FEDERAL UNIVERSITY OF TECHNOLOGY,

PMB 1526
OWERRI

CHE 505/510: RESEARCH PROJECT REPORT

ON

PRODUCTION OF ETHYLENE FROM BIO-ETHANOL

USING ZEOLITE COMPOSITE CATAYSTCATALYST
FROM LOCALLY-SOURCED CLAY

DONE BY

AGHA JOSEPH I.
REGISTRATION NUMBERO.

20091640383
SUPERVISED BY

ENGRMR. I.SIOMA J. OKOLIE

SUBMITTED TO

THE DEPARTMENT OF CHEMICAL ENGINEERING,

SCHOOL OF ENGINEERING AND ENGINEERING TECHNOLOGY (SEET)

FEDERAL UNIVERSITY OF
PMB 1526

TECHNOLOGY, OWERRI
1

IN PARTIAL FUFILLMENTFULFILLMENT OF THE

REQUIREMENTS FOR A BACHELOR S DEGREE IN CHEMICAL
ENGINEERING (B.ENG)

OCTOBER,OCTOBER 2014

CERTIFICATION
This is to certify that the work, PRODUCTION OF ETHYLENE FROM BIOETHANOL USING ZEOLITE COMPOSITE

CATAYSTCATALYST

FROM

LOCALLY-SOURCED CLAY presented in this report is the original work of

AGHA

JOSEPH

IFEANYICHUKWU,

with

registration

number

20091640343. The project was carried out by Chemical Engineering

Project Group 10 of the 2013/2014 academic session, including:
AGHA

JOSEPH

IFEANYICHUKWU

(GROUP

LEADER)
20091640383
JONNWAKALO

OKECHUKWU
20091640723

C. (ASST. G.L.)
20091641133
UDENSI CHIKA JOSEPH
20091640653
EZEILO ONYEDIKA S.
20091640903
OGUIKE

TOBECHI

MARY20091690303

AGNES
20091663713
EKWEM

PATRICIA

OGOCHUKWU
NNAMANI NDUBUISI M.

MENGR. I.SIOMA J. OKOLIE

(PROJECT SUPERVISOR)

SIGNATURE/DATE

ENGR. DR. M. S. NWAKAUDU

(HEAD OF DEPARTMENT)PROF.
KENNETH OKPALA
(PROJECT CO-ORDINATOR)

SIGNATURE/DATE

SIGNATURE/DATE

PROF. E. E. ANYANWU
(DEAN OF S.E.E.T.)

SIGNATURE/DATE

PROF. E. O. EKUMANKAMA
(EXTERNAL
EXAMINER)ENGR.
DR. M. S. NWAKAUDU
(HEAD OF DEPARTMENT)

SIGNATURE/DATE

SIGNATURE/DATE

PROF. E. E. ANYANWU
(DEAN OF S.E.E.T.)

SIGNATURE/DATE

DEDICATION
I dedicate this piece entirely to the Almighty God and my Sweet Mother.

ACKNOWLEDGEMENTS
I wish to acknowledge the Head of Department, Chemical Engineering
Department in the Federal University of Technology, Owerri, Engr. Dr. M. S.
Nwakaudu for his efforts at tending to the welfare of students of this project
group throughout the course of our work.

I wish to also express sincere appreciation to our Supervisor, MrEngr. I. J.

Okolie, for his overwhelming support, advice and tremendous help in
making this research project a success.
I acknowledge the efforts of all the lecturers of the chemical engineering
department for their relentless efforts at imparting valuable knowledge
throughout these years, which has formed the basis for the aptitude
employed in this work.
Greatest acknowledgement goes to my mother, Mrs. Agha Chinyere Bridget,
who has spared nothing to give me everything. Your efforts will never be in
vain, God bless you.
I wish to express sincere appreciation to our Supervisor, Engr. I. J. Okolie, for
his overwhelming support, advice and tremendous help in making this
research project a success.
I cannot fail to acknowledge the support and contributions of all my
colleagues in providing the required intellect for executing this project
workfor their dedication and co-operation towards making this project a
success.

ABSTRACT
Increasing fossil fuel prices and concerns over greenhouse gas (GHG)
emissions have now focused the attention

of recent research and

development efforts on renewable feedstock for ethylene production as

against production based on petroleum-based feedstock. As a consequence,
bio-ethanol obtained from various biomass has been considered as an
attractive precursor of ethylene due to its technical and economic potential.
This process is enhanced by the use of an efficient catalyst ranging from
organic acids to solid desiccant catalysts Zeolites. In this reportwork,
experiments were carried out using a simple laboratory-scale setup, to
observe the effects of a locally-synthesized composite zeolite catalyst in the
dehydration of a bio-ethanol batch. Reaction conditions were monitored with
a view to establish micro-kinetic behavior of the reaction, however, within
the limits of available equipment, only mostly the macro-kinetics were
investigated. In the experiments conducted, the formation of ethylene was
confirmed by the de-colorization of bromine water, and the attendant
increase in the volume of bromine water due to dissolved ethylene. A
characteristic pungent smell also confirmed the presence of diethyl-ether, a
5

side-product of this reaction. These results reassures the potential of the

catalyst used for industry-scale alcohol dehydration processes.

TABLE OF CONTENTS
COVERPAGE
CERTIFICATION
DEDICATION
ACKNOWLEDGEMENTS
ABSTRACT
TABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES

i
ii
iii
iv
v
vi
vii

CHAPTER ONE: INTRODUCTION

1.1 Background
1.2 Problem Statement
1.3 Aim of Study
1.4 Justification of Study
1.5 Scope of Study

1-3
4
4-5
5
5

CHAPTER TWO: LITERATURE REVIEW

2.1 Background of Ethylene
2.2 Methods of Ethylene Production
2.3 Ethylene from Bio-Ethanol
2.4 Polymer Grade Ethylene
2.5 Applications of Ethylene
2.6 Commercial ETE Plants and Research Activities

6
6-13
13-27
28-29
29-31
31-33

CHAPTER THREE: MATERIALS AND METHODS

3.1 Materials Required
3.2 Preparation Methods

34-36
36-40

CHAPTER FOUR: RESULTS AND DISCUSSION

4.1 Results and Outcomes
4.2 Discussion/Analysis

41-43
43-49

CHAPTER FIVE: CONCLUSION AND

6

RECOMMENDATIOINSRECOMMENDATIONS
5.1 Conclusion
5.2 Recommendations
REFERENCES
APPENDICES

50-51
51-52
vii-ix
x

LIST OF TABLES
Table 1.1:

Summary of the physical properties of pure Ethylene

Table 2.1:

Summary of the Properties of Different Catalysts Used for the

Production of Ethylene from Ethanol

Table 2.2:

Operating Condition and Product Composition of Lummus

Technology

Table 2.3:

Typical Composition of Polymer Grade Ethylene

Table 4.1:

Table of Results for Trial 1

Table 4.2:

Table of Results for Trial 2

LIST OF FIGURES
Figure 2.1: Flow Diagram of an Ethylene Production Plant Using Liquid Feeds
Figure 2.2: Ethylene Product Yield at Using Different Feedstocks
Figure 2.3: Process Flowscheme of MTO Process
Figure 2.4: Laboratory Set-Up for the Production of Ethylene
Figure 2.5: Process Description for Industrial Production of Ethylene from
Ethanol
Figure 2.6: Basic Structure of Zeolites
Figure 2.7: Process Flow Diagram of Lummuss Fluidized ETE Process
Figure 2.8: Process Flow Diagram of Halcon Scientic/Chematur Engineering
Figure 2.9: Process Flow Diagram of SINOPECs ETO Process
Figure 2.10:

Block Diagram of Petrobrass Co-processing Process

Figure 2.11:

Ethylene Column and Striper Section

Figure 3.1: Sieve Shaker with Sieve Trays (75m & 106m)
Figure 3.2: Weighing Balance
Figure 3.3: Hotplate Stirrer
Figure 4.1: Volume of Ethylene produced verses time graph for temperature
range (310-350oC)
8

Figure 4.2: Volume of Ethylene produced verses time graph for temperature
range (310-320oC)

