Faculty of

Chemical
Engineering
(FChE)

SKKK 4153 PLANT DESIGN

2014/2015-SEM 1

FINAL REPORT
PROPYLENE PRODUCTION PLANT

LECTURER
ASSOC. PROF. IR. DR. SHARIFAH RAFIDAH WAN ALWI

DESIGN TEAM
EQUINOX

NO. TEAM MEMBERS MATRIC NO

1. EMAD MOHAMMED NOMAN AL-DHUBHANI AA103001
2. MUHAMMAD FAIRIS BIN HADIPORNAMA A11KK0022
3. KELVIN RAWING SEBASTIAN A11KK0065
4. NUR FADZLYANA BINTI HAMDAN A11KK0035
5. MIMI KHAIRIAH BINTI AWANG A11KK0169

1
 TABLE OF CONTENTS

Page
TABLE OF CONTENTS 2

CHAPTER 1 INTRODUCTION
1.1 Background of Propylene 5
1.2 Uses of Propylene 6
1.3 Propylene Manufacturing 8
1.4 Market Survey 9
1.5 1.4.1 Introduction 9
1.4.2 Production of Propylene 9
1.4.3 Propylene Consumption 11
1.4.4 Outlook for Production of Propylene in Malaysia 12
1.4.5 Market Prices of Polypropylene 12
1.5 Raw Materials 14
1.5.1 Source of Raw Materials 14
1.5.2 Raw Material Specifications 14

CHAPTER 2 PROCESS SYNTHESIS STEP

2.1 Step 1-Eliminate Differences in Molecular Type 15
2.2 Step 2- Distribute the Chemicals 24
2.2.1 Basic Material Balances 24
2.3 Step 3- Eliminate Differences in Compositions 26
2.4 Step 4 –Eliminate Differences in Temperature, Pressure and Phase 28
2.5 Step 5- Task Integration 30

CHAPTER 3 MATERIAL,ENERGY BALANCES AND PROCESS SIMULATION

3.1 Material Balance 33
3.1.1 Overall Mass Balances 33
3.1.2 Mass Balances for Separation Unit 1 35
3.1.3 Mass Balance for Mixer 36

2
 3.1.4 Mass Balance for Reactor 37
3.1.5 Mass Balance for Separation Unit 2 38
3.1.6 Mass Balance For Separation Unit 3 39
3.1.7 Mass Balance For Separation Unit 4 40
3.2 Energy Balances 40
3.3 Simulation Result from ASPEN HYSYS 60
3.3.1 Material Balance 60
3.3.2 Energy Balances 60
3.4 Percentage Differences between Manual Calculation and HYSYS 61
3.4.1 Mass Balances 61
3.4.2 Energy Balances 61

CHAPTER 4: HEAT INTEGRATION

4.1 Process Energy Integration 62
4.2 Algorithm Table 63
4.3 Heat Exchanger Network 64
4.4 Process Flow Diagram Heat Exchanger Network 64

CHAPTER 5: PROCESS OPTIMIZATION 66

CHAPTER 6: EQUIPMENT SIZING AND COSTING

6.1 Introduction 69
6.2 Reactor 69
6.2.1 Sizing of reactor 69
6.2.2 Costing of reactor 70
6.3 Pump 70
6.3.1 Sizing of pump 70
6.3.2 Costing of pump 70
6.4 Distillation columns (S1) 70
6.4.1 Sizing and costing of the main vessel 70
6.4.2 Sizing and costing of the reflux drum 71
6.4.3 Sizing and costing of the condenser 72
6.4.4 Sizing and costing of the re-boiler 73
6.5 Compressor 74
3
 6.5.1 Sizing of compressor 74
6.5.2 Costing of compressor 74
6.6 Heat exchanger (HE2) 74
6.6.1 Sizing of Heat exchanger (HE 2) 74
6.6.2 Costing of Heat Exchanger (HE2) 76

CHAPTER 7: TOTAL CAPITAL INVESTMENTS 77

CONCLUSIONS 79

APPENDICES A
APPENDICES B
APPENDICES C
APPENDICES D
APPENDICES E

4
 CHAPTER 1

INTRODUCTION

1.1 Background of Propylene

Propylene, also called propene is generally described as a volatile and a colorless gas
at room temperature. It has same empirical formula with cyclopropane but different ways of
atom connected. Propylene is categorized as a alkene hydrocarbon compound with a
molecular formula of C3H6. The presences of the double bond make it slightly lower boiling
point than propane and thus more volatile. The existences of natural propylene are in the
environment from sources such as vegetation and combustion such as fires, motor vehicle
exhaust, and tobacco smoke. Propylene is not expected to persist in the environment. Since
propylene is a gas, the exposure of propylene into the air is expected to be lower amount
when released into the environment. Because of its relatively short half-life in the atmosphere
and typically low environmental concentrations, propylene’s contribution to potential global
warming is considered minor and its ozone depletion potential is negligible.

