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CHAPTER 1
INTRODUCTION
1.1
1.1.1
Process Background
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
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].
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.
4
Food Production
Pharmaceutical
Cosmetics
Others industries
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.
Chronic
effect
(mouse)
on Cause damage to the following organs: mucous membrane,
humans
1.5.2
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
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 1.2: Production rate of ethyl acetate from 2005 to 2013 [9]
Figure 1.3: Ethyl acetate market price from 2004 to 2013 [10]
A)
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.
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.
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.
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.
13
In the process to produce ETAC, ethanol, acetic acid and ethylene are the major
feedstocks to be used in industries.
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.
14
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
a) Fisher esterification
b) Tischenko reaction
A)
c)
d)
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.
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
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.
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.
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
Ethylene
C
( 2 H 4 )
28.05
0.834
88.11
0.93
Technon Orbichem
www.cleancaroptions.com
Ethyl acetate
(C H 3 COOC 2 H 5 )
Hydrogen
( H2 )
23
Fisher esterification
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
Overall Chemical Equation
2C H 3 CHO
Kmole
Molecular Weight (kg/kmol)
Weight
Weight / Weight EA
Price of Component ($/kg)
Gross profits ($/kg 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
C2 H 4
C H 3 COOH
Products
C H 3 COO C 2 H 5
Kmole
Molecular Weight (kg/kmol)
1
28.05
1
60.05
1
88.11
24
Weight
Weight / Weight EA
Price of Component ($/kg)
Gross profits ($/kg 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
Overall Chemical Equation
Reactants
2C 2 H 5 OH
Kmole
Molecular Weight (kg/kmol)
Weight
Weight / Weight EA
Price of Component ($/kg)
Gross profits ($/kg 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
Fisher esterification
Tischenko reaction
Dehydrogenation of
Acetaldehyde
aluminum alkoxide; sodium
Ethanol
Copper Oxide,
25
acid, para-
alkoxide
Zinc Oxide,
ion-exchange resins).
0.332
-2.57
0.391
0.591
-Technique is advance;
-Feedstock is quite a
small molecules;
few;
toluenesulfonic acid or
Gross Profit
($/kg)
Advantages
and alternative
-low corrosiveness
-Simple Technique;
Producing cost
-Low corrosiveness,
water
relatively low
investment, energy
-Relatively friendly to
-High corrosiveness
environment
equipment
as it may
-Catalyst is expensive
producealuminium
Technology
available
Hoechst A.G
hydroxide
Hoechst A.G
Avada by INEOS;
Davy technology
26
27
1.8
It
is
important
to
conduct
feasibility
study
before
starting
plant
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.
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.
The production of ethyl acetate uses ethanol and acetic acid as the
main raw material.
identify and considered. This is crucial if large volumes of raw material are
required for production.
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.
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.
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
38.00 sen/kWh
44.10 sen/kWh
42.70 sen/kWh
29.60 RM/kW
33.70 sen/kWh
23.70 RM/kWh
33.60 sen/kWh
31
TARIFF E2 - MEDIUM VOLTAGE PEAK/OFF-PEAK INDUSTRIAL TARIFF
For each kilowatt of maximum demand per
month during the peak period
37.00 RM/kW
35.50 sen/kWh
21.90 sen/kWh
32.90 RM/kW
33.60 sen/kWh
19.10 sen/kWh
35.50 RM/kW
33.70 sen/kWh
20.20 sen/kWh
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.
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
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
Gebeng,
Pengerang,Johor.
Kuantan, Pahang.
40km from
42km from
9.6km from
Kuantan Town.
Johor Bahru
Kemaman Town
5km from
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
from Petronas
Bhd., Kertih.
Bhd., Kertih
35
Water Supply
Semambu Water
pipe line)
77km of pipes from the Sungai
Terengganu
Treatment Plant
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
Kenyir Dam
Paka Power Station
Gelang, Kuantan.
TNB 900 Mw
(800Mw)
600 MW
TNB 400 Mw
36
Transport Facilities
Main road to
Kuala Lumpur,
to coastline traversing
Singapore.
Kuala Terengganu
Railway
Carriers (VLCCs)
Kuantan Airport
highway.
Kuantan Port
Kuala Terengganu
airport
Kertih airport
Labour
Kemaman Port
University Technology MARA
(UTM)
Malaysia (IIUM)
Polytechnic
(TATI)
Polytechnic
Center (JSDEC)
Centre (TSTC)
completion.
naphtha cracker complex with a
Incorporating a training
C4 and C5 olefins
37
processing centre as well as raw
derivates.
servicing facilities.
Chemicals Produced
Gasoline
Syngas
Diesel
Butyl Acrylate
Polyisobutylene
Oxo-alcohols
Isononanol
non-ionic surfactants
Plasticizers
methanesulfonic acid
Butanediol
hydrogen peroxide
Tetrahydrafurane
C4 co-monomer
Gamma-butyrolactone
oxo-products.
