RECOVERY OF ETHYLENE

FROM WOODY BIOMASS

GASIFICATION GAS

Supervisor: P.J. De Wild

Authors: ATHUL BALAJI HEMANT KUMAR (S3440338)

SHAJIF RAVI (S3466833)

September 26, 2017

Table of Contents

ABSTRACT ................................................................................................................ 3
Introduction: ............................................................................................................... 3
Research Questions: .................................................................................................. 5
Methodology: .............................................................................................................. 5
Overview of Ethylene: ................................................................................................ 6
• Brief History of Ethylene: .............................................................................. 6
• Brief Definition of Ethylene: .......................................................................... 7
• Physical and Chemical Properties of Ethylene and Biomass: ...................... 8
• Life Cycle Assessment of Ethylene: ............................................................. 9
Thermal Conversion Process: .................................................................................. 10
• Pyrolysis: .................................................................................................... 10
• Combustion: ............................................................................................... 11
• Liquefaction: ............................................................................................... 11
• Gasification: ............................................................................................... 11
➢ Parameters of Gasification: ..................................................................... 12
➢ Types of Gasifiers: .................................................................................. 13
Production of Ethylene: ............................................................................................ 17
• Process description: ................................................................................... 18
• MILENA Indirect Gasification: .................................................................... 19
• Tar reformer: .............................................................................................. 20
• LO-CAT-Liquid Oxygen Catalyst: ............................................................... 21
• Fischer-Tropsch synthesis: ........................................................................ 21
• Olefins Metathesis Catalysis: ..................................................................... 22
Economic Evaluation of Ethylene Production: .......................................................... 23
Results & Discussion:............................................................................................... 25
• Maximisation of Bio-ethylene: .................................................................... 25
• Catalysts selection: .................................................................................... 27
• Impact of bio-ethylene within Polyester Value Chain: ................................ 28
Conclusion: .............................................................................................................. 29
References: .............................................................................................................. 30

2
 ABSTRACT
The aim of this work is to analyse an economical extraction method of bio-ethylene
from woody biomass gasification gas and how to maximize the yield with having a
minimum effect on feasibility. To accomplish that, characteristics of ethylene and the
several processes involved will be studied upon in detail. The report is further more
supported by analysing the catalyst compositions and separation techniques used to
feasibly and efficiently extract bio-ethylene from many other by-products and finally
the impact of bio-ethylene within the polyester value chain will also be discussed.

Introduction:
Many of the current chemicals utilized by the society are based on
petrochemicals. With the current dependence on fossil fuels, an undesirable issue and
with continuous rise in renewable technology’s sophistication and efficiency, using
biomass as a raw material in order to synthesize bio-based products instinctively
becomes a source to tap energy from [1]. The most important aspect of the current
generation is the sustainability of energy and resources. This is important for the safety
and economic stability to avoid further climatic problems in the future. Hence, the
challenge of sustaining renewable energy fuels has become an issue to consider in
major European and Asian countries. This shows that the demand for renewable
energy is a major trend in the current scenario.

In this research paper, the developmental fronts of current technologies for the
usage of sustainable feedstock is studied upon in detail. The prime topic that is
focused in this paper is the production of ethylene from woody gasification gas.
Different types of biomass feedstock include agricultural residues, woody energy
crops, forest resources, industrial, and algae. It is important that the selection of
biomass needed for the ethylene production is done through comparisons between
biomasses [1].

As mentioned above, biomass plays an important thus needs to be defined in brief.

It is defined as organic matter mass at a ratio to the unit surface area. The key biomass
discussed in this section is woody biomass (ligno-cellulose biomass). Few examples
of woody biomass include grass, hard woods, and straw. Woody biomass comprises
of three key components, lignin, cellulose, and hemi-cellulose. More often or not
lignocellulose biomass becomes the desired feedstock for ethylene production due to
low cost and low negative impact on the environment. The conversion from
lignocellulosic biomass to ethylene has significant difficulty due to the bonding of lignin
and cellulose that is difficult to break down. Figures 1 & 2 below shows the chemical
compound of cellulose and hemicellulose for further research:

3
 Figure 1: Cellulose [36]

Figure 2: Hemicellulose [36]

Biomass breaks down to the value of energy efficiency. This is important for the
selection of the biomass needed for the production of bio-ethylene. As shown above,
sustainability plays a major role for the energy efficiency. However, pertaining issues
surrounding the energy input include major aspects such as investment, continuous
supply of woody biomass, and yield efficiency of product. Besides that, one of the
major concerns surrounding the impact of increasing demand for biomass, is the
‘carbon neutral’ policy framework. This is defined as plan to achieve zero net carbon
emission into the atmosphere. This is necessary to ensure successful reduction of
greenhouse gas emission within the context of environmental policy in Europe (IEEP,
2010).

Studies have shown that ethylene is one of highly used chemical product that
stands in an annual production of 127 million tonnes [28]. The major contribution of
high production rate is due to various uses and applications of ethylene. A major
application of ethylene is the production of plastic (polymer chain) via polymerisation
process. Polyethylene is one of the major products being used in the polymer industry.
Moreover ethylene further contributes to the plant control growth . In addition, the rise
in demand of ethylene is further documented by the fact that some of the leading
petrochemical industry such as Sinopec and Exxonmobil [32] uses ethylene for fuel
additives and intermediates purpose. Furthermore, biomass is a major energy field in

4
USA. The figure below shows the various energy consumptions of biomass in various
energy fields:

Percent of Total U.S Energy

Consumption
4.80% 2.40% 8.50%
0.20%
0.50% 29%

1.90% 36.20%
16.10%

Natural Gas Petroleum Coal Wind Solar

Geothermal Biomass Hydroelectric Nuclear

Figure 3: Pie chart of Energy Consumption percentage of Biomass [37]

Research Questions:
For this report, the processes and the sub-processes of extracting ethylene from
the synthetic gas will be reviewed and assessed. The main question is the question
that will be used to cover the main body of the report. Thus, the following question is:

• How to extract bio-ethylene from woody biomass via gasification and how to
maximize the yield?
To add more validity and structure into the main body of the report, two research sub-
questions were added subsequently. They are listed below in a random order:

• What is the most feasible catalyst to use in the production of ethylene in terms
of economical, selectivity, yield, and safety aspects?
• What is the impact of ethylene derived from woody biomass within the polyester
value chain?
This is also essential to remove the uncertainty surrounding the report.

