Production of 100,00 Metrics Tonnes Per Year of N-Propanol

1
CHAPTER I
PROCESS BACKGROUND AND SELECTION
1.0 Introduction
Propanol is a clear, colorless liquid with alcohol odor, it is also miscible in

water, and organic solvent such as ethyl ether and alcohols. It can forms azeotrope
with water appearance. It is consist of three carbons, eight hydrogens and one
oxygen with the molecular formula of C3H7OH. In addition, it is a primary alcohol
thats also known as 1-propanol, 1-propyl alcohol, n-propyl alcohol, n-propanol, or
simply propanol. It has an isomer called 2-propanol which also known as
isopropanol (IPA). n-propanol is not considered a hazardous air pollutant (HAP)
solvent by the U.S. Environmental Protection Agency.
Source: http://www.inchem.org/
n-propanol can occurs in nature in fuel oils and forms from fermentation and
spoilage of vegetable matter. For commercial production of n-propanol, its involved
two steps of complicated process called oxo-process which consists of ethylene
hydroformylation using carbon monoxide and hydrogen at 80-120C and 2.0 MPa in
the presence of cobalt or rhodium carbonyl followed by hydrogenation on copper-
chromium or nickel-chromium catalyst. Other than that, certain industry practice
other process such as conversion of glycerol, sasol fischer-tropsch process,
homologisation and also fermentation to produce n-propanol.
2
3
Table 1.1: Physical Properties of n-propanol
Property Description
Molecular Formula C3H8O
Molar Mass 60.1 g/mol
IUPAC Name Propan-1-ol
1-propanol
Other Name
propyl alcohol
n-propanol
n-propyl alcohol
propanol
Form Liquid
Colour Colourless
Adour Alcoholic
pH 7
Melting Point Temperature -126.2oC
Boiling Point Temperature 97.2 C
Flash point 15 C; closed cup

23 C; open cup
Vapour Pressure 27.998 kPa; 25 C
Density 805 kg/m3
Water Solubility completely miscible
Viscosity 2.170 MPa.s
4
1.1 Uses And Application
n-propanol is not sold for direct consumer use. The major use of n-propanol is
as a solvent which used as carrier and extraction solvent for natural products, such
as flavourings, vegetable oils, resins, waxes, and gums, and as a solvent for
synthetic polymers, such as polyvinyl butyral, cellulose esters, lacquers, and PVC
adhesives. Other solvent applications include the use of n-propanol in the
polymerization and spinning of acrylonitrile, in flexographic printing inks, and in the
dyeing of wool. n-propanol is used for both its solvent and antiseptic properties in
drugs and cosmetics, such as lotions, soaps, and nail polishes. It is a chemical
building block for the manufacture of chemical intermediate of esters, amines, and
halides such as in the manufacture of propanal, 1-bromopropane, O,O-
dipropylphosphoro-dithioic acid, n-propyl amines, esters (propyl acetate, propyl
carbamate), alcoholates, and xanthates.
Other than that, n-propanol is used in a broad range of applications, including

coatings, dispersing agents, pesticide formulations, metal degreasing fluids,
adhesives polishing compounds (window cleaners, floor polishes), and brake fluid,
as coupling and as a ruminant feed supplement. Because of its relative inertness
and low odor, this material is also used for packaging and food-contact applications.
In the current usage of engines, the characteristic of n-propanol from the aliphatic
alcohols group has the potential to use as a liquid fuel due to its characteristics
which improves the water tolerance of motor fuels. Pie chart in Figure 1 shows the
general uses of n-propanol as a solvent in United State.
5% 5%
n-Propyl acetate
15% 41% Direct Solvent
Glycol Ethers
Other
34% n-Propyl-amines
Figure 1.1 U.S Uses for n-propanol
5
1.2 Reaction Mechanism

There are two steps involves on the production. The first step is hydroformylation
reaction and the process is then proceeding with the second step which is
hydrogenation process after the complete reaction in the previous step.
1.2.1 Hydroformylation Reaction :

This reaction is a reaction mixtures that produce substantial amounts of aldehydes
and alcohols due to rection between olefins with syngas which were carbon
monoxide and hydrogen at elevated temperature and pressure in the presence of
catalyst. In order to produce n-propanol, the type of olefin will be ethylene. It will
react with carbon monoxide and hydrogen gas at specific order to produce
propionaldehyde at certain temperature and pressure.
General reaction :
C 2 H 4 CO H 2 c CH 3CH 2 CHO
atalyst, , presu ure
1.1
Ethylene Carbon Hydrogen Propionaldehyde
monoxide
1.2.2 Hydrogenation Reaction :

A process where aldehyde is converted into alcohol in the addition of hydrogen gas
with the presence of certain catalyst as an additive to the reaction. The reaction took
part in the desired temperature and pressure condition. The propionaldehyde
produced from hydroformylation will be then undergo second reaction with hydrogen
to produce n-propanol.
General Reaction:
CH 3CH 2CHO H 2 c CH 3CH 2CH 2 HO
1.2
Propionaldehyde Hydrogen n-propanol
6
Mechanics of ethylene hydroformylation and hydrogenation can be shown as below:
adol C6 H14 0
C2 H 6 dipropylether
H
condensation
ethane
CH CH C H C H CO C H CHOC H CH OH
2 2 H 2 5 CO 2 5 H 2 5 2H 2 5 2
ethylene
1.2.3 alkyl intermediates propanoyl propionaldehyde n-propanol
2H
C2 H 5CH 2O
H C2 H 5CH 2OH
propoxide n-propanol
.
Source from :Journal of Molecular Catalysis A: Chemical 138 _1999. 155176
2.0 Side Reaction and By-product
2.0.1 Hydroformylation Reaction.

Minor by-products from this process include propionaldehyde, ethane, and some
heavy ends. The composition of these by-products produced will be depending on
the condition of the process itself and the catalyst used.
2.0.2 Hydrogenation Reaction

The main product in this reaction will be n-propanol. However, certain impurities
tend to be formed from the adol condensation of the propanal such as n-propyl
propionate, dipropylether (DPE) and also 2-methylpentenal. The synthesis of C6
aldehydes from propanal via aldol condensation reaction occur in ionic liquid media
with NaOH as a catalyst. NaOH is used as the activated agent in preparing the
dicobalt octacarbonyl catalyst. The production and composition of these by-products
also depend on the catalyst used. Different chose of catalyst resulting in different
composition of by-product produced.
Journal of Molecular Catalysis A: Chemical 278 (2007) 135144

7
1.4 Process Background
1.4.1 Method Selection

There are three processes that have commercially being used in the industrial in
order to produce n-propanol. They were the oxo process, glycerol conversion and
also homologisation process. Each of this process has their own benefits due to raw
material, catalyst and equipments used. Below are the general descriptions for all
the processes.
8
Table 1.2 : Process Descriptions of Methods in Producing n-propanol.

Characteristic Oxo Process Conversion of Glycerol Homologisation
i)Gas dehydration (endothermic)
i)Hydroformylation (exothermic) Temperature = 200-400 oC
Temperature = 90-130 oC Pressure = 0.1-3 Mpa
Pressure = 2-5 Mpa ii)Hydrogenation of acrolein
Temperature = 150-250 oC
Process Condition ii)Hydrogenation (exothermic) (exothermic)
Pressure = 20-60 Mpa
Temperature = 120 -180 oC iii)Hydrogenation of aldehyde
Pressure = 3-5 Mpa (exothermic)
Temperature = 200-250 oC
Pressure = 5-20 Mpa
Ethylene, Hydrogen, Carbon Methanol, Hydrogen, Carbon
Raw Material Glycerol, Hydrogen
Monoxide Monoxide
Group 8-10 (VIII) metal catalyst in Cobalt catalyst together with organic
the liquid phase and also Group 9 Pt, Ru, Pd and Ni catalysts with and inorganic iodine compouns, and
Catalyst like cobalt carbonyl(Co), rhodium the support of ion-exchange ammonium or phosphonium
triphenylphosphine (Rh) and Raney resin. compund, as well as a rhuthenium
nickel(Ni). compound as promoters.
Conversion 50%-70% 45%-65%
Ethane gas and heavy carbon Ethylene-glycol, Ethanol, Methane, ethane and propane,
By Product
compound from adol condensation Methane, Acetol, 1,2- various ethers as well as methyl
9
Cont
of the propanal such as n-propyl propanediol, 2-propanol acetate, ethyl acetate, propyl
propionate, dipropylether (DPE) and acetate, acetaldehyde-dimethyl-
also 2-methylpentenal acetal, acetaldehyde-methyl-
ethylacetal and acetaldehyde-diethyl-
acetal
Rate of hydroformylation is increase Low price of raw material Large amount of water increase
Advantages with increasing of hydrogen and The use of glycerol solution conversion of product.
decreasing in carbon monoxide at the lowest purity which is
partial pressure. at 40 wt% - 60 wt%.
Carbon monoxide could cause High concentrations of

Numerous different individual
poison for the second reaction ethylene-glycol, the main
compound occur as undesired
which is hydrogenation that can side reaction product,
by product in the large amount.
effect product yield. appear with a selectivity
Disadvantages Expensive industrial process to
Formation of water could value of around 10%.
isolate hydrogenation,
produce azeotrope with n- Formation of water could
saponification and distillation from
propanol which lead to complex produce azeotrope with n-
useful product fraction and by-
separation propanol which lead to
products
complex separation
18
From all the processes that already compared in the table above, oxo process is
chosen as a method in producing n-propanol because this process produced fewer
impurities with low industrial process cost.
1.4.2 Catalyst Selection

In order to fasten the reaction, a number of transition- metal carbonyls like cobalt
carbonyl, Raney nickel, rhodium triphenylphosphine, rutherium, and iron is used to
catalyze the oxo reaction. The most commercialized catalysts in the industries
nowadays are cobalt carbonyl and rhodium triphenylphosphine due to their
advantages compared to other catalysts. Catalyst selection also is based on the
types of reactor use in the process because reactor and catalysts using is
interrelated. Besides that, cost of catalyst is also considered in order to choose the
best catalyst for the oxo process. The advantages and disadvantages of each
catalyst and price ratio between them are shown below.
Table 1.3: Comparisons of Catalysts.
Catalyst Advantages Disadvantages
Cobalt Carbonyl Economic practical choice. Thermally unstable.

(Co) Very cheap/inexpensive. Easily decompose to
Highest yield cobalt and carbon
Longest life time. monoxide.
Produce predominantly
linear alkanes.
Reduce impurities.
Energy required is low.
Most reactive in reaction of
synthesis gas.
Raney Nickel (Ni) Large amount of
impurities in no or
presence of water. (di-
n-propylether,DPE and
n-propyl
19
propionate,prpr).Cont
Makes separation and
purification of n-
propanol difficult
because of binary
azeotrope between
water and n-propanol.
High energy
consumption.
Need larger purification
column.
Rhodium Economic practical choice. Very expensive
Triphenylphosphine High reaction rate. catalyst.
(Rh) Greater stability.
Low operation pressure.
Lower by product
production.
More active than cobalt.
Result in less high boiling
point of by product.
Table 1.4: Price Ratio Between the Catalysts.
Metal Price Ratio
Iron 1
Cobalt 230
Nickel 250
Rutherium 31 000
20
Rhodium 570 000
Source from : Rhodium-Catalyzed Hydroformylation.(2000)
Based on the tables above, cobalt carbonyl has been choosing to be use in the oxo
process. This is because the catalyst is commercialized enough in the chemical
industries and has it own benefits like low cost compared to others. Cobalt carbonyl
will be used in the first reactor at the hydroformylation process and also second
reactor at the hydrogenation process.
1.4.3 Equipment Selection

Besides catalyst selection, reactor selection also plays an important role in the oxo
process to increase the process efficiency. There are different types of reactor that
can be considered for oxo process such as fixed bed reactor, fluidized bed reactor,
slurry reactor, and batch reactor. Catalyst form also affects the selection of reactor.
For the fixed bed, the raw material or reactant of the process must be between liquid
and gas and the catalyst in the form of pellet. This kind of reactor also can react any
two gas phase. Meanwhile for the slurry bed, the reactant is between gas and gas.
Catalyst form is in liquid form. This shown that selection of reactor and catalyst is
very important consideration. Table below shows advantages and disadvantages of
each reactor.
Table 1.5: Reactor Selection
Types of Reactor Advantages Disadvantages
Fixed Bed Reactor Simple analysis. Poor heat transfer in

High efficiency. fixed bed reactor.
Low cost. Non uniform flow
Low maintenance. pattern.
Little loss or attrition. Swelling of the catalyst
High ratio of catalyst to and deformation of
reactants. reactor.
Little wear of catalyst and Regeneration or

21
equipment. replacement of catalyst

Only practical and economical is difficult and need
reactor at high pressure. shutdown. Cont
Efficient-long residence time High pressure drop for
and achieve near complete small beads or pellets.
reaction.
Fluid Bed And Frequent regeneration of the Complicated.
Slurry Reactor catalyst. Extensive investment
Rapid mixing of solids in beds and high maintenance.
means uniform gas Low residence time and
composition. conversion maybe
Efficient temperature control. limited.
Small diameter particles in Attrition and loss of
fluid minimize pore diffusional catalyst.
resistance.
High heat transfer rates.
1.5 Process Description

Worldwide production of n-propanol has been carried out in two complex reactions
which were hydroformylation of ethylene followed by hydrogenation of
propionaldehyde or propanol, the product of the first reaction
.
By referring to the process PFD at the APPENDIX A, the main equipment processes
were elaborate.
22
Hydroformylation Of Ethylene (Slurry Bed Reactor)
C3H6O
C2H4
C2H
H2
4
CO
H2
C2H6
CO
Figure 1.2 First reactor
The oxo process or hydroformylation reaction is a reaction where the synthesis gas,
carbon monoxide and hydrogen react with ethylene to produce propionaldehyde.
Propionalehyde is an aldehyde group that also known as propanal. Besides that,
hydroformylation reaction also produced by product known as ethane. The formation
of propionaldehyde and ethane are shown in below equation.
CH 2 CH 2 CO H 2 c
ata
lyst,
, pr
esu
ureCH 3CH 2 CHO
1.3
Ethylene Carbon Hydrogen Propionaldehyde
monoxide
C2H 4 H 2 C2 H 6
Ethylene Hydrogen Ethane
1.4
Hydroformylation, was carried out initially with a dicobalt octacarbonyl, CO2CO8,

catalyst at temperatures of about 90-130C and 2-5 Mpa. A breakthrough was the
discovery that rhodium chloride with ligands such as triphenylphosphine allowed the
23
reaction to take place at temperatures of around 100C and 12.5 Mpa. Chemo
selectivity to aldehydes is high for all Rh catalysts.
Slurry bed reactor is for a gas-liquid contacting accompanied by chemical reaction.

The most attractive technical process is with a slurry reactor due to its heat removal
capability, low investment, and high one-pass conversion. With the raw material of
ethylene, carbon monoxide and hydrogen in gas phase, the use of slurry bed in
contacting the liquid cobalt carbonyl is the ideal reactor where gas solubility is low
and a large liquid holdup is required.
The reacting feed gas (mixed with recycle) is introduced through sparger. It bubbles
through the column, keeping the catalyst in suspension, aerating the liquid and
supplying the agitation necessary for mass transfer as it reacts. Because of the
reaction is highly exothermic, cooling coils are provided in the reaction zone.
Condenser
The highly exothermic hydroformylation reaction (28-35 kcal/mol) requires sufficient
cooling area. The condenser also needed in order to condensate the vapor propanal
into liquid phase.
Stripper
CO
C3H6O
C2H4
H2
CO
C2H6
24
C3H6O
C2H4
H2
C2H6
Figure 1.3 Stripper
After condensation, the propanal is sent to a carbon monoxide-stripping column to

remove traces of carbon monoxide prior to hydrogenation. Carbon monoxide is then
recycle back to the reactor to reduce the feedstock. Carbon monoxide need to be
drawn out because it could cause poison for the second reaction.
HydrogenationOf Aldehyde (Fixed Bed Reactor)
C3H8O
C3H6O H2
H2 CO
CO C2H4
C2H4 C3H6O
C2H6 C6H14O
H2O
C2H6
H2
Figure 1.4: Second reactor

25
Hydrogenation of the aldehyde to the alcohol takes place with a dicobalt

octacarbonyl at 0.2-0.3 Mpa at about 120 180C and hydrogen pressure of about
3-5 Mpa, a catalyst loading of about 2 to about 20 wt% preferably about 8 to about
10 wt% based on the weight of the feed in the liquid feed. The equation is as follow
CH 3CH 2CHO H 2 c CH 3CH 2CH 2 HO

1.5
Propionaldehyde Hydrogen n-propanol
In addition the liquid feed should contain for example, either substantially no water,
or an amount of water, for example up to about 3 wt% preferably about 0.0 to about
1.0 wt% based on the weight of crude hydrogenation reaction product. Substantially
no water, means that no water is added to the hydrogenation reactor or in the
fractionating column and the only water present in the reactor and optionally in
column is that form during the hydrogenation itself and in the hydroformylation
reactions.
The reactor used in this reaction was fixed bed reactor. The liquid propanal is fed
from the top of the column counter current with the hydrogen gas from the bottom of
the reactor. With the pellet physical of the dicobalt octacarbonyl make the liquid and
gas interphase in the fixed bed. Undesirable certain impuritiy tend to be form in the
little or no water as a result of side reaction of the hydrogenation form adol
condensation which is dipropylether
Two Tower Purification System
C3H8O
H2
C2H4
C6H14O
C2H6
C3H8O
H2
C2H4
C3H6O
C6H14O
H2O
C2H6
26
C3H6O
H2O
Figure 1.5 :First distillation column
The crude n-propanol (after hydrogenation) is purified in a standard two-tower

purification system. By using a dicobalt octacarbonyl in the hydrogenation process,
the components that have higher boiling point are drawn out at the bottom of the
distillation column. Hydrogen and ethane will be then separated by other compound
by using the gas separator into different storage tank. At certain time both gases will
be recycle back into stream process to avoid waste.
Recovery Column
C6H14O
C2H6
C3H8O
C6H14O
C2H6
27
C3H8O
Figure 1.6 : Second distillation column
Purification of the n-propanol from the hydrogenation zone is carried out by

fractional distillation is the presence of small quantity of water. No addition of water
into the system is needed because water presence will formed azeotrope with the
product. The amount of water that produce in both hydroformylation and
hydrogenation is up to 3 wt% preferably about 0.1 to about 1 wt%, based on the
weight feed to the fractionating column is already enough. The amount of water
entering the column is generally the same as in the hydrogenation effluent, desired
to the column for its cooling effect. Most of the water are drawn out at the bottom. n-
propanol is collected at the bottom of the column while the impurities are drawn out.
Liquid recycle is necessary to avoid waste. The amount of heat entering the column
from the reboiler and with the feed must equal the amount heat removed by the
overhead condenser and with the products.
CHINESE JOURNAL OF CATALYSIS .Volume 30, Issue 8, August 2009
U.S. Pat. 5,8667,725 (Feb. 2, 1999), J.D. Unruh and D.A. Ryan (to Celanese
International Corporation)
CHAPTER II
MARKET ANALYSIS
28
2.0 INTRODUCTION
The Malaysian petrochemicals sector has been growing at an impressive pace. The
governments investor-friendly policies and easy availability of feedstock have been
chiefly responsible for this growth. The country is also strategically located and
boasts strong physical infrastructure. About 39 companies are in operation in the
nations petrochemicals industry. Major players in the industry include state-owned
Petronas and local Titan Chemicals, Germany-based BASF, UK-based BP,
Netherlands-based Royal Dutch Shell, Japan-based Mitsui, Toray Industries and
Kaneka, as well as US-based Exxon Mobil, DOW Chemical and Eastman Chemical
and China-based Dairen Chemicals.
Malaysian rank seventh place in Business Monitor International Ltd (BMIs)
Petrochemicals Business Environment Rankings for Asia with 63.4 points. While it
has significant petrochemicals production base, it lags in terms of infrastructure.
Nevertheless, oil and gas reserves should sustain some expansion of the
companys petrochemicals sector over the next decade.
Malaysia is home to well-developed, integrated petrochemicals zones that
offer world-facilities. The Malaysian government is working towards developing
Bintulu (Sarawak), Gurun (Kedah), Tanjung Pelepas (Johor) and Labuan into new
petrochemicals zones. Existing petrochemicals zones including Kertih and Telok
Kalong (Terengganu), Gebeng (Pahang) and Pasir Gudang-Tanjung Langsat
(Johor) will also be leveraged futher. The country also possesses a well developed
financial infrastructure and a world class power infrastructure.
Malaysian Petrochemicals Annual Report 2010, ( Source: Business Monitor

International (BMI) ).
29
2.1 SUPPLY AND DEMAND OF N-PROPANOL
2.1.1 Production Of n-Propanol Worldwide
Based on the most recent publicly available information, in 2005, global n-propanol
production was about 140,000 metric tonnes (308.6 million pounds). In 1993, there
are six n-propanol producers in the world, ie, Hoechst Celanese, Texas Eastman,
and Union Carbide in the United States; BASF AG and Hoechst AG in Western
Europe; and Sasol in South Africa.
In addition, n-Propanol economics pricing are sensitive to the raw material
costs of ethylene and the feedstock for synthesis gas, ie, natural gas or liquid
petroleum feedstocks. Natural gas-based technology is slightly more economical.
Consequently, the demand for n-propanol has declined by during the recent
recession.
Source: Kirk-Othmer Encyclopedia of Chemical Technology.Copyrightc, John Wiley

& Sons, Inc. All rights reserved.
World Consumption of n-Propanol ( 2008 )
Source: http://www.sriconsulting.com/CEH/Public/Reports
Figure 2.1: World Consumption of n-Propanol in 2008

30
2.1.2 The Global Demand Of n-Propanol
In chemical industries, n-propanol is used commercially to produce glycol ethers.

The n-propanol is dictated by their solvent properties, its high water miscibility and
by its potential for introducing the propyl group into chemical intermediates. In 1988,
over 75% if the n-propanol in the United States was employed in solvent
applications, either directly or in the form of acetate ester or glycol ether derivatives.
As a solvent, n-propanol is used principally in many types of industries such as inks,
paints, cosmetics, pesticides and insecticides. The Eastman Company used about
100000 tonnes of n-propanol in 1988. In Germany, BASF coverts most of its
propanal into n-propanol for printing inks, cosmetics, solvents and intermediates for
propylamines used in pharmaceuticals and pesticides. In Japan, 1000-2000 tonnes
of n-propanol was consumed in 1988 for printing inks and paints, all of which was
imported.
Source:ANTHONY J. PAPA, Union Carbide Chemicas and Plastic Company. Inc.,

South Charleston, WV 25303, United States.
Figure 2.2 shows the global demand of n-Propanol in the world. The demand
of n-Propanol was decreased from 2008 until 2010 for United States but increased
in United Kingdom, Japan and Malaysia.
Global Demand of n-Propanol

30000
25000
capacity ( t/y)
20000
15000 2008
10000
2009
5000
2010
0
US UK Japan Mas
Country
Source: Malaysian External Trade Development Corporation (MATRADE)

Figure 2.2: The Global demand of n-Propanol
31
2.1.3 n-propanol In Malaysia
There are no chemical plants that produce n-propanol in Malaysia, but n-propanol is
exported as a by-product from chemical companies. Malaysia has already exported
around 8.25 tonnes per year in 2008, 5.68 tonnes in 2009 and 7.86 tonnes in 2010.
The demands of n-propanol have increased from year to year, so this plant will help
to cover the demand of n-propanol for future. Table 2.1 shows the Malaysias
exports of n-propanol by country.
Table 2.1: Table of Malaysias Exports of n-Propanol by Country.

