Chapter 1 To 4

0
CHAPTER 1
INTRODUCTION
1.1
1.1.1
Process Background
Chemical Background of Ethyl Acetate
Ethyl acetate (ETAC or EA) is the organic compound that is an ester derive from the
reaction of ethanol and acetic acid. Its chemical formula can be written as
CH3COOCH2CH3 or can be simplified as C 4H8O2. It is a colourless liquid and has a
smell that is slightly sweet and fruity. According to Gaspar [1], ethyl acetate has been
largely used as a solvent in paints, coatings, inks and adhesives. Besides, it also has been
used as a solvent in many chemical process replacing aromatic compound which
generate serious damage to the environmental and human beings. Other than that, its
physiologic harmlessness in combination with its oleophilic characters has made it
especially suitable for extraction processes in the food industry and for the preparation
of cosmetics. Its low boiling point is the basis for its application as a high grade
defatting agent. Therefore, because there is no ETAC supply in Malaysia as well as
increase in demand globally, ethyl acetate has been chosen as a product for this study
2
1.2 Chemical and Physical Properties of Ethyl Acetate
Table 1.1: Physical and Chemical Properties of Ethyl Acetate [2]
Properties
Formula
Molecular weight
Melting point
Boiling point
Flash point
Critical temperature
Vapour density
Vapour pressure
Values
C4H8O2
88.11g/mol
-83.6
77.1
-3
250
Viscosity
3.04 (Air=1)
12.4kPa (@20
0.46mPa.s (@20
Specific gravity
Appearance
Odour
Odour threshold
Solubility
0.902
Colourless liquid
Ether-like, fruity
3.9ppm
Soluble in cold water, hot water, diethyl
Heat of combustion
Heat of vaporization
Suface tension
ether, acetone, alcohol, benzene

2238.1 kJ/mol
35.60kJ/mol
24dynes/cm (@20
1.3 Manufacturing Process of Ethyl Acetate
Ethyl acetate is synthesized in industry via classic Fisher esterification. This

method is the first method that has been commercializes in industry. The process of the
reaction is between ethanol and acetic acid. According to Katikaneni and Cheryan
[3],these mixtures will converts to the ester in about 65- 75 % of theoretical. The
reaction of this mixture can be accelerated by adding acid catalyst.
Besides, Tishchenko Reaction is one of the method to produce ethyl acetate. From
the research of Seki et al [4], this method was first discovered by Claisen. This method
used the catalytic dimerization of aldehydes that will produce the corresponding ester.
In view of synthetic organic chemistry, the Tishchenko Reaction is one of the most
ideals methods for preparing ester because no toxic reagent require for the reaction to
occur[4].
Ethyl acetate also can be produced by dehydrogenation process of ethanol. Ethanol

is dehydrogenated to acetaldehyde which further reacts to form ethyl acetate. Since it is
only one feedstock, it will reduce the production and investment costs. This process was
developed by Davy Process Technology Limited. This process has been industrially
employed and used copper as the catalyst.
The alkylation of acetic acid and ethylene is one of the manufacturing process to
produce ethyl acetate. According to Yamamoto et al [5], this method has attracted much
attention because it is ideally has no by-product is produced with this reaction. This
method has been commercialized named Avada technologies.
1.4 Application and Uses of Ethyl Acetate
Ethyl acetate can be used in a wide variety of industries including; food

production, beverage, pharmaceutical, cosmetics and various other industries.
Table 1.2: Uses of ethyl acetate in various industry [6]
4
Food Production
Ethyl acetate is commonly used as a flavour enhancer in food

production.
Some example of the flavour is in essence
manufacturing of pineapple, bananas, strawberries and other fruit

flavours and whiskey, cream.
Beverage
It is usually used as a flavour enhancer in beverage.
Pharmaceutical
Ethyl acetate is widely used as extraction gent, intermediate in the

pharmaceutical.
Cosmetics
Ethyl acetate is often used as aroma enhancer in cosmetic especially

in perfumes. Other than that, it is used in nail polisher and nail
polisher remover.
Others industries
It is widely used as industrial solvent in various other industries

such as in coatings, adhesives and rayon to dissolve material.
Beside, ethyl acetate is used as a solvent for varnishes, lacquers, dry
cleaning and may also present in wines.
1.5 Process Safety of Ethyl Acetate

1.5.1
Toxicology Information of Ethyl Acetate
The toxicity data were extracted from Material Safety Data Sheet (MSDS). These
data were used to indicate the toxic level of the chemical and it is needed as references
when deciding the design of the plant.
Table 1.3: Toxicity information of ethyl acetate [2]

Entry routes
Toxicity to animals
Absorbed through skin, eye contact, inhalation, ingestion

Acute oral toxicity (LD50): 4100mg/kg (mouse)
Acute toxicity of the vapour (LC50): 45000mg/m 3 -3 hours
Chronic
effect
(mouse)
on Cause damage to the following organs: mucous membrane,
humans
upper respiratory tract. May cause damage to the following
organs: blood, kidneys, liver, central nervous system (CNS).

Other toxic effects on Hazardous in case of ingestion, inhalation. Slightly hazardous
humans
in case of skin contact( irritant, permeator)
Special remarks on May effect genetic material (mutagenic).

Chronic Effects on Ay cause reproductive effects( based on animal test data)
Humans
Special remarks on Acute potential health effects:
other toxic effects in
humans
1. Skin: May cause skin irritation

2. Eyes: May cause eye irritation. May cause irritation of
conjunctiva
3. May cause respiratory tract and mucous membrane
irritation
4. May affect gastrointestinal tract(nausea, vomiting)
5. May affect behavioural/ central nervous system(mild
central nervous depression-exhilaration, talkativeness,
slowed reaction time, dizziness, etc)
1.5.2
Storage and Handling of Ethyl Acetate

Ethyl acetate is a flammable clear liquid, which is used in spectrophotometry and
environmental testing. Since it is flammables, it is recommended a safe chemical storage

building that meets specific regulations for storing the ethyl acetate. It must be keep
separated from incompatibles substances such as oxidizers.
Other than that, it is
suggested that it need to be away from the source of ignition and must be store in a
tightly closed container. Besides, store it in a cool, dry and well-ventilated area.
6
As for handling, use proper personal protective equipment and wash thoroughly
after handling. Avoid contact with eyes, skin, and clothing and avoid breathing vapour or
mist. If spilled, absorb it with inert material (e.g. vermiculite, sand) and then place in
container. Provide ventilation and remove all sources of ignition.
7
1.6 Market Survey and Outlook
1.6.1 Market Demand
The global production of ethyl acetate (ETAC) grew by over 80% from 2004 to
2011 and exceeded 2.5 million tonnes in 2013 [7]. Asia-Pacific captured the biggest
share of the global production volume and China is an unrivalled leader of the world
ETAC market, accounting for over half of the global ETAC production. It is followed by
India, the UK, Japan and Brazil. The combined ETAC supply volume was more than
2.57 million tonnes in 2013 (Figure 1.2).
Figure 1.1: Global Ethyl Acetate (ETAC) Production in 2013 [8]
Figure 1.2: Production rate of ethyl acetate from 2005 to 2013 [9]
Figure 1.3: Ethyl acetate market price from 2004 to 2013 [10]
A)
North American [11]
9
According to ICIC Business Chemical, there are five ETAC plants capacity that
serve the US market - two owned by Eastman, two by Solutia, and one by Celanese in
Mexico - totals around 102,500 tonnes. Celanese's ETAC plant in La Cangrejera,
Mexico, sends about 20% of its 92,000-tonne annual capacity to the US according on
Mexicos export to the US. US imports in the first 11 months of 2011 totaled 37,892
tonnes, a 10% increase over 34,585 tonnes in the same period of 2010. The increase
partly is due to cracker outages and increases in market demand. The high demand of
ETAC come from inks and coatings which represents 60%, and 10% comes from
adhesives and cosmetics. According to US retail research firm NPD Group. Sales of nail
polish, a popular downstream use, soared in 2011.
Figure 1.4: The capacity of ethyl acetate in North America [11]

B)
Europe [12]
Burridge (2011) from ICIS Business Chemical reported that, Europe still relies
on imports to meet demand, with material sourced mainly from Eastern Europe, India,
10
China and Brazil. Large import volumes arrived in Europe from India and China in
2011. Players are concerned that the current uncertainty and slower demand will push
prices down. The price of ETAC keep rising, however, prices dropped heavily in August
to 976/tonne. Figure 1.5 shows the list of company in Europe that serve the Europe
market totals around 441,000 tonne annual capacity.
Figure 1.5: Prices of Ethyl Acetate from 2009 to 2011[12]
11
A)
Asia [14]
According to ICIS Business Chemical, China is the largest ETAC producer and
exporter in the world, with an estimated capacity of 3m tonnes/year as of May 2013.
Demand in China has been estimated by market participants at 1m tonnes/year. Other
countries in Asia that produce ETAC are India, Indonesia, Japan, Singapore, South
Korea and Taiwan. However, several of these countries purchase volumes from China
due to the price competitiveness of Chinese material so as to meet local demand. Japan,
South Korea and Taiwan were China's three largest markets by volume in 2012. Asia
ETAC capacity per year is shown in Figure 1.6.
Figure 1.6: Asia ETAC capacity tonnes per year [15]

1.6.2 Market Outlook [11,12,14]
12
A study done by ICIS Chemical Business generally agrees that ETAC in Asia is
in oversupply due to capacity expansion in China and India in recent years. This results
in supply overhang in which has prevented several Asian producers from to utilize their
plant in full capacity since 2012. Despite Chinas overcapacity in ETAC, Kamel (2010)
believe that it was not a threat to the world market especially Europe as the European
market requires a certain quality and realibility of products. He added that Chinese are
definitely not a competitior as Chinese continuing to supply China. New venture of
ETAC expansion in Middle East happen for the first time In May 2013. Saudi Arabia's
Saudi International Petrochemical (Sipchem) started up a 100,000 tonne per year of
ETAC plant in Al-Jubail. Large part of ETAC is likely to be market in Europe. The
technology is provided by Rhodia and the feedstock of ethanol will obtained from
Brazil.
The US will continue to depend on imports to satisfy demand, because this niche
product is a mature market with growth tracking GDP. Moreover, Zeachem attempts to
start up and produce ETAC from biomass as they received a $232.5 million grant from
the US Department of Agriculture. Making ETAC from biomass is cost effective. This
could be affect the plant capacity in that region. Moreover, China's Taixing Jinjiang has
started its new 200,000 mt/year ethyl acetate plant in June 2015 [16].
Overall, Southeast Asia is set to become the most important region globally for ethyl
acetate production and consumption, where demand is growing rapidly by 5 to 6% per
year [17]. For Southeast Asia outlook, ETAC imports from China by volume were led
by Indonesia and Vietnam, Thailand, the Philippines, Malaysia and Singapore.
1.6.3 Market Price of Raw Materials
13
In the process to produce ETAC, ethanol, acetic acid and ethylene are the major
feedstocks to be used in industries.
In the recent years, ethanol production from
renewable sources as an alternative for a low cost ethanol availability has shown
interest among industries. This scenario has favored many to study the production of
different chemical for instance, ethyl acetate from bio-ethanol due to low cost and
environmental friendly. Many believe that, ethanol represents a promising alternative
source of feedstocks over ethylene, acetic acid and acetaldehyde as raw materials for
manufacturing ethyl acetate. According to Platts Financial (2015), Philippines is one of
the country that produce bioethanol recently (Figure 1.7), thus, this would be an
advantages for industries to market ETAC in Southeast Asia especially Malaysia, due to
lower price of feedstock. Figures below show the price of the major feedstock to
manufacture and process ETAC. Asian acetic acid output was estimated to be 8 million
to 9 million tonnes per year in 2015 with below 500 usd dollar per tonne while , global
ethylene prices tumbled 15% in January 2015 to $834 per metric ton from $977 per
metric tonne in December.
Figure 1.7: Ethanol market price on December 2015 [18]
14
Figure 1.8: Acetic acid market price on December 2015 [19]
Figure 1.9: Ethylene market price on December 2015 [17]

1.6.4 Market Price of Ethyl Acetate
15
In 2011, according to Kelly et al. (2012), the prices of ETAC range, jumped 29%
mostly because of increases in raw materials such as industrial ethanol (+8%) and
ethylene (+29%). To market ETAC globally was still promising as the distributor spot
prices rose to 84 to 87 cent per pound ($1,852-1,918/tonne), consistent with Kelly et al.
(2012) [20]. In October 2012, the price of ETAC increase to an average of $927.50 per
tonne FOB China and it is expected to increase annually for over years. In European
market, the price of ETAC is an average of $1,082.27 to $1,126 per tonne in midOctober 2011 studied by ICIS Business Chemical. While in recent report study by ICIS
shows that in January 2014, the price of ETAC was dropped an average of $ 957.40 per
tonnes contrary with the previous expectation by the distributors due to Chinas
economic slowdown and low price of feedstocks and crude oil globally.
Figure 1.10: Ethy acetate market price in US Gulf on January 2012 [20]
1.7
Process Selection
16
Ethyl acetate is an important environmental friendly solvent, industrially used in

a wide range of applications including printing inks, surface coating, flavors and essence
and pharmaceuticals. Ethyl acetate can be synthesized into four possible processes;
a) Fisher esterification
b) Tischenko reaction
A)
c)
d)
The akylation of acetic acid with ethylene

