variations in operating conditions of hydrotreating up-
stream units, TBR feed composition usually changes during operation.
These variations inevitably lead to a change in heteroatomic com-
pounds quantities introduced to hydrotreating TBRs. Fig. 11A and B,
Fig. 12A and B show the behavior of these compounds inside the TBR
under investigation.
5.6.1. Sulfur compounds
Reactivity of sulfur compounds decreases with complexity of the
molecular geometry. Moreover, hydrotreating reactions rate is strongly
influenced by structure of the compounds present in the feed. This
71
Fuel 212 (2018) 61–76
Fig. 9. Effect of TBR pressure on: A- hydrotreating severity
inside TBR; B- sulfur content difference between TBR inlet
and outlet liquid streams; C- nitrogen content difference
between TBR inlet and outlet liquid streams; D- Cetane
number difference between TBR inlet and outlet liquid
streams; E- Catalyst remaining lifetime during the study
period. TBR inlet temperature = 290.4 °C, H2:HC mass
ratio = 0.0326, LHSV = 0.8752 h−1, H2S concentration in
recycle gases = 464 ppm, TBR feed IBP:FBP = 268:390 °C.
explains the reason for the slight change in the conversion of hydro-
treating reactions inside the TBR and also in the remaining life time of
the catalyst in the presence of alkylbenzothiophene (Fig. 11A and B).
Alkyl group existing in aromatic ring adjacent to thiophene decreases
the reactivity of this compound due to steric hindrances that slow down
the reactions rate inside the TBR. Sulfur compounds do not cause the
catalyst deactivation; however, temperatures rise resulting from HDS
reactions decreases the catalyst lifetime.
5.6.2. Nitrogen compounds
Nitrogen compounds are strongly adsorbed on active sites due to
their higher polarity compared to other compounds. Thus, the presence
of these compounds reduces the available active sites required for hy-
drotreating, leading to a decrease in the conversion of reactions inside
the TBR (Fig. 12A). However, heavy nitrogen compounds adjacent to
polycyclic aromatic rings also contribute to the catalyst deactivation as
shown in Fig. 12B. These heavy compounds are mainly the coke pre-
cursors and their adsorption on the catalyst surface is the main causa-
tive of coke formation. Heavy nitrogen compounds with high polarity
readily combine with olefins in order to undergo to oligmerization and
polymerization reactions, causing coke deposits on the catalyst surface.
E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Fig. 10. Effect of H2S and NH3 in recycle gases on: A- hy-
drotreating severity inside TBR; B- specific gravity differ-
ence between TBR inlet and outlet liquid streams; C-
Catalyst remaining lifetime during the study period. TBR
inlet temperature = 290.4 °C, TBR pressure = 35 bar,
H2:HC mass ratio = 0.0326, LHSV = 0.8752 h−1, TBR feed
IBP:FBP = 268:390 °C.

Fig. 11. Effect of sulfur compounds in liquid feed on: A-

hydrotreating severity inside TBR; B- Catalyst remaining
lifetime during the study period. TBR inlet
temperature = 290.4 °C, TBR pressure = 35 bar, H2:HC
mass ratio = 0.0326, LHSV = 0.8752 h−1, H2S concentra-
tion in recycle gases = 464 ppm.

6. Model application to process optimization variables in Coker Complex Hydrotreating unit. Variations in TBR feed
IBP and FBP lead to a change in the charge quality (including amount of
From the previous analysis, it can be concluded that TBR feed PONAs) introduced to TBR. The TBR investigated in this case study was
composition and TBR inlet temperature are the dominant process designed to handle distillates with IBP = 250 °C and FBP = 352 °C,

72
E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Fig. 12. Effect of nitrogen compounds in liquid feed on: A-

hydrotreating severity inside TBR; B- Catalyst remaining
lifetime during the study period. TBR pressure = 35 bar,
H2:HC mass ratio = 0.0326, LHSV = 0.8752 h−1, H2S con-
centration in recycle gases = 464 ppm.