CHAPTER ONE
INTRODUCTION
1.1 BACKGROUND
Ethylene is the primary component in most plastics, making it economically
valuable. It is produced primarily by steam-cracking of hydrocarbons, but can
alternatively be produced by the dehydration of ethanol, which can be produced
from fermentation processes using renewable substrates such as glucose, starch
and others. Due to rising oil prices, researchers now look at alternative reactions
to produce green ethylene, but the process is far from being as economically
competitive as using fossil fuels. Many studies have investigated catalysts and
new reaction engineering technologies to increase ethylene yield and to lower
reaction temperature, in an effort to make the reaction applicable in industry and
most cost-efficient.
In addition to the crude oil issues, the technologies used for ethylene production
have significant impact on the environment. Steam cracking is the most energy
consuming process in (Placeholder1) the chemical industry and it currently
accounts for approximately 180 to 200 million tonnes of CO emissions worldwide
(Neelis et al., 2006 (Neelis et al., 2006) (Neelis et al., 2006)). Goals to develop
alternative routes for ethylene production which have favourable energy
consumption and greenhouse gases emission have been brought up. In a
nutshell, from both environmental and economic perspectives, it is therefore of

interest to study alternative sources for ethylene production as well as energy

saving potentials offered by alternative processes.
Catalytic dehydration of ethanol to ethylene, called Ethanol-to-Ethylene (ETE)
was first reported since 1979 (Morschbaker, 2009)(Morschbacker, 2009). This
process utilizes ethanol as feedstock which is obtained through fermentation
process using agricultural products such as sugarcane, corn and biomass.
Compared to the petrochemical equivalent, the main advantages of bio-ethylene
are that it can reduce greenhouse gas lifetime emissions and the dependence of
the chemical industry on fossil-fuels (Neelis et al., 2006).
An efficient catalyst is the key technology to the industrialization of dehydration
of microbial ethanol to ethylene. Reported catalysts for ethanol dehydration
include silica alumina (Roca et al., 1969)(Roca et al., 1969), activated alumina
(Kojima et al., 1981)(Kojima et al., 1981), heteropolyacid (Ali et al., 2010), and
zeolites (Mao et al., 1987).
Catalysts based on activated alumina (zeolites) are the most important kind of
catalyst for bio- ethanol dehydration, and are the catalysts dominantly used in
current

industrial production. Scientific Design/Chematur has developed an

improved alumina catalyst, Syndol which having has a main composition of Al2O3
MgO/SiO2. It offers high productivity that allows a reduction of total reactor
volume (Chen, 2010). Besides, it has high yield conversion and selectivity which
leads to better utilization of the ethanol feed and less by-products formation. The
most important issue is Syndol catalyst has high resistance to deactivation

and thus, it permits longer runs of operation (Chematur Engineering Group,

n.d.2011).
Zeolite catalyst of HZSM-5 is also preferred as its activity and selectivity are the
highest among the other catalyst at the lower temperature. It gives almost 100 %
of ethanol conversion and ethylene selectivity (Chen, 2010).
1.1.1 PROPERTIES OF ETHYLENE
Ethylene has four hydrogen atoms bound to a pair of carbon atoms that are
connected by a double bond. All six atoms that comprise ethylene are coplanar.
The molecule is also relatively rigid: rotation about the

CC

bond is a high

energy process that requires breaking the -bond. The -bond in the ethylene
molecule is responsible for its useful reactivity. The double bond is a region of
high electron density, thus it is susceptible to attack by electrophiles. Many
reactions of ethylene are catalyzed by transition metals, which bind transiently to
the ethylene using both the and * orbitals.
Property

Value

Molecular weight (g/mol)

28.05

Critical temperature (oC)

9.5

Critical pressure (atm)

50.5

Boiling point (oC)

-104

Melting point (oC)

-169.2

Gas Density @ 21 (oC) 1 atm (kg/m3)

1.169

Specific Volume @ 21 (oC) 1 atm (kg/m3)

219.45

Specific Gravity

0.992

Specific Heat @ 70 oF (Btu/lbmol -oF)

10.28

Table 1.1: Summary of the physical properties of pure Ethylene (Air

Products Inc., 2014)
3

CHEMICAL PROPERTIES OF ETHYLENE

Ethylene is an extremely important building block in the petrochemical
industry. It can undergo many types of reactions that generate a large
number of chemical products. Some of its major reactions include
polymerization, oxidation, halogenation and hydro-halogenation,
alkylation, hydration, oligomerization, and oxo-reactions.
P1.2 PROBLEM STATEMENT
For catalytic reactions, development of an effective catalyst is the foundational
and critical step. We hope to achieve the production of renewable ethylene from
ethanol with locally sourced catalyst as compared with ethylene from fossil fuel
with imported catalyst used in the industry.
1.3
AIM OF STUDY
The objectives of this thesis are summarized in the following outlines:

To study the dehydration of bio-ethanol to produce ethylene;

To study the influence of locally-sourced zeolite catalyst for the dehydration

process;

To operate a laboratory-scale of the process and establish the ability of the

catalyst to foster the formation of ethylene by means of simple tests for
olefins;

To closely monitor, and hence optimize the dynamics of process parameters

such as temperature, pressure, quantity of catalyst, etc., to produce
ethylene closely to its maximum possible rate; and

Possibly explore the prospects of expanding the process from the

experimental-scale to industry-scale.
4

1.4

JUSTIFICATION OF STUDY

Ethylene is currently the most consumed intermediate product in the world. In

2009 it was estimated that the world demand for ethylene was over 140 million
tons per year, with an approximate yearly increase of 3.5%. One of the most
important uses of ethylene is the production of polyvinyl chloride (PVC).
currently serves over 70% of the construction market.

PVC

This includes plastics,

dominating pipe and fittings, widows, siding, decking and fencing. In addition,
PVC serves 60% of the wire and cable plastics market and 25% of the coatings
market. This increase in demand for ethylene as a petrochemical feedstock and
consequently in the economic gains are a strong motivation for studies into the
development of efficient technologies capable of providing ethylene, and hence
this project. The viability of this project is also prompted by the availability of the
raw resources required to synthesize the zeolite catalyst in use.

1.5

SCOPE OF STUDY

Catalyst would be prepared by reduction to appropriate size.

Arrangement of the appropriate experimental setup.

Catalytic dehydration of Ethanol to Ethylene using the zeolite catalyst.

Collection and analysis of various products of the reaction

CHAPTER TWO
LITERATURE REVIEW
2.1 BACKGROUND OF ETHYLENE
Ethylene is a high demand product because it is an essential raw material in the
production of plastics, in particular low and high density polyethylenes and PVC.
In the US alone, the yearly demand is approximately 5MM tonnes of ethylene.
Traditionally, ethylene is produced by cracking of heavy hydrocarbons from fossil
fuels. In fact, in the 1960s this process was so profitable that ethylene was used
to produce ethanol in the reverse of the process used by this plant. However, a
worldwide oil crisis in 1973 raised petroleum prices making cracking a much less
economically reasonable method of ethanol production. Since plastics remain in
high demand, ethylene production via ethanol is being explored again.
2.1.1 PROPERTIES OF ETHYLENE
Ethylene has four hydrogen atoms bound to a pair of carbon atoms that are
connected by a double bond. All six atoms that comprise ethylene are coplanar.
The molecule is also relatively rigid: rotation about the
6

CC

bond is a high

energy process that requires breaking the -bond. The -bond in the ethylene
molecule is responsible for its useful reactivity. The double bond is a region of
high electron density, thus it is susceptible to attack by electrophiles. Many
reactions of ethylene are catalyzed by transition metals, which bind transiently to
the ethylene using both the and * orbitals.
The properties of ethylene are summarized in Table 1.1
Table 1.1: Summary of the physical properties of pure Ethylene (Air Products
Inc., 2014)
Property

Value

Molecular weight (g/mol)

28.05

Critical temperature (oC)

9.5

Critical pressure (atm)

50.5

Boiling point (oC)

-104

Melting point (oC)

-169.2

Gas Density @ 21 (oC) 1 atm (kg/m3)

1.169

Specific Volume @ 21 (oC) 1 atm (kg/m3)

219.45

Specific Gravity

0.992

Specific Heat @ 70 oF (Btu/lbmol -oF)

10.28

CHEMICAL PROPERTIES OF ETHYLENE

Ethylene is an extremely important building block in the petrochemical industry. It
can undergo many types of reactions that generate a large number of chemical
7

products. Some of its major reactions include polymerization, oxidation,

halogenation and hydro-halogenation, alkylation, hydration, oligomerization, and
oxo-reactions.
2.2 METHODS OF ETHYLENE PRODUCTION
There are a number of established processes for the production of ethylene, both
industrially and locally. Some of these processes are discussed in the following
sections:
2.2.1 STEAM CRACKING
Steam cracking of hydrocarbons has been the major source of light olefins
production for more than half a century. The following chemical reactions are
some of the processes involved in steam cracking to ethylene.

