Antonio Espuña, Moisès Graells and Luis Puigjaner (Editors), Proceedings of the 27th European

Symposium on Computer Aided Process Engineering – ESCAPE 27

October 1st - 5th, 2017, Barcelona, Spain © 2017 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/B978-0-444-63965-3.50141-0

Model Based Analysis of a Petroleum Refinery

Plant with Hydrotreating as a Pre-treatment Unit
Mohammad Alkandaria, Iqbal M. Mujtabab, Harvey Arellando-Garciaa
a
Department of Chemical and Process Engineering, University of Surrey, Guildford,
GU2 7XH, United Kingdom
b
School of Engineering, University of Bradford, West Yorkshire, BD7 1DP, UK
h.arellano-garcia@surrey.ac.uk

Abstract
Catalytic hydrotreating is one of the processes used intensively in the modern petroleum
refining industry. It is series of reactions considered as a mature process that improves
the quality of petroleum products and removes Sulphur and undesired impurities. This
study aims to develop and enhance the performance of a whole petroleum refining plant,
which follows the concept of crude oil hydrotreating (HDT). The study was carried out
using Aspen HYSYS simulator building a model-based analysis for the refinery plant.
Two refineries have been simulated separately; one with a crude oil hydrotreating and the
other followed the conventional method. The comparison and analysis focused on
enhancing the yield of middle distillates while reducing the total energy consumption and
overall costs. Hydrodenitrogenation and Hydrodesulfurization were the two reactions that
took place in the trickle bed reactor at 400°C and 10MPa. The hydrotreated crude oil
enters then the atmospheric distillation column, where six main products were distilled
(LPG, Light Naphtha, Heavy Naphtha, Kerosene and Residual crude). In the model-based
analysis, the crude HDT process configuration was completed first using Kirkuk crude
oil, and to confirm the significance of the study, Siberian crude was used as an alternative
feedstock. Finally, the results confirmed that the crude oil hydrotreating method can be
followed using different types of feedstock around the world.
Keywords: Hydrotreating, Petroleum Refinery, Crude Oil, Model Based Analysis.

1. Introduction
Nowadays, modern refining industry tends to clean fuel products, optimized plants and
environmentally friendly emissions. The new standards of fuels require ultra-low sulphur
contamination achieved by specific reactors and process variables. Also, from an
economic perspective, reducing associated costs to construction and refinery operations
will lead to increasing the profitability of the project. Hydrotreating process (HDT) is a
major energy-consumption unit within a refinery and a key unit for removing sulphur and
undesirable contaminants (Gary et al., 1994). Therefore, this work focuses on the HDT
unit, as the aim is to develop and enhance the performance of a petroleum refinery plant
by crude oil hydrotreating in a pre-treatment HDT. The aim is accomplished through
achievement of the following objectives: enhancing the yield of middle distillates,
converting heavy hydrocarbons into higher value products, reducing capital, operating
and utilities cost, reducing utilities consumption, optimizing operating conditions for the
HDT reaction and applying the method into different crude feedstock.
836 M. Alkandari et al.

2. Methodology
In this work, the two refinery models were simulated using the HYSYS simulation
software environment. Also, the analysis on the performance and viability of the plants
were constructed using specific tools in HYSYS. Fluid packages in this tool consist of
thermodynamic models that are used to present the vapour-liquid equilibrium behaviour
and energy level of mixture systems. In this work, Peng-Robinson is used in all
simulations as it gave accurate results for both dew point and bubble point curves for
crude systems. The feedstock is Iraqi Kirkuk crude with a flow rate of 50,000 kg/h and
contaminations of 2% wt of Sulphur and 0.1% wt of Nitrogen. The catalyst used is cobalt-
molybdenum on alumina (Co-Mo/γ-Al2O3). The two reactions taking place in the HDT
trickle bed reactor are Hydrodesulphurization (HDS) and Hydrodenitrogenation (HDN).
- HDS reaction: R-S + H2 → R + H2S
- HDN reaction: R-NH2 + H2 → RH + NH3
The kinetic reactions are considered to be only forward reactions, where the reaction rate
constant equation is obtained in Eq. (1):
‫ܣܧ‬
݇ ൌ ‫ܣ‬௢ ݁‫ ݌ݔ‬൬െ ൰ (1)
ܴܶ

Where:
Ai0 Pre-exponential factor for reaction, (mol/cm3)1-ni (cm3/g.sec) (mol/cm3)-m
k kinetic constants, (wt%) -n sec-1
EA Activation energy, J/mol
R Universal gas constant, J/mol.K
T Temperature, K
m Order of reaction of hydrogen in reaction j
ni Order of reaction of compound i in reaction j

The following process variables are obtained from Jarullah (2011).