The dehydrogenation of ethanol
Fisher esterification
A conventional method of producing ethyl acetate is by esterification of ethanol
with acetic acid (reaction 1) which is synthesized mainly in industry in the presence of
catalyst. The reaction can obtain 90% acetic acid conversion and 100% ethyl acetate
selectivity [21]. The reaction is expressed as follow;
C2 H 5 OH +C H 3 COOH C H 3 COO C2 H 5 + H 2 O
(1)
The technology for this route was described by Hoechst A.G. The pilot plant
uses three distillation columns (Figure 1.1). Dehydration and the azeotropic distillation
of ethyl acetate and water take place in the first column. Acetic acid and ethanol are fed
into the bottom of the column. At the second column consist of ester, water, and alcohol
at the distillate while pure ethyl acetate is obtained as the bottom product. The third
column to give waste water at the base while at the top is recycled to the reaction
column.
17
Figure 1.11: Pilot plant of ETAC from acetic acid and ethanol by Hoechst A.G [22]
B)
Tischenko reaction
In this route, ethyl acetate is produced by dimerization of acetaldehyde in the
presence of catalyst such as aluminum alkoxide, sodium alkoxide or solid bases like
alkaline earths oxides [23]. The conversion can be achieved to 61% yield of the ester by
adding aluminum ethoxide at -20C [24]. This technology took place mainly in europe
during the first half of this century and the overview of the process for production of
ethyl acetate was described by Hoechst as shown in Figure 1.1.The reaction is expressed
by
2C H 3 CHO C H 3 COO C2 H 5
(2)
18
Figure 1.12: Tishchenko process for ethyl acetate. Hoechst A.G. [22]
C)
The process to produce ethyl acetate in this route involving the alkylation of
acetic acid with ethylene is shown below in reaction 3. Ethyl acetate is respectively the
addition of ethylene to acetic acid.
This technology (Avada) has been
commercialized.by INEOS (formerly as BP) for this process at its plant in Hull based on
ethylene and acetic acid as a feedstock with a solid catalyst [13]. This process is
preferable at locations where competitive ethanol is not available. Figure 1.13 shows a
process flow diagram of AVADA technology for production of ethyl acetate.
C2 H 4 +C H 3 COOH C H 3 COO C 2 H 5
(3)
19
Figure 1.13: Addition of ethylene to acetic acid for production of ethyl acetate by
AVADA team in 2001 [13]
D)
Dehydrogenation of ethanol
Ethyl acetate can also be obtained by dehydrogenation of ethanol, in a

competitive way with respect to the before mentioned processes. In particular, this
process has become very attractive as ethanol is the only feedstock needed for the
process as well as the growing production of bio-ethanol. This method is cost effective
than esterification, however, it results in surplus of ethanol feedstock in the plant. A
conversion of 65% with selectivity to ethyl acetate of 99% can be obtained at 240C and
20 bar [26].
20
The side reaction may be obtained as shown in Figure 1.4. The overall reaction of direct
conversion of ethanol to ethyl acetate, according to the following reaction:
2C 2 H 5 OH C H 3 COO C 2 H 5 +2 H 2
(3)
This technology has developed by Davy Process Technology from UK. This
method, which only uses ethanol feedstock, is used by South Africa's Sasol in a 50,000
tonne/year plant in Secunda. The ethanol is dehydrogenated to acetaldehyde, which
further reacts to form ethyl acetate. The Davy dehydrogenation system applies a simple
reaction vessel containing multiple catalyst beds and the reactants continue downward
through the catalyst beds for dehydrogenation process and being re-heated along the
way. The schematic diagram of the flowsheet is described in Figure 1.3.
Figure 1.14: Davy Process flowsheet of ethyl acetate production [25]
21
Figure 1.15: Ethyl acetate process dehydrogenates ethanol in a two-stage reaction [25]
Figure 1.16: A simplified scheme of the process based on the use of copper/copper
chromite commercial catalyst by Santacesaria et al. (2012) [26]
1.7.1 Economic Potential (EP)
22
Economic considerations are obviously major constraints on any engineering
design. The EP is calculated based on the gross profit (i.e., the profit excluding the cost
of equipments and operating costs) pathway. The gross profit is used as a vehicle for
screening out the process path that cannot be profitable. The gross profit is computed as
the income derived from the sales of products and byproducts less the costs of feedstock
as a mass basis. The average price of raw materials and products based on year 2015
and 2016 are shown in Table 1.3.
Table 1.3: The average price of raw materials and products

Chemicals
C
Ethanol )
Molecular
Cost
Weight (g/mol) (US dollar/kg)
46.07
0.626
References
Platts McGraw Hill financial
Acetic acid
(C H 3 COOH )
60.05
0.4
Tecnon Orbichem
Acetaldehyde
(C H 3 CHO)
44.05
3.5
Orchid Chemical Supplies Ltd.
Ethylene
C
( 2 H 4 )
28.05
0.834
Platts McGraw Hill financial
88.11
0.93
Technon Orbichem
www.cleancaroptions.com
Ethyl acetate
(C H 3 COOC 2 H 5 )
Hydrogen
( H2 )
23
Overall Chemical Equation
Kmole
Molecular Weight (kg/kmol)
Weight
Weight / Weight EA
Price of Component ($/kg)
Gross profits ($/kg EA)
Reactants
C2 H 5 OH
C H 3 COOH
1
46.07
46.07
0.52
0.59
Products
C H 3 COO C 2 H 5
1
1
60.05
88.11
60.05
88.11
0.68
1
0.4
0.93
0.93(1) 0.4(0.68) 0.626(0.52) = 0.332
H2O
1
18
18
0.20
0
Tischenko reaction
Reactants
2C H 3 CHO
Kmole
Weight
Weight / Weight EA
Products
C H 3 COO C 2 H 5
2
44.05
88.11
1
3.5
1
88.11
88.11
1
0.93
0.93 3.5 = -2.57

Reactants
C2 H 4
C H 3 COOH
Products
C H 3 COO C 2 H 5
Kmole
1
28.05
1
60.05
1
88.11
24
Weight
Weight / Weight EA
28.05
0.32
0.834
60.05
0.68
0.4
1(0.93) 0.68(0.4) 0.32(0.834) = 0.391
88.11
1
0.93
Dehydrogenation of ethanol
Reactants
2C 2 H 5 OH
Kmole
Weight
Weight / Weight EA
2
46.07
92.14
1.045
0.629
C H 3 COO C 2 H 5
Products
2 H2
1
88.11
88.11
1
0.93
0.045(7) + 0.93(1) 0.626(1.045) = 0.591
2
2
4
0.045
7
1.7.2 Detailed Analysis of Process Selection
Detailed analysis on Fisher esterification and Tischenko reaction

Aspect
Overall Reaction
Path
Raw Material
Catalyst
Tischenko reaction
The akylation of acetic
Dehydrogenation of
acid with ethylene

ethanol
C2 H 5 OH +C H 3 COOH C
2CHH33COO
CHOCC
+H
2C 2 C
H25 H
OH
2 H 5H
3 COO
2 O C 2 HC
5 2 H 4 +C H 3 COOH C H 3 COO
5 C H 3 COO C 2 H 5 +2 H 2
Ethanol and acetic acid
acid catalysts (sulfuric
Acetaldehyde
aluminum alkoxide; sodium
Ethylene; Acetic acid

sulfuric acid or solid acid
Ethanol
Copper Oxide,
25
acid, para-
alkoxide
catalyst (Avada process).
Zinc Oxide,
ion-exchange resins).
0.332
-2.57
0.391
0.591
-Technique is advance;
-Reaction without loss of
-Feedstock is quite a
small molecules;
few;
toluenesulfonic acid or
Gross Profit
($/kg)
Advantages
-High product yield rate
-High product yield
and alternative
-low corrosiveness
-Simple Technique;
-Able to produce high
-producing low acid waste
Producing cost
-Low corrosiveness,
quality of ethyl acetate
water
relatively low
investment, energy
-Relatively friendly to
consumption and pollution

Disadvantages
-High corrosiveness
environment
-Only competitive when the -Ethyl acetae unit should
which cause high
raw material cost is low,
maintenance fee for
-Not environment friendly
equipment
as it may
-Catalyst is expensive
build with ethylene unit

which result in high capital
cost
producealuminium
Technology
available
Hoechst A.G
hydroxide
Hoechst A.G
Avada by INEOS;
Davy technology
26
27
1.8
It
is
Project Feasibility and Site Study
important
to
conduct
feasibility
study
before
starting
plant
construction to determine whether our plant is feasible to be built in term

of economic aspect, safety, environmental impact controllability and the
flexibility for our plant. Otherwise, it will leads to poor performance of the
project and cause losses and damage in various aspect.
1.8.1 Site Study
Location for the chemical plant plays very important role because it
can effect on the plant operation and its success. Besides, it is also must
be taken into consideration in order to maximize profitability of the project,
minimize cost of production and distribution as well as for the future
expansion of the plant. However, other factors such as room of expansion
and safe living conditions for plant operation as well as surrounding
community are also need to be considered. For the construction of the
ethyl acetate, we have listed three main industrial estates that located at
east and south of Peninsular Malaysia. The industrial estates are:
Teluk Kalong, Terngganu.
Gebeng Industrial Area, Pahang
Pengerang,Johor.
1.8.2 Factors in Selecting Site
28
A suitable site must be found for a new project, the site and
equipment layout planned because for long term period, the plant site can
consequence capital cost, operational cost and market price. Therefore, it
is essential to consider many factors in selecting site. Here the factors of
the final site are choose based on a complete survey of raw material
availability and price, source of power and water, reasonable land price,
good transportation network (via land, sea and air), the advantages of
various geographical areas and last but not least facility and infrastructure
of the site.
1.8.3 Raw Material Availability
The production of ethyl acetate uses ethanol and acetic acid as the
main raw material.
Therefore, source of this raw material need to be
identify and considered. This is crucial if large volumes of raw material are
required for production.
The distance between the site and source of
supply should be given attention because if the raw material is far from
the site, it have to be exported in such a distance. Thus, the site must be
located near to port which has excellent infrastructures and good
transportation network.
1.8.4 Land Price
Sufficient land must be available for the purposed of plant and future
expansion. The cost of the land and premise also need to be included in
29
the site selection because it will affect the final cost of the project. The
cost of the land depends on the location and it should be economical as
possible to reduce the total investment and construction cost. Besides,
the geographical of the land should be ideally be flat, suitable load-bearing
characteristics, well drained and contour structure of the land.
1.8.5 Electric and Water Supply
In chemical industrial plant, large quantities of water and electric

supply are required for plant operation. Thus, this two utilities are very
important and their source should be available near to site location to
minimize the cost. For water supply, process water can be drawn from a
river, wells or purchased from a local authority.
Meanwhile, the power
supply is easily available and obtained from Tenaga Nasional Berhad (TNB)
in Peninsular Malaysia. Table 1.1 shows industrial tariff by TNB.
30
Table 1.1 : Industrial Tariff by TNB
Table 1.1 (continued)

TARIFF CATEGORY
CURRENT RATE (1 JAN 2014)
TARIFF D - LOW VOLTAGE INDUSTRIAL TARIFF

For the first 200 kWh (1 -200 kWh) per
month
38.00 sen/kWh
For the next kWh (201 kWh onwards) per

month
44.10 sen/kWh
The minimum monthly charge is RM7.20

TARIFF DS SPECIAL INDUSTRIAL TARIFF (FOR CONSUMERS WHO
QUALIFY ONLY)
For all kWh
42.70 sen/kWh

TARIFF E1 - MEDIUM VOLTAGE GENERAL INDUSTRIAL TARIFF
For each kilowatt of maximum demand per
month
29.60 RM/kW
For all kWh
33.70 sen/kWh

TARIFF E1S SPECIAL INDUSTRIAL TARIFF (FOR CONSUMERS WHO
QUALIFY ONLY)
month
23.70 RM/kWh
For all kWh
33.60 sen/kWh
31
TARIFF E2 - MEDIUM VOLTAGE PEAK/OFF-PEAK INDUSTRIAL TARIFF
month during the peak period
37.00 RM/kW
For all kWh during the peak period
35.50 sen/kWh
For all kWh during the off-peak period
21.90 sen/kWh

QUALIFY ONLY)
32.90 RM/kW
33.60 sen/kWh
19.10 sen/kWh

TARIFF E3 - HIGH VOLTAGE PEAK/OFF-PEAK INDUSTRIAL TARIFF
35.50 RM/kW
33.70 sen/kWh
20.20 sen/kWh

QUALIFY ONLY)
29.00 RM/kW
31.70 sen/kWh
17.50 sen/kWh
32
1.8.6 Transport Facilities
Since freight charges of raw materials and finished goods enter into the cost of production,
therefore transportation facilities are becoming the governing factor in economic location of
the plant. Depending upon the volume of the raw materials and finished products, a suitable
method of transportation like rail, road, water transportation (through river, canals or sea) and
air transport is considered and accordingly plant location is decided.
In fact, storage and shipping are considerable important if the raw material supply and the
product distributions are dealing with important and exportation. Important consideration
should be that the cost of transportation should remain fairly small in comparison to the total
cost of production.
1.8.7 Politics and Economics
Since new chemical plant is to be build, other than creating employment opportunities, this
project will generate tax revenue and income for the government in terms of payroll tax. The
establishment of such factory will have a foreign exchange saving effect to the country by
substituting the current imports. The project will also create backward and forward linkage
with the chemical production sub sector and the manufacturing sector, respectively.
In terms of government incentives, it can influence foreign and local investors to invest in the
specific area. If more incentives are offered, then these incentives will give more feasibility
for the plant to be built.
33
1.8.8 Other Facilities
Despite electric and water supply, and transport facilities, waste and disposal facilities
should be taken into consideration. It is one of the most crucial part in plant design as
improper design and ways of dumping will resulted in environmental and society problem.
Thorough study should be made regarding disposal of water like effluents, solids, chemicals
and other waste products likely to be produced during the production process. The site
selected should have satisfactory and efficient disposal system for plant wastes or effluents
such as drainage system and dumping
1.8.9 Availability and Stability of Labour and Services

