Chemical Papers 68 (12) 1716–1724 (2014)

DOI: 10.2478/s11696-014-0620-0

ORIGINAL PAPER

Modelling of catalytic hydrocracking and fractionation

of refinery vacuum residue

Eduard Manek, Juma Haydary*

Department of Chemical and Biochemical Engineering, Institute of Chemical and Environmental Engineering,
Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, 812 37 Bratislava

Received 3 December 2013; Revised 12 May 2014; Accepted 6 June 2014

Dedicated to the memory of professor Elemír Kossaczký

The main objective of this work was to create a kinetic model of refinery vacuum residue hydro-
cracking and to monitor the impact of the operating conditions on the product yields. Data and
yield measurements were gathered from a residual hydrocracking unit (RHC). Reaction tempera-
ture ranged from 401 ◦C to 412 ◦C at the pressure of 18–20 MPa. A simplified kinetic yield model
was applied; where the feed and each product fraction are represented by one lump (reactant or
product of cracking) represented by the number of pseudo-components. The product fractions were
determined by fractional distillation of the output mixture from the reactor. The kinetic model
includes eight reaction steps and the following six fractions: vacuum residue, vacuum distillate, gas
oil, kerosene, naphtha, and gas. In addition, a model for hydrodesulphurisation has been proposed.
The average relative deviation between model and experimental yields was 5.36 %, and that for the
sulphur conversion model was 1.04 %. An Excel file with the kinetic model was implemented in the
Aspen Plus program using a user-defined model of the reactor. This model allows to input/output
data between the Aspen Plus and Excel programs. The Excel subroutine calculates the reaction
kinetics of cracking from the set temperature and residence time, and distributes the products into
30 pseudo-components created in the Aspen Plus program. The remaining part of the RHC unit was
simulated in the Aspen Plus environment. The effects of the reaction conditions such as temperature
and residence time on the conversion of the feed and on the distillation curves of the output mixture
from the reactor were investigated. The model was verified by comparison of the distillation curves
of simulated and real products.

c 2014 Institute of Chemistry, Slovak Academy of Sciences

Keywords: vacuum residue, catalytic hydrocracking, mathematical model, chemical kinetics

Introduction valuable products meeting actual requirements have

The petroleum industry, like many other indus-
tries, has to be dynamically adapted to actual market
demands, which is the impulse for the development
and implementation of new technologies and innova-
tions. Since the launch of the first oil refinery, more
than 150 years ago, the capacity and product range of
modern refineries have significantly expanded. From
a simple idea to distil crude oil into a few fractions,
more ideas on how to process these fractions into more
been gradually added. The use of the lowest boiling
point fractions (vacuum tower products) has always
been complicated. Therefore, cracking units, which
increase the conversion of crude oil into lighter and
more valuable products, play a crucial role in every
refinery processing heavier feedstocks. Currently, var-
ious types of commercial scale cracking units differ-
ing in the equipment layout, operating temperature
and pressure, the use of hydrogen and catalysts, and
enabling the processing of different heavy fractions