For HDS reaction: Ao = 2026.23, EA = 50264.1
For HDN reaction: Ao = 2.85x107, EA = 71775.5
The four significant process variables of the HDT reaction are:
1- Reaction temperature: 400 °C
2- Partial hydrogen pressure: 10 MPa
3- Liquid Hourly Space Velocity (LHSV): 0.5 hr-1
4- H2:Oil ratio: 250
Model Based Analysis of a Petroleum Refinery Plant with Hydrotreating as a 837
Pre-treatment Unit

Figure 1: Crude HDT simplified process flow diagram

Fig. (1) illustrates the process flow diagram in HYSYS for crude HDT method. The main
sections are feed preheating, reaction, high pressure separation, hydrotreated crude
fractionation and finally sweetening process and recycle gas. On the other hand, the
conventional simulation started with the fractionation section followed by separate HDT
units (including reaction, separation, and recycle gas systems) for each product.
Crude HDT simulation has started with simulating the trickle bed reactor. Crude oil,
Nitrogen and Sulphur contaminations were introduced as three separate streams then
mixed in a mixer, representing the sole hydrocarbon feed into the system. Hydrogen is
then mixed with an optimized rate of 246.7 kg/h, which gives a maximum conversion in
the reactor, operating at 400ºC and 10 MPa. The reactor dimensions are set to be the
minimum dimensions of an industrial TBR (1m in diameter, and 10m in length). Quench
line of recycle gas is to be fed into the reactor into two stages, for intercooling and
maximizing product yield. Reactor product is separated in a high pressure separator,
where the gases enters amine sweetening process to remove sulphur contaminations, then
is fed with pure hydrogen prior compressing and recycling with crude. The aim of
sweetening process (H2S absorber) is to recover hydrogen and eliminate the maximum
quantity of H2S, NH3 and HCs of the stream. The absorber liquid is 30% DE Amine and
70% water.The hydrotreated crude leaving the bottom of high pressure separator is
depressurized and then preheated to 400ºC, prior entering the atmospheric distillation
column. The six distillates are leaving the distillation column at the following boiling
ranges (ºC): Gases (-40 – 0), L. Naphtha (30–85), H. Naphtha (85–200), Kerosene (170–
270), Gas oil (180–240), Residual crude (>540). The quality and economic analysis of
both methods of crude refining have been conducted using the data generated by both
simulations. Economic analysis tool is available in Aspen HYSYS for a whole evaluation
of the refinery.
838 M. Alkandari et al.

3. Results and discussion

The data and results extracted from the converged two simulations are expressed in
column charts according to each objective of this work. The first objective is to enhance
the yield of middle distillates, and converting heavy hydrocarbons into higher value
products. From Fig. (2), the middle distillates (Light Naphtha, Heavy Naphtha, Kerosene
and Gas oil) showed an enhancement in productivity using the crude oil Hydrotreating
method, however only the kerosene has shown a drop regarding productivity. Kerosene
product in the conventional method contains 8% wt of H 2S, where in the crude HDT
method the product is free of any Sulphur contaminations. Clean Kerosene in the crude
HDT method will require no further processing, such as H2S stripping unit. Also, Gas oil
product in the conventional method contained 2% wt of H2S while in the crude HDT
method was also free from H2S. The crude HDT method achieved 30% reduction in R.C.R
productivity, 29% enhancement in Naphtha productivity, 726% enhancement in Gas oil
productivity, and 115% enhancement in LPG productivity.

