Volume 8, Issue 6, June – 2023 International Journal of Innovative Science and Research Technology

ISSN No:-2456-2165

Comparative Study on Technologies for Crude Oil

Desulphurization in Modular Refineries
Jackson Idikwu1 Ayoade Kuye2
NLNG Centre for Gas, Refining and Petrochemical Department of Chemical Engineering University of Port
Engineering, University of Port Harcourt, Port Harcourt Port Harcourt, Nigeria
Harcourt, Nigeria

Akachidike Kanu3
NLNG Centre for Gas, Refining and Petrochemical Engineering, University of Port Harcourt Port Harcourt, Nigeria

Abstract:- This study compares the performance and groups of sulphur compounds, thiophenes, comes in several
economic viability of two different sulphur removal different types. The remaining sulphur molecules can be
methods from crude oil, namely, hydrodesulphurization broken down into methacrylic acid, sulphides, and
(HDS) and oxidative desulphurization (ODS) processes. disulphides. The existence of sulphur compounds in gaseous
The results indicate that HDS is more effective in fuels has a negative effect on cars not only because of their
removing dibenzothiophene, achieving an absorption harmful influence but also because of their toxicity.
rate of 90%, while ODS achieved an absorption rate of
80%. However, both methods were equally effective in According to the International Energy Agency (IEA)
removing other sulphur compounds such as B and P- in 2020, fossil fuels accounted for approximately 80% of
Disulphide, and Thiophene. Economic comparison global primary energy consumption. Most hydrocarbon oil
suggests that ODS is a more cost-effective process is used to produce transportation fuels like gasoline, diesel,
compared to HDS. The study highlights the importance and aeroplane fuel. Sulphur-containing gasoline
of considering various factors, including crude oil significantly affects how well catalytic converters in cars
composition, required degree of desulphurization, and work [5]. Because of their tendency to inactivate crude oil
environmental regulations, in choosing the appropriate processing and cause rust in pipes, pumping equipment, and
sulphur removal method. Overall, the study concludes refinery equipment, sulphur compounds are not accepted in
that both HDS and ODS are effective methods for the refining process. Sulphur oxide emissions result from
removing sulphur-containing compounds from crude oil, unburned sulphur compounds in gasoline and diesel fuel [6].
and the choice of method depends on specific application When these gases combine with atmospheric water, they
requirements and environmental considerations. produce sulphates and acid rain, which in turn harm
buildings, eat away at car paint, make dirt acidic, and lead to
Keywords:- Hydrodesulphurization, Oxidative- the death of trees and other habitats [7].
Desulphurization, Crude Oil, Sulphur, Aspen Hysys and
Modular Refinery. To comply with environmental requirements, reduced
sulphur concentrations in transportation fuels must be
I. INTRODUCTION achieved, and this requirement serves as the primary
impetus for the efforts that are being made to achieve this
Sulphur compounds and dispersed particles constitutes goal today. To ensure access to affordable clean energy,
less than 0.1% to around 5% of composition of crude oil innovative techniques for removing sulphur from materials
samples depending on the specific composition of the oil of poorer quality are required. The pollution that is produced
and its source. Different geological conditions yield by automobiles has a significant impact on the quality of the
different types of crude oil, and even repeated extractions air that is available to us to consume in our urban areas [4].
from the same well yield different types of crude oil due to Combustion turns sulphur compounds into sulphur oxides,
the passage of time. Despite this, all crude share the same which in turn contribute to acid rain and other
underlying physical properties [1]. After carbon and environmental problems. Sulphur compounds also
hydrogen, sulphur is the most common non-hydrogen contribute to the formation of sulphuric acid [8].
ingredient in fossil fuels [2]. Thiophene, thiols, and
sulphides predominate among the organic sulphur molecules When sulphur compound fuels are consumed, sulphur
found in crude oil. Both organic and inorganic sulphide dioxide and other pollutants related to combustion are
substances can be found in crude oil. Crude oil may contain generated. Sulphur dioxide and other combustion-related
a mixture of pyrite and hydrogen sulphide. This is due to the pollutants contribute to haze, as well as global warming and
presence of organic sulphur molecules in the oil [3]. There is environmental contamination [3]. Exhaust gas from diesel
a direct correlation between the API (American Petroleum engines contains a significant amount of particulate matter
Institute) gravity of petroleum oil (a measure of its specific (PM), which has been linked to an increased risk of lung
gravity) and the sulphur content of that oil, which in turn cancer in people who operate diesel vehicles [4]. As a result,
directly affects its market value [4]. One of the four main