Country Capacity (kg/year)
Singapore 773070
Sri Lanka 4374
China 2950
Thailand 2510
Vietnam 1630
Hong Kong 1630
Malaysia not only export but also import n-propanol from other countries to
fulfil to demand of industry. As in 2008, 3835.56 tonnes n-propanol has imported,
the value for 2009 decreases to 3612.87 tonnes however and it increased back to
4784.72 tonnes in 2010. Malaysia imports most of n-propanol from Japan as shown
in Figure 2.1.3. Although United States is the most country that produced n-
propanol,, Japan was selected because it is much nearer to Malaysia thus reducing
the cost of transport.
32
Malaysia's Demand for n-Propanol

capacity (tonnes/year)
4784.72
3835.56 3612.869
2008 2009 2010
Figure 2.3: Table of Malaysias Demand of n-Propanol By Year.
Malaysia - Imports
n-Propanol
2% 2%
japan
12% singapore
31%
south afric
26% taiwan
united state
27%
others
Figure 2.4: Shows the Malaysias Imports of 1-Propanol by Country

33
2.2 SUPPLY AND DEMAND OF RAW MATERIAL
2.2.1 Ethylene
BMI estimates that total global ethylene capacity amounted to around 132.7 millions
tonnes per annum ( tpa ) in 2008, with Asia Pacific representing 32.7% of installed
capacity (China contributed 29% of Asian capacity ) and North America 25.6%
Although the Middle East and Africa are the largest source of oil and gas,
the region contributed just 17.2% of total capacity. This is set to change over the
medium to long terms as new capacity comes online, with global capacity set to
reach 174.8 million tpa in 2014. Gulf countries are expected to account for around
20% of the worlds ethylene production by 2010 compared to the current 8%. Some
50% of all new ethylene projects being developed in the world are located in the
region. Saudi Arabia represent around 63% of total investment in the region , while
Qatar comes second, with a 14% share. The gulf Petrochemicals and Chemicals
Association ( GPCA ) has forecast that the region will account for 40% of total global
petrochemical production within 10 years.
Malaysian Petrochemicals Annual Report 2010, ( Source: Business Monitor

International (BMI) ).
Table 2.2 : World Ethylene Production By Country, 2009 and 2014 (1000 tonnes
capacity)
Country 2009 2014
US 27,387 25,500
China 12,610 20,910
Saudi Arabia 9,370 18,300
Japan 8,760 8,760
South Korea 7,360 7,580
Germany 5,745 5,745
Iran 5,606 9.006
Canada 4,951 4,951
Taiwan 4,045 4,765
Netherlands 3,980 3,980
India 3,025 4,460
UK 2,885 2,885
34
Qatar 2,600 6,000

Thailand 2,570 4,470
Belgium 2,540 2,540
Singapore 1,990 3,790
Malaysia 1,770 1,770
e/f = estimate/forecast. Source: (Business Monitor International Ltd)BMI
Ethylene Capacities By Region

2009 Estimates
20%
20%
Asia Pacific ( excl. China )

Western Europe
4% Eastern Europe
Middle East and Africa
13% NAFTA
South America
China
23%
5%
15%
Source: (Business Monitor International Ltd) BMI
Figure 2.5 : Ethylene Capacities By Region ( 2009 Estimate )

35
Ethylene Capacities By Region

2014 Forecast
12%
25%
5% Asia Pacific ( excl. China )
Western Europe
Eastern Europe
Middle East and Africa
19% 11% NAFTA
South America
China
5%
23%
Source: (Business Monitor International) BMI
Figure 2.6 : Ethylene Capacities By Region ( 2014 Forecast )
2.2.2 Production and demand of Ethylene in Malaysia
There are three companies that produce ethylene in Malaysia which are Titan
Petchem (M) Sdn Bhd that situated in Tanjung Langsat, Johore, Ethylene Malaysia
Sdn Bhd and Optimal Olefins (M) Sdn Bhd, both of them situated in Kertih,
Terengganu. The productions of ethylene from these three companies are
1,630,000 metric tonnes per annum.
The demands of ethylene have increased from year to year, but the
production of ethylene from these three plants still cannot fullfill the industrys
demand in Malaysia. To overcome this problem, Malaysia has import the bulk of
ethylene from other countries. Table 2.3.2 shows the Malaysias exports of
ethylene by country from 2008 until 2010. Malaysia has import 3115482 kg of
ethylene in 2008, 1758982 kg of ethylene in 2009 and 3096795 kg of ethylene in
2010.
Source : Department of Statistic Malaysia (MATRADE)

36
Table 2.3 : Malaysias exports of ethylene by country from 2008 until 2010
2008 2009 2010

Country kg kg Kg
Thailand 1,320,408 1,758,982 1,046,596
Hong Kong 0 0 523,684
China 1,157,708 144,440 484,199
Singapore 2,324 3,596 413,031
South Korea 428,153 774,103 327,290
UK 18,640 84,400 154,800
US 157434 75080 73501
Italy 0 0 28800
Japan 15,090 8,280 15,720
Belgium 0 37,352 15,600
Taiwan 0 16,000 8,313
India 0 0 4,504
Canada 0 25 737
Spain 0 0 20
Australia 380 0 0
Pakistan 15,200 0 0
Netherland 145 9,360 0
Qatar 0 410,436 0
2.2.3 Production and demand of carbon monoxide
Generally, production of carbon monoxide comes from the partial oxidation

of carbon-containing compounds; it forms when there is not enough oxygen to
produce carbon dioxide (CO2). This happen when operating a stove or an internal
combustion engine in an enclosed space. A major industrial source of CO is gas
producer, which involves a mixture containing mostly carbon monoxide and
nitrogen, formed by combustion of carbon in air at high temperature when there is
an excess of carbon. In modern technology, there are few processes produce
carbon monoxide as a byproduct such as, iron smelting and production of ammonia.
37
For the worldwide production, about 5 x 1012 kilograms per year carbon
monoxide was produce due to photochemical reactions in the troposphere which
generate. In the Saudi Arabia, the production capacity is about 335,000 tonnes per
year. Other natural sources of carbon monoxide include volcanoes, forest fires, and
other forms of combustion. In Malaysia, the Petronas Ammonia Sdn Berhad produce
carbon monoxide as a byproduct with 300USD/tonne.
Carbon monoxide is a very important industrial compound. The worldwide
carbon monoxide demand is estimated to be growing at about +4% per year. In the
petrochemical industry, carbon monoxide is mainly used in the production of acetic
acid, polyurethane intermediates and propanol production through oxo-process.
Other than that, in the form of producer gas or water gas, it is widely used as a fuel
in industrial operations. Besides, this gases also an effective reducing agent.
2.2.4 Production and demand of hydrogen
Hydrogen production can be defined as a large and growing industry in oil and gas
production industry. In 2004, about 50 million metric tons of hydrogen that is also
equal to about 170 million tons of oil equivalent was produced globally. The growth
rate is around 10% per year. In the United States production, for year 2004 the
production was about 11 million metric tons. At year 2005, the economic value of all
hydrogen produced worldwide is about $135 billion per year.
Source : Arno A. Evers FAIR-PR". Fair-pr.de. Retrieved 2009-09-19
Nowadays, the global hydrogen production is 48% from natural gas, 30%
from oil, and 18% from coal; water electrolysis accounts for only 4%. From an
ecological perspective, hydrogen should be generated through electrolysis of water,
using energy from renewable resources, preferably solar or wind energy.
38
Global Hydrogen Production

natural gas oil coal water electrolysis
4%
18%
48%
30%
Source : Global Hydrogen Production". Hydrogenassociation.org.
Figure 2.7: Global hydrogen production
For the worldwide production of n-propanol, global investments in building the

hydrogen economy cost over $1.3 billion in 2006 and are rise to nearly $1.7 billion in
2007 and are expected to increased to $5.5 billion in 2012. This figure below
represents a Compound Annual Growth Rate (CAGR) of 27.0% over the next 5
years.
Production of Hydrogen
900
800
700
600
$ mill
500
400
300
200
100
0
2006 2007 2012
Year
Figure 2.8 : Global hydrogen production

39
For the past ten years, the hydrogen (H2) consumption has increased quite
substantially. Opportunities in hydrogen look strong during the forecast period
(20092014). Most of this hydrogen usually is produced by the consumer at the site
where it will be used. Nowadays, there are two primary uses for hydrogen today
which is to produce ammonia (NH3) via the Haber process, which is then used
directly or indirectly as fertilizer. It is because the world population and the intensive
agriculture used to support it are growing, ammonia demand is growing. The other
half of current hydrogen production is used to convert heavy petroleum sources into
lighter fractions suitable for use as fuels and also in methanol production.
Worldwide Demand of Hydrogen

500
billion cubic meter
400
300
200
100
0
2003 2008 2013
year
Figures 2.8: Worldwide demand of hydrogen
2.3 SUPPLY AND DEMAND OF CATALYST
2.3.1 Production Cobalt Carbonyl Worldwide
Dicobalt octacarbonyl or Cobalt Carbonyl is the inorganic compound Co2(CO)8. This

metal carbonyl is a reagent and catalyst in organometallic chemistry and organic
synthesis. It is used as a catalyst for hydroformylation, the conversion of alkenes to
aldehydes. World cobalt carbonyl production capacity is estimated at 46900 metric
tonnes per year. The pie chart below shows the global production of Cobalt
Carbonyl.
Source: Cobalt Facts 2006

40
Global Production of Cobalt Carbonyl
3% 3% Republic of Congo
3% 5% Zambia
24% Australia
7%
Canada
Russian Federation
10%
Cuba
19%
11% New Caledonia
brazil
15%
Morocco
Source: Cobalt Facts 2006
Figure 2.9: The global Production of Cobalt Carbonyl
The total global production of cobalt in 2003 is 46 900 tonnes, with the principal nine
producing countries as follows (production in tonnes) which is Democratic Republic
of Congo, 11000; Zambia, 9000; Australia, 7000; Canada, 5200; Russian
Federation, 4800; Cuba, 3400; New Caledonia, 1500; Brazil, 1300; Morocco, 1300;
and other countries, 2400.
2.4 ECONOMIC DATA
An estimation of the operating cost, the cost of the producing the product, is needed
to judge the viability of a project, and to make choices between possible alternative
processing schemes. These cost of producing a chemical product will include the
items listed below They are divided into two group which are :
(a) Fixed Capital Cost : cost that do not vary with the production rate.
These are the bills that have to be paid whatever the quantity produced.
(b) Variable Fixed Cost : costs that are dependent on the amount of
product produced.
2.4.1 Fixed Capital Cost/ Investment

41
Apart from focusing only on the price of the raw materials, a large sum of investment
to establish a fully operational plant must be made. Fixed capital investment is
simply the sum of money required to be invested at the early stage of the
construction of a fully operating plant. Purchasing of necessary equipments plus the
installation is crucial as it will be the core investment that will determine the
compatibility of the plant as well as piping installation, land, instrumentation,
services and the land where the plant is going to be established. Table 2.4 listed the
equipments necessary for the n-propanol plant operation.
Equipment Cost
The cost of the purchased equipment is used as the basis of the factorial method of
cost estimation and must be determined as accurately as possible. It should
preferably be based on recent prices paid for similar equipment. Several assumption
have been made which are :
(a) The cost of equipment is select based on their size unit ( power, length,
area and capacity ) of the equipment.
(b) The cost equipment is selected based on the material that build up the
equipment.
(c) All the cost of each equipment is just the estimation because the details
calculation on size of equipment is done in Design Project 2.
(d) equipment cost estimation calculated using CEPCI 2008 and 2009.
Sample of calculation using CEPCI index 2008 and 2009 :
(a) For reactor, distillation column and gas separator, the cost index in
2008 is 642.4 and cost index in 2009 is 645.8. Hence :
Using equation : C1I1 = C2I2
Known C1 = cost of equipment in base time.
C2 = cost of equipment in the desire time.
I1 and I2 = index of cost at that time.
To calculate the cost of equipment ( reactor ) :

C2 = C1(I2/I1)
C2 = RM 765,611.00 (645.8/642.4)
= RM 769,663.00
(b) For cooler, heater and storage tank, using the cost index in 2008 is
618.4 and the cost index in 2009 is 603.4
42
(c) For compressor, the cost index in 2008 is 850.5 and the cost index in
2009 is 902.1
(d) The calculation of each equipment are same as shown in sample of
calculation.
Table 2.4: Equipment Costs for n-propanol Plant
Equipment Unit Cost/unit (RM) Total Cost (RM)

Reactor 2 769,663.00
1,539,326.00
Distillation Column 1 1,171,304.00 1,171,304.00
Heater 4 11,192.00 44,768.00
Storage Tank 1 184,513.00 184,513.00
Cooler 1 58,681.00
58,681.00
Gas Seperator 1 343,986.00 343,986.00
Compressor 2 136,445.00 272,890.00
Total Equipment Cost, Ce RM
3,615,468.00
Source : http://matche.com and Plant Cost Index 2009
The land needed for the construction of n-propanol plant have been
estimated about 20 acres which is approximately to 80,937.1284 m2. This value of
land is including the future expansion of the plant. Based on the site and location
selection in Chapter 3, Telok Kalong Industrial Area in Terengganu has been
chosen to construct this plant. According to Ministry of Industrial Development
Authority (MIDA), the land value in Telok Kalong Industrial Area is RM 60.00 for
each 1 m2. The total cost needed for this land show in Table 2.5.
The fixed capital investment will be consisting of two category, direct cost
and indirect cost. The components of the direct costs and indirect costs are justified
based on the percentage from the total equipment cost, obtained from Table 2.5.
Table 2.5 :Fixed Capital Investment of the n-propanol Plant

Component Estimation Cost (RM)
43
Direct Cost
Total Equipments Costs From Table 2.4 3,615,468.00
Equipment Installation
(includes 40% of total equipment cost
insulation and painting) 1,446,187.20
Piping System Installation 50% of total equipment cost 1,807,734.00
Instrumentation and Control 20% of total equipment cost 723,093.60
Electrical System Installation 15% of total equipment cost 542,320.20
Service facilities 50% of total equipment cost 1,807,734.00
Building, process and
1,446,187.20
auxiliary 40% of total equipment cost
Land (1m2 = RM60),
4,856,227.70
Yard Improvement 12% of total equipment cost 433,856.16
Total
16,678,808.06
Indirect Costs
Engineering and supervision 10% of total direct cost
1,667,880.80
Construction expenses
1,667,880.80
Legal expenses 10% of total direct cost
1,667,880.80
Contractors fee 5% of total direct cost
833,940.40
Contingencies 12% of total direct cost 2,001,456.97
Total 7,839,039.77
Fixed Capital Investment Direct Costs + Indirect Costs 24,517,847.83
2.4.2 Operating Capital Cost
Operating capital represents costs (variable cost plus fixed capital cost) necessary
to operate the plant. Listed below are the components of the working capital that
need to be taken account.
1. Raw materials.
2. Labour Cost.
3. Catalyst.
4. Utilities
5. Waste Treatment
2.4.3 Annual cost of raw materials

44
The production of n-Propanol is to be expected reach 100000 metric tonne per year.
The cost of raw material needed for this production rate are :
Assumption:
(a) To get 100000 metric tonne of n-propanol per year, the plant must
produce 11574.00 kg/hr of n-propanol.
(b) Using 6419.30 mol/hr as a basis of production of n-propanol.
(c) Ratio of raw material needed is 0.1 of ethylene, 0.45 of carbon monoxide
and 0.45 of hydrogen.
(d) Assume that ethylene is recycle back for every 4 hour after it is enough
store in the storage tank.
(e) Assume that hydrogen is recycle back for every 2 hour after it is enough
store in the storage tank.
(f) Assume that carbon monoxide is recycle back for every 2 hour after it is
enough store in the storage tank.
Table 2.5: Annual cost for raw material
Amount Cost / kg
Raw Material Cost (RM/yr) Supplier
(kg/hr) (RM/kg)
Ethylene (M) Sdn. Bhd.
Ethylene 18009 3.00 116,698,320.00
Kertih, Terengganu.
MOX-LINDE Sdn. Bhd.
Hydrogen 5824 1.20 30,191,616.00
Kertih, Terengganu.
Petronas Ammonia
Carbon
80912 2.80 489,355,776.00 Sdn.Bhd. Kertih,
Monoxide
Terengganu.
Total 636,245,712
2.4.4 Estimation of operating labor cost
Using Alkahayat and Gerrard Method :
NOL = ( 6.29 + 31.7P2 + 0.23NNP )0.5

NOL : Number of operator shifts
P : Number of processing steps involving particulate solids
45
NNP : Number of non particulate processing steps
2.4.5 Equipment that needs an operator to operate
Table 2.6: Equipment that needs an operator to operate

Equipment Quantity Total
Reactor 2 2
Distillation Column 1 1
Heater 4 4
Storage Tank 1 0
Cooler 1 1
Gas Seperator 1 1
Compressor 2 2
Total = NNP 11
p= 0
NOL = 2.9 operator per shift
3 operator per shift
2.4.6 Number of operator needed for one equipment
Assumption:
(a) A chemical plant normally operates 24 hours per day. This requires:
3 shifts x 330 days = 990 shift
day year year
(b) A single operator works on average 49 weeks a year. This is due to 3

weeks time off for vacation and sick leave. Hence,
1 shift x 5 days x 49 week = 245 shift .
day.operator week year operator.year
(c) Number of operator needed are :

990 shifts x year.operator = 4.00 operators
46
year 245 shifts
From the assumption, total number of operator needed for all equipments are:
Number of operator needed x NOL
4.00 operators x 3.00 = 12 operators
Table 2.7: Total operating labor cost
Position Quantity Salary Annual

(RM/month) Salary
(RM/year)
Engineering Department
i. Senior Engineer 1 5000.00 60,000.00
ii. Appliance Service 1 2500.00 30,000.00
Engineer 5600.00 67,200.00
iii. Engineer 2 10800.00 129,600.00
iv. Operator 12
Technical Department
i. Senior Technician 1 3000.00 36,000.00
ii. Service Supervisor 1 2000.00 24,000.00
iii. Technician 2 3000.00 36,000.00
iv. Appliance Service 1 1200.00 14,400.00
Technician
Sales
i. Sales Supervisor 1 3000.00 36,000.00
ii. Sales Assistant 1 2000.00 24,000.00
iii. Sales Clerk 2 2400.00 28,800.00
Total 40,500.00 486,000.00
47
2.4.7 Catalyst Annual Cost
The catalyst used in the production of n-Propanol is cobalt carbonyl. These catalyst
was used for both hydroformylation and hydrogenation process. The uses of cobalt
carbonyl have been estimated by 3% of total feed/ hour.
0.3 x 104,745.2 kg /hr of feed = 31,423.56 kg/hr of cobalt carbonyl
Table 2.7: Annual cost for catalyst

Catalyst Amount Cost / kg (RM) Total Cost (RM)
(kg)
Cobalt Carbonyl 3,142.36 145.70 457,841.85
Source: ICIS.com 2010
2.4.8 Estimation of Utilities Cost
This term includes power, steam, cooling and process water and the effluent
treatment, unless costed separately. The quantities required can be obtained from
the energy balance. The price should be taken from the primary sources and the
plant location. The sample calculation in Table 2.8 shows the preliminary estimation.
The current cost of utilities supplied by the utility companies such as electricity and
water can be obtained from their local area offices.
According to the Ministry of Industrial Development Authority (MIDA), the

water rate from Centralized Utilities Facilities, Kertih is RM 1.15 per meter cube and
the electrical power rate from Tenaga Nasional Berhad (TNB) is RM 0.266 for 1
kW/h. The total rate for cooling water and electrical power are shown in Table 2.8.
For electricity cost, the electricity price must be multiply by 1.5 for industrial rate.
48
Table 2.8 : Estimation of Utilities Cost and Cost of Land

Water Cost ( RM ) Unit
Water price :-
a) Industrial 1.15 /m3
Amount of water needed for the first startup 103 m3/day
Total 39,088.00 /year
Electricity
electricity price :-
Tariff E1 Medium Voltage General 6.6kV 0.266 x 1.5 /kWh
66kV supply
total power required 50000 kW

Total electricity cost per day 19,950 /day
Total electricity cost per year 7,182,000.00 /year
Total utilities 7,221,088.00
Total of Variable Cost = Raw Material + Labor Cost + Catalyst + Utilities

+ Waste Treatment Cost
The waste treatment cost is not considered in this plant and it is assume as external
waste treatment plant. Hence :
= RM636,245,712.00 + RM486,000.00 + RM457,841.85 +
RM 7,221,088.00 + 0.00 ( not included )
= RM 644,410,641.90
Operating Cost = Fixed Capital + Variable Cost

= RM 24,517,847.83+ RM 644,410,641.90
= RM 668,928,489.70
2.4.9 Start Up-Cost
Costs allocated for starting up the plant operation are start-up costs. Some of the
examples of start-up costs are process modifications, start-up labor and loss in
49
production. Douglas also estimated the total start-up cost of the plant operation is to
be 10% of the fixed capital investment.
Start-up Costs = 0.10 x fixed capital investment

= 0.10 x RM 24,517,847.83
= RM2,451,784.80
2.4.10 Total Investment
As stated earlier, total capital investment is the sum of the fixed capital investment
and the working capital plus the start-up costs.
Total capital investment = Fixed capital investment + Operating capital investment

+ Start-up costs
= RM 24,517,847.83 + RM 668,928,489.70+
RM 2,451,784.80
= RM 695,898,122.30
2.4.11 Product credit

Table 2.9: Total annual sales
Selling Item Selling Price Production Rate Income

(RM/ kg) (kg/ yr) (RM /yr)
Product
i. n-propanol (99%
7.70 100,000,000.00 770,000,000.00
purity)
Source: ICIS.com 2010
The price of n-propanol is the 10% addition from the total price of raw material :
(a) Ethylene = RM 3.00
(b) Hydrogen = RM 1.20
(c) Carbon Monoxide = RM 2.80
(d) Addition 10% = RM 0.70
Hence the price of n-propanol is RM 7.70.