5
 Figure 1: Structural formula of Propylene.

Propylene reacts violently with oxide of nitrogen and also a number of other
substances and condition. Essentially all of the propylene produced for chemical purposes is
consumed as a chemical intermediate in other chemical manufacturing processes. This
hydrocarbon is widely used in the manufacture of cumene, resins, fibres, elastomers and other
chemicals which enable the manufacture of many chemicals and plastics. In addition to its
use as a chemical intermediate, propylene is produced and consumed in refinery operations
for the production of gasoline components.

1.2 Uses of Propylene

Propylene is a major product of the petrochemical industry. It is one of the highest

volume chemicals produced globally. Propylene is primarily used as an intermediate for the
production of other chemical raw materials that are subsequently used to manufacture a large
variety of substances and products. Manufacture of polypropylene, a widely used plastic,
consumes more than half of the world’s production of propylene. Propylene is also used in
the manufacture of acrylonitrile, oxo process chemicals, cumene, isopropanol, polygas
chemicals, and propylene oxide. Table 1.1 below highlights several of the main applications
of propylene and its derivatives.

6
 Table 1.1: Selected Propylene Application

Product Application Application Description

Polypropylene  Polypropylene is used to make many well-known plastic

products.
 Polypropylene resins can be injection molded and extruded
(into fibers, film, and sheets) to make a variety of products.
 Polypropylene may also be blow-molded or thermoformed,
but these processes are less often used.
 Polypropylene is extremely corrosion resistant, lightweight,
flexible, and formed or welded.

Propylene Oxide  Used mainly as a chemical intermediate in the production of

polyurethane polyols and propylene glycols.
 Used in the manufacture of propylene glycol, which helps to
make antifreeze, resins for reinforced plastics,
pharmaceuticals, packaging materials, dyes, and hydraulic
fluids, and humectants for foods, drugs, cosmetics, and pet
foods.
 Derivatives of propylene oxide include polyether polyols;
propylene glycol; di- and tripropylene glycol; poly
(propylene glycol)s; surfactants; glycol ethers; and
isopropanolamines.

Isopropanol  A variety of solvent applications, such as in printing inks,

surface coatings, and as a solvent for resins, shellacs, and
gums.
 As a component of personal care products, such as after-
shaves; and as an antiseptic and disinfectant, such as rubbing
alcohol.
 Used in the production of acetone, methyl isobutyl ketone
(MIBK), iso-propylamines and isopropyl acetate.

Cumene  Alkylation of benzene with propylene yields cumene.

 Consuming in phenol production for the manufacture
phenolic resins, caprolactam and bisphenol A.

Ethylene-Propylene  About half of the worldwide production of EP elastomer

Elastomers goes into the manufacture of automobile body and chassis
parts, hoses, weatherstripping, and tires.
 Also used to make thermoplastic polyolefin elastomers,
polymer modifiers, and other products used in automobile
components beside used in single-ply roofing.

7
 Oxo Process Chemicals  Propylene is used to manufacture Isobutyraldehyde, which is
converted to isobutanol solvent for surface coatings.
 Propylene is also used to make n-Butyraldehyde, which is
converted to n-butanol or 2-EH. n-Butanol is a solvent for
lacquers and coatings, and is an intermediate for several
chemicals.

Polygas Chemicals  Refinery production of polymer gasoline also yields nonene,

(nonene, dodecene, dodecene and heptene and propylene is consumed to yield
heptenes) these polygas chemicals.
 Nonene is used in nonylphenol and isodecyl alcohol that act
as an intermediate for surfactants, lubricating oil additives,
and phosphite antioxidants.
 Heptenes are consumed to make isooctyl alcohol, which is
used in the manufacture of another phthalate ester.

1.3 Propylene Manufacturing

Lotte Chemical Titan Holding Sdn. Bhd. is one of the manufacturer and supplier of
propylene, located at Pasir Gudang, Johor Bahru. This company will be the benchmark of
Equinox Team to design a plant that can produce 100,000 lb/hr of propylene. The team will
propose a variety of production reactions of propylene and there are several production
processes such as catalytic dehydrogenation of propane, reformation of olefins reaction
(metathesis reaction), and the conversion of methanol to propylene. The most sustainable and
economically reaction processes will be chosen for the plant design. This includes the
comparison between the cost of raw materials, safety, environmental impacts, percentage
yield of conversion, energy consumption, and other factors that might affect the reaction
process.

8
1.4 Market Survey

1.4.1 Introduction

Market survey or market outlook will cover a review on the production and
consumption of propylene in addition to that there will be another section to discuss the
prices of propylene and its raw materials.

