INTEGRATED PROJECT

BKF 3463
UNIT OPERATION
SEM 1 2013/2014







NAME
MATRIC NO
TAN YONG CHAI KA11206
LIM SOON YEE KA11195
ROSSHILA BINTI IDRIS KA11186
ZAKIRAH BINTI MOHD
ZAHARI
KA11188

CONTENTS


CONTENTS PAGE
Chapter 1(INTRODUCTION)

1.1 Introduction of product

1.2 Application of product

1.3 Market Survey

1.4 Economic Potential

1.5 Screening of Synthesis Route

Chapter 2( PROCESS SYNTHESIS AND FLOW SHEETING)

2.1 Process Flow Diagram

2.2 Manual Material & Energy Balance

2.3 Simulation Using Aspen Plus V12.1

Chapter 3 (PROCESS EQUIPMENT SIZING)

3.1 Determine the number of stages required

3.2 Determine the Height of the Distillation Column

3.3 Simulation Using Aspen Plus

4.Conclusion

5.Reference

6. Appendix


CHAPTER 1 : INTRODUCTION
1.1 INTRODUCTION OF ETHANOL
Ethanol (ethyl alcohol, grain alcohol) is a clear, colourless liquid with a characteristic, with a pleasant smell.
Ethanol, C
2
H
5
OH, is an alcohol, a group of chemical compounds whose molecules contain a hydroxyl group, -
OH, bonded to a carbon atom. Ethanol has a formula weight of 46.0 g/mol.
Figure 1 Structure of ethanol

Ethanol melts at -144.1 C, boils a t 78.5C, and has a density of 0.789 g/ml at 20C. Its low freezing point has
made it useful as the fluid in thermometers for temperatures below - 40C, the freezing point of mercury, and
for other low temperature purposes, such as for antifreeze in automobile radiator. There are 2 processes for
production of ethanol which are fermentation and from ethane and steam.
FERMENTATION
Ethanol has been made by fermentation of sugar. All beverages ethanol and more than half of industrial ethanol
is still made by this process. Simple sugar are the raw material. Zymase (enzyme from yeast), changes the
simple sugars into ethanol and carbon dioxide. The fermentation reaction, represented by the simple equation
which is :
C
6
H
12
O
6
2 CH
3
CH
2
OH + 2CO
2
It is impure cultures of yeast produce varying amounts of other substances, including glycerine and various
organic acids. In the production of beverages, such as whiskey, the impurities supply the flavour. Starches from
potatoes, corn, wheat, and other plants can also be used production of ethanol by fermentation. However, firstly,
the starches must be broken into a simple sugar. An enzyme released by germinating barley and converts
starches into sugars.
The production of ethanol from fermentation has ranges in concentration until up to 14 percent. Above this 40
percent, the ethanol will destroy the enzyme and stop fermentation. Ethanol is normally concentrated by
distillation of aqueous solutions, but the composition of the vapour from the aqueous ethanol is 96 percent
ethanol and 4 percent water. Thus, pure water cannot be obtained by using distillation.



Ethanol is used as an automotive fuel by itself and can be mixed with gasoline to form gasohol. Ethanol is
miscible in all proportions with water and with most organic solvents. It is useful as a solvent for many
substances and in making perfumes, paints, lacquer, and explosives.

MAKING ETHANOL FROM ETHENE AND STEAM
Ethanol can be made by reacting ethane (from cracking crude oil fractions) with steam. A catalyst of phosphoric
acid is used to ensure a fast reaction.
Ethane + steam ethanol
C
2
H
4
+ H
2
O C
2
H
5
OH
Ethanol is the only product. The process is continuous process as long as ethane and steam are fed into one end
of the reaction vessel, ethanol will be produces. These features make it an efficient process, but since ethane is
made from crude oil, which is a non- renewable resources. It cannot be replaced once it is used up and it will
run out in a one day. (Prof.Shakhashiri, 2009)
1.2 APPLICATION OF ETHANOL
Ethanol has been used by humans since pre-historical time. It is obtained from natural raw materials or
produced from industrial chemical processes. It can be used in many ways, either ethanol is used as it is or it is
used as solvent to dissolve other substances.
1.2.1 Consumable Ethanol
This type of ethanol is usually obtained from natural raw materials and is used in many products consumed by
humans. It also acts as a solvent to dissolve other substance for consumption or used by humans. For example,
food colouring in baking, flavouring in manufactured or processed food and natural preservation such as
vinegar.
1.2.2 Household Ethanol
Household ethanol can be either produced from natural raw materials or from industrial chemical processes. It
is presented as solvent in many non-consumable products that we humans used daily. For example, it acts as a
solvent for glass cleaning liquids, paint strippers and hand-wash detergents. It also can be used as a type of fuel
for heating, cooking and lighting.
1.2.3 Biofuel Ethanol
Ethanol is a renewable alternative source to traditional fossil fuels for motors vehicles and industries, and also
in some aircraft type. Brazil, the Worlds second biggest sugar cane producer, uses ethanol produced from sugar
cane as biofuel. While the United States is the Worlds biggest producer of ethanol as biofuel, the States mainly
uses corn as the natural raw material for the production of ethanol. It is known that ethanol as a biofuel has
many advantages over traditional fossil fuels such as coal and petroleum. Ethanol rely on raw materials which
can be grown year-after-year, thus, it is a renewable energy source.
1.2.4 Beverage Ethanol