Methodology:
Methodology applies to the aim and the outcome of the report, that is to answer
the research questions needed for the body of the literature report. To begin with, the
overview and history of ethylene and woody biomass used are discussed in the next
section. The types of woody biomass investigated in this report are oak, poplar,
redwood, and Subabul wood. Properties of woody biomass are discussed. More
applies for the overview of the processes involved in the production and recovery of
ethylene. Besides that, gasification comparison of the processes are noted and

5
explained in a detailed manner to analyse the feasibility of the chosen processes with
an alternative technology.

To observe the suitability of the gasification technique, available gasifiers are

investigated. Milena gasifier is chosen as the preferred route for ethylene production.
Milena gasifier will influence the physical properties and requirement of biomass
feedstock and fuel. Next different types of process paramaters are observed for the
selection of type of process used, mainly temperature, residence time, gasifying agent,
and biomass source. Further research allows further justification on the selection of
Milena gasifier in terms of process suitability.

In addition, the chosen process based on the feasibility and the accuracy of the
research question are discussed in the result and discussion section. The economic
evaluation is derived from capital cost estimation. This include the estimation cost of
major and minor equipments used in the industry. Based on the findings above, the
information given will lead to the finalized answer to the research questions as stated
in the section above, thus completing the report body.

Overview of Ethylene:
Brief History of Ethylene:
Production of ethylene was dated as early as year 1669 (17 th century) by
Johann Joachim Becher. The method of identifying ethylene is by using heating
ethanol in the presence of sulfuric acid. However, this theory is not strongly approved
as the evidence backup is not sufficient. Further research for ethylene related to
physical and chemical properties are conducted and reviewed by four renowned
scientists, Anthoni Lauwerenburgh, Johann Rudolph Deimann, Nicolas Bondt, and
Adrien Paets van Troostwyck. It was discovered that ethylene primarily consists of two
main atoms, hydrogen and carbon atom. Going further into the timeframe, a German
scientist August Wilhelm von Hofmann confirmed that ethene hydrocarbon is named
after ethylene in year 1866. This is further proven by denoting hydrocarbon
nomenclature in forms of -ene, -ane, and -one. Further going through the timeline,
Neljubov, a Russian student publicly proven that ethylene is a biologically active
compound in year 1979. In year 1934, ethylene was proven to be a natural product of
plants, using fruits to produce ethylene. This theory was confirmed by Gane.

In year 1963, 2-chloroethyl-phosphonic acid was formed. This compound

breaks down to form ethylene when absorbed into plants. Furthermore, in year 1979,
Sisler introduced inhibitors for ethylene action, known as volatile unsaturated ring
compounds [33].

6
Brief Definition of Ethylene:
Ethylene is defined as the subsequent product of ethanol using
electrochemical reduction or synthetic gas from Modified Fischer-Tropsch (MFT)
process or Milena gasifier. It is known as the least complex form of hydrocarbon that
consists of carbon-carbon double bond (H2C=CH2). Ethylene is known as a colourless
gas with a slight hint of sweet odour [21]. The chemical compound of ethylene is shown
below:

Figure 4: Chemical Compound of Ethylene (Ethene) [22]

. Ethylene is found in nature through fruits such as banana, apple, and pears.
The effect of ethylene caused on fruit is ripening effect that causes changes on the
colour, texture, and flavour of the fruits [23], although smaller fruits such as
strawberries do not produce high percentage of ethylene as the ripening effect is
negligible. Furthermore, the uses of ethylene in major cities of Europe increasingly
becoming more prominent. This is due to the market demand of ethylene by vendors
and suppliers. This aspect is discussed in the section below. The figure below
describes the pipeline flow of ethylene across major countries in Europe:

Figure 5: Ethylene Pipeline across Europe [38]

Ethylene has major advantages and disadvantages that should be discussed

in this section. Being as a major commodity in fruit ripening, ethylene causes negative
side effects on fruits and plants, such as shortening of stem, and reduction of
chlorophyll and cell wall [23]. Thus importance is considered for the temperature of the

7
environment, development stage, and ethylene concentration. Fulfilling these
conditions prevent damage on the crops by ethylene.

There are many ways of producing ethylene through conventional methods for
the past decade. The major method of producing ethylene is known as catalytic
cracking of hydrocarbons such as methanol or ethanol. In other words, catalytic
cracking is defined as the process to break down complex hydrocarbon chain into a
smaller hydrocarbon with a small number of carbon atoms (one, two, three, and four).
This process occurs at a high temperature due to heating of petroleum or complex
hydrocarbon chain. Ethylene can also be produced from syngas using another
conventional process known as reaction of steam and coal that produces different
types of hydrocarbons that include ethylene. Besides that, the chemical equation of
production of ethylene from ethanol via catalytic dehydration is as below:

Equation 1: Catalytic dehydration of Ethanol to Ethylene

From the equation above, ethylene is produced as the main product in a gaseous state
and water is produced as a by-product under gaseous state.

