© JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

Modelling and Optimizing 2-Ethylhexanol Production

from Propylene and Synthesis Gas, Using A Case Study
of Aspen Hysys
PATRICK E. OKOSE
Petroleum Engineering Technology, Teesside University, Middlesbrough, England

Abstract- 2-Ethylhexanol (2-EH) is a branched, manufacturer (Chongran et al., 2023). 2-

eight-carbon alcohol with the molecular formula Ethylhexanol is an alcohol that is a colourless liquid
C8H18O. It is an eight-carbon alcohol that belongs at room temperature with a slightly floral odour or it
to the family of branched alcohols. 2. Ethylhexanol is a clear, mobile and neutral liquid with a
is a colourless liquid that is soluble in organic characteristic odour. It is miscible with most common
solvents but insoluble in water. It also has a slight organic solvents but its miscibility with water is very
odour. By using ASPEN HYSYS as a case study, limited (Poulikidou et al., 2017). 2-Ethylhexanol is
this research project aims to simulate and optimize an important organic chemical as it is used as a
the manufacture of 2-Ethylhexanol from propylene chemical intermediate and an alternative fuel. For
and synthesis gas. Using Aspen HYSYS chemical example, its carboxylic acid esters such as dioctyl
engineering software, a process plant was simulated terephthalate (DOTP), dioctyl phthalate (DOP) and
to produce 5000 tons of 2-ethylhexanol annually dioctyladipate (DOA) are widely used as plasticizers,
using propylene and synthesis gas as feedstocks. To especially in polyvinylchloride manufacturing. Other
remove contaminants that could harm the rhodium uses include the production of intermediates for
catalyst used in the hydroformylation process, fresh acrylic surface coatings, diesel fuel and lube oil
propylene and syngas are treated. The plant needed additives and surfactants. 2-Ethylhexanol is used as a
to be optimized when the simulation was over, thus pesticide-inert ingredient in pesticide formulations
an optimizer that was included in the program and applied to growing crops, raw agricultural
an optimizer spreadsheet containing the parameters commodities (RAGs) or animals (Dennis and Elliot,
were used. With this, an energy analysis was 2012).
activated to calculate the amount of energy saved.
The energy analyzer showed 2.45% energy savings The industrial production of Ethylhexanol comprises
once the first simulation results were made of three reaction steps: propylene hydroformylation
available, which provided a sense of the changes. to n-butanal, n-butanal self-condensation to 2-ethyl-
The simulation results showed that the process can 2-hexenal (2E2H) and 2-ethyl-2-hexenal
produce 2-ethylhexanol with a purity of 100% after hydrogenation to 2-Ethylhexanol. The hydrogenation
optimizing. of 2-ethyl-2-hexenal is composed of the following
processes: crude hydrogenation and refined
I. INTRODUCTION hydrogenation with the support of some catalysts like
Cu or Ni (Raghda and Alaa, 2019). Today, nearly
1.1 Background of Study all2-Ethylhexanol is produced by catalytic hydro
formylation of Propylene with Synthesis gas (Carbon
2-Ethylhexanol (2-EH) is a branched, eight-carbon monoxide and Hydrogen). The catalytic process now
alcohol with the molecular formula C8H18O. After the mostly uses Rhodium catalysts rather than the older
lighter alcohols (those with one to four carbons such cobalt hydro carbonyl catalysts (Reinhard and
as methanol or butanol) 2-Ethylhexanol is the most Hermann, 2014).
important synthetic alcohol (Mohammad et al.,
2020). 2-Ethylhexanol occurs naturally in food, as it Optimization of a process is simply to maximize the
is used as a flavour volatile and is approved as an production of 2-Ethylhexanol while minimizing the
indirect food additive by the U.S. Food and Drug consumption of resources such as raw materials,
Administration (FDA). A flavour volatile is a energy, and catalysts. The optimization process
compound naturally present in a food or added by the involves the running of a simulation with various

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 435

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

input parameters and constraints to identify the a powerful simulation tool widely used in the
optimal operating conditions that lead to the highest industry for such purposes as it describes the reaction
possible production of 2-Ethylhexanol while meeting mechanism, the catalyst used, and the key process
the desired product specifications. This optimization parameters that influence the conversion and
will contribute to a more efficient and cost-effective selectivity of the reaction (Ikpaki et al., 2021). Using
production process. This is achieved by utilizing simulation software like Aspen HYSYS, you can
Aspen HYSYS and Aspen Optimizer. input the models and parameters to simulate the
entire production process virtually. This allows for
Heat integration is a crucial aspect of the project, observation of the system’s behaviour under various
aiming to enhance the overall energy efficiency of the conditions, test different process configurations, and
2-Ethylhexanol production process. It involves the predict the process performance without conducting
integration of heat exchangers and process streams to actual experiments (Ghaemi and Zerehsaz, 2018).
minimize heat losses and maximize heat recovery
within the plant. Yu et al., (2016) stated that using In this work, modelling, simulation, and optimization
Aspen HYSYS will identify potential heat integration will be integrated to accelerate the development
opportunities in the process, such as the recovery of process, minimize experimental efforts and achieve a
waste heat from reaction steps, distillation columns, more reliable and efficient production of 2-
and other unit operations. The integration of heat Ethylhexanol.
exchangers will help transfer heat from hot streams
to cold streams, reducing the need for additional 2.1 Overview of Propylene
energy inputs. In this work, the optimal heat
exchanger network and heat integration scheme to Propylene, also known as propene, with the relative
improve the energy efficiency of the 2-Ethylhexanol molecular mass of 42.08 has its structural and
production process will be determined as this will molecular formula to be H2C=CH-CH3 and C3H6
lead to lower operating costs and a more sustainable respectively is an important organic compound in the
operation. petrochemical industry that is a gaseous hydrocarbon
that belongs to the alkene group of compounds,
Energy recovery is identifying and implementing characterized by a double bond between two carbon
strategies to recover and reuse energy within the 2- atoms. Propylene is derived from fossil fuels,
Ethylhexanol production process. Energy recovery primarily petroleum, through various refining and
can be achieved through various methods, including cracking processes. Propylene is one of the fastest
process stream recycling, power generation from growing petrochemicals driven primarily by the high
waste heat, and heat-to-power conversion growth rate of polypropylene and the consumption of
technologies (Poulikidou et al., 2017). The ultimate propylene is 64% (Ahlgren et al., 2015). Propylene is
aim of energy recovery aspect is to minimize energy a crucial compound in the petrochemical industry,
wastage and increase the overall energy efficiency of playing a significant role in the production of plastics,
the production process. This not only contributes to chemicals, fuels, and other materials that are widely
cost savings but also reduces the environmental used in our daily lives. Propylene is primarily
impact of the plant. By integrating optimization, heat produced as a by-product of the petroleum refining
integration, and energy recovery aspects into the process and the cracking of hydrocarbon feed stocks,
project, the study aims to provide a comprehensive such as naphtha, gas oil, or propane. It can also be
and sustainable approach for the efficient production produced from other sources, such as coal, natural
of 2-Ethylhexanol from propylene and synthesis gas. gas, or biomass. The largest application of propylene
Modelling and simulation play a crucial role in the is in the production of polypropylene (PP), which is
design and optimization of chemical processes. one of the most widely used plastics worldwide. PP
Modelling involves creating mathematical is used in a variety of products, including packaging
representations of the chemical reactions and materials, textiles, automotive parts, and consumer
physical phenomena involved in the production of 2- goods (Hackl et al., 2016). Propylene is a versatile
Ethylhexanol. These models help to understand the building block for the production of various chemical
underlying mechanisms, predict behaviour and intermediates, such as propylene oxide, acrylonitrile,
identify potential bottlenecks or limitations in the cumene, and isopropanol. These intermediates are
production process (Mike, 2016). ASPEN HYSYS is further processed to manufacture a wide range of