Ethanol is also used as a base-spirit for the production of distilled alcohol beverages, commonly known as
spirit. Spirit may be produced from any natural raw materials which can produce ethanol. For example, grains
such as rice, fruits such as grape, vegetables and other sources that is consumable.
1.2.5 Medical Ethanol
Ethanol is used for processing and the production of a wide range of medicines and pharmaceutical products. It
acts as a solvent to dissolve other substances and as colouring or flavouring agents. For example, ethanol is used
in decongestant elixirs, cough preparation (syrups and medicines), mouthwash, iodine solution and liquid
medicines. The pharmaceutical industry uses ethanol in processing many types of antibiotics, vaccines, tablets
and liquid medicines. The most common seen is the use of ethanol in antibacterial and antiseptic products.

1.3 MARKET SURVEY
The production of ethanol in the world fuel of ethanol showed the competition between the other country
through the world.If we can see in the production route for synthetic ethanol,the largest portion producers that
contribute is come from SASOL industry which produce around 35 billion tonnes/year.It is followed by the
SADAF,BP,Equistar,Sodes,Mossgas,Japan Ethanol,Jilin Chemicals,Neftochim,Chempetrol and Aprechim
industry that shows the increment that reach around 10 billion tonnes/year. The production of ethanol by type
which are in industrial,beverage and fuel shows that the increment in year 1975 which is 100000 tonnes/year,in
1985 which is 250000 tonnes/year and have a dramatically increase in the year 2005 which is reach to 600000
tonnes/year.(Christoph Berg,F.O.Licht)
The ethanol production by feedstock shows the sugar crops contribute the large amount compared to grains in
the market world which is 61 percent and 39 percent respectively.In the USA,the production of corn reached
350000 litres/tones and the cost per litre of fuel ethanol reached to the 24 billion US Cents/litre while in Brazil
shows 75000 litre/tones of cane production in the feedstock and 8 billion US Cents/litre in the fuel of
ethanol.The demanding of ethanol production are increased and unlimited through the year since ethanol are
good for the environment and also good for rural areas.In Brazil,the economics of ethanol vs sugar shows the
ups and down in their market demand.But,in the year 2003 it shows that more than 50 percent of domestic
sugar/ethanol production are produced. (Christoph Berg,F.O.Licht)


Graph of Ethanol production by type
A more diverse global ethanol market has started to take form in recent years in terms of an internationality
traded commodity.According to F.O.Licht,about 700 million litres of ethanol were traded internationally in
2004,reduces 20 percent of total traded volumes and relatively low volume given by the global market
potential.Further development of an international ethanol market will require a larger number of producers and
exporters,a more feedstock types and an increased number of global producing and exporting countries.
World production of ethanol from all possible starch and sugar feedstock increased 30 billion litres to 46 billion
litres between year 2000 and 2005.A global consumption of ethanol is expected to reach 54 billion litres in the
year 2010 which is equivalent to about one percent of world oil consumption(World Energy Council).The
consumption and trade of fuel ethanol have increased significantly in recent years nearly doubling between
2000 and 2005.Brazil and the United States are the largest producers and consumers of fuel ethanol,with Brazil
the primary consume for production,trade and consumption of sugar-based fuel ethanol.Global demand for fuel
ethanol has increased significantly over the past few years.The global supply of fuel ethanol is expected to
increase by 45 percent over the same period which is increased output in the Japan,China,India,Thailand and
EU. (Christoph Berg,F.O.Licht)



1.4 ECONOMIC POTENTIAL
The market price of ethanol
Species Price (US $/MT)
Ethene 1287
Ethanol 1300

The EP calculation (level 1) for the market survey
The reactions just only need one condition and can be conducted without any catalyst. According to the
literature, the production of side product can be neglected for a rough calculation at this level as compared to
other species. The prices of products and raw materials in the global market are listed accordingly.
1 Metric Ton (MT) = 1000kg
Since the demand of ethanol in the world is in the range of 541300 tons per year,so we assumed to produce
27065 tons per year for our production at the first level due to world production of ethanol by hydration of
ethene is just 5 percent of the total production of ethanol.
Therefore,in order to produce 27065 tons per year,we assume operation hour is 8000 hours per year.
Economic Potential (EP1) = Revenue Raw Material costs
EP = Price of product (ethanol) Price of reactant(ethene)