Table 6 while the current distillates have boiling range between 268 and 390 °C.
Operating conditions of the unit at the base operating point and at the optimum operating The design distillates have better properties compared to the current
point. distillates. These properties of design distillates guarantee longer op-
Process Variable Base Operating Point Optimum Operating Point
eration period of investigated hydrotreating unit and higher perfor-
mance of its TBR. For example, the design distillates have actually
TBR inlet temperature [oC] 290.4 334.9 lower CCR that leads to a decrease in the coke formation rate inside
H2:HC mass ratio 0.033 0.026 TBR followed by increasing the catalyst lifetime. It should be noted that
LHSV [h−1] 0.875 0.878
the model stream with boiling range between 250 and 352 °C has spe-
cifications similar to the design feed recommended to be introduced to
the TBR, in terms of contaminants amount. Upstream units' operators
can easily control TBR feed boiling range by adjusting draw-tray

Fig. 13. Variation of TBR feed specific gravity with IBP and FBP.

73
E.S. Sbaaei, T.S. Ahmed Fuel 212 (2018) 61–76

Fig. 14. Variation of temperature rise through TBR bed with IBP and FBP at base
operating conditions.

Fig. 15. Variation of TBR catalyst remaining lifetime with IBP and
FBP at base operating conditions during the study period.

Table 7 temperatures of gas oil fractions that will be treated inside TBR, without
Expected remaining lifetime of investigated catalyst after finishing this study. overlapping with lighter or heavier fractions.
The operating manual permits TBR operators to increase the inlet
Operating Scheme Catalyst Remaining Lifetime [days]
temperature so long as the outlet temperature does not reach the
Base 27 maximum allowable (400 °C). However, as mentioned before, ap-
Optimum 456 proaching TBR inlet temperature to 310 °C under the base operating
conditions leads to destroying the catalyst lifetime. Therefore, TBR feed
boiling range should be adjusted in order to fulfill the optimum op-
Table 8
eration of investigated unit.
Variation in plant performance after applying the optimized scheme.
Two questions will come to refiners’ mind before optimizing a
Parameters Before After Differences process: “What if a change happened to one or more of the process
Optimization Optimization variables?” and “How to maximize profits?”. Refiners are always in
attempts to find solutions for confronting “What-if” challenge and
Plant operating variables:
Total heat required [MJ/ 36,273 31,757 −4,516
“How-to” challenge. Optimization studies need a precise monitoring
h] and analysis of process performance, and applying corrective adjust-
Fuel gas required [kg/h] 3,108 2,721 −387 ments to the actual operations. This scenario has been covered in the
Total waste heat [MJ/h] 37,337 35,697 −1,640 previous analysis of operating variables. On the other hand, refiners
Hydrogen required [kg/ 1,035 823 −212
usually seek to maximum profit. In reality, this challenge is the main
h]
Compressor horsepower 49 35 −14 obstacle that should be faced during the process optimization.
required [kW]

Plant productivity: 6.1. Optimization of the industrial process

Diesel fuel [kg/h] 10,356 14,629 4,273
In order to optimize the process, the notes obtained from the first