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 436

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

products, including polyurethanes, solvents, paints, evaporates into the air. At room
adhesives, and synthetic fibres. Propylene can be temperature, its vapour pressure is
used as a fuel for heating, cooking, and as a propellant approximately 502.5mmHg (Han et al.,
in aerosol products. It is also a component in 2021).
liquefied petroleum gas (LPG) and can be used as a vi. Flammability: Propylene is highly
substitute for propane in certain applications. flammable and can ignite easily. Its lower
Propylene is used as a refrigerant in certain systems flammability limit (LFL) is 2.1% by volume
due to its low boiling point and favourable in air, while the upper flammability limit
thermodynamic properties (Zhang et al., 2016). It is (UFL) is 11.4%. These limits indicate the
considered an environmentally friendly alternative to range of concentrations in air where
chlorofluorocarbons (CFCs) and hydro- propylene can form flammable mixtures.
chlorofluorocarbons (HCFCs), which contribute to vii. Chemical Reactivity: Propylene is an
ozone depletion and global warming. Propylene finds unsaturated hydrocarbon, containing a
applications in various other industries, such as double bond between two carbon atoms.
pharmaceuticals, cosmetics, detergents, lubricants, This double bond makes propylene more
and rubber manufacturing. Propylene is flammable reactive than its saturated counterpart,
and should be handled with caution. It can form propane. It can undergo addition reactions,
explosive mixtures with air and can be ignited by such as hydrogenation or halogenation, to
open flames, sparks, or electrical equipment. Proper form various derivatives (Both et al., 2016).
storage, handling, and ventilation are necessary to viii. Stability: Propylene is relatively stable
ensure safe usage (Fujiwara et al., 2019). under normal conditions. It is not prone to
decomposition or degradation at typical
2.1.1 Physicochemical Properties of Propylene temperatures and pressures. However, it
The physicochemical properties of propylene and its may undergo reactions under specific
overview are; conditions, such as in the presence of
i. Boiling and Melting Points: The boiling catalysts or under high temperatures.
point of propylene is -47.7°C (-53.9°F), ix. Toxicity: Propylene is generally considered
which means it readily vaporizes at to have low toxicity. It is not known to be
relatively low temperatures. The melting carcinogenic or mutagenic to humans.
point of propylene is -185.2°C (-301.4°F), However, it is important to handle
indicating that it is a solid at extremely low propylene with caution as it is flammable,
temperatures. and its combustion products, such as carbon
ii. Physical State: At room temperature and monoxide and carbon dioxide, can be
atmospheric pressure, propylene exists as a harmful if inhaled in high concentrations
colourless gas. It has a slightly sweet odour, (Hreczuch et al., 2016).
similar to gasoline. However, it can also be
liquefied under moderate pressure, allowing 2.2 Synthesis Gas
for ease of storage and transportation. Its
molecular weight is 42.08 g/mol (Albanese, The concept of synthesis gas can be traced back to the
2023). late 18th century when researchers began
iii. Density: The density of propylene gas is experimenting with the production of gases by
about 0.493g/cm³ at 25°C (77°F). In its heating various organic materials. In the late 18 th
liquid state, the density of propylene is century, researchers like Alessandro Volta and
approximately 0.626 g/cm³. Philippe Lebon discovered that heating organic
iv. Solubility: Propylene is sparingly soluble in materials such as wood, coal, and oil in the absence
water. It has a low solubility due to its of oxygen produced flammable gases (Chen and
nonpolar nature, meaning it does not readily Smith, 2017). These early experiments led to the
mix with polar solvents like water. development of several gasification processes,
However, it is more soluble in organic including wood gasification and coal gasification,
solvents such as ethanol and acetone. which involved heating these materials to produce
v. Vapour Pressure: Propylene has a relatively gases like hydrogen, carbon monoxide, and methane.
high vapour pressure, meaning it easily In the early 19th century, the Industrial Revolution

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 437

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

sparked increased interest in gasification as a means hydrogen (H2) as the major constituents.
of producing fuel for lighting, heating, and industrial The molar ratio of CO to H2 can vary
processes (Ghaemi, 2018). Coal gasification became depending on the production process and
particularly popular during this period, with the first feedstock used. The ratio of CO to H2 is
practical coal gas plant built in England in 1813 by often referred to as the “Synthesis Gas ratio”
Frederick Winsor. Coal gasification involved the and is an important parameter for specific
heating of coal in a controlled environment, applications.
producing a mixture of hydrogen, carbon monoxide, ii. Heating Value: Synthesis Gas has a
methane, and other gases, which could be used as relatively high heating value, which refers to
fuel. In the early 20th century, the focus shifted to the the amount of heat released when the gas is
production of synthetic fuels from coal, especially combusted. The heating value is influenced
during times of fuel shortages such as World War I by the composition of the Synthesis Gas and
and World War II. Germany, in particular, developed can vary depending on the production
large-scale coal gasification plants to produce method and feedstock. The higher heating
synthetic fuels like gasoline, diesel, and aviation fuel value of Synthesis Gas ranges from about 10
(Ku et al., 2017). The Fischer-Tropsch process, to 30 mega joules per cubic meter (MJ/m³)
developed by German scientists Franz Fischer and or 250 to 750 British thermal units per
Hans Tropsch in the 1920s, allowed for the synthesis standard cubic foot (BTU/scf).
of liquid hydrocarbons from coal-derived Synthesis iii. Flammability: Synthesis Gas is highly
Gas, which played a crucial role in the German war flammable and can be used as a fuel in
effort. In the mid-20th century, natural gas became various applications. It can be combusted
the dominant fuel source, and the interest in synthesis directly in gas turbines, internal combustion
gas declined. However, the oil crises of the 1970s led engines, or boilers to generate heat or
to renewed interest in alternative energy sources, electricity. The flammability limits of
including Synthesis Gas (Li et al., 2016). Today, Synthesis Gas, which indicate the range of
synthesis gas is primarily produced from natural gas concentrations where it can sustain
and biomass through various processes such as steam combustion, depend on the composition of
methane reforming, partial oxidation, and biomass the gas but typically range between 6% and
gasification. Over the centuries, the understanding 75% volume concentrations (Bocque et al.,
and utilization of synthesis gas have evolved 2016).
significantly, driven by the need for alternative iv. Energy Density: Synthesis Gas has a
energy sources and the development of more efficient relatively low energy density compared to
and environmentally friendly processes. Its liquid or solid fuels. However, its high
versatility and potential as a clean energy source heating value compensates for this, making
continue to make it a subject of interest for it suitable for a wide range of applications.
researchers and engineers today (Raghda and Alaa, The energy density of synthesis gas is
2019). typically expressed in mega joules per cubic
meter (MJ/m³) or British thermal units per
2.2.1 Properties of Synthesis Gas standard cubic foot (BTU/scf).
Synthesis gas, often abbreviated as Syn Gas, is a v. Carbon Monoxide Toxicity: Carbon
versatile fuel and chemical intermediate that is monoxide (CO) is a component of synthesis
produced through the gasification or reforming of gas and is highly toxic to humans and
carbonaceous materials such as coal, natural gas, animals. It is odourless, colourless, and
petroleum, biomass, or other carbon-containing feed tasteless, making it difficult to detect
stocks. It is a mixture of carbon monoxide (CO), without specialized equipment. Proper
hydrogen (H2), and other minor gases, with CO and handling, ventilation, and safety measures
H2 being the primary components. Synthesis Gas has are essential when working with Synthesis
several properties that make it valuable for various Gas to prevent exposure to high levels of
applications (Arvidsson et al., 2016). Here are some carbon monoxide.
key properties of synthesis gas: vi. Synthesis Gas Ratio: The ratio of carbon
i. Composition: Synthesis Gas typically monoxide (CO) to hydrogen (H2) in
consists of carbon monoxide (CO) and synthesis gas, known as the synthesis gas