1.4.2 Production of Propylene

Propene production increased in (Europe and North America only) from 2000 to
2008, it has been increasing also in East Asia, most notably Singapore and China. Total world
production of propene is currently about half that of ethylene. About 56% of the worldwide
production of propylene is obtained as a co-product of ethylene manufacture, and about 33%
is produced as a by-product of petroleum refining. About 7% of propylene produced
worldwide is on-purpose product from the dehydrogenation of propane and metathesis of
ethylene and butylenes; the remainder is from selected gas streams from coal-to-oil processes
and from deep catalytic cracking of vacuum gas oil (VGO). The supply of propylene remains
highly dependent on the health of the ethylene industry as well as on refinery plant
economics.

In 2010, production of polypropylene represented 65% of total world propylene

consumption, ranging from 53% in North America to more than 90% in Africa and the
Middle East.

Table 1.2: Annual Production of Propene (Propylene)

World 80.0 million tones

Europe 14.3 million tons
US 14.3 million tones

Figure 1.1 below shows how the production of propylene increased from 11 million
tons in 1994 to 16 million tons in 2007 but it had dropped since that time to 14.3 million tons
in 2013.

9
Figure 1.1: Wastern European Propylene Capacity, Production and Consumption 1994-2013

Top world companies are leading the production of propylene with LyondellBasell,
Netherlands on top of propylene producing companies by 2009. The top propylene-producing
companies are listed as bellow:

Propylene Top Producers

Relliance Industries, India Formosa Plastics Group, Taiwan
PetroChina, Bejing, China SABIC, KSA
ExxonMobil Chemical, USA Ineos Group, England
Total SA, France Sinopec, China
LyondellBasel Industries, Netherlands

3.8
4
4
4
5
5.8
6.1
9
15.8

Figure 1.2: Propylene top producers

10
1.4.3 Propylene Consumption

After experiencing zero growth or declines in 2008 and 2009, global propylene
consumption grew at a rate of almost 7.5% in 2010, led by Asia at 11% year-on-year. The
economic recession of 2008/2009 reflected both a reduction in pull-through demand for
polypropylene, as well as a supply-chain inventory rundown, reminiscent of the early 1980s
downturn. World petrochemical industries have historically witnessed very few upheavals
that combined the effects of both energy volatility and depressed downstream demand.

The fifteen largest worldwide producers of propylene accounted for almost 51% of
world capacity as of 2010, representing about the same level of concentration as five years
ago. The most significant changes in the last two years have been Sinopec taking over the top
spot, a position long occupied by ExxonMobil, and PetroChina jumping from the seventh
spot to number four.

World consumption of propylene is forecast to grow slightly better than global gross
domestic product (GDP) rates over the next five years. Average growth will be 5% per year,
higher than GDP in general and higher than ethylene specifically, with growth for
polypropylene being much better than that for polyethylene. Growth will be led by the
Middle East, Asia, Central and Eastern Europe, and South America at 12.5%, 6.5%, 5%, and
4.5% per year, respectively. Asia is a mixed bag of growth rates with China and India at 8–
10% annually and the mature economies of Japan, the Republic of Korea, and Taiwan at 1–
2% per year. Near-term growth will be relatively slow in the mature economies of North
America and Western Europe.

11
 Mexico, 1 Oceania, 1 other western other asia, 3 canada, 0.5
europe, 2
Brazil, 3
France, 3
India, 4 USA, 20

Taiwan, 5

Benelux, 6
China, 19
Germany, 6

Japan`, 7
Middle Rep. of
east , 7 korea ,
8

Figure 1.3: World Consumption of Propylene in 2010

1.4.4 Outlook for Production of Propylene in Malaysia

Malaysia’s petrochemical sector has contributed significantly to the development of

local downstream plastic processing activities. Malaysia is one of the largest plastics
producers in Asia, providing a steady supply of feedstock materials for the plastic processing
industry such as propylene.

Table 1.3: Production, Import, Export and Consumption of PP in Malaysia

Product Unit: KTPA 2007 2008 2009 2010 change

Propylene Production 839 870 867 808 0.3%
Import 33 40 25 8 0%
Export 78 97 95 50 -2%
Consumption 765 811 797 744 -5%

12
1.4.5 Market Prices of Polypropylene

Polypropylene prices are on the rise since the last decade and it is expected to
continue rising as the demand increases for the chemical material, Capacity and Prices for
Polypropylene - End-Use Sectors in Asia-Pacific to Drive Growth" 2014 market research
report says worldwide polypropylene capacity increased at a Compound Annual Growth Rate
(CAGR) of 5.2% from 2003, reaching 65 million tons per year (MMTY) in 2013, and is
expected to continue rising to 86 MMTY by 2018, at a slightly higher CAGR of 5.8%. It
forecasts China and Russia to be the leading contributors to future polypropylene capacity
increases, and will account for a combined 45% of global additions over the next five years.
As Malaysia is part of the global market it is normal for prices in Malaysia to be affected by
the global prices, following are prices of PP and its raw material (propane, ethylene, butene
and methanol) as achieved from ICIS.com.

