Table of content

Contents
Chapter one Introduction...........................................................................................

1.1 Introduction to Ethylene Production..................................................................................

1.2 The main uses of ethylene.................................................................................................

1.3 General production............................................................................................................

1.4 Ethylene and its significance in the chemical industry......................................................

1.5 The sources of ethylene.....................................................................................................

Chapter two Production method

2.1Production of Ethylene.......................................................................................

2.1.1 Objectives of the process..................................................................................................

2.2 Synthesis of Ethylene from Methanol.................................................................................

2.3 Methanol to Olefins (MTO).................................................................................................

2.3.1 Process Evaluation............................................................................................................

2.3.2 Process Solution................................................................................................................

2.3.3 Process Flow Diagram......................................................................................................

2.4 Ethylene from natural gas....................................................................................................

2.5 Ethylene Production via Cracking of Ethane-Propane........................................................

2.6 Production from naphtha.....................................................................................................

2.7 Demand of Ethylene............................................................................................................

2.8 Process selection and advantage..........................................................................................

 2.9 The differences in efficiency and cost between the different ethylene production
methods......................................................................................................................................

2.10 The different methods affect the quality of the ethylene produced...................................

2.11 Factors influence the choice of ethylene production method for a particular application.

Chapter Three Material Balance

Chapter Four Energy Balance

 Ch
apt
1.1 Introduction to Ethylene Production
Ethylene is an important organic compound and

er chemical intermediate, used in a large number of

industrial processes such as energy, plastics,
automobiles, and chemicals. It is widely used in the
chemical industry as a small hydrocarbon gas [1].
Annual worldwide production of ethylene currently

one
exceeds 150 million tons [1]. It is synthesized via
reaction processes derived from fossil fuels and
biomass-based resources [2]. Ethylene production
contributes to considerable amounts of CO2, which
is contributing to climate change [1]. Ethylene is one
of the most important petrochemically derived

Int
monomers, and the largest of the olefin markets [3].
The primary objective of research in this area is to provide a comprehensive
overview of ethylene production technologies and its commercial significance in
the world market [3]. Ethylene is used as a feedstock for the production of various
commercially useful chemical products such as polyethylene, polymers, fibers, etc.
[3]. Ethylene is important because it is the simplest olefin,only attached to
hydrogen atoms, with both double bond carbon atoms in ethylene not substituted
[3]. Ethylene is also significant for polymer synthesis,and it serves as a raw
material for making important chemicals such as ethanol and acetaldehyde [3].
There has been considerable interest in the selective trimerisation of ethylene to 1-
hexene over the past fifteen years [4]. Ethylene is also used in agriculture, where it
acts as a plant hormone involved in signal transduction [1][5].

1.2 The main uses of ethylene

Ethylene has a variety of uses in industrial processes, making it a highly
valuable chemical compound. One major use of ethylene is as a feedstock in fluid
catalytic cracking (FCC) units, commonly used in refineries to convert heavy
hydrocarbons into lighter products. Ethylene is also used as a feedstock in the
production of ethylbenzene, which is a key ingredient in the production of styrene
monomer, one of the most widely used plastics in the world [6]. In addition, dilute
ethylene is becoming an increasingly attractive option for use in ethylene crackers
as it has the potential to debottleneck the process, allowing for increased
production of other chemicals and plastics [6]. Ethylene is also used for alkylation
of aromatics in commercial processes, as well as being the main feedstock for the
production of various chemicals and plastics [6]. Furthermore, dilute ethylene from
FCC off-gas streams can be used as a feedstock in various industrial processes,
including the dilute ethylene process commercialized at Shell's Stanlow UK
refinery and the Mobil-Badger process [6]. Overall, the versatility of ethylene
makes it a crucial component in many industries and chemical processes.