.
The plant should be placed in an area where sufficient labour supply is available. Available
manpower from local technical institutes will give a beneficial contribution to run the plant
smoothly. Besides that, inexpensive manpower from the surrounding area will contribute in
reducing the cost of operation.
The few factors to be considered regarding availability of labours and services are:
availability of men power of requisite skill, competitive wage rates of workers, other
enterprises which are complementary or supplementary regarding raw materials, other input,
labour and skill required, moderate taxes and the absence of restricting laws, a favourable
cooperative and friendly attitude towards the industry and favourable living conditions and
standards keeping in view the availability of medical and educational facilities, housing, fire
service, recreational facilities, cost of living etc.
34
Overview and Comparison of Site Location
Table 1.5: Site location characteristics comparison

Selection Criteria
Location
Gebeng,
Pengerang,Johor.
Teluk Kalong, Terengganu
Kuantan, Pahang.
40km from
42km from
9.6km from
Kuantan Town.
Johor Bahru
Kemaman Town
5km from
116km from Senai International
Kuantan Port.
Airport
147km to Changi Int. Airport
407km from KLIA
Type of Industries
Area Available
Land Price
Feedstock Sources
Petrochemical
120km from JB
Refinery
Heavy Industries
Chemical and
Petrochemica;
Chemical
plastic
1011.72 hectares
8,093 hectareshectares
Petrochemical
1500 hectares planned
RM 12 - 15/ft
Natural Gas from
RM 8/ft
Natural Gas
4800 hectares.
RM 14 16/ft
Natural Gas from
Petronas Gas Sdn.
from Petronas
Petronas Gas Sdn.
Bhd., Kertih.
Gas Sdn. Bhd.,
Bhd., Kertih
35
Water Supply
(PGU III pipe line)
Kertih. (PGU III
Semambu Water
pipe line)
77km of pipes from the Sungai
Terengganu
Treatment Plant
Seluyut Dam to PIPC
Waterworks
Department capacity
of some 75.3 mgd.
Industrial Water
Production plant
upstream Paka River
under construction.
Has capacity of 50
mgd.
Energy Sources
TNB Tanjung
Pengerang co-generation plant
Kenyir Dam
Paka Power Station
Gelang, Kuantan.
(PCP) generates 1.22GW of
TNB 900 Mw
(800Mw)
electricity and supplies power to
Paka IPP Station YTL
the entire PIC complex.
600 MW
It also produced continuous
Kenyir Hydro Station
supply of steam up to 1,480t an
TNB 400 Mw
hour for plants within the

complex.
36
Transport Facilities
Main road to
The construction of a deepwater
Trunk roads parallel
Kuala Lumpur,
jetty facility with water dept of
to coastline traversing
Johor Bahru and
24 metres, would facilitate
from North to South.
Singapore.
handling Very Large Crude
Kuala Terengganu
Railway
Carriers (VLCCs)
Kuala Lumpur new
Kuantan Airport
highway.
Kuantan Port
Kuala Terengganu
East coast Highway
airport
Kertih airport
Labour
University Technology MARA
University Technology Malaysia
Kemaman Port
University Technology MARA
Islamic International University
(UTM)
Terengganu Advance Institute
Malaysia (IIUM)
Polytechnic
(TATI)
Polytechnic
Johore Skills Development
Terengganu Safety Training
Center (JSDEC)
Centre (TSTC)
Expected to employ 70,000
Terengganu Plastic Technology
workers during construction and
Training Center (TPTTC)
generate 4,000 new jobs upon

Other Facilities
Environment Technology Park
completion.
naphtha cracker complex with a
Toxic waste treatment
capacity of 3Mtpa of propylene,
and recycling plan.
Incorporating a training
centre, waste collection and
C4 and C5 olefins
37
processing centre as well as raw
petrochemical and polymer
material management and storage
complex to produce C4 and C5
facilities, maintenance and
derivates.
servicing facilities.
Chemicals Produced
East coast Highway

Acrylic Acid and Esters
Gasoline
Syngas
Diesel
Butyl Acrylate
Polyisobutylene
Oxo-alcohols
Isononanol
Phathalic Anhydride and
non-ionic surfactants
Plasticizers
methanesulfonic acid
Butanediol
hydrogen peroxide
Tetrahydrafurane
C4 co-monomer
Gamma-butyrolactone
oxo-products.
Propylene
The chemical plants will
Ethanol
produce up to 250,000t/y of
Polypropylene
hydrogen peroxide, 220,000t of
Polybutane Terepthalate
isononanol (INA) and 110,000t of
(PBT)
1-butene. T
MTBE
Polypropylene
Ethylene
Polyethylene
Vinyl Chloride Monomer
Polyvinyl Chloride (PVC)
Ammonia/ Syngas
Acetic Acid
Aromatics
Olefins
Ethylene Oxide, Ethylene Glycol
Ethylene Derivatives
Low Density Polyethylene
38
39
1.8.11 Site Selection
After considering the three locations on the basis of several factors, we have decided
to build the proposed 50,000 MTA of ethyl acetate plant at the newly open industrial
land, Pengerang, Johor Bahru based on its competitive advantages for our plant setup
and production. Pengerang's Strategic location to international sea lanes and natural
attributes such as sheltered harbour and deepwater makes it an ideal location to serve
as an oil, gas and petrochemical hub.
Figure : Map of Industrial Area in Pengerang
Figure shows the map of Pengerang industrial area. Strategically located open
to the access to existing major international shipping lanes: Middle East - Singapore
China and its natural attributes such as sheltered harbour and deepwater makes it
an ideal location to serve as an oil, gas and petrochemical hub. Besides that, The
construction of a deepwater jetty facility with water dept of 24 metres, would
facilitate handling Very Large Crude Carriers
(VLCCs) and very few
Environmentally Sensitive Areas (ESAs) which are easily preserved are affected.
40
Pengerang is one of the largest pieces of investments in the Pengerang district
and located on a single plot measuring about 20,000 acres. The project will house oil
refineries, naphtha crackers, petrochemical plants as well as a liquefied natural gas
(LNG) import terminals and a regasification plant. The focus on oil and gas projects,
arising from the Economic Transformation Programme, will create a more dynamic
and progressive oil and gas industry in Malaysia. Malaysia companies will be able to
partake with local and foreign investors to invest in new technologies, new products
as well as create countless job opportunities as several of these petrochemical
projects take off in the near future.
Other than that, easy access of water and energy supply from 77km of pipes
from Sungai Seluyut Dam to PIPC to supply raw water to the complex and
Pengerang co-generation plant (PCP) generates 1.22GW of electricity and supplies
power to the entire PIC complex, respectively makes it an promising choice besides
having low negative socioeconomic impact as it is relatively unpopulated thus leads
to minimal population relocation.
41
CHAPTER 2
PROCESS SYNTHESIS
2.1
Introduction
As discussed in Chapter 1, there were several process routes have been

identified in order to produce Ethyl Acetate such as Fisher esterification, Tishchenko
reaction, dehydrogenation process of ethanol, and alkylation of acetic acid and
ethylene. After doing the economic potential analysis and considering the
advantages, disadvantages, safety factor and the raw material availability,
dehydrogenation process of ethanol has been chosen as the process route. Next, step
is to determine the suitable process flow diagram from a several PFD exists. The
database is needed to proceed this step.
2.2
Process Database
Table 2.1 is the summary of all the database for each chemical that involved
in this process.
42
Table 2.1: Relevant Database for chemicals involved
Molecular Formula
MW, g/mol
Density (liquid)
Ethanol
C2H6O
46.07
785.1
Acetaldehyde
C2H4O
44.06
1833
Hydrogen
H2
2.02
70.99
Ethyl Acetate
C4H8O2
88.10
901
kg/m3
Vapour Pressure,
5.95 kPa (at 20
101 kPa at 20C
0.15(20C)
psig
Physical form
Boiling point, C
Melting point, C
Flash point, C
Critical point, C
Solubility in water
Viscosity, cP (25
C
Colourless liquid
78.37
-114
16
241
miscible
0.0012 Pa s (at
Colourless liquid
20.8
- 123.5
-40.0
334
miscible
0.21 mPa s at 20
Colourless gas
-253
-259
-38.0
-240
Not soluble
0.0084 (15C)
Colourless liquid
77.1
-84
-4.0
260
Soluble
0.5285 mPas at 0
C)
20 C),
deg C
0.001074 Pa s
0.4546 mPas at
(at 25 C
20 C
0.3668 mPas at
NFPA
Rating (0-
HR
FR
RR
4)
TWA, ppm
STEL, mg/mm3
Heat of
0
3
0
2
4
2
0
4
0
40 C
1
3
0
1000
1000
38.6
50
238
377
0.46
15
25
36.32
0.117
2850
-286
-3239.3
vaporization, kJ/mol
Heat of fusion,
5.7
kJ/mol
Heat of combustion, -1785.7
kJ/mol
Heat of formation,
-249.4
kJ/mol
2.3
Five Key Shynthesis
43
2.3.1 Step1: Elimination of Differences in Molecular Type
For the manufacture of ETAC, data from the chemical involving reaction shown
in Table 2.2.
Selection of process being done based on the economic potential,
environmental factor and safety factor. The advantages and disadvantages of each route
has been discussed in chapter 1. Dehydrogenation of ethnanol was choosen because the
reaction can achieved high product yield, low corrosiveness and produce low acid waste
water.
2.3.2 Step2: Distributions of the chemicals
Figure 2.1: Distribution of chemical

By using copper chromite catalyst, a maximum of 9899% of selectivity has
been obtained for 6065% of ethanol conversion. This performance, never obtained
44
before, has been achieved by operating at 220240 C, 10 bars and an ethanol residence
time of 97.5 g h/mol. In this process, valuable chemical like pure hydrogen (exempt of
CO) and acetaldehyde are produced in mild conditions as by product[1]. In this project,
ethanol dehydrogenation to ethyl acetate, in one step reaction, has been studied by using
the low-cost ethanol availability with copper chromite catalyst to produce ETAC in
large scale 50,000 MTA.
Elimination of chemcial is based on decreasing relative
volatility so that the most difficult splits are made in the absence of other components
(ethanol and ethyl acetate) rather than remove early sequence , those components of
greatest molar percentage in the feed.
2.3.3 Step 3: Elimination on Differences in Composition
Figure 2.2: Flowsheet 1, elimination of different composition by using pressure swing

distillation (PSD)
45
Figure 2.3: Flowsheet 2, elimination of different composition by using extractive

distillation
It is difficult to separate a mixture comprising ethyl acetate, ethanol and water so

as to recover substantially pure ethyl acetate therefrom because the boiling points of
ethyl acetate and ethanol lie close to one another and both compounds form a binary
azeotrope with ethyl acetate whose boiling points are close to that of ethyl acetate. In
addition ethyl acetate, ethanol and water form a ternary azeotrope whose boiling point is
also close to that of ethyl acetate.
In order to overcome this problem, pressure swing distillation (PSD) and
extractive distillation can be alternatives to break the azeotrope. PSD technique to break
the azeotrope of ethyl acetate-ethanol-water mixtures has been published by European
patent EP 1117629 B1. While, extractive distillation has been proposed in the prior art
for separating ethyl acetate from ethanol and water, using of an extraction agent
comprising polyethylene glycol, diethylene glycol, or triethylene glycol for this purpose
has been described in US-A-4569726, while use of an extractive agent comprising
dimethyl sulphoxide for the same purpose has been suggested in US-A-4379028. PSD
technique is selected due to high purity of product can be obtained. The comparison
between two technques is summarized in Table 2.2.
46
Table 2.2: Comparison between PSD and extractive distillation

Pressure Swing Distillation
More easier to gain high purities
Avoid the potential problem of product
Extractive Distillation
Difficult to attain higher purities
May have impurities ( as it involves
contamination
Higher total annual cost
Does not need separating agent
High energy consumption
Heat integration is straightforward
solvent)
Lower total annual cost
Require solvent for the separation process
Lower energy consumption
Need temperature differential driving force
47
2.3.4 Step 4: Eliminate Differences in Temperature, Pressure, and Phase
Figure2.4: Flowsheet with temperature, pressure, and phase change operations in the ETAC process
48
In this synthesis step, however, the states are assumed to be fixed and operations
are inserted to eliminate the temperature, pressure, and phase differences between the
feed sources, the product sinks, and the reaction and separation operations. For the
reaction, there are two alternatives, reaction at high pressure ( 20 bar to 30 bar) or low
pressure (10bar). In this project, low pressure is chosen as the operating cost could be
minimized.
Figure 2.3 shows possible flowsheet and the process undergoes the
following operation:
1. Its pressure is increased to 10 bar to a reactor pressure

2. Its temperature is raised and the dry ethanol vaporize to the reactor temperature,
260C
3. The hot vapor effluent from the reactor is cooled to -10C to condensed the heavy
products.
4. Light component, hydrogen is removed from flash drum
5. The pressure of liquid effluent from flash drum is lowered to 1 bar and the
temperature is raised to 40C
6. The azeotrope mixtures of ethyl acetate, ethanol and water is separated by using
pressure swing from moderate pressure of 15 bar to low pressure 1 bar at bubble
point temperature according to pattern EP 1 117 629 B1.
49
2.3.5 Step 5:
Task Integration
Figure 2.5: Flowsheet showing task integration for the ETAC process
50
The production of EA in this plant is based on the dehydrogenation of ethanol
process. This process involves the catalytic reaction which the catalyst will be placed
in the packed bed reactor. The bioethanol is dried first in order to eliminate the water
in the ethanol. Then, the ethanol is heated up to the desired temperature which is
260oC. The reaction occur at temperature and pressure, 260 oC and 10 bar
respectively. The reactor label as R-101.
The product then is separated according to the specific characteristic.