The current feedstocks for olefin production are derived from crude oil and
natural

gas

such

as

naphtha

and

ethane.

The availability of feedstock

depends on the composition of crude oil and natural gas and their production
volume (Rahimi & Karimzadeh, 2011). For instance, steam cracking of light

naphtha produces about twice the amount of ethylene obtained from steam
cracking of vacuum gas oil under nearly similar conditions.
The typical process of steam cracking is shown in Figure 2.1 below. Generally,
liquid feed are cracked with lower residence times and higher steam dilution
ratios than those used for gas feedstocks. Besides, maximum olefin yields can be
obtained at lower hydrocarbon partial pressures, pressure drops, and residence
times for liquid feeds (Matar & Hatch, 2000). Cracking process operated at higher
severity increases the ethylene product and by-product methane and decreases
propylene and butylenes.

Figure 2.1: Flow Diagram of an Ethylene Production Plant Using Liquid

Feeds
[Source: Matar & Hatch, 2000]

Generally, liquid feed are cracked with lower residence times and higher steam
dilution ratios than those used for gas feedstocks. Besides, maximum olefin
yields can be obtained at lower hydrocarbon partial pressures, pressure drops,
and residence times for liquid feeds (Matar & Hatch, 2000). Cracking process
operated at higher severity increases the ethylene product and by-product
methane and decreases propylene and butylenes.
The largest energy component is the heat used in cracking which is necessary to
provide the heat of reaction and the sensible or latent heat to bring the reactants
to the desired reaction temperature of 750 C to 900 C (Gielen et al). It accounts
for 40 % of the total energy consuming every year in the entire petrochemical
industry and results in high amount of CO2 emission (Rahimi & Karimzadeh,
2011).
In addition to high energy consumption and CO2

emission, a typical steam

cracking process which cracks the naphtha into smaller molecules in gaseous
state has a problem of coking that will cause inefficient of steam cracker (Tao, ,
2006). Great efforts have been dedicated to the researches on developing a novel
process that can overcome the deficiencies of steam cracking.
2.2.1.1

Catalytic Cracking of Naphtha

The current method of producing olefins via steam cracking of naphtha has
several drawbacks such as the high energy consumption, the deposition of coke
in the tubes, and the relatively low selectivity in ethylene from heavy feeds. This

10

leads to catalytic pyrolysis which has been studied extensively to overcome

the shortcoming of steam cracking.
Catalytic cracking is a process in which the heavy hydrocarbon molecules are
converted into lighter molecules by contacting the heavy hydrocarbon with
the zeolite catalyst. From the Table 2.3, it was noted that the ethylene yield is
lower while the propylene yield is higher in comparison with conventional steam
cracking process (Nexant, 1997).It has been established however that ethylene
yield is lower, with higher propylene yield, when the catalytic cracking process is
compared to the steam cracking process (Nexant, 2013).
The performance of a fluid catalytic cracking (FCC) unit is dependent on a large
number of parameters whichparameters that influence the conversion process in
their own way. The parameters that have been studied include the feed
composition,

residence

time,

temperature,

catalyst-to-oil

ratio

(CTO),

hydrocarbon partial pressure, catalyst properties, and riser hydrodynamics in

order to find out the optimal condition for conversion process (Dupain et al.,
2006).
There are several studies on the optimization of FCC processes. Lid and Strand
(1997) reported the implementation of on-line optimization and model- predictive
control to a residual catalytic cracking (RCC) unit. While Ellis, Li & Riggs (1998)
presented an optimization model by combining an empirical yield prediction
model for cracking products with macroscopic mass and energy balances for the
unit.

11

2.2.1.2

Cracking of Vegetable Oils

Researches on various alternative sources as crude oil substitute for ethylene

production were carried out to avoid the problems associated with crude oil.
Zamostny, Belohlav, & Smidrkai (2011) have disclosed the use of vegetable oils
which is one of the premium renewable resources as crude oil for short alkenes
production via steam cracking. Figure 2.2 shows the product yield obtained based
on different feedstocks used in steam cracking process.

Figure 2.2: Ethylene Product Yield Using Different Feedstock

[Source: Zamostny et al., 2011]
Vegetable oils form the similar products as traditional crude-oil-based feedstocks
under the condition matching with the gas oil steam cracking. Besides, the long
linear chain of vegetable oil leads to comparatively high content of ethylene as
well as propylene and butadiene in a product mixture. Since the mechanisms of
pyrolysis reactions of both the rapeseed oil and crude oil fractions are similar, it
would be possible to employ well-known hydrocarbon pyrolysis technologies to
vegetable oil cracking (Zamostny et al., 2011).
12

In addition, multiple studies regarding the topic have been published. For
instance, Bielansky et al. (2010) and Dupain, Costa, Schaverien, Makkee, &
Moulijn (2007) have studied on catalytic cracking of rapeseed oil to high octane
gasoline and light olefins. The researches again found that the vegetable oils can
be used in fuel production and

petrochemical industries and

form similar

products as traditional crude oil feedstock under the comparable operating

condition. Furthermore, the vegetable oil can be blended with the feed of an
existing FCC unit at which no synergetic effects between both feeds appear to be
present.
As a result, catalytic cracking of vegetable oil mixed with conventional FCC
feedstock is a potential alternative for increasing the share of renewable fuels in
the market. However, this alternative should be evaluated further in terms of
technical, economic viability and environmental impacts since the products
contain large amounts of aromatics (Dupain et al., 2007).
2.2.2.1 Alternative Process Technologies for Ethylene Production
A. Methanol-to-Olefins
Steam cracking and fluid catalytic cracking are unable to cover the expected
demand for propylene. Thus, new technologies such as methanol-to-olefins (MTO)
are developed due to the fact that MTO can provide a wider and more flexible
range of ethylene to propylene ratio to meet market demand.

13

Figure 2.3: Process Flowscheme of MTO Process

[Source: UOP, 2011]
According to the MTO process shown in Figure 2.3, the methanol is mainly
produced from synthesis gas which can be obtained from any source of carboncontaining materials such as natural gas, coal or biomass (George et al.,
Goeppert, & Prakash, 2009). In addition, MTO can provide much lower costs of
production and higher returns on investment than naphtha crackers and
ethane crackers.
The MTO process employs a turbulent fluid-bed reactor system at which the
coked catalyst is continuously withdrawn and burned in a regenerator to burn off
the coke formed. It gives 99 % conversion of methanol and having lower
magnitude of coke yield and catalyst circulation than in FCC (Othmer, 1999). The
MTO process is an acid catalyzed reaction of which SAPO-34 and ZSM-5 are the
most common catalysts. However, SAPO-34 was observed to be a more efficient
catalyst

in terms of activity and

selectivity for

light

olefins Since SAPO-34

seems to be a desirable catalyst for MTO, detailed research on the products

14

change with the reaction conditions applying SAPO-34 catalyst and modification
of SAPO-34 have been done.
2.2.1 LABORATORY PREPARATION

Figure 2.4: Laboratory Set-Up for the Production of Ethylene

The set-up above shows a laboratory-scale process for the production of
ethylene. Ethanol liquid soaked in mineral wool is evaporated at the bottom of
the test tube shown. The ethanol vapour stream passes through a section in the
tube containing heated catalyst, during this contact of the catalyst and the
ethanol vapour the reaction takes place, forming ethylene. The gaseous stream
leaving the reactor test tube contains the ethylene and steam produced and
some unreacted ethanol, they pass through a delivery tube to a bath of water
where water and ethanol dissolve in the water and insoluble ethylene is collected
as gas into a glass tube.
2.3 ETHYLENE FROM BIO-ETHANOL

15

The major benefit of using ethanol as the raw material for ethylene production
instead of fossil fuels is that ethanol is renewable; it can be produced from
fermentation of feedstocks such as corn or sugar cane. If the demand for
ethylene remains high while the supply of fossil fuels is diminished, the selling
price of ethylene may be driven up, making this process profitable.
Additionally, as environmental awareness becomes more socially prevalent,
governments are encouraging companies to move away from fossil fuels because
they are non-renewable and have high carbon emissions.
2.3.1 PROCESS DESCRIPTION
Figure 2.5 below shows a general process flowscheme for the production of
ethylene from ethanol. The process highlights various units required for the
industrial production of polymer grade ethylene.