Physical and Chemical Properties of Ethylene and Biomass:

To identify the feasibility of using woody biomass to produce ethylene in a large
scale, the properties of ethylene and woody biomass are needed. Four major woody
biomass were considered, oak, poplar, redwood, and Subabul wood. Based on the
research, the properties are listed as below:

Woody biomass:

Aspect Species
Oak wood Poplar Redwood Subabul wood
Carbon (%) 67.7 85.48 75.6 83.61
Ash content (%) 14.9 4.6 2.3 3.95
Volatile matter (%)
25.8 7.4 30 21.65

Fixed carbon (%) 59.3 88 67.7 74.4

Calorific value
24.28 28.99 28.12 29.92
(MJ/Kg)
Table 1: Chemical Properties of Woody Biomass [29]

8
 As seen above, the four species are commonly used woody biomass in
chemical industries. The selection is based on the volatile content of each wood as
opposed to the ash content. This is important as high content of ash could affect the
overall efficiency of the process, and high volatile matter content is also decisive. From
the data extracted from the table above, redwood is chosen as the type of biomass
needed for the gasification process due to having the lowest ash content and highest
volatile matter content. Physical properties of ethylene for further details shown as
below:

Ethylene:

Physical Properties
Formula C2H4
Molecular Weight (lb/mol) 28.05
Critical Temperature (oF) 49.1
Critical Pressure (psia) 742.7
Boiling Point (oF) -154.8
Melting Point (oF) -272.5
Gas Density @ 70oF 1 atm (lb/ft3) 0.073
Specific Volume @ 70oF 1 atm (ft3/lb) 13.7
Specific Gravity 0.992
Specific Heat @ 70oF (Btu/lbmol-oF) 10.28
Table 2: Properties of Ethylene [26]

Life Cycle Assessment of Ethylene:

The life cycle assessment of ethylene formation via gasification of woody
biomass provides intricate details of the life cycle steps starting from biomass
treatment to the end product of ethylene formation through various processes. This
method is known as the cradle-to-gate approach. This method allows the user to
determine the most feasible approach to produce ethylene chemically through minimal
consumption of energy resources [25]. Alternately, the environmental impact largely
plays a role in the life cycle route of biomass as it includes the final oxidation process
of the assessment [27].

This approach is predictable for the feasibility of ethylene production as shown

above. To be considered a success in global industrial market, the quantities produced
should be in a scale of industrial scale expectations. Besides, biomass limitation could
potentially affect the ethylene production scale due to storage area specifications, and
costing of transportation. This leads to negative assessment on the life cycle of
ethylene, thus it is important to allow consideration prior to construction of life cycle
assessment.

9
 This is also important in terms of literature research as goes for the alternative
processes of ethylene production. Gasification is touted as the most feasible process
of producing ethylene based on the research conducted on different alternatives
reported as pyrolysis, fermentation, and anaerobic digestion. This statement strongly
supports the theory needed to discuss in details of the gasification process in the
report.

Thermal Conversion Process:

The thermo-chemical conversion of biomass can be defined as the conversion
to produce energy products by the application of several chemical processes and heat.
These thermochemical processes consist of multiple stages. Firstly, the biomass is
converted from a solid state into a gaseous state. Secondly, the gases are condensed
into oils. The third and the final stage is when the oil is conditioned and synthesized to
produce syngas. Syngas primarily is known as synthetic natural gas or Bio-methane
and is predominantly made up of carbon and hydrogen. There are four types of thermal
conversion process namely,

• Pyrolysis
• Combustion
• Liquefaction and finally,
• Gasification [2].

Pyrolysis:
Pyrolysis is considered to be the first step in a combustion as well as a
gasification process and basically means the decomposition of a material by heat. It
also known as a de-volatilization process in the absence of air and therefore no
oxidization takes place. Pyrolysis occurs in three stages namely,

• Pre-pyrolysis is where the biomass is heated at a temperature between 120°C

and 200°C.
• Main pyrolysis takes place at higher temperatures above 200°C resulting in
severe weight loss and the decomposition of the solid matter.
• A continuous de-volatilization of char takes place which further proceeds to the
breaking up of C-H and C-O bonds [3].

The by-products of pyrolysis are char as in a solid state, tar liquid and volatile gases.
Char are generally known as charcoals that are carbon rich and several volatile gases
can still remain inside it depending on the process parameters. Although after the
complete pyrolysis no volatile gases are left inside the char except the fixed carbon
present in it [2].

10
Combustion:
Combustion on the other hand is generally the decomposition process in the presence
of oxygen or air, meaning a full oxidation takes place. In a broad sense, this process
can be written as [4],

CxHyOz + ([y/4] + x – [z/2]) O2 xCO2 + [y/2] H2O

The process can be divided into two stages, firstly, at a moderate temperature volatile
substances gets released from the biomass and finally, the process of char oxidation
takes place at higher temperatures [5]. Although a real life, incomplete combustion of
biomass leads to the formation of water, carbon dioxide, methane, carbon monoxide
and other minor compounds.

Liquefaction:
The process of converting a substance’s state from a solid or gaseous state into a
liquid phase is called as liquefaction. In order to phase change a substance, energy
must either be applied or removed from the substance in the form of heat as different
states of matter possesses different amounts of energy in order to change its state [6].
In liquefaction of gases, when the gases are held in a confined space at high pressures
heat is given off when compression takes place eventually resulting in its phase
change to form liquid and thus this process does not require extreme cooling settings
[7].