Hydrogen is separate first as it is easier and has large amount.. Hydrogen is separated
based on different phase. Hydrogen can be seperated by using two alternatives, flash
drum or phase seperator. Phase separator is chosen as there would be no pressure
drop during the process compare to flash drum. The other product, which are ethyl
acetate, acetaldehyde, unreacted ethanol and water is separated after that.
Acetaldehyde is separate after the hydrogen by using the distillation column which
label D-101 at pressure and temperature, 1 bar and 68.4 oC respectively.
Acetaldehyde will become the distillate product and ethyl acetate and ethanol will be
separate in the next distillation column.
According to the distillation theory, ethanol and ethyl acetate form a minimum binary
azoetrope mixture (Pattern EP-A- 0 151 886). Therefore, pressure swing distillation
is introduce to the plant as it can break the azeotropes. The second distillation
column which labelled as D-102 is used to separate ethyl acetate from ethanol. The
separation occur at temperature, 170 oC and pressure, 15 bar. Ethyl acetate will
become the bottom product and the ethanol, water and unseparated ethyl acetate will
be the distillate. The distillate from the second distillation column become the feed
for the third distillation column. The purpose of this distillation column is to separate
ethanol from the remaining ethyl acetate to be recycle back to the reactor. However,
not all of the ethanol can be separated. The unseparated ethanol and ethyl acetate
which is the distillate product of the third distillation column is recycle back to the
first distillation column.
51
2.4
Equipment Selection
2.4.1 Reactor (Packed Bed Reactor)
Reactor are vessels designed to contain chemical reaction. Chemical engineer

design the reactor to ensure the reaction proceed with the highest efficiency towards
the desired product and then producing high yield of the product while requiring least
amount of money to build and operates. There are several type of reactor which are
Continuous Stirred Reactor (CSTR), Plug Flow Reactor (PFR) and Packed Bed
Reactor (PBR). Every reactor have their own characteristic.
For producing ethyl acetate, Packed Bed Reactor (PBR) has been chosen as it
is allowing continuous process (Figure 2.5). Besides, the characteristic of the reactor
which allow the catalytic process made it become chosen as the dehydrogenation
process need catalyst. In addition, packed bed reactor is effective in high temperature
and pressure. Other than that, it can produce high yield of ethyl acetate with the
present of suitable catalyst. This reactor also is easy to build and has low cost of
construction, operation and maintenance. For the EA plant, there only one reactor
due to only one reaction happened. The reaction is the dehydrogenation of ethanol in
a gas phase, which at 2600C and at pressure 10 bar. Catalyst being used in the
dehydrogenation process of ethanol is BASF Cu-1234 or known as Copper
Chromite. The average price for the catalyst would be in the range of US $5-30/
kilogram. The lifespan of the catalyst in the process can last until 3-5 years. Table
2.3 shows the characteristic of the catalyst.
52
Table 2.3: The characteristic of catalyst for dehydrogenation of ethanol
Sample
Composition given by
the companies
BASF K-310
CuO-ZnO-Al2O3 40-402-% b.w.)

Sud-Chemie TCuO/CuCr2O
4466
CuO/Cr2O3 =53/45)
Basf Cu-1234
CuCr2O4-CuO-CuBaCrO4-Al2O3 45-1-1311-30% b.w.)
Surface area
(m2/g)
Pores volume
(cm3/g)
Copper dispersion
(%)
106
0.29
1.97
21
0.11
1.48
127
0.41
1.22
Figure 2.6: Schematic diagram of Peck Bed Reactor (PBR)

2.4.2 Flash Separator
Flash drum is one of the separation unit in the industrial sector. It is used
specifically to separate different phase of matter, which is vapour-liquid separation.
In this plant, hydrogen is produce as by product and flash drum is used to separate
the hydrogen from the product which is EA. The hydrogen then is sell in order to get
the benefit.
53
2.4.3 Distillation column
Distillation column is the most common separation unit that has been used in any
chemical industries. Distillation works by the application and removal of heat to
exploit differences in relative volatility. The heat causes components with lower
boiling and higher volatility to be vaporized, leaving less volatile components as
liquids. Mixture with high relative volatility are easier to separate. There are three
distillation column used in this plant which label as D-101,D-102 and D-103.
2.4.4 Mixer
Mixer is a unit operation that involve manipulation of a heterogeneous physical

system with the intent to make it more homogeneous. In this plant, the unreacted
ethanol is recycled back to the feed and it need to be mixed in order to make it
become more homogeneous with the incoming feed. The remaining acetaldehyde is
recycle back to the second distillation column.
2.4.5 Process Operating Condition .
Table 2.4: Operating Process Condition

Equipment
Temperature,
Pressure
Phase
Justification
R01
T (C)
260
, P (bar)
10
Vapour
This reactor operates
(Dehydrogenation
depending on the type of
Reactor)
catalyst used. For commerical
Packed Bed
copper/copper chromite
54
Tubular Reactor
catalyst, supported on alumina
(PBR)
and containing barium

chromite as promoter, it is
preferable to operate the
reactor at high temperature and
pressure in order to reach a
high ethanol conversion (65%)
and high selectivity of EA
(ethyl acetate) (93% - 98.5%).
Since the reactor temperature
is high, the reactor should be
design well with suitable
PS-01
34
10
Phase Separator
Mixtur
materials for construction.

Acetaldehyde and other
products are separated as liquid

bottoms stream in flash drum
and then sent to next
distillation column while
hydrogen will be removed as
vapour distillate stream.
Table 2.4 (Continued)

D-101
68.4
Liquid
Distillation column 1 was functioned
Distillation
as acetaldehyde flash drum. The
column 1
acetaldehyde is separated as overhead

in this distillation column.
Meanwhile, EA and other products
will be separated at bottom stream and
D-102
170
15
Mixture
flows to next distillation column.

From bottom stream of distillation
Distillation
column 1, the products such as EA,
column 2
ethanol, and water are then sent to

second distillation column C-101 for
separation between EA (bottom
55
product) and other heavy key
components (overhead product).
However, there are still EA component
D-103
76
flow to overhead stream.

Product from overhead stream of
Liquid
Distillation
distillation 2 will enter distillation
column 3
column 3 in order to recover large

amount of ethanol to be recycled to
reactor. Besides, EA will be separate
at overhead stream to be recycled to
E-0 1
260
10
Liquid
distillation column 1.
Ethanol feed and recycled ethanol are
Evaporator
mixed and then sent to E-100 for
H-01
heating to 260oC.
The bottom product from flash drum
68.4
Liquid
will be heated to 68.4oC.
Heater 1
Table 2.4 (Continued)

H-02
170
15
Liquid
Heater 2
Product from bottom stream of

distillation column 1 will be
heated to 170oC before
C-01
34
10
Vapor
cooled to 34oC and then will be
Cooler 1
C-02
76
15
Liquid
Cooler 2
C-03
entering distillation column 3.

Product from reactor will be
sent to flash drum.
Overhead product produced
from distillation 2 are cooled in
25
15
Liquid
E-104.
Before recycled to distillation
Cooler 3
column 1, overhead stream will
C-04
Liquid
be cooled to 40.oC.
Mixture is cooled from 72.4 to
Liquid
68 oC
Mixture is cooled from 78 oC to
Liquid
25 oC
This mixer comprises stream
Cooler 4
C-05
Cooler 5
M-01
68.4
25
25
1
1
1
56
Mixer 1
from bottom product of

distillation column 3 and fresh
M-02
68.4
Liquid
feed.
Overhead stream of distillation
Mixer 2
column 3 and bottom stream of
P-01
phase separator will be mixed..

Liquid stream from mixer 1
25
1 to 10
Liquid
Pump 1
will be pump to 10 bar and will
P-02
enter evaporator directly.

Before entering Distillation 2,
71.6
1 to 8
Liquid
Pump 2
bottom poduct from distillation

column 1 will be pump to 8
P-03
71.6
8 to 15
Liquid
bar.
Before entering Distillation 2,
Pump 3
poduct from pump 2 will be
V-01
pump to 15 bar.
Valve 1 will reduced a pressure
34
10 to 1
Liquid
Valve 1
bottom flash drum from 10 bar

to 1 bar before entering
V-02 & V-03
74
15
Liquid
Valve 2 & 3
distiilation 1.
This 2 valve are required to
reduced a pressure product
from distillation 2 from 15 bar
to 1 bar and then will be sent to
V-04
25
15 to 7
Liquid
Valve 4
V-05Valve 5
25
7 to 1
Liquid
distillation column 3.
This 2 valve are required to
reduced a pressure product
from distillation 2 from 15 bar
to 1 bar and stored to storage
XC-01
260
Liquid
tank.
External heater to ensure that
the temperature in reactor is
maintained at 260 oC
57
2..5
Heuristics Applied for PFD
Heuristics 4: Introduce purge streams to provide exits for species that enter the
process as impurities in the feed or are formed in irreversible side reactions,
when these species are in trace quantities and/or are difficult to separate from
other chemicals.
A large amount of hydrogen need to be removed before entering distillation column
because it will increase energy required and make a separation process difficult.
Heuristic 5: Do not purge valuable species or species that are toxic and
hazardous, even in small concentrations, add separators to recover valuable
species or add reactors to eliminate toxic and hazardous species.
The unconverted ethanol are recycled and in kept of safe handling before being
treated or sold. Meanwhile, flash drum and distillation column is used to recover
byproducts produced such as hydrogen, acetaldehyde, and others.
Heuristic 9: Separate liquid mixtures using distillation, stripping, enhanced

(extractive,
azeotropic,
reactive)
distillation,
liquid-liquid
extraction,
crystallization and/or adsorption.

There are one flash drum and three distillation column that is used to separate the
chemical components. The flash drum column is used to separate hydrogen from
acetaldehyde and other products. The first column is used to separate acetaldehyde
from product stream. The second column is used to separate azeotrope mixture (ethyl
acetate, ethanol and water) from product stream in order to get high purity of desired
product which is ethyl acetate, while the last column is used to separate the unreacted
ethanol to be recycled to reactor.
Heuristic 43: To increase pressure of a stream, pump a liquid rather than
compress a gas, unless refrigeration is needed.
In step 4 of choosing the Process Flow Diagram (PFD) to eliminate the differences of
temperature, pressure and phase, PFD 1 is chosen because it attempt to eliminate the
58
differences in pressure first before attempting to eliminate the differences in
temperature and phase. This result in the capability of using a pump to compress a
liquid rather than using a compressor to increase
59
CHAPTER 3
MATERIAL AND ENERGY BALANCES
3.1
Material Mass Balance
The plant is designed to produce 50,000 MTA of Ethyl Acetate

with molecular weight of 88 kg/kmole. This production plant is
mainly to produce ethyl acetate by reaction of dehydrogenation of
ethanol. By feeding dry ethanol to reactor at optimum condition,
highest yield of ethyl acetate can be obtained.
3.1.1 Procedure for Material Balance Calculation
There are several rules of thumb to be followed. Below are

the guidance followed when performing material balance
calculation.
(a) Flowchart is constructed and all given variable values are
filled in.
60
(b)A basis of calculation need to be done in order to know the
amount or flowrate for each stream. If one such quantity is
given, it is usually most
61
convenient to use it as basis of the calculation; all
subsequently calculated quantities will then be correctly
scaled. If no amounts or flow rate is specified, normally it
assumes the amount of a stream with a known composition.
This value then will be put in the flowchart.
(c) All unknown stream variables on the chart, particularly mass
and molar flow rates and mass or mole fractions of the
stream components are labeled. Relationship between
unknown quantities in the labeling should be incorporated as
well.
(d)Problems are being book kept. Unknown and relations among
them are identified. If the number are equal, lie out the
problem solution; if not, there are still more information to be
gathered (the flow chart may not consist the all required
information).
(e) Known stream volumes or volumetric flow rates will be
converted to mass or molar quantities using tabulated
densities or gas laws.
(f) For given mixed mass and mole units for a stream (e.g., a
total mass flow rate and component mole fractions or
conversely), they needed to be converted to one basis or the
other method.
(g) For information that is given in the problem but has not been used in labeling
the flowchart, they are translated into equations in the variables defined in
step (c).
(h)Material balance equations are written. If no reactions occur and there are N
species present, there will be the most N balances, either on each component
or on total mass or moles and all but one species. Balances are written in
order such that those involve the fewest unknowns; if not, either the problems
is underspecified or a relationship between the variables not yet put in
consideration.
(i) Equations derived in step (g) and (h) are solved for the unknown quantities.
When the value of an unknown has been calculated, the value should be
62
written down in the flowchart immediately. This value will then be
substituted for calculation of unknowns in any equations.
(j) If a stream quantity or flow rates was given in the problem statement and
another value Q was either taken as a basis or calculated for this stream, they
must be scaled
3.1.2 Assumption of Material Balance Calculation
Mass balance is the basis factor needs to be considered for