Figure 2.5: Process Description for Industrial Production of Ethylene from

Ethanol

16

2.3.2 MECHANISM OF REACTION

This reaction is zero-order and endothermic. In the catalytic dehydration of
ethanol to form ethylene, an acid catalyst first protonates the hydroxyl group,
which leaves as a water molecule. The conjugate base of the catalyst then
deprotonates the methyl group, and the hydrocarbon rearranges into ethylene.
This mechanism is depicted in Figure 3the equation below. The reaction is
endothermic, and because of this, the optimal reaction temperature is fairly high,
ranging from 180 C to 500 C. Maintaining the reaction temperature constitutes
much of the energy cost in industrial application of the reaction, since competing
reactions into diethyl ether or acetaldehyde are favored outside of the
temperature range and so decrease ethylene yield.

2.3.4 CATALYSIS OF THE REACTION

Development of an effective catalyst is the foundational and critical step for
catalytic process. Many catalysts have been studied for ethylene production via
ethanol dehydration process. Doheim, Hanafy & El-Shobaky (2002) developed
Na2O-doped Mn2O3/Al2O3 catalyst which able to convert as high as 97 % of
ethanol at 300 C and at low space velocity. Chen, Li, Jiao & Yuan (2007)
has

also developed a catalyst doped with TiO 2

17

which resulted high ethanol

conversion of 99.96 % and ethylene selectivity of 99.4 %. The catalyst under

study in this work is a composite zeolite catalyst synthesized from locally-sourced
Nsu clay. Its preparation is discussed in the following section.
3.2.2 PREPARATION OF CATALYST
Zeolite is a multi-purpose material normally sourced from clay and is usually used
for many Engineering applications. The basic structures of zeolites are shown in
Figure 2.6 below.

Figure 2.6: Basic Structure of Zeolites

Clay generally is unreactive in the natural form, therefore for the catalyst
preparation. Subsequently, it iwas transformed to a more reactive (amorphous)
forzm, meta-kaolin. This process of calcination (thermal treatment) is done by
subjecting the beneficiated clay to heating at 600C before using it as a reactant.
De-alumination of meta-kaolin iwas carried outdone by leaching out the structural
alumina with sulphuric acid, to meet the silicaalumina mole ratio required for the
targeted zeolite.

18

Sodium hydroxide and de-ionized water are used to aid the synthesis process.
Then, analyses are performed on the samples using infrared spectroscopy,
qualitative and quantitative X-ray diffractometry and ion exchange capacity to
characterize and determine the suitability of the zeolites synthesized.
SYNTHESIS PROCEDURE:
The development of Zeolite A from local clay (Nsu) involves the following:
Beneficiation of Nsu Kaolin Clay:
Clay lumps are crushed and screened with a 2mm and 1mm sieve to remove
large and coarse particles such as pebbles, stones and grit. At this stage, the
chemical composition is determined using x-ray fluorescence.
The resulting clay material is dispersed in ratio of 100grams of clay in 1 litre of
10% Hydrogen peroxide (HO). This is to remove or oxidize any coloured organic
and inorganic matter in the clay (Ainsworth-Jienken, 1994).
The suspension is then agitated and allowed to stand for 2hrs. The clear
supernatant liquid is decanted and the clay re-suspended in 1L 0.5 M Sodium
hydroxide (NaOH) solutions for a period of 2hrs with moderate agitation with a
mechanical stirrer.
The resulting solution is diluted with de-ionized water to siphon off the less than
2m clay. The residue is re-dispersed in the water, agitated and the process of
sedimentation and siphoning is repeated until very little clay is left in the
19

suspension. Again, X-ray fluorescence is used to determine the chemical

composition at this stage.
Metakaolinization:
This would involve the calcinations of the beneficiated and dried clay(thermal
treatment) at a temperature range of 600-800oC to form metakaolin.
Zeolitization:
This would involve the hydrothermal treatment of metakaolin with an alkali to
form zeolite.
CHARACTERIZATION
The basic analytical techniques that would be employed in this research work are
X-ray fluorescence (XRF) and X-ray diffraction (XRD) coupled with FTIR
1. X-Ray

Fluorescence

(ED-XRF):

This

is

for

analyzing

the

elemental

composition of the starting, intermediate and the final product. X-ray

fluorescence (XRF) is the emission of characteristic secondary (or
fluorescence)

X-rays

from

material

that

has

been

exited

while

bombarding with high energy X-rays or gamma rays. The method employed
in this research is the energy-dispersive analysis (ED-XRF
2. X-Ray Diffraction (XRD): This gives the crystallographic structural status
and phases of the entire component in amaterial. X-ray Powder diffraction
(XRD)

is

an

efficient

analytical

20

technique

used

to

identify

and

characterizeunknown crystalline material. Phase characterization of the

synthesis Nsu clay was done using XRD.
3. Fourier Transform Infra-red Spectra (FTIR): The infrared spectra deal with
complex organic molecules (Prabu & Natarajan, 2012)(Prabu & Natarajan,
2012).
Information about the nature of a compound can be extracted not only from the
frequencies that are present but alsoby peak shape and intensity.

The reactors used in industry are usually the tube-array fixed bed reactors with
low liquid hourly space velocity (0.3 h1 0.6 h1), low ethylene yield, and
relatively high reaction temperature (350 C 450 C), resulting in high energy
consumption and low utilization of equipment capacity (Chen et al., 2007). Thus,
investigations over zeolites have been done in order to develop a catalyst which
allows reaction carried out at lower temperature with good catalytic performance.
HZSM-5 zeolite offered an ethanol conversion of 98 % at lower temperature (300
C) (Phillips & Datta, 1997).

21

Figure 2.7: Ethanol Conversion over Temperature for Different Catalysts

[Source: Zhang et al., 2008]
Zhang, Wang, Yang, & Zhang (2008) have compared the catalytic performance of
alumina catalyst, HZSM-5, SAPO-34 and modified SAPO-34

catalysts.

They

found out that HZSM-5 catalyst gives the highest ethanol conversion at
lowest temperature which has shown in Figure 2.73.

Figure 2.7: Ethanol Conversion over Temperature for Different Catalysts

22

[Source: Zhang et al., 2008]

Other catalyst types used for carrying out this process are discussed in the
following sections:
Heteropolyacids:
Heteropolyacid salts have attracted attention as potential catalysts due to the
multifunctional properties of the salt formation. Particularly, Ag3PW12O40
hasAg3PW12O40 has demonstrated high catalytic ability, making it a promising
catalyst for the dehydration of ethanol to ethylene, but its high acidity reduces its
stability.
Others areOthers are summarized in the following table:
Table 2.1: Summary of the Properties of Different Catalysts Used for the
Production of Ethylene from Ethanol

23

Table 2.1: Summary of the Properties of Different Catalysts Used for the
Production of Ethylene from Ethanol
2.3.4 EXISTING TECHNOLOGIES FOR THE ETE PROCESS
The ETE technologies are generally referring to catalytic dehydration of gas
phase of ethanol which has been studied extensively. The reaction can be carried
out in either a fixed-bed or fluid-bed reactor where by the fixed-bed route is
licensed by Chematur Engineering AB/ Halcon Scientific Design and fluidized bed
technology is licensed by Lummus (Nexant, 2008). There are few others ethanol
dehydration process have been reported or patented which are including
Petrobras Technology (Barracas et al., Joao, & Coutinho, 1978) and Sinopec
Technology (Teng, Wang, Xie, & Gan et al., 2008).

24

2.3.4.1

Lummus Fluidized Bed Technology

Fluidized bed system has been developed since 1979 to improve the ethylene
yield by controlling the temperature which in turn avoiding the hot and cold
spots. The ethylene yield had increased to 99.5 % with ethylene selectivity of
99.6 % and ethanol conversion of 99.6 % (Tsao & Howard, 1979). The catalyst
used can be any variety of dehydration catalyst such as alumina, silica-alumina,
activated clays and zeolites. In this technology, silica-alumina is preferred due to
its availability and it is periodically regenerated to remove the carbon and tars
formed during the reaction. Lummus has dedicated a pilot plant development
program for ethanol dehydration (Fariha, 2010).
The operating conditions, reactor effluent composition and process flow diagram
for Lummus Fluidized Bed system are shown in Table 2.1 and Figure 2.7 based on
Tsou & Howard (1979):

Table 2.2: Operating Condition and Product Composition of Lummus

Technology [Source: Tsou & Howard, 1979]

Temperature, F
Average superficial velocity, ft/s
Residence time, s
Pressure, psig

750
0.74
2.7
9.6

Effluent Composition, mol %

Water

50.02

25

Ethylene
Acetaldehyde
Ethanol

49.75
0.04
0.19

Table 2.2: Operating Condition and Product Composition of Lummus

Technology [Source: Tsou & Howard, 1979]

Figure 2.7: Process Flow Diagram of Lummuss Fluidized ETE Process

[Source: APEC, 2009]
Chematur has developed a polymer grade ethylene production process using the
fixed bed system as shown in Figure 4.2.8. It uses a new catalyst called Syndol
catalyst which was developed by Halcon Scientific Design for their production
process. Halcon claims that Syndol can stay in continuous operation for eight
months without the need of regeneration and able to handle adiabatic operation
(APEC, 2008). This enabled fixed bed reactor to be used and operated

26

adiabatically at temperature range of 599 F to 797 F. The reported ethylene

yields and ethanol conversion are of 99 % and 99.8 % respectively (Fariha, 2010).