Gasification:
This process converts solid fuel into a gaseous fuel through partial oxidisation.
This process can be divided into two stages apart from the drying, namely,

• De-volatilization and
• Gasification of the char [2]

Firstly, the de-volatilization is a stage where the volatiles of the biomass is

released in the form of gases by raising the temperature between 200-600°C in the
absence of an oxidizing agent. The main difference between the presence of an
oxidization agent and in its absence is that with plenty of oxygen the biomass
combusts into the formation of primarily water and carbon dioxide whereas with
respect to its latter, big molecules can still change into productive components through
cracking [8].

Finally, the prime reason for the gasification of char is to produce a gas called
the syngas also known as the synthetic natural gas, consisting predominantly of
carbon monoxide and hydrogen. This process can be written as, [4]

CxHyOz + (x-y)CO2 (2x-z)CO + (y/2)H2

11
Substitution of the general composition of biomass produces,

CH1.4O0.6 + 0.4CO2 1.4CO + 0.7H2

Bio-syngas is majorly used to produce electricity, bio-fuels and chemicals. This

research paper aims to gain an insight in the production of bio-ethylene from syngas
through Fisher-Tropsch catalyst method.

Parameters of Gasification:
There are several parameters which influence the gasification process namely,

➢ the gasification temperature

➢ residence time
➢ gasifying agent and
➢ the biomass source
These parameters will be discussed in detail below.

Temperature:
The gasification temperature affects the formation of products, the higher the
temperature the faster are the reactions and at different temperatures different
reactions are active. For example, at higher temperatures such as 1000-1100°C and
above a reaction called the water gas reaction (C+H2O⇔CO+H2) takes place whereas
at lower temperatures between 500-600°C the so called water–gas shift reaction
(CO+H2O⇔H2+CO2) attains significance. Moreover, the process of tar cracking which
is the breakdown of unwanted tars into smaller molecules takes place at temperatures
above 600 °C. Thus this shows the composition of the final gas and the amount of tar
produced varies with gasification temperature [9].

Residence time:
The residence time of a biomass plays a significant role in the completion of the
reaction. If the feed remains in the gasifier for a shorter duration, then the process of
gasification remains unfinished as there is not enough time for the reaction to reach
equilibrium. The final product of the reaction will predominantly be made up of
unreacted material when the residence time is too short and further leading to lower
conversion of H2 and CO gases [10].

Gasifying agent:
The gasifying agent is generally the gas that is filled up in a gasifier during the
process of gasification. It makes up the atmosphere around the biomass feed within a
gasifier. There are several gasifying agents such as steam (H2O), carbon dioxide
(CO2), air or pure oxygen (O2). Different gasifying agents are used for various gas
compositions and reactivity. For example, it is known from various research that
oxygen as a gasifying agent is more reactive than steam or carbon dioxide whereas
when air is used as an agent the 78.1% of nitrogen combines with the product stream
resulting in an expensive nitrogen removal process [10] [11].

12
Biomass source:
The final factor influencing this process is the type of biomass used as feed.
From various research it can be pointed that the composition of the gas is directly
linked to the type of biomass used. As this research paper is primarily focused on
woody biomass, these sources are explained further. The main combustible
components of woody biomass are cellulose, hemicelluloses, and lignin, which are
basically made up of carbon, hydrogen, and oxygen. Other components that are
present in a minor quantity and are combustible are fats, resins, and waxes. The prime
non-combustible component of wood is water making up to nearly 50% of freshly cut
wood. Furthermore, the amount of water leads to the additional decrease in the
temperature of the gasifier. Therefore, wood species with low moisture level are
suitable for the process. It is known that gas cleaning or tar reforming is a labour
intensive process indicating that the ash content of various wood species which
possess a low percentage are suitable fuels for gasifiers. Finally, the volatile matter in
a wood species is directly proportional to the amount of fuel recovered from the
reaction [12].

Types of Gasifiers:
There are several gasifiers being developed and can be broadly differentiated
into either a fixed bed or a fluidized bed. They are also classified based on the
directional of flow of both the biomass and oxidant, means of supporting the biomass
in the reactor vessel and finally the way heat is supplied to the reactor. There are
namely four types of gasifiers,

➢ Fixed bed –Updraft

➢ Fixed bed –Downdraft
➢ Fluidized bed –Bubbling
➢ Fluidized bed –Circulating [12].

Gasifier Flow Direction Support Heat source

Fuel Oxidant
Fixed bed Descending Ascending Grate Coal partial
Updraft combustion

Fixed bed Descending Descending Grate Volatile partial

Downdraft combustion
Fluidized bed Ascending Ascending None Coal and volatile
Bubbling partial combustion
Fluidized bed Ascending Ascending None Coal and volatile
Circulating partial combustion
Table 3: Type of gasifiers

13
The advantages and disadvantages of the above mentioned gasifiers will be
explained.

Figure 6: Updraft gasifier.

I. Fixed bed –Updraft

➢ The advantages of an Updraft gasifier are,
o It is regarded as the simplest form of gasifier.
o Low cost process.
o It has the capacity to handle high moisture and high inorganic
feed such as the municipal waste.
o It is a proven technology as from several papers it is known as
the first type of gasifier used.
➢ The disadvantages are
o This gasifier produces approximately 10-20% of tar which
requires intensive clean-up.
o Limited ability to handle coal fines
o Longer feedstock residence time in gasifier

Figure 7: Downdraft gasifier.