designing a chemical plant. During our design, mass balance is
consists of two parts: calculated manually and carried out by using
simulation program. The basic concept that is applied for manual
calculation is based on the general balance equation.
Unit operation
Min (kh/hr)
Mout(kh/hr)
The general mass balance equation is:
Input + Generation - Output - Consumption = Accumulation
Where,
Input = total mass enters through system boundary
Generation = total mass-produced within the system
Output = total mass leaves though system boundary.
Consumption = total mass consumed within the system
Accumulation = total mass build up within the system
In this manual calculation, there are a few assumptions made and
needed to be highlighted. They are:
63
This plant design is based on a basis of 50,000MTA of Ethyl Acetate
production.
Operating days for the plant is 350 days, 24 hours a day.
The system is steady state.
The entire components in the system behave as ideal gas.
Catalyst used in reactor do not contribute in mass.
No leakage in pipes and vessel in the system.
The total input of any substance either to pump, valve, expander,
mixer, or heat exchanger is assumed equal to the total output of
the substance where no reaction occur in that devices.
3.1.3 Manual Material Balance
Target production of Ethyl Acetate is 50,000 MTA. Thus, the

desired production of Ethyl Acetate is,
50000
MT 1000 kg
1 year
1 day 1 kmol
year
1 MT
350 days 24 hr 88 kg
= 67.64 kmol/hr EA
The summary of the result of manual calculations regarding

the material balance is given in the table below from table to table.
For the production of 50000 MTA Ethyl Acetate, the initial setting of
the material balance parameter is given as following.
64
3.1.3.1
Compone
nt
H2
Acetaldehy
de
EA
Ethanol
3.1.3.2
Mass Balance for Mixer 1, M-01
Stream 1
Stream 29
Stream 2
(Freshfeed)
kmole/
kg/hr
hr
(Recycle)
kmole/
kg/hr
hr
(Outlet)
kmole/
kg/hr
hr
0
44.0
0.000
0.000
0.000
0.000
0.000
0.000
0
88.0
0.000
0.000
0.000
0.000
0.000
0.000
0
46.0
0.000
150.09
0.000
6904.1
0.000
0.008
3438.9
0.000
224.85
0.008
10343
0
150.09
4
6904.1
74.761
8
3438.9
1
224.85
.1
10343
74.761
.1
MW
2.00
Mass Balance for Reactor, R-01
65
1) Reaction path:
C2H5OH C2H4O + H2
C2H5OH + C2H4O C4H8O2 + H2
2C2H5OH C4H8O2 + 2H2
(Overall Equation)
2) Conversion = 65% (Ethanol)

3) Selectivity,
EA = 93%
Acetaldehyde = 7%
Compone
nt
H2
Stream 4 (Inlet)
MW
Stream 5 (Outlet)
kmole/h
kg/hr
r
146.152
kmole/hr
kg/hr
0.0000
0.0000
292.3058
44
88
46
0.0000
0.0001
224.8506
0.0000
0.0077
10343.1288
10.2307
67.9612
78.6977
303.042
450.1510
5980.5846
3620.0951
10343.136
224.8507
10343.1365
Acetaldeh
yde
EA
Ethanol
3.1.3.3
Mass Balance for Phase Separator, FS-01
66
Componen
t
H2
Acetaldeh
yde
EA
Ethanol
Total =
3.1.3.4
Stream 6 (Inlet)
MW
2.00
kmole/h
r
146.15
kg/hr
Stream 7
(Overhead)
kmole/
kg/hr
hr
143.67 287.3
Stream 9
(Bottom)
kmole/h
kg/hr
r
0
44.0
292.306
41
60.44
2.482
4.965
389.70
00
88.0
10.231
450.151
1.374
8
101.6
8.857
3
5878.9
00
46.0
67.961
5980.585
1.155
81
39.63
66.806
03
3580.4
00
78.698
303.04
3620.095
10343.13
0.862
147.06
9
489.1
77.836
57
9854.0
09
155.981
27
Mass Balance for Mixer, M-02
67
Componen
Stream 27
Stream 11
Stream 12
(Recycle)
kmole
kg/hr
/hr
(Inlet)
kmole/
kg/hr
hr
2.482
4.964
(Outlet)
kmole/
kg/hr
hr
2.482 4.964
0
0.000
0
0.041
317
8.856
634
389.7
317
8.857
63
389.7
44
94
0.008
6
0.762
88
66.80
02
5878.
83
66.81
44
5879.
88
66
23.60
84
1085.
57
77.83
90
3580.
43
101.4
66
4666.
46
86
23.61
99
1086.
60
155.9
45
9854.
44
179.5
45
1094
82
80
80
02
99
0.8
MW
t
H2
Acetaldeh
yde
EA
Ethanol
Total =
3.1.3.5
Mass Balance for Distillation 1, D-01
Compone
nt
H2
Acetaldeh
2
44
Stream 12
Stream 13
Stream 14
(Inlet)
kmole/
kg/hr
hr
4.9646
(Overhead)
kmole/
kg/hr
hr
4.964
(Bottom)
kmole/
kg/hr
hr
2.4823
8.8578
2.4823
8.8569
0.0000
0.0010
3
389.74
63
389.7
0
0.0419
68
yde
EA
Ethanol
66.814
5
5879.6
88
4
101.44
7
4666.4
2.0044
9
72.09
0
99.877
8
4594.3
46
46
5
10940.
1.5672
29
643.1
6
10297.
179.60
83
14.91
164.69
68
total =
3.1.3.6
03
176.3
64.810
8
5703.2
Stream 17
Stream 18
Stream 22
(Inlet)
kmole/
kg/hr
hr
0.000 0.000
(Overhead)
kmole/
kg/hr
hr
0.000 0.000
(Bottom)
kmole/
kg/hr
hr
0.000 0.000
44
0.001
64.81
0.042
5703.
0.001
0.042
0.000
64.80
0.000
5702.
88
0
99.87
27
4594.
0.009
98.36
0.771
4524.
5
69.37
46
7
164.6
36
10297
9
98.37
9
4525.
1.508
66.30
5
5771.
88
.6
Compone
nt
H2
Acetaldeh
yde
EA
Ethanol
Total =
69
3.1.3.6
Componen
t
H2
M
W
EA
Ethanol
kmole/
hr
0.000
Stream 28
(Overhead)
kmole/
kg/hr
hr
0.000
(Bottom)
kmole/
hr
0.000
kg/hr
0
0.000
0.0000
0
0.000
0.0000
0
0.000
0.0000
44
9
0.008
0.0416
9
0.008
0.0416
0
0.000
0.0000
88
8
98.36
0.7706
4524.9
7
23.60
0.7628
1085.9
1
74.76
0.0077
3438.9
46
92
98.37
85
4525.7
86
23.61
96
1086.8
06
74.76
8
3438.9
89
97
82
00
07
96
total =
3.2
kg/hr
Stream 26
Acetaldehy
de
Stream 21 (Inlet)
Energy balance
3.2.1 Energy Balance Calculation Methods
70
In designing, it is important to determine the overall energy requirement for the
process. Manual calculation for energy balance begins with the mixer and ends up
with the distillation columns. A few assumptions has been made which are:
The process system is a steady state
Potential and kinetic energy is neglected
All equipment is in steady state condition
Standard reference state for enthalpy is P = 1 bar and To = 298.15 K.
Adiabatic process where no heat loss to the environment.
All the liquid and gas heat capacities are constant at certain temperature
So, the law become
Q = H = noo - nii
Where
Q = heat duty
no = flow rate at outlet stream
o = specific enthalpy at outlet stream
ni = flow rate at inlet stream
i = specific enthalpy at inlet stream
Each enthalpy calculation is different depend on the phase for the stream. If
the phase is in vapour phase, the specific enthalpy is calculated by using the
equation;
H v (T, y) H f H T y k H f ,k (T1 ) y k Cp k (T)dT
T2
T1
If the phase is in liquid form, the specific enthalpy can be calculated by the
equation;
71
H L (T, x ) x k (H f ,k Cp k ( )d H kvap (T))

T
T0
Where:
H kvap (T ) H kvap (Tb )[
(Tck T ) 0.38
]
(Tck Tb )
If the stream is in the liquid-vapour mixture form, the specific enthalpy can be
calculated by using Equation
H(T, z ) H V (T, y) (1 ) H L (T, x )
3.2.2 Manual Energy Balance Calculation
This section shows the example of the energy balance of certain equipment in this
plant.
Component
Hydrogen
A
27.14
Cp Constant
B
C
Tb (K)
Tc (K)
9.27E-03
-1.38E-05
7.65E-09
20.35
33.2
7.716
7.235
9.014
1.82E-01
4.07E-01
2.14E-01
-1.01E-04
-2.09E-04
-8.39E-05
2.38E-08
2.85E-08
1.37E-09
293.55
350.25
156.6
461
523.2
516.2
Acetaldehyd
e
Ethyl Acetate
Ethanol
72
Evaporator, E-01
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
Flow Rate
(kmol/hr)
0
0
0.053
223.6896
Inlet
Temperature
(C)
Outlet
Flow
Rate Temperature
(kmol/hr)
0
0
0.053
223.6896
25
-5.96E+07
(C)
260
-4.82E+07
(kJ/hr)
1.15E+07
Reactor, R-01
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
(kJ/hr)
Phase Separator, FS-01
Inlet
Flow Rate
Temperature
Outlet
Flow
(kmol/hr)
0
0
0.053
223.6896
(kmol/hr)
145.3982
10.1779
67.6632
78.2914
(C)
260
-4.82E+07
Rate Temperature
(C)
-4.50E+07
3.14E+06
260
73
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
Inlet
Flow Rate Temperatur
Outlet
Outlet
(kmol/hr)
145.3982
10.1779
67.6632
78.2914
(kmol/hr)
142.9287
1.3667
1.1504
0.8573
(kmol/hr)
2.4695
8.8112
66.5128
77.4341
stream(kJ/hr)
Heat duty
e (C)
30
-1.1E+07
e (C)
30
-8.87E+05
(kJ/hr)
e (C)
30
-5.40E+07
-4.40E+07
Distillation Column 1, D-01
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
Inlet
Flow Rate Temperatu
Outlet 1
Outlet 2
Flow
Temperat Flow
(kmol/hr)
Rate
re (C)
2.4695
8.8112
68.7822
68
100.6761
-6.1E+07
stream(kJ/hr)
Heat duty
ure (C)
(kmol/hr)
2.4695
8.7671
2.0635
47.2
1.9058
-3.14E+06
Temperature
Rate (C)
(kmol/hr)
0.0000
0.0441
66.7187
71.6
98.7703
-5.7E+07
8.11E+05
(kJ/hr)
Distillation 2, D-02
Component
Inlet
Flow
Temperat
Outlet 1
Flow
Tempera
Rate
Rate
(kmol/hr)
ure (C)
(kmol/hr)
Outlet 2
Flow
ture (C) Rate

(kmol/hr)
Temperatu
re (C)
74
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
0.0000
170
0.0441
66.7187
98.7703
-5.40E+07
0
0.0441
2.2205
167.8
97.2789
-2.49E+07
stream(kJ/hr)
Heat duty
0
0
64.4982
188.8
1.4914
-2.89E+07
2.81E+05
(kJ/hr)
Distillation 3, D-03
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat
duty(kJ/hr)
Inlet
Flow
Temperat
Outlet 1
Flow
Tempera
Outlet 2
Flow
Temperatu
Rate
Rate
Rate
(kmol/hr)
0
0.0441
2.2205
97.2789
ure (C)
77
-2.54E+07
(kmol/hr)
0
0.0441
0.8057
23.3469
ture (C)
167.8
-6.48E+06
(kmol/hr)
0
0
1.4148
73.9319
re (C)
188.8
-1.99E+07
-9.50E+05
CHAPTER 4
SIMULATION OF MASS AND ENERGY BALANCE4.2
75
4.1
Process Simulation
ASPEN is a process simulation software package widely used in industry

worldwide. Given a process design and an appropriate selection of thermodynamic
models, ASPEN uses mathematical models to predict the performance of the process.
This information can then be used in an iterative fashion to optimize the design. This
accurate modeling of, thermodynamic properties is particularly important in the
separation of non-ideal mixtures, and ASPEN has a large data bases of regressed
parameters. ASPEN can handle very complex processes, including multiple-column
separation systems, chemical reactors, distillation of chemically reactive compounds,
and even electrolyte solutions.
Process simulation is used to analyse every unit operations in plant as well as

their combination to complex processes. The obtained mass and energy balances give
insight into interdependencies of different process steps. The simulation results are
valuable for design, improvement, optimisation, and scale-up of processes. There is
another Industrial standard process simulation software tools (Aspen Plus, Aspen
Hysys, gPROMS) which are also applicable for process simulation
For our study, we are using AspenOne Plus V8.8 as our process simulator.
This simulator we invented and developed by Aspen Technology Inc. The computer
simulation is carried out after performing the material and energy balance manually.
The simulation results were compared with the manual calculation to get the
percentage error of the calculation.
4.2
Selecting Thermodynamics Model
76
When faced with choosing a thermodynamic model, it is helpful to at least a
logical procedure for deciding which model to try first. Elliott and Lira (1999)
suggested a decision tree as shown in Figure 1-5. The property packages available in
Aspen plus allow you to predict properties of mixtures as shown in Figure 4.1. For
this study, NRTL is chosen as the process involves with non-ideal mixtures
(azeotropic mixtures) of ethanol and ethyl acetate.
Figure 4.1: Selecting flowsheet of thermodynamic model
77
4.3
Comparison between Manual Material Balance and Simulation
The results obtained by manual calculation and simulation is compared to get

the error deviation. The formula to calculate the percentage error as below:
Error % = [ Manual Calculation Simulation Result] x 100%