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 438

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

ratio, can influence its suitability for i. Power Generation: Syngas can be used as a
different applications. A higher CO content fuel in gas turbines or internal combustion
is often desirable for chemical synthesis engines to generate electricity. It offers
processes, while a higher H2 content is flexibility by allowing the use of different
advantageous for fuel production and feedstocks, reducing reliance on fossil fuels,
energy applications. and facilitating the transition to cleaner
vii. Impurities: Synthesis Gas may contain energy sources.
impurities depending on the feedstock and ii. Chemicals and Fertilizer Production:
gasification/reforming process used. Syngas serves as a crucial precursor in the
Common impurities include sulphur production of a wide range of chemicals.
compounds, nitrogen compounds, trace Through various chemical reactions, syngas
metals, particulates, and tars. These can be converted into methanol, ammonia,
impurities need to be removed or treated synthetic natural gas (SNG), and other
before the synthesis gas can be used in valuable compounds. These chemicals are
specific applications, such as fuel cells or essential for manufacturing plastics,
downstream chemical processes (Chang et solvents, fertilizers, and other industrial
al., 2022). products.
viii. Synthesis Gas Clean-up: To make Synthesis iii. Synthetic Fuels: Syngas can be converted
Gas suitable for various applications, such into liquid fuels through a process called
as catalytic reactions or fuel cells, it often Fischer-Tropsch synthesis. This enables the
requires cleaning or conditioning. Synthesis production of synthetic hydrocarbons, such
Gas clean-up involves removing impurities, as synthetic diesel or gasoline, which can be
adjusting the synthesis gas ratio, and used as drop-in replacements for
controlling the temperature and pressure to conventional fossil fuels. Synthetic fuels
meet the requirements of specific processes. derived from syngas can help reduce carbon
ix. Versatility: Synthesis Gas is a highly emissions and provide an alternative to
versatile fuel and chemical feedstock. It can petroleum-based fuels.
be used as a fuel for power generation, iv. Hydrogen Production: Syngas is an
heating. important source of hydrogen, a clean and
x. Density: The density of Synthesis Gas versatile energy carrier. Hydrogen produced
varies depending on its composition. It is from syngas can be used in fuel cells for
generally lighter than air, with a density electricity generation, as a feedstock in
ranging from 0.6 to 1.2 kilograms per cubic various chemical processes, or as a potential
meter (kg/m³). The density decreases with fuel for hydrogen-powered vehicles
an increase in the hydrogen content of the (Obringer et al., 2023).
synthesis gas. v. Waste Treatment and Recycling: Syngas
xi. Boiling Points: The boiling points of CO can be generated from waste materials
and H2 are relatively low. Carbon monoxide through gasification, offering an efficient
has a boiling point of -191.5℃ (-312.7℉), and environmentally friendly method for
while hydrogen boils at -252.9 ℃ (-423.2 waste treatment. By converting waste into
℉). These low boiling points make it easier syngas, it is possible to recover energy and
to separate and purify the components of valuable by-products while minimizing the
synthesis gas (Muller et al., 2018). environmental impact of waste disposal.
vi. Carbon Capture and Storage (CCS): Syngas
2.2.3 Applications of Synthesis Gas production can be integrated with carbon
The application of syngas, also known as synthesis capture technologies to mitigate greenhouse
gas, is wide-ranging and encompasses various sectors gas emissions. By capturing and storing
including energy production, chemicals carbon dioxide (CO2) generated during the
manufacturing, and transportation. Its versatility and gasification process, syngas production can
potential as a feedstock have led to numerous become a cleaner and more sustainable
practical applications (Poulikidou et al., 2019). energy option (Subagjo and Gunawan,
2019).

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 439

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

iii. Melting Point: The melting point of 2-

ethylhexanol is around -78.2°C (-108.8°F).
This is the temperature at which the solid
form of the compound starts to melt and
convert into a liquid.
iv. Boiling Point: The boiling point of 2-
ethylhexanol is approximately 183-186°C
(361-367°F). This is the temperature at
which the liquid form of the compound
starts to vaporize and convert into a gas.
v. Density: The density of 2-ethylhexanol is
about 0.832 g/cm³ at 20°C (68°F). Density
is the mass of a substance per unit volume
Figure 2.1: Applications of 2-ethylhexanol in and is an important property for determining
different fields. the behaviour of a substance in various
conditions.
2.3 2-Ethylhexanol vi. Solubility: 2-Ethylhexanol is slightly
2-Ethylhexanol is a chemical compound with the soluble in water, with an estimated
molecular formula C8H18O and the structural formula solubility of about 1.1 g per 100 mm of
CH3 (CH2)3CH (C2H5) CH2OH. It is an eight-carbon water at 25°C (77°F). It is more soluble in
alcohol that belongs to the family of branched organic solvents such as ethanol, acetone,
alcohols. 2-Ethylhexanol is a colourless liquid with a and benzene.
mild odour and is insoluble in water but soluble in vii. Vapour Pressure: The vapour pressure of 2-
organic solvents (Zhang et al., 2016). ethylhexanol is relatively low. At 20°C
2-Ethylhexanol was first discovered and synthesized (68°F), the estimated vapour pressure is
in the early 20th century. It was primarily derived around 0.03 mmHg. Vapour pressure is the
from the reaction of n-butyraldehyde and pressure exerted by the vapour of a
ethylmagnesium bromide, resulting in the formation substance when it is in equilibrium with its
of 2-ethylhexyl magnesium bromide. This compound liquid phase.
was then subjected to hydrolysis to obtain 2- viii. Refractive Index: The refractive index of 2-
ethylhexanol. The industrial production of 2- ethylhexanol is approximately 1.431 at
ethylhexanol began in the mid-20th century. It is 20°C (68°F). The refractive index is a
typically produced through the aldol reaction, where measure of how much light is bent or
n-butyraldehyde is condensed with isobutyraldehyde, refracted when passing through a substance.
followed by hydrogenation. The resulting product is ix. Flash Point: The flash point of 2-
a mixture of isomers, including 2-ethylhexanol. Like ethylhexanol is approximately 86°C
many organic compounds, 2-ethylhexanol should be (187°F). This is the lowest temperature at
handled with care. It is flammable and may emit toxic which the vapour of a substance can ignite
fumes when heated or exposed to flames. It can cause in the presence of an ignition source.
eye and skin irritation upon direct contact. Proper x. Viscosity: 2-Ethylhexanol exhibits a
safety measures, including the use of protective relatively low viscosity, which means it
equipment, should be employed when working with flows easily. The estimated viscosity of 2-
2-ethylhexanol (Hackl et al., 2016). ethylhexanol at 20°C (68°F) is about 4.28Cp
(Asmaa et al., 2022).
2.3.1 Physicochemical Properties of 2-Ethylhexanol
Here are the physicochemical properties of 2- 2.3.2 Uses of 2-Ethylhexanol
ethylhexanol: i. Plasticizers: One of the primary applications
i. Molecular Weight: The molecular weight of of 2-ethylhexanol is as a raw material for the
2-ethylhexanol is approximately production of plasticizers. It is a key
130.23g/mol. ingredient in the manufacturing of phthalate
ii. Physical State: 2-Ethylhexanol exists as a esters, such as di-2-ethylhexyl phthalate
liquid at room temperature and atmospheric (DEHP). Plasticizers are added to polymers
pressure.

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 440

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

and resins to improve their flexibility, lubricity, reduces friction, and provides better
durability, and processability. They are resistance to oxidation and corrosion.
widely used in the production of PVC ix. Herbicides: Some herbicide formulations
(polyvinyl chloride) products, including incorporate 2-Ethylhexanol as a co-formulant
cables, vinyl flooring, automotive parts, and or an additive to improve the efficacy and
medical devices. spreading properties of the active ingredients
ii. Solvents: 2-Ethylhexanol is used as a solvent (Ikpaki et al., 2021).
in various applications. It can dissolve a wide
range of substances, including oils, resins, 2.4 Pathways of 2-Ethylhexanol Production
waxes, and dyes. Its solvency properties
make it useful in industries such as paints, There are three pathways of production;
coatings, inks, adhesives, and cleaning
agents. 2.4.1 2-Ethylhexanol Production through Biomass
iii. Chemical Intermediates: 2-Ethylhexanol Fermentation and Ethanol
serves as an important intermediate in the The ethanol- based 2- EH production route is based
synthesis of other chemicals. It is used in the on a cellulosic ethanol production process, followed
production of various compounds, including by acetaldehyde production and conversion to
esters, acrylates, and ethoxylates. For crotonaldehyde, n- butyraldehyde and finally
example, it is a precursor in the aldolization and hydrogenation to 2-Ethylhexanol.
manufacturing of 2-ethylhexyl acrylate (2-
EHA), which finds applications in adhesives, The process description is as follows:
paints, and textiles (Yu et al., 2018). i. Production of Acetaldehyde: The first step
iv. Fragrances and Flavours: Due to its mild is to produce acetaldehyde. Acetaldehyde
odour and compatibility with other fragrance can be obtained through various methods,
ingredients, 2-ethylhexanol is utilized in the but one common method is the oxidation of
production of fragrances and flavours. It acts ethanol. Ethanol is oxidized using a suitable
as a diluent or carrier for the aroma catalyst, such as a silver-based catalyst, to
compounds and helps enhance their stability produce acetaldehyde as shown in Equation
and diffusion. 2.1.
v. Emollients and Personal Care Products: 2- 2C2 H5OH + O2 → 2CH3CHO + 2H 2O
Ethylhexanol is employed in the formulation
Equation 2.1
of personal care products, particularly in the
ii. Aldol Condensation: In the next step,
production of emollients and moisturizers. It
acetaldehyde undergoes aldol condensation.
imparts a smooth, non-greasy feel and helps
This reaction involves the self-condensation
in the absorption of cosmetic products into
of acetaldehyde to form crotonaldehydeas
the skin.
shown in Equation 2.2.
vi. Fuel Additives: In some cases, 2-
ethylhexanol is used as an additive in fuel 2CH3CHO → CH3CH = CHCHO + H 2O
formulations, primarily in diesel fuels. It can Equation 2.2
enhance the lubricity and improve the flow iii. Hydrogenation of Crotonaldehyde: The
properties of diesel, which can help reduce crotonaldehyde produced in the previous
wear on fuel system components (Chongran step is hydrogenated to produce 2-
et al., 2023). ethylhexanol. This reaction requires a
vii. Agrochemicals: 2-Ethylhexanol can be hydrogen source and a suitable catalyst,
utilized in the production of pesticides and typically a metal catalyst such as nickel or
herbicides. It can act as a solvent or a palladium as shown in Equation 2.3.
component in pesticide formulations to CH3CH = CHCHO + 6H 2 → CH3 ( CH 2 )4 CH ( OH ) CH3
improve their efficacy and stability. Equation 2.3
viii. Lubricants: 2-Ethylhexanol can be used as a iv. Purification and Refining: After the
lubricant additive to enhance the hydrogenation step, the crude 2-
performance of oils and greases. It improves ethylhexanol is obtained. However, it may
contain impurities and other by-products.

