CHAPTER 1

INTRODUCTION
1.1 BACKGROUND AND HISTORY
Ethanol also called ethyl alcohol is the second member of aliphatic alcohol series
(Donal OLeary, 2000). Ethanol has a molecular formula CH
3
CH
2
OH is a clear and
colourless liquid that has a characteristics of agreeable odour with a pleasant smell. Ethanol
has a sweet flavour in dilute aqueous solution and has a burning taste in more concentrated
solution. The chemical compound of ethanol has a molecule that contain hyroyl group
OH hich one ith a caron atom. oiling point of ethanol is . C an the melting
point of ethanol is -. C ith the ensity of 0. gmL at 20 C. Ethanol alreay een
made long time ago by the fermentation of sugars (Prof. Shakhashiri, 2009).


Figure 1: Ethanol-2D-flat. Figure 2: Ethanol 2D structure
Ethanol burn in air will produce blue flame and forming carbon dioxide and water.
Ethanol reacts with active metal to form metal ethoxide and hydrogen for example ethanol
reacts with sodium to form sodium ethoxide. Ethanol also reacts with certain acid to form
ester (The Columbia Electronic Encyclopaedia, 2012).
Ethanol is an important industrial chemical that used as a solvent in the synthetic of
other organic chemicals and also as an additive to automotive gasoline. Ethanol also used as
the intoxicating ingredient of many alcoholic beverages (Encyclopaedia Britannia, 2014). All
ethanol is used industrially except for alcoholic beverages is a mixture of 95% of ethanol and
5% of water which is known simply as 95% of alcohol. Ethanol is prepared as 95% alcohol
y istillation solution hich the result from the fermentation of sugar (Donal OLeary, 2000.

1.2 APPLICATIONS OF ETHANOL
Ethanol is a simple molecule containing only 9 atoms and known to humans long
before the advent of modern chemistry. It has many everyday uses ranging from solvents,
cleaning products, fuel for table top cookery, industrial applications and even medical uses.
Ethanol even finds its way into thermometers where it is coloured red. However, you are
probably most familiar with ethanol as the psychoactive drug in alcoholic drinks such as
beers, wines and spirits. The applications of alcohol are ; in the manufacture of alcoholic
drinks, e.g. Vodka, etc., as a widely used solvent for paint, varnish and drugs, in the
manufacture of ethanal, (i.e. acetaldehyde), and ethanoic acid, (i.e. acetic acid), as the fluid in
thermometers, and in preserving biological specimens. Ethanol is used extensively as a
solvent in the manufacture of varnishes and perfumes; as a preservative for biological
specimens; in the preparation of essences and flavorings; in many medicines and drugs; as a
disinfectant and in tinctures (e.g., tincture of iodine); and as a fuel and gasoline additive
(see gasohol). Medically, ethanol is a soporific, i.e., sleep-producing; although it is less toxic
than the other alcohols, death usually occurs if the concentration of ethanol in the
bloodstream exceeds about 5%.

1.3 RAW MATERIAL
Ethylene is a basic reactive monomer for the chemical industry, and it is one of the
largest volume organic chemicals produced globally. Ethylene is produced commercially
from petroleum and natural gas feed stocks (council, december 2004). It is a simplest of the
organic compounds known as alkenes, which contain carbon-carbon double bonds and a very
flammable liquid or vapor with a high vapor pressure. It is in the form of gas at the
atmospheric pressures and temperatures (Dow chemical company, August 16).
The other raw material used in this process is steam water. Pure water is a colorless, odorless,
and tasteless liquid. Tastes and odors in water are due to dissolved gases, such as sulfur
dioxide and chlorine, and minerals. The two main water supplies are surface and ground.

1.4 PRODUCTION AND TECHNOLOGIES
Figure 1: Block Flow Diagram of Direct Catalytic Hydration of Ethylene



Figure 1 describes the flow process of hydration of ethylene to form ethanol. The feed
enters the reactor is ethylene at high temperature of 2 C an pressure aout 00 kPa with
presence of phosphoric acid catalyst to promote the reaction process. Ethanol is synthetically
produced during the catalytic hydration of ethylene in the reactor (Nexant Inc., 2006).

Figure 2: Block Flow Diagram of Indirect Hydration of Ethylene


Figure 2 shows the indirect hydration of ethylene to form ethanol. This is the
traditional method to produce ethanol and has been used industrially since 1930. The indirect
hydration of ethylene consists of three steps process:
Absorption of ethylene in concentrated sulfuric acid to form monoethyl sulfate and
diethyl sulfate
Hydrolysis of ethyl sulfate to ethanol
Reconcentration of dilute sulfuric acid