74
E.S. Sbaaei, T.S. Ahmed
Table 9
Variation in diesel fuel specifications after applying the optimized scheme.
Product Before After Limits
Specifications Optimization Optimization
Specific gravity 0.846 0.840 0.83 min–0.87 max
Sulfur content [wt. 0.75 0.50 1 max
%]
Cetane number 55.7 63.0 46 min
Flash point [oC] 97.4 97.6 65 min
Pour point [oC] −20.1 −21.2 15 max
Kinematic viscosity 3.7 3.6 1.9 min–4.1 max
[cS ]
scenario (analysis of TBR operating variables) should be implemented.
Table 6 presents the conditions of the investigated industrial unit at the
base operation. As indicated earlier, TBR treats heavier cuts than what
it is designed. Therefore, the first step is to change feed IBP and FBP to
the boiling range of 250–352 °C which TBR is designed originally to
treat. Fig. 13 presents the change in TBR feed specific gravity with IBP
and FBP. The next step is to vary TBR inlet temperature and hydrogen
flow rate simultaneously to fulfill a maximum yield of diesel fuel with
identical specifications and minimize, if possible, operating cost of the
investigated unit. TBR inlet temperature has been raised until the re-
actions severity approached the equilibrium in order to enhance the
plant productivity. Use of the base operating conditions in order to treat
the design distillates leads to a decrease in the processing severity in-
side TBR as shown in Fig. 14. Nevertheless, the catalyst lifetime in-
creases theoretically 23 times compared to the actual distillates as il-
lustrated in Fig. 15. Thus, the return to the designed boiling ranges of
distillates permits TBR operators to increase the inlet temperature
during hydrotreating, while maintaining the catalyst lifetime. Table 7
exhibits the change in remaining lifetime of catalyst after applying the
optimized scheme. It is noted in this table that the continuation in
treating the current distillates with boiling range of 268–390 °C at base
operating conditions will lead to destroying the TBR catalyst lifetime
after 27 days. It should be emphasized that petroleum cuts utilized in
Figs. 13–15 were calibrated according to the different quantities of
impurities, which have been actually introduced to the TBR catalyst
during its lifetime.
As a rule of thumb to avoid coke deposition, TBR should not be
operated at H2:HC mass ratio less than 0.025 at any time as shown
before in Fig. 7E. H2:HC ratio has been reduced to the lowest possible
value in order to decrease the plant operating cost, while preserving
hydrotreating severity. The quantity of make-up hydrogen used affects
heat transfer coefficients in both the hot and cold combined exchangers
and consequently, influences the outlet temperatures. The lowest pos-
sible H2:HC mass ratio in the TBR is 0.026, which is still far higher than
the allowable minimum. Table 8 shows the comparison between the
plant performance at the base and optimum operation.
6.2. Model predictions after optimization
Results shown in Tables 8 and 9 illustrate that about 4273 kg/h can
be added to the diesel fuel yield with more improvement in the fuel
specifications by following the suggested optimized scheme. Savings in
the diesel fuel yield are mainly attributed to an increase in the thermal
decomposition reactions activity inside TBR by increasing the inlet
temperature. Since approximately 212 kg/h of pure hydrogen in-
troduced to TBR can be saved by applying the optimum scheme. This
surplus in make-up gas can be added to fuel gases system in order to
provide approximately 16,000 MJ/h. Moreover, recycle gases com-
pressor work is decreased by 14 kW. The total fire heaters duty of both
sections of the optimized scheme is diminished by 4516 MJ/h, resulting
in about 387 kg/h decrease in the fuel gases required to both furnaces.
The optimized scheme provides less specific gravity to TBR effluent,
75
Fuel 212 (2018) 61–76
causing a decrease in the total fheat supply to the unit as exhibited in
Table 8. Furthermore, this scheme decreases the total heat wasted in the
air and water coolers of the unit by 1640 MJ/h. Therefore, the total
energy required will be saved in Coker Complex Hydrotreating unit by
applying the suggested optimized scheme.
From the outlined above, applying the optimization scheme saves
energy consumption of the process, as well as enhances the process
productivity of diesel fuel with better specifications. Thus, the optimi-
zation scheme has achieved the desired economic target of the unit
investigated in the current case (higher diesel fuel yield with lower fuel
consumption). It should be mentioned here that saving in the energy
and product yield are mainly proportional to the plant capacity.
Finally, the model may be utilized to forecast the plant performance
at different operating points. The model is quite useful for predicting
proper operating conditions, especially when hydrotreating unit suffers
from fluctuations in TBR feed IBP and FBP. This can be implemented by
integrating the model into a real time optimization (RTO) scheme. In
this situation, it is recommended that the model be finely tuned to
match the plant performance strictly.
7. Conclusion
A process model for an industrial Coker Complex Hydrotreating
process was developed using Aspen HYSYS Petroleum Refining
Hydroprocessor Bed module. The model could track the plant perfor-
mance competently. In addition, the model was utilized for in-
vestigating the effect of each process variable on the process perfor-
mance. Among all process variables, TBR feed boiling range and TBR
inlet temperature were the most dominant factors to influence the
process performance. Finally, the model was used for optimizing the
process at steady state conditions. Results acquired from the model
showed that a considerable increase in product yield could be achieved
by adjusting the TBR feed boiling range to reach the IBP and FBP which
the TBR is designed to treat, while lowering the hydrogen partial
pressure inside the TBR to the lowest possible practical value and in-
creasing the TBR inlet temperature to the equilibrium limit. The surplus
in make-up gas may be diverted to fuel gas system, resulting in sig-
nificant fuel savings. Applying the optimization scheme saves the plant
consumption of energy as well as enhances the plant productivity of
diesel fuel with better specifications. The model may also be integrated
into a real time optimization scheme. In this situation, the model should
be finely tuned to match the plant performance strictly.
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