1.3 General production

There are several methods for producing ethylene, including natural and
synthetic processes. Traditionally, ethylene has been produced via the steam
cracking of petroleum-based feedstock [7]. However, sustainable and carbon-
neutral methods of producing ethylene from renewable feedstock are being
explored [8]. Biologically produced ethylene is one option, which is expected to be
free of metals and other contaminants commonly found in fossil-derived ethylene
stream [7]. Microbes produce ethylene via an ethylene-forming enzyme (EFE),
which uses α-ketoglutarate and arginine as substrates [7]. The expression of a
single gene is sufficient for ethylene production in the absence of toxic
intermediates [7]. Ethylene can also be produced naturally by plants and some
microbes, such as four pathovars of Pseudomonas syringae and a few species of
fungi such as Penicillium digitatum, by an ethylene-forming enzyme (efe) [7][9].
In microorganisms, ethylene is synthesized in two ways depending on which
precursor is used, either 2-oxo-4-methylthiobutyric acid (KMBA) or 2-
ketoglutarate [9]. The stoichiometries for the production of ethylene are calculated
through computational analysis by considering all possible routes for conversion of
organic/inorganic carbons to ethylene [7]. Additionally, direct photosynthetic
production of ethylene after the recycling of carbon dioxide shows great potential
[8]. However, it must be noted that there are safety concerns when O2 is co-
produced with ethylene due to flammability issues [7]. Thus, innovative and
sustainable ways to produce ethylene need to be explored urgently, particularly
considering the environmental pollution caused by traditional ethylene production
methods [8].

1.4 Ethylene and its significance in the chemical industry

Ethylene is a colorless and flammable gas with a melting point of -169.4°C
and a boiling point of -103.9°C. It is a crucial building block in the petrochemical
industry, produced by heating either natural gas or petroleum, and then separating
the mixture of gases to obtain ethylene [1][2]. Ethylene is an important industrial
organic chemical and sometimes referred to as the "king of petrochemicals" due to
its versatility in producing plastics, solvents, cosmetics and many other products
[2][3]. Ethylene has several favorable properties and technical and economic
factors, including its relatively low cost of production via refinery processes,
generating fewer by-products compared to other olefins, and being a large-volume
product manufactured worldwide primarily by steam-cracking of hydrocarbons [4]
[5]. Ethylene is used to produce monomers, which are precursors to polymers.
Copolymerization of ethylene with other olefins can produce copolymers with
improved properties. For example, it can be polymerized into polyethylene, which
is the largest-volume thermoplastic polymer, used in the production of packaging
films, wire coatings, and squeeze bottles [4][2]. Furthermore, ethylene can be
combined with benzene to produce ethylbenzene, which is used in the manufacture
of polystyrene, another important plastic [1]. Ethylene can also be chlorinated to
produce 1,2-dichloroethane, which can be converted to the plastic known as
polyvinyl chloride [1]. Increasing demand for ethylene has led to a steady increase
in US production since 2008, and ethylene production is viewed as a leading
indicator of growth in the manufacturing sector [6]. Ethylene is considered the
"World's Most Important Chemical" and a significant compound in the chemical
industry, used as an intermediate in the manufacture of other chemicals [6][1][6].

1.5 The sources of ethylene

Ethylene is a versatile chemical with many applications in industry and
agriculture. Ethylene is produced through several different pathways, which vary
depending on the organism involved. Plants natively produce ethylene through the
ACC pathway or the Yang cycle, which involves a three-step reaction starting with
methionine and ending with the production of ethylene via amino-propane
carboxylic acid (ACC) [10]. In contrast, microorganisms like Pseudomonas
syringae pv. phaseolicola produce ethylene via the KMBA pathway, which
involves converting methionine to 2-keto-4-methylthiobutyric acid (KMBA) using
an NADH:Fe-EDTA oxidoreductase [10][11]. Some plant pathogens like
Pseudomonas syringae and Pencillium digitatum have also been found to produce
ethylene, likely to weaken their host's defenses [10]. Additionally, ethylene can be
produced in non-native bacterial hosts like Escherichia coli and cyanobacteria
through heterologous expression of the ethylene-forming enzyme (EFE) [11].
Ethylene is also a feedstock for the chemical industry and can be produced from
naphtha, ethane, and ethanol [12][8]. Overall, the sources of ethylene are diverse
and include both biological and non-biological pathways.
 Chap
ter two
Prod
uction
 method