= $351,845/year



1.5 SCREENING OF SYNTHESIS ROUTES
Fermentation
This is the oldest and most widely used biological method of producing drinkable ethanol. This process uses
yeast under anaerobic condition to convert sugar into ethanol and carbon dioxide.The common sugar source are
sugar cane, barley, corn, grape or coconut juice which are fermented to produce various kind of alcoholic drink
such as beer, wine and liquor.
The overall chemical formula for alcoholic fermentation is:
C6H12O6 + Zymase 2 C2H5OH + 2 CO2

Theoretically 10 kg of sugar will produce 6.5 L (5.1 kg) of ethanol and 4.9 kg (4900L) of carbon dioxide. In
doing so, some energy is released too (about 2.6 MJ/kg of ethanol).
Yeasts are single-cell fungi organisms. The most important ones used for making ethanol are members of the
Saccharomyces genus, bred to give uniform, rapid fermentation and high ethanol yields, and be tollerant to wide
ranges of temperature, pH levels, and high ethanol concentrations. Yeasts are facultative organisms - which
means that they can live with or without oxygen. In a normal fermentation cycle they use oxygen at the start,
then continue to thrive once it has all been used up. It is only during the anaerobic (without oxygen) period that
they produce ethanol.





Cellulosic ethanol
Cellulosic ethanol is a biofuel produced from wood, grasses, or the inedible parts of plants. Cellulose are
composed of long chain of sugar molecule which can be broken down into individual sugar molecule by
enzymes. Cellulose is hydrolyzed into sugar which then can be fermented into ethanol. This is a very important
renewable technology because any usable part of plants can be turn into biofuel. For example, wild grass which
grows fast without care, wasted wood chips from wood industrial, wither leaves can all turn into renewable
biofuel. Unlike fermentation process, cellulosic ethanol doesnt have to compete with food supply in order to
produce ethanol fuel because it uses inedible part of plant rather than sugar.






Ethylene hydration
Ethanol can be produced by synthetic route based on ethene, water and phosphoric acid in vapor phase.
Phosphoric acid is used as catalyst which usually absorbed onto a porous support(usually silica gel or
diatomaceous earth)
Only 5% of the ethene is converted into ethanol
at each pass through the reactor. By removing
the ethanol from the equilibrium mixture and
recycling the ethene, it is possible to achieve an
overall 95% conversion.
Since ethenes boiling is considerable low at -103.7C compared to
ethanol (78.37C) and water(100C ), it can be easily separate by
condensing water and ethanol into liquid phase and ethene in the gas
phase. The unreacted ethene is then recycle back to the reactor. The
condense ethanol and water mixture is distilled using fractional
distillation until distillate is about 95% ethanol which approach
azeotropic point of ethanol-water mixture. Further purification of ethanol required more advanced method such
as Molecular sieves, Extractive Distillation using Ethylene glycol, Azeotropic Distillation using Benzene.
In molecular sieves method, ethanol-water mixtures is pass through 3A
zeolite which the zeolite will adsorb the remaining water to produce nearly
pure ethanol.




In Extractive Distillation using Ethylene glycol, Ethylene glycol is used as
solvent to extract ethanol which utilize partial vaporization process in the
presence of a non-volatile and high boiling point entrainerwhich does not
form any azeotropes with the original components of the azeotropic mixture.









In Azeotropic Distillation using Benzene, benzene is added to ethanol-water
mixture and formed a new azeotropic point which is lower than ethanol
boiling point. The benzene, water and ethanol can be separated with
fractional distillation where most of ethanol is obtained in the distillate with
trace amount of benzene and water. However, this system is very sensitive
to other component.

Syngas Fermentation
Ethanol is produced through thermochemical pathways involve the gasification of biomass into synthesis gas or
syngas (a mixture of CO and H2), and then converting the syngas to biofuels by using chemical catalysts
process or by using microbial catalysts known as syngas fermentation.Biological catalysts (such as Clostridium
ljungdahlii, Clostridium autoethanogenum, Acetobacteriumwoodii, Clostridium carboxidivoransand
Peptostreptococcusproductus) are able to ferment syngas into liquid fuel more effectively than the use of
chemical catalysts(e.g., iron, copper or cobalt) (Heiskanen et al., 2007; Henstra et al.,2007).Syngas-fermenting
microorganisms use acetyl-CoA pathway to produce ethanol, acetic acid and other byproducts such as
butanoland butyrate from syngas.
The overall biochemical reactions that take place in the reductive acetyl-CoA pathway are shown in Eqs. (1)
(4).
6CO + 3H
2
O C
2
H
5
OH + 4CO
2
H =-217.9 kJ mol
-1
(1)
2CO
2
+ 6H
2
C
2
H
5
OH + 3H
2
O H =-97.3 kJ mol
-1
(2)
4CO + 2H
2
OCH
3
COOH + 2CO
2
H=-154.9 kJ mol
-1
(3)
2CO
2
+ 4H
2
CH3COOH + 2H
2
O H=-75.3 kJ mol
-1
(4)
(Pradeep ChamindaMunasinghe, Samir Kumar Khanal)