Table 1.4: Propylene and raw products prices

Price
Product
RM/Ib RM/Kg
Propylene 1.962 4.326
Propane 0.79 1.742
Ethylene 2.158 4.758
Butene 1.118 2.465
Methanol 1.635 3.609

13
1.5 Raw Materials

1.5.1 Source of Raw Materials

The raw material that is utilized in this process is liquefied petroleum gas (LPG)
propane. The term LPG actually encompasses more than one variety of gaseous fuel. There
are a number of hydrocarbon gases that fall into the classification of “LPG”. Their common
distinguishing characteristic is that they can be compressed into liquid at relatively low
pressures. LPG is stored under pressure, as a liquid, in a gas bottle. It turns back into gas
vapor when you release some of the pressure in the gas bottle by turning on your appliance.
Almost all of the uses for LPG involve the use of the gas vapor, not the liquefied gas.

The gases that fall under the “LPG” label, including Propane, Butane, Propylene,
Butadiene, Butylene and Isobutylene, as well as mixtures of these gases. The two most
common are Propane and Butane.

The main supplier of LPG used in this process is Kleenheat Gas which is part of
Wesfarmers Chemicals, Energy and Fertilizers, one of eight divisions of Wesfarmers
Limited, with origins dating back to 1914.

They have a long history in the Australian gas industry with over 55 years of
experience retailing and distributing Liquefied Petroleum Gas (LPG), over a decade of
experience distributing Liquefied Natural Gas (LNG) and advancing technology through their
brand EVOL LNG, and most recently retailing natural gas in Western Australia.

1.5.2 Raw Material Specifications

Table 1.5: LPG propane supplied by Kleenheat Gas Australia

LPG specification
CAS Number 74-98-6

Component Mole percentage (%)

Propane 80

Butane 18

Butanes ,pentanes ,butadiene and heavier 2

14
 CHAPTER 2

PROCESS SYNTHESIS STEP

2.0 SYNTHESIS STEPS

Process synthesis involves the selection of processing operations to convert raw

materials to products, given that the states of the raw material and product streams are
specified. The most widely accepted approach for process synthesis is introduced by Rudd,
Powers, and Siirola (1973) in a book entitled Process Synthesis. There are 5 key synthesis
steps which are:

1. Eliminate differences in molecular types

2. Distribute the chemicals by matching sources and sinks
3. Eliminate differences in composition
4. Eliminate differences in temperature, pressure, and phase
5. Task integration; combination of operations into unit processes and decide between
continuous and batch processing

2.1 Step 1 – Eliminate Differences in Molecular Type

A. Propylene from Propane via Dehydrogenation

Dehydrogenation is an endothermic equilibrium reaction; it is carried out in

the presence of heavy-metal catalyst (chromium). The following equation shows the
propane dehydrogenation reaction:

Propane Dehydrogenation Reaction

15
About 86 wt% of propane is converted to propylene. To mitigate cracking reactions,
dehydrogenation reaction in this technology occurs in conditions such as temperature
ranges between 580 and 650 °C, and pressures slightly below atmospheric. For further
information, Table 2.1 shows the thermophysical property data for this process.

Figure 2.1: Commercial process flow diagram (Dehydrogenation)

Figure 2.2: Detailed process flow diagram (Dehydrogenation)

16
Process Description of Propylene Dehydrogenation

The propane dehydrogenation process is used to supply polymer-grade

propylene from propane to meet the growing propylene market, independent of a
steam cracker or Fluid Catalytic Cracking (FCC) unit. It provides a dedicated, reliable
source of propylene to give more control over propylene feedstock costs.

From Figure 2.2, the process flow diagram consists of a reactor section,
product recovery section and catalyst regeneration section. Hydrocarbon feed is
mixed with hydrogen-rich recycle gas and is introduced into the heater to be heated
into the desired temperature (over 540 °C) and then enter the reactors to be converted
at high mono-olefin selectivity. Several interstage heaters are used to maintain the
conversion through supplying heat continuously since the reaction is endothermic.
Catalyst activity is maintained by continuous catalyst regenerator (CCR) or shutting
down reactors one by one and regenerating the reactor by the regeneration air, the
continuous catalyst regenerator is where the catalyst is continuously withdrawn from
the reactor, then regenerated, and fed back to the reactor bed.