 2.1Production of Ethylene
The process of producing ethylene gas or otherwise known as ethene
(IUPAC name) comprises a series of chain reactions that involve cracking (steam
and catalytic) of a variety of hydrocarbons. The productions however vary with
places and this is largely attributed with the presence of the feedstock that is
essential in its production. Countries such as Asia and Europe produce ethylene by
cracking gasoline and naphtha while other countries such as the United Sates
produce the gas by cracking propane and ethane .The process involved in the
different countries both produce ethylene gas, the difference only arise in the
structural design of the plants. For instance, cracking ethane and propane to give
ethylene like in the instance of the United Sates makes the plant cheaper and easy
to operate
2.1.1 Objectives of the process

The main aim of the production plant is to break down the hydrocarbons in
the feedstock to produce the required ethylene gas. The gas has a wide application
in the field of chemistry including its important role in the production of polymers
such as the chloroethene, ethyl benzene and poly (ethene) it is also important for
the production of other chemical substances such as ethanol and epoxy [13]

The process also has been highly utilized due to its,

 High demand of the ethylene gas which thus makes it to be a highly sought
after chemical product . This has called for the industrial production of the
gas.
 The relative advantage that it has such as ease of production operations and
its cost effectiveness.
 The production also has environmental concerns in that it does not produce
other hazardous chemicals in to the environment

2.2 Synthesis of Ethylene from Methanol

The production of ethylene is mainly divided into three sections (1) methanol
production, (2) methanol to olefins (MTO), (3) product purification and separation.
The first section for ethylene production can be excluded if methanol has been
purchased as the feedstock.

2.3 Methanol to Olefins (MTO)

The MTO process is described into four stages which are reaction stage,
conditioning stage, first separation stage, and second separation stage. In the
reaction stage and conditioning stage, the raw material – methanol is converted
into olefins mixture where this mixture is then quenched and purified. In the first
separation stage, the product from the reaction and conditioning stage is divided or
separated into three components which are light components, heavy components,
and C2-C3 mixture. Next, the C2-C3 mixture is flowed into second separation
stage where processes like C2-splitting and C3-splitting are conducted in the flow.
The second separation stage is aimed to acquire pure products like ethylene and
propylene where both of these products are targeted to reach purities of 99.5 mol%.
(Design and Optimization of the Methanol-to-Olefin Process. Part I: Steady-State
Design and Optimization)

In Asia Pacific region, the buying price of the raw material - methanol is USD 0.39
per kg which is equivalent to RM 1.72 per kg. The methanol is obtained as a raw
material for the process of MTO, which aimed to produce ethylene as product and
propylene as sub-product. This pricing of methanol is valid from 1st of April 2017
to 30th of April 2017

2.3.1 Process Evaluation

The overall process pathways are further evaluated with several alternatives and
summarized in Table 1-5. The major pathways of Ethylene plant design are
catalytic reaction, which SAPO-34 is chosen as it has high selectivity to Ethylene
and fast activation that promoted high efficiency and effectiveness of the process.
Process pathway is CO 2 removal by Amine gas treating method, where
Diglycolamine (DGA) is used to remove 50% of CO 2. Then, water quench
purification is carried out to purify products from entrained catalyst fines and
water, as well as heavy by products. Last but not least, cryogenic scheme of
product recovery is carried out to form high purity of Ethylene, propylene and
byproduct [14].

Table 2.1Process evaluation of Ethylene process pathway

Process Advantages Disadvantages

 High selectivity to  Slow activation.
aromatics and paraffins due
to its medium pore opening
Zeolite ZSM-5 side.
 Major olefin product is
propylene.
Catalytic
Reaction  Very high selectivity for  High reaction
olefins. temperature.