14
 II. Fixed bed –Downdraft
➢ The advantages of a downdraft gasifiers are,
o Its main advantage is that; it consumes nearly 99.9% of the tar
formed therefore requiring minimal or no clean-up.
o Minerals remain in the char or ash in turn reducing the need for
cyclones.
o As similar to the updraft this gasifier is also stated as a proven,
simple and a low cost technology.
➢ The disadvantages are as follows,
o It requires a feed of a low moisture content (below 20%), thus a
pre-drier is used.
o The fuel gas leaves the gasifier at high temperatures, hence
requires cooling before use.
o It results in about 4-7% of unused or unconverted carbon.

Figure 8: Bubbling Fluidized Bed Gasifier.

III. Fluidized bed –Bubbling

➢ The advantages of a bubbling gasifier are,
o Yields a uniform syngas.
o Maintains almost the same temperature distribution throughout
the reactor.
o It is more energy efficient as it is an endothermic process. The
required heat will be generated only to maintain the process at an
optimum temperature.
o It is capable of accepting a wide range of fuel particles sizes.
o High conversion of flue gas is possible with low formation tar and
significantly lower unconverted carbon.
➢ The disadvantages are,
o The bypass of flue gas can occur through the bed by the use of
large size bubbles.

15
 Figure 9: Circulating Fluidized Bed Gasifier

IV. Fluidised bed –Circulating

➢ The advantages of a circulating bed are as follows,
o Highly capable for rapid reactions.
o Can withstand high heat transport rates due to presence of high
heat capacity material of the bed.
o High conversion rates are possible with minimal tar formation and
unconverted carbon.
➢ The disadvantages of this process are,
o Prone to temperature gradients in the direction of the solid flow.
o High velocities of particles may result in equipment erosion.
o Heat transfer less efficient than bubbling fluidized bed [12].

16
 Production of Ethylene:

Figure 10: Thermochemical Conversion process

17
Process description:
The thermochemical design is illustrated in Fig. 1 and uses woody
feedstock namely oak, redwood. Wood chips instead of corn stover are converted to
ethylene and other higher aliphatic hydrocarbons though a series of solid and gas-
phase reactions. The following steps explains the process,

1) Wood chips are brought to the plant and then screened, milled as shown in the
feed prep and dried using a drier.
2) The dried wood is then gasified using a gasification process called MILENA
developed by the Energy research centre of the Netherlands (ECN). This
process uses an indirect gasification system with a bubbling fluidized bed.
3) Biomass char and a small slipstream of unreformed synthesis gas are
combusted and this heat is transferred to the gasifier through the circulation of
hot sand called olivine between the two process vessels.
4) The crude synthetic natural gas (syngas) is primarily composed of CO, H2, CO2,
CH4, tar, and water. The tar is a mixture of compounds extensively consists of
laevoglucose, furan derivatives and phenols including benzene, which are then
separated from the raw syngas using a fluidizeable tar reforming catalyst.
5) The de-activated tar reforming catalyst is then separated from the effluent
syngas and regenerated on-line similar to fluidized catalytic cracking (FCC)
technology used in petroleum refining.
6) The hot syngas is then cooled through a series of heat exchange as shown in
the fig.1 by using a quencher and then undergoes water scrubbing steps. The
scrubber removes impurities such as particulates and residual tars. This
scrubber water is sent for a primary treatment onsite to recover a portion of the
quench water, while the rest is sent offsite for further wastewater treatment.
7) The cooled syngas is compressed to about 435 psi before it enters an amine
unit to remove a majority of the acid gases present such as the CO2 and H2S.
The CO2 is vented to the atmosphere whereas the sulphur is captured in its
elemental form using a Klaus-like unit called, LO-CAT.
8) The cleaned and conditioned syngas is further compressed for the required
synthesis pressure and sent through a fixed-bed reactor compromising an
unsupported cobalt-manganese-based catalyst (Fischer-Tropsch) to
synthesize the first product stream comprising of a variety of mixed aliphatic
hydrocarbons, primarily ethylene and propylene.
9) After synthesis, the hydrocarbons are cooled and condensed away from the
remaining unreacted syngas. This unreacted syngas is recycled to the tar
reformer while the condensed hydrocarbons undergo a series of distillation and
purification to recover pure ethylene and propylene.
10) Firstly, a depropanizer is used to split the first product stream into the second
and the third streams. The second product stream compromising of the
overheads, lighter aliphatic hydrocarbons with two or less carbon atoms,
whereas, the third stream consists of higher aliphatic hydrocarbons.

18
 11) Then the overheads, lighter compounds undergo further multiple distillation
processes (demethanizer and de-ethanizer) till the production of pure ethylene,
pure propylene and other lighter hydrocarbon streams. This impure mixture of
lighter hydrocarbons primarily of hydrocarbons with 3 or less carbon atoms are
recycled to the synthesis reactor in order to boost the yields of ethylene and
other higher aliphatic hydrocarbon yields.
12) Finally, the third stream which is the bottom, heavier product from the
depropanizer is sent to a fixed bed reactor containing the second catalyst
composition to form the fourth product stream. This second catalyst
composition is an olefin metathesis catalyst suitable for converting 1-butylene
and 1-hexene into ethylene and propylene.
13) This fourth product stream undergoes a separation process to extract BTX
(benzene, toluene and xylene). The BTX is sent to the tar reformer whereas the
stream with propylene and ethylene is fed back to the first product steam into
the depropanizer.
14) The pure propylene (C3H6) is then sold as a co-product based on an assumed
fuel value ($3.16/gallon). In the design above, the steam cycle is integrated
throughout the process while driving compressors and generating electricity as
Well [13].

MILENA Indirect Gasification:

The MILENA indirect gasification process is highly suitable for conversion of
woody biomass into sustainable Synthetic Natural Gas or syngas (SNG) due to its high
efficiency. SNG has the same properties as conventional natural gas and can be used
to replace natural gas in all applications.