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 441

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

Therefore, purification and refining iii. Product Recovery: The fermentation broth
processes are carried out to obtain a pure containing acetone, butanol, and ethanol is
form of 2-ethylhexanol. This typically collected after the fermentation process.
involves distillation and other separation iv. Separation: Solid-liquid separation
techniques to remove impurities and isolate methods, such as centrifugation or filtration,
the desired product. are employed to separate the biomass from
v. Further Processing: The purified 2- the broth.
ethylhexanol can undergo further v. Distillation: The separated fermentation
processing steps depending on its intended broth undergoes a multistage distillation
use. It can be used directly or undergo process. Acetone, butanol, and ethanol are
additional reactions to produce other separated based on their boiling points. The
chemicals or derivatives (Chrongen et al., desired product, butanol, is isolated as the
2023). main fraction during distillation.
vi. vi. 2-Ethylhexanol Synthesis: The separated
butanol is then subjected to a chemical
conversion process to produce 2-
ethylhexanol. Catalytic dehydrogenation or
oxo-process are commonly used methods
for this conversion. The reaction conditions
involve specific temperature and pressure
ranges suitable for the reaction to proceed.
vii. Purification and Refining: The synthesized
2-ethylhexanol is further purified to remove
impurities and byproducts. Additional
distillation or purification steps are
performed to obtain a high-purity 2-
ethylhexanol product.
Figure 2.2: 2- Ethylhexanol Production Pathway viii. Final Product: The purified 2-ethylhexanol
through Biomass Fermentation and Ethanol as is collected and stored for various industrial
Intermediate Chemical (Poulikidou et al., 2019). applications, including plasticizers,
solvents, and chemical intermediates.
2.4.2 2-Ethylhexanol Production through ABE
Fermentation and Butanol
The 2-EH production pathway through Guerbet
condensation of n- butanol is based on published data
for corn stover- based acetone- butanol- ethanol
(ABE) fermentation. However, this process has been
adjusted to account for forest residues as feedstock
using published data for both corn stover and forest
ethanol.
The process description is as follows:
i. Feedstock Preparation: Biomass or
feedstock (such as agricultural residues) is
collected and prepared for the fermentation Figure 2.3: 2- Ethylhexanol Production Pathway
process. through ABE Fermentation, Obtaining Butanol as
ii. Fermentation: The feedstock is subjected to Intermediate Chemical (Poulikidou et al., 2019).
ABE fermentation using Clostridium
bacteria. Fermentation takes place in a 2.5 Oxo-Process Route of Production of 2-
bioreactor under controlled conditions of Ethylhexanol
temperature and pressure. Bacteria convert
the sugars in the feedstock into acetone, The Oxo process is a chemical route for the
butanol, and ethanol through metabolic production of 2-ethylhexanol (2-EH), which is an
processes. important industrial chemical used in the

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 442

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

manufacturing of various products, including ii. Separation: In the separator, which follows
plasticizers, solvents, and synthetic lubricants. The the Oxo-reactor, the catalyst solution is
Oxo process involves the hydroformylation of separated from the oxo-raw product &
propylene followed by hydrogenation. recycled to the Oxo reactor.
iii. Stripper: In the stripper, the unconverted
The step-by-step process description is as follows: propylene is removed from the Oxo-product
i. Oxo Reactor (Hydro-formylation): The first using fresh synthesis gas. This synthesis gas
step of the process is Hydro-formylation is recycled to the Oxo reactor.
(Oxo reaction) from which the main product iv. Distillation Column (1) Alcohol/Aldehyde
is n-butyraldehyde. The reactor operates at Separation: The Oxo-product from the
1300C and 350bars. The reactor residence stripper passes to a distillation column,
time is 1-2 hours. The feeds to the reactor which gives a top product of mixed
are synthesis gas (CO/H2 mixture) and butyraldehyde & the bottom product
propylene in the molar ratio 2:1. The alcohols.
catalyst used is Cobalt Carbonyl in the v. Distillation Column (2) n- and iso
solution (0.1-1.0 wt% Cobalt Butyraldehyde Separation: The
concentration). The synthesis gas may butyraldehydes are passed into a 2nd
contain several percent methane which acts distillation column which separates the two
as an inert in the reactor. Traces of water butyraldehydes into an iso-butyraldehyde
introduced with the synthesis gas are not (top) stream containing 1.3% moles
harmful. Impurities such as hydrogen nbutyraldehyde & an n-butyraldehyde
sulfide and triethylamine should be (bottom) stream containing 1.2% mole is
carefully excluded, however to prevent butyraldehyde.
reaction with the active cobalt complex to vi. Aldolization: The n-butyraldehyde stream
form catalytically inactive complexes. passes on into an Aldolization reactor. In
Oxygen should be excluded from the the Aldolization reactor, n-butyraldehyde
system, during the start-up phase when the reacts very quickly to give 2-Ethylhexanal.
active catalyst concentration is being 2% w/w aqueous NaOH is employed as the
established. Oxygen has been shown to standard industrial catalyst. The conversion
inhibit cobalt hydrocabonyl formation, but efficiency is 90%. The temperature is 80-
once the system is operating, concentration 1300C & pressure 3-10 atmospheres. The
up to 2% can be tolerated CO2 acts in the Aldolization reactor may be a mixing pump,
same manner as oxygen, with concentration a packed column or a stirring vessel.
up to 4% permissible. vii. Second Separation: The product from the
Polymer grade (99+ %) pure propylene may Aldolization reactor passes on to a separator
be fed. Propylene feed should be vaporized where 2-Ethyhexanol is separated and then
& fed into the reactor as a gas. Designing for sent to a hydrogenation unit.
propylene conversions of greater than 95% viii. Hydrogeneration: The 2-Ethylhexanal is
per pass will minimize propylene losses in reduced to 2-Ethylhexanol by hydrogen in
the blow down vent stream. the presence of a Raney Nickel Catalyst
The main reaction products are n- and iso with a 99% conversion rate. The selectivity
butyraldehyde in the ratio of 4:1, the former attained is greater than 99%. In the
being the required product for subsequent subsequent stages 99.8% of 2-Ethyl hexanol
conversion to 2-Ethylthexanol. Within the is recovered at a purity of 99% by weight
reactor, however 6% of n-butyrablahyle (Poulikidou et al., 2019).
product is reduced to n-butanol, 4% of
isobytyraldehylde product is reduced to iso-
butanol & other reactions occur to a small
extent yielding molecular weight
compounds (heavy ends) to the extent of 1%
by weight of the butyraldehyde/butanol
mixture at the reactor exit.

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 443

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

acetone, butanol, and ethanol in varying

ratios, making it less efficient for
specifically targeting 2-ethylhexanol
production.
ii. Process Complexity: ABE fermentation
involves multiple steps, including
fermentation, product recovery, and
purification, making the overall process
complex and potentially costlier.
iii. Strain Sensitivity: The performance of
Clostridium bacteria is sensitive to process
conditions, which can lead to variations in
product quality and yield.