Figure 2: Comparison of productivity percentages for middle and heavy distillates by the two method of
refineries, crude HDT method

The second objective focuses on the economic analysis, where the aim is reducing capital,
operating and utilities costs. Fig. (3) shows the reduction tendency in the crude HDT
method among all the costs. The total project capital cost is reduced by 48%, due to the
large reduction in the purchased equipment. The total operating cost has also been
reduced by 16%, which means annual $3M savings of a 20 years’ project plan. Moreover,
the total utilities consumption is reduced by 8%.

Figure3: Comparison of capital, operating and utilities cost in the two method of refineries, crude HDT
method and conventional method
Model Based Analysis of a Petroleum Refinery Plant with Hydrotreating as a 839
Pre-treatment Unit

Figure 4: Comparison of the number of equipment purchased in the two refineries, crude HDT method and
conventional method.

The third objective is reducing the number of purchased equipment. From Fig. (4), it can
be noted that for the crude HDT method, almost eight types of equipment have been
reduced to half or more than the quantity purchased. The thermosiphon reboiler number
remained the same in both cases, as they were used in the side strippers in the distillation
column.

Figure 5: Comparison of utilities consumption between both refining methods.

The fourth objective is reducing utilities consumption throughout the plant. Fig. (5)
compares the utilities consumption in the crude HDT method and the conventional
method, where they are classified in a distribution percentage for each utility. Steam
consumption (at 165psi and 100psi) was significantly reduced in the crude HDT method.
Also, Freon 12 refrigerant and electricity consumptions are reduced in the HDT method
in comparison to the conventional method. On the contrary, cooling water consumption
in the crude HDT method is significantly higher. However, cooling water is one of the
utilities that has a relatively low cost. Objective five is concerned with the sensitivity
analysis on the crude HDT method. The make-up hydrogen fed to the reactor has a high
value, therefore, a study was performed in HYSYS in order to optimize the required
amount. The results indicated that 31.5 kgmole/h is the minimum flow rate required to
remove the maximum contaminations of sulphur and nitrogen. Another sensitivity
analysis was performed in order to optimize the operating parameters for the reactor. The
840 M. Alkandari et al.

results confirmed that 400°C and 10 MPa are the optimal operating parameters that assure
the maximum conversion and least free gases emissions.
The sixth objective evaluates the viability of crude HDT method on different feedstocks.
The crude feedstock in the HYSYS simulation was changed to Siberian crude oil with a
sulphur content of 0.442% wt and a nitrogen content of 900 ppm. The results showed a
similar tendency in the refinery performance. The Siberian crude had two advantages over
the Kirkuk crude, where R.C.R production slightly decreased and the Gas oil production
increased according to Fig. (6). The outcome of this objective assures that the crude HDT
method can be followed using different types of feedstock around the world.

Figure 6: Comparison of Gas Oil and R.C.R productivity percentage between the Siberian and Kirkuk crude
feedstock.

4. Conclusions
The model-based analysis was done on the petroleum refinery plant with hydrotreating
as a pre-treatment unit, and then compared according to the introduced objectives with
the conventional refinery approach. The hypothesis of the study was to confirm a greater
yield for middle distillates in the crude HDT method refinery and overall a better refinery
with less capital, operating, and utilities cost. The results showed improvement in
Naphtha and Gas Oil productivities by 29% and 700% respectively. LPG productivity has
also been increased by 115%. Residual crude has been reduced by 30%. On the other
hand, Kerosene productivity has noticed a reduction, but with free Sulphur product,
compared to 8% wt in the conventional method. Also from economics perspective, crude
HDT method has significantly reduced the total project capital cost, total operating cost
and total utilities cost by 48%, 16% and 8%, respectively. Moreover, energy consumption
diminished because of utilities consumption reduction. The hypothesis of the study has
been confirmed and current experimental studies are performed to further verify the
validity of the proposed process configuration.

References
A. Jarullah, 2011, Kinetic modelling simulation and optimal operation of trickle bed
reactor for hydrotreating of crude oil
J.H. Gary and G.E. Handwerk, 1994, Petroleum Refining: Technology and Economics,
3rd edition, New York, Marcel Dekker.