Figure 2.8: Process Flow Diagram of Halcon

Engineering ABs ETE Process [Source: APEC, 2009]

2.3.4.2

Scientic/Chematur

SINOPEC Technology

SINOPEC has

developed

an

activated

alumina

catalyst which

has

high

carbon selectivity to ethylene in fixed bed reactor. The coking tendency is

suppressed efficiently and thus, no regeneration is required for this system. As a
result, the ethylene selectivity and ethanol conversion obtained in this system
are 97 % and 99 % in the operating temperature range of 340 C to 390 C
according to Teng et al. (2008). The process flow diagram of SINOPEC ETE process
has shown in Figure 4.32.9.

27

Figure 2.9: Process Flow Diagram of SINOPECs ETO Process [Source: Teng
et al., 2008]

2.3.4.4

Petrobras Technology

Petrobras has developed a reactor system which is a series of fixed bed reactors
that operated adiabatically. The arrangement involves simultaneous introduction
of fresh feed and reactor effluent which worked as sensible heat carrying fluid
between the reactors as shown in Figure 4.42.10 (Barracas, et al., 1978). The
preferred catalyst for this invention is alumina and silica alumina due to its
availability.
The adiabatic

fixed-bed

process had

an ethanol conversion of 98

and

ethylene yield of 99.2 % at operating temperature of 355 C to 390 C. This

process increases the catalyst life at which the catalyst will sustain a period of
around six to twelve months before being regenerated (Morschbacker, 2009). The

28

process is also designed to lower the formation of unwanted by-products, hence,

is economical by saving on cost of equipments and maintenance (Fariha, 2010).
On the other hand, Petrobras has developed a co-processing of ethanol and
hydrocarbon
athrough

fromhydrocarbon
fluidizeda

from

petroleum

catalyticfluidized

refining

throughrefining

crackingcatalytic

unitcracking

whichunit that is flexible (Rezende et al., , Amilcar Ramos, & Fernando, 2008). as
shown in Figure 4.5.

In the process, the feedstocks are introduced separately into two reactiontworeaction zone of the reactor and contact

withcontact with zeolite catalyst

forcatalyst for reaction to occur. Ethanol is dehydrated in a first reaction zone at

temperature 530 C to

650

C,

while the catalytic

cracking

of

the

hydrocarbons occurs in a second reaction zone at temperature of 500 C to

620 C. This combination gives ethylene production at 15 wt % to 90 wt % of the
stream of fuel gas obtained by co-processing.

29

Figure 2.10: Block Diagram of Petrobrass Co-processing Process

[Source: Andrea Rezende et al., 2008]

2.3.5 COMPARATIVE ADVANTAGES OF THE ETE ROUTE

This comparison is made in term of energy use, CO2, CO2

emission, production

cost and ethylene yield for petrochemical production.

Steam cracking is the most energy consuming process compared to FCC and ETE.
It is the most energy consuming in the chemical industry and emitted nearly 200
million tonnes of CO2 due to the combustion of fossil fuels in year 2000 (Tao at
el., 2008). Cracking provides the heat of reaction and the sensible or latent heat
to bring the reactants to the desired reaction temperature whichtemperature that
is very high, 750 C to 900 C (Gielen et al, n.d.2012). It uses maximum energy of
40 GJ per ton of ethylene and emitted around 2 tonnes of carbon dioxide for

30

every ton of ethylene produced which is the highest among the others (Tao et al.,
2006).
Besides, the energy use and CO2 emission for cracking process are higher due to
the formation of coke in the cracker. Additional energy is required for decoking or
defouling for various sections of a steam cracker. This additional energy use in
decoking and defouling is not taken into consideration in the result. With the
addition of energy used for shutdown and related maintenance, approximately 1
% to 2 % of total energy used are added (Tao et al., 2006). Therefore, further
studies on reducing the coke formation in the steam cracker is required to extend
the furnace life and increase the intervals between shutdowns which in turn,
reduce the energy consumption and operating cost.
On the other hand, Tao & Patel (2009) have reviewed on Maize starch ETE and
Sugarcane ETE process which have integrated with the ethanol production. This
leads to significant difference in term of the issues concerned as compared to
stand- alone ETE process. However, both of the ETE processes are enjoying a
lower energy use and CO2 emission in ethylene production as compared to
naphtha steam cracking process.
In term of product yield, ethylene yield obtained from ETE routes is higher
compared to cracking process as cracking process will produce by-products such
as propylene, butylenes and aromatics. The typical ethylene yield obtained from
ETE routes is more than 99 wt % which is significantly more than cracking routes.

31

Besides, the energy cost of naphtha cracking process is high where the energy
cost of pyrolysis sector had accounted for 70 % of production cost in
typical naphtha-based olefins plants (Tao et al. 2006). In term of the raw material
cost, the material cost of naphtha cracking is also higher than ETE process as the
naphtha price is USD 1067/MT (Petrochemical Asia, 2012) while the ethanol
selling price is USD 690/MT (Agricultural Marketing Resource Center, 2012).
Furthermore, ETE process requires no equipment for distillation leading to lower
investment (Kjellin & Johansson, 2010). The technologies such as fluidized bed
and adiabatic fixed bed require no external heating fluid enhances the heat
transfer and efficiency which in turn, reduces the energy cost and enjoying lower
energy cost as compared to naphtha cracking process.
2.4 POLYMER GRADE ETHYLENE
In order to produce polymer grade ethylene, a further treatment of
ethylene stream is required as shown in Figure 4.82.11.

32

Figure 2.11: Ethylene Column and Striper Section [Source: Chematur

Engineering Group, 2011n.d.]
The chemical grade ethylene is fractionated in a distillation and stripping systems
to remove heavy and light contaminants. The bottom product of ethylene column
consists of heavier carbohydrates, ethanol, diethyl ether, and acetaldehyde and
the carbon monoxide, methane, and hydrogen are separated from ethylene as
top products in the stripper. The light by-products separated in the stripper are
vented to air while the condensed phase which is mainly ethylene is recirculated
to ethylene column and stripper to obtain the final product with purity adequate
for most kinds of polymerization catalytic system. Table 24.3 shows the typical
composition of polymer grade ethylene.
Table 2.3: Typical Composition of Polymer Grade Ethylene
[Source: Arvidsson & Lundin, 2011]
Component

Composition

Ethylene (vol %)

99.95

Carbon Monoxide (vol ppm)

Carbon Dioxide (vol ppm)

10

Ethane

0.05

2.5 APPLICATIONS OF ETHYLENE

33

Ethylene was first obtained from ethanol in the 18 th century, when ethanol was
passed over a heated catalyst. The plastics industry gave rise to several ethanol
dehydration units which operated from the 1930s up until the 1960s. The advent
of naptha (liquefied petroleum gas) cracking rendered these dehydration units
defunct.

Naptha cracking involves a liquid feed of saturated hydrocarbons

diluted with steam and heated to extreme temperatures in the absence of

oxygen.

The functionality of this process reversed industrial trends, turning

ethylene into a raw material for ethanol, as opposed to a derivative of it.

Ethene is the leading synthetic organic chemical in the world in terms of scale of
production. Although ethene is widely used as a starting material in the
production of many chemicals and products, most of the ethene produced in
Australia (about 60%) is used to make polyethene, which is used to produce:

Plastic equipment eg. bowls, buckets, bins, glad wrap.

Covers for metal containers eg. piping that is susceptible to corrosion.
Insulating materials.

Other uses of ethene include:

The production of ethanol, which is used as:

Solvents such as methylated spirits.

Solvents in cosmetics, drugs and perfumes.
A raw material in the manufacture of other chemicals.
Herbicides.
The production of ethylene glycol which is used as an antifreeze solution.
The production of teflon which is used to make non stick cooking utensils.