1.5.1 Comparison of the synthesis route:
Fermentation Hydration of ethene Cellulosic ethanol Syngas fermentation
Raw Material 1. Sugar
2. Yeast(Saccharomyces
cerevisiae)
(price from sigma-
aldrichcatalog)
1.Ethene gas from
petroleum cracking
2. Steam
3. phosphoric(V) acid
coated onto a solid
silicon dioxide support
1. xylose-extracted
corncob residue
2. -
glucosidase(enzymes for
breaking the cellulose
into sugar)
1. Carbon monoxide 2.
Carbon dioxide,
3. Hydrogen gas
4.Alkalibaculumbacchi
CP11
T
, CP13 and CP15
Abubackar, H.N.; Veiga,
M. C.; Kennes, C.
(2011)
Effectiveness 1. Maximum glucose
conversion is 14%
because the yeast cannot
grow under high ethanol
concentration.
1.5% of the ethene is
converted into ethanol
per pass through the
reactor.
2.By recycling the
ethanol, overall 95%
conversion of ethanol
can be achieved
1. conversion efficiency
with added -
glucosidase was 55%,
43%, and 24% for 15%,
25%, and 35% solids
loading
(Z. Lewis Liua, 2012)
1. Conversion from
33.3% to 100%,
2. Yield from CO from
10.7% to 50% (as shown
in Table.
(Kan Liu et al, 2013)
Advantage 1. Low pressure and low
temperature.
2. Carried out in
anaerobic conditions
3. Uses renewable
sources of material.
1. Continuous process
and high production rate.
2. Produces 100%
percentage yield
3. Few worker is needed
to monitor the process.
4. Notreatment is needed
to get rid of impurity.

1. Renewable biomass
2. Cheap, Non-Food
Feedstocks(Bothast and
Saha, 1997, Wheals et
al., 1999 and Zaldivaret
al., 2001).
3. No Crop
Displacement
4. Greenhouse Gas
Reduction
1. Low Pressure and
ambient Temperature
Operating condition.
2. Tolerate higher
amount of sulfur
compound and doesnt
require specific ratio to
CO2 and H2.
3.utilization of the whole
biomass including lignin
irrespective of the
biomass quality
4. elimination of
complex pretreatment
steps and costly
enzymes.
5. higher specificity of
the biocatalysts

6. no issue of noble
metal poisoning.
Disadvantage 1. enzyme zymase stops
functioning after alcohol
concentration of 14% so
limits concentration of
ethanol made
2. If aerobic conditions
introduced - can turn
into toxic products.
3. Produces very impure
ethanol which needs
further processing
4. Uses food sources as
raw material which will
drive the cost of food for
humans.
5. Slow Production Rate
1. High temperatures
and pressures expend lot
of energy when
manufacturing ethanol
2. Ethene finite source
and is made by burning
fossil fuels
1. Enzymes for
cellulosic ethanol
production are projected
to cost 79.25 US dollars,
meaning they are 20-40
times more expensive.
Sainz, M. B. (2011).
Commercial cellulosic
ethanol: the role of
plant-expressed
enzymes. Biofuels
2. Produces very impure
ethanol which needs
further processing
3. Slow Production Rate
1. Gas-liquid mass
transfer limitation
2. low volumetric
productivity
3. inhibition of
organisms.
4. Produces very impure
ethanol which needs
further processing
5. Slow Production Rate
(Pradeep
ChamindaMunasinghe,
Samir Kumar Khanal)
Type of Reactor Batch Continuous Batch Continuous

We have chosen hydration of ethene for our synthesis route because the process is very simple and high production rate. Since no pretreatment is needed and
no extra step is needed to purify the ethanol besides remove the water, the process is relatively simple to control. The overall conversion is only depend on how
well ethene is able to separate from the mixtures of ethanol and water and unreacted ethene is mostly recycle back to the reactor.






1.5.2 Comparison Purification Method of ethanol :
Distillation Molecular sieves Extractive Distillation
using Ethylene glycol.
Azeotropic Distillation
using Benzene
Solvent or Solid uses - 1. 3A Zeolite(adsorption
of water)
1.Ethylene glycol 1. Benzene
Advantage 1. Distillation can be
done up to 96% purity
using the difference in
boiling of water and
ethanol without using
any reagent.