Reactor effluent is compressed, dried and sent to a cryogenic separator where

net hydrogen is recovered. The olefin product is sent to a selective hydrogenation
process where dienes and acetylenes are removed. The propylene stream goes to a de-
ethanizer where light-ends are removed prior to the propane-propylene splitter.
Unconverted feedstock is recycled back to the depropanizer where it combines with
fresh feed before being sent back to the reactor section.

Table 2.1: Physical And Chemical Properties Of Reactant And Product For
Dehydrogenation Reaction

REACTION PROPANE  PROPYLENE HYDROGEN

Properties

Molecular formula C3H8 C3H6 H2

Molar mass 44.10 g mol−1 42.08 g mol−1 2.016 g mol-1

17
Appearance Colourless gas Colourless gas Colourless gas

Odor Odourless Gassy/ aromatic

Density 2.0098 mg mL−1 (at 0 1.81 kg/m3, gas (1.013 0.08988 g/L (at 0 °C,
°C, 101.3 kPa) bar, 15 °C) 101.325 kPa)
3
613.9 kg/m , liquid

Melting point −187.7 °C; −305.8 °F; − ,185.2 °C (−301.4 °F; 13.99 K (−259.16 °C,
85.5 K 88.0 K) −434.49 °F)

Boiling point −42.25 to −42.04 °C; − 47.6 °C (−54 °F; 20.271 K (−252.879 °C,
−44.05 to −43.67 °F; 226 K) −423.182 °F)
230.90 to 231.11 K

Solubility in water 40 mg L−1 (at 0 °C) 0.61 g/m3

Vapor pressure 853.16 kPa (at 21.1 °C) 144.06 psia 100kPa (at 20 ºC)

Thermochemistry

Std enthalpy of −105.2–−104.2 kJ mol−1 +20.41 kJ/mol 0

formation ΔfHo298

Std enthalpy of −2.2197–−2.2187 MJ -2058.4 kJ/mol -285.84 kJ/mol

−1
combustion ΔcH o
298 mol

To screen out whether this reaction will bring profit or not, the gross profit is calculated as
shown below:

C3H8  C3H6 + H2

C3H8 C3H6 H2

lbmol 1 1 1
Molecular weight 44.09 42.08 2.016
lb 44.09 42.08 2.016
lb/lb of propylene 1.0478 1 0.048
RM/lb 0.79 1.96 11.30

18
Gross profit for reaction path 1 = 1.96(1) + 11.30(0.048) – 1.0478(0.79) = RM 1.67 /lb
propylene

B. Propylene from Ethylene and Butenes via Metathesis

Metathesis is a general term for a reversible reaction between two olefins, in

which the double bonds are broken and then reformed to form new olefin products. In
order to produce propylene by metathesis, a molecule of 2-butene and a molecule of
ethylene are combined to form two molecules of propylene. Some of the
thermophysical property data is shown on table 2.

Metathesis Reaction

Figure 2.3: Commercial process flow diagram (Metathesis)

19
 Figure 2.4: Detailed process flow diagram (Metathesis)

Process Description of Metathesis of Ethylene and Butene

Propylene is formed by the metathesis of ethylene and butene-2, and butene-1

is isomerised to butene-2 as butene-2 is consumed in the metathesis reaction. In
addition to the main reactions, numerous side reactions between olefins also occur.
Ethylene feed can be polymer grade ethylene or a dilute ethylene stream. Any
saturated hydrocarbons, such as ethane and methane, do not react.

From Figure 2.4, fresh C4s (plus C4 recycle) are mixed with ethylene feed
(plus recycle ethylene) and sent through a guard bed to remove trace impurities from
the mixed feed. The feed is heated prior to entering the vapour phase fixed-bed
metathesis reactor where the equilibrium reaction takes place. The reactor is
regenerated in-situ on a regular basis. The catalyst promotes the reaction of ethylene
and butene-2 to form propylene and simultaneously isomerises butene- 1 to butene-2.
The per-pass conversion of butylene is greater than 60 per cent, with overall
selectivity to propylene exceeding 90 per cent.

The product from the metathesis reactor is primarily propylene and unreacted
feed. Reactor effluent is sent to the ethylene recovery tower where the unreacted
ethylene is recovered and recycled to the reactor. The C2 tower bottom is processed in
the C3 tower to produce propylene product and a C4 recycle stream. Purge streams
containing non-reactive light material, C4s and heavier are also produced. Ultra-high

20
 purity propylene exceeding polymer grade specification is produced without a
propylene fractionation system, since the only source of propane is that contained in
the C4 and ethylene feeds.