According to ECN the working of Milena is explained in detail. As illustrated in

fig 2, the feed that is the woody biomass is fed into the gasifier riser. A small amount
of superheated steam is injected from below. This gasifier consists of a hot bed made
up of sand or olivine (0.2 – 0.3 mm), maintained at a temperature of 925°C. This bed
material heats the biomass to 850°C in the gasifier section, degasifying and partially
converts the biomass into gas. This unreformed syngas from the biomass creates a
vertical velocity over the length of the gasifier riser to approximately 6 m/s. This vertical
velocity is found to increase along the riser creating a turbulent carrying together the
bed material and the degasified biomass particles known as char. This vertical velocity
of the gas loses its momentum in the top chamber of the gasifier called the settling
chamber, resulting in the separation of larger solids (bed material and char) from the
gas and fall down into the downcomer. The producer gas exits the reactor from the top
and is sent to the cooling and tar reformer section. The typical residence time of the
gas is several seconds.

19
 Figure 11: Milena Gasifier

The combustor acts as a bubbling fluidized bed (BFB). The downcomers

transport bed material which is hot sand and char from the gasification section into the
combustor where the heavier particles like dust, tar and char are burned in the
presence of air to heat the bed material to approximately 925°C. The raw syngas is
then sent to the coolers and then the cyclones and tar reformers [14].

Tar reformer:
This reformer uses catalytic breaking up of tar. The type of catalyst used is
based up on nickel. In general, the composition of Ni-based catalysts consists of an
active catalyst, promoter, and support. The Ni element is the active site of the catalyst.
The promoter increases activity and stability, while the support gives a high surface
area, durability, and coking resistance. Example of such composition, Ni as the active
catalyst, Mo as a promoter and y-Al2O3 as a support, this composition effectively works
at a temperature range between 250–650 ̊C and has a high Benzene selectivity over
Ni-Mo catalyst. From studies, it is proved that steam reformed catalysts are highly
effective in eliminating heavy tar with a destruction efficiency greater than 99%. Tar
compounds majorly comprises of three compounds namely levoglucosan, furan
derivatives and phenols as shown in figure 7 [15] [16].

Figure 12 [17]: Levoglucosan Furan Phenol

20
LO-CAT-Liquid Oxygen Catalyst:
This process is used to convert H2S to an elemental sulphur. This process takes
place by using two vessels as shown in figure 8, namely an absorber and an oxidizer.
The absorber vessel using an iron based catalyst to convert the sour gas into a sweet
gas through one pass, whereas the oxidiser is used for two purposes,

• To regenerate the spent catalyst.

• And finally to concentrate the sulphur particles into a slurry.

This slurry is then filtered, washed and are made into elementary sulphur cakes. Thus
this process does not use or produce any hazardous chemicals [18].

Figure 13: LO-CAT process.

Fischer-Tropsch synthesis:
Fisher-Tropsch(FT) synthesis is the process of converting syngas into aliphatic
hydrocarbons using metal catalysts. In this process, H2 and CO present in the syngas
is converted hydrocarbon product stream. The most common metal catalyst used in
this reaction are based on metals such as iron, cobalt, nickel and ruthenium.
Generally, Ni catalyst are comparatively more selective for the production of methane,
where Co catalyst is more selective for hydrocarbons with two or more carbon atoms
and supress the CH4 selectivity. Moreover, from several research it is found that the
selectivity of C2+ hydrocarbons can be increased by the following,

➢ Decreasing the ratio of H2:CO in syngas

➢ Decreasing the reactor pressure and temperature.

Although this reaction is highly suitable for production of hydrocarbons, this F-T
synthesis process in a general term bears a disadvantage which is the production of
a mixture of desired products [19]. In this study, the first catalyst composition used is
an unsupported cobalt catalyst in a FBR. The composition of the catalyst obtained
from a research patent is given as follows:

21
 CoMnaLabPcMdOx, where,
o M stands for elements selected from the group consisting of alkali
metal, alkaline earth metal and transition metal.
o a is about 0.8 - 1.2;
o 0 < b (and/or) c is < 0.005;
o d is 0 - 0.005; and
o x is a number determined by the valence requirements of the
other elements present [20].

Olefins Metathesis Catalysis:

Metathesis catalysis is a process needed to produce ethylene and propylene
from higher aliphatic hydrocarbons such as 2-butene and ethylene. Metathesis is
defined as a catalytic reaction where exchange of the double bonds occurs among a
group of molecules. This is further demonstrated by the reaction of 2-butene and
ethylene when the double carbon bond swapped with one another. Hence, new carbon
bonding takes place, yielding two propylene molecules. The catalyst composition used
in the industry generally consists of oxides of transition metal oxide group, such as
tungsten, rhenium and molybdenum [30]. Besides that, the transition metal catalyst
can either be supported or unsupported. Suitable examples of supports are silica,
alumina, titania, zirconia. In this process a catalyst suitable for the selectivity of
ethylene over propylene must be used. Henceforth, a catalyst made up of tungsten
oxide is used with caesium as a promoter. This catalyst is supported preferably by
inert silica. Whereas on the other hand, magnesium oxide can be used as a support
to tungsten catalyst for the production of propylene. Besides that, the process is
profitable by the acidity of the selected catalysts. This can be improved by treating the
catalyst with an inorganic or organic acid. The favourable operating conditions for the
entire process of olefins catalysis include temperature ranging from 100 – 600oC and
pressure ranging from 0 psig to 200 psig.