1. Easy to regenerate
2. Minimal Labor
3. The process is inert.
Since no chemicals are
used, there are no
material handling or
liability problems, which
might endanger workers
4. Near theoretical
recovery
5. Has very few
operation parts
6. The molecular sieve
desiccant material has a
very long potential
service life.
7. Molecular sieves can
easily process ethanol-
containing contaminants
1. Smaller Distillation
Column.
2. Low energy cost
3. Low equipment cost
1. Widely used in
industry.
Disadvantage 1. Unable to purified
alcohol beyond 96%
because water and
ethanol form azeotropic
mixtures.
1. Zeolites is expensive 1. Need to add make-up
ethylene glycol
2. The system has
recycle stream which
advance process control
maybe needed.
3. Ethylene glycol is
weakly toxic.
1. Benzene is
carcinogenic and is
unsafe for medical or
chemical uses.
2. High Capital Cost and
energy cost.
3. Unacceptable number
of tower plate.

We have chosen to use molecular sieve as our purification method of ethanol because it doesnt use any solvent which may contaminate the ethanol.
Furthermore, once zeolites is saturated with water, it can be easily regenerated by heating it to remove the water molecule.

2.1 Production rate of Ethanol (
8
)
27065 tons 1000kg 1 year 1 kmol
year 1 tons 8000hours 46.07kg
= 73.4348 kmol/day
*Assume 8000 operating hours.
2.2 Material & Energy Balance
2.2.1 Assumption
1. Composition of Top distillate is 95%ethanol and 5% water.
2. Molecular sieve is able to fully separate ethanol and water to 100% purity.
3. 90% of the ethanol is recover from steam 4 at distillate stream 5 at Separator 2
4. Separator 1 is able to fully separate ethane into vapour phase and ethanol-water mixture into liquid
phase.
5. Single Pass Conversion is 5% of ethane, since all the ethene is being recycled. Overall Conversion is
100%
6. No heat to surrounding and pressure drop in all the components.
7. Based on the rule of thumb, reflux ratio is set to 1.5R
m
. Aspen calculate the minimum reflux is 0.9131. We
assume the reflux ratio is 1.3697.
8. Composition of reactor outlet stream 2 is calculated based on conversion and stoichiometry ratio.
9. Assume Feed condition entering the Separator 2 is q=1

Overall material balance:
n
0
= n
9
+ n
8
x
0
n
0
= x
9
n
9
+ x
8
n
8
y
0
n
0
= y
9
n
9
+ y
8
n
8
z
0
n
0
= z
9
n
9
+ z
8
n
8

Material Balance at Separator 1:
n
2
= n
3
+ n
4

x
2
n
2
= x
3
n
3
+ x
4
n
4
y
2
n
2
= y
3
n
3
+ y
4
n
4
z
2
n
2
= z
3
n
3
+ z
4
n
4

Material Balance at Mixer:
n
0
+ n
3
= n
1

x
0
n
0
+ x
3
n
3
= x
1
n
1
y
0
n
0
+ y
3
n
3
= y
1
n
1
z
0
n
0
+ z
3
n
3
= z
1
n
1
Material Balance at Separator 2:
n
4
= n
5
+ n
6

x
4
n
4
= x
5
n
5
+ x
6
n
6
y
4
n
4
= y
5
n
5
+ y
6
n
6
z
4
n
4
= z
5
n
5
+ z
6
n
6
Material Balance at Reactor:
n
1
= n
2

x
1
n
1
= x
2
n
2
y
1
n
1
= y
2
n
2
z
1
n
1
= z
2
n
2
Material Balance at Molecular Sieve:
n
5
= n
7
+ n
8

x
5
n
5
= x
7
n
7
+ x
8
n
8
y
5
n
5
= y
7
n
7
+ y
8
n
8
z
5
n
5
= z
7
n
7
+ z
8
n
8



Assumption Information:

Ethanol produced is 73.4348kmol/h. Therefore n
9
=73.4348kmol/h, since all ethanol is fully recover with
molecular sieve.
Ethanol is fully separated. x
9
=1 y
8
=1
Ethanol is 90% recover from stream 4 at stream 5. 0.9x
4
n
4
=x
5
n
5

Ethane is fully separated at the separator 1. z
3
=1 z
4
=

2.2.2 Mole Balance for reactor
From literature review, http://www.chemguide.co.uk/physical/equilibria/ethanol.html
Single pass Conversion of the reaction is 5%, ethene to water ratio is 1:0.6
Mole Balance on the Reactor
Species Initial feed Change Outlet
Ethene F
A0
- F
A0
X

( )
( )

Water 0.6F
A0
-F
A0
X

( )
( )

Ethanol 0 F
A0
X F
A0
X=P
Total 1.6 F
A0
- F
A0
X
(

)

P=amount of ethanol produce by the reactor= n
2
x
2
. Solving composition for n
2
stream.
Outlet Mole Faction of ethanol=

)
canceling the P, substitute X=0.05
X
2
=0.03226
Outlet Mole Faction of water=
()

)
canceling the P, substitute X=0.05
Y
2
=0.3235
Outlet Mole Faction of Ethene=
()

)
canceling the P, substitute X=0.05
Z
2
=0.6129
Solving all the material balance using Excel and Goal Seek, all stream data is tabulate as below.