Table 1: Comparison of Technologies in Production of Ethanol

Fermentation Direct Catalytic
Hydration of Ethylene
Indirect Catalytic
Hydration of Ethylene
Process Process in one group.
All material is put into
a container and then left
until fermentation is
complete. Collection of
this material is then
removed and a new
reaction took place.
This process is
inefficient.
Continuous flow process.
Reagent flow is
continuously passed over
a catalyst. This method is
more efficient.
Involving three steps
process: absorption of
ethylene in concentrated
sulfuric acid to form
monoethyl sulfate and
diethyl sulfate,
hydrolysis of ethyl
sulfate to ethanol, and
reconcentration of the
dilute sulfuric acid
Reaction
Rate
Very slow Very fast Slow
Product
Quality
Ethanol produced very
not pure and requires
further processing
Ethanol produced very
pure
Ethanol produced less
pure
Conditions
during
Reaction
Using medium
temperature and
medium pressure
Using high temperature
and high pressure
Using medium
temperature and
medium pressure

Table 1 shows the comparison between fermentation, direct catalytic hydration of
ethylene and indirect catalytic hydration of ethylene in order to form ethanol. From these
three processes, direct catalytic hydration of ethylene is more efficient as it produce high
purity of ethanol compared to the other two processes. This process has to be conducted at
high temperature and pressure which will require high heat input.



1.5 REACTION KINETICS
Direct Catalytic Hydration of Ethylene
Ethylene is generally product of petrochemical industry process. Ethylene can be used
as the raw material in synthetizing ethanol. Hydration of ethylene will produce ethanol. In the
beginning, Asian ethylene production capacity does not even close to 20% of total world
production; most of the consumption is based on excess petrochemicals in US. In the next
five years, ethylene production capacities in the Middle has risen more than double, rising
from over 13 million metric tons in 2007 to over 29 million metric tons in 2012. Now, almost
half of the world productions of ethylene are made in Asian. In Malaysia, Ethylene is
produced in Kerteh, Terengganu and Pasir Gudang Tanjung Langsat, Johor. This product
will be further modified into derivative of ethylene. As per 2010, the ethylene capacity
closure for Malaysia reaches 407000 Metric Ton with an average of 80% operating capacity.
The direct catalytic gas phase hydration reaction is considered as the main reaction
(R1) governing ethylene and steam concentrations along the reactor. It assumed to be there is
no side reactions and catalyst deactivation. The main reaction that is considered in this direct
catalytic hydration of ethylene is as follows:
Main Reaction
C
2
H
4
+ H
2
O C
2
H
5
OH

(R1)

According to Qing et al., (2011), LangmuirHinshelwood (LH) kinetic models for
catalytic ethylene gas phase hydrogenation on Pt-Sn/Al
2
O
3
are proposed based on the
reaction mechanisms that take into account the one step or two-step dehydrogenation.
Besides, LH establishes the kinetic models by assuming different reaction mechanisms and
rate-determining steps.
In the first mechanism, direct catalytic hydrogenation of gas phase molecule to ethene
on Pt surface, hydrogen dissociative adsorption, and ethylene desorption are involved.
Surface reaction (S1): C
2
H
4
+ S

C
2
H
4.
S
(S2): H
2
O + S

H
2
O.S

Adsorption (S3): C
2
H
4
.S + H
2
O.S

C
2
H
4.
S + H
2
O.S K
3
=

*Eley-rideal (S3): C
2
H
4
.S + H
2
O (g)

C
2
H
4.
S + H
2
O.S
Desorption (S4): C
2
H
5
OH

C
2
H
5
OH + S K
2
=

In fact, this is a simple mechanism that lumps up all the possible hydrogenation steps.
By assuming the surface reaction (S1) as the rate-determining step, the rate of ethylene
conversion is:

and




K
-1
K
a3
K
a2
K
-2
Where

)

[]

)

[]

)

[]

)










REFERENCES
References for Background and History
Journal
1. Prof. Shakshiri. (Revised: 5 Feb 2009), General chemistry, Ethanol.
Website
1. http://www.ucc.ie/academic/chem/dolchem/html/comp/ethanol.html (Accessed
14:22, Mar 22, 2014)
2. http://global.britannica.com/EBchecked/topic/194354/ethyl-alcohol (Accessed
14:30, Mar 22, 2014)
References for Raw Material
1. Ethylene Product Stewardship Guidance Manual, American Chemistry Council,
December 2004, page 1-10.
2. Ethylene Material Safety Data Sheet, The Dow Chemical Company, No. 1088,
August 16, 2005, Physical and Chemical Properties section.
3. http://water.me.vccs.edu/courses/env110/Lesson2_print.htm

References for Production and Technologies
1. Nexant Chem System, February 2006, Ethanol New Report Alert, (04/04-8).
2. Santosh Kumar, Neetu Singh, Ram Prasad, 2010, anhydrous ethanol: A renewable
source of energy, Renewable and Sustainable Energy Reviews. 14(2010): 1830-1844.




References for Market Survey
1. http://www.meti.go.jp/report/downloadfiles/g30819b40j.pdf (Accessed 12:30, Apr
3rd, 2014)
2. http://www.platts.com/price-assessments/agriculture/ethanol (Accessed 12:30, Apr
3rd, 2014)
3. http://www.icispricing.com/il_shared/Chemicals/SubPage496.asp (Accessed 12:30,
Apr 3rd, 2014)