SAPO-34  Fast activation.

 Low partial pressure.
 Low contact time.
Amine Gas Treating  About 50% for removing  High energy
CO2. consumption.
 Digycolamine
(DGA) is used for  Harder to transfer CO2
CO2 the plant from gas into amine at
removal low gas pressure.
 High effectiveness due to  High investment and
Cryogenic Separation differences in boiling. operating cost for
further optimization.

2.3.2 Process Solution

Block Flow Diagram (BFD) of MTO process is illustrated and shown in Figure 2.1
Figure 2.1: Block flow diagram of Ethylene process

2.3.3 Process Flow Diagram

The figure below showed a process flow diagram of the Methanol to Ethylene
process. This is drawn after the selection of equipment for each stage.
Figure2.2 : Process flow diagram of Methanol to Ethylene process

2.4 Ethylene from natural gas

Most of the feedstock used to produce the gas is natural oil and gas. The process
involves mostly the cracking of these natural oil or gases, cracking can be either
through catalytic process or by steam process. Catalytic process from the name
speeds up the process by utilizing on the reaction of temperatures [15]Catalytic
process lowers the temperature that is required to crack the hydrocarbons in the
natural oil. To achieve the lowest temperature for cracking, the process uses a
fluidized catalytic cracking technique which is used to pass over the feedstock. The
temperature of the products, the catalyst and the time taken to pass the unit is used
to determine the proportion of the products. The proportion is then separated to get
back the catalyst and the ethylene gas [16]

Figure 2.3: process of Ethylene from natural gas

Steam cracking is also a process similar to catalytic cracking only that in this
process, the feedstock is preheated using steam vapor to a temperature of 1050 to
1150. They are then vaporized in a reactor that is tubular in shape. After
vaporization, the products are converted to relatively low molecules to separate the
gas and other by-products such and the propylene and benzene gas. In a nut-shell,
steam cracking is a pyrolysis process since it first of all involves the cracking or
breaking down of petroleum components through the use of its steam [17]
2.5 Ethylene Production via Cracking of Ethane-Propane
Ethylene is a critical building block for the petrochemical industry, and is among
the most produced organic compounds. It is usually produced in steam-cracking
units from a range of petroleum-based feedstocks, such as naphtha, and is used in
the manufacture of several major derivatives [18].

The process shown in Figure 2.4 is a steam-cracking process for ethylene

production from an ethane-propane mixture. The process can be divided into three
main parts: cracking and quenching; compression and drying; and separation.

Figure 2.4. This process diagram shows an ethylene-production process via the
cracking of an ethane-propane mixture

Cracking and quenching. Initially, an ethane-propane mixture is fed to furnaces in

which, under high-severity conditions, it is cracked, forming ethylene, propylene
and other byproducts. The furnace outlet stream is subsequently fed to a water-
based quench, to prevent further reactions and formation of undesirable
byproducts.
From a decanter downstream from the quench tower, heavies, condensed dilution
steam, tar and coke are removed. Cracked gas from the quench is then directed to
compression and separation[19].

Compression and drying. The compression of the cracked gas is performed across
five stages. After the third stage of compression, carbon dioxide and sulfur are
removed from the cracked gas by caustic soda and water washes in a caustic
scrubber. The compressed cracked gas is cooled and subsequently dried by
molecular sieves that remove most of the water.

Separation. The dried cracked gas is fed to a cold box for the removal of hydrogen
and light hydrocarbons, while minimizing ethylene losses.

At this point, condensates from the chilling train are fed to a series of separation
columns. In the first column (demethanizer), methane is obtained from the top and
further used in the cold box, while the bottom stream is fed to a second column
(deethanizer)[20].