Oxo Route
i. Versatility in Feedstocks: The oxo route
offers more flexibility in feedstock
selection, including various olefins derived
from crude oil or natural gas, which are
more readily available and less dependent
on agricultural cycles.
ii. Higher Yields and Purity: The oxo process
is designed to specifically target the desired
Figure 2.4: Process Flow Diagram of aldehyde (2-ethylhexanal) with higher
Hydroformulation Process (Asmaa et al.,2022). selectivity and yield compared to other
routes, resulting in better purity for
2.5.1 Advantages of the Oxo-Process Route downstream conversion to 2-ethylhexanol.
The oxo-process route is commonly used to produce iii. Controlled Reaction: The oxo process
2-ethylhexanol because it offers an efficient and provides better control over reaction
economical method for its synthesis. The limitations conditions, temperature, and pressure,
of producing 2-ethylhexanol from ethanol and ABE which can lead to improved efficiency and
fermentation in comparison to the oxo route are: consistency in product quality.
Ethanol Route iv. Economic Feasibility: While the oxo
i. Energy Intensive: Dehydration of ethanol process might require initial investment in
requires energy-intensive processes to catalysts and equipment, its overall
remove water and produce ethylene. This efficiency, product purity, and versatility
can impact the overall energy efficiency of often make it a more economically feasible
the process. option (Chongran et al., 2023).
ii. Raw Material Cost: Ethanol itself can be a
costly feedstock, especially if it’s used in 2.6 Simulation and Optimization
large quantities for chemical synthesis
rather than other applications like fuel. The simulation and optimization process focuses on
iii. Limited Carbon Chain Length: The ethanol the modelling and simulation of the production
route typically produces smaller carbon process of 2-ethylhexanol from propylene and
chain alcohols, which may need additional synthesis gas. This process involves a series of
processing to produce 2-ethylhexanol with a chemical reactions and separation steps to obtain the
longer carbon chain. desired product by using Aspen Hysys software to
create a comprehensive process flow diagram (PFD)
ABE Fermentation Route and simulate the entire production process.
i. Productivity and Yields: ABE fermentation
can have lower product yields compared to
other routes. Clostridium bacteria used in
the fermentation might produce a mix of

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 444

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

2.6.1 Simulation 2.6.3 Methods of Optimization

The production of 2-ethylhexanol from propylene Most optimization methods entail the application of
and synthesis gas involves a series of reactions and statistical software to optimize the control variables
unit operations. The main reactions include the (extraction time, sample weight, solvent volume,
hydroformylation of propylene to produce nature of solvent, seeds’ variability, and particle size,
butyraldehyde, which is then hydrogenated to form etc.) that seek to reduce cost and increase
2-ethylhexanol. The process flow diagram (PFD) performance while at the same time minimizing
comprises of reactors, distillation columns, heat deterioration of the quality of the product as much as
exchangers, and other essential equipment (Ghaemi possible. Design-Expert is a widely used software
and Zerehsaz, 2018). tool that is specifically designed for experimental
design and analysis, including optimization. It is
Aspen Hysys a powerful process simulation tool is developed by Stat-Ease, Inc. and provides a user-
employed to model the production process. The friendly interface for designing experiments,
software allows us to define reaction kinetics, analyzing data, and optimizing processes. Design-
thermodynamics, and various operating conditions. Expert offers a range of features and tools for
The process flow diagram (PFD) is constructed by experimental design, including factorial designs,
assembling the necessary unit operations and response surface designs (such as central composite
connecting them in a logical sequence. Reactors are design and Box-Behnken design), mixture designs,
configured with the appropriate reaction kinetics, and and more. It allows users to define experimental
distillation columns are designed to separate the factors, their levels, and constraints, and generates an
products from by-products and unreacted feed. Key optimized experimental design based on the selected
parameters such as reaction rates, heat transfer design criteria (Divine and Anuanwen, 2020).
coefficients, and equilibrium constants are specified
based on available literature or experimental data. Response Surface Methodology (RSM) uses a
Assumptions are made regarding ideal behaviour, number of mathematical and statistical techniques
pressure drop calculations, and other factors to which are employed to model and analyze problems
simplify the simulation while maintaining reasonable in two or more process variables that have an
accuracy. The simulation generates results such as influence on the intended response and the objective
product yields, concentrations, temperatures, is to identify the optimal operating conditions for a
pressures, and flow rates. These results are compared system under study. Amongst the many RSM designs
with experimental data from literature or previous available, the central composite design (CCD) and
studies to validate the simulation’s accuracy. Any the Box-Behnken design (BBD) have been popularly
discrepancies are analyzed and explained based on used for chemical processes (Subroto et al., 2014).
the assumptions and simplifications made during the
simulation (Ikpaki et al., 2021). 2.7 Process Integration and Pinch Technology

2.6.2 Optimization Process integration is a systematic approach that aims

The history of optimization processes showcases a to optimize the design and operation of chemical
progression from traditional methods to modern processes by maximizing resource utilization, energy
techniques with a focus on maximizing yield, efficiency, and overall process performance. It
improving quality, and implementing sustainable involves combining different process units and
practices. In recent decades, there has been increased streams in a way that minimizes waste, energy
interest in optimizing chemical processes to improve consumption, and environmental impact. During the
yield, quality, and efficiency. Optimization involves production of 2-ethylhexanol from propylene and
studying and optimizing parameters such as solvent synthesis gas, process integration plays a crucial role
type, solvent-to-solid ratio, temperature, extraction in optimizing the entire production process. The goal
time, and pre-treatment methods. These parameters is to minimize energy consumption, improve heat
are adjusted to maximize oil yield, minimize recovery, and enhance resource efficiency by
degradation and enhance the bioactive compound integrating different units and streams (Ghaemi and
profile of the product (Mariano et al., 2017). Zerehsaz, 2018). Process integration techniques can
be applied to identify opportunities for heat and mass
exchange, process synergies, and potential process

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 445

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

modifications. For example, heat exchangers can be iii. Aspen Energy Analyzer
strategically placed to recover heat from high- iv. Material Property Data Sheet
temperature streams and supply it to those requiring
heat. By optimizing the integration of various process 3.2 Methods
units, the overall energy consumption of the
production process can be reduced, leading to Chemical process design and simulation are carried
economic and environmental benefits (Ikpaki et al., out using computer software called the Aspen
2021). HYSYS simulator. It has unit operating modules,
libraries of chemical components, thermodynamic
Pinch Technology is a subset of process integration calculation techniques, user-defined units, and a
that focuses specifically on energy optimization in pseudo-FORTRAN programmer specifically for
chemical processes. It involves identifying the "pinch hydrocarbon components. Case studies and steady
point," which is the point where the hot and cold state mass and energy balance computations may be
utility requirements of a process come closest performed using it.
together. Pinch Technology seeks to minimize the
temperature difference across the pinch point, The following stages may be used to define a
thereby reducing the need for external utilities and standard simulation the process: The data input
improving energy efficiency. Pinch Technology is a comprises of the following: (1) a process flow
valuable tool for optimizing the energy consumption diagram made up of chosen unit operations connected
of the 2-ethylhexanol production process. By by streams; an appropriate thermodynamic method
analyzing the heat exchange opportunities and the from the current thermodynamic method libraries,
temperature profiles of the process streams, pinch user-defined methods, or CAPE (Computer-Aided
analysis can identify the optimal placement of heat Process Engineering)-OPEN resources; and the
exchangers and the integration of heat recovery selection of components and their properties (from
networks (Iman et al., 2018). In the case of 2- current component libraries or the thermodynamic
ethylhexanol synthesis, pinch analysis can help data manager, TDM). This stage entailed adding the
determine the minimum hot and cold utility relevant components—whether they were mixtures
requirements, as well as the optimal approach or pure chemicals—to the process along with their
temperatures for heat exchangers. By designing the related characteristics, which could be calculated
process to operate as closely as possible to the pinch further; (2) process simulation, which involved
point, the overall energy consumption can be simulating the process using the originally estimated
minimized, leading to reduced operating costs and parameters. Step one involved determining the
improved process sustainability. In this work, process feasibility of the process; step two involved process
Integration and pinch technology provide powerful optimisation to find the optimal set of processing
methods to enhance the efficiency and sustainability conditions to achieve a desired result, like the
of the 2-ethylhexanol production process. By maximum amount of 2-ethylhexanol subject to
optimizing heat and mass exchange, minimizing certain property constraints; and step three involved
energy consumption, and identifying synergies energy process analysis using a parametric case
between process units, these techniques contribute to study.
a more efficient and environmentally friendly
production process (Poulikidou et al., 2019). 3.2.1 Composition for Simulation
recovery were not detected but all these will be in this Table 3.1 displays the composition of the
present work. components utilized in the plant simulation, along
with their respective types. This includes the
3.1 Material presence of 2-ethylhexenal, a compound whose
structure was constructed using a structure builder
This research project was centered on the simulation tool. The compound's properties were determined
design of the 2-Ethylhexanol Production Plant from based on the UNIFAC structure incorporated in the
propylene and synthesis gas, hence the material that software, which is specifically designed for
were used to achieve the research objective include: hypothetical hydrocarbon compounds.
i. Aspen HYSYS Version 11.0
ii. Aspen Optimization Tool