*Corresponding author, e-mail: juma.haydary@stuba.sk

 E. Manek, J. Haydary/Chemical Papers 68 (12) 1716–1724 (2014)
like atmospheric residue, vacuum distillate, or vac-
uum residue, are used. The economic result of a crack-
ing unit is mainly dependant on the feedstock conver-
sion into desired products; therefore, conversion is the
most prominent indicator of the unit efficiency. Hydro-
cracking consists of two groups of processes: endother-
mic hydrocarbon cracking and exothermic hydrogena-
tion of unsaturated hydrocarbons, sulphur and nitro-
gen organo-compounds. The overall enthalpy balance
shows that the process is exothermic. The increasing
temperature leads to higher vacuum residue conver-
sion into lighter components but also to operational
complications and unwanted effects such as coke and
sediment generation and to suppression of the exother-
mic hydrodesulphurisation and hydrodemetalisation.
Therefore, the operation temperature must be care-
fully chosen based on experience and a kinetic model
if available.
Kinetic model is a useful tool for the reactor de-
sign, yield and conversion prediction as well as for unit
simulations. Various papers on different approaches to
the kinetic study of heavy oil fractions hydrocracking
have been published. Puron et al. (2014) developed a
lumped kinetic model for vacuum residue hydrocrack-
ing, testing two catalysts: Ni–Mo/Al2 O3 (aluminum–
nickel–molybdenum) and Ni–Mo/Al2 O3 –Cr (alumina
doped with chromium). All proposed models consist of
four lumps (products with the boiling point > 450 ◦C,
products with the boiling point < 450 ◦C, gas, and
coke) at various complexity levels. Kinetic data were
obtained in a microbomb batch reactor. Morawski
and Mosio-Mosiewski (2006) observed the effect of
temperature, space velocity of feed, partial hydro-
gen pressure, and of the Ni–Mo/Al2 O3 (aluminum–
nickel–molybdenum) catalyst content during the vac-
uum residue hydrocracking on the product composi-
tion and quality. The experiment was run in an ex-
perimental scale continuously stirred fixed bed reac-
tor and the yields of the reactor output products
were determined by atmospheric and vacuum distil-
lation. Liu et al. (1994) chose a dispersed catalyst
phase and their experiment results suggest that the
dispersed phase of the Mo catalyst considerably in-
hibits thepolycondensation of resins and asphaltenes,
and delays the coke formation by promoting hydro-
genation and hydrodesulphurisation. Lababidi et al.
(2011) developed a model of the hydrocracking pro-
cess predicting the product quality of the vacuum
gas oil (VGO). Model validation results showed that
the proposed model is capable of predicting distilla-
tion curves of the hydrocracked products. Kinetics of
non-catalytic hydrocracking of heavy residue oils was
studied by Ramírez et al. (2012) using the lumping
approach. The results confirmed that hydrocracking
reactions proceed by a cascade mechanism from the
heavier to the lighter fractions. Naphtha does not hy-
drocrack to form gases under the operating conditions
studied. Martínez and Ancheyta (2012) developed a
1717
five-lumped model with ten reaction pathways for at-
mospheric residue hydrocracking. Experiments were
performed with a commercial size tetra lobular cata-
lyst. The model also incorporates the effectiveness fac-
tor, and a time-dependant deactivation function for
obtaining the intrinsic kinetic parameters. Galiasso
Tailleur (2005) studied mild hydrocracking catalyst
deactivation with hydrodesulphurised vacuum gas oil
as the feed and WNiPd/TiO2 Al2 O3 as the catalyst.
The results confirmed that the deactivation changes
the relative rate of the hydrogenation/hydrogenolysis,
cracking, and dealkylation reactions. Stochastic recon-
struction, reconstruction by enthropy maximisation
and the kinetic Monte Carlo method for the two-step
kinetic modelling strategy of the hydroconversion pro-
cesses were used by Pereira de Oliveira et al. (2014).
This novel method was applied to the Ural vacuum
residue hydroconversion and, given that this method-
ology is molecule-based, a vast array of details was
provided by the reactor simulation. Molecular mod-
elling and the FTIR (Fourier transform infrared spec-
troscopy) technique were used by Rodrigues Coelho et
al. (2006) to determine the characteristics of aliphatic
chains in vacuum residues.
Most of the current papers deal with hydrocrack-
ing of vacuum distillates. Commercial scale resid-
ual hydrocrackers processing vacuum tower bottoms
(vacuum residues) are a relatively unique technology.
There are only a few RHC units in oil refineries all
over the word, mostly in the USA, Canada, and Eu-
rope (Martínez et al., 2010).
Experimental
Data were collected using a commercial scale resid-
ual hydrocracker unit (RHC), which is a part of an oil
refinery complex. A commercial catalyst based on Ni–
Mo/Al2 O3 pellets was applied for this process. The
purpose of this unit is to process vacuum residue
from the vacuum tower bottom into lighter hydro-
carbon fractions and concurrently remove sulphur, ni-
trogen, and oxygen from heterocyclic molecules via
hydrogenation. Metal content is removed via chemi-
cal adsorption on a catalyst surface. Vacuum residue
is the heaviest fraction from primary crude oil dis-
tillation containing substances with high molecular
mass (about 600 kg kmol−1 ), distillation curve is in
the range of 440–750 ◦C, and density is approximately
1020 kg m−3 at 20 ◦C. High content of sulphur (about
3.00 mass %), nitrogen (0.50 mass %), and metals
(vanadium: 0.021 mass %, nickel: 0.006 mass %) makes
this fraction complicated to be processed in other
units. RHC consists of three reactor series with an
ebullated catalyst bed. The ebullated bed reactor sys-
tem has been comprehensively described by Martínez
et al. (2010). Hydrocarbon cracking is an endother-
mic and hydrogenation is an exothermic process, the
overall effect is exothermic. Effluent from the first to