50
2.4.12 Break Even Analysis
Breakeven analysis is performed to determine the value of variable or parameter of

a project that makes two elements equal, for example the sales volumes that
equates revenue and costs.
Therefore,
Selling Price = Product
= RM 770,000,000.00
= RM 770,000,000.00 kg/year
Contribution = selling price - variable cost

= RM770,000,000.00 - RM 695,898,122.30
= RM 74,101,877.69
Break Even point = Fixed Capital Cost

Revenue-variable cost
= RM 24,517,847.83
(RM 700,000,000.00- RM 695,898,122.30)
= 0.331 RM/year x 100000 tonne/yr

= 33,100 metric tonne/year
51
Break Even Graf

1E+09
900000000
800000000
700000000
600000000
FC + VC
500000000
FC + VC
400000000
TC
300000000
200000000
100000000
0
0 40000 80000 120000
Capacity
The intersection shows the break point value of this plant. The break point value
shows the minimum value of production of n-propanol that must be produced within
the payback period. The value of production of n-propanol is 33,100 metric
tonne/year.
Payback period
700,000,000.00
cumulative cash flow (RM)
600,000,000.00
500,000,000.00
400,000,000.00
300,000,000.00
200,000,000.00 payback
100,000,000.00 period
-
(100,000,000.00) 0 2 4 6 8 10
time (year)
Payback period = 2.26 3 year

52
Fixed Capital
End of Investment - Cost of (R-COMd-dk)*(1-
year (k) Investment Depreciation Depreciation Revenue Manufacturing t)+dk Cash Flow Cumulative Cash Flow
0 4,856,227.70 24,517,847.83 (404,685.64) (404,685.64)
1 12,258,923.92 24,517,847.83 (12,258,923.92) (12,663,609.56)
2 12,258,923.92 24,517,847.83 (12,258,923.92) (24,922,533.47)
3 4,903,569.57 19,614,278.26 770,000,000.00 695,898,122.30 74,101,877.70 74,101,877.70 49,179,344.23
4 7,845,711.31 11,768,566.96 770,000,000.00 695,898,122.30 74,101,877.70 74,101,877.70 123,281,221.93
5 4,707,426.78 7,061,140.18 770,000,000.00 695,898,122.30 74,101,877.70 74,101,877.70 197,383,099.63
6 2,824,456.07 4,236,684.11 770,000,000.00 695,898,122.30 52,718,651.21 52,718,651.21 250,101,750.84
7 2,824,456.07 1,412,228.04 770,000,000.00 695,898,122.30 52,718,651.21 52,718,651.21 302,820,402.05
8 1,412,228.04 0.00 770,000,000.00 695,898,122.30 52,294,982.80 52,294,982.80 355,115,384.85
9 770,000,000.00 695,898,122.30 51,871,314.39 51,871,314.39 406,986,699.24
10 770,000,000.00 695,898,122.30 51,871,314.39 51,871,314.39 458,858,013.63
11 770,000,000.00 695,898,122.30 51,871,314.39 51,871,314.39 510,729,328.02
12 8,533,904.87 774,856,227.70 695,898,122.30 55,270,673.78 63,804,578.65 574,533,906.68

CHAPTER III
PLANT LOCATION AND SITE SELECTION
3.0 Introduction
In developing an industrial plant, the geographical location of the plant can give a
big influence and success of the industrial venture. Plant location study must be
done in selecting the suitable plant site since it can gives crucial effect on the
profitability of the project. Many factors must be considered before the plant location
been selected. For example, the plant must be located where the minimum cost of
production and distribution can be obtained but, other factors such as room for
expansion and utility suppliers for plant operation as well as the surrounding
community are also important.
Malaysia has allocated designated areas that are mainly located in over 200
industrial estates or parks and 13 Free Industrial Zones (FIZs) developed throughout
the country for constructing a plant. The choice of the final site should first be based
on a complete survey of the advantages and disadvantages of various geographical
areas and ultimately, on the advantages and disadvantages of the available real
estate. The various principal factors that must be considered while selecting a
suitable plant site are.
The factors to be considered are:
a) Raw material availability.
b) Location (marketing area).
c) Availability of suitable land.
d) Transport facilities.
e) Availability of labours.
f) Availability of utilities ( water and electricity )
g) Environmental impact and effluent disposal.
h) Local community considerations.
i) Political considerations
3.0.1 Raw material availability
One of the most important factors that influencing the selection of a plant site is the
source of raw materials because large volumes of ethylene, hydrogen gas and
carbon monoxide gas are consumed in the production of propanol. The purchased
price of the raw materials, availability and reliability of supply, purity of raw materials
and storage requirements should be given attention. Thus, the plant is supposed to
be located near the raw material supplier to reduce of the transportation and storage
charges.
3.0.2 Location ( marketing area )
The location of the selected site location should also be nearest to the port for
distribution and shipping matters. The location of markets or distribution centres is
important since it will affects the cost of product distribution and the time required for
shipping. The markets for the final product and the by-product are important
consideration in the selection of a plant site, because the buyer usually finds it
advantageous to purchase from near by sources.
3.0.3 Prices and geographical structure of the land.
The characteristics of the land at a proposed plant site should be examined

carefully. The topography of land and the soil structure must be considered, since
either or both may have a pronounced effect on construction costs. The price cost of
the land is the most important, as well as local building costs and living conditions.
Future changes may make it desirable or necessary to expand the plant facilities.
Therefore, even though no immediate expansion is planned, a new plant should be
constructed at a location where additional space is available.
3.0.4 Transport facilities
The final product will be exported to other countries such as Europe, Saudi Arabic,
East Asia, and also South Africa due to the worldwide demand that are currently
increasing. For shipping and product distribution, a site should be selected nearby
the port. The kind and quantity of products and raw materials determine the most
suitable type of transportation facilities. Motor trucking facilities are widely used and
can serve as a useful supplement to water facilities. If possible, the plant site should
have access to other types of transportation such as railway and airport. There is
usually a need for convenient air and road transportation facilities between the plant
and the company head quarters, and effective transportation facilities for the plant
personnel are necessary.
3.0.5 Availability of labours.
Labors will be needed for plants construction and operation. Skilled construction
workers will usually be brought in from outside the site, but there should be
supervised by the trained operators to do maintenance work at the plant. Local trade
union customs and restrictive practices will have to be considered when assessing
the availability and suitability of the labors for recruitment and training. Consideration
should be given to prevailing pay scales, restrictions on number of hours worked per
week, competing industries.
3.0.6 Availability of utilities
The process industries use large quantities of water for cooling, washing, steam
generation, and as a raw material in process. Hence, the plant must be located
where a dependable supply of water and are available. Besides water, electricity
supply is also important to maintain the operating plant thus ensure the plant
operate continuously.
Water: -
Deminerialized water, from which all the minerals have been removed is used where
pure water is needed for the process use, in boiler feed. Natural and forced draft
cooling towers are generally used to provide the cooling water required on site.
Electricity: -
Power and steam requirements are high in most industrial plants and fuel is
ordinarily required to supply these utilities. Power, fuel and steam are required for
running the various equipments like generators, motors, turbines, boiler, plants
lighting and for general use.
3.0.7 Environmental impact and effluent disposal.
Before selecting a plant site, the regional history of the natural event of the process
should be examined and the consequences of such occurrences from the process
effluent must be considered. Facilities must be provided for the effective disposal of
the effluent without any public nuisance. As all industrial processes produce waste
products, full consideration must be given to the difficulties and coat of their
disposal. The disposal of toxic and harmful effluents will be managed according to
local regulations, and the appropriate authorities must be consulted during the initial
site survey to determine the standards that must be met. In Malaysia, chemical
waste must be send to Kualiti Alam for waste disposal.
3.0.8 Local community considerations.
The proposed plant must fit in with and be acceptable to the local community. Full
consideration must be given to the safe location of the plant so that it does not
impose a significant additional risk to the community. Facilities such as religious
centres, libraries, schools, civic theatres, concert associations, and other similar
groups do much to make a community progressive. The tradition, character, and
tradition of the location should be considered.
3.0.9 Political and strategic consideration.
The political and strategic consideration from the government such as capital grants,
tax concessions, and other inducements is used to direct new investment to
preferred locations; such as areas of high unemployment. The availability of such
grants can be the overriding consideration in site selection.
Source: http://www.goarticles.com
3.1 Site Location Selection
There are three places in Malaysia, which are suitable for the location of the
propanol plant. The suggested industrial areas are:
a) Tanjung Langsat Industrial Area in Johor.

b) Gebeng Phase III Industrial Park in Pahang.
c) Telok Kalong Industrial Park in Terengganu.
3.1.1 Tanjung Langsat Industrial Area in Johor
Figure 3.1 Tanjung Langsat,Johor Bahru

(Source:google map)
Tanjung Langsat industrial area is one of the petrochemical industrial areas that
located in Pasir Gudang next to the Johor Port. To cope with the needs of the
growing petrochemical industry, the adjacent Tanjung Langsat site has been
developed to enhance manufacturing capacity. There are some world class facilities
and infrastructures that provided in Pasir Gudang Industrial Area, which are:
Peninsular Gas Utilisation (PGU) project.
Tank farms are being developed for bulk storage of petrochemical liquid.
Johor Port - With a 1,000-metre berth and a hazardous cargo jetty.
- Three hazardous liquid bulk terminals to handle LPG,
chemicals and petrochemicals.
Tanjong Pelepas Port - a world class container port.
Tanjung Langsat Port - Located adjacent to the 4,000 acres of industrial
land.
- Equipped with a tein-berth jetty consisting of outer
(30,000 DWT) and inner (7,000 DWT) berths.
List of Petrochemical plants that located in Pasir Gudang Tanjung Langsat
industrial area are as below.
Table 3.1 List of Petrochemical Plant located in Pasir Gudang

Petrochemical Plant Product
Titan Petchem (M) Sdn Bhd Ethylene, Propylene, BTX ,
Polyethylene, Propylene
Petrochemicals (M) Sdn Bhd Polystyrene
Idemitsu SM (M) Sdn Bhd Ethylbenzene, Styrene Monomer
BASF (M) Sdn Bhd Expandable Polystyrene
Dairen Chemical (M) Sdn Bhd Ethylene Vinyl Acetate
Source: Ministry of industrial Development Authority (MIDA)

3.1.2 Gebeng Phase III Industrial Park in Pahang
Figure 3.2 Gebeng,Kuantan,Pahang.

(Source:google map)
Gebeng is the petrochemical hub for multinational players like BASF, Amoco,
Kaneka and Eastman. The petrochemical zone provides an integrated environment
that meets the specific needs of a petrochemical industry Peninsular Gas utilities
(PGU) project. Facilities and infrastructure that provided here are:
Centralised utility facilities such as power, industrial gas, water and steam.
Kuantan Port - Centralised tankage facilities.
- Pipeline and piperack system connecting Gebeng to Kuantan
Port.
- Container and bulk liquid port.
- Railway linking Kertih, Gebeng, and Kuantan Port.
Environment Technology Park - Incorporating a training centre, a waste
collection and processing centre as well a
raw material management and storage
facilities, maintenance and servicing
facilities.
Transportation - East Coast Highway.
List of the Petrochemical plants that situated in Gebeng industrial area are shown as
below.
Table 3.2 List of Petrochemical Plant and Their Product

BASF Petronas Chemical (M) Sdn Bhd Butyl Acrylate, Oxo-alcohols, Acrylic Acid
and Esters, Syngas, Phthalic Anhydride and
Plasticizers, Butanediol, Tetrahydrofurane
and Gamma-butyrolactone
Eastman Chemicals (M) Sdn Bhd Polyester Copolymers
Amoco Chemicals (M) Sdn Bhd Purified Terephthalic Acid
Kaneka Paste Polymers Sdn Bhd Dispersion Polyvinyl Chloride
Kaneka Malaysia Sdn Bhd Methyl Methacrylates Copolymers
MTBE (Malaysia) Sdn Bhd MTBE, Propylene
Polyplastics Asia Pacific Sdn Bhd Polyacetals
Polypropylene (M) Sdn Bhd Polypropylene
Toray BASF PBT Resin Sdn. Bhd. Polybutylene Terephthalate (PBT)

3.1.3 Teluk Kalong Industrial Park in Terengganu
(Source:google map)
Figure 3.3 Teluk Kalong,Kemaman,Terengganu
Teluk Kalong is a newly developed industrial area situated 9.6 km from Kemaman
City, which is near to Petrochemical Hub area (Gebeng). Facilities and infrastructure
that provided here are:
Gas processing plant.
Centralized Utilities Facilities (CUF) project.
Centralised utility facilities such as power, industrial gas, water and
steam.
Institut Teknologi Petroliam - Training center.
Kuantan Port - Centralised tankage facilities.
- Pipeline and piperack system connecting Gebeng to
Kuantan Port.
- Container and bulk liquid port.
- Railway linking Kertih, Gebeng, and Kuantan Port.
Transportation - East Coast Highway.
Table 3.3 List of Petrochemical Plant and Their Product

BASF See Sen Sdn Bhd Ultra pure Sulfuric Acid (PPT Grade)
Huntsman Tioxide Sdn Bhd Titanium dioxide pigment
Petronas Penapisan (T) Sdn Bhd Paraxylene, Benzene
Petronas Ammonia Sdn Bhd Ammonia
BP Petronas Acetyls Sdn Bhd Acetic Acid
Ethylene (M) Sdn Bhd Ethylene
Polyethylene (M) Sdn Bhd Polyethylene
Optimal Olefins (Malaysia) Sdn Bhd Ethylene and Polyethlene
Optimal Chemical (Malaysia) Sdn Bhd Ethanolamines,Ethoxylates,Glycol

Ethers,Butanol and Butyl Acetate
Optimal Glycol (Malaysia) Sdn Bhd Ethylene Oxide,Ethylene Glycol
MOX-LINDE Gases Sdn Bhd Hydrogen, Nitrogen, Oxygen, Carbon
Monoxide.

3.2 Factors That Effect Site Location Selection
Table 3.4 Factors That Effect Site Location Selection
LOCATIONS
FACTORS
Teluk Kalong Industrial Area Gebeng Industrial Area Pasir Gudang Industrial Area
Distance from
9.6 km from Kemaman 31 km from Kuantan 48 km from Johor Bharu
town
Types of
Petrochemical Heavy and Petrochemical Medium and Petrochemical
industry
Marketing Area Gasoline industry Gasoline industry Gasoline industry
i) Ethylene from Ethylene (M) Sdn ii) Ethylene from Ethylene (M) Sdn Bhd,
i) Ethylene from Titan Petrochemical
Bhd,Kerteh,Terengganu Kerteh,Terengganu.
(M) Sdn. Bhd,Pasir Gudang,Johor.
i) Hydrogen gas from MOX-LINDE iii) Hydrogen gas from MOX Sdn Bhd,
Raw material ii) Hydrogen gas from MOX Sdn Bhd,
Gases Sdn Bhd, Kerteh, Kerteh, Terengganu.
source Pasir gudang,Johore.
Terengganu. iv) Carbon Monoxide Gas from Petronas Cont
ii) Carbon Monoxide Gas from Ammonia Sdn Bhd, Kerteh,
Petronas Ammonia Sdn Bhd, Terengganu.
Kerteh, Terengganu.
Port i) Kertih Port,Terengganu i) Kertih Port, Terengganu i) Johor Port,Johor.

ii) Kuantan Port,Kuantan ii) Kuantan Port,Kuantan ii) Pasir Gudang,Johor.
iii) Tanjung Pelepas Port,Johor.
i) 1000 meter berth and hazardous

i) Kertih Port,Terengganu i) Kertih Port,Terengganu
cargo jetty
- Centralized tank facilities and mainly - Centralized tank facilities and mainly
ii) hazardous liquid terminal
Port Facilities bulk liquid port bulk liquid port
ii) Kuantan Port,Kuantan ii) Kuantan Port,Kuantan
- Centralized tankage facilities and - Centralized tankage facilities and
container bulk and liquid port container bulk and liquid port
i) Sultan Ahmad Shah,Kuantan i) Sultan Ahmad Shah,Kuantan

Air Port Senai Aiport,Johor Bahru
ii) Kerteh airport,Terengganu ii) Kerteh airport,Terengganu
i) Jerangau-Johor Highway
i) Jerangau-Johor Highway
ii) Karak-Kuantan Highway i) North South Highway (Bukit Kayu
ii) Karak-Kuantan Highway
Road Facilities iii) Kuala Terangganu-Kerteh-Telok Hitam to Singapore)
iii) Kuala Terangganu-Kerteh-Telok
Kalong-Gebeng-Kuantan-Kuala Lumpur ii) Pasir Gudang Tanjung Kupang
Cont
Kalong-Gebeng-Kuantan-Kuala
Highway
Lumpur Highway
Disposal
Kualiti Alam Sdn. Bhd. Kualiti Alam Sdn. Bhd. Kualiti Alam Sdn. Bhd.
Facility
Water Supply Centralized Utilities Facilities Centralized Utilities Facilities Lembaga Air Johor
(CUF),Kerteh,Terengganu (CUF),Gebeng,Kuantan.

Water Rate Per
RM 1.87 RM 1.87 RM 2.22
1M3
Electricity
Tenaga National Berhad (TNB) Tenaga National Berhad (TNB) Tenaga National Berhad (TNB)
Supply
Electricity
RM 0.266 RM 0.266 RM 0.266
RatePer kWh
Availability of
150 hectares 209.51 hectares 1,115.55 hectares
Land
Land Prices
RM 60 RM 96.88 RM 172.22
Per m2
Fire Station, Chukai Fire Station, Gebeng Fire Station, Pasir Gudang
Other Facility Police Station, Kemaman. Police Station, Gebeng. Police Station, Pasir Gudang
Hospital, Kemaman. Hospital Tengku Ampuan Afzan, Hospital Penawar Sdn Bhd, Pasir
Kuantan Gudang
Petronas Aromatics Sdn Bhd Petrochemical (M) Sdn. Bhd.

Arnoco Chemical (M) Sdn, Bhd
Petronas Ammonia Sdn Bhd Idemitsu SM (M) Sdn. Bhd.
Kaneka Paste Polymers Sdn. Bhd
BP Petronas Acetyls Sdn Bhd Dairen Chemical (M) Sdn. Bhd.
Petrochemical Eastman Chemical Sdn. Bhd
Ethylene (M) Sdn Bhd Titan Petrochemical (M) Sdn. Bhd.
Plant BASF Petronas Chemical (M) Sdn. Bhd
Polyethylene (M) Sdn Bhd Titan Polyethylene (M) Sdn. Bhd.
Polyplastics Asia Pacific Sdn. Bhd
Optimal Olefins (Malaysia) Sdn Bhd Titan PP Polymer (M) Sdn. Bhd.
Polypropylene (M) Sdn. Bhd.
Optimal Chemical (Malaysia) Sdn Bhd Natural Oleo (M) Sdn. Bhd.

Cont
Optimal Glycol (Malaysia) Sdn Bhd

Petlin Sdn Bhd
Vinyl Chloride (M) Sdn Bhd
Incentive for 15% tax of statutory income for 5 years 30% tax of statutory income for 5 years 30% tax of statutory income for 5 years
investment
Source: Ministry of industrial Development Authority (MIDA),http://www.yellowpages.com.my
Table 3.5 Industrial Land Information

Name of Distance Industrial land Selling Quit Annual Lease Type of Industry
Industrial From Price Rent Assesment Period Prefered
Estates Nearest Total Total Total Total Sq.M per Rate ( % of (Years)
Town Hectares Hectares Hectares Hectares (RM) Sq.M property
Developed Saleable Allocated still per Value )
Available annum
(RM)
Telok 9.6 KM 1,429 1,200 1,032 150 60.00 0.08- 7% - 9% 60 i. medium
Kalong from 0.20 ii. heavy
Kemaman
Gebeng 31 KM 566.57 491.24 281.73 209.51 96.88 0.15 7.5% 66 i.heavy
Industrial from
Area Kuantan
Pasir 48 KM 1,736.89 1,246.24 130.69 1,115.55 172.22 - 0.85% 60 i. light
Gudang from ii. medium
Industrial Johor iii. heavy
Area Bahru

3.3 Plant Site Location Selected
The selection on a few proposed plant sites were narrowed down based on the
factors in table 3.2 which include distance from town, types of industry, marketing
area, raw material source, facilities, utility source, land avaibility and sources. After a
detailed study, each site was given a weighage and estimated as tabulated in Table
3.6, Teluk Kalong Industrial Park was found to be the most suitable place to build
the plant, based on highest score of 26 as compared to other Industrial Parks.
Table 3.6 Weighage study for the proposed plant
Definition Excellent Very Good Moderate Good Not

Good
Rate 5 4 3 2 1
Telok
Weightage Pasir Gudang Gebeng III
Kalong
Total land
5 5 4 3
available
Price of land 5 3 4 5
Raw material 5 2 4 5
sources
Labor Cost 5 3 4 5
Utilities (water 5 3 4 4
and electric
rate)
Transportation 5 4 4 4
Cost
Total 30 20 24 26
Based on our evaluation and weighage study, it can be conclude that the best
site for our plant is in Telok Kalong Industrial Park, which is located in Terengganu
Darul Iman. Telok Kalong is a newly developed industrial area situated 9.6 km from
Kemaman City and is near to the Petrochemical Hub area (Gebeng). Telok Kalong
Industrial Park fulfils most of the criterias mentioned earlier with total avalbility of the
land is about 150hectares which is enough for plant construction. It is closely
located to the three integrated Petrochemical Complexes (IPC) available in
Malaysia. An added advantage to this particular industrial park is that it has the
Centralized Utilities Facility (CUF), which is owned and operated by Petronas. CUF
supplies utilities including electricity, steam, demineralized water and gases such as
nitrogen, oxygen and argon to meet the requirement of petrochemical complexes.
The utility costs are lower as compared to the normal rate. Moreover, emergency
facility such as fire-fighters, police station and hospital also near with the area and is
available for any emergency purposes.
The availability of raw materials is important to the industry. The nearest

supplier the raw material is the Hydrogen gas from MOX-LINDE Gases Sdn Bhd,
Kerteh, Terengganu for hydrogen supply, Petronas Ammonia Sdn Bhd for cabon
monoxide gas supply and Ethylene Malaysia Sdn Bhd for ethylene supply which all
located in Kerteh. This factor can reduce transportation cost since the raw material
is near since the raw materials are pipe directly to the plant from the source.
Besides, Telok Kalong is situated closely to the Kuantan Port and has complete
facilities to transport the product to the customers for shipping activity.
Since Teluk Kalong is situated in the East Coast, skilled labors will not be a
problem. Graduates are available from KUKTEM (Kolej Kejuruteraan Teknologi
Malaysia) situated in Pahang Darul Makmur, Institut Teknologi Petroliam Training
Center, located in Terengganu Darul Iman and also Universiti Teknologi Mara in
Selangor Darul Ehsan. These institutes are known for their highly skilled and
knowledgeable graduates in Chemical Engineering. Therefore, jobs can be offered
to these graduates, thus the labour cost can be reduce.
In addition, Telok Kalong is the most suitable plant area since there is
sufficient land to build our plant. Besides that, the price of land is also cheaper as
compared to other Industrial Parks based on the Table 3.5. Other than that, the
Incentive for investment tax for 5 years is much lower compared to other In dustrial
Parks based on the Table 3.2.
CHAPTER IV
ENVIRONMENTAL AND SAFETY CONSIDERATION
4.0 PROPERTIES OF RAW MATERIALS AND N-PROPANOL
For the safety precautions of the plant, there are certain properties of raw material,
product, by products and also catalyst that need to be considered. Properties that
need to be considered are molecular weight, boiling point, melting point, density,
relative vapor density, vapor pressure, flash point, ignition temperature and
explosion limits.
Raw Materials
Table 4.1: Properties of Ethylene Gas
Physical State Gas

Molecular weight 28.05 g/mole
Boiling point 103.7 C
Melting point 169.2 C
Density 1.178 kg/m3 at 15 C
Relative vapor density 0.96
Vapor pressure 8273.7 kPa
Flash point -136oC
Explosive limits (vol%):
Upper
3.1% - 32%
Lower
Ignition temperature 450oC
Table 4.2 : Properties of Carbon Monoxide Gas
Physical State Gas

Boiling point 191.5
Melting point 205 C
Density 1.145 g/cm3 at 25 C, 1 atm
Relative vapour density 0.97
Vapor pressure >220.4 kPa
Flash point 191 C
Upper
12%-75%
Lower
Ignition temperature 610C
Table 4.3: Properties of Hydrogen Gas
Physical State Gas