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 446

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

Table 3. 1 Composition Used in the Simulation 3.2.3 Reactions Involved in the Simulation
Components Type
Propene Pure Component Table 3. 2 Reaction and Type of Reaction Used in
H2O Pure Component the Simulation
2-ethylhexenal* User Defined Reaction Type of Reaction
Hypothetical Hydroformylation Kinetic
Component Aldol Condensation Kinetic
2-ETH Pure Component Hydrogenation-1 Kinetic
i-Butanol Pure Component
Hydrogenation-2 Kinetic
1-Butanol Pure Component
n-Butanal Pure Component
3.3 Process Description
tert-Butanol Pure Component
i-Butanal Pure Component
The present simulation approaches 2-Ethylhexanol
Propanal Pure Component
(2-EH) production from propylene and syngas. The
Nitrogen Pure Component
process under analysis comprises three major
Methane Pure Component
sections: (1) Propylene Hydroformylation; (2) EHAL
CO Pure Component
Formation; and (3) EHAL Hydrogenation.
Hydrogen Pure Component
Propane Pure Component
3.3.1 Propylene Hydroformylation
Fresh propylene and syngas are treated to eliminate
3.2.2 Selection of Fluid Package
impurities that might poison the rhodium catalyst
The use of UNIQUAC fluid packages in Aspen
utilised in the hydroformylation process, which
HYSYS software is preferred for modelling the
yields n-butyraldehyde (NBAL) and iso-
manufacture of 2-ethylhexanol due to its capability to
butyraldehyde (IBAL) as products. The reactor
accurately represent phase equilibria in liquid
(CSTR-100) output is degassed, and unreacted
mixtures that deviate from ideal behaviour.
gaseous reactants return to the reactor via a Vent Gas
UNIQUAC, abbreviation for universal quasi
Compressor (K-100), while a liquid stream is
chemical, is an activity coefficient model that
channelled to two absorber columns running
considers the effects of mixing on entropy and
alternately for catalyst regeneration from a gas stream
enthalpy contributions. UNIQUAC is capable of
that is supplied to a C3 Stripper (T-100). This stripper
handling systems including both polar and non-polar
recovers propylene, which is transported to the C3
components, as well as systems containing
Absorber (T-101) and subsequently returned to
electrolytes and azeotropes. UNIQUAC serves as the
hydroformylation, while an aldehyde stream is
basis for the group contribution technique UNIFAC,
directed to a distillation column (T-102) to separate
which may predict the model's parameters based on
the NBAL from the IBAL, recycling the NBAL in the
the molecular structure of the components (Zhao,
hydroformylation reactor.
2016).

3.3.2 EHAL Formation

Ikpaki et al. (2021) used the UNIFAC fluid package
The IBAL is supplied to the Aldol Condensation
for the alkali-catalyzed process of 2-ethylhexanol
Reactor (PFR-100) together with a caustic soda
synthesis, whilst the UNIQUAC fluid package was
solution, where 2-ethyl-hexenal (EHAL) or
utilised in Aspen HYSYS for the heterogeneous-
isobutyraldehyde is produced. The resultant mixture
catalyzed process. These findings indicate that the
is transferred to the Reactive Column (T-103) to strip
UNIQUAC fluid package is better suited for the
out unreacted NBAL, which is returned to the reactor.
heterogeneous-catalyzed process, which entails the
The bottom stream from the reactive column is
presence of a solid catalyst and a liquid phase
transported to the heat exchanger (E-103) before
reaction. The UNIQUAC fluid package can account
being mixed with pure hydrogen before going to the
for the non-ideal behavior of the liquid mixture and
hydrogenation reaction zones.
the interactions between the reactants and the
catalyst.
3.3.3 EHAL Hydrogenation
The mixed stream of pure hydrogen and 2-ethyl-
hexenal (EHAL) is sent to two hydrogenation zones

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 447

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

(PFR-101, 102), where it reacts with hydrogen in the • Aldol condensation of isobutyraldehyde to 2-
presence of heterogeneous catalysts (copper and ethylhexanal
nickel) to produce 2-ethyl-hexanol. The product • Hydrogenation of 2-ethylhexanal to 2-
stream is routed via a column (T-104) to remove light ethylhexanol
ends while obtaining 2-EH from the bottom. 3.4 Process Optimization and Energy Analysis
After the simulation completed, the plant needed to
3.4 Kinetic Data Used for the Simulation be optimised; consequently, an optimiser built into
There is limited kinetic data available for the the programme was employed, along with an
production of 2-ethylhexanol from propylene and optimizer spreadsheet displaying the parameters.
synthesis gas. However, some kinetic data can be With this, an energy analysis was activated to
inferred from the kinetic data for the following calculate the amount of energy saved.
reactions:
• Hydroformylation of propylene to IV. RESULTS AND DISCUSSION
isobutyraldehyde
4.1 Process Simulation

Figure 4. 1 Process Flow Diagram of 2-ETH Production Plant from Propylene and Synthesis Gas.

Synthesis gas stream contain 48.6% H2, 49.5% CO, pressure and temperature of 350 bar and 165 oC,
0.4% CH4 and 1.5% N2. Synthesis gas to propylene which is consistent with the patent presented by
feed to the hydroformylation reactor was 2:1, where Beadle et al., (2008) for hydroformylation reactions
the propylene stream contained 93% propylene and using rhodium-based catalysts and typically operate
7% of propene. at pressures from 50 to 350 bar, preferably 150 or 250
to 350 bar, and optimum temperatures ranging from
The hydroformylation followed two catalytic routes: 120oC to 190oC, preferably 165oC to 185oC to
(1) the reaction of propylene and H2 to propane prevent decomposition of the catalyst (Xie, 2013).
(0.4723 act. Conversion% of propylene and 57.05
reaction extent). The biphasic aldol condensation of n-butyraldehyde
𝐶𝐻3 𝐶𝐻=𝐶𝐻2 𝐻2
𝑃𝑟𝑜𝑝𝑦𝑙𝑒𝑛𝑒
+ 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 → 𝐶𝐻𝑃𝑟𝑜𝑝𝑎𝑛𝑒
3 𝐶𝐻2 𝐶𝐻3 (nBAL), catalysed by an aqueous sodium hydroxide
(2) the reaction of propylene, CO, and H2 to iso- solution, yields 2-ethylhexanal prior to the final
butyraldehyde and n-butyraldehyde (18.82 act. reaction, with 3.634% conversion and 8.805 extent of
Conversion% of propylene and 757.8 reaction reaction for the first reaction and 99.99% conversion
extent). and 95.87 extent of reaction for iso-butyraldehyde for
𝐶𝐻3 𝐶𝐻=𝐶𝐻2 𝐶𝑂 𝐻2 the first and second reaction respectively.
𝑃𝑟𝑜𝑝𝑦𝑙𝑒𝑛𝑒
+ 𝐶𝑎𝑟𝑏𝑜𝑛−𝑚𝑜𝑛𝑜𝑥𝑖𝑑𝑒 + 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 →
𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻𝑂 𝐶𝐻3 𝐶𝐻2 𝐶𝐻𝑂
𝐼𝑠𝑜 𝑏𝑢𝑡𝑦𝑟𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
+ 𝑛−𝑏𝑢𝑡𝑦𝑟𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 1.242𝐼𝑠𝑜𝑏𝑢𝑡𝑦𝑟𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 + 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 → 1 −
𝑏𝑢𝑡𝑎𝑛𝑜𝑙 (1)
Bernas et al., (2008) conducted kinetic 2.483𝐼𝑠𝑜𝑏𝑢𝑡𝑦𝑟𝑎𝑑𝑒𝑙ℎ𝑦𝑑𝑒 → 2 − 𝑒𝑡ℎ𝑦𝑙ℎ𝑒𝑥𝑒𝑛𝑎𝑙 +
modelling of propene hydroformylation with Rh/TPP 𝑊𝑎𝑡𝑒𝑟 (2)
and Rh/CHDPP catalysts with activation energy and In this simulation process, the temperature condition
pre-exponential factor of 68100 kJ/mol and 171000 was set to operate at 110oC which was consistent to
m3mol-2s-1, which was used in the process at a control the intrinsic reaction rate was obtained in the