Simulation Result
Table 4.2: Comparison of manual material balance and simulation results

Stream
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Manual Calculation
Simulation
(kg/hr)
(kg/hr)
6818.218
10276.18
10276.18
10276.18
10276.18
10276.18
522.9764
9753.205
9753.205
9753.205
10931.28
619.4234
10311.86
10311.86
10311.86
10311.86
4635.844
4635.844
4635.844
4635.844
5676.012
1177.881
1177.881
3457.963
3457.963
Error %
78
4.4
Comparison between Manual Energy Balance and Simulation
Table 4.3: Comparison of manual equipment heat duty and simulation

Stream
Manual(Kj/Hr)
Simulation(Kj/Hr)
Percentage Error (%)
-4.01E+07
-4.11E+07
2.424
-5.98E+07
-6.19E+07
3.462
-5.96E+07
-6.19E+07
3.642
-4.82E+07
-4.80E+07
-0.284
-4.50E+07
-4.51E+07
0.253
-1.09E+07
-5.56E+07
80.426
-8.87E+05
-1.11E+06
19.749
-9.17E+05
-1.11E+06
17.025
-5.40E+07
-5.45E+07
0.957
10
-5.41E+07
-5.45E+07
0.735
11
-5.32E+07
-5.35E+07
0.471
12
-6.11E+07
-6.01E+07
-1.687
13
-3.14E+06
-2.63E+06
-19.693
14
-5.72E+07
-5.72E+07
0.050
15
-5.71E+07
-5.71E+07
-5.72E+07
-5.72E+07
0.195
0.159
17
-5.40E+07
-5.40E+07
-0.106
18
-2.49E+07
-2.53E+07
1.588
19
-2.54E+07
-2.69E+07
5.670
20
-2.54E+07
-2.69E+07
5.493
21
-2.55E+07
-2.69E+07
5.317
22
-2.89E+07
-2.87E+07
-0.895
23
-2.92E+07
-3.10E+07
5.747
16
79
4.5
24
-2.93E+07
-3.10E+07
5.411
25
-2.93E+07
-3.10E+07
5.411
Simulation Conclusion and Remarks
From the table 4.2, the total mass flowrate calculated by manual calculation
is not significant different compare to the simulation data. The percentage error is
not more than 5%, which is acceptable.
Thus it can be concluded that the
assumption made in the system are reasonable and acceptable for the calculation.
For the energy balance, it was calculated based on the data from yaws'
handbook of thermodynamic and physical properties of chemical compounds,
several stream had shown larger errors compared to simulation results. This is due to
the differences of reference points and thermodynamic properties which were
applied between the data we use in manual calculation and simulation. The
simulation software used the different correlation and equations to calculate the
energy balance, which is NRTL includes the effect of temperature and pressure
whereas using the data proposed, we only consider the temperature different.
Moreover, stream 6 give significant error due to the mixture in the stream contain 2
phase of mixture (liquid and gas) in which more detailed correlation and equation is
needed
80
REFERENCE
[1]
[2]
[3]
[4]
[5]
[6]
[7] Overall Ethyl Acetate Supply Registered 4% YoY Increase in 2012. (2013,
December 20). Retrieved from http://mcgroup.co.uk/news/20131220/ethyl-acetatesupply-registered-4-yoy-increase.html
[8] http://incolors.club/collectionedwn-ethyl-acetate.htm
[9] Jagger, A. (2010). Rhodia will target etac from the planned project in Al-Jubail,
Saudi
Arabia,
at
Europe.
Retrived
from
http://www.icis.com/resources/news/2010/08/16/9385165/projects-sipchem-rhodiaplan-saudi-etac-project/
[10] Chemical market insight and foresifgt on a single page ethyl acetate. Retrived
from http://orbichem.com/userfiles/CNF%20Samples/eac_13_11.pdf
[11] Kelley, L. Mirasol, F. (2012). US Chemical profile: Ethyl acetate Retrieved
from http://www.icis.com/resources/news/2012/02/13/9531149/us-chemical-profileethyl-acetate/
[12] Ethyl acetate Europe prices, markets & analysis. Retrieved from
http://www.icis.com/chemicals/ethyl-acetate/europe/?tab=tbc-tab2
[13] Dobson, D. I. (2003). Leaps of innovation. Retrieved from
http://pubs.rsc.org/en/content/articlehtml/2003/gc/b304290c
[14] http://www.icis.com/resources/news/2013/05/26/9672001/chemical-profile-asiaethyl-acetate/
[15] http://www.icis.com/resources/news/2013/05/26/9672001/chemical-profile-asiaethyl-acetate/
[16] http://www.platts.com/news-feature/2015/petrochemicals/asia-petrochemicaloutlook/acetic-acid
81
[17] http://www.icis.com/resources/news/2006/07/25/2015325/chemical-profileethyl-acetate/
[18] biofuelscan, plats mcgrill
[19]http://www.orbichem.com/userfiles/KICHEM
%202012/KICHEM2012_3_Acetyls_KW.pdf
[20] http://www.icis.com/resources/news/2012/02/13/9531149/us-chemical-profileethyl-acetate/
[21] Synthesis of ethyl acetate by esterification of acetic acid with ethanol over a
heteropolyacid on montmorillonite K10 http://ac.elscdn.com/S1003995309600487/1-s2.0-S1003995309600487-main.pdf?
_tid=0a4d974a-ddf7-11e5-97a700000aab0f01&acdnat=1456649060_bd189dec3bd06fe929005fa7869ce504
[22] Hoechst A.G, DOS 2,545,845 (1977)
[23]
[24]W. Tishenko, J. Russ. Phys. Chem. Soc., 38, 398 (1906). W. C. Child and H.
Adkins, J. Am. Chem. Soc., 45, 3013 (1923)
[25] http://davyprotech.com/what-we-do/licensed-processes-and-coretechnologies/licensed-processes/ethyl-acetate/specification/
[26] Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite
catalysts E. Santacesaria, G. Carotenuto, R. Tesser, M. Di Serio
[27]
[28]
[29]
[30]
[31]
[32]
[33]
82
APPENDIX A
MATERIAL AND ENERGY BALANCES
A.1
Material Balance Calculation
A.2
Energy Balance Calculation
A.3
Process Flow Diagram with Complete Stream Table
83
A.1
Material Balance Calculation
Mixer M-01
Stream 1 and 29 Stream 11

Sample Calculation (Ethanol)
F2
= F1+ F29
= 150.09 + 74.761
= 224.851 kmol/hr
Component
MW
Stream 1
Stream 29
(Freshfeed)
kmole/h
kg/hr
r
0.000
0.000
(Recycle)
Stream 2 (Outlet)
kmole/hr
kg/hr
0.000
kmole/h
kg/hr
0.000
r
0.000
0.000
H2
Acetaldehyd
2.000
44.00
0
88.00
0.000
0.000
0.000
0.000
0.000
0.000
0
46.00
0.000
0.000
6904.14
0.000
0.008
3438.98
0.000
0.008
10343.1
150.090
0
6904.14
74.761
9
3438.99
224.851
29
10343.1
150.090
74.761
224.851
36
EA
Ethanol
Pump P-01
84
Assuming mass in = mass out

Stream 2 Stream 3
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
44
88
46
Stream 2 (Inlet)
kmole/hr
kg/hr
0.000
0.000
Stream 3 (Outlet)
kmole/hr
kg/hr
0.000
0.000
0.000
0.000
224.851
224.851
0.000
0.000
224.851
224.851
0.000
0.008
10343.129
10343.136
0.000
0.008
10343.129
10343.136
Evaporator E-01

Stream 3 Stream 4
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
44
88
46
Stream 3 (Inlet)
kmole/hr
kg/hr
0.000
0.000
Stream 4 (Outlet)
kmole/hr
kg/hr
0.000
0.000
0.000
0.000
224.851
224.851
0.000
0.000
224.851
224.851
0.000
0.008
10343.129
10343.136
0.000
0.008
10343.129
10343.136
85
Reactor R-01
Stream 4 Stream 5
Reaction path:
C2H5OH C2H4O + H2
C2H5OH + C2H4O C4H8O2 + H2
2C2H5OH C4H8O2 + 2H2
(Overall Equation)
The calculation were based on overall equation,

Component
MW
H2
Acetaldehyd
Inlet
kmole/hr
0.000
e
EA
Ethanol
44
0.000
88
46
0.000
224.851
0+
(C2H5OH)in - 2
Based on conversion of ethanol = 0.65,

(C2H5OH)in - 2 = 0.65
= 73.0765 kmol/hr
Outlet
0 + 2
86
Thus,
Moles H2 produced = 0 + 2 (72.6991) = 146.153 kmol/hr
Moles Ethanol left = 223.79 - 2 (72.6991) = 78.698 kmol/hr
However, according to journal, the product formed have the following selectivity,
EA = 93% of weight
Acetaldehyde = 7% of weight
Therefore,
Weight of EA produced = [(72.6991 x 88) x 0.93] + 4.664 = 5954.3600 kg/hr
Weight of Acetaldehyde produced = (72.6991 x 88) x 0.07 = 447.8266 kg/hr
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
44
88
46
Stream 4 (Inlet)
kmole/hr
kg/hr
0.0000
0.0000
Stream 5 (Outlet)
kmole/hr
kg/hr
146.1529
292.3058
0.0000
0.0001
224.8506
224.8507
10.2307
67.9612
78.6977
303.0425
0.0000
0.0077
10343.1288
10343.1365
450.1510
5980.5846
3620.0951
10343.1365
Cooler C-01

Stream 5 Stream 6
Stream 5 (Inlet)
kmole/hr
kg/hr
146.1529
292.3058
Stream 6 (Outlet)
kmole/hr
kg/hr
146.1529
292.3058
44
88
10.2307
67.9612
10.2307
67.9612
Component
MW
H2
Acetaldehyd
e
EA
450.1510
5980.5846
450.1510
5980.5846
87
Ethanol
46
78.6977
303.0425
3620.0951
10343.1365
78.6977
303.0425
3620.0951
10343.1365
88
Phase Separator FS-01
Stream 6 Stream 7 and Stream 9
Component
Flowrate
(kmole/hr)
H2
Acetaldehyd
146.1529
e
EA
Ethanol
10.2307
67.9612
78.6977
Antoine Constant
A
2.94928
B
67.5078
C
275.7
4.1814
1070.6
236
4.21248
4.92365
1238.15
1410.46
217.205
208.514
Pk (bar)
k/n
535.1183
373.1314
1.4341
0.1599
0.1024
1.0000
0.1115
0.0714
log P = A-B / (T+C), P in bar, T in Celcius

Guess 2 = 0.13428401
P = 10 bar
T = 30 0C = 303.15 K
Relative volatility, k/n = P0k / P0n
The recoveries of non key component, k =

k
H2
Acetaldehyd
e
EA
Ethanol
k
(kmole/hr)
k / n n
1 ( k / n 1) n
lk
xk
(kmole/hr
yk
xk
0.9769
0.0159
5.9381
0.0568
k/n
0.9830
143.6706
)
2.4823
0.1343
1.3738
8.8569
0.0093
0.0568
1.1555
0.8617
147.0616
66.8057
77.8360
155.9809
0.0079
0.0059
0.4283
0.0478
0.4990
0.0356
6.0783
0.0170
0.0109
total =
89
Component
H2
Stream 7
Stream 6 (Inlet)
MW
(Overhead)
Stream 9 (Bottom)
kmole/hr
kg/hr
kmole/hr
kg/hr
kmole/hr
kg/hr
2.000
146.153
292.306
143.671
287.341
2.482
4.965
44.000
88.000
46.000
10.231
67.961
78.698
303.043
450.151
5980.585
3620.095
10343.136
1.374
1.155
0.862
147.062
60.448
101.681
39.639
489.109
8.857
66.806
77.836
155.981
389.703
5878.903
3580.457
9854.027
Acetaldehyd
e
EA
Ethanol
Total =
Determine the pressure and temperature by bubble point calculation.