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Volume 8, Issue 6, June – 2023 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165
the desulphurization of products derived from hydrocarbons The process of hydrodesulphurization (HDS) is
is an absolute requirement. currently used in industry to purge fuels of sulphur. HDS is
a chemical process that operates at high temperatures and
Sulphur affects these pollution control systems pressures to remove sulphur from fuels. This means that
because it firmly adsorbs to the valuable metal catalysts, HDS (desulphurization at high temperatures) is a capital-
stopping the uptake and reaction of various pollutants like intensive process. The toxic substance 4,6-
hydrocarbons, nitrogen oxides, and carbon monoxide. In dimethyldibenzothiophene (DMDBT) and its parent
addition to this, sulphur compounds found in petroleum can component dibenzothiophene (DBT) are not being
be corrosive to the components of internal combustion adequately cleared from the environment. (4,6-DMDBT).
engines and refineries. This is because sulphur oxyacids are Desulphurization methods such as oxidative (ODS),
formed when the products of combustion react with sulphur oxidation-extraction (OEDS), adsorptive (ADS), and bio-
compounds [9]. desulphurization (BDS) can be used to create ultra-clean
fuels. Sulphur-containing substances in ODS can be
Diesel fuel and gasoline in the United States have to oxidised with the help of oxidants like hydrogen peroxide
have at least a 25% reduction in sulphur content because of (H2O2), sulphuric acid (H2SO4), and other sulphur-
rules from the United States Environmental Protection containing molecules. For ADS, adsorbents utilised in this
Agency (USEPA). In 2006, the Environmental Protection procedure are created with sulphur extraction in mind.
Agency (EPA) set a limit on the amount of sulphur that Adsorption capacity can be increased by stacking active
could contain no more than 15 parts per million (ppm). By adsorbents on top of a permeable, non-reactive base. The
the year 2020, the sulphur concentration of petrol was molecules of sulphur adhere to the adsorbent on the
expected to decreased to less than 10 parts per million substrate through a process called adsorption, and they stay
(ppm), as stipulated by new laws passed by the European there for the length of the reaction, whether a fuel is present.
Union (EU). Additional sulphur regulations for on-road BDS has been in the news a lot lately for its innovative and
diesel fuel and gasoline entered into force on June 1, 2006, environmentally favourable methods of handling natural
in Canada and the United States, respectively. Gasoline and fuels. However, a major drawback of the BDS method is the
diesel fuel for on-road cars were included in the scope of elimination procedure itself [5].
these rules. The restrictions resulted in a decrease in sulphur
concentration of 500 mg kg-1 to 15 mg kg-1 and,  Some Essential Necessities for a Modular Refinery to
correspondingly, 350 mg kg-1 to 30 mg kg-1. Both in the Operate Profitably and Sustainably are:
United States and in Europe, the maximum amount of
sulphur that can be present in diesel gasoline is now capped  Types of available crude Oil. Crude oils are classified
at 10 milligrams kg-1. The most recent legislation to be according to their API, which is based on their
implemented in India was in 2010, and it resulted in a viscosity; the greater the API number, the lighter the
reduction in the amount of sulphur found in petrol and diesel petroleum is [13]. The production of more outputs from
in India's most populous regions from 150 to 50 parts per heavy crude oil results in a product of lesser value,
million (ppm) and 350 to 50 parts per million, respectively which requires additional distillation and incurs
(ppm) [10]. In Nigeria, the Department of Petroleum additional costs. On the other hand, the production of
Resources (DPR) is the regulatory body responsible for high-value products from light crude oil does not
setting and enforcing the limits on sulphur content in require any additional distillation [9].
petroleum products. Gasoline (Petrol) is set at a maximum  The complexity of a modular refinery can be inferred
of 150 parts per million (ppm) or 0.015% sulphur content, from its structure.
the sulphur limit for diesel fuel used for on-road vehicles in  Classification of finished goods.
Nigeria is set at a maximum of 50 ppm or 0.005% sulphur  Finished goods quality.
content. The sulphur limit for kerosene used as a household
fuel in Nigeria is set at a maximum of 2000 ppm or 0.2% Refineries, from a purely economic standpoint, need to
sulphur content. strike a balance between the production cost and the market
worth of refined goods to maximise their refining profits [6].
There are four different methods of desulphurization: A refinery's only recourse, given that the price of petroleum
hydro, extractive, oxidative, and biological [11]. Elemental is set by uncontrollable factors like supply and demand on
sulphur can be recovered from a variety of materials, global markets or the spot price system, is to keep running
including molten metals, hydrocarbon oil, and exhaust costs as low as possible. This means that a refiner should
fumes. A variety of desulphurization methods available to always aim to maximize efficiency. The administration of
eliminate sulphur from crude oil is necessary because the the supply chain is an essential component of the company
presence of sulphur in crude oil increases the heating range that needs to be optimized and systematically managed to
and is harmful to the ecosystem [12]. The desulphurization maintain profitable operations over time. Although they are
of aromatic sulphur compounds is much more challenging standard across the board, it goes without saying that each
than that of aliphatic sulphur compounds due to the presence refinery is highly specialized and one of a kind in every
of high viscosities and API gravities [13]. Sulphur, in the aspect.
form of acyclic aliphatic sulphides like thioethers and cyclic
thiolate, is abundant in crude oil.