Boiling point -252.8oC
Melting point -86oC
Density 0.72 g/cm3 at 20oC
Flash point 25oC
Upper
1.4% - 7.9%
Lower
Ignition temperature 570oC
Product
Table 4.4 : Properties of n-propanol
Physical State Liquid

Boiling point 97.2 oC
Melting point -125.2 oC
Density 0.806 g/cm3
Vapor pressure 27.998 kPa at 25 oC
Flash point 23 oC
Explosion limits (vol%):

Lower
2.1%-13.7%
Upper
Ignition temperature 371 oC
By product
Table 4.5 : Properties of propanal

Boiling point 49C
Melting point -81C
Density 0.81 g/cm3
Vapor pressure 31.33 kPa at 20C
Flash point -30 C
Explosion limits (vol%) 2.6%-17.0%
Lower
Upper
Ignition temperature 207 C
Table 4.6 : Properties of dipropyl ether

Boiling point 87-91 oC
Melting point -122 oC
Density 0.7 g/cm3
Vapor pressure 8.33 kPa at 25 oC
Flash point 21 oC
Explosion limits (vol%):

Lower
1.3 %-7 %
Upper
Ignition temperature 188 oC
Table 4.7 : Properties of ethane
Physical State Gas

Boiling point -88.6 C
Melting point -181.76 C
Density 1.282 kg/m3
Flash point -135 C
Explosion limits (vol%) 3 %-12.4 %
Lower
Upper
Ignition temperature 472 C
Table 4.8 : Properties of water

Boiling point 100 C
Melting point Not available
Density 1000 g/cm3
Relative vapor density
Vapor pressure 2.3 kPa at 20 C
Flash point Not applicable
Explosion limits (vol%) Not applicable
Lower
Upper
Ignition temperature Not applicable
Table 4.9 : Properties of cobalt carbonyl catalyst.
Physical State Solid

Boiling point 52 C
Melting point 51 C
Density 1.7 g/cm3
Relative vapor density Not available
Vapor pressure 0.2 kPa at 20 C
Flash point Not available
Explosion limits (vol%) Not available
Lower
Upper
Ignition temperature Not available
4.1 ENVIRONMENT CONSIDERATION
The most complex problems faced by the industry in running a plant will be the
proper control and use of the natural environment. Establishment of plans for
environmental planning and management requires that a number of natural and
societal factors must be taken into consideration. Insights into the inherent dynamics
of nature as well as the role that past human activities have played for establishing
the current condition of the landscape and the natural environment in general are
essential.
Many natural and man-made changes occur over time scales of decades or
centuries, and these are difficult to comprehend without a historical perspective.
One of the dominant impacts of environmental regulations is that the lead time
required for the planning and construction of the new plants is substantially
increased. When the new plants generate major environmental complexities, the
implications can be profound. Of course, the exact extent of addition to lead time will
vary widely from one case to another depending on which permit requirements apply
and on what difficulties are encountered.
In the plant level, there were numbers of ways and things could be done in
order to minimize the impact of the environmental quality requirements such as:
a) Maintaining an accurate source-emission inventory

b) Continuously evaluate process operation in order to identify potential
modifications that might be reduced the impact of environment.
c) Ensuring the good housekeeping and strong preventive-maintenance
programs are exist and followed.
d) Investigating available and emerging pollution-control technologies
e) Closely working with the regulatory agencies
f) Implementing the environmental management system (EMS)
EMS is a continual cycle of planning, implementing, reviewing, and
improving the process and actions that an organization undertakes to meet its
business and environmental goals. EMSs are built on the Plan, Do, Check, Act
leads to continual improvement. Planning includes identifying environmental aspect
and establishing goals (plan); implementing includes training and operational
controls to do (do); checking includes monitoring and corrective action (check); and
reviewing includes progress review and acting to make needed changes to EMS
(act).
4.1.1 Air Quality
The Clean Air Act is the law that defines EPA's responsibilities for protecting and
improving the nation's air quality and the stratospheric ozone layer. The last major
change in the law, the Clean Air Act Amendments of 1990, was enacted by
Congress in 1990. Legislation passed since then has made several minor changes.
U.S EPA (Environmental Protection Agency) under clean Air Act 1970 has identified
eight major air pollutants that are potentially hazardous to public health and welfare
as shown in Table 4.5.
Table 4.10: Eight major air pollutants
Health And
Pollutant Environmental Sources
Environmental Concern
Respiratory and visual Dust, combustion and
Particulates
irritant minerals processes
Respiratory irritant, Combustion and minerals
Sulfur dioxide
vegetation damage processes
Automobiles, combustion,
Cardiovascular, nervous
Carbon monoxide minerals processes, natural
and pulmonary system
sources
Respiratory illness and High temperature combustion
Nitrogen dioxide
lung damage and natural sources
Respiratory irritant;
Ozone Atmospheric reactions
vegetation damage
Combustion, minerals
Retardation and brain
Lead processes and natural
damage
sources
Respiratory and visual Automobiles, combustions
Hydrocarbons
irritant and natural sources
Respiratory and visual
Photochemical
irritant; vegetation Atmospheric reaction
oxidants
damage
Source: Perrys Chemical Engineering Handbook
The Clean Air Act empowered EPA to establish national ambient air quality
standard (NAAQS). In order to control air quality, EPA imposed limits for the
prevention of significant deterioration (PSD) in those areas of the country that were
already cleaner than required by NAAQS. EPA established an area classification
scheme to be applied in all such regions. The basic idea was to allow a moderate
amount of industrial development but not enough to degrade air quality to a point at
which it barely complied with standards. In addition, states were to designate certain
areas where pristine air quality was especially desirable.
There are three classes of air quality areas under PSD:
1. Class I : Pristine areas that are subjected to highly restrictive controls.

2. Class II : Areas of moderate industrial growth.
3. Class III : Areas of major industry activity.
The EPA regulation also establish another critical concept known as the
increment as a numerical definition of the amount of additional pollution that may be
allowed through the combine effects of all new growth in particular locality (see
Table 4.6). To control this EPA has specified that every new major plant should
install best available control technology (BACT) to limit the emission. BACT is
determined based on a case-by-case engineering analysis. A major stationary
source was defined as any source like fossil-fuel-fired steam, coal cleaning plant,
kraft-pulp mills and etc. with the potential to emit 100 tons per year or more of any
pollutant regulated under the Clean Air Act (CAA) or any other source with the
potential to emit 250 tons per year or more of any CAA pollutant. The potential to
emit is defined as the maximum capacity to emit the pollutant under the applicable
emission standard and permit condition.
Table 4.11: PSD Air quality increments / m

3
Class I Area Class II Area Class III Area

Sulfur Oxide
Annual 2 20 40
24-h 5 91 182
3-h 25 512 700
PM10
Annual 4 17 34

24-h 8 30 60
Nitrogen Dioxide
Annual 2.5 25 50
Source: Perrys Chemical Engineering Handbook
As can be seen the n-propanol process plant used carbon monoxide that very
poisoning to the human and environment. In order to release unreacted carbon
monoxide to the atmosphere, the effects to the air quality must be prioritizes and
follow the regulation stated in the law.
4.1.2 Recommended Malaysian Air Quality Guideline (RMAQG)
There are no ambient air quality standards in Malaysia. The Malaysian

government, however, established ambient air quality guidelines in 1988. Pollutants
addressed in the guidelines include ozone, carbon monoxide, nitrogen dioxide,
sulfur dioxide, total suspended particles, particulate matter under 10 microns, lead
and dust fall. The averaging time, which varies from 1 to 24 hours for the different air
pollutants in the RMAQG, represents the period of time over which measurements is
monitored and reported for the assessment of human health impacts of specific air
pollutants.
Table 4.12: RMAQG (at 25oC and 101.13 kPa) adopted in API calculation
Malaysia guidelines
Pollutant Averaging time
(ppm) g/m3
Ozone 1 hour 0.10 200
AS 2524 8 hour 0.06 120
Carbon monoxide (mg/m3) 1 hour 30 35
AS 2695 8 hour 9 10
Nitrogen dioxide 1 hour 0.17 320
AS 2447 24 hour 0.04 -
10 minute 0.19 500
Sulfur dioxide
1 hour 0.13 350
AS 2523
24 hour 0.04 105
PM 10 24 hour - 150
AS 2724.6 1 year - 50
Total suspended 24 hour 260
particulate (TSP) 1 year 90
Lead 3 month 1.5
Dust fall 1 year 133/mg/m2/day
Source: Department of Environment (1989)
The API system closely follows the PSI system of the U.S. As such, the API
breakpoints; at 100 for the various air pollutants correspond to the respective RMG
concentration regarded as being "safe levels". In other words, air quality with API
values exceeding 100 are considered likely to cause health effects to the general
public. Further, a linear correlation is assumed from API 0 to API 100, with the
breakpoint at API 50 corresponding to 50% of the RMAQG concentration standards
for the various air pollutants. Air quality in terms of human health impacts and
implications are categorized as follows under the API system adopted in Malaysia.
Table 4.13: Summaries additional information on general human health effects on

API status indicator
Air Status Level of pollution Health Measure

0-50 Good Low, no ill effects on health No restriction of activities
for all groups
51-100 Moderate Moderate pollution, no ill eff No restriction of activities
ects on health for all groups
101-200 Unhealthy Mild aggravation of symptoms Restriction of outdoor
among high risk groups, activities for high-risk
e.g. those with heart or lung persons
disease
General population
should reduce vigorous
outdoor activity
201-300 Very Signifi cant aggravation of Elderly and persons with
symptoms and decreased known heart or lung
unhealthy
exercise tolerance in persons disease should stay
with heart or lung disease
indoors and reduce
physical activity
General population
should avoid vigorous
outdoor activity
Those with any health
problems to consult
doctor
301-500 Hazardous Severe aggravation of Elderly and persons with
symptoms and a danger to existing heart or lung
health disease should stay
indoors and reduce
physical activity
General population
should avoid vigorous
outdoor activity
>500 Emergency Severe aggravation of Emergency General

symptoms and a danger to population advised to
health follow the orders of the
National Security Council
and always follow
announcements through
the mass media
Source :API Status Level of Pollution Health Measure
Table 4.14: Significant harm level to API value of 500
Concentration
Pollutant Averaging time
m/m3 ppm
Carbon monoxide (CO) 8 hour 57 500 50
Nitrogen dioxide (NO2) 1 hour 3 700 2.0
3
Ozone (O ) 1 hour 1 200 0.6
Particulate matter (PM10) 24 hour 600 -
Sulfur dioxide (SO2) 24 hour 2 620 1.0
The averaging time that varies from 1 to 24 hours for different air pollutants
in the RMAQG, represents the period of time over which measurements is
monitored and reported for the assessment of human health impacts of specific air
pollutants. As such, the air pollution indices are normally monitored and reported for
the same averaging times as those employed for the air quality
standards/guidelines.
4.1.3 Air Pollutant Index (API) Calculation
The following is an outline of the procedures involved in calculating the API values:
1. Continuous air quality data is collected for the five air pollutants in the
API system for sufficient averaging time periods.
2. The necessary calibration, validation, quality control and quality
assurance in the process of data collection is conducted.
3. The average concentration of the specific air pollutants for the specified
averaging time periods is calculated.
4. The sub-index value for each of the five air pollutants based on the
average concentrations calculated and with the use of the sub-index is
calculated.
5. The API at a given time for the preceding averaging period is reported
(the common end of 1 hour, 8 hour or 24 hour for all five pollutants is
taken) in terms of the highest sub-index value obtained; i.e. API = Max
{sub-indices of all five air pollutants}
4.1.4 Environmental Impact Assessment (EIA)
An EIA is a study to identify, predict, evaluate and communicate information

about the impacts on the environment of a proposed project and to detail out the
mitigation measures prior to project approval and implementation. It seeks to avoid
costly mistakes in project implementation, either because of the environmental
damages that are likely to arise during project implementation, or because of
modifications that may be required subsequently in order to make the action
environmentally acceptable. In Malaysia, an EIA is required under Section 34A,
Environmental Quality Act, 1974. The objectives of EIA are:
1. To examine and select the best from the projects options available.
2. To identify and incorporate into the project plan appropriate abatement
and mitigating measures.
3. To predict significant residual environmental impacts.
4. To determine the significant residual impacts predicted.
5. To identify the environmental costs and benefits of the projects to the
community.
EIA is essentially a planning tool for preventing environment problems due

to an action. It seeks to avoid costly mistakes in project implementation, either
because of the environmental damages that are likely to arise during project
implementation, or because modifications that may be required subsequently in
order to make the action environmentally acceptable. There are two EIA procedures
adopted in Malaysia, namely the Preliminary EIA and the Detailed EIA, that can be
described as follows:
a) Preliminary EIA
Preliminary EIA is assessment of impacts due to those activities that are

prescribed. The Preliminary EIA report that is prepared is reviewed by a technical
committee consisting of the Department of Environment States and other relevant
government agencies. The number of Preliminary EIA report to be submitted to the
Department of Environment States Offices for review is 15 copies, and 3 copies to
the Department of Environment Headquarters.
b) Detailed EIA
Detailed EIA is a procedure undertaken for those projects with

major/significant impacts to the environment. The detailed assessment involve EIA
report display for the public and affected community to comment. The Director
General of Environment has the prerogative to request a detailed assessment of a
project which has significant impacts to the environment of projects which are
located in or adjacent to environmentally sensitive areas.
c) Terms of Reference (TOR)
For projects which have been determined to require detailed assessment,

the project initiator must submit the terms of reference (TOR) in accordance to the
format outlined in specific EIA guidelines. To assist project proponents in submitting
a project-related and site-specific TOR, the Department of Environment has
prepared a general guidance in TOR preparation prior to submission of a detailed
EIA report. The TOR will outline the environmental data collection that are required,
determine the assessment procedures to be used and identify the appropriate
methodologies for impact prediction and assessment. The TOR has to be project
specific and site specific.
The draft TOR for Detailed Assessment are prepared by the project initiator
and to be confirmed by the expert Review Panel and are prepared in consultation
with relevant environment related agencies and the project initiator. The number of
TOR to be submitted to the Department of Environment is 35 copies.
d) Detailed Assessment
Detailed assessment is carried out based on specific terms of reference

issued by an ad hoc Review Panel appointed by the Director General. The EIA
Report is reviewed by the ad hoc Review Panel chaired by the Director General.
The Department of Environment maintains a list of experts who may be called upon
to sit as members of any Review. The selection of the experts depends on the areas
of environmental impacts to be reviewed.
The number of Detailed EIA report to be submitted to the Department of

Environment Headquarters for review is 50 copies. Review of EIA reports is carried
out internally by the Department of Environment, DOE with the assistance from the
relevant technical agencies for preliminary assessments reports and by an ad hoc
Review Panel for detailed assessment reports. Recommendations arising out of the
review are transmitted to the relevant project approving authorities for
considerations in making a decision on the project. According to the DOE's Client
Charter, the period allocated for a review of a term of reference and EIA reports are
as follows:
1. Term of Reference - 2 months

2. Preliminary EIA Report - 3 months
3. Detailed EIA Report - 5 months
4.2.0 Environmental impact assessment
EIA is a process assessing the overall impacts on the environment of developments

projects proposed by the public and private sectors. EIA is an important procedure
for ensuring that the likely effects of new development on the environments are fully
understood and taken into account before the development is allowed to go ahead.
The objectives of EIA are:
1. To examine and select the best from the projects options available.
2. To identify and incorporate into the project plan appropriate abatement
and mitigating measures.
3. To predict significant residual environmental impacts.
4. To determine the significant residual impacts predicted.
5. To identify the environmental costs and benefits of the projects to the
community.
EIA is essentially a planning tool for preventing environment problems due

to an action. It seeks to avoid costly mistakes in project implementation, either
because of the environmental damages that are likely to arise during project
implementation, or because modifications that may be required subsequently in
order to make the action environmentally acceptable. In Malaysia, EIA is required
under section 34A, Environmental Quality Act, 1974.The EIA procedure adopted in
Malaysia consists of three major steps that are:
1. Preliminary assessment of all prescribed activities.

2. Detailed assessments of those prescribe activities for which significant
residual environmental impacts have been predicted in the preliminary
assessment.
3. Review of assessment reports.
A preliminary assessment should normally be initiated during the early

stages or project planning. Standard procedure steps are provided and the
assessment might be conducted "in house", or by a consultant. Some form of public
participation is mandatory. Environmental data collection may be necessary and
close liaison between the assessor and relevant environment related agencies is
encouraged. The results of preliminary assessment are reported formally for
examination and approval by the project approving authority and the Director
General of Environmental Quality.
Preliminary assessment requires resources that are a small proportion of

the man hours, money, skills and equipment committed to a feasibility study and the
assessment should be completed within the time frame of that study.
Detailed assessment should continue during project planning until the project
plan is finalized. Standard procedure steps are provided and specific terms of
reference based on the results of preliminary assessment are issued for each
project. The assessment method is selected according to the nature of the project;
some form of public participation is required. Environmental data collection is almost
certainly necessary. The result of detailed assessment is reported formally.
Review of EIA reports is carried out internally by the Department of

Environment, DOE with the assistance from the relevant technical agencies for
preliminary assessments reports and by an ad hoc Review Panel for detailed
assessment reports. Recommendations arising out of the review are transmitted to
the relevant project approving authorities for considerations in making a decision on
the project. According to the DOE's Client Charter, the period allocated for a review
of a term of reference and EIA reports are as follows:
1. Term of Reference - 2 months

2. Preliminary EIA Report - 3 months
3. Detailed EIA Report - 5 months
4.3 WASTE MANAGEMENT
Generally, the objective of waste management is to minimize the impact residues on

the environment by managing the chemical waste that obtains from the operating
plant. The concept of waste management are encompass waste avoidance by
avoiding or reducing the quantity of residues and the recycling of residues as well as
the disposal of the remaining residues as waste. Based on the Environmental
Quality (Scheduled waste) Regulation 1989, waste management required to treat or
disposed the waste.
Source : Coulson & Richardsons, Chemical Engineering, volume 9.
4.3.1 Spills and Leaks
Facilities for plant operation in n-propanol production should implement a sound

spills prevention and emergency response plant. Here, the plan should have:
Spill detection methods emergency-notification procedures

Community contacts for notification and advice on evacuation needs
Fire prevention and protection provision for spill containment and cleanup
Compliance with applicable national and local regulation or laws
The phenomena of spills and leaks can be minimized by the installation of

the curbs and impervious containment area. The containment area should be
designed and constructed of impermeable material such as concrete, synthetic
linear or compacted clay. Besides that, the total volume of the containment is
adequate to handle a worst-case release of chemicals. For storage tank, the
capacity of the containment area is generally the volume of the large storage tank in
the dam area. The design of the curbing should also provide an allowance for
accumulated rainfall or water used control fire.
Pumps, piping and equipment are designed to operate within potential areas
should be compatible and free of potential ignition source. Besides that, all the
pumps and ancillary equipment should be provided with curbing to collect drips,
leaks and minor spills. Any discharging occurs should be dilute with copious
quantities of water to reduce the fire and explosion hazard. Fire fighting foam also
applies in the spill and leak area to minimize potential fire hazard from vaporization
of the raw material and products. The other alternative depending on the volume
and location of the spill area, it can be removed by using vacuum truck or absorbed
with solid sorbent and placed in drums for disposal.
All the power equipment used in cleanup must meet appropriate electrical
safety codes for areas where flammable liquids and vapors are present. The use of
water for cleanup should minimize but residual chemicals flushes with water into a
sump or collection area for subsequent treatment or disposal.
Source:Daniel A.Crowl/Joseph F. louver, Chemical Process Safety, fundamental

with application.
4.3.2 Potential Impact of Accidental Chemical Spills/Leaks and Gas/Vapors

Cloud Release
These include possible leaks or spills of raw materials during handling and transport
of raw materials, product during storage, from pipelines and during chemical
processing. The main chemicals involved would be ethylene, carbon monoxide,
hydrogen, n-propanol and also by-products.
The n-propanol and by-products which form as a liquid phase are stored in
large covered atmosphere tanks in internal floating roof at the port storage area and
in smaller similar tanks at the plant site. On the other hand, the raw materials which
are ethylene, carbon monoxide and hydrogen are in the gaseous phase. The liquid
and gaseous products or reactants are transport through underground pipelines.
The major chemical hazards are chemicals spills. These hazards caused by:
Rupture of pipelines and Instrument failures.