Table 2.2: Physical And Chemical Properties Of Reactant And Product For Metathesis
Reaction

REACTION ETHYLENE BUTENE  PROPYLENE

Properties

Molecular formula C2H4 C4H8 C3H6

Molar mass 28.05 g/mol 56.10 g/mol 42.08 g mol−1

Appearance Colorless gas colorless Colorless gas

Odor Odorless odorless Gassy/ aromatic

Density 1.178 kg/m3 at 15 °C, gas 0.62 g/cm3 1.81 kg/m3, gas (1.013 bar,
15 °C)
613.9 kg/m3, liquid

Melting point −169.2 °C (104.0 K, - −185.3 °C (−301.5 °F; − ,185.2 °C (−301.4 °F;
272.6 °F) 87.8 K) 88.0 K)

Boiling point −103.7 °C (169.5 K, - −6.47 °C (20.35 °F; − 47.6 °C (−54 °F; 226 K)
154.7 °F) 266.68

Solubility in water 3.5 mg/100 mL (17 °C)[ 0.61 g/m3

Thermochemistry

Std enthalpy of 52.28 kJ mol−1 1.17 kJ/mol +20.41 kJ/mol

formation ΔfHo298

Std enthalpy of -1410.99 kJ mol−1 -2718.6 kJ/mol -2058.4 kJ/mol

combustion ΔcH o
298

21
To screen out whether this reaction will bring profit or not and whether it is better from
reaction A, the gross profit is calculated as shown below:

C2H4 + C4H8  2C3H6

C2H4 C4H8 C3H6

lbmol 1 1 2
Molecular weight 28.05 56.10 42.08
lb 28.05 56.10 84.16
lb/lb of propylene 0.33 0.667 1
RM/lb 2.16 1.18 1.96

Gross profit for reaction path 2 = 1.96(1) – 2.16(0.33) – 1.18(0.667) = RM 0.46 /lb
propylene

22
 Table 2.3: Summary of Review and Screening of Alternative Processes
Metathesis of from Ethylene
Dehydrogenation of propane
& Butenes
C3H8  C3H6 + H2
C2H4 + C4H8  2C3H6
Gross Profit
RM 1.67 / lb propylene RM 0.46/lb propylene
(Appendix 1)

Type of process Continuous process Continuous process

Butane and ethylene is

Safety Propane is flammable. flammable, and ethylene also
may cause dizziness

By-product Hydrogen No by-product

Temperature: 560 – 650 ºC

Operating Temperature: 90-100ºC
Pressure : slightly below atmospheric
condition Pressure: 100 – 110 bar
pressure

Conversion 86% percent of conversion 90% percent of conversion

Flammability Flammable Flammable

From the table above, it shows that the dehydrogenation of propane reaction is a better
process compared to the metathesis reaction.

23
2.2 Step 2 – Distribute the Chemicals

2.2.1 Basic Material Balance

Reactor
T = 500 OC
m1C3H8 F lb/hr C3H8 P = 1 bar
m2C3H6
gfrgfr
m3H2

R lb/hr C3H8

Overall Reaction Equation :

C3H8 C3H6 + H2

Basis : 100000 lb/hr of propylene (C3H3)

86% of conversion

C3H8 C3H6 H2
stoichiometry 1 1 1
Mass flowrate (lb/hr) m1 m2=100,000.00 m3

MW (lb/lbmol) 44.10 42.08 2.01

n, (lbmole/hr) 2376.43 2376.43 2376.43

Number of moles of propylene formed

= (100,000 lb/hr)/42.08
= 2376.43 lbmole/hr C3H6

Assume 100% conversion, the mass flow rate of feed, m1 = 2376.43 x 44.1
= 104800.56 lb/hr

24
for 86% conversion, the mass flow rate of recycle, R = (1-0.86)/0.86 x 104800.56
R = 17060.53 lb/hr
Mass flowrate of H2 , m3
= (no. of mole) X (molecular weight)
= (2376.43) x (2.01)
= 4776.62 lb/hr

Mass flowrate feed to the reactor, F = m1 + R

= 104800.56 + 17060.53 = 121861.09lb/h

25
2.3 Step 3 – Eliminate Differences in Composition

Pt-Sn C3H6
0.99 C3H8 H2 H2 C3H8 C3H6
0.009 C4H10 C3H8 -137.1˚c 40˚C
0.001 C5H12 Reactor C3H6
600˚C, 1.0 bar C4H8 33˚C
47°C
C4H10
C5H12
10 bar
17.5 bar
S2
52.°C
S1 15 bar S3 S4 15 bar
LPG: -137.1°C 42˚C
C3H8
C4H10
C5H12 -137.1˚C
C3H8
C3H6
108.4˚C
110.7°C C4H8
C4H10 C4H8 42˚C
C4H10
C5H12 C5H12 C4H10 C3H8
C5H12

Figure 2.5: Flowsheet with separation units of propylene production process

In order to enable all chemicals involved to be supplied to their sinks, separation operations are
needed. Figure 2.5 shows the separation units that are needed in a propylene production process. Since the raw
material using in this process is from LPG that consists 80% propane, 18% butane and 2% pentane, so S1 as a
separating unit is needed to separate propane from butane and pentane. However, the separation is not perfect.
There will still have some butane and pentane that will be distillate but in a small proportion. As referred to
table 2.4, S1 will be operated at 15bar. The bubble point at distillate product is 47˚C and the dew point of
mixtures at the bottom product is 110.7˚C.