The production of PVC (polyvinyl chloride) which is used for:

34

Insulation around electrical cables.

Packaging.
Products traditionally produced from glass, rubber.

The production of polystyrene which is used for:

Tape and film reels, toys, packaging.

Audio cassette boxes.
Casings for TV's and radios.
Thermal insulation.
Production of fibres.
Production of co-polymers, such as ABS (a plastic made from polymer
chains of three monomers styrene, acrylonitrile and butadiene).

2.6 COMMERCIAL ETE PLANTS AND RESEARCH ACTIVITIES

Given the public concern about global warming, scarcity of fossil fuels and
increasing

oil

prices,

bio-based

polyethylene

has

become

increasingly

attractive today. Besides, customer interest in renewably sourced materials,

particularly in the packaging area, is the primary demand driver for bio-based
polyethylene. Customers have started to exert pressure on polymer-producing
companies especially polyethylene producers to deliver sustainable solutions
where renewable feedstock is an important factor. It is inevitable that there is a
large potential market demand for bio-ethylene. The following companies have
planned to produce bio-ethylene from bio-ethanol at certain capacity:

Braskem Ethanol-to-Ethylene Plant, Brazil

Braskem, a Brazilian petrochemicals company has inaugurated the first large

scale ethylene plant in the Rio Grande do Sul state of Brazil in September 2010.
35

The production capacity of 200 000 tonnes per year uses 100 % renewable raw
materials which is the sugarcane based ethanol as feedstock (Net Resources
International, 2011). In addition, Braskem planned to establish the second
factory to produce polyethylene

from sugarcane-based ethanol, once the

first plant commenced operation in October, 2010.

Dow Chemical Company and Crytsalsev, Brazil

Dow Chemical Company, the worlds largest producer of polyethylene has joint
venture with Crystalsev, one of Brazil largest ethanol producers to produce biobased polyethylene at annual production capacity of 350 000 tonnes in 2012
(EnvaPack, 2007).

Solvay, Brussels

The Solvay group, one of the worlds leading vinyls producer had created an
integrated plant to produce ethylene with ethanol originating from sugarcane.
The purpose for this investment is to expand and increase the competiveness of
its vinyl production plant in Santo Andre, Brazil. This expansion of Santo Andre
plant was estimated to be completed by 2010 with annual installed capacity of
360 000 tonnes of polyvinylchloride (PVC) and 60 000 tonnes sugarcane
based bio-ethylene (BioPact, 2007).

Borealis, Austria

Borealis is an organisation which focuses on producing plastic materials using the

feedstocks of naphtha, butane, propane and ethane. Due to the existing

36

production capacities are unable to meet the demand, Borealis had planned to
expand its production of ethylene at Stenungsund, Sweden, by using bioethanol as a raw material (Nexant, 2009).

Total, IFPEN and Axens

Total Petrochemicals, IFP Energies Nouvelles (IPFEN) and its subsidiary Axens
have entered into a partnership to develop new technology that can produce bioethylene by dehydrating ethanol. The technology is expected to be available for
industrial implementation by the end of 2011 (Natural Resources International,
2011).

Greencol Taiwan Corporation Bio-MEG Plant, Taiwan, China

Greencol Taiwan Corp., a joint venture between China Man-Made Fiber Corp. and
Toyota Tsusho Corp. has planned to build a 100 000 tonnes bio-based ethylene
plant in Kaoshiung, Taiwan (Natural Resources International, 2010). The feedstock
used will be the sugarcane based ethanol supplied by Petrobras.

Chinas Companies

Sinopec has planned to expand a 7000 tonnes per year bio-ethylene experiment
unit at Sichuan Vinylon Works. Another company in China, Anhui BBCA
Biochemical Co has included one million tonnes per year of bio-ethylene project
in its 11th Five- Year Plan (2006-2010). Besides, according to Jilin government
official, Songyuan Jian Biochemical Group Co is also considering a project to
produce 300 000 ton/year of ethylene from corn (ICIS, 2005).

37

CHAPTER THREE
MATERIALS AND METHODS
Experimental studies were carried out at New Concept laboratories Obinze,
Owerri, Imo state.
3.1 MATERIALS REQUIRED
3.1.1 GLASSWARES
1. PippettePipette
2. Combustion tube as a fixed-bed micro reactor
3. Conical/round bottomed flasks
4. Condenser tube
5. Industrial thermometer
6. Measuring cylinders

3.1.2 REAGENTS REQUIRED

Distilled water: used for preparing bromine water

Analytical grade ethanol (99.7% purity)

Bromine water : used for testing the presence of ethylene

Hydrochloric acid

Sodium hypochlorite (household laundry bleach)

38

Sodium bromide (NaBr)

Ice block

NB: Catalyst Used is Zeolite Y Composite

3.1.3 EQUIPMENT LIST
Sieve Trays: The size of sieve trays used in this experiment were 75 & 106m as
shown in Figure 3.1. The sieve trays were used to size the zeolite catalyst that
was be used. The sizing of the catalyst was very important to ensure
homogenityhomogeneity and size reduction . reduction.

Figure 3.1: Sieve Shaker with Sieve Trays (75m & 106m& 106m)
Weighing Balance: It is used to weigh the sample or chemicals need for the
experiment.

39

Figure 3.2: Weighing Balance

Hotplate Stirrer
Used for heating reagents (especially the ethanol)

Figure 3.3: Hotplate Stirrer

Other apparatus used are

Boiling tubes

Delivery tubes

Stop watch

Retort Stand

Test-tubes

Funnel

3.2 PREPARATION METHODS

3.2.1 PREPARATION OF ETHANOL

40

Absolute Ethanol of 99.7% purity, with a density of 0.789-0.791g/mL was used as

the reactant.
CATALYST PREPARATION:

The zeolite was crushed in a mortar into fine particles.

The particles were screened with a 100m sieve to remove large and
coarse particles. This gave the catalyst a larger surface area, and allowed
effective contacting.

3.2.3 PREPARATION OF BROMINE WATER

REAGENT REQUIRED:

Glass bottle with screw cap, labeled Br2(aq).

1.1g Sodium Bromide/Potassium Bromide (NaBr/KBr).

10.7mL 1M HCl.

7.6mL Sodium Hypochlorite (household laundry bleach).

32mL water (distilled water).

PROCEDURE:

NaBr/KBr was dissolved in HCl, and transfer to the labeled bottle.

Sodium Hypochlorite was added into it.

The resulting mixture was swirled and capped when not in use.

3.2.4 SETUP OF APPARATUS

SETUP 1

41

The arrangement for setup 1 is shown in figure 3.1, and its procedure is as
follows
A dropping burette was inserted into a two way delivery tube.
At the bottom of the delivery tube was the catalyst in measured quantity.
The delivery tube was held vertically with a clamp attached to a retort stand,
and was balanced upon an electric heater.
The second outlet of the delivery tube was linked to a condenser by a
connecting tube.
Water was passed into the outer shell of the glass condenser in a counter
current flow configuration to the flow of gas.
The inner tube of the condenser was connected to a two way recovery glass
placed in a bath of ice.
The outlet of the recovery tube was connected via a rubber tube into a
calibrated test tube holding a measured amount of bromine water.
The decolorisation of bromine water showed the presence of ethylene, and the
increase in its volume indicated the amount of ethylene absorbed.

42

Figure 3.1: Setup 1

SETUP 2
The catalyst was placed in between two roundly cut ashless filter paper in a
horizontally placed cylindrical glass tube open on both sides.
Holes were bored into two corks to allow the insertion of glass tubes and a
thermometer.
A thermometer and tube were inserted into one of the corks, while the other cork
held only a tube.
Each cork was used to shut the cylinder air-tight, thereby avoiding gas leakages.
A side of the cylinder was held tightly with a clamp on a retort stand.
A corked round bottom flask containing a measured amount of ethanol was
placed on an electric heater.
43

The tube protruding from the cork that had a thermometer stuck into it was
connected into the cork for the round bottom flask.
The other connecting tube to the glass cylinder was stuck into a condenser.
Water was passed through the condenser in a counter current flow configuration.
The inner tube of the condenser was connected to a two- way recovery glass in
an ice bath.
The outlet of the recovery tube was connected via a rubber tube into a calibrated
test tube holding a measured amount of bromine water.
The decolorisation of bromine water showed the presence of ethylene, and the
increase in its volume indicated the amount of ethylene absorbed.
A Bunsen burner was used a heating source.