Rupture of the storage tanks
Storage tank failure
Rupture of pressurized storage tanks.
Source:Daniel A.Crowl/Joseph F. louver, Chemical Process Safety, fundamental

with application.
4.3.3 Waste Handling and Storage
The workers which involves must be thoroughly trained, suitably protected and
familiar with all relevant information and legislative requirements to manage
handling, storage, transportation and disposal of hazardous wastes. In addition,
specific requirement regarding the storage of hazardous waste should be contained
in the operating permits and national or local regulation. In particular, there should
have separate areas designed so that any spillage of waste is collected. The person
who is handling chemical waste must wear personal protective equipment. Carefully
vent any internal pressure before removing closure and isolate, vent, drain, wash
and purge systems or equipment before made maintenance or repair.
4.3.4 Waste Treatment and Disposal
Environment Quality Act 1974 (Act 127) is an Act related to the prevention,
abatement, control of pollution and enhancement of the environment and purposes
connected therewith. This Act also required implementation waste treatment and
disposal under Environment Quality (Scheduled Wastes) regulation 1989.
n-propanol can be removed from waste water by biodegradation. Removal

of the compound from waste water by reverse osmosis may be successful,
depending on the type of membrane. Generally, wastes may burn in on-site as fuel
energy recovery. Hydrocarbon liquid contains DPE, ethane and propyl propionate,
and propanal which have low flash point can be disposed by using incinerator
reactor. That also directly produces heat as the energy recovery.
Source : Environmental Health Criteria,International Program on Chemical Safety.
(1990)
4.3.5 Wastewater Treatment
Preliminary treatment is needed to remove solid and other hydrocarbon form in the
water. Here, the operation involved screening, comminuting, gritting, and settling
/sedimentation. The chemicals and solids will be remove from the wastewater by
sludge waste treatment before it sent to Kualiti Alam for further treatment.
The BOD5 level will reduce in each part of treatment and the suspended
solids settle down as sludge and treated by the natural biodegrading process and
the remain of sludge will pass through in the dewatering and disposed by
combustion. Before it enters the drainage route, the low BOD5 of water then filtered
through the multimedia sand filter. The drainage route of the wastewater and storm
runoff passes through nearest river and ocean.
Source : Environmental Engineering,Howard S.Peavy, Donald R.Rowe.George

Tchobanoglous.
4.3.6 Air treatment
Generally, the Oxo process is mainly use gaseous reactant as the raw material such
as ethylene, carbon monoxide and hydrogen. Here, this component those easily
disperse in the air. Hence, we selected direct combustion using flare at high
temperature to treat this waste and to make sure that component burned in
complete combustion to prevent hazardous gases produce into air.
4.3.7 The other considerations for disposal
Drums and other containers used for produce n-propanol should be drain. Rinse
water generated by this washing should be collected and dispose by incineration. It
may be advisable to complete a certificate of cleaning that documents that the
containers have been appropriately cleaned and can be reused. Any container that
has not been completely water-washed should be considering a potential fire or
explosion risk and should not be cut, burned, soldered, or welded.
As a conclusion, from the plant process, there are couples of material involved
which are n-propanol, ethylene, hydrogen, carbon monoxide, propanal, ethane,
dipropylether and water. Each of the components is in either liquid or gas phases
and not all of the material are byproducts. Materials that have been considered as
waste from the plant are unreacted ethylene, unreacted hydrogen, unreacted carbon
monoxide, the byproducts that consist of propanal, ethane, dipropylether and also
the catalyst which is cobalt carbonyl. Table below shows the summary of waste of
the process and possible method or way to treat them.
Table 4.15 Summary of treatment.
Waste form Gases Liquid Solid

Waste sources Ethylene Water Catalyst- cobalt
Hydrogen carbonyl
Carbon monoxide
Propanal
Ethane
Dipropyl ether
Treatment method Flare system Biological process Dump

-burning at the by lagoon and
high flare stack. pond. Sent to Kualiti
-inject steam to Alam.
reduce smoke
emission. Landfill
4.4 WASTE MINIMIZATION
Waste minimization is a waste management approach that focuses on reducing the

amount and toxicity of hazardous waste that is generated. In addition to hazardous
wasted regulated under Resource Conservation and Recovery Act (RCRA) and
Environment Protection Agency (EPA) encourages waste minimization techniques
that focus on preventing waste from ever being created, (source reduction) and
recycling. There are three general methods of waste minimization which are source
reduction, recycling, and treatment. Waste minimization is important because it
helps to protect the environment and it makes good business sense. Waste
minimization saves money through avoided disposal costs, creates safer working
conditions for employees, and protects human health and the environment.
4.4.1 Source Reduction
Source reduction is a changing practices and processes to reduce or eliminate the

generation of hazardous wastes and materials. Some source reduction methods
include chemical substitution, process modification, and improved operating
procedures. There are some examples in doing source reduction which are :
Not mixing hazardous and non-hazardous waste streams. This action helps
to reduce the amount of hazardous waste to be disposed.
Good housekeeping practices include seal and contain processes to prevent
the escape of fumes or leaks to the environment. Another practice is taking
care when weighing and transferring chemicals to minimize spills.
Consider the use of micro scale laboratory experiments which means uses
smaller amounts of chemicals.
Minimize your inventory and buy chemicals in quantities that will be used in
the near future. A lot of hazardous chemical waste is generated when too
much of a chemical is bought and having it go bad before it is used.
Date all chemical containers when received. Use a first-in, first-out inventory
system. This method will help to prevent chemicals expiring before they are
used.
Maintain labels on all chemicals and if chemicals are transferred to
secondary containers, the new container should be labelled with the
chemical name. This helps to prevent the generation of unknown wastes.
Unknown chemical wastes are harder and much more expensive to dispose.
4.4.2 Recycling
Another method of waste minimization is recycling. Recycling is when a waste
material is used for another purpose, treated and reused in the same process, or
reclaimed for another process. The process include :
Purchasing gas cylinders, including lecture bottles from manufacturers who

will accept the return of the partially used or empty cylinders.
Redistilling used solvents.
Recirculate unused or excess chemicals within your department.
4.4.3 Treatment
The last technique for waste minimization is treatment of waste. Some wastes can
be treated to render them non-hazardous or less hazardous. If treatment is not a
part of the end step of an experiment and is done separately from the experiment, it
is considered hazardous waste treatment. Some treatment of waste can be done on
site like neutralizing or detoxifying a chemical as the final step of an experiment.
These steps could decrease or eliminate toxicity or help to reduce the volume of
waste. Permission must be taken first from the Environmental Health and Safety
Office before initializing any treatment procedures of hazardous waste.
Source : Waste Minimization Program, Office of Environmental Health and Safety,
Feb 2005.
4.5 PROCESS SAFETY STUDY
a) Site Facilities
n-propanol and most of the by-product are highly volatile liquid and should be
handle safely. In storage, transfer and processing area where workers might come
in contact with these hazardous chemicals, quick drenching facilities and
equipment including shower and eyewash station will be provided. Besides that,
washing facilities are required for cleaning before workers consuming food or using
tobacco. Ventilated area also provided for workers to take their breaks and eats
meals. For contaminated work clothing cleaning and stored, the laundry facilities
also provided. The smoking area is provided to limit the area thus make sure the
plant is safe from any ignition that can cause damage and fatality.
b) Hygiene Practices
Those working with or around plant should use proper personal hygiene practices
such as the following:
a. Do not consume/use or store food, tobacco, or cosmetics in the plant area.

b. Wash hands with soap or detergent and water after handling n-propanol,
ethylene, propanal, and other hazardous chemicals.
c. Wash hands before eating, smoking, drinking, applying cosmetics, or using
toilet facilities.
Work clothing that has been contaminated should be thoroughly air dried
before it is placed in a laundry hamper. Electrometric protective clothing (gloves,
hoods, boots, and aprons) should be wash with detergent and water after each use,
then water-rinsed and hung up to dry in a well-ventilated area. Respirators should
decontaminate and stored according to the manufacturer's instructions and the site's
written respiratory-protection procedures. Leather goods, such as belts, wallets, and
shoes, contaminated should air-dried until free of odor before reuse or should be
disposed of properly as contaminated waste.
c) Respiratory Protection
Since the raw material used in this production of n-propanol is mostly form as a
gaseous phase, such as carbon monoxide, hydrogen and ethylene, the respiratory
protection is provided to prevent over exposure to the air. In addition, the worker
should wear respiratory protection when handling the highly volatile chemical such
as n-propanol, DPE, ethane gas and etc.
Moreover, respirator needed for non-routine operations such as confined

space entry into tanks and in emergency arising from spills/leaks and fire/explosion.
Hence, complete respiratory protection program that includes training, maintenance,
inspection, fit testing, medical surveillance, cleaning and evaluation should be
implement.
d) Chemical Protective Clothing
Personal protective equipment (PPE) will be provided for workers when contact with
n-propanol, carbon monoxide, hydrogen gas, ethylene, ethane gas, DPE, propryl
propanoate, propanal and water during handle and fire fight. There is several
protective clothing:
i. Eye protection
Eye protection equipment is provided with industry specification. The workers should
wear safety glasses or goggles when handling, storing, and transferring,
maintenance and processing operation. Individual wearing contact lenses also must
wear it for safety.
ii. Head protection

Safety helmets should be worn where there is danger from falling objects or
overhead leaks and spills. Helmets should meet the appropriate national/industry
specifications for protection. Manufacturers have adapted helmets so that ear
protection and face shields easily attached.
iii. Foot protection

Heavy over boots are provided and worn over leather shoes or boots to protect the
leather from contamination. Leather items may absorb n-propanol, DPE, proryl
propanoate, and propanal thereby increasing the risk of dermal (skin) exposure.
Rubber boots should be worn under trouser legs to prevent it from entering the boot.
Where the potential for falling objects exists, steel-toed rubber boots or safety shoes
with over boots should be worn.
iv. Skin protection

The workers must wear protective clothing and glove during contact with absorb n-
propanol, DPE, proryl propanoate, and propanal. Where the potential for exposure
to n-propanol liquid exists, workers should wear a liquid tight containment suit or
slicker suit. These suits are design to protect employees from skin contact with n-
propanol. All suits should be inspected routinely to identify any damage or wear. If
damage is observe, exit the contaminated area and replace the clothing.
4.6 HAZARD IDENTIFICATION
4.6.1 Identification of Material and Chemical Hazards.
In this study, there is also identification of materials and chemical hazards that
involved MSDS is a detailed information bulletin prepared by the manufacturer or
importer of a chemical that describes the physical and health hazards, routes of
exposure, precautions for safe handling and used, emergency and first-aid
procedures, and control measures. All these information helps employers and
employees to respond effectively to daily exposure situations as well as to
emergency situations. MSDS for carbon monoxide, hydrogen, ethylene, n-propanol,
dipropylether, propanal, ethane, water and cobalt carbonyl were attached in
APPENDIX 1. In the n-propanol production. Materials that need to be identified are
shown below in the Table 4.15.
Table 4.15 : Materials involved in hazard identifications.
Raw material Product Byproduct

Ethylene n-propanol Propanal
Hydrogen Ethane
Carbon monoxide Dipropyl ether
Water
4.7 HAZARD CONTROL
4.7.1 Assessment Risk Management

Table 4.16 shows the assessment risk management for the material that considered
in this study to control the chemical and hazards. It consists of raw material, product,
by product and catalyst that involved in the production of n-propanol.
Raw Material
Table 4.16: Assessment risk management for raw material.
Chemicals
Ethylene Hydrogen Carbon Monoxide
Name
Fire Fighting Flammable gas. Flammable gas . Extremely flammable
Lower Explosion LEL(%):4 gas.
Limit ,LEL(%): 3.1 UEL(%): 74 LEL(%): 12.5
Upper Explosion UEL(%): 74.0
Limit, UEL(%): 32 Extinguishing Media:
CO2 , dry chemical, Fire and Explosion
Fire and Explosion water spray or fog. Hazards:
Hazard: Explodes Do not extinguish Having almost the
spontaneously until hydrogen source same density as air, it
when mixed with is shut off. will not diffuse by
chlorine in rising as with some
sunlight. Instruction: lighter flammable
Immediately cool gases such as
Extinguishing container with water hydrogen or natural
Media: spray from maximum gas (methane).
Carbon dioxide, distance, taking care Flammable in air over
dry chemical or not to extinguish a very wide range.
water spray. flames. If flames are Reacts violently with
accidentally oxygen
Instruction: extinguished, difluoride and barium
If possible stop the explosive re-ignition peroxide.
flow of gas supply. may occur. Stop flow
Use water spray to of gas if without risk Extinguishing Media:
cool adjacent while continuing Water, dry chemical,
areas. cooling water spray. carbon dioxide.
Instructions:
If possible, stop flow
of gas by using water
spray to cool
surrounding
containers.
Hazards and Eye Effects: Eye Effects: Eye Effects:
Health None anticipated None anticipated. None anticipated.
Effects as product is a gas
at room Skin Effects: Skin Effects:Cont
temperature. None anticipated. None anticipated.
Skin Effects: Inhalation Effects: Ingestion Effects:

None anticipated. Asphyxiant. Lower None anticipated.
flammability limit of
Ingestion Effects: hydrogen in air would Inhalation Effects:
None known. be exceeded and Inhaled carbon
Ingestion is causing an oxygen- monoxide binds with
unlikely. deficient and blood hemoglobin to
explosive form
Inhalation Effects: atmosphere. carboxyhemoglobin
Simple that can Cont
asphyxiants may Exposure to not take part in
include rapid moderate normal oxygen
breathing, concentrations can transport, greatly
diminished mental cause dizziness, reducing the bloods
alertness, impaired headache, nausea ability to transport
muscular and oxygen. Can cause
coordination, faulty unconsciousness. headache, dizziness,
judgement, heart palpitations,
emotional Exposure to weakness,
instability, atmospheres confusion, nausea,
and fatigue. As containing 8-10% or and even
asphyxiation less oxygen quickly convulsions, eventual
progresses, will bring unconsciousness and
nausea, vomiting, unconsciousness death.
prostration, and without warning.
eventually leading Lack of sufficient
to convulsions, oxygen may cause
coma, and death. serious injury or
death.
First Aid Eyes: Eyes: Eyes:

Measures Never introduce None required. None required.
ointment or oil into
the eyes without Skin: Skin:
medical advice. If None required. None required.
pain is present,
refer to an Ingestion: Ingestion:
opthalmologist for None required. None required
treatment and
follow up. Inhalation: Inhalation:
Victims should be Conscious persons
Skin: removed to fresh air. should be assisted to
Adverse effects If victim is not an uncontaminated
are not anticipated breathing, administer area quickly and be
as product is a gas artificial respiration. If treated with
at room breathing is difficult, supplemental
temperature. administer oxygen. oxygen. Unconscious
Ingestion: Obtain prompt persons should be
None required. medical attention. moved to an
ed area
uncontaminatartificial
Cont
Inhalation: and be given
Victims should be respiration and
assisted to an oxygen at the same
uncontaminated time. Obtain
area and inhale prompt medical
fresh air. Quick attention.
removal from the Rescue personnel
contaminated area should be equipped
is most important. with self-contained
If breathing has breathing apparatus.
stopped administer
artificial
resuscitation and
supplemental
oxygen. Further
treatment should
be symptomatic
and supportive.
Keep victim warm
and quiet. Obtain
prompt medical
attention.
Exposure Eye Protection: Eye Protection: Eyes Protection:
Protection Safety goggles or Safety goggles or Safety goggles or
glasses. glasses. glasses.
Skin Protection: Skin Protection: Skin Protection:

Plastic or rubber Plastic or rubber Any material
gloves. Protective gloves. protective gloves.
gloves made of
any suitable Respiratory Respiratory
material. Protection: Protection:
Positive pressure air Positive pressure air
Respiratory line with mask or line with full-face
Protection: selfcontained mask and escape
Positive pressure breathing apparatus bottle or self-
air line with full should be available contained breathing
face piece and for emegencu used. apparatus should be
escape bottle or available for
self-contained General Protection: emergency use.
breathing Safety shoes, safety
apparatus should shower. General Protection:
be Safety shoes.
available for
emergency use.
General
Protection:
safety shoes,
safety shower,
eyewash
"fountain."
Toxicology Hydrogen is a simple Reproductive:
asphyxiant. Toxic effects to
fertility in female rats
exposed to 1 mg/m3
for 24 hours. Similar
effects to others
mammalian species.
Mutagenic:
Genetic changes
observed in
mammalian cell at
exposures of 1500 to
2500 ppm for 10
minutes.
Cont
Other:
Degenerative
changes to the brain
in rats chronically
exposed to 30
mg/m3.
Handling and Use in well- Storage areas should Can handled in all
Storage ventilated areas. be well-protected, commonly used
Do not drag, slide well-ventilated, dry metals up to
or roll the cylinder. and separated from approximately 3450
Use suitable hand combustible kPa. Above the
truck to move the materials. Do not pressure it forms
cylinder. When allow temperature toxic and corrosive
connect the the where it stored carbonyl compounds
o
cylinder to lower exceed 52 C. with some metals.
Cont
pressure Cylinders of Store in cool, dry,

(<2000psig) hydrogen should well-ventilated areas
pipimg, use separated from from emergency
pressure oxygen/oxidizers by exits. Do not allow
regulator.do not minimum distance of temperature exceed
heat cylinder to 7 m and barriers of 54oC. Use first in-
increase the non-combustible first out to avoid full
discharge rate of material at least 2m cylinders being
product from high. Do not open stored for excessive
cylinder. Use hydrogen cylinder periods of time. Do
check valve or trap valve before not drag,slide or roll
to prevent connecting it cylinders but used
hazardous back because self ignition suitable hand truck.
flow into cylinder. can occur. Hydrogen Use pressure
Store in cool, dry is the lightest gas so reducing regulator
and well- it may collect in the when connected to
ventilated area of top of building lower pressure
non-combustible without proper (<3000psig) and do
construction away ventilation. Leak not heat cylinder.
from emergency check system with
exits. Do not allow leak detection
temperature where solution never with
cylinders are flame. Use piping
stored to exceed and equipment
54oC.Post No adequately designed
Smoking or Open to withstand
Flames pressures to be
encountered.
Product
Table 4.17: Assessment risk management for product.

Chemicals
n-propanol
Name
Fire Fighting Highly flammable gas.
Fire and Explosion Hazards:

Flash back possible over considerable distance.
Extinguishing Media:
Water spray, alcohol-resistant foam, dry chemical, carbon
dioxide.
Instructions:
Cool containers / tanks with water spray. Wear self-contained
breathing apparatus and protective suit.
Hazards and Particular risks to human beings and the environment

Health Effects
Frst Aid Eyes:
Measures Rinse thoroughly with plenty of water for at least 15 minutes and
consult a physician.
Skin:
Wash off immediately with soap and plenty of water while
removing all contaminated clothes and shoes. If skin irritation
persists, call a physician.
Ingestion:
If swallowed, seek medical advice immediately and show this
container or label.Never give anything by mouth to an
unconscious person.
Inhalation:
Move to fresh air in case of accidental inhalation of vapours. If
breathing is irregular or stopped, administer artificial respiration.
Exposure Eyes Protection:
Protection Safety glasses with side-shields.
Skin Protection:
Protective suit and safety shoes.
Respiratory Protection: Wear suitable respiratory equipment.

Cont
Hand Protection (suitable gloves):
Material is butyl-rubber, break through time is 4 hours and
material thickness is 0.5 mm.
Hand Protection (unsuitable gloves):

Material is polyvinylchloride, leather, nitrile rubber/nitrile latex,
natural rubber/natural latex.
General Protection:
Wear suitable protective equipment
Handling and Provide sufficient air exchange and/or exhaust in work rooms and
storage take precautionary measures against static discharge. All
equipment is electrically grounded before beginning transfer
operations. Keep away from heat and sources of ignition. Use
explosion proof equipment. Keep containers tightly closed in a
dry, cool and well-ventilated
place.
By Product
Table 4. 18: Assessment risk management for byproduct.
Chemicals Name Propanal Dipropyl Ether

Fire Fighting Flammable gas. Formed a mixture of explosive
LEL (%): 2.6 vapor if above 21oC.
UEL(%): 17 LEL(%): 1.3
UEL(%): 7.0
Flammable in presence of Fire and Explosion Hazards:
open flames and sparks, of Severe fire hazard. Flammable
heat. in the presence of open
flames, sparks, and smokes.
Extinguishing Media: Explosion-proof electrical
Flammable liquid, soluble or equipment.
dispersed in water.
Instruction: Alcohol-resistant foam, carbon
Use dry chemical dioxide, regular dry chemical,
powder(small fire) and use water.
alcohol foam, water spray or
fog (large fire). Instruction:
Cool containers with water
spray until well after the fire is
out.
Hazards and Eyes Effects: Eyes Effects:
Health Effects Irritation. Irritation.
Skin Effects: Skin Effects:

Irritation. Irritation, absorption may
occur.
Ingestion Effects:
None anticipated. Ingestion Effects:
Digestive disorders, symptoms
Inhalation Effects: of drunkenness.
Cont
None anticipated.
Inhalation Effects:
Irritation, symptoms of
drunkenness.
First Aid Eyes: Eyes:
Measures Remove any contact lenses. Flush eyes with plenty of water
Immediately flush eyes with for at least 15 minutes. Get
running cold water for at least immediate medical attention.
15 minutes, keeping eyelids
open. Do not use an eye Skin :
ointment. Get medical Wash skin with soap and water
attention. for at least 15 minutes while
removing contaminated
Skin: clothing and shoes. Get
Wash immediately with plenty medical attention. Clean and
of water, gently and dry contaminated clothing and
thoroughly wash the shoes before reuse.
contaminated skin with
running water and non- Ingestion:
abrasive soap. Cover the If vomiting occurs, keep head
irritated skin with an lower than hips to help prevent
emollient. aspiration. If unconscious, turn
head to side and get medical
Ingestion: attention immediately.
Examine the lips and mouth
to ascertain whether the Inhalation:
tissues are damaged. Loosen If adverse effects occur,
tight clothing such as a collar, remove to uncontaminated
tie, belt or waistband. If the area. Give artificial respiration
victim is not breathing, if not
perform mouth-to-mouth breathing.
resuscitation. Seek
immediate medical attention.
Inhalation:
Allow victim to rest in a well
ventilated area. If serious,
evacuate the victim to a safe
area as soon as possible.
Loosen tight clothing such as
a collar, tie, belt or waistband.
If breathing is difficult,
administer oxygen. If the
victim is not breathing,
perform mouth-to-mouth
resuscitation. Seek medical
attention.
Exposure Eye Protection: Eye Protection:
Protection Splash googles. Wear splash resistant safety
goggles. Provide an
Skin Protection: emergency eye wash fountain
Lab coat, gloves. and quick drench shower in the
immediate work area.
Respiratory Protection:
Vapor respirator. Skin Protection: Cont
Wear appropriate chemical
General Protection: resistant gloves.
Full suit, boots.
Chemical cartridge respirator
with organic vapor cartridge(s),
full facepiece and organic
vapor cartr idge(s), any air-
purifying respirator with a full
facepiece and an organic
vapor canister. Depend on the
frequency and concentration of
exposure.
Toxicology Toxicity (animals): Toxicity:
Acute oral toxicity (ld50): 163 gm/m3/15 minute(s)
1200 mg/kg [rat], acute inhalation-mouse lc50, slightly
dermal toxicity (ld50): 5040 toxic through inhalation.
mg/kg [rabbit], acute toxicity
of the vapor (lc50) 10900
ppm 4 hour(s) [mouse].
Toxicity (humans):
Very hazardous in case of
ingestion, inhalation, skin
contact (irritant).
Handling and Keep away from heat and Store and handle in
Storage sources of ignition. Ground all accordance with all current
equipment containing regulations and standards.
material. Do not ingest, Grounding and bonding
breathe gas/fumes/ required. May form peroxides
vapour/spray. Wear suitable during prolonged storage. Do
protective clothing, not evaporate or distill to
respiratory equipment In case dryness. Store in a cool, dry
of insufficient ventilation. place and tightly closed
If ingested, seek medical container. Store under an inert
advice immediately and show atmosphere. Keep separated
the container or the label. from incompatible substances.
Avoid contact with skin and
eyes. Flammable materials
should be stored in a
separate safety storage
cabinet or room.
Keep container tightly close
in a cool, well-ventilated
place. A refrigerated room
would be preferable for
materials with a flash point
lower than 37.8C (100F).
Table 4. 19: Assessment risk management for byproduct.
Chemical Names Ethane Water

Fire Fighting Extremely flammable. Not flammable.
LEL(%): 3
UEL(%): 12.4 Fire and Explosion Hazards:
Not applicable.
Ethane is slightly heavier than Extinguishing Media: Not
air and may travel a applicable.
considerable distance to an
ignition source. Should flame Instruction: Not applicable.
be
extinguished and flow of gas
continue, increase ventilation to
prevent flammable mixture
formation in low areas
or pockets.
Extinguishing Media: Carbon

dioxide, dry chemical or water
spray.
Instruction: If possible stop the

flow of gas supply. Use water
spray to cool adjacent areas.
Hazards and Eyes Effects: Not anticipated as Eyes Effects: Non-irritating

Health Effects product is a gas at room and non-corrosive.
temperature.
Skin Effects: Not anticipated. Skin Effects: Non-corrosive

and non-irritant.
Ingestion Effects: Not
anticipated. Ingestion Effects: Non-
hazardous.
Inhalation Effects: Ethane is a
simple asphyxiant. High Inhalation Effects: Non-
concentrations of ethane to the hazardous.
lungs causes dizziness, deeper
breathing due to air hunger,
possible nausea and
unconsciousness. It may cause
anesthetic effect.
First Aid Measures Eyes: No ointment or oil into Eyes: Not applicable.
the eyes without medical
advice! If pain is present, refer Skin : Not applicable.
to doctor.
Ingestion: Not applicable.
Skin : Not anticipated.
Inhalation: Not applicable.
Ingestion: Not anticipated. Cont
Inhalation: Assisted to an
uncontaminated area and
inhale fresh air. If breathing has
stopped administer artificial
resuscitation and supplemental
oxygen. Keep victim warm and
quiet.
Exposure Eye Protection: Eye Protection:

Protection Safety googles. Not Applicable.
Skin Protection: Skin Protection:

Plastic or rubber gloves. Lab coat, gloves.
Respiratory Protection: Respiratory Protection:

Positive pressure air line with Not Applicable.
mask and escape bottle or self-
contained breathing apparatus. General Protection:
Lab coat.
General Protection:
Safety shoes, safety shower,
eyewash "fountain."
Toxicology Toxicity: Toxicity:
No data available. Non- toxic to animal and
human.
Handling and Ethane is non-corrosive can be No specific safety is
Storage used with any common applicable for this material.
structural material. Use only in
well-ventilated areas. Store in
cool, dry, well-ventilated area of
non-combustible construction
away from heavily trafficked
areas and
emergency exits. Do not drag,
slide or roll cylinders. Use a
suitable hand truck for cylinder
movement. Use a pressure
regulator when connecting
cylinder to lower pressure
(<2000 psig) piping or systems.
Do not heat cylinder to increase
the discharge rate of product
from the cylinder. Use a check
valve or trap in the discharge
line to prevent hazardous back
flow into the cylinder. Do not
allow the temperature stored to
exceed 130oF (54oC).
Catalyst
Table 4. 20: Assessment risk management for catalyst.