Propylene
Ethanol
produce up to 250,000t/y of
Polypropylene
Polybutane Terepthalate
(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 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
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
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,
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
43
For the manufacture of ETAC, data from the chemical involving reaction shown
in Table 2.2.
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.
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.
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.
45
46
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:
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.
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
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
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
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
Temperature,
Pressure
Phase
Justification
R01
T (C)
260
, P (bar)
10
Vapour
(Dehydrogenation
Reactor)
Packed Bed
copper/copper chromite
54
Tubular Reactor
(PBR)
PS-01
34
10
Phase Separator
Mixtur
68.4
Liquid
Distillation
column 1
D-102
170
15
Mixture
Distillation
column 2
55
product) and other heavy key
components (overhead product).
However, there are still EA component
D-103
76
Liquid
Distillation
column 3
E-0 1
260
10
Liquid
distillation column 1.
Ethanol feed and recycled ethanol are
Evaporator
H-01
heating to 260oC.
The bottom product from flash drum
68.4
Liquid
Heater 1
170
15
Liquid
Heater 2
C-01
34
10
Vapor
Cooler 1
C-02
76
15
Liquid
Cooler 2
C-03
25
15
Liquid
E-104.
Before recycled to distillation
Cooler 3
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
M-02
68.4
Liquid
feed.
Overhead stream of distillation
Mixer 2
P-01
25
1 to 10
Liquid
Pump 1
P-02
71.6
1 to 8
Liquid
Pump 2
P-03
71.6
8 to 15
Liquid
bar.
Before entering Distillation 2,
Pump 3
V-01
pump to 15 bar.
Valve 1 will reduced a pressure
34
10 to 1
Liquid
Valve 1
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 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.
azeotropic,
reactive)
distillation,
liquid-liquid
extraction,
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
3.1
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
Mout(kh/hr)
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.
50000
MT 1000 kg
1 year
1 day 1 kmol
year
1 MT
350 days 24 hr 88 kg
= 67.64 kmol/hr EA
64
3.1.3.1
Compone
nt
H2
Acetaldehy
de
EA
Ethanol
3.1.3.2
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
65
1) Reaction path:
C2H5OH C2H4O + H2
C2H5OH + C2H4O C4H8O2 + H2
2C2H5OH C4H8O2 + 2H2
(Overall Equation)
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
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
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
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
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
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 )
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
Flow Rate Temperatur
Outlet
Flow Rate Temperatur
(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
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
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
75
4.1
Process Simulation
4.2
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.
77
4.3
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
Manual(Kj/Hr)
Simulation(Kj/Hr)
-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
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.
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
A.1
A.2
A.3
83
A.1
Mixer M-01
= 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
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
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)
MW
H2
Acetaldehyd
Inlet
kmole/hr
0.000
e
EA
Ethanol
44
0.000
88
46
0.000
224.851
0+
(C2H5OH)in - 2
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 (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
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
T = 30 0C = 303.15 K
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 =
= 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
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
MW
H2
Acetaldehyd
2
44
e
EA
Ethanol
Total =
88
46
Heater H-01
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
= 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
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
93
log PETAC 4.21248
ii.
y
P
Kk k k
xk
P
0.79698
0.001388
574.19481
K ETAC
iii.
1238.15
0.79698 bar
70 (217.205)
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
(1 hk )
N m ln lk
ln lk hk
hk (1 lk )
N m (ln
0.9998(1 0.03)
) (ln 6.04309) 7.011 trays
0.03(1 0.9998)
94
v.
kNm hk
1 ( kNm 1) hk
C2 H 4
vi.
14.786260.03
1 (14.78626 1)0.03
= 0.03
Dk k f k
and
B k (1 k )f k
kmol/hr
vii.
kmol/hr
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
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
Assuming mass in = mass out
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
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
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.
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
kmol/hr
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
Based on ASPEN PLUS, bubble point and dew point temperature can be estimate by using
mole fraction of component,
Component
MW
H2
Acetaldehyd
e
EA
Ethanol
total =
2
44
88
46
Stream
Stream 17 (Feed)
Stream 18 (Distillate)
Stream 22 (Bottom)
Cooler C-02
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
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
MW
H2
Acetaldehyd
e
EA
Ethanol
Total =
Cooler C-03
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
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
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
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 )
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
kmol/hr
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
Based on ASPEN PLUS, bubble point and dew point temperature can be estimate by using
mole fraction of component,
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 18 (Distillate)
Stream 22 (Bottom)
T dew (oC)
77.7
76.8
78
Cooler C-04
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
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
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
121
2) Process Simulation of Process Flow Diagram