Stream Data
0 1 2 3 4 5 6 8 9
Temperature(C) 300 300 300 30 30 78.75 99.62 25 25
Pressure(atm) 65 65 65 1 1 1 1 1 1
Total Mass flow(kg/hr) 16457.4 56319.082 56822.97 39860.88 18462.15 3452.789 15009.42 178.0606 1323.295
Total Mole flow(kmol/hr) 897.6661 2318.7312 2318.592 1421.065 897.527 77.2998 820.2272 3.865 73.4348
Mass Fraction
Water 0.952035 0.2782152 0.237864 0 0.796392 0.020171 0.97495 0 1
Ethene 0.047965 0.7217848 0.701492 1 0 0 0 0 0
Ethanol 0 0 0.060643 0 0.203608 0.979829 0.02505 1 0
Mass flow(kg/hr)
Water 15668.02 15668.826 13516.16 0 14703.11 69.64712 14633.43 0 1323.295
Ethene 789.3784 40650.256 39860.88 39860.88 0 0 0 0 0
Ethanol 0 0 3445.934 0 3759.044 3383.142 375.9893 178.0606 0
Mole Fraction
Water 0.9686 0.375 0.3235 0 0.90909 0.05 0.99005 0 1
Ethene 0.03135 0.625 0.6129 1 0 0 0 0 0
Ethanol 0 0 0.03226 0 0.09091 0.95 0.00995 1 0
Mole flow(kmol/hr)
Water 869.4794 869.5242 750.0645 0 815.9328 3.86499 812.0659 0 73.4348
Ethene 28.14183 1449.207 1421.065 1421.065 0 0 0 0 0
Ethanol 0 0 74.79778 0 81.59418 73.43481 8.161261 3.865 0

2.2.3 Energy Balance
Reactor:






Figure : Calculation Path for Hydration of Ethene Production

H
f 298C
Ethanol (gas) : -235100 J/mol
H
f 298C
Ethene(gas) : 52510 J/mol
H
f 298C
Water (gas) : -241818 J/mol (J.M.Smith, 1925)
H
298C
= H
f 298C
Ethanol (gas) - H
f 298C
Ethene(gas) - H
f 298C
Water (gas)
= (-235100) 52510 - (-241818)
= - 45792 J/mol

)(

)
Where (

) [

( )

] and

Table: Heat Capacities of Components for H
R
(J.M.Smith, H. V., 1925).

From T
0
=573.15 K to T=298 K

) [

()( )

)
]

Species n a n*a b n*b c n*c d n*d state
Ethene 1 4.08E-02 4.08E-02 1.15E-04 1.15E-04 -6.89E-08 -6.89E-08 1.77E-11 1.77E-11 g
Ethanol 0 6.13E-02 0.00E+00 1.57E-04 0.00E+00 -8.75E-08 0.00E+00 1.98E-11 0.00E+00 g
Water 1 3.36E-02 3.36E-02 6.88E-06 6.88E-06 7.60E-09 7.60E-09 -3.59E-12 -3.59E-12 g
Sum 7.44E-02 1.22E-04 -6.13E-08 1.41E-11
T=25C
C2H5OH
T=300C
C2H5OH
T=300C
C2H2+ H20


T=25C
C2H2 + H20




H
R
= (

) ( ) ( )
Species n a n*a b n*b c n*c d n*d state
Ethene 0.95 4.08E-02 3.87E-02 1.15E-04 1.09E-04 -6.89E-08 -6.55E-08 1.77E-11 1.68E-11 g
Ethanol 0.05 6.13E-02 3.07E-03 1.57E-04 7.86E-06 -8.75E-08 -4.37E-09 1.98E-11 9.92E-13 g
Water 0.95 3.36E-02 3.19E-02 6.88E-06 6.54E-06 7.60E-09 7.22E-09 -3.59E-12 -3.41E-12 g
Sum 7.37E-02 1.23E-04 -6.26E-08 1.44E-11
Table: Heat Capacities of Components for H
P
(J.M.Smith, H. V., 1925).
From T
0
=573.15 K to T=298 K

) [

()( )

)
]

H
P
= (

) ( ) ( )

= 291.7690 + (-45792) + (-291.1637)
= - 45791.39 J
2.3 Simulation Using Aspen Plus V12.1
Manual Calculation of MEB allow the rough estimate but based on many assumption. Aspen enable us to
simulate close to actual unit operation and eliminate some of assumption. In real situation, it is impossible to
fully recycle ethene because it is impossible to fully separate ethene from ethanol and water mixture even
though the boiling point of ethene and ethanol-water mixtures is very far apart. We can compare the actual
amount of reactant we suppose to used and condition needed to separate the all the component to desired
composition.
2.3.1 PFD of Aspen