Chemicals Name Cobalt Carbonyl
Fire Fighting Spontaneously flammable in air.
Do not use water directly on fire and get water inside
containers. Cool containers with flooding quantities of
water until well after fire is out. Use dry chemical, soda
ash, lime or sand (small) and dry sand or withdraw from
area and let fire burn (large).
Instruction:
Evacuate area and fight fire from a safe distance.
Hazards And Health Eyes Effects:
Effects Irritation.
Skin Effects:
Irritation and sensitization, an allergic reaction, which
becomes evident upon re-exposure to this material.
Ingestion Effects:
Gastrointestinal irritation with nausea, vomiting and
diarrhea. May be harmful if swallowed.
Inhalation Effects:
Respiratory tract irritation, metal fume fever, which is
characterized by flu-like symptoms with metallic taste,
fever, chills, cough, weakness, chest pain, muscle pain
and increased white blood cell count.
First Aid Measures Eyes:

Flush eyes with plenty of water for at least 15 minutes,
occasionally lifting the upper and lower eyelids.
Skin:
Flush skin with plenty of water for at least 15 minutes
while removing contaminated clothing and shoes. Wash
clothing before reuse.
Ingestion:
If victim is conscious and alert, give 2-4 cupfuls of milk
or water. Never give anything by mouth to an
unconscious person. Get medical aid immediately.
Inhalation:
Remove from exposure and move to fresh air
immediately. If not breathing, give artificial respiration. If
breathing is difficult, give oxygen. Do NOT use mouth-
to-mouth resuscitation.
Cont
Exposure Eye Protection:

Protective eyeglasses or chemical safety goggles.
Skin Protection:
Protective gloves.
Respiratory protection program.
Toxicology Inhalation for rat:

LC50 = 165 mg/m3.
Handling and Storage Separated from strong oxidants. Well closed. Keep in a
well-ventilated room.
As a conclusion, majority of the materials involved in the production of n-propanol

need the same handling and storage method. Materials like propanal, ethane, n-
propanol and ethylene itself need to be far from the sourced of heat and ignition
because they are flammable materials. There are specific temperatures needed to
store the materials in order to maintain it in the phases required. All materials also
need to be conducted in well ventilated, dry and cool areas. The procedures
required to handle the materials should be follow to avoid any incidents.
4.7.2 Potential Hazards
It is compulsory to consider the possible hazard that may arise from the n-propanol
production plant. The types of hazards are divided into three which are toxicity, fires
and explosion. Fires and explosion can be caused by any liquid chemical spillage or
gases cloud release from the storage or tank. Table shows the hazards sources
from the process plant and method or ways to deal with it. It is important to minimize
and prevent the potential to spread.
Table 4.21 Summary of Hazard Identification.
Types of Hazards Liquid Sources Gases Sources Solid Sources
(Ethylene, (Catalyst-cobalt
hydrogen, carbon carbonyl)
monoxide,
propanal, dipropyl
ether, ethane.)
Chemical Spills Installation of curbs - -
and Leaks and impervious
containment area.
Cont
Use impermeable
material. (synthetic
linear and
compacted clay)
Remove using
vacuum truck or
absorbed with solid
sorbent.
Dilute with water.
Collect drips, leaks

and spills.
Chemical spill kit.
Protection
equipment.
Clean up material.
Neutralized
material.
Gases Cloud - Formed by the spillage of liquid and

Release vaporized.
Similar prevention and method to deal

with the chemicals.
Fires Eliminate or avoid any sources of ignition.
Use inflammable material.
Apply proper fire extinguishing.
Proper protection equipment.
No open flames, no sparks and no smoking.
Explosion Cause by liquid leak.

Apply intrinsic safety.
Avoid any combustible material and flying sparks.
Protect combustible material with cover made of fire resistant

material.
Provide fire extinguisher and protection equipment.
4.8 MALAYSIA LAW AND REGULATION
4.8.1 The Occupational Safety And Health (OSHA), 1974
The Occupational Safety and Health Act (OSHA) 1994, defines the general duties of
employers, employees, the self-employed, designers, manufacturers, importers and
suppliers of plant or substances. Although these duties are of a general character,
they carry a wide ranging set of responsibilities. The general duties of employers,
employees, the self-employed, designers, manufacturers, importers and suppliers of
plant or substances are clearly defined under OSHA 1994. Employers must
safeguard so far as is practicable, the health, safety and welfare of the people who
work for them. This applies in particular to the provision and maintenance of a safe
plant and system of work. Arrangements must also be made to ensure safety and
health in the use, handling, storage and transport of plant and substances. Under
OSHA 1994, plant includes any machinery, equipment, appliance, tool and
component, whilst substance means any natural or artificial substance whether in
solid, liquid, gas, vapour or combination form.
Risks to health from the use, storage or transportation of substances must

be minimised. To meet these aims, all practicable precautions must be taken in the
proper use and handling of any substance likely to cause a risk to health. It is the
duty of employers to provide the necessary information, instruction, training and
supervision in safe practices, including information on the legal requirements.
Employers need to consider the specific training needs of their organisations with
particular reference to processes with special hazards.
An employer employing 40 or more persons must establish a safety and

health committee at the workplace. The committees main function is to keep under
review the measures taken to ensure the safety and health of persons at the
workplace and investigate any related matters arising. An employer must notify the
nearest occupational safety and health office of any accident, dangerous
occurrence, occupational poisoning or disease which has occurred or is likely to
occur at the workplace.
Some operation, installation, maintenance and dismantling of equipment

and process need competent persons. Thus, during the installation of machinery
and equipment such as cranes, lifts and local exhaust ventilation systems,
competent persons are compulsory to ensure safe erection, whilst a boilerman and
a steam engineer are required to operate high risk equipment such as boilers.
Processes that use hazardous chemicals require competent persons to conduct the
air quality and personal monitoring, and a safety and health officer and an
occupational health doctor are required to ensure the proper surveillance of the
workplace.
There are seven regulations under OSHA 1994 that enforced by DOSH. They are:
1. Employers Safety and Health General Policy Statements (Exception)

Regulations, 1995
2. Control of Industrial Major Accident Hazards Regulations, 1996
3. Classification, Packaging and Labelling of Hazardous Chemicals Regulations,
1997
4. Safety and Health Committee Regulations, 1996
5. Safety and Health Officer Regulations, 1997
6. Use and Standards of Exposure of Chemicals Hazardous to Health
Regulations, 2000
7. Notification of Accident, Dangerous Occurrence, Occupational Poisoning and
Occupational Disease Regulations, 2004
Contravention of some of the requirements can lead to prosecution in court. A
person who fails to comply with an improvement or prohibition notice that is served
on him is liable to prosecution, with a maximum fine of RM 50,000 or imprisonment
for a term not exceeding 5 years, or both.
4.8.2 Environmental Quality Act (EQA), 1974
The 1974 Environmental Quality Act (EQA) provides the framework for
environmental regulation in Malaysia. The EQA framework is based upon the
issuing of licenses and the prescription of premises to be regulated. The Minister, in
consultation with the Environment Quality Council, may prescribe the occupation or
use of specific premises to be an offence unless the occupant is the holder of an
appropriate license. Conditions for the occupation and use of prescribed premises
are attached to the license by the Director General the licensing authority.
EQA is an enabling piece of legislation for preventing, abating and

controlling pollution, and enhancing the environment, or for other related purposes.
Pollution, as declared in EQA, includes the direct or indirect alteration of any quality
of the environment or any part of it by means of a positive act or act of
omission.Pollution is controlled through the mechanism of licenses issued by the
Department of Environment. The mode of control is by prescribing, by means of a
ministerial regulation, that licences are mandatory for:
The use and occupation of prescribed premises.

Discharging or emitting wastes exceeding acceptable conditions into the
atmosphere, as well as noise pollution, polluting or causing the pollution of
any soil or surface of any land.
Emitting, discharging or depositing any wastes or oil, in excess of acceptable
conditions, into inland waters or Malaysian waters.
While a number of appropriate measures were taken by the government over

the last few years, the number of offences prosecuted under the Environmental
Quality Act and related regulations has seen steady increases over the period from
1980 to 1996. In 1984, there were 14 prosecutions, but this number increased to
130 in 1992. The situation would be further exacerbated if enforcement also
tightened over the same period. On the other hand, the large number of offences
would also suggest that environmental quality is steadily deteriorating despite
growing efforts by the enforcement agencies. Enforcement activities have been
backed by new environmental legislation to cover sewerage, natural resources,
management of hazardous chemicals, the use of chlorofluorocarbons (CFCs), and
occupational safety and health.
A person is deemed to have pollute any soil or surface of land if places in

or on any soil in any place where it may gain access to soil any matter whether
liquid, solid or gaseous; establish a refuse dump, garbage tip, soil and rock disposal
site, sludge deposit site, waste injection well for disposal of solid or liquid waste so
as to be obnoxious or offensive to human beings or interfere with underground water
or detrimental to soil. The penalty is a maximum of RM100,000 or jail terms of up to
5 years or both. A person is deemed to have pollute any inland waters if places
waste in or on any waters or in any place where it may gain access water; causes
the temperature of the receiving waters to be raised or lowered by more than the
prescribed limits. The penalty is a maximum of RM100,000 or jail terms of up to 5
years or both.
CHAPTER V
MASS BALANCE
5.0 INTRODUCTION
The Law of Conservation of Mass states that mass can neither be created nor
destroyed. To calculate the mass balance or material balance, this law must be
followed. The statement total mass of input = total mass of output is applied for a
steady-state process. The design of new process or analysis of an existing one is
not complete until it is established at steady state that the inputs and the outputs of
the entire process and of each individual unit satisfy balance equations.
In the n-propanol production, the proposed plant use continuous process that
means the inputs and the outputs flow continuously throughout the duration of the
process. A balance on a conserved quantity in a system may be written in the
following general way:
Input + Generation Output Consumption = Accumulation

(5.1)
For this process (continuous process) at steady state, the accumulation term in the
general balance equation equals to zero. Hence
Input + Generation = Output Consumption (5.2)
If the balance is on a non-reactive process or on a total mass, the generation

and consumptions term equals zero and the equation reduces to:
Input = Output (5.3)

5.1 OVERALL BALANCE
Assumptions made
i Process is steady state

ii Operation = 330 days per year
iii Catalyst used in the process do not involved in the reaction and do not give
any effect to the mass flow.
100000tonne 1month 1day 1year

Total mass flowrate required = x x x
year 30day 24hr 12 month
1000kg
x
1tonne
kg
= 11,574.07
h
From the backward calculation, 10,816.80 kg/hr of n-propanol is produced by using

6000 kmole/hr basis. Based on this information, scale up factor has been made to
produce 11,574.07 kg/h in order to achieve 100,000,000 kg/year. From the
calculation, the scale up ratio are :
i. 1000 kmole/hr basis produce 2066.80 kg/hr
11 574.40 kg/hr need = 11574.40 kg/hr = 1.07

10816.80 kg/hr
= 6000 kmole/hr x 1.07
= 6420 kmole/hr of basis
5.2 DESCRIPTION ON EACH STREAM
The mass balance on each stream on this plant was calculated by using the basis of
5600 kmole/hr. Knowing that the fraction of the raw material are 0.1 for ethylene
( C2H4 ), 0.45 for carbon monoxide ( CO ) and 0.45 for hydrogen ( H2 ).
5.2.1 Reactor 1(Hydroformylation Process)
C2H4
H2
C2H4
CO
H2
CO
C3H6O
Stream 4 Stream 7 C2H6
Stream 5
Stream 6
R1
Figure 5.1: First reactor
Hydroformylation process is occurred in the first reactor and produced propanal. The
reaction also produced by product which is ethane. The reactions involved in the
reactor are shown below:
CH2 CH2 CO H2 c
ata
lyst,

,presu
ure CH3 CH2 CHO
(5.4)
Ethylene Carbon Hydrogen propionaldehyde
monoxide
C2H4 H2 C2H6 (5.5)

Table 5.1: Details of Component at the Input of Reactor 1

Component Molecular Weight Mole Flow Rate Mass Flow Rate
(kg/kmole) (kmole/h) (kg/h)
C2H4 28.05 642.00 18008.10

CO 28.01 2889.00 80920.89
H2 2 2889.00 5778.00
Total 6420.00 104706.99
Given that:
The conversion of ethylene to form propanal is 60 % meanwhile conversion of

ethylene to form ethane is 10 %. From the feed stream of ethylene, the output of
propanal and ethane shown below;
60 x 642 kmol of ethylene = 385.20 kmol of propanal

100 hr hr
10 x 642 kmol of ethylene = 64.20 kmol of ethane

100 hr hr
Table 5.2: Details of Component at the Output of Reactor 1
Component Molecular Weight Mole Flow Rate Mass Flow Rate

(kg/kmole) (kmole/h) (kg/h)
C2H4 28.05 n n
1 1
CO 28.01 n n
2 2
H2 2.00 n n
3 3
C3H6O 58.08 385.20 22372.42
C2H6 30.07 64.20 1930.49
To check the degree of freedom:
Unknown variable =3
Independent atomic species balance (C,H,O) = -3
Nonreactive molecular species balance (CO, C2H4) = 0
Degree of freedom =0
Thus the degree of is 0. The equation is possible to solve.
Molecular balance :
1. Molecular C3H6O balance: Generation = Output

Generation C3H6O = 385.20 kmol C3H6O
hr
2. Molecular C2H6 balance: Generation = Output

Generation C2H6 = 64.20 kmol C2H6
hr
3. Molecular C2H4 balance : Input = Output + Consumption
642 kmol C2H4 = n1 kmol C2H4 + Cons kmol C2H4

hr hr hr
4. Molecular CO balance : Input = Output + Consumption
2889 kmol CO= n2 kmol CO + Cons kmol CO
hr hr hr
5. Molecular H2 balance : Input = Output + Consumption

2889 kmol H2 = n3 kmol H2 + Cons kmol H2
hr hr hr
By using atomic balance:
Atomic C balance:
1284kmol C + 2889kmol C = 1155.6kmol C + 128.4kmol C + 2n1 kmol C + n2 kmolC

hr hr hr hr hr hr
4173 kmol C = 1284 kmol C + 2n1 kmol C + n2 kmol C

hr hr hr hr
2889 kmol C = 2n1 kmol C + n2 kmol C

(5.6)
hr hr hr
Atomic H balance:
2568kmol H + 5778 kmol H= 2311.2 kmolH + 385.2 kmol H + 4n1 kmol H + 2n3 kmol
hr hr hr hr hr hr
5649.6 kmol H = 4n1 kmol H + 2n3 kmol H2 (5.7)

hr hr hr
Atomic O balance:
2889 kmol O =385.2 kmol O + n2 kmol O (5.8)

hr hr hr
n2 kmol O = 2503.8 kmol O = 2503.8 kmol of CO

hr hr
Insert n2 into equation 5.6,Hence :
2n1 + n2 = 2889
2n1 +2184 = 2889
n1 = 192.60 kmol of C2H4
Insert n1 into equation 5.7,Hence :
4n1 + 2n3 = 5649.6

4(192.6) + 2n3 = 5649.6
n3 = 2439.60 kmol of H2
Table 5.3: Details of Each Component at The Reactor 1
Input Output
Component
Stream 4,5,6 Stream 7
Molar Flow Mass Flow Molar Flow Mass Flow

Rate In Rate Out Rate out
(kmol/hr) Rate in (kg/h) (kmol/hr) (kg/h)
C2H4 (stream 4) 642.00 18008.10 192.60 5402.43
CO (stream 5 ) 2889.00 80920.89 2503.80 70131.44
H2 ( stream 6 ) 2889.00 5778.00 2439.60 4879.20
C3H6O - - 385.20 22372.42
C2H6 - - 64.20 1930.50
Total 6420.00 104706.99 5585.40 104715.99

5.2.2 Gas Separator 1
C2H4
Stream 10 C3H6O
C2H6
vapor CO
H2
C2H4
C3H6O
Stream 9
C2H6
H2O
H2
CO
C2H4
C3H6O
C2H6
Stream 11
H2
liquid
Figure 5.2: Gas Separator 1
Gas separator is used to separate vapour and liquid phase of the product. Based on
the Hysys Program the composition of the vapor and liquid phase product can be
obtained. Table 5.4 shows the mass and molar flow of each on the gas separator.
Table 5.4: Mass and Molar Flow of Component at Gas Separator 1

Output
Input
Stream 10 Stream 11
Stream 9
( vapor ) ( liquid )
Component
Mole Mass Mass
Mass Mole Mole Flow
Flow Flow Flow
Flow Rate Flow Rate Rate
Rate Rate Rate
(kg/hr) (kmole/hr) (kmole/hr)
(kmol/hr) (kg/hr ) (kg/hr)
C2H4 5402.43 192.60 5329.50 190.00 72.93 2.60
C3H6O 22372.42 385.20 3539.40 60.94 18817.92 324.00
C2H6 1930.50 64.20 1896.82 63.08 32.78 1.09
H2 4879.20 2439.60 4878.32 2439.16 1.6 0.80
CO 70131.44 2503.80 70100.07 2502.68 29.69 1.06
TOTAL 104715.99 5585.40 85744.11 5255.86 18954.92 329.54
5.2.3 Reactor 2 (Hydrogenation Process)
Stream 15 C3H8O
C2H4
Vapor C6H14O
liquid C3H6O
mixture C2H6
H2O
C3H6O Stream 12
H2 H2
C2H4
C2H6
Stream 14
H2
Figure 5.3: Second reactor
Hydrogenation process is occurred in the second reactor and produced propanol.

The reaction also produced by product which are ethane,di propyl ether (Dpe) and
water. The reactions involved in the reactor are shown below:
There are three reactions occur in this second reactor. The reactions are :
C H O H c
obaltC H O
3 6 2 3 8
propanal hydrogen n-propanol (5.9)
C2H4 H2
C2H6
Ethylene hydrogen ethane
(5.10)
2C3H8O C6H14O H2O

(5.11)
n-p ropanol dipropylether water
By using atomic balance:
Unknown variable =7
Independent atomic species balance (C,H,O) = -3
Nonreactive molecular species balance ( C2H6 ) = -3
Related equation ( conversion of propanal ) = -1
Degree of freedom =0
Molecular Balance
1. Knowing that the conversion of propanal to n-propanol is 60%. Hence,

balance 40% of propanal is not reacted. So :
0.6 reacted C3H6O x 324 kmole x 1 mol C3H8O = 194.40 kmole of C3H8O
hr 1 mol C3H6O hr
0.4 unreacted C3H6O x 324 kmole of C3H6O = 129.60 kmole of C3H6O

hr hr
2. But, from the reaction 5.11, 1% of n-propanol is used to produce di-Propyl
ether (Dpe). Hence 99% unreacted n-propanol will produce in these second
reactor.
0.99 unreacted C3H8O x 194.40 kmole of C3H8O = 192.46 kmole of C3H8O

hr hr
0.01 reacted C3H8O x 192.46 kmole x 1 mol C3H14O = 0.96 kmoleC6H14O

hr 2 mol C3H8O hr
3. From the reaction 5.10, 10% of ethylene is convert into ethane. Hence :
0.90 unreacted C2H4 x 2.60 kmole of C2H4 = 2.34 kmole of C2H4

hr hr
0.10 reacted C2H4 x 2.34 kmole x 1 mol C2H6 = 0.23 kmole of C2H6
hr 1 mol C2H4 hr
1.09 kmole of C2H6 from feed stream + 0.23 kmole = 1.32 kmole of C2H6
hr hr hr
Table 5.5: Total Value of Component at the Output of Reactor 2
Component Variable Molecular Weight Mole Flow Mass Flow

(g/mole) Rate (mole/h) Rate (kg/h)
C3H8O - 60.10 192.46 11566.85
C2H4 - 28.05 2.34 65.64
C6H14O - 102.18 0.96 98.10
C3H6O - 58.08 129.60 7527.17
C2H6 - 30.07 1.32 39.70

H2 n1 2.00 - -
H2O n2 18.02 - -
By using Atomic Balance:
Atomic C Balance:
(324 x 1) kmole C = (129.60 x 1) kmole C + (192.46 x 1) kmole C + n2 kmol C

hr hr hr hr
+ (0.96 x 1) kmol C
hr
324 kmole C = n2 kmole C + 323.02 kmole C

hr hr hr
n2 kmole C = 0.98 kmole of H2O (5.12)

hr hr
Atomic H Balance:
(2.60 x 4) kmol H + (324 x 6) kmol H + (1.09 x 6) kmol H + (1000 x 2) kmol H

hr hr hr hr
= (2.34 x 4) kmol H + 2n1 kmol H + (129.60 x 6) kmol H + (1.32 x 6) kmol H +

hr hr hr hr
(192.46 x 8) kmol H + 2n2 kmol H + (0.96 x 14) kmol H

hr hr hr
3960.94 kmole H = 2n1 kmole H + 2n2 kmole H + 2348.00 kmole H (5.13)

hr hr hr hr
Insert equation 5.12 into equation 5.13 Hence :
3960.94 kmole H = 2n1 kmole H + (2 x 0.98) kmole H + 2348.00 kmole H

hr hr hr hr
n1 kmole C = 805.49 kmole of H2

hr hr
Table 5.6: Total Value of Component at the Output of Reactor 2

Component Variable Molecular Weight Mole Flow Mass Flow
(g/mole) Rate (mole/h) Rate (kg/h)
C3H8O - 60.10 192.46 11566.85
C2H4 - 28.05 2.34 65.64
C6H14O - 102.18 0.96 98.10
C3H6O - 58.08 129.60 7527.17
C2H6 - 30.07 1.32 39.70
H2 n1 2.00 805.49 1610.98
H2O n2 18.02 0.98 17.74
TOTAL 1131.15 20926.10
From Figure 5.3 it shown that two phase of product will be produce from the reaction
in the second reactor. The mass and molar flow of component at the reactor 2
shows on Table 5.7 and Table 5.8.
Table 5.7: Mass Flow of Component at the Reactor 2
Component Mass Flow Rate ( kg/hr )

Input Output
Stream 12 Stream 14 Stream 15

(vapor)
C3H8O - - 11566.85
C2H4 72.93 - 65.64
C6H14O - - 98.10
C3H6O 18817.92 - 7527.17
C2H6 32.78 - 39.70
H2 1.6 2000 1610.98

H2O - - 17.64
TOTAL 20925.23 2000 20926.10
Table 5.8: Molar Flow of Component at the Reactor 2
Component Molar Flow Rate ( kmole/hr )

Input Output
Stream 12 Stream 14 Stream 15
(vapour)
C3H8O - - 192.46
C2H4 2.60 - 2.34
C6H14O - - 0.96
C3H6O 324.00 - 129.60
C2H6 1.09 - 1.32
H2 0.80 1000 805.49
H2O - - 0.98
TOTAL 328.49 1000 1131.15