22
Economic Evaluation of Ethylene Production:
The evaluation of ethylene production from biomass via gasification process is
conducted throughout the detailed modelling. The current design technologies used
for this literature report have been commonly used in the commercial industries with
detailed known information. Assuming that the ethylene plant operates at an annual
rate of 7000 hours accounting the cost for the labour, start-up, and plant shut-down.
Besides that, tax rate should be included into the account due to tax laws imposed by
the government. The tax income is taxed at a flat rate of 25% in the Netherlands as
the plant is built in Netherlands. The calculations steps are estimated based on the
literature reviews and the approximate costs of the equipment and the operating cost.

Based on the number of equipment used for the gasification process of

biomass, it is assumed that the plant operates at a large-scale industry. This include
the major and minor including compressors, pumps, and heat exchangers. The price
of redwood biomass in the current market is 600 USD per cubic metre (Alibaba.com).
This is necessary to determine the feasibility of the process operation. The product
obtained from the gasification process until olefins metathesis reaction is ethylene and
propylene. The ethylene is the main product and it is used as a commercial product
for market demand, whereas the propylene is produced as a by-product and can be
used for added profit for the investors. The price of ethylene in July 2017 done by
pricing forecast is approximately 950 USD per metric ton of ethylene. This information
is extracted from the graph that is shown below:

1200
1150
1100
1050
($/mt)

1000
950
900
850
800

Figure 14: Cost of ethylene from August 2016 to July 2017 [39]

Based on the graph shown above, the value of ethylene fluctuates monthly, the lowest
value being 840 USD per metric ton and highest value being 1100 USD per metric ton
of ethylene.

23
 The type of gasifier chosen for this process is known as MILENA gasifier. The
data and specifications of the process vessels is not known as well as other minor
equipments. The estimations of the equipment cost are calculated taken into account
as the current price in the market, and the income tax that is 25%. Table below shows
the cost estimation of the equipments:

Equipment Price (2017) (Euro)

Grinder 18,667.90
Dryer 60,039.29
Gasifier 44,261.69
Char combustor 50,274.58
Heat exchanger 2,969.76
Tar reformer 61,937.63
Catalyst regeneration chamber 6,788.03
Quencher 2,121.26
Scrubber 40,827.44
Syngas compressor 71,077.40
Amine absorption column 668,682.45
Gas compressor 71,077.40
Mixed alcohol synthesis reactor 12,121.69
Gas/alcohol separation chamber 33,124.22
Depropanizer 665,453.85
FBR 59,365.08
Multi-distillery column 1,381,796.08
Ethylene storage tank 5,180.46
Propylene storage tank 3,129.64
Condenser 25,081.76
Reboiler 5,072.54
Reflux drum 25,992.24
Total Equipment Cost 3,315,042.39
Table 4: Estimated Cost of Process Equipment [40]

The costing is done through estimation as the data for the detailed calculation
of the equipment costing and the subsequent calculation of the capital cost is absent.
Researches are done through reputable online market website such as Alibaba. This
shows that the amount of profit made from the sales of ethylene and propylene should
be higher than the investment made for the purchase of equipment.

24
 The analysis of ethylene sensitivity towards the market industry is done to
ensure future profit of the investors. This could include aspects such as Return on
Investment (ROI), and Pay Back Period (PBP). However, PBP and ROI could not be
calculated due to the absence of mass and energy balance data. Based on further
literature research, the optimum value for ROI and PBP in chemical plants are 30%
and 4 years. Price of ethylene and propylene could impact the market price within five
to ten years. This is indicated by the amount of ethylene demand forecast increasing
gradually within the selected timeframe. The graph below is extracted from a literature
review:

90
Million Metric Tons, Ethylene

80
70
60
50
40
30
20
10
0
10 11 12 13 14 15 16 17 18 19 20
Year

Domestic Derivation Ethylene Demand Net Equivalent Imports (Exports)

Figure 15: Production of Ethylene from year 2010 to 2020

Based on the graph shown above, the expected production of ethylene in year
2020 is 80 million metric tonne. Changes occur from time to time due to the fluctuation
in the market price of feedstock used (biomass), and changing of equipment prices
from different vendors. However, it is noted that the amount of ethylene produced in
year 2017 is 65 million metric tonne. This is appealing for the investors seeking huge
profit from the investment on biomass and ethylene production industry. Beyond the
year 2020, there is an expected rise in the feasibility of ethylene project due to the
increase in demand of the ethylene. Therefore, this project is feasible for the investors.

Results & Discussion:

Maximisation of Bio-ethylene:
The processes used to enhance the yields of ethylene are as follows,

• Reasons for the use of MILENA gasifier:

a) Firstly, due to the nature of the gasifier used, which is an indirect
bubbling fluidized bed gasifier. This type is used to produce better yields
of SNG and this can be explained by using the figure below,

25
 Efficiency
80% 70% 67%
64%
54% 58%
60% 53%

Efficiency
40%

20%

0%
Entrained Flow CFB Indirect
System

BioSNG BioSNG and net power

Figure 16: Gasifiers Efficiencies for Bio-Syngas [14].

b) Secondly, as regarded in the research paper above, in order to increase

the yield of ethylene the H2:CO ratio must be maintained low and this is
explained by using the figure 12.

Chart Title
H2
CO 22% 30%
C6Hy
14%
C2Hy
N2 27%

CH4
1%
CO2 1%
5%

Figure 17: Pie Chart of Biomass [14].