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Volume 8, Issue 6, June – 2023 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165
The economic viability of a proposed production Table 2 Major Feed Composition for HDS and ODS Process
method, product, or service is evaluated through a techno- Components Flow Rate (Kg/Hr)
economic analysis, (Abbreviated TEA). Software modelling, n-Eicosane 56508.002
which is affected by both technical and financial input n-Triacontane 9301.578
variables, is commonly used to make estimates of income, 1-Eicosene 83314.147
routine expenses, and capital costs. Many software packages t-Decalin 17834.250
exist to facilitate TEA, including but not limited to Aspen c-Decalin 17834.250
HYSYS, Aspen Plus, Prosimplus, and Umberto. In addition, n-Pcychexane 0.000
the introduction of Industrial Revolution 4.0 is transforming n-Bcychexane 0.000
conventional manufacturing into what is known as "smart n-BBenzene 4026.660
manufacturing". n-PBenzene 3605.820
1-Tetradecen 0.000
The purpose of this research is to investigate the
Anthracene 16219.203
various strategies for recovering sulphur, including how
they function, how effective they are, how much energy they B-diSulphide 3567.000
require, the components that they make use of, how much it DiBZThiphene 552.783
will cost to implement them based on previous studies, and Quinoline 2583.200
both their positive and negative aspects in general. Pyrrole 134.182
Thiophene 420.680
II. METHODOLOGY P-diSulphide 3006.000
Phenol 188.226
Aspen Hysys version 11 was used in this work to (Source: Aspen Hysys Assay Databank, Version 11)
simulate the design of two desulphurization units namely
HDS and ODS. HDS is used in refineries to reduce sulphur  Step by Step Procedure Used for HDS Simulation
in fuels. It involves treating sulphur compounds with
hydrogen under high temperature and pressure, converting  Step 1:
them to H2S. A modified Claus process is used to handle the Open Aspen hysys software environment (interactive
resulting H2S and convert elemental sulphur. ODS refers to section) for component selection for the process.
Oxidative Desulphurization, which is another process used
in refineries to remove sulphur from fuels. In ODS, sulphur  Step 2:
compounds are oxidized using an oxidizing agent, such as The component list was clicked to gain access to the
hydrogen peroxide or air, to convert them into water-soluble required components used in the desulphurization process
compounds that can be easily separated from the fuel. This from the library.
method offers an alternative approach to reducing sulphur
content in fuels.  Step 3:
Begin the desulphurization procedure by initiating the
The energy analysis for the processes were performed necessary processes. All reactions were conversion reactions
using the aspen energy analyzer which is a sub software and were also balanced (to gain balance error of zero).
installed along with aspen hysys. It is used in energy
management for optimizing energy consumption based on a  Step 4:
user’s input. Pinch technology helps accomplish this goal by Select a suitable fluid package (i.e the thermodynamic
providing insights and energy saving recommendations that relation that will help to carry out background calculations
lead to increased efficiency and decreased pollution. where necessary) was selected and it was believed that the
process would remain in a constant condition throughout.
Tables 1 - 3 show the input data used for the work.
The crude oil used in the process has an API gravity of  Step 5:
37.27 (which signifies SG of 0.838 and it is a light crude). The simulation environment was entered to create the
The temperature of the feed stream is 38 degrees Celsius, process flowsheet.
and the pressure is 8.172 atmospheres per square centimetre.
The feed streams’ flow rate is 39486.387 bbl/d which is  Step 6:
within the normal flow rate range for modular refineries. To The crude oil feed is pumped into a mixer where it is
provide a fair comparison of the desulphurization processes, mixed with, heated, and sent to the reactor for reaction to
the input flow rate was kept constant for both processes occur. Here, sulphur compounds were converted to H2S.

Table 1 Inlet Feed Condition and Flow Rates of Crude Oil  Step 7:
Phase Fraction 0 The product from the reactor was used to carry out a
Feed Temperature (oC) 80 preheating process on the feed stream and further cooled
Feed Pressure (kPa) 828 before sending it to the knockout (KO) drum.
Feed flow rate 39486.387bbl/d,
(261.6m3/hr)
(Source: Hernandez, C. P. 2020)