Figure 3.2:

Setup 2

44

3.2.5 COLLECTION OF PRODUCTS

The design for product collection is based on separation of gaseous products by
the condensation of heavier components including unreacted ethylene, water and
diethyl-ether, using ice as cooling source. The ethylene formed will not condense
when in contact with ice due to its very low boiling temperature, therefore it is
collected alongside possible trace amounts of other light reaction products as
gas. This gas stream is then corked to a tube containing bromine water for
immediate dissolution as consequent discoloration of the bromine water.

3.3 SET-UPS
Numerous experimental setups were tried in the course of this reaction, and
various

modifications

were

made

overtime

whenever

challenge

was

encountered or an inconsistency with the setup was noticed. Two basic

arrangements were used and their process overview and limitations are
discussed below.
3.3.1 SET-UP 1
In this setup ethanol was dropped at a controlled rate from the burette into the
catalyst chamber, due to the high temperature in the reaction chamber the
ethanol immediately vaporized and contacted the catalyst. The vapour stream
left through the side arm of the tube into the condenser where supposed diethyl

45

ether and unreacted ethanol were condensed, ethylene which has a very low
boiling point was left uncondensed and absorbed in bromine water.
STRENGTHS OF SET-UP
This arrangement was easy to setup, making it suitable for laboratory
experiments. Also, the flowrate of ethanol could be obtained by counting the
number of drops of ethanol into the chamber per minute giving control over an
extra variable in the experiment.
LIMITATIONS
This setup had the following limitations:

Due to the arrangement of the catalyst in the catalyst bed, poor contacting

between the catalyst and the ethanol was observed.

The heating mantle was more of an open heat source, and since the heat
was not concentrated, heat distribution along the catalyst was uneven due

to the nature of the tube, the catalyst arrangement and heating source.
The desired temperature of the reaction could not be obtained using this
setup because water was used as the heating fluid and was unable to
exceed its boiling point due to atmospheric conditions.

3.3.2 SET-UP 2
Due to the limitations encountered in the first setup and alternative configuration
was made to overcome the challenges of the previous setup.
The general procedure is as stated in the experimentation chapter of this report.

46

STRENGTHS OF SET-UP
This setup has overcame the challenge of poor contacting between the catalyst
and the ethanol, also the ethanol was vaporized before entering the catalyst
chamber to avoid ethanol vapour form by-passing this catalyst chamber into the
condenser. The use of a Bunsen burner ensured that the catalyst was adequately
heated to the required reaction temperature
LIMITATIONS
The following limitations were encountered with this setup

Inability to regulate or measure flowrate of the ethanol or ethylene

Poor temperature regulation due to the use of a Bunsen burner as heating

source
Gas leakages occurred due to the inappropriate corking of the tubes this

lead to often fires

Pressure buildup in the system (due to the reduced tube length) lead to
overpressure of the system creating a hazardous effect.

47

CHAPTER FOUR
RESULTS AND DISCUSSION
4.1 RESULTS AND OUTCOMES
The following results were obtained from the Setup 2The results presented in
Tables 4.1 and 4.2 were obtained using Setup 2 discussed in Chapter 3. with
Different trials, each trial had a slight difference in the arrangement to amend for
errors and complications encountered with the previous arrangement with
different configurations of reaction apparatus were used in the course of
experimentation, this was to improve the integrity of the results thus obtained..
Table 4.1

Table of Results for Trial 1

Run

Ethanol
Volume used

Temperatur
e (oC)

1
2
3
4

15ml
20ml
40ml
40ml

310-350
310-350
310-350
310-350

Time
(Seconds
)
420
900
650
869

48

Volume of Ether
+ unreacted
Ethanol + water
8.0ml
13.0ml
47.0ml
39.4ml

Volume of
Ethylene
produced
3.0ml
0.5ml
3.6ml
0.8ml

Table 4.2
Ru
n
1
2

Table of Results for Trial 2

Temperatur
e (oC)
310-3250
310-3250
310-320

Time (Secs)
600
660
2160

Volume of ether +
Volume of
unreacted Ethanol + Water
ethylene
4.2ml
0.4ml
10.3ml
0.5ml
40.9ml
0.1ml

V
o
l
u
m
e
o
f
E
t
h
a
n
o
l
p
r
o
d
u
c
e
d
4
.
6
m
l
1
0
.
8
m
l

Table 4.3 Computed Fractions Ethylene in Product Stream

49

Temperature
(oC)

Time
(Minutes)

310-350
310-350

7
11.8

310-350

14.5

310-350

15

310-320

10

310-320

Fraction of
Ethylene in
Product Stream
0.375

Percentage
Ethylene in product
Stream
37.5

0.076596

7.659574

0.020305

2.030457

0.038462

3.846154

0.095238

9.52381

0.048544

4.854369

0.002445

0.244499

11

310-320

36

Fraction of Ethylene in product Stream

0.4
0.35
0.3
0.25

Fraction of Ethylene in
product Stream

0.2
0.15
0.1
0.05
0
7

11.8

14.5

15

Fig 4.1: Volume of Ethylene produced verses time graph for temperature range
(310-350oC)

50

Fraction of Ethylene in product Stream

0.1
0.08
Fraction of Ethylene in
product Stream

0.06
0.04
0.02
0
10

11

36

Fig 4.2: Volume of Ethylene produced verses time graph for temperature range
(310-320oC)

4.2 DISSCUSSION/ANALYSIS
The results presented in section 4.2above represent the approximate outcomes
of the different runs conducted to test the catalyst. Each run in reality provided
an avenue for improvements in the next run and hence in the overall utility of the
catalyst. These modifications sought to eliminate and in other cases assuage
the effects of the limitations experienced in previous runs.
The reaction conditions of utmost interest in the reaction procedure included
regulation of temperature of catalyst, proper condensation of reaction products
(excluding ethylene), contacting of the ethylene gas with the bromine water
solution, contacting of the ethanol vapour with the catalyst bed for maximized
conversion of ethanol. As stated in Chapter 3, the timing of the experiment was
taken to begin from the point where the first bubble of ethanol vapour rises into

51

the reactor chamber. As indicated also by the results presented above, the times
of reaction were fixed for some runs, while in the other runs, time recording was
stopped at the point where all liquid ethanol has just been evaporated.
Figure 4.1 indicates that for increasing times of reaction, lesser amounts of
ethylene were produced, this is seen by the downslope trend of the plot. Hence,
from this trend, the amount of ethylene produced cannot be said to be directly
proportional to time spent in the reaction, this owes to the sophistication of the
setup used. This also owes largely to the integrity of the measuring procedures
employed to measure the quantities of ethylene produced.
Another fundamental explanation for the empirical deviation of Figure 4.1 is in
the fact that not all ethylene produced were dissolved into the bromine water.
From the nature of the experimental setup, ethylene is to be collected as gas,
which is channeled directly into the bromine water solution. However, during the
process of ethylene recovery, bubbles of gas ethylene and possible trace
amounts of other non-condensibles were observed to escape the pool of
bromine water into the space inside the collection tube. Therefore, not all
ethylene produced effectively dissolved into the bromine water. Also there were
no simple means of verifying the fraction of ethylene produced, that was always
not dissolved in the bromine water solution. The premise above thus indicate that
the increase in volume of the bromine water was not entirely an effective
measure of ethylene produced by reaction, and hence the non-reliability of Figure
4.1, and data presented in Table 4.1.
Considering the wide temperature range of Trial 1, and the rational possibility
that some of the runs may have tended towards one of the temperature
extremes thus compromising the uniformity of the quantities of ethylene
produced (temperature difference as small as 10 0C can have considerable
influence on the amount of ethylene produced), we considered limiting the
52

temperature range to 310-3200C. The results are presented in Table 4.2 and the
corresponding plot in Figure 4.2, from where we can conclude that there is no
distinction from previous results.
These inconsistencies in the nature of results obtained may be due to the
inadequacy of the equipment used for the reaction studies. However, the critical
objective of the project, namely, the confirmation of the ability of the catalyst
used, to effect the formation of ethylene from ethanol, was accomplished. This
was confirmed by the consistent discoloration of orange bromine water with an
accompanying increase in the volume of the bromine water.From Fig 4.1
(Ethylene volume produced verses time graph) the amount of ethylene produced
cannot be said to be directly proportional to the amount of time spent in the
reaction. Because of the nature of the setup obtainable, the amount of ethylene
produced at any given point of time could not be ascertained; hence the
experiment could not be carried out as a continuous process.
The experiment was conducted batchwise and time was fixed at various values to
check the relationship between ethylene formed and time elapsed. But due to the
number of complications encountered in the course of the experiment, this
relationship could not be effectively concluded, as it can be seen from graph, the
relationship is inconclusive because at the shortest time of the reaction the
greatest yield of ethylene was recorded and at the longest time of reaction the
smallest yield of ethylene was recorded. This is probably due to the
inconsistencies and limitations of the experimental setups used and the available
apparatus and materials.
From Tables 4.1 to 4.3 the maximum percentage of ethanol converted to ethylene
is about 20%, this value is quite low to be of any significant industrial relevance.
This result may be due to a number of reasons which may include: the
experimental setup used which may have led to poor contacting of ethanol with
the catalyst, or then nature of the catalyst used. Since prior data on the
performance of this catalyst could not be obtained, it cannot be ruled out that the
catalyst is ineffective in producing a reasonably large quantity of ethylene from a
53

given amount of ethanol hence the catalyst b=may have low activity, selectivity
and performance.