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 448

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

industrially relevant range 110–150oC and 0.76–1.9 reactor, while a reaction extent of 56.90 and 151.2%
M NaOH of biphasic aldol condensation with average conversion of 2-ethylhexanal was achieved for the
values of the activation energy and the pre- second reactor.
exponential factor were determined to be
56388kJ/mol and 171200000 m3mol-2s-1, respectively 4.2 Process Optimization and Energy Analyzer
(Lee et al., 2013).
The energy analyzer showed 2.45% energy savings
The hydrogenation of 2-ethylhexenal is the final step once the first simulation results were made available,
in the production of 2-ethylhexanol, which is an which provided a sense of the changes shown in
important chemical intermediate and solvent. The figure 4.3. The energy savings increased to 6.8%
hydrogenation reaction converts the aldehyde group when the modification was carried out in accordance
of 2-ethylhexenal into the alcohol group of 2- with the suggestion to replace the cooler and heater
ethylhexanol using hydrogen gas and a metal with a heat exchanger. Figure 4.4 illustrates the
catalyst, such as nickel and copper, respectively. Liu significant increase in energy savings that occurred at
et al., (2017) The reaction is usually performed at 8% when optimisation was implemented.
high temperature and pressure to achieve high Specifically, the temperature inlet into the
conversion and selectivity of 100 and 99.1%, hydroformylation reactor was optimised from
respectively, when the reaction was carried out at 1463oC to 1469oC, and the pressure of the aldol
240°C for 7 h within the range of the simulated condensation reactor was increased from 35 bar to 70
results at the first and second hydrogenation reactors bar, all while maintaining a temperature below
at 280oC and 403oC, respectively. The product 2- 100oC. The optimised settings that were taken from
ethylhexanol can be separated from the catalyst and the simulation programme are shown in Figure 4.2.
the unreacted 2-ethylhexenal by distillation and
purification. This process is usually carried out by
forcing hydrogen to the point of saturation in a high-
pressure container into the aldehyde to be reduced in
the presence of a catalyst (Nadine, 2022) in the liquid
phase.
2 − 𝑒𝑡ℎ𝑦𝑙ℎ𝑒𝑥𝑒𝑛𝑎𝑙 + 2𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 → 2 −
𝑒𝑡ℎ𝑦𝑙ℎ𝑒𝑥𝑎𝑛𝑜𝑙 (3)

The reaction described above followed the kinetic

data provided by an experimental study by Virgana et
al., (2019) of 3.9498 m3mol-2s-1 and activation Figure 4. 2 Optimizer Function of 2-ethylhexanol
energy of 58.39 kJ/mol by the reaction extent of Production Plant
52.42 after 58% conversion was achieved for the first

Figure 4. 3 PFD before Optimization

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 449

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

Figure 4. 4 PFD after Optimization

CONCLUSION REFERENCES

The production of 2-ethylhexanol from synthesis gas [1] Ahlgren, S., Björklund, A., Ekman, A.,
and propylene is a three-step process that involves the Karlsson, H., Berlin, J., Börjesson, P., Ekvall,
hydroformylation of propylene to n-butyraldehyde T., Finnveden, Janssen, G. and Strid, M. (2015).
and i-butyraldehyde, followed by the aldol Review of methodological choices in life-cycle
condensation and hydrogenation of 2-ethylhexanal to assessment (LCA) of biorefinery systems - key
2-ethylhexanol. The process was simulated at steady issues and recommendations, Biofuels,
state using UNIQUAC fluid package, which is a Bioproducts and Biorefining, Environmental
thermodynamic model that can predict the phase and Energy Systems Studies. 9(7): 606-619.
equilibrium and the physical properties of the system. [2] Andreas Bernas, Päivi Mäki-Arvela, Juha
The simulation results showed that the process can Lehtonen, Tapio Salmi, Dmitry Yu. Murzin.
produce 2-ethylhexanol with a purity of 100%. The (2008). Kinetic modeling of propene
process was also optimized by varying the operating hydroformylation with Rh/TPP and Rh/CHDPP
parameters, such as the temperature, pressure, and catalysts. Industrial Chemistry and Reaction
tank volume of the hydroformylation reactor, to Engineering, 47(13), 4317-4324.
achieve the maximum conversion, selectivity, and doi:[Link]
energy efficiency. The optimization results showed [3] Albanese, D. C. (2023). Conversion of adipic
that the process can save energy by 8% compared to acid to Bis-2-ethylhexyl adipate overcoming
the base case, by reducing the heating and cooling equilibrium constraints: A laboratory
duties of the reactors and the distillation columns. experiment. Journal of Chemical Education,
The process was also evaluated for its economic 100(1): 361–365.
feasibility and environmental impact, by estimating [4] Arvidsson, M., Haro, P., Morandin, M., and
the capital and operating costs. The evaluation results Harvey, S. (2016). Comparative
showed that the process can be profitable and thermodynamic analysis of biomass
sustainable. The process can also be integrated with gasification-based light olefin production using
other processes, such as the production of propylene methanol or DME as the platform chemical,
from propane and the production of synthesis gas Chemical Engineering Research and Design,
from natural gas, to form a complete plant for the 115, 182-194.
production of 2-ethylhexanol from natural gas. The [5] Asmaa, A., Chrakhan, K., Sumaya, Z., and
production of 2-ethylhexanol from synthesis gas and Aysha, A. (2022). Production of 2-
propylene is a promising technology that can provide Ethylehexanol. Scholars Journal of
a valuable chemical intermediate and solvent for Engineering and Technology, 9(2), 8-22.
various applications, such as plasticizers, lubricants, [6] Bhuiya, M. M. K., Rasul, M. G., Khan, M. M.
and coatings. K., Ashwath, N., Azad, A. K. and Mofijur, M.
(2015). Optimisation of oil extraction