When the separation between propane, butane and pentane is done, propane as a reactant will enter the
reactor which will be operate at 600˚C and 1 bar. These pressure and temperature is selected because the
dehydrogenation process of propylene only will occur at these conditions.

After the reaction occurs, there have a lot of products produced. In order to separate the products, 3
separation units will be used. The first product that will be separated is hydrogen gas. The reason is, hydrogen
gas has a low value of critical pressure and it will be difficult to separate the other products if the hydrogen
26
maintain in the product mixtures. S2 will be used as separation unit that will be operated at pressure 10 bar
and temperature -137.1 at dew point of vapor of the product mixture.

Next, after separate hydrogen gas, we will separate propane and propene from the side product. From
Table 2.4 at 1 atm, the boiling point of C3 is very low, - 48˚C, and hence if C3 were recovered at 1 atm as the
distillate of the S3, very costly refrigeration would be necessary to condense the reflux stream. At 18 bar , the
bubble point of propane and propylene mixture is at 40˚C and much less cost refrigeration could be used. The
bottom products which are consists butane, butene and pentane has a dew point 108.4˚C at 17.5 bar.

After separation unit S3 is inserted into the process design, S4 follows naturally. The distillate from S3
is separated into nearly pure species in the S4, which is specified at 15 bar. Under these conditions, the
distillate (nearly pure propylene) boils at 33˚C and can be condensed with inexpensive cooling water, which is
available at 25˚C. However, S4 need special separation unit due to small difference of boiling point between
propane and propylene.

Table 2.4: Boiling points and critical constant

Normal Critical constant

boiling Boiling point (˚C)
Chemical
point
(1atm, ˚C) 15 bar 17.5 bar 20 bar Tc (˚C) PC (bar)
H2 -252.78 - - - -240.01 12.96
C3H8 -42.11 41.00 45.00 53.55 96.74 42.51
C3H6 -47.62 33.00 35.85 42.65 91.06 45.55

27
2.4 Step 4 – Eliminate Differences in Temperature, Pressure, and Phase

Figure 2.6: Flowsheet with temperature-, pressure-, and phase-change operations in the propylene production process.

28
 Figure 2.6 shows the changes of the state of chemicals. Since the original state of the raw
material (LPG) is at 20°C and 18 bar, its temperature is raised to 52°C at 15 bar. The LPG is then
introduced into a separation column (S1) at 15 bar with 99% conversion that separates the
propane gas from other LPG products. Here, only 99% of LPG is converted to propane gas
where another 1% is butane gas and pentane gas.

The process begins by mixing the upper products from S1 (propane gas, butane gas and
pentane gas) with a stream of recycle propane gas at 47°C and 15 bar. The mixing of upper
products from S1 and recycle propane undergoes the following operations:

1. The product mixture is preheated before it is introduced to the reactor. The reaction
occurs at around 600oC and 1 bar.
2. The products mixture is then cooled to its dew point -137.1oC at 10 bar.
3. Then, the product mixture is introduced into a condenser (S2) that separates the hydrogen
gas from other liquid products.

In addition, the liquid mixture that condensed at -137.1oC at 10 bar from the condenser is
operated upon as follows:

1. Its pressure is increased to 17.5 bar.

2. The temperature is then raised to a liquid at its bubble point, 42oC at 17.5 bar.
3. Then, the liquid mixture is introduced into a separation column (S3) that separates the
propane gas and propylene gas from other liquid products.

Next, the upper products (propane gas and propylene gas) from separation column (S3) are
then entered into separation column (S4) at 40oC. The propylene gas with a boiling point of 33oC
at 15 bar is come out as an upper product from separation column (S4).

Finally, the propane liquid from the recycle stream (at 42oC and 15 bar) undergoes the
operation where its temperature is raised to the mixing temperature at 47 oC at 15 bar.

29
2.5 Step 5 – Task Integration

Figure 2.7 shows task integration for the propylene production process. At this stage in process
synthesis, it is common to make the most obvious combinations of operations, leaving many
possibilities to be considered when the flowsheet is sufficiently promising to undertake the
preparation of a base case design. Below are the descriptions of unit process shown in Figure 2.7:

1. Heat exchanger
Heat exchanger is needed to increase or decrease the temperature of the stream. A heat
exchanger is a piece of equipment built for efficient heat transfer from one medium to
another. The media may be separated by a solid wall to prevent mixing or they may be in
direct contact.