The specific outcomes of the different runs and experimental configurations are
discussed in the following sections:

4.2.1 SET-UPS
Numerous experimental setups were used in the course of this reaction, and
various

modifications

were

made

overtime

whenever

challenge

was

encountered or an inconsistency with the setup was noticed. Two basic

arrangements were used and their process overview and limitations are
discussed below.
4.2.1.1 SET-UP 1
In this setup ethanol was dropped at a controlled rate from the burette into the
catalyst chamber, due to the high temperature in the reaction chamber the
ethanol immediately vaporized and contacted the catalyst. The vapour stream
left through the side arm of the tube into the condenser where supposed diethyl
ether and unreacted ethanol were condensed, ethylene which has a very low
boiling point was left uncondensed and absorbed in bromine water.

STRENGTHS OF SET-UP

54

This arrangement was easy to setup, making it suitable for laboratory

experiments. Also, the flowrate of ethanol could be obtained by counting the
number of drops of ethanol into the chamber per minute giving control over an
extra variable in the experiment.
LIMITATIONS
This setup had the following limitations:

Due to the arrangement of the catalyst in the catalyst bed, poor contacting

between the catalyst and the ethanol was observed.

The heating mantle was more of an open heat source, and since the heat
was not concentrated, heat distribution along the catalyst was uneven due

to the nature of the tube, the catalyst arrangement and heating source.
The desired temperature of the reaction could not be obtained using this
setup because water was used as the heating fluid and was unable to
exceed its boiling point due to atmospheric conditions.

4.2.2.2 SET-UP 2
Due to the limitations encountered in the first setup and alternative configuration
was made to overcome the challenges of the previous setup.
The general procedure is as stated in the experimentation chapter of this report.

STRENGTHS OF SET-UP

This setup has overcame the challenge of poor contacting between the
catalyst and the ethanol, also the ethanol was vaporized before entering the
55

catalyst chamber to avoid ethanol vapour form by-passing this catalyst

chamber into the condenser. The use of a Bunsen burner ensured that the
catalyst was adequately heated to the required reaction temperature
LIMITATIONS
The following limitations were encountered with this setup

Inability to regulate or measure flowrate of the ethanol or ethylene

Poor temperature regulation due to the use of a Bunsen burner as heating

source
Gas leakages occurred due to the inappropriate corking of the tubes this

lead to often fires

Pressure buildup in the system (due to the reduced tube length) lead to
overpressure of the system creating a hazardous effect.

4.2.2 GENERAL EXPERIMENTAL/PROJECT LIMITATIONS

From the foregoing, the entire experimental procedure for the establishment of
reaction kinetics using our catalyst was limited by a number of crucial factors,
resulting in our inability to effectively evaluate the characteristic properties of our
catalyst for the reaction. A number of these factors are discussed as follows:
4.2.3.1 TEMPERATURE REGULATION
Catalyst performance varies at different reaction temperatures from literature
review, lower reactor temperature at around 200-250oC favor the production of
diethyl ether over ethylene, while temperatures above 300 oC conveniently favors

56

production of the desired product ethylene. For the estimation of catalyst

performance at different reaction temperatures adequate temperature regulation
becomes very important especially in observing the temperature of best
performance. In the course of our experiment a manual Bunsen burner served as
our heating source, hence our inability to closely control temperature left us
operating within the range of 310-350. For this reason, catalyst best performance
temperature could not be easily observed and kinetics modeling was impractical.
4.2.3.2 REACTOR CONFIGURATION
The configuration of a reactor plays an important role in determining the
efficiency of product recovery as well as the degree of conversion achievable for
a batch of reactant(s). This becomes even more significant for reactions involving
solid catalysts as it is desired to optimally contact the reactants with the catalyst
bed. The limited laboratory apparatus available to us placed a constant on the
degree of sophistication we would have attained in configuring our setup and as
such more quantities of ethanol were recovered in the product stream as
compared to results from industry scale configurations read off from literature.
4.2.3.3 ANALYSIS OF REACTION PRODUCTS
Besides verifying the compounds present in the product stream by simple
laboratory techniques, it is also important to check the amounts by which these
components are present. These amounts help to determine their concentrations,
which in turn form the basis for evaluating such parameters as the conversion of
ethanol, the yield of each product (diethyl ether and ethylene) and selectivity of
57

each products. Also proper analysis of product stream helps to get partial
pressure data which are very useful for modeling of reaction kinetics.
4.2.3.4 FLOW MONITORING
As described in the analysis, the first setup provided the best means of
controlling flowrate of the ethanol, by counting the number of drops of liquid
ethanol dropping per time. The accuracy of this method however was unreliable
and most importantly could not take care of the Flowrate of gases, which form
the majority of the phases being dealt with in the experiment. Flowrate is usually
a useful paramenter to monitor for this reaction as it helps to indicate quantities
of materials per time, and invariably the specific kinetic pattern of the reaction.

CHAPTER FIVE
CONCLUSION AND RECOMMENDATIONS
5.1 CONCLUSION
Today, almost all ethylene is produced from petroleum derivatives, but biomass
can also be used as an alternative feedstock for the production of bio-ethylene. In
doing this, a catalyst which provides for faster reaction and enhanced yields of
58

ethanol is inevitable. Among the catalysts capable of enhancing this class of

reactions are Zeolite catalysts, and in this research work, the efficiency of a
locally-sourced zeolite catalyst was tested.
Within the limits of available equipment and financial resources, we were able to
successfully carry out a basic bio-ethanol dehydration process to verify the ability
of our catalyst to selectively produce ethylene. However, monitoring of essential
reaction conditions such as temperature of reaction, partial pressure of gaseous
products, flowrates of reactants and products alike, and space-time in reactor
chamber, proved difficult. To a large extent several modifications to the simple
setup were used to improve the quality of results got and thus approximate the
performance of the given catalyst. It is believed that From the outcome of our
experimentation it is convenient to state that the catalyst promisesshows a lot of
economic potential for the industrial-scale production of ethylene. This assertion
is made on the grounds that in the configuration of the third setup (which
supposedly optimized catalyst-ethanol vapour contact), lower amount of ether
and unreacted ethanol amount was achieved, invariably meaning that in the
presence of sufficient temperatures and proper contacting of catalyst and
reactant, there will be very efficient yields of ethylene.
Finally, the potential for bio-ethylene production is large, but its implementation
will depend on the future availability and price of the biomass feedstock, which
are linked to developments in food demand and the use of biomass for biofuels,
heat and electricity production. The cost of bio-ethylene is highly dependent on

59

the local price of the biomass feedstock and is still higher than that of
petrochemical ethylene in most situations.
In Nigeria the availability of the Nsu clay primary precursor for the catalyst used
for the reaction makes for so much financial gains, hence the need for further
research into the prospects of fully developing this catalyst for greater economic
growth, and the accompanying engendering of a greener future.

5.2 RECOMMENDATIONS
For the success of further study of the catalyst thus tested it is essential to
consider the following recommendations:

The products obtained should be analysed with a Gas Chromatography unit

in order to provide parameters necessary for kinetic studies.

An electric heater with thermostat should be used to ensure that reaction

takes place at specific temperatures.

A reactor configuration should be used to allow for better contacting
between ethanol and the catalyst to ensure adequate measurement of

catalyst performance.
The pressure of the system should be measured to enable kinetic studies of
the reaction.

60

61

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APPENDIX

Figure A: Image Showing Bromine Water, before and after Dissolving Ethylene

Figure B: Experimentation at New Concepts Lab., Obinze

Figure C: View of Entire Process Set-Up from Ethanol Vaporization to Ethylene

Dissolution in Bromine Water