The top of the deethanizer, composed primarily of ethylene and ethane, is fed to an
acetylene converter and then fractionated in the C2-splitter. In this column, lights
are removed from the overheads and recycled to the compression system, while
polymer-grade (PG) ethylene is drawn from the column as a side stream. Ethane,
from C2-splitter bottoms, is recycled to the cracking furnaces.

The deethanizer bottom stream is fed to a depropanizer, which distills C3

components in the overheads. This overhead stream is catalytically hydrotreated
for methyl acetylene and propadiene removal, and then fed to the C3-splitter. In
this column, lights are removed from the overheads and recycled to the
compressors, while polymer-grade (PG) propylene is drawn from the column as a
side stream. Propane from C3-splitter bottoms is recycled to the cracking furnaces.
A C4+ stream is obtained from the depropanizer bottoms.

2.6 Production from naphtha

In this work, shale gas from Marcellus region in the U.S. is analysed for the
production of ethylene and propylene, as olefins projects in this region are drawing
particular interest. from shale gas are developed. Each design includes shale gas
processing and olefins manufacturing stages [21]

Figure 2.5 shows the process flowsheets for the processing of Marcellus shale gas,
which consists of fivesections: acid gas removal, dehydration, NGLs recovery,
compression, and NGLs fractionation. Figure 2.5(a)shows a monoethanolamine
(MEA)-based absorption unit to remove acid gas. Raw shale gas is fed into
thebottom of an absorber (T-101) and contacts with a lean MEA solution from the
top of the absorber to removeacid gas. The rich MEA solution from the bottom of
the absorber T-101 is fed into a stripper (T-102) forregeneration. After removing
acid gas, the sweet gas is water-saturated. Water must be removed to
preventhydrate formation in the cryogenic separation process. Figure 1(b) shows a
triethylene glycol (TEG)-basedprocess for water removal. The sweet gas enters an
absorber (T-201) from the bottom and contacts with alean TEG stream. The rich
TEG stream from the absorber T-201 is introduced into a distillation tower (T-
202)for TEG regeneration. The lean TEG stream from the bottom of tower T-202
is sent to a stripper (T-203) tofurther reduce the water content. Most of the dried
gas is introduced into an NGLs recovery section, as shownin Figure 1(c). In the
NGLs recovery section, the dry gas is first cooled in a cold box. The gas product
from theseparator V-301 flows through an expander (EX-301) to further lower its
temperature, and then it entersanother separator V-302. Liquid products from
separators V-301 and V-302 are introduced into ademethanizer (T-301). Gas
products from the separator V-302 and the demethanizer T-301 are methane-
rich.These two streams are merged and then sent to the compression section, as
shown in Figure 1(d). The NGLsproduct from the demethanizer T-301 is then
introduced into an NGLs fractionation unit as shown in Figure1(e), where it is
separated into ethane and propane (see Table 1). Note that in the co-cracking
design, sinceethylene and propylene are produced via the steam cracking of
ethane-propane mixture, the NGLsfractionation section is excluded at the shale gas
processing stage.

2.7 Demand of Ethylene

Table 2.2: Demand of ethylene in Malaysia
 Year 2002 2003 2004 Change (%)

Import of Ethylene (mil tonnes) 27 31 65 110

Export of Ethylene (mil tonnes) 116 82 115 40

Production of Ethylene (mil tonnes) 1560 1494 1564 5

Consumption of Ethylene (mil tonnes) 1471 1443 1514 5

From the table above, it showed that the import and export of ethylene of Malaysia
are averagely increased. Besides, the ethylene production and consumption of
Malaysia are also gradually increasing. This might be resulted from the used of
ethylene to produce ethylene oxides, ethylene dichloride and so on. Ethylene may
also be used to produce as an intermediate material in order to produce plastic.
[20,21,22]

2.8 Process selection and advantage

Methanol can be synthesis by using coal, natural gas and coke-oven gas. These raw
materials have replaced methanol as feedstock and provided a cost advantage
alternative in order to gain a higher profit. Large range of catalyst and high
selectivity can be obtained .