2.3.2 Assumption
1. Conversion of the reactor B2 is assumed to be 5% of ethene.
2. Flash Drum S1 operating condition is set to 1 atm, 30C to condense as much ethanol and water
as possible.
3. Heater H1 is set to heat Stream 6 from 30C to Stream 95C.
4. Recovery of Distillation Column is Light Key Recovery. Ethanol at 0.95 whereas heavy key
Recovery water is set at 0.003
5. Heater H2 is set to heat Stream 4 from 30C to 300C and output pressure of 65atm to stream 5.
6. Based on the rule of thumb, reflux ratio is set to 1.5R
m
. Aspen calculate the minimum reflux is
9.95. We assume the reflux ratio is 15
2.3.3 Aspen Result
2.3.4 Heat Duty at Each Component
Reactor B2 Heat Duty= -770866.51 Watt (Cooling)
Heater H1 Heat Duty= 2532425.48 Watt (Heating)
Heater H2 Heat Duty= 6393769.33 Watt (Heating)
Flash Drum Heat Duty= -27625919 Watt (Cooling)
Reboiler heating required: 14651001 Watt
Condenser cooling required: 13587693.4 Watt
Ethanol Production Plant
Stream ID 1 2 3 4 5 6 7 8 9
Temperature C 300.0 293.9 300.0 30.0 300.0 30.0 95.0 80.1 101.7
Pressure atm 65.000 65.000 65.000 1.000 65.000 1.000 1.000 1.000 1.000
Vapor Frac 1.000 1.000 1.000 1.000 1.000 0.000 < 0.001 1.000 0.000
Mole Flow kmol/hr 1480.200 3084.757 3003.389 1604.586 1604.557 1398.803 1398.803 81.268 1317.535
Mass Flow kg/sec 7.634 20.045 20.045 12.411 12.411 7.634 7.634 1.009 6.625
Volume Flow cum/sec 0.245 0.563 0.555 11.023 0.315 0.008 0.009 0.637 0.007
Enthalpy MMkcal/hr -77.362 -55.780 -56.443 16.085 21.582 -96.282 -94.105 -4.499 -88.691
Mass Flow kg/sec
WATER 7.000 7.248 6.841 0.248 0.248 6.593 6.593 0.020 6.573
ETHYL-01 0.634 12.682 12.048 12.047 12.047 < 0.001 < 0.001 < 0.001 trace
ETHAN-01 0.116 1.157 0.116 0.116 1.041 1.041 0.989 0.052
Mass Frac
WATER 0.917 0.362 0.341 0.020 0.020 0.864 0.864 0.020 0.992
ETHYL-01 0.083 0.633 0.601 0.971 0.971 16 PPM 16 PPM 118 PPM trace
ETHAN-01 0.006 0.058 0.009 0.009 0.136 0.136 0.980 0.008
Mole Flow kmol/hr
WATER 1398.789 1448.332 1366.963 49.545 49.543 1317.418 1317.418 3.952 1313.466
ETHYL-01 81.411 1627.375 1546.006 1545.991 1545.964 0.015 0.015 0.015 trace
ETHAN-01 9.051 90.419 9.050 9.051 81.369 81.369 77.301 4.068
Mole Frac
WATER 0.945 0.470 0.455 0.031 0.031 0.942 0.942 0.049 0.997
ETHYL-01 0.055 0.528 0.515 0.963 0.963 11 PPM 11 PPM 188 PPM trace
ETHAN-01 0.003 0.030 0.006 0.006 0.058 0.058 0.951 0.003

CHAPTER 3: DISTILLATION COLUMN SIZING
3.1 Determine the number of stages required.
Given Equilibrium Data
Equilibrium
Data
Vapor-Liquid Equilibria,
Mass fraction of ethanol
Vapor-Liquid Equilibria, Mole
fraction of ethanol
Temperature xa ya Xa Ya
100 0 0 0 0
98.1 0.02 0.192 0.049598753 0.377972007
95.2 0.05 0.377 0.118622771 0.607448676
91.8 0.1 0.527 0.221262739 0.740199725
87.3 0.2 0.656 0.389980869 0.829829708
84.7 0.3 0.713 0.522884966 0.863998008
83.2 0.4 0.746 0.630284291 0.882497159
82 0.5 0.771 0.718877758 0.895936486
81 0.6 0.794 0.793207149 0.907887433
80.1 0.7 0.822 0.856460703 0.92192965
79.1 0.8 0.858 0.910942381 0.93921371
78.3 0.9 0.912 0.958358566 0.963638472
78.2 0.94 0.942 0.975646792 0.976488286
78.1 0.96 0.959 0.983967194 0.98355611
78.2 0.98 0.978 0.992082431 0.991279923
78.3 1 1 1 1