There are some error in the input and output in reactor 2. These error is due to the
decimal point and the density of each component taken during calculation are
different. Other reason is the assumption of there is no carbon monoxide in the
reactor.
5.2.4 Distillation Column
C3H8O
Stream 18 C2H4
C6H14O
C3H6O
C2H6
C3H8O
H2O
C2H4
C6H14O H2
C3H6O
C2H6
Stream 17
H2O
H2
C3H8O
C6H14O
Product C3H6O
Stream
Figure 5.4: Distillation Column 1
Distillation column acts as purifying equipment that purifies the desired product
which is (n-propanol). Two outlet streams (stream 18 and product stream ) in the
distillation column show the product produce after the purifying process. Table 5.9
shows mass and molar flow of component at distillation column 1.
Table 5.9 : Mass and Molar Flow of Component At Distillation Column 1
Input Output
Stream 17 Stream 18 Stream Product

Component
( liquid ) ( vapor ) ( liquid )
Mass Mole Mass Mass

Mole Mole Flow
Flow Flow Flow Flow
Flow Rate Rate
Rate Rate Rate Rate
(kmole/hr) (kmole/hr)
(kg/hr) (kmol/hr) (kg/hr ) (kg/hr)
C3H8O 11566.85 192.46 - - 11566.85 192.46
C2H4 65.64 2.34 65.64 2.34 - -
C6H14O 98.10 0.96 - - 98.10 0.96
C3H6O 7527.17 129.60 7527.17 129.60 - -
C2H6 39.70 1.32 39.70 1.32 - -
H2 1610.98 805.49 1610.98 805.49 - -
H2O 17.14 0.98 13.94 0.80 3.20 0.18
TOTAL 20926.10 1131.15 9257.95 939.55 11668.15 193.60
Assume that the composition of component is equal to zero when the value of
composition is less than 10-4 . In this case the composition of DPE and n-propanol in
stream 18 and the composition of ethane, hydrogen, water and propanal in product
stream are equal to zero due to this condition.
5.3 SUMMARY OF MASS BALANCE
Table 5.10: Summary of Mass Balance

Stream Mass Flow Rate ( kg/hr) Molar Flow Rate ( kmole/hr)
By Hysys By Calculation Percentage Error By Hysys By Calculation Percentage

(%) Error (%)
Stream 1 18008.58 18008.10 0.00 641.93 642.00 0.01
Stream 2 80912.29 80920.89 0.01 2888.60 2889.00 0.01
Stream 3 5824.22 5778.00 0.79 2889.00 2889.00 0.00
Stream 4 18008.58 18008.10 0.00 641.93 642.00 0.01
Stream 5 80912.29 80920.89 0.01 2888.60 2889.00 0.01
Stream 6 5824.22 5778.00 0.79 2889.00 2889.00 0.00
Stream 7 104744.82 104715.99 0.03 5585.02 5585.40 0.01
Stream 8 - - - - - -
Stream 9 104744.82 104715.99 0.03 5585.02 5585.40 0.01
Stream 10 85776.14 85744.11 0.04 5255.24 5255.86 0.01
Stream 11 18968.68 18954.92 0.07 329.78 329.54 0.07
Stream 12 18968.68 18954.92 0.07 329.78 329.54 0.07

Stream 13 2016.00 2016.00 0.00 1000.00 1000.00 0.00
Stream 14 2016.00 2016.00 0.00 1000.00 1000.00 0.00
Stream 15 20984.68 20926.10 0.28 1134.98 1131.15 0.34
Stream 16 - - - - - -
Stream 17 20984.68 20926.10 0.28 1134.98 1131.15 0.34
Stream 18 9263.03 9257.95 0.05 940.44 939.55 0.09
Product Stream 11721.65 11668.15 0.46 194.54 193.60 0.48

CHAPTER VI
ENERGY BALANCE
6.1 INTRODUCTION
In the process plant, the energy balance is calculated as the flow of the stream is
change due to the temperature and pressure of the process. According to The First Law
of Thermodynamic, energy cannot be created or destroyed, only modified in form as the
internal energy is equal to the heat supply to the system minus the work shaft to the
system. It can be written in the formula below:
Initial system energy = Ui + Uki + Epi

Final system energy = Uf +Ukf + Epf
Energy transferred = Q-W
Thus, Q Ws H Ek Ep
6.2 METHOD OF CALCULATION
6.2.1 Assumptions in Calculations
(i) The system is an open system at steady state.
(ii) There are no moving parts in the system, can ne neglected.

(iii) No work shaft in the system, thus can be neglected.
(iv) All streams enter and leave the process at a single height, can be
neglected.
(v) Since the effect of pressure difference to the energy balance in the process
gives a very small value as compared to the values contributed by the
sensible heat and the heat of formation, heat obtained from the pressure
difference is assumed to be negligible,
(Source from Chemical Process Principal.2005)
6.2.2 Equations Used in Calculations
6.2.2.1 General Equations
Q Ws H Ek Ep (6.1)
Kinetic energy and potential energy can be neglected since there are no moving parts in
the system, the position of the system is in the same stream as the potential energy, no
work shaft to the system and no work done by the system.
Based on the assumptions stated above,
Ws 0, Ek 0, Ep 0
Hence equation (6.1) can be reduced to
Q H (6.2)
6.2.2.2 Equation for Reactive Process

H n H i H f n H i H f
(6.3)
i i

Outlet Inlet
6.2.2.3 Equation for Process with Phase Changes
Tbp dT
C dT T C
H i = T p(l ) H v Tbp p(v) (6.4)

ref
6.2.2.4 Equation for Non-reactive Process
H n C dT
T
i T
ref
i p
Or
H n Tbp
dT
C dT T C
i i Tref p(l ) H v Tbp p(v)
6.2.2.5 Equation for Heat Capacity, Cp

(a) For component in ideal gas phase
Cp a bT cT 2 dT 3 eT 4 (6.5)
Hence for sensible heat,
T
C dT
T
a bT cT 2

dT 3 eT 4 dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT (6.6)
2 3 4 5
ref
T
Also
Cp
a bT cT 2 dT 3 eT 4 (6.7)
R
Where R, gas constant= 8.314 kJ/kmol.K
Therefore,
1T dT a bT cT
T
2

dT 3 eT 4 dT
RTref
C p Tref
T
bT 2 cT 3 dT 4 eT 5
= aT R
2 3 4 5
ref
(6.8)
T
(b) For component in liquid phase
2 2
5
C C 3 C sinh C
3
C C 5 cosh C (6.9)
p 1
T T
4
T T
T
H C p(l ) dT
Tref
6.2.2.6 Total Heat for the Energy Balance (for Non-reactive Process):
i
HTotal (HOutlet stream H Inlet stream ) (6.10)
i1
6.2.3 REFERENCE CONDITIONS
Tref = 25C @ 298 K

Pref = 1 atm
Therefore, when T = Tref there will be no sensible heat. Hence the sensible heat of the
substances in standard condition = 0. All the heat capacities data was taken from the
table source in the basis of reference state at 25oC.
6.3 CALCULATIONS ON ENERGY BALANCE
6.3.1 Balance at First Heater
Stream 1 Stream 4
T= 27oC T=100 oC
E-103
Figure 6.1 Inlet and outlet streams of the heater
References: C2H4(g) at 25 oC and 1 atm

Inlet stream, S1, T=27 oC Outlet stream, S4, T=100 oC
Substances Phase

nInlet H Inlet H Inlet nOutlet H Outlet H outlet
(kmol/h) (kJ/h) (kmol/h)
(kJ/kmol) (kJ/kmol) (kJ/h)
Ethylene
g 649.13 H1 H1 649.13 H4 H4
H inle H outlet
Heat Capacity of the Components

a b c d
Ethylene 40.75 10-3 11.47 10-5 -6.891 10-8 17.66 10--12
Source from Chemical Process Principal.2005
Where Cp kJ /(mol.K) or Cp kJ /(mol.o C)

T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
T
H 1 C p( g ) dT
Tref
Ethylene:
Where
C
27
T
C p(l ) dT p(l ) dT
Tref 25
27
bT 2 cT 3 dT
4
aT
2 3 4 25
11.47x105 2 8
3 25 3
40.75x10 3 27 25 27 25 2 (6.891x10 ) 27
2 3
27 25
17.66x1012 4 4
4
0.087372kJ / mol

H1 0.087372 kJ / mol

H1 n1 H 1
649.13 0.087372 1000
56715.78 kJ / h
The calculation were then repeated with outlet stream using the same equation
i
H outlet H 2(outlet)
i1
nH 2
(649.13) 3.571735 1000
2318.52 kJ / h
Enthalpy for stream 1
Inlet stream, S1, T=27 oC

nInlet H Inlet H Inlet
Substances Phase
(kmol/h) (kJ/kmol) (kJ/h)
Ethylene g 649.13 87.372 56.71 103
56.71 103

Outlet stream, S4, T=100 oC

nOutlet H Outlet H outlet
Substances Phase
Ethylene g 649.13 3571.735 2318.52 103
2318.52 103
Hence,
H Total H Outlet H inlet
2318.52103 56.17 103

2266804.63kJ / h
Hysys = 2293580 kJ/h
Error,% =1.39%
The error between manual calculation and hysys is small and acceptable. This error
happens due to the round up number during calculation.
6.3.2 Balance at Second Heater

Stream 2 Stream 5
T= 27oC T=100 oC
E-104
Figure 6.2 Inlet and outlet streams of the second heater
References: H2(g) at 25 oC and 1 atm

Substances Phase


Hydrogen G 649.13 H2 H2 649.13 H5 H5
H inle H outlet

a B c d
Hydrogen 28.84 10-3 0.0076 10-5 0.3288 10-8 -0.8698 10--12

T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
T
H 1 C p( g ) dT
Tref

Substances Phase
Hydrogen g 2889 57.688 166660.32
166660.32


Substances Phase
Hydrogen g 2889 2164.413 6252989.15
6252989.15
Hence,
6252989.15 166660.32
6086328.8kJ / h
Hysys =6228080 kJ/h
Error,% =2.28%
6.3.3 Balance at Third Heater

Stream 3 Stream 6
T= 27oC T=100 oC
E-105
Figure 6.3 Inlet and outlet streams of the third heater
References: CO(g) at 25 oC and 1 atm

Substances Phase

Carbon
Monoxide
g 2889 H3 H3 2889 H6 H6
H inle H outlet

a b c d
Carbon
28.95 10-3 0.411 10-5 0.3548 10-8 -2.22 10--12
Monoxide

T
C dT
T
a bT cT 2
dT eT
3 4
dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
T
H 1 C p( g ) dT
Tref


Substances Phase
Carbon Monoxide g 2889 58.118 167902.902
167902.902


Substances Phase
Carbon Monoxide g 2889 2191.625 6331604.625
6331604.625
Hence,
6331604.625 167902.902
6163699kJ / h
Hysys =6019850 kJ/h
Error, % =2.39%
6.3.4 Balance at First Reactor

Stream 4
Stream 5 Stream 7
o
Stream 6
o
CRV-1
Figure 6.4 Inlet and outlet streams of the first reactor
References: C2H4(g),H2(g),CO,C3H6O(g),C2H6(g) at 25 oC and 1 atm

Inlet stream, S4,S5,S6, T=100oC

Substances Phase

Ethylene g 649.13 H1 H1

Hydrogen g 2889 H2 H2

Carbon monoxide g 28829 H3 H3

Ethane g 0 H4 H4

1-propanal g 0 H5 H5
H inlet

Outlet stream, S7, T=170oC

Substances Phase


Hydrogen g 2439.6 H7 H7

Carbon monoxide g 2503.4 H8 H8

Ethane g 64.193 H9 H9

1-propanal g 385.16 H 10 H 10
H outlet

a b c d
Ethylene 40.75 10 -3
11.47 10 -5
-6.891 10 -8
17.66 10--12
Hydrogen 28.84 10-3 0.0076 10-5 0.3288 10-8 -0.8698 10--12
Carbon
28.95 10-3 0.411 10-5 0.3548 10-8 -2.22 10--12
Monoxide
Ethane 49.37 10-3 13.92 10-5 -5.816 10-8 7.28 10-12

T
C dT
T
a bT cT 2
dT eT
3 4
dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
T
H 1 C p( g ) dT
Tref
Ethylene:
Where
100
C
T
Tref
C p(l ) dT
25 p(l ) dT
bT 2 cT 3 dT 4 100
aT
2 3 4 25
11.47x105 (6.891x108 ) 3
40.75x10 100 25
3
1002 25 2 100 25 3
2 3

1004 25
17.66x1012

4
4
3571.73493kJ / kmol

H1 n1 H 1
649.133571.73493
2318520.295 kJ / h
The calculation were then repeated with other components by using the same equation
except for:
Heat Capacity for 1-propanal

C1 C2 C3 C4 C5
1-propanal 0.72 105 1.91 105 2.014 103 1.17 105 930.6
Source from Perrys Chemical Engineering Handbook 8 Edition.2007 th
Propanal:
T
H 5 C p(l ) dT
Tref
Where
C p(v) dT C p(v) dT
T 100
Tbp 25
= 5021.8 kJ/mol.K
Enthalpy for reactor inlet stream

Inlet stream, S4,S5,S6 T=100oC

Substances Phase
Ethylene g 649.13 3571.735 2318.52 103
Hydrogen g 2889 2164.413 6252989.15
Carbon monoxide g 28829 2191.625 6331604.625
Ethane g 0 0 0
1-propanal g 0 0 0
14903113.78
Enthalpy for reactor outlet stream


Substances Phase
(kmol/h) (kJ/kmol) (kJ/hr)
Ethylene g 192.58 7421.514 1429235
Hydrogen g 2439.6 4188.06 10217192
Carbon monoxide g 2503.4 4261.184 10667447
Ethane g 64.193 9033.166 579866
1-propanal g 385.16 5021.8 1934196
24827937
Heat of formation, (kJ/kmol) for all component

Ethane -8.8320 104
1-propanal -1.8630 105
CO -1.105 105
Ethylene 5.251 104
Hydrogen 0
n 60 0
v C H O
3 6
60kmol
CHO 1
36
Heat of reaction = Heat of formation (product) Heat of formation (reactant)

^ ^ ^
H r H f ,i
product
H
reactan t
f ,o
For main product reaction:

Reaction 1:
C2 H 4 CO H 2 c
atal
yst,
, pr
esu
ureCH 3CH 2 CHO 6.1
Ethylene Carbon Hydrogen 1-propanal
monoxide
^
H r ,1 1.863103 (1.105105 5.251104 )
= -1.2828105 kJ/kmol
For by-product reaction

Reaction 2:
C2H 4 H 2 C2 H 6
6.2
^
H r ,2 8.832 104 5.251104
= -1.4083105 kJ/kmol
Therefore, addition of both heat of reaction will be:

^ ^ ^
H r H r ,1 H r ,2
= 1.2828105 (1.4083105 )
=-2691105 kJ/kmol
^ ^ ^
H Total H r H outlet H inlet
= 60(-269110) +24827937-14903113.78
= -6.2218106 kJ/h
Hysys = -4.72107 kJ/h

Error,% = 86.80
The error between manual calculation and hysys is big and not acceptable. This error
happens due to the round up number during calculation and also because of the
difference value of heat capacity used in manual calculation different from hysys.
6.3.5 Balance on First Compressor
s7 s9
T= 170oC T=271oC
P=1000 kPa K-101 P=2000 kPa
Figure 6.5 Inlet and outlet streams of the first compressor

Inlet stream, S7, T=170oC

Substances Phase
(kmol/hr) (kJ/kmol) (kJ/hr)





1-propanal g 385.16 H5 H5
H inlet

Substances Phase





1-propanal g 385.16 H 10 H 10
H outlet
a b c d
Ethylene 40.75 10-3 11.47 10-5 -6.891 10-8 17.66 10--12
Hydrogen 28.84 10-3 0.0076 10-5 0.3288 10-8 -0.8698 10--12
Carbon
28.95 10-3 0.411 10-5 0.3548 10-8 -2.22 10--12
monoxide
Ethane 49.37 10-3 13.92 10-3 -5.816 10-3 7.28 10-3
Source from Chemical Process Principal(2005).
T
H 6 C p( g ) dT
Tref

T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p
T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
Heat Capacity for 1-propanal
C1 C2 C3 C4 C5
1-propanal 0.7174 105 1.914 105 2.0144 103 1.1708 105 930.6
Source from Perrys Chemical Engineering Handbook 8th Edition.2007
Propanal:
T
H 5 T C p(l ) dT
ref
Where
C p(v) dT C p(v) dT
T 27
Tbp 25
Compressor inlet stream


Substances Phase
Ethylene g 192.58 7421.514 1429235
Hydrogen g 2439.6 4188.06 10217192
Carbon monoxide g 2503.4 4261.184 10667447
Ethane g 64.193 9033.166 579866
1-propanal g 385.16 5021.8 1934196
24827937
Compressor outlet stream


Substances Phase
Ethylene g 192.58 13767.5068 2651346.452
Hydrogen g 2439.6 7118.03029 17365146.69
Carbon monoxide g 2503.4 7291.86322 18254450.38
Ethane g 64.193 16837.2888 1080836.078
1-propanal g 385.16 7245.74 7245.74
39359025.34
Since, there is pressure change in the compressor:

1 m3 8.314 J /(mol.K ) kg
PV (P2 P1 )atm 1000 mw

kg 0.08206 L.atm /(mol.K ) mol
Hence,
For ethylene component:
PV 1 m3 (0.986923)atm 8.314 J /(mol.K ) 1000 28 kg

1.178 kg 0.08206 L.atm /(mol.K ) kmol
This equation is then applied for other component.

Moleculer PV
Substances Phase Density,
weight, mw (kJ)
Ethylene g 1.178 28 23767008
Hydrogen g 0.72 2 2777533.3
Carbon monoxide g 1.145 28 24451996
Ethane g 1.28 30 23435437
1-propanal g 0.81 58 71598637
146030612
Hence,
HTotal HOutlet H Inlet PV
39359025.34 24827937 146030612
193.75106 kJ / h
Hysys = 20.68109 kJ/h
Error, % = 99.1%
6.2.6 Balance on Separator
s10
T=10oC
s9
T=271oC s11
T= 10oC
V-100
Figure 6.6 Inlet and outlet streams of the separator

nInlet
Substances Phase H Inlet H Inlet
(kmol/hr)
(kJ/kmol) (kJ/hr)





1-propanal g 385.16 H5 H5
H inlet


Substances Phase





1-propanal g 385.16 H 10 H 10
H outlet


Substances Phase

Ethylene l 192.58 H 11 H 11

Hydrogen l 2439.6 H 12 H 12

Carbon monoxide l 2503.4 H 13 H 13

Ethane l 64.193 H 14 H 14

1-propanal l 385.16 H 15 H 15
H outlet
a B c d
Ethylene 40.75 10-3 11.47 10-5 -6.891 10-8 17.66 10--12
Hydrogen 28.84 10-3 0.0076 10-5 0.3288 10-8 -0.8698 10--12
Carbon
28.95 10-3 0.411 10-5 0.3548 10-8 -2.22 10--12
monoxide
Ethane 49.37 10-3 13.92 10-3 -5.816 10-3 7.28 10-3
1-propanal 99.306 0.11573 0 0

T
H 6 C p( g ) dT
Tref

T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p
T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
Heat Capacity for 1-propanal in gas phase

C1 C2 C3 C4 C5
1-propanal 0.7174 105 1.914 105 2.0144 103 1.1708 105 930.6
Source from Perrys Chemical Engineering Handbook 8th Edition.2007
1-propanal:
T
H 5 C p(l ) dT
T ref
Where
T 271
Tbp
C p(v) dT 25 C p(v) dT
Separator inlet stream


Substances Phase
Ethylene g 192.58 13767.5068 2651346.452
Hydrogen g 2439.6 7118.03029 17365146.69
Carbon monoxide g 2503.4 7291.86322 18254450.38
Ethane g 64.193 16837.2888 1080836.078
1-propanal g 385.16 7245.74 7245.74
39359025.34
Separator outlet stream (gas outlet)


Substances Phase
Ethylene g 189.98 -641.0244942 -1.217818 105
Hydrogen g 2438.9 -432.6358962 -1.055156 106
Carbon monoxide g 2502.4 -435.3459603 -1.089410 106
Ethane g 63.1 -776.8071627 -4.901653 104
1-propanal g 60.922 -1076.1 -6.555816 104
-2.380922 106
Separator outlet stream (liquid outlet)


Substances Phase
Ethylene l 2.6012 -2732.433371 -7.107606 103
Hydrogen l 0.79623 -367.2649794 -2.924274 102
Carbon monoxide l 1.0565 0 0
Ethane l 1.093 -735.5194298 -8.039227 102
1-propanal l 324.24 -1519.969125 -4.928348 105
-5.0104 105
HTotal HOutlet H Inlet

= (-5.0104105 +-2.380922106) - 39359025.34
= -4.903106107
Hysys = -6.1353107 kJ/h
Error,% = 20.1 %
The error between manual calculation and hysys is still acceptable. This error happens
due to the round up number during calculation and also because of the difference value
of heat capacity used in manual calculation different from hysys.
6.3.7 Balance on Fourth Heater
s11 s12
T= 10 oC T=100oC
E-100
Figure 6.7 Inlet and outlet streams of the fourth heater


Substances Phase

Ethylene l 2.6012 H1 H1

Hydrogen l 0.79623 H3 H2

Carbon monoxide l 1.0565 H2 H3

Ethane l 1.093 H4 H4

1-propanal l 324.24 H5 H5
H inlet


Substances Phase





1-propanal l 324.24 H 10 H 10
H outlet
a B c d
Ethylene 40.75 10-3 11.47 10-5 -6.891 10-8 17.66 10--12
Hydrogen 28.84 10-3 0.0076 10-5 0.3288 10-8 -0.8698 10--12
Carbon
28.95 10-3 0.411 10-5 0.3548 10-8 -2.22 10--12
monoxide
Ethane 49.37 10-3 13.92 10-3 -5.816 10-3 7.28 10-3
1-propanal 99.306 0.11573 0 0

T
H 6 C p( g ) dT
Tref
T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p
T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
Heater inlet stream


Substances Phase
Ethylene g 2.6012 -2732.433371 -7.107606 103
Hydrogen g 0.79623 -367.2649794 -2.924274 102
Ethane g 1.093 -735.5194298 -8.039227 102
1-propanal g 324.24 -1519.969125 -4.928348 105
-5.0104 105
Heater outlet stream


Substances Phase
Ethylene g 2.6012 7539.993516 1.961303 104
Hydrogen g 0.79623 1921.487041 1.529946 103
Ethane g 1.093 16496.72311 1.803092 104
1-propanal g 324.24 7990.434375 2.590818 106
2.6300 106
Hence,
= 2.6300106 (-5.0140105)
= 3.13037106 kJ/h
Hysys = 3.9683106 kJ/h

Error,% = 21.1 %
The error between manual calculation and hysys is still acceptable. This error happens
due to the round up number during calculation and also because of the difference value
of heat capacity used in manual calculation different from hysys.
6.3.8 Balance on second compressor
s13 K-100 s14

o
T= 27 C T= 116.8 oC
Figure 6.5 Inlet and outlet streams of the second compressor

Inlet stream, S9, T=27 oC Outlet stream, S10, T=116.8 oC

Substance Phase
(kmol/h) (kJ/kmol) (kJ/h) (kmol/h) (kJ/kmol) (kJ/h)