2.9 The differences in efficiency and cost between the different

ethylene production methods
The assessment of different ethylene production methods has revealed that the
NTO production route is the most cost-effective and environmentally friendly
option [23]. This is primarily due to the fact that it has the lowest life cycle GHG
emissions [24]. The integration of carbon capture and storage (CCS) unit with
CTO can reduce carbon emissions, but the eco-efficiency of CTO-CCS is still 31-
47% lower than the other two production routes [25]. In terms of eco-efficiency,
NTO outperforms both OTO and CTO by 30.2% and 176.6%, respectively
Furthermore, the NTO route has the highest net value added of ethylene product
[26]. These findings suggest that the NTO route is a more sustainable and
economically viable method for producing ethylene. However, further research is
needed to fully understand the long-term implications and potential drawbacks of
each production method.

2.10 The different methods affect the quality of the ethylene

produced
Several methods have been developed to control the production of ethylene and to
preserve the quality of ethylene produced. Ethylene scavengers have proven to be
effective in reducing the rate of ethylene production in refrigerated conditions and
in removing a significant amount of ethylene produced in both refrigerated and
non-refrigerated conditions [27]. In non-refrigerated conditions, ethylene
scavengers were able to remove a large majority of the total ethylene production
compared to samples without scavengers [28]. Meanwhile, active EO sheets have
exhibited promising results, with samples showing up to 32% and 70% lower
ethylene production after 26 days at 2°C and after the corresponding
commercialization period, respectively [29]. Studies have also shown that EOs
have inhibited ethylene biosynthesis in several fruits and vegetables [30].
Additionally, reduced endogenous ethylene production can be used to control
ethylene, which can be achieved through genetic modification or reduced
sensitivity to ethylene [36]. CO2 production has also been observed to have a
similar trend as ethylene production, with maximum CO2 production observed
after the commercialization period of sample storage for 5 and 26 days [35]. It is
evident that packaging treatment and storage temperature interaction significantly
affect ethylene production [35]. Moreover, reduced sensitivity to ethylene can also
be used to control ethylene, which can be achieved through genetic modification or
reduced sensitivity to ethylene [36]. In CTRL samples stored at 8°C for ≥26 days,
no ethylene or CO2 production was measured due to incipient physiological
disorders observed [35]. Although ethylene production remained low from day 2
until day 26 in CTRL samples stored at 2°C [35], it is important to investigate
further methods to control ethylene production and preserve the quality of ethylene
produced.

2.11 Factors influence the choice of ethylene production method for

a particular application
When it comes to choosing the most suitable method for ethylene production, there
are many factors that must be taken into consideration [37]. The specific
application for which the ethylene is intended must be considered, and the required
balance between stiffness and toughness and interfacial adhesion must be
evaluated [38]. Furthermore, the concentration of ethylene and the choice of
ethylene sensor depend on the requirements of the application [37]. Quantification
of ethylene production is necessary for each sample, rather than monitoring over
time [37]. The biomass of seedlings is another factor that influences the choice of
ethylene production method, as is the need for larger sample sizes in some
applications [37]. Additionally, environmental performance and economic factors
are also important considerations when selecting a method for ethylene production
[39][40]. In terms of bio-based alternatives, bio-ethylene derived from bio-ethanol
is used in the synthesis of other polymers like PVC and rubber, although it is
generally more expensive than petrochemical PE [38]. In contrast, PS, epoxy resins
and rubbers like ethylene propylene diene monomer rubber (EPDM) could be
promising bio-based candidates for the use of bio-based ethylene [38]. While
ethylene oxide has wide-ranging uses in the production of glycols, glycol ethers
and surfactants, its primary application is in glycol synthesis [40]. It is worth
noting that certain production methods, such as PVC, have been criticized for their
environmental impacts and difficulty in separating from post-consumer waste [38].
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