Graph 1 is plotted to find the pinch point and hence find the minimum reflux ratio using McCabe-Thiele
Method. (see appendix)
Assume feed condition q=1. The chemical that leave the product is cool sufficiently to saturated liquid
condition.
From Graph 1, the pinch point is determined y=0.54 , x=0.091

Operating line is draw from x
D
and with slope 1.3697 at Graph 2. (see appendix)
Theoretical Stage Obtained=11.5 stages

3.2 Determine the Height of the Distillation Column
The entering and exiting composition of ethanol for Seperator 2 is
X
4
=0.091 , X
5
=0.95 , X
6
=0.01
At , X
6
=0.01. Boiling Temperature is

At, X
5
=0.95, Dew Point is

Solve T
W
=78.75C Solve T
D
=99.62C

= 89.19C
Using Table A.3-12 and Fig A.3-4 at 89.19C:
(ethanol)=0.385cp (water)=0.345cp

L
=0.385(0.0909) +0.345(0.90909)
=0.3486cp
Vapour Pressure
log (P_sat) = A - B/(T+C) : P_sat [torr], T [C]
torr x 133.22 = Pa
source: Perry 13-4
Species A B C
Ethanol 8.1122 1592.864 226.184
Water 8.07131 1730.63 233.426
P(ethanol)= 152.6kPa P(Water)=67.4kPa
=(152.6/67.4)=2.2641
E
0
=0.492(
L
)
-0.245

=0.0492(0.3486 x 2.2641)
-0.245
=0.5124

Assume Mid-size tower where 0.6m Tray Spacing for 1.0m diameter tower.
HETP=(0.6/0.5124)
=1.1507m/theoretical Stage
number of step=11.5-condenser- reboiler =9.5 Steps
Tower Tray Height=1.1507 x 9.5= 10.931m

3.3 Simulation Using Aspen Plus
Distillation column Sizing D1

Assume Tray Spacing of 0.8m for 4m tower in
diameter (large tower)
Tower Height= 13.927(0.8)=11.1m


4.Conclusion
Based on the manual MEB calculation for producing ethanol, ethanol obtained at stream 9 is 73.4348kmol/h
and the feed required is 869.46kmol/h of water and 28.141kmol/h of ethene. Compared to aspen simulation,
Ethanol obtained is 77.301kmol/h which is close to our targeted production rate, but the feed is required is
much higher at 1398.78kmol/h of water and 81.411kmol/h. This is due to the fact that ethene cannot be fully
separate from ethanol-water mixtures. Composition of feed in aspen simulation is adjusted so that distillate
of separator 2 is producing nearly azeotropic mixture of water ethanol mixtures. Based on McCabe-Thiele
Method, were graph were hand draw and assumption of constant molar flow rate throughout the distillation
column is made, 11.5 Theorectical Stage is estimated requirement. However, from aspen result obtained,
13.927 stages were actually required to separate ethanol-water mixtures close to the azeotropic point.

5.REFERENCES:

1. Prof.Shakhashiri,2009,ethanol,retrieved from:
http://scifun.org/GenChem/Enrichment/Strang[Jan09].htm
2. World Fuel Ethanol Analysis and Outlook,Dr Christoph Berg,F.O.Licht,April 2004.
3. Ethylene Highlights,Retrieved on 19 December 2013.Retrieve from:
http://www.fibre2fashion.com/textile-market-watch/ethylene-price-trends-industry-reports.asp
4. Platss Global Ethylene Price Index,Retrieved on 19 December 2013.
Retrieve from:
http://www.platts.com/news-feature/2013/petrochemicals/pgpi/ethylene
5. Jim Clark,April 2013, The manufacture of ethanol, retrieved from:
http://www.chemguide.co.uk/physical/equilibria/ethanol.html
6. Tony Ackland, 5 March 2012, Fermenting.Retrieved from: http://homedistiller.org/wash/ferment
7. Ethanol information India. Retrieved from:
http://www.ethanolindia.net/molecular_sieves.html
8. Comparison of the main ethanol dehydration technologies through process simulation, Paola A.
Bastidas,aIvn D. Gil,a Gerardo Rodrgueza
9. Ethanol dehydration by azeotropic distillation with a mixed-solvent entrainerA. Chianese,F.
Zinnamosca.
10. C.J.Geankoplis, (2003). Transport Processes and Separation Process Principles. Fourth edition.
11. J.M.Smith, H. V. (1925). Introduction to Chemical Engineering Thermodynamics. New York:
McGraw-Hill.
12. Berg, USDA. (July 2006). The Economic Feasibility of Ethanol Production from Sugar in the United
States. 78. Retrieved from
http://www.usda.gov/oce/reports/energy/EthanolSugarFeasibilityReport3.pdf
13. Kan Liu et al (2013). Continuous syngas fermentation for the production of ethanol, n-propanol and
n-butanol.
14. Chao Fan et al. (2013). Efficient ethanol production from corncob residues by repeated fermentation
of an adapted yeast

6. Appendix