Hydrogen g 1000 H1 H1 1000 H2 H2
Properties of hydrogen heat capacity at the streams

Component a b c d
Hydrogen 28.84 10-3 0.0076 10-5 0.3288 10-8 -0.8698 10--12

T
H 1 C p( g ) dT
Tref

T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p
T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
Enthalpy for inlet and outlet compressor

Inlet stream, S13, T=27 oC Outlet stream, S14, T=116.8 oC

Substance Phase
(kmol/h) (kJ/kmol) (kJ/h) (kmol/h) (kJ/kmol) (kJ/h)
57.688
Hydrogen g 1000 0.057688 1000 2.649696 2649.696
37
HTotal HOutlet HInlet

= (2649.696 57.68837)*1000
= 2592007kJ/h
Hysys = 2577178.8 kJ/h

Error,% = 0.573 %
6.3.9 Balance on second reactor
s12 s15
T= 100 oC T= 150oC
CRV-2
s14
T=100 oC
Figure 6.8 Inlet and outlet streams of the second reactor


Substance Phase nInlet H Inlet H Inlet





1-propanal l 324.24 H5 H5
H inlet


ninlet H inlet H inlet
Substance
Phase (kmol/h) (kJ/h)
(kJ/kmol)

Hydrogen g 1000 H6 H6
H inlet

nOutlet H Outlet
Substances Phase H Outlet




Ethane g 1.3531 H 10 H 10

1-propanal g 129.69 H 11 H 11

Dipropylether g 0.97271 H 12 H 12

water g 0.97271 H 13 H 13

1-propanol g 192.6 H 14 H 14
H outlet

a b c d e
Ethylene (l) 247 -4.43 4.09 10 -2
-1.70 10 -4
2.68 10-7
Ethylene (g) 40.75 10-3 11.47 10-5 -6.89 10-8 17.66 10--12 0
Hydrogen (l) 2.88 3.68 10-3 -7.72 10-6 6.92 10-9 -2.13 10-12
Hydrogen (g) 28.84 10-3 0.01 10-5 0.33 10-8 -0.87 10--12 0
Carbon
0 0 0 0 0
monoxide (l)
Carbon
28.95 10-3 0.41 10-5 0.35 10-8 -2.22 10--12 0
monoxide (g)
Water (g) 33.5 0 0 0 0
Water (l) 75.4 6.88 10-3 7.60 10-6 -3.59 10-9 0
1-propanol (l) 159 -0.635 1.97 10-3 0 0
1-propanal (l) 99.306 0.11573 0 0 0
Dipropylether
0 0 0 0 0
(l)
Dipropylether
1.862 0.534 -2.29 10-4 2.44 10-8 0
(g)
Ethane (l) 4.18 -4.43 10-3 5.66 10-3 -6.65 10-6 2.49 10-11
Ethane (g) 49.37 10-3 13.92 10-3 -5.816 10-3 7.28 10-3 0
T
H
Tref C p( g ) dT
T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
For component Hydrogen and Ethane in liquid gas, use equation 6.7
Heat Capacity for 1-propanal and 1-propanol

C1 C2 C3 C4 C5
1-propanol (g) 61.9 202 1.63 129 0.72
1-propanal (g) 0.72 10 5
1.91 10 5
2.01 10 3
1.17 10 5
930.6
Source from Perrys chemical Engineering Handbook
Propanal:
T
H
Tref C p(l ) dT
Where
C p(v) dT C p(v) dT
T 27
Tbp 25
Enthalpy for reactor inlet stream (liquid inlet)


Substances Phase
Ethylene l 2.6012 7539.993516 1.961303 104
Hydrogen l 0.79623 1921.487041 1.529946 103
Carbon monoxide l 1.0565 0 0
Ethane l 1.093 16496.72311 1.803092 104
1-propanal l 324.24 7990.434375 2.590818 106

2.6300 106
Enthalpy for reactor inlet stream (gas inlet)


ninlet H inlet H inlet
Substance
Phase (kmol/h) (kJ/kmol) (kJ/h)
Hydrogen g 1000 2885.4543 2.89 106
2.89 106
Enthalpy for reactor outlet stream

nOutlet H Outlet
Substances Phase H Outlet (kJ/hr)
(kmol/hr) (kJ/kmol)
g 2.3411 2.3411 1.468654 104

Ethylene
Hydrogen g 805.99 805.99 2.909143 106
Carbon monoxide g 1.0565 1.0565 3.874603 103
Ethane g 1.3531 1.3531 1.032354 104
1-propanal g 129.69 129.69 1.250536 106
Dipropylether g 0.97271 0.97271 5.656427 103
water g 0.97271 0.97271 9.508311 103
1-propanol g 192.6 192.6 1.510456 104
4.2188 106
Heat of formation (kJ/kmol) for all component
Component Hf
Ethane -8.8320 104
1-propanal -1.8630 105
CO -1.105 105
Ethylene 5.251 104
Hydrogen 0
1-propanol -2.5460 105
DPE -328820
Water -2.42 105
n 3.28 0
v C H O
3 6
3.28kmol
CHO 1
36
^ ^ ^
H r H f ,i
product
H
reactan t
f ,o
Reaction 1:
^
H r ,1 -2.5460 105 (1.8630 105 1.105 105 )
= -6.8300E104 kJ/kmol
Reaction 2:
^
H r ,2 (2.42 105 - 328820) - 2x (-2.5460105 )
= -6.143410
4
kJ/kmol
Therefore,
^ ^ ^
H r H r ,1 H r ,2
= -6.8300104 +-6.1434 104
= -4.3175106 kJ/kmol
Hence,
^ ^
H Total H r H Outlet H Inlet
= 3.28(-4.3175106 ) + 4.2188 106- (2.6300106+2.89 106)

= -1702864 kJ/h
Hysys =-1943400kJ/h
Error,%= 12.4 %
6.3.9 Balance on cooler
E-101
s15 s17
T=150oC T=70oC
Figure 6.6 Inlet and outlet streams of the third cooler

inlet stream, S15, T=150oC

Substances Phase nInlet H Inlet H Inlet
l
Ethylene 2.34 H7 H7
l
Hydrogen 805.99 H8 H8
l
Carbon monoxide 1.01 H9 H9
l
Ethane 1.35 H 10 H 10
l
1-propanal 129.69 H 11 H 11
l
di-methyl ether 0.97 H 12 H 12
l
water 0.97 H 13 H 13
l
1-propanol 192.60 H 22 H 22
H o u tlet


Substances nOutlet H Outlet
H Outlet (kJ/hr)
Phase (kmol/hr) (kJ/kmol)
l
Ethylene 2.34 H 14 H 14
l
Hydrogen 805.99 H 15 H 15
l
Carbon monoxide 1.06 H 16 H 16
l
Ethane 1.35 H 17 H 17
l
1-propanal 129.69 H 18 H 18
l
di-methyl ether 0.97 H 19 H 19
l
water 0.97 H 20 H 20
l
1-propanol 192.60 H 21 H 21
H outlet
a B c d E
Ethylene (l) 2.4739E+02 -4.4280 4.0936E-02 -1.6970E-04 2.6816E-07
Hydrogen (l) 2.8830E+00 3.6810E-03 -7.7200E-06 6.9200E-09 -2.1300E-12
CO (l) 0 0 0 0 0
Water (l) 7.5400101 6.880010-3 7.604010-6 -3.593010-9 0
1-propanol (l) 1.5876E+02 -6.3500E-01 1.9690E-03 0 0
1-propanal (l) 99.306 0.11573 0 0 0
DPE (l) 0 0 0 0 0
Ethane (l) 4.1780E+00 -4.4270E-03 5.6600E-03 -6.6510E-06 2.4870E-11
T
H 6 Cp( g ) dT
Tref

C dT
T
a bT cT 2

dT 3 eT 4 dT

T
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
inlet stream, S15, T=150oC
Substances Phase
Ethylene g 2.34E+00 6273.349775 1.46796E+04
Hydrogen g 8.06E+02 3609.403126 2.90914E+06
Carbon monoxide g 1.06E+00 3667.395394 3.70407E+03
Ethane g 1.35E+00 7629.543581 1.02999E+04
1-propanal g 1.93E+02 0 0
di-methyl ether g 1.30E+02 5815.122126 5.64067E+03
water g 9.73E-01 4182.5 4.05703E+03
1-propanol g 9.73E-01 0 0
2.947524E+06
Substances Phase
nOutlet H Outlet
H Outlet (kJ/hr)
(kmol/hr) (kJ/kmol)
Ethylene g 2.34E+00 2071.505726 4.85E+03
Hydrogen g 8.06E+02 1298.316117 1.05E+06
Ethane g 1.35E+00 2512.886277 3.39E+03
di-methyl ether g 1.30E+02 5815.122126 1.16E+03
Water g 9.73E-01 4182.5 1.46E+03
1-propanol g 9.73E-01 0 0
1.056130E+06
Hence,
1.056x106 - 2.947524x106
1.89 106 kJ / h
Hysys = 1.51 x 107 kJ/h

Error,% = 113%
6.3.10 Balance on first distillation column
S18
S17
T=-9.273 oC
T=70 oC
Product
T=107.6 oC
T-100
Figure 6.9 Inlet and outlet streams of the first distillation column
References: C2H4(g),H2(g),CO,C3H6O(g),C2H6(g), C3H8O(g), C6H140 at 25 oC and 1 atm

Substances Phase
g
Ethylene 2.34E+00 H1 H1
g
Hydrogen 8.06E+02 H3 H2
g
Carbon monoxide 1.06E+00 H2 H3
g
Ethane 1.35E+00 H4 H4
g
1-propanol 1.93E+02 H 5 H5
g
1-propanal 1.30E+02 H1 H1
g
DPE 9.73E-01 H3 H2
g
water 9.73E-01 H2 H3
H inlet

Outlet stream, S18, T= -9.273oC

Substances Phase nOutlet H Outlet H Outlet
g
Ethylene 2.34E+00 H7 H7
g
Hydrogen 8.06E+02 H8 H8
g
Carbon monoxide 1.06E+00 H9 H9
g
Ethane 1.35E+00 H 10 H 10
g
1-propanal 1.29E+02 H 11 H 11
g 2.03E-13
DPE H 12 H 12
g 7.61E-01
water H 13 H 13
g 3.45E-17
1-propanol H 22 H 22
H outlet
Outlet stream, S product, T=107.6 oC
Substances Phase
nOutlet H Outlet H Outlet

Ethylene l 1.95E-28 H 14 H 14

Hydrogen l 7.47E-43 H 15 H 15

Carbon monoxide l 1.95E-28 H 16 H 16

Ethane l 1.95E-28 H 17 H 17

1-propanal l 7.60E-01 H 18 H 18

DPE l 9.73E-01 H 19 H 19

water l 2.12E-01 H 20 H 20

1-propanol l 1.93E+02 H 21 H 21
H outlet

a B c d e
Ethylene (l) 2.47102 -4.43 4.0910-2 -1.7010-4 2.6810-7
Hydrogen (l) 2.88 3.6810-3 -7.7210-6 6.9210-9 -2.1310-12
CO (l) 0 0 0 0 0
Water (l) 7.54101 6.8810-3 7.6010-6 -3.5910-9 0
1-propanol (l) 1.59102 -6.3510-1 1.9710-3 0 0
1-propanal (l) 99.306 0.12 0 0 0
DPE (l) 0 0 0 0 0
Ethane (l) 4.18 -4.4310-3 5.6610-3 -6.6510-6 2.4910-11
T
H 6 C p( g ) dT
Tref

T
C dT
T
a bT cT 2
dT 3 eT 4 dT
Tref p T ref
T
bT 2 cT 3 dT 4 eT 5
= aT
2 3 4 5
T ref
For component hydrogen and ethane in liquid gas, equation 6.7 were used

Outlet stream, S17, T= 70oC

Substances Phase
Ethylene g 2.34E+00 2071.505726 4.85E+03
Hydrogen g 8.06E+02 1298.316117 1.05E+06
Ethane g 1.35E+00 2512.886277 3.39E+03
1-propanol g 1.93E+02 0 0
DPE g 9.73E-01 5815.122126 1.16E+03
water g 9.73E-01 4182.5 1.46E+03

1.06E+06
Outlet stream, S18, T= -9.273oC
Substances Phase
nOutlet H Outlet
H Outlet (kJ/h)
(kmol/h) (kJ/kmol)
Ethylene g 2.34E+00 -1427.161528 -3.34E+03
Hydrogen g 8.06E+02 -988.471718 -7.97E+05
Carbon monoxide g 1.06E+00 -993.3302281 -1.05E+03

Ethane g 1.35E+00 -1729.255531 -1.93E+02
DPE g 2.03E-13 -206.3491382 -4.19E-11

water g 7.61E-01 -1146.77458 -8.72E+02
1-propanol g 0 0
3.45E-17
-8.011084E+05
Enthalpy for stream Product

Outlet stream, S product, T= 107.6oC

Substances Phase
nOutlet H Outlet H Outlet
Ethylene l 1.95E-28 8073.454727 1.57066E-24
Hydrogen l 7.47E-43 2123.01208 1.58539E-39
Carbon
l 1.95E-28 0 0
monoxide
Ethane l 1.95E-28 2842.69716 5.53025E-25
1-propanal l 7.60E-01 8836.457057 6.72005E+03
DPE l 9.73E-01 0 0
water l 2.12E-01 6268.71544 1.33022E+03
1-propanol l 1.93E+02 10443.45788 2.01137E+06

2.019422E+06
Hence, duty in reboiler,

= 2.019x106 -1.058 x106
= 0.96 x106 kJ/h
Hysys = 32753702.83 kJ/h
Error,% = 96.07%
Whereas for duty in condenser,

= -8.011x105 -1.058 x106
= - 1.859x106 kJ/h
Hysys = 31722522.26 kJ/h

Error,% = 105.86%
The error between manual calculation and Hysys at the condenser and reboiler is big
and not acceptable. This error happens due to the round up number during calculation
and also because of the difference value of heat capacity used in manual calculation
different from hysys.
Table 6.1. Summary of Energy Balance
Duty Calculate Duty Hysys Error

Temperature Inlet Temperature Outlet
Equipment State
(oC) (oC)
(kJ/h) (kJ/h) (%)
Cooler E-100 g 10 100 2.97E+06 3.97E+06 25
Cooler E-101 g 150 70 -2.11E+05 -3.70E+05 113
Cooler E-103 g 27 100 2.26E+06 2.29E+06 13.9

Cooler E-104 g 27 100 6.09E+06 6.23E+06 2.28
Cooler E-105 g 27 100 6.16E+06 6.02E+06 2.39
Reactor 1 g 100 170 -6.20E+06 -4.72E+07 86.9
Reactor 2 g/l 100 150 -1.71E+06 -1.94E+06 12.1
Gas separator V-100 g/l 271 10 -4.90E+07 -6.14E+07 20.1
Compressor K-100 g 13.99 100 2.48E+06 2.47E+06 0.57
Compressor K-101 g 170 271 1.61E+08 2.07E+10 99.2
Condenser g 70 -9.273 -2.16E+03 3.17E+07 105.86
Reboiler l 70 107.6 8.80E+03 3.28E+04 96.07

Conclusion
In order know the total energy and power consumed by the plant proposed, energy
balance calculation need to be done. Energy balance can be presented as energy flows
and transformations in a system. By using the first law of thermodynamics, it states that
energy cannot be created or destroyed, only modified in form.
In engineering, energy balances are used to quantify the energy used or
produced by a system. The internal energy supply to the system is equal to the heat
supply to the system minus the work done by the system. This can be used to build
complex differential equation models to design and analyze real systems.
There are a few assumption made before calculate the energy balance, which
are the system is an open system at steady state, where the system is not chance with
time. Besides, there are no moving parts in the system, thus kinetic energy in the
system is assumed negligible. There is no work shaft in the system, thus work shaft can
be neglected. In addition, all streams enter and leave the process at a single height,
thus the potential energy can be assumed neglected. Since the effect of pressure
difference to the energy balance in the process gives a very small value as compared to
the values contributed by the sensible heat and the heat of formation, heat obtained
from the pressure difference at several point is assumed to be negligible.
The range of error between manual calculation of duty and Hysys are between
0.57% to 105%. These errors occur due to the difference of heat capacities, Cp, used
between Hysys and the manual calculation. Different source of heat capacities were
resulting into different method and formula for enthalpy calculation for each component.
Besides that, while performing the energy balance, we had made round up numbers,
thus causing error in the calculation. The biggest error found in distillation column are
due to negligence of kinetic energy between trays at the reboiler and condenser with
the feed trays. Some calculation ended with the small rounded up no resulting in
difference value with Hysys.
As a conclusion, the total energy required for the operating plant is 2.064E+10
kJ/h , and the power consumed is 5.734E+06 kW. This value will be used to calculate
the total electricity consumption in Chapter 2.
CHAPTER VII
HYSYS SIMULATION
7.0 Introduction
HYSYS is powerful software that was created by Hyprotech for simulation of

chemical plants and oil refineries. It includes tools for estimation of physical properties
and liquid-vapor phase equilibrium, heat and material balances, and simulation of many
types of chemical engineering equipment. In hysys we have to put all the equipment
that we used and after it converges we know that our process is all in good condition
and well operated. Firstly the feed was set condition state at vapor phase with basis
6420 kgmole/h at temperature 100 c and pressure 1000 kpa with mole fraction 0.1
Ethylene, 0.45 CO, 0.45 Hydrogen. First reactor is to produce propanal by the reaction
of ethylene, hydrogen and CO. The operation condition for first reactor is 170 c and
1000 kPa. Propanal stream turn out to be vapor so condenser was installed to reduce
the temperature to create mixture phase to put in gas separator to separate CO. After
that stream 12 that full with propanal enter the second reactor with operation condition
temperature 170 c and pressure 2000 kpa. Hydrogen was discharged in this reactor
because it is hydrogenation process to produce propanol. The propanol stream
separate into two. There are stream 18 which as vapor stream and stream `product as
liquid stream. At the product stream we manage to achieve our target. There is our final
production that we set to get 11517 kg/hr with 99% propanol for production of 1 million
tons per year. However hysys is just a simulation for us to make estimation to observe
how our production operates. To gain the accurate result to built a plan we have to build
really pilot plant and by that way we can manage the accurate result to the real cases.
TABLE OF STREAMS Cont
Stream Temperature(oC) Pressure(Kpa) Component Molar Flow (kgmole/hr)

Ethylene ,C2H4 192.58
Carbon Monoxide, CO 2503.44
Hydrogen, H2 2439.65
propanal, C3H6O 385.16
Stream 7 170 1000 di-propylether, C6H14O 64.19
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 0
Ethylene ,C2H4 0
Carbon Monoxide, CO 0
Hydrogen, H2 0
propanal, C3H6O 0
Stream 8 170 1000 di-propylether, C6H14O 0
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 0
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 64.19
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 64.19
Ethylene ,C2H4 2.57
Hydrogen, H2 0.79
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 1.08
Ethylene ,C2H4 2.57
Hydrogen, H2 0.79
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 1.08
Cont

Ethylene ,C2H4 0
Hydrogen, H2 1000
propanal, C3H6O 0
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 0
Ethylene ,C2H4 0
Hydrogen, H2 1000
propanal, C3H6O 0
Stream 14 116.8 2000 di-propylether, C6H14O 0
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 0
Ethylene ,C2H4 2.31
Hydrogen, H2 806.95
Water, H2O 0.97
n-propanol, C3H8O 191.65
Ethane, C2H6 1.34
Ethylene ,C2H4 0
Hydrogen, H2 0
propanal, C3H6O 0
Water, H2O 0
n-propanol, C3H8O 0
Ethane, C2H6 0
Ethylene ,C2H4 2.31
Hydrogen, H2 806.95
Water, H2O 0.97
Ethane, C2H6 1.3351
Ethylene ,C2H4 2.31
Hydrogen, H2 806.95
Stream 18 -9.38 50 di-propylether, C6H14O 0.97
Water, H2O 0.97
Ethane, C2H6 1.3351
Cont

Ethylene ,C2H4 0
Hydrogen, H2 0
Stream Product 107 150 di-propylether, C6H14O 0.97
Water, H2O 0.20
Ethane, C2H6 0
8.0 References
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A. 22
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Production of 100,00 Metrics Tonnes Per Year of N-Propanol

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Production of 100,00 Metrics Tonnes Per Year of N-Propanol

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1

PROCESS BACKGROUND AND SELECTION

Propanol is a clear, colorless liquid with alcohol odor, it is also miscible in

Table 1.1: Physical Properties of n-propanol

Molecular Formula C3H8O

Molar Mass 60.1 g/mol

IUPAC Name Propan-1-ol

Melting Point Temperature -126.2oC

Boiling Point Temperature 97.2 C

Flash point 15 C; closed cup

Vapour Pressure 27.998 kPa; 25 C

Density 805 kg/m3

Water Solubility completely miscible

Viscosity 2.170 MPa.s

1.1 Uses And Application

Other than that, n-propanol is used in a broad range of applications, including

Figure 1.1 U.S Uses for n-propanol

1.2 Reaction Mechanism

1.2.1 Hydroformylation Reaction :

1.2.2 Hydrogenation Reaction :

Mechanics of ethylene hydroformylation and hydrogenation can be shown as below:

2.0 Side Reaction and By-product

2.0.1 Hydroformylation Reaction.

2.0.2 Hydrogenation Reaction

Journal of Molecular Catalysis A: Chemical 278 (2007) 135144

1.4 Process Background

1.4.1 Method Selection

Table 1.2 : Process Descriptions of Methods in Producing n-propanol.

Carbon monoxide could cause High concentrations of

1.4.2 Catalyst Selection

Table 1.3: Comparisons of Catalysts.

Catalyst Advantages Disadvantages

Cobalt Carbonyl Economic practical choice. Thermally unstable.

Table 1.4: Price Ratio Between the Catalysts.

Metal Price Ratio

Rhodium 570 000

Source from : Rhodium-Catalyzed Hydroformylation.(2000)

1.4.3 Equipment Selection

Table 1.5: Reactor Selection

Types of Reactor Advantages Disadvantages

Fixed Bed Reactor Simple analysis. Poor heat transfer in

Little wear of catalyst and Regeneration or

equipment. replacement of catalyst

1.5 Process Description

Hydroformylation Of Ethylene (Slurry Bed Reactor)

Figure 1.2 First reactor

Hydroformylation, was carried out initially with a dicobalt octacarbonyl, CO2CO8,

Slurry bed reactor is for a gas-liquid contacting accompanied by chemical reaction.

Figure 1.3 Stripper

After condensation, the propanal is sent to a carbon monoxide-stripping column to

HydrogenationOf Aldehyde (Fixed Bed Reactor)

Figure 1.4: Second reactor

Hydrogenation of the aldehyde to the alcohol takes place with a dicobalt

CH 3CH 2CHO H 2 c CH 3CH 2CH 2 HO

Two Tower Purification System

Figure 1.5 :First distillation column

The crude n-propanol (after hydrogenation) is purified in a standard two-tower

Figure 1.6 : Second distillation column

Purification of the n-propanol from the hydrogenation zone is carried out by

Malaysian Petrochemicals Annual Report 2010, ( Source: Business Monitor

2.1 SUPPLY AND DEMAND OF N-PROPANOL

2.1.1 Production Of n-Propanol Worldwide

Source: Kirk-Othmer Encyclopedia of Chemical Technology.Copyrightc, John Wiley