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Volume 8, Issue 6, June – 2023 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165
 Step 8: When these steps are followed, and there is
The Product from the reactor was then sent to a convergence, the process flow will be as shown in Figure 2.
knockout (KO) drum to flash out light ends of the stream
and the vapour from the KO was sent to an absorber to carry  Basis for Comparing Both Processes
out amine treatment process using the DEAmine. The light The basis for comparison is the energy saving
ends which consist of majorly hydrogen is recycled to the potential, the capital and utilities cost, and the estimation of
hydrogen line. equipment cost. The processes are compared based on the
capacity to capture the sulphur compound present in the
 Step 9: crude oil stream and the total cost which covers the
The liquid product from the KO was sent to a 25-stage equipment cost, operating cost, installation cost, utility cost
distillation column unit to remove any trace of H2S and and the CO2 emission from the process.
other light components from the oil stream. Steam (3% of
the quantity of the feed to the column) was added to the The cost estimation calculation was done using the
distillation column to add the required amount of heat Aspen Hysys software and it was based on the equipment
needed to cause the separation. The desulphurized oil was index as indicated in the software. The costing was based on
collected at the base of the column. When these steps are major equipment such as compressors, reactors, columns,
followed, and there is convergence, the process flow will be and pumps.
as shown in Figure 1.
The cost of equipment has increased over the years
Table 3 Extra Feed Inlets for ODS because of inflation. The method usually used to update
Stream Flow rate (kg/hr) historical cost data makes use of published costs, which
H2O2 10664.5 relates present costs to past costs:
H2O 53.198
ZnCl2 21791.21 𝑪𝒐𝒔𝒕 𝒊𝒏 𝒀𝒆𝒂𝒓 𝑿 × (𝑰𝒏𝒅𝒆𝒙 𝒚𝒆𝒂𝒓 𝒀)
𝑪𝒐𝒔𝒕 𝒊𝒏 𝒀𝒆𝒂𝒓 =
1-n-Butyl-3-Methylimidazolium 21596.26 (𝒊𝒏𝒅𝒆𝒙 𝒚𝒆𝒂𝒓 𝑿)
Chloride
(Source: Gao et al., 2019) To account for developments in technology, building
methods, labour efficiency, and the index's own formulation,
 Step by Step Procedure Used for ODS Simulation experts advise only utilizing the index for the previous five
years, see Figure 3 (Chemical Engineering Plant Cost
 Step 1 to Step 5 in HDS process was repeated in the Index).
ODS setup before entering the simulation environment.
Step 6. After the above reaction sets were carried out in III. RESULTS & DISCUSSIONS
the properties section of the process, the components
were also selected before entering the simulation The HDS and ODS results for energy analysis,
environment. economic analysis for utilities, equipment costing, and
 Step 7. Three material streams (oil feed, H2O2 and ionic sulphur content analysis for ODS can be found in the full
Liquid (IL)) were created and sent into the reactor, work [14].
wherein the reactions were performed under the various
circumstances shown in Table 3. Figure 4 shows the cost comparison between HDS and
 Step 8: The reactor products were collected and sent to ODS processes. The costs include those associated with
a decanter where the de-sulphurised oil was separated operation, utilities, equipment, and installation. This
from the sulfone, sulfolane and IL. indicates that, compared to hydrodesulphurization, oxidative
desulphurization may be the more cost-effective option. It is
 Step 9: The stream from the decanter containing
worth noting, however, that other variables, such as the
sulfone, sulfolane and IL is mixed with water and sent
application at hand, environmental considerations, and the
to a filtration unit where the sulfone was filtered out.
degree of sulphur elimination sought, may influence the
 Step 10: The IL (which absorbed the sulfone and
final decision.
sulfolane compounds) stream and water was sent to a
heater where it was heated up to the required
The results for removing sulphur-containing molecules
regenerated temperature, thereafter it was sent to a
from crude oil are shown in Figure 5. The results indicate
regenerator to separate the remaining water, sulfone and
that the HDS process was more effective in removing
sulfolane compounds from IL compounds.
dibenzothiophene, with an absorption rate of 90%,
 Step 11: To keep the procedure going, the IL is returned compared to ODS, which achieved an absorption rate of
to the IL input source. 80%.
 Step 12: To aid in the sorting process, water was
introduced as an entrainer. The IL with water mixture Furthermore, both methods showed complete removal
was heated to raise the temperature and pressure and of B and P-Disulphide compounds from the crude oil,
sent into a flash drum to knock off water vapor from the indicating that both HDS and ODS are effective in removing
IL stream. these types of sulphur compounds. Another sulphur-

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Volume 8, Issue 6, June – 2023 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165
containing substance that was eliminated during both REFERENCES
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ISSN No:-2456-2165

Fig 1 Complete Flowsheet of Fig 4 Cost Comparison between Both Processes

Hydrodesulphurization Process Using Aspen Hysys

Fig 2 Complete Flowsheet of Oxidation Desulphurization Fig 5 Comparison of the Sulphur Absorption from the Crude
Process Using Aspen Hysys Oil Using HDS and ODS

Fig 3 Chemical Engineering Plant Cost Index

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