• Advantages of using a FBR:

In order to enhance the yield of ethylene it is known that the catalytic reactor
must be able to perform using low pressure and temperature. Thus the process
reactor used requires just a temperature of about 150-350°C and uses a
pressure between the atmospheric and 5 MPa.
• Benefit of olefin metathesis reaction:
It is regarded that when a catalyst such as the Fischer-Tropsch is used, a
disadvantage is produced which is the formation of several undesired products.
Due to this reason the process of olefin metathesis catalysis is used in order to
convert the unwanted higher aliphatic hydrocarbons into the desired product
that is ethylene. Thus, resulting in a higher yields of ethylene.

26
 Catalysts selection:
Process Catalysts Advantages Disadvantages
Fischer- 1. Cobalt • Absence of nitrogenous • The reaction is
Tropsch • Highly active compounds in the exothermic (Heat is
• Feedstock is product stream. removed from the
natural gas system).
• able to operate • Higher selectivity for C2
at a lower hydrocarbons.
pressure
• yield less olefins

2. Nickel • Relatively low • Catalysts deactivate

• Favours concentration of sulphur at a faster rate
methane content in the product compared to other
formation stream. processes.
• Catalysts have
too high
hydrogenolysis
activity

3. Iron • The energy stored

• Suitable for low (Cetane energy) is 80% • The composition of
hydrogen higher than required for the feedstock
content petrochemical diesel changes.
synthetic gases fuel.
• Lower feedstock
quality, biomass
or coal

4.Ruthenium • Excellent methanation

• Very Expensive catalyst at high • Costly as synthetic
• Rarely used in temperatures. gas cleaning is
Fischer-Tropsch • Most active when pure. required.

Table 5: Advantages and Disadvantages of Fischer-Tropsch Mechanism [19].

Process Catalysts Advantages Disadvantages

Metathesis Olefins 1. Magnesium oxide • Produces fewer • Frequent plant
undesired by- shutdown due
products to increase in
compared to system
other organic pressure drop
reactions
• Metathesis
• Olefins in catalyst
2. Tungsten oxide general are including
relatively cheap tungsten oxide

27
 breaks down
• The mechanism easily
3. Molybdenum oxide of the process is
not complex

•
Olefins
metathesis • Tolerance to
4. Rhenium oxide reactions can be functional group
performed on is limited
larger scales
Table 6: Advantages and Disadvantages of Olefins Metathesis Process [19]

Impact of bio-ethylene within Polyester Value Chain:

The final research question of the report is ‘What is the impact of ethylene
derived from woody biomass within the polyester value chain?’. To answer this
question, a series of continuous research have been done to obtain sufficient
information that has high validity. Based on the research conducted, we must first
derive the term polyester value chain. So polyester chain is functioned to produce
plastic bottles, and fibres. Polyethylene Terephthalate (PET) is mainly produced from
the reaction known as continuous polymerisation of terephthalic acid and ethylene
glycol. As there is major concern involving the future of polyester value in the industries
due to global environmental impact, sustainable routes were proposed. This include
using biomass as a feedstock instead of natural gas for the production of ethylene.

This route effectively reduces the greenhouse gas emission and requires
minimal changes to current technologies. The impact of ethylene on the polyester
value chain occurs on economy and environment. This can be identified using Life
Cycle Assessment (LCA). LCA is commonly used to identify the environmental
impacts using ethylene as a product via biomass feedstock. Diagram below shows an
overview of the steps involved in the production of polyester using crude oil and
biomass feedstock:

Figure 18: Life Cycle Assessment of Polyester Value Chain [35]

28
 The polyester value chain consists of step-by-step method in which the first
stage involves continuous polymerisation as explained in the above paragraph. The
second stage involves solid state polymerisation process due to higher molecular
weight of the PET in a bottle compared to the fibre products, usually in a mass of 23.5g
[34]. Furthermore, the next step in value chain is the process of injection and stretch
blow moulding. This is defined as moulding into preforms prior to stretch blow to make
multiple bottles for the purpose of distribution. One of the impact shown by ethylene is
increase in biomass usage and reduction in natural gas feedstock. This reduction
accounts for 16% of the fossil fuel usage. This is an advantage of ethylene due to the
small energy requirement, therefore subsequently decreasing the potential effect of
global warming during conversion of ethanol to ethylene. However, the net energy
efficiency is lower in conversion of biomass to ethylene. Besides that, the amount of
land required for the biomass wood could affect the ecosystem [35

In addition, Substantial profit is accessible through the production of ethylene from

woody biomass. This could lead to positive production of PET bottle that results in
39% reduction in fossil fuel energy use, and approximately 14% reduction in global
warming probability. This further creates emphasises on renewable alternatives for
fossil energy sources in chemical industries [31].

Conclusion:
Production of chemicals from biomass through pyrolysis has been a technique of the
past until the discovery of petroleum refining techniques resulting in a change of feed
for those production processes. With increasing awareness of the public and scientific
sector regarding the pollution caused by non-biodegradables has led to tremendous
growth in research to produce bio-based alternatives for chemicals produced from
petroleum feedstocks. The research paper focuses on an alternate method of
producing raw materials for the production of polyester. The alternative method is an
advanced and modified process of pyrolysis called gasification. The production
method studied in this paper is highly environmental friendly because it uses wood as
a fed to produce ethylene, a product predominantly obtained from processing of crude
oil. These woods can also be unwanted or wasteful wood that might have ended in a
landfill. Ethylene production from biomass has seemed to face a tough competition
from the crude oil derived ones because the cost of production is significantly high as
compared to the latter mainly because of the quantity produced. Although by the use
of a second reactor comprising of olefin metathesis catalyst for further conversion of
ethylene from higher aliphatic hydrocarbons have proved significantly to improve the
quantity produced. Thus concluding that the process described in the research paper
to be both beneficial and economical.

29
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