Bubble point calculation:
= Pk/n / P02 = 1.64575
Pk (T )
= x*k/n = 30.0014
k /nP
1x10
1.6457
6.0763
1070.6
(236) 34.0101C
(4.1814 log 1.64575)
Expander EX-01

Stream 7 Stream 8
90
Component
MW
H2
Acetaldehyd
2
44
e
EA
Ethanol
Total =
88
46
Stream 7 (Inlet)
kmole/hr
kg/hr
Stream 8 (Outlet)
kmole/hr
kg/hr
143.671
287.341
143.671
287.341
1.374
1.155
0.862
147.062
60.448
101.681
39.639
489.109
1.374
1.155
0.862
147.062
60.448
101.681
39.639
489.109
Valve CV-01

Stream 9 Stream 10
Component
MW
H2
Acetaldehyd
2
44
e
EA
Ethanol
Total =
88
46
Heater H-01

Stream 10 Stream 11
Stream 9 (Inlet)
kmole/hr
kg/hr
Stream 10 (Outlet)
kmole/hr
kg/hr
2.482
4.965
2.482
4.965
8.857
66.806
77.836
155.981
389.703
5878.903
3580.457
9854.027
8.857
66.806
77.836
155.981
389.703
5878.903
3580.457
9854.027
91
Component
MW
H2
Acetaldehyd
2
44
2.482
8.857
4.965
389.703
2.482
8.857
4.965
389.703
88
46
66.806
77.836
155.981
5878.903
3580.457
9854.027
66.806
77.836
155.981
5878.903
3580.457
9854.027
e
EA
Ethanol
Total =
Stream 10 (Inlet)
kmole/hr
kg/hr
Stream 11 (Outlet)
kmole/hr
kg/hr
Mixer M-02
Stream 11 and 27 Stream 12

Sample Calculation (Ethanol)
F12
= F11+ F29
= 23.609 + 77.836
=101.44 kmol/hr
Stream 27
Component
H2
M
W
Stream 12
hr
2.4823
4.9646
(Outlet)
kmole/
kg/hr
hr
2.4823 4.9646
kmole/
kg/hr
0
0.0009
0
0.0416
17
8.8568
34
389.70
17
8.8578
34
389.74
44
88
46
0.0086
4
0.7628
84
66.805
29
5878.9
3
66.814
45
5879.6
Acetaldehy
de
EA
(Recycle)
kmole/
kg/hr
hr
Stream 11 (Inlet)
92
Ethanol
46
Total =
69
23.608
47
1085.9
72
77.836
03
3580.4
39
101.44
66
4666.4
62
23.618
96
1086.8
01
155.98
57
9854.0
46
179.59
53
10940.
23
01
09
27
92
83
Distillation Column D-01
Stream 12 Stream 13 and 14

Inlet stream 12
T feed
P feed
70 C
1 bar
Specify
Light key
Heavy key
Top P
Bottom P
Acetaldehyde
ETAC
lk
hk
0.99989
0.03
1 bar
1 bar
* We choose ethyl acetate as the example for calculation

i.
Calculation of vapor pressure is base on Antoine equation.
93
log PETAC 4.21248
ii.
Use ideal Raolt's Law to calculate Kk:
y
P
Kk k k
xk
P
* where Pk is the vapor pressure, and P is the column pressure
0.79698
0.001388
574.19481
K ETAC
iii.
1238.15
0.79698 bar
70 (217.205)
Relative volatility respect to key component:
k / n
Kk
P
k
K n Pn
* where Pk is the vapor pressure of the component and Pn is the vapor pressure of the key
component
ETAC / ETAC
iv.
0.79698
1.0000
0.79698
Calculate the minimum number of stages by Frenske equation:
(1 hk )
N m ln lk
ln lk hk
hk (1 lk )
* where lk/hk is the relative volatility of light key to heavy key
N m (ln
0.9998(1 0.03)
) (ln 6.04309) 7.011 trays
0.03(1 0.9998)
94
v.
Calculated split fraction of each component:
kNm hk
1 ( kNm 1) hk
* where k is the relative volatility of the component to heavy key
C2 H 4
vi.
14.786260.03
1 (14.78626 1)0.03
= 0.03
Distillate (D) and bottom (B) flowrate:
Dk k f k
and
B k (1 k )f k
* where fk is the feed flowrate of the component

DETAC 0.03 x 66.8144 2.0044
kmol/hr
BETAC (1 0.03) 66.8144 64.81
vii.
kmol/hr
Distillate fraction (yD) and bottom fraction (xB):
yD D k / D i
y D , ETAC
x B Bk / Bi
and
2.0044
0.1344
14.9109
x B , ETAC
and
64.81
0.3935
164.6883
Results :
Component
Formula
a k/hk
xk
dk
bk
95
712.120723
2.4823168
hydrogen
Acetaldehy
H2
4
6.04309440
6
8.8568759
de
CH3CHO
0.9998923
7
2.0044316
0.000953988
EA
C4H8O2
1
0.03
6
0.90775455 0.01544918 1.5672366
64.8100
Ethanol
C2H5OH
1
720.071572
99.8774
total
2
14.910861
Component
Stream 12 (Inlet)
kmole/h
r
H2
kg/hr
Stream 13
Ethanol
Stream 14
(Overhead)
kmole/h
kg/hr
r
4.9646
(Bottom)
kmole/h
kg/hr
r
2.4823
4.96463
2.4823
3
389.70
0.0000
44
88
8.8578
66.8144
101.444
389.745
5879.67
8.8569
2.0044
3
176.39
72.092
0.0010
64.8100
0.04198
5703.28
46
4666.45
10940.8
1.5672
99.8774
4594.36
10297.6
179.60
14.91
643.15
164.69
Acetaldehyd
e
EA
164.6883037
total =
Based on ASPEN PLUS, bubble point and dew point temperature can be estimate by using
mole fraction of component,
Component
H2
Acetaldehyde
EA
Ethanol
total =
MW
2
44
88
46
Stream 12 (Inlet)
mole
0.0138
0.0493
0.3720
0.5648
1.00
mass
0.0005
0.0356
0.5374
0.4265
1.00
Stream 13 (Overhead)
mole
0.1665
0.5940
0.1344
0.1051
1.00
mass
0.0077
0.6059
0.2743
0.1121
1.00
Stream 14
(Bottom)
mole
mass
0.0000
0.0000
0.0000
0.0000
0.3935
0.5538
0.6065
0.4462
1.00
1.00
96
T bubble (oC)
69.4
-213.4
71.7
Stream
Stream 12 (Feed)
Stream 13 (Distillate)
Stream 14 (Bottom)
T dew (oC)
71.1
47.4
72.5
Pump P-02

Stream 14 Stream 15
Stream 14 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
Pump P-03
kmole/hr
kg/hr
0.0000
0.0000
44
88
46
0.0010
64.8100
99.8774
164.69
0.04198
5703.28
4594.36
10297.68
Stream 15 (Outlet)
kmole/h
kg/hr
r
0.0000
0.0000
0.0010
64.8100
99.8774
164.69
0.04198
5703.28
4594.36
10297.68
97
Stream 15 Stream 16
Stream 15 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
kmole/hr
kg/hr
0.0000
0.0000
44
88
46
0.0010
64.8100
99.8774
164.69
0.04198
5703.28
4594.36
10297.68
Stream 16 (Outlet)
kmole/h
kg/hr
r
0.0000
0.0000
0.0010
64.8100
99.8774
164.69
0.04198
5703.28
4594.36
10297.68
Heater H-02

Stream 16 Stream 17
Stream 16 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
kmole/hr
kg/hr
0.0000
0.0000
44
88
46
0.0010
64.8100
99.8774
164.69
0.04198
5703.28
4594.36
10297.68
Stream 17 (Outlet)
kmole/h
kg/hr
r
0.0000
0.0000
0.0010
64.8100
99.8774
164.69
0.04198
5703.28
4594.36
10297.68
98
Stream 17 Stream 18 and 22

Inlet stream 17
T feed
P feed
170 C
15 bar
Specify
Light key
Heavy key
Top P
Bottom P
Ethanol
Ethyl Acetate
lk
hk
0.992
0.0151
15 bar
15 bar
i.
log PETAC 4.21248
ii.
1238.15
10.3471 bar
170 (217.205)
y
P
Kk k k
xk
P
K ETAC
10.3471
0.01502
688.9218
99
iii.
k / n
Kk
P
k
K n Pn
where Pk is the vapor pressure of the component and Pn is the vapor pressure of the key
component
ETAC / Ethanol
iv.
10.34713
0.6569
15.7522
(1 hk )
N m ln lk
ln lk hk
hk (1 lk )
N m (ln
v.
0.992(1 0.0151)
) (ln 2.223888) 11.2581 trays
0.0151(1 0.992)
kNm hk
1 ( kNm 1) hk
0.6568711.25810.0151
1 (0.6568711.2581 1)0.0151
= 0.000135
100
vi.
Dk k f k
and
B k (1 k )f k

DETAC 0.0001351 x 64.81 0.00876
kmol/hr
BETAC (1 0.00001351) 64.81 64.8012
vii.
kmol/hr
yD D k / D i
y D , ETAC
x B Bk / Bi
and
0.00876
0.000089
98.3789
x B , ETAC
and
64.8012
0.9773
66.3094
Results:
Component
hydrogen
Acetaldehyde
EA
Ethanol
total
Formula
H2
CH3CHO
C4H8O2
C2H5OH
a k/hk
39.8542
2.2239
0.6569
1.0000
43.7349
Stream 17 (Inlet)
xk
1.0000
0.9920
0.0001
0.0151
dk
0.0000
0.0009
0.0088
98.3692
98.3789
bk
0.0000
0.0000
64.8012
1.5081
66.3094
Stream 18
Stream 22
(Bottom)
kmole/
kg/hr
hr
0.000
0.000
kmole/
H2
Acetaldehy
hr
0.000
0.000
(Overhead)
kmole/
kg/hr
hr
0.000
0.000
de
44
0.001
0.042
0.001
0.042
0.000
0.000
5702.50
88
64.810
5703.276
0.009
0.771
64.801
Component
EA
kg/hr
101
Ethanol
4524.98
46
99.877
164.68
4594.360
10297.6
98.369
5
4525.79
1.508
69.375
5771.88
Total =
8
78
98.379
7
66.309
1
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
total =
2
44
88
46
Stream
Stream 17 (Feed)
Stream 22 (Bottom)
Cooler C-02

Stream 18 Stream 19
Stream 17 (Inlet)
Stream 18
Stream 22
(Bottom)
mole
mass
0.0000 0.0000
0.0000
0.9773
0.0227
1.00
mole
0.0000
mass
0.0000
(Overhead)
mole
mass
0.0000 0.0000
0.0000
0.3935
0.6065
1.00
0.0000
0.5538
0.4462
1.00
0.0000
0.0001
0.9999
1.00
T bubble (oC)
170.5
170.5
189
0.0000
0.0002
0.9998
1.00
0.0000
0.9880
0.0120
1.00
T dew (oC)
172
190
190
102
Stream 18 (Inlet)
Component
MW
kmole/
kg/hr
Stream 19
(Outlet)
kmole/
kg/hr
hr
0.0000
0
H2
Acetaldehy
hr
0.0000
de
44
0.0009
0.04164
0.77055
0.0009
0.04164
0.77055
88
0.0088
98.369
3
4524.98
0.0088
98.369
3
4524.98
46
2
98.378
5
4525.79
2
98.378
5
4525.79
EA
Ethanol
Total =
Valve CV-02

Stream 19 Stream 20
Stream 19 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
kmole/hr
kg/hr
0.0000
44
88
46
0.0009
0.0088
98.3692
98.3789
0.04164
0.770553
4524.985
4525.797
Stream 20 (Outlet)
kmole/h
kg/hr
r
0.0000
0
0.0009
0.0088
98.3692
98.3789
0.04164
0.770553
4524.985
4525.797
103
Valve CV-03

Stream 20 Stream 21
Stream 20 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
Cooler C-03

Stream 22 Stream 23
kmole/hr
kg/hr
0.0000
44
88
46
0.0009
0.0088
98.3692
98.3789
0.04164
0.770553
4524.985
4525.797
Stream 21 (Outlet)
kmole/h
kg/hr
r
0.0000
0
0.0009
0.0088
98.3692
98.3789
0.04164
0.770553
4524.985
4525.797
104
Stream 22 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
kmole/hr
kg/hr
0.0000
0.0000
44
88
46
0.0000
64.8012
1.5081
66.3094
0.0003
5702.5057
69.3748
5771.8808
Stream 23 (Outlet)
kmole/h
kg/hr
r
0.0000
0
0.0000
64.8012
1.5081
66.3094
0.000336
5702.506
69.37484
5771.881
Valve CV-04

Stream 23 Stream 24
Stream 23 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
kmole/hr
kg/hr
0.0000
0.0000
44
88
46
0.0000
64.8012
1.5081
66.3094
0.0003
5702.5057
69.3748
5771.8808
Stream 24 (Outlet)
kmole/h
kg/hr
r
0.0000
0
0.0000
64.8012
1.5081
66.3094
0.000336
5702.506
69.37484
5771.881
105
Valve CV-05

Stream 24 Stream 25
Stream 24 (Inlet)
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
kmole/hr
kg/hr
0.0000
0.0000
44
88
46
0.0000
64.8012
1.5081
66.3094
0.0003
5702.5057
69.3748
5771.8808
Stream 25 (Outlet)
kmole/h
kg/hr
r
0.0000
0
0.0000
64.8012
1.5081
66.3094
0.000336
5702.506
69.37484
5771.881
106
Inlet stream 21
T feed
P feed
73.7 C
1 bar
Specify
Light key
Heavy key
Ethyl Acetate
Ethanol
Top P
Bottom P
lk
hk
0.99
0.24
1 bar
1 bar

i.
log PETAC 4.21248
ii.
y
P
Kk k k
xk
P
K ETAC
iii.
1238.15
0.9042 bar
73.7 (217.205)
0.90423
0.00157
577.3053
k / n
Kk
P
k
K n Pn
* where Pk is the vapor pressure of the component and Pn is the vapor pressure of the key
component
ETAC / Ethanol
iv.
0.904231
1.0727
0.84297
107
(1 hk )
N m ln lk
ln lk hk
hk (1 lk )