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 450

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

process from Australian Native Beauty Leaf Ethylhexenal Using Supported-Metal Catalysts
Seed (Calophyllum inophyllum). Energy for Production of 2-Ethylhexanol. Catalysis
Procedia 2015(75), 56-61. Letters, 147, 987–995.
[7] Bocqué, M., Voirin, C., Lapinte, V., Caillol, S., doi:[Link]
and Robin, J. J. (2016). Petro-based and bio‐ [17] Hackl, R., Julie, H., Maria, T. and Selma, B.
based plasticizers: chemical structures to (2016). The potential for electrofuels
plasticizing properties. Journal of Polymer production in biogenic CO2 point sources.
Science Part A: Polymer Chemistry, 54(1):11– Frontiers in Energy Research, 5(4), 1-12.
33. [18] Han, X., Li, S., An, H., Zhao, X., andWang, Y.
[8] Both, R., Dulf, E. H., and Cormos, A. M. (2021) Improvement of n-butanol Guerbet
(2016). Advanced Control of a Complex condensation: a reaction integration of n-
Chemical Process. Brazil Journal of Chemical butanol Guerbet condensation and 1,1-
Engineering, 33(1): 155–168. dibutoxybutane hydrolysis. Reaction Chemical
[9] Chang, T. T., Lin, Z. W., Zhang, L. Q., Liu, W. Engineering, 6(10):1845–1853.
B., Zhou, Y., and Ye, B. C. (2022). Efficient [19] Hreczuch, W., Dąbrowska, K., Chruściel, A.,
Biodegradation of Di-(2- Ethylhexyl) Phthalate Sznajdrowska, A., and Materna, K. (2016). 2-
by a Novel Strain Nocardia Asteroides LMB-7 Ethylhexanol Derivatives as Nonionic
Isolated from Electronic Waste Soil. Research Surfactants: Synthesis and Properties. Journal
Square. 12(1), Surfactant and Detergent, 19(1), 155–164.
[10] Chen, M., and Smith, P. M. (2017). The U.S. [20] Ikpaki, C. F., Dagde, K. K., Goodhead, T. O.,
cellulosic biofuels industry: Expert views on and Elelu, M. C. (2021). Plant Design for the
commercialization drivers and barriers. Production of 2-Ethylhexanol from Propylene
Biomass Bioenergy, 102, 52–61. and Synthesis Gas. Scholars Journal of
[11] Chongran, S., Shuangfei, Z., Binyuan, G., Tao, Engineering and Technology, 9(2): 8-22.
Y., Haina, C., Yuguang, W., Hongbo, Z., and [21] Iman, N., Lars, P. and Dennis, J. M. (2018).
Zhu, Chen. (2023). Potential utilization of Continuous Condensed-Phase Ethanol
lignocellulosic biomass to a high-value Conversion to Higher Alcohols: Experimental
platform chemical -- 2-ethylhexanol. Research Results and Techno-Economic Analysis. A
Square, 12(1), 1-39. Manuscript, Published by Elsevier. 1-37.
[12] Dennis, B. M., and Elliot, I. B. (2012). [22] Ikpaki CF, Dagde KK, Thankgod Oweifa
Introduction to Industrial Polypropylene Goodhead, Elelu MC. (2021). Plant Design for
Properties, Catalysts, Processes. Publishers by the Production of 2-Ethylhexanol from
John Wiley & Sons and Scrivener. 1 st edition, Propylene and Synthesis Gas. Scholars Journal
pp: 4-12. ISBN 978-1-118-06276-0. of Engineering and Technology, 9(2), 8-22.
[13] Divine, B. N. and Anuanwen, C. F. (2020). doi:10.36347/sjet.2021.v09i02.001
Optimization Methods for the Extraction of [23] Kazeem, A. (2016). Using Response Surface
Vegetable Oils: A Review. Processes, 8(209), Methodology for Modeling and Optimization
1-21. of Propene/Propane Separation Column. Austin
[14] Fujiwara, M., Mimura, N., Sato, O., and Chemical Engineering, 3(4), 1041.
Yamaguchi, A. (2019). Surface modification of [24] Ku, J. T., Simanjuntak, W., and Lan, E. I.
H-ZSM-5 with organodisilane compound for (2017). Renewable synthesis of n-
propylene production from dimethyl ether. butyraldehyde from glucose by engineered
Microporous Mesoporous Material, 280, 219– Escherichia coli. Biotechnology Biofuels, 10(1),
226. 291.
[15] Ghaemi, A., and Zerehsaz, M. H. (2018). [25] Li, Y., Liu, X., An, H., Zhao, X., and Wang, Y.
Experimental study on operating conditions of (2016). One-Pot Sequential Aldol
2-ethylhexanol manufacturing process. Condensation and Hydrogenation of n-
Material Manufacturing Processes, 33(8), Butyraldehyde to 2-Ethylhexanol. Industrial
829–834. and Engineering Chemistry Research,
[16] Guoxiu Liu, Shiwei Liu, Siyuan Liu, Shitao Yu, 55(22):6293–6299.
Lu Li, Fusheng Liu, Congxia Xie & Xiuyan [26] Mariano, C., Salvatore, F., Maura, S. and Luca,
Song. (2017). Hydrogenation of 2- A. (2017). Optimization of hemp seeds (canapa

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 451

 © JUN 2020 | IRE Journals | Volume 3 Issue 12 | ISSN: 2456-8880

sativa l.) Oil mechanical extraction. Chemical [37] Subagjo, S. V. and Gunawan, M. L. (2019). A
Engineering Transition, 58(1), 373–378. kinetics study of 2-ethyl-2hexanol
[27] Mike, K. (2016). Propylene Process Summary. hydrogenation of 2-ethyl-hexanol over nicked
Process Economics Program Review, based catalyst. IOP Conference Series:
2016(11), 1-6. Material and Engineering. 543(1), 1-9.
[28] Mohamed, B., Danh, C. V., Phuc, H., Elizabeth, [38] S Virgana, Subagjo and M L Gunawan. (2019).
R., Jihyun, P., Thi, L. H. and Alexandra, N. D. A Kinetics study of 2-ethyl-2-hexenal
(2020). Health risk assessment of volatile hydrogenation to 2-ethyl-hexanol over Nickel
organic compounds at daycare facilities. Indoor based catalyst. Materials Science and
Air, 2021(00), 1–12. Engineering, 543, 012009. doi:10.1088/1757-
[29] Müller, G., Chylenski, P., Bissaro, B., Eijsink, 899X/543/1/012009
V. G., and Horn, S. J. (2018). The impact of [39] Shinbeom Lee, Arvind Varma. (2013). Kinetic
hydrogen peroxide supply on LPMO activity study of biphasic aldol condensation of n-
and overall saccharification efficiency of a butyraldehyde using stirred cell. Chemical
commercial cellulase cocktail. Biotechnology Engineering Science, 104(18), 619-629.
Biofuels, 11(1), 1–17. doi:[Link]
[30] Nadine. (2022). How is 2-Ethylhexanol [40] Subroto, E., Robert, M., Hero, J. H. and
Produced and Used? China: GuideChem. Antonius, A. B. (2014). Optimization of
[31] Obringer, C., Lester, C., Karb, M., Smith, mechanical oil extraction from Jatropha curcas
A.,and Ellison, C. A. (2023). Impact of L. Kernel using response surface method.
chemical structure on the in vitro hydrolysis of Industrial Crops Production, 1-9.
fatty esters of 2-ethylhexanoic acid or 2- [41] Stephen Wayne Beadle, R. D. (2008). USA
ethylhexanol and extrapolation to the in vivo Patent No. US 7405329B2
situation. Regular Toxicology Pharmacology, [42] Taghvaei, M., Seid, M. J., Elham, A., Shahram,
137, 105315. N. and Omran, A. (2014). Optimization of
[32] Pawar, K., Amar, G., Jaishree, D., Pavan, G. microwave-assisted extraction of cotton seed
and Shubham, T. (2019). Extraction of Neem oil and evaluation of its oxidative stability and
(Azadirachta indica) Seed Oil and Its physicochemical properties. Food Chemistry,
Applications. International Journal of 160, 90–97.
Pharmacy and Biological Sciences-IJPBSTM, [43] Xie, Z. (2013). Greener hydroformylation with
9(3), 1205-1212. nanofilterable rhodium catalysts in a stirred
[33] Poulikidou, S., Heyne, S., and Grahn, M. membrance reactor. Kansas: Graduate Faculty
(2017). “Investigating the potential of advanced of the University of Kansas.
tailor-made biofuels - A well-to-tank [44] Yu, L., Li, S., Ma, G., and Sun, J. (2016).
environmental analysis of 2-ethylhexanol as a Experimental Research on the Effect of 2-
drop-in diesel alternative. Proceedings of 5th ethylhexanol on Water Boiling Heat Transfer at
Tailor-Made Fuels from Production to Subatmospheric Pressure. Heat Transfer—
Propulsion, Aachen, 20-22. Asian Research, 45(2), 199–208.
[34] Poulikidou, S., Heyne, S., Grahn, M., and [45] Zhao, Y. (2016). Property package. Chemical
Harvey, S. (2019). Lifecycle energy and Engineering Design Projects.
greenhouse gas emissions analysis of biomass- [46] Zhang, T., Nilsson, L. J., Björkholtz, C.,
based 2‐ethylhexanol as an alternative Munch, K., and Denbratt, I. (2016). Effect of
transportation fuel. Energy Science using butanol and octanol isomers on engine
Engineering, 7(3), 851–867. performance of steady state and cold start
[35] Raghda, A. E., and Alaa, A. G. (2019). Syngas ability in different types of Diesel engines,
Production, Properties, and Its Importance. Fuel, 184, 708-717.
Sustainable Alternative Syngas Fuel, Author: [47] Zhang, R., Xie, Y., Song, J., Xing, L., Kong, D.,
Licensee IntechOpen. 1-8. Li, X. M., and He, T. (2016). Extraction of
[36] Reinhard, R., and Hermann, H. (2014). Boron from Salt Lake Brine using 2-
Biomass gasification for synthesis gas Ethylhexanol. Hydrometallurgy, 160, 129–136
production and applications of the syngas.
WIREs Energy and Environment. 3(4), 1-21

IRE 1710881 ICONIC RESEARCH AND ENGINEERING JOURNALS 452