N m (ln
v.
0.99(1 0.24)
) (ln 1.07267) 81.9297 trays
0.24(1 0.99)
kNm hk
1 ( kNm 1) hk
vi.
1.0727 81.92970.24
1 (1.0727 81.9297 1)0.24
= 0.99
Dk k f k
and
B k (1 k )f k

DETAC 0.99 x 0.0088 0.00867
kmol/hr
B ETAC (1 0.99) 0.0088 0.000088
vii.
kmol/hr
yD D k / D i
and
x B Bk / Bi
108
y D , ETAC
0.00867
0.00037
23.6182
x B , ETAC
and
0.000088
0.000
74.7607
Results:
Component
hydrogen
Acetaldehyde
EA
Ethanol
Water
total
Component
M
W
Formula
H2
CH3CHO
C4H8O2
C2H5OH
a k/hk
676.4845
6.2906
1.0727
1.0000
xk
1.0000
1.0000
0.9900
0.2400
684.8478
Stream 21 (Inlet)
kmole/hr
kg/hr
dk
0.0000
0.0009
0.0087
23.6086
bk
0.0000
0.0000
0.0001
74.7606
23.6182
74.7607
Stream 26
Stream 28 (Bottom)
(Overhead)
kmole/hr
kg/hr
kmole/hr
kg/hr
H2
Acetaldehyd
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
e
EA
Ethanol
total =
44
88
46
0.0009
0.0088
98.3692
98.3789
0.0416
0.7706
4524.9852
4525.7974
0.0009
0.0087
23.6086
23.6182
0.0416
0.7628
1085.9965
1086.8009
0.0000
0.0001
74.7606
74.7607
0.0000
0.0077
3438.9888
3438.9965
Component
MW
Inlet
Outlet
109
H2
kmole/hr
kg/hr
kmole/hr
kg/hr
0.000
0.0000
0.0000
0.0000
0
0.000
44
0.0000
0.0000
0.0000
0
0.000
88
0.0000
0.0000
0.0000
0
1.000
46
1.0000
1.0000
1.0000
0
1.000
1.0000
1.0000
1.0000
Acetaldehyd
e
EA
Ethanol
Total =
T bubble (oC)
77.5
75.8
78
Stream
Stream 17 (Feed)
Stream 22 (Bottom)
T dew (oC)
77.7
76.8
78
Cooler C-04

Stream 26 Stream 27
Component
MW
H2
Acetaldehyd
Stream 26 (Inlet)
kmole/h
kg/hr
r
0.0000
0.0000
44
0.0009
0.0416
0.0009
0.04164
0.76284
88
46
0.0087
23.6086
0.7628
1085.996
0.0087
23.6086
7
1085.99
EA
Ethanol
Stream 27 (Outlet)
kmole/h
kg/hr
r
0.0000
0
110
5
1086.800
Total =
23.6182
6
1086.80
23.6182
Cooler C-05

Stream 28 Stream 29
Component
H2
Acetaldehyde
EA
Ethanol
Total =
MW
2
44
88
46
Stream 28 (Inlet)
Stream 29 (Outlet)
kmole/h
kg/hr
kmole/hr
kg/hr
r
0.0000
0.0000
0.0000
0
0.0000
0.0000
0.0000
0
0.0001
0.0077
0.0001 0.007706
74.7606 3438.9888 74.7606 3438.989
74.7607 3438.9965 74.7607 3438.996
111
112
A.2
Energy Balance Calculation
Mixer 1, M-01
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream (kJ/hr)
Heat duty
Inlet
Flow Rate
Temperature
Outlet
Flow
(kmol/hr)
0
0
0.053
223.6896
(kmol/hr)
0
0
0.053
223.6896
(C)
25
-5.98E+07
Rate Temperature
(C)
25
-5.98E+07
(kJ/hr)
Pump, P-01
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
Flow Rate
Temperature
(kmol/hr)
0
0
0.053
223.6896
(C)
Outlet
Flow Rate
Temperature
(kmol/hr)
0
0
0.053
223.6896
25
-5.98E+07
(C)
25
-5.96E+07
(kJ/hr)
1.35E+05
Cooler, C-01
Inlet
Component
Hydrogen
Acetaldehyde
Flow Rate
Temperature
(kmol/hr)
145.3982
10.1779
(C)
Outlet
Flow Rate
Temperature
(kmol/hr)
145.3982
10.1779
(C)
113
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
67.6632
78.2914
260
67.6632
78.2914
-4.50E+07
30
-1.1E+07
(kJ/hr)
3.41E+07
Expander, EX-01
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
Flow Rate
Temperature
(kmol/hr)
142.9287
1.3667
1.1504
0.8573
(C)
Outlet
Flow Rate
Temperature
(kmol/hr)
142.9287
1.3667
1.1504
0.8573
30
-8.87E+05
(C)
30
-9.17E+05
(kJ/hr)
-2.99E+04
Valve, CV-01
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Flow Rate
Temperature
Flow Rate
(kmol/hr)
2.4695
8.8112
66.5128
77.4341
(C)
(kmol/hr)
2.4695
8.8112
66.5128
77.4341
-5.40E+07
30
Outlet
Temperature
-5.41E+07
(C)
30
114
Heat duty
(kJ/hr)
-1.21E+05
Heater, H-01
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
Flow Rate
Temperature
(kmol/hr)
(C)
2.4695
8.8112
30
66.5128
77.4341
-5.4E+07
stream(kJ/hr)
Heat duty
Outlet
Flow Rate
Temperature
(kmol/hr)
(C)
2.4695
8.8112
68
66.5128
77.4341
-5.3E+07
8.81E+05
(kJ/hr)
Mixer, M-02
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
(kJ/hr)
Inlet 1
Flow Rate Temperat
(kmol/hr)
ure (C)
2.4695
8.8112
66.5128
77.4341
-5.32E+07
68
Inlet 2
Flow
Temperatur
Rate
e (C)
(kmol/hr
)
0
0
68
2.2694
23.242
Outlet
Flow Rate Temperatu
(kmol/hr)
re (C)
-7.24E+06
-6.11E+07
-6.58E+05
2.469
8.811
68.782
100.676
68
115
Pump 2, P-02
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
Flow Rate
Temperature
(kmol/hr)
(C)
0.0000
0.0441
66.7187
71.6
98.7703
-5.7E+07
stream(kJ/hr)
Heat duty
Outlet
Flow
Rate Temperature
(kmol/hr)
0.0000
0.0441
66.7187
98.7703
(C)
71.6
-5.7E+07
9.96E+04
(kJ/hr)
Pump 3, P-03
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
Flow Rate
Outlet
Flow Rate
Temperature
Temperature
(kmol/hr)
(C)
0.0000
0.0441
66.7187
71.6
98.7703
-5.7E+07
stream(kJ/hr)
Heat duty
(kmol/hr)
(C)
0.0000
0.0441
66.7187
71.6
98.7703
-5.7E+07
0
(kJ/hr)
Heater 3, H-03
Component
Inlet
Flow
(kmol/hr)
Rate Temperature
(C)
Outlet
Flow
(kmol/hr)
Rate Temperature
(C)
116
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
0.0000
71.6
0.0441
66.7187
98.7703
-5.7E+07
stream(kJ/hr)
Heat duty
0.0000
0.0441
66.7187
98.7703
170
-5.4E+07
3.03E+06
(kJ/hr)
Cooler 3, C-03
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
Flow Rate
Temperature
(kmol/hr)
(C)
0
0.0441
2.2205
167.8
97.2789
-2.49E+07
stream(kJ/hr)
Heat duty
Outlet
Flow Rate
Temperature
(kmol/hr)
(C)
0
0.0441
2.2205
77
97.2789
-2.54E+07
-5.29E+05
(kJ/hr)
Cooler 4-C-04
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Flow Rate
Temperature
Flow Rate
(kmol/hr)
0
0
64.4982
1.4914
(C)
(kmol/hr)
0
0
64.4982
1.4914
-2.89E+07
188.8
Outlet
Temperature
-2.92E+07
(C)
72.4
117
Heat duty
(kJ/hr)
-2.83E+05
Valve 2, CV-02
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
Inlet
Flow Rate
Temperature
Outlet
Flow
(kmol/hr)
0
0.0441
2.2205
97.2789
(kmol/hr)
0
0.0441
2.2205
97.2789
(C)
77
-2.54E+07
Rate Temperature
(C)
77
-2.54E+07
(kJ/hr)
-4.76E+04
Valve 3, CV-03
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
(kJ/hr)
Valve 4, CV-04
Flow Rate
Temperature
(kmol/hr)
0
0.0441
2.2205
97.2789
(C)
77
Outlet
Flow Rate
Temperature
(kmol/hr)
0
0.0441
2.2205
97.2789
-2.54E+07
-2.55E+07
-4.76E+04
(C)
77
118
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
Flow Rate
(kmol/hr)
0
0
64.4982
1.4914
Inlet
Temperature
(C)
Outlet
Flow
Rate Temperature
(kmol/hr)
0
0
64.4982
1.4914
72.4
-2.9E+07
(C)
72.4
-2.9E+07
(kJ/hr)
-1.04E+05
Valve 5, CV-05
Inlet
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
Flow Rate
Temperature
(kmol/hr)
0
0
64.4982
1.4914
(C)
72.4
Outlet
Flow
(kmol/hr)
0
0
64.4982
1.4914
-2.9E+07
(kJ/hr)
Rate Temperature
(C)
72.4
-2.9E+07
0
Cooler 4, C-04
Component
Inlet
Flow Rate
Temperature
Outlet
Flow
(kmol/hr)
(kmol/hr)
(C)
Rate Temperature
(C)
119
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
0
0
1.4148
73.9319
0
0
0.053
73.5996
188.8
-1.99E+07
(kJ/hr)
25
-1.97E+07
2.0E+07
Cooler 5, C-05
Component
Hydrogen
Acetaldehyde
Ethyl Acetate
Ethanol
Heat duty
stream(kJ/hr)
Heat duty
(kJ/hr)
Inlet
Flow Rate
Temperature
(Mol/hr)
(C)
0
0.0441
167.8
0.8057
23.3469
-6.48E+06
Outlet
Flow
Rate Temperature
(Mol/hr)
(C)
0
0.0441
68
0.8057
23.3469
-6.63E+06
-1.49E+05
120
A.3
1) Manual Calculations
Process Flow Diagram With Complete Stream
121
2) Process Simulation of Process Flow Diagram
Process Simulation Stream Table

Chapter 1 To 4

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Chemical Background of Ethyl Acetate

ether, acetone, alcohol, benzene

1.3 Manufacturing Process of Ethyl Acetate

Ethyl acetate is synthesized in industry via classic Fisher esterification. This

Ethyl acetate also can be produced by dehydrogenation process of ethanol. Ethanol

1.4 Application and Uses of Ethyl Acetate

Ethyl acetate can be used in a wide variety of industries including; food

Table 1.2: Uses of ethyl acetate in various industry [6]

Ethyl acetate is commonly used as a flavour enhancer in food

Some example of the flavour is in essence

manufacturing of pineapple, bananas, strawberries and other fruit

It is usually used as a flavour enhancer in beverage.

Ethyl acetate is widely used as extraction gent, intermediate in the

Ethyl acetate is often used as aroma enhancer in cosmetic especially

It is widely used as industrial solvent in various other industries

1.5 Process Safety of Ethyl Acetate

Toxicology Information of Ethyl Acetate

Table 1.3: Toxicity information of ethyl acetate [2]

Absorbed through skin, eye contact, inhalation, ingestion

upper respiratory tract. May cause damage to the following

organs: blood, kidneys, liver, central nervous system (CNS).

in case of skin contact( irritant, permeator)

Special remarks on May effect genetic material (mutagenic).

1. Skin: May cause skin irritation

Storage and Handling of Ethyl Acetate

environmental testing. Since it is flammables, it is recommended a safe chemical storage

Other than that, it is

1.6.1 Market Demand

Figure 1.1: Global Ethyl Acetate (ETAC) Production in 2013 [8]

North American [11]

Figure 1.4: The capacity of ethyl acetate in North America [11]

Figure 1.5: Prices of Ethyl Acetate from 2009 to 2011[12]

Figure 1.6: Asia ETAC capacity tonnes per year [15]

1.6.3 Market Price of Raw Materials

In the recent years, ethanol production from

Figure 1.7: Ethanol market price on December 2015 [18]

Figure 1.8: Acetic acid market price on December 2015 [19]

Figure 1.9: Ethylene market price on December 2015 [17]

Ethyl acetate is an important environmental friendly solvent, industrially used in

The akylation of acetic acid with ethylene

The akylation of acetic acid with ethylene

This technology (Avada) has been

Ethyl acetate can also be obtained by dehydrogenation of ethanol, in a

Figure 1.14: Davy Process flowsheet of ethyl acetate production [25]

Table 1.3: The average price of raw materials and products

Orchid Chemical Supplies Ltd.

Platts McGraw Hill financial

The akylation of acetic acid with ethylene

1.7.2 Detailed Analysis of Process Selection

Detailed analysis on Fisher esterification and Tischenko reaction

The akylation of acetic

acid with ethylene

Ethylene; Acetic acid

catalyst (Avada process).

-Reaction without loss of

-High product yield rate

-High product yield

-Able to produce high

-producing low acid waste

quality of ethyl acetate

consumption and pollution

-Only competitive when the -Ethyl acetae unit should