2. Depropanizer
A propane rich liquefied petroleum gas (LPG) feedstock is sent to a depropanizer to
reject butanes and heavier hydrocarbons.

3. Furnace
Since the outlet temperature from the mixer is 47˚C and we need to increase the
temperature to 600˚C, the furnace is used to heat up the stream. This follows heuristics 26
which explained near-optimal minimum temperature approaches in heat exchangers
depend on the temperature level. For 250 to 350˚F, the stream must be heat up in a
furnace for flue gas temperature above inlet process fluid temperature. An industrial
furnace or direct fired heater is equipment used to provide heat for a process or can serve
as reactor which provides heats of reaction. Furnace designs vary as to its function,
heating duty, type of fuel and method of introducing combustion air.

4. Oleflex Reactor
The UOP Oleflex process is a catalytic dehydrogenation technology for the production of
light olefins from their corresponding paraffins. One specific application of this
technology produces propylene from propane. The Olexflex process uses a platinum
catalyst to promote the dehydrogenation reaction

30
5. Pump
Since the pressure change operation involves a liquid, it is accomplished by a pump,
which requires only 66 Bhp, assuming an 80% efficiency. The enthalpy change in the
pump is very small and the temperature does not change by more than 1˚C

6. Distillation Column
To separate the mixture of C3 and butane, butane and pentane, distillation column is
selected as the best separation unit. Distillation is based on the fact that the vapour of a
boiling mixture will be richer in the components that have lower boiling points.
Therefore, when this vapour is cooled and condensed, the condensate will contain more
volatile components. At the same time, the original mixture will contain more of the less
volatile material.

7. Propane-Propylene Splitter
C3 splitters are frequently designed with vapor-recompression heat pumps when
sufficient low-energy heat sources are not available. The heat of vaporization of
propylene and propane at 100psia are nearly identical. The only energy needed for a C 3
splitter heat pump is the compressor duty, which is typically only 11-12% of the total
reboiler duty. Therefore, the energy savings are significant. In addition, C 3 splitter heat
pump system operates at much lower pressure than conventional columns without heat
pumping. The high-pressure compressor discharge stream is the same as the conventional
tower’s top pressure.

31
P-P Splitter

Figure 2.7: Flowsheet task integration for the propylene production process

32
 CHAPTER 3

MATERIAL AND ENERGY BALANCES AND PROCESS SIMULATION

3.1 MATERIAL BALANCES

3.1.1 Overall Mass Balance

Reactor
T = 500 OC
m1C3H8 F lb/hr C3H8 P = 1 bar
m2C3H6
gfrgfr
m3H2

R lb/hr C3H8

Overall Reaction Equation :

C3H8 C3H6 + H2

Basis : 100000 lb/hr of propylene (C3H3)

86% of conversion

33
 C3H8 C3H6 H2
stoichiometry 1 1 1
Mass flowrate (lb/hr) m1 m2=100,000.00 m3

MW (lb/lbmol) 44.10 42.08 2.01

n, (lbmole/hr) 2376.43 2376.43 2376.43

34
3.1.2 Mass Balance for Separation Unit 1
2
D1 lb/hr
0.990 C3H8

0.009 C4H10

0.001 C5H12
1
F1 lb/hr S-1
0.80 C3H8

0.18 C4H10

0.02 C5H12
3
B1 lb/hr
0.90 C4H10

0.10 C5H12

Stream 1 Stream 2 Stream 3

No. Component Mass Mass Mass

Mole Mole Flowrate, Mole
Flowrate, Flowrate,
Fraction Fraction (lb/hr) Fraction
(lb/hr) (lb/hr)

1 Propane 0.80 104800.56 0.990 104800.56 0 0

2 Butane 0.18 31076.58 0.009 1116.11 0.9 29960.47
3 Pentane 0.02 4286.49 0.001 346.38 0.1 3940.11

35
3.1.3 Mass Balance for Mixer

D1 = 106263.1 lb/hr F = 123323.6 lb/hr

M-1
3 4 a1 C3H8
0.990 C3H8
a2 C4H10
0.009 C4H10

10
a3 C5H12
0.001 C5H12
R = 17060.53 lb/hr
1.0 C3H8

Stream 3 Stream 4 Stream 10

No. Component Mass Mass Mass

Mole Mole Flowrate, Mole
Flowrate, Flowrate,
Fraction Fraction (lb/hr) Fraction
(lb/hr) (lb/hr)

1 Propane 0.990 104800.56 0.991 121861.09 1.0 17060.53

2 Butane 0.009 1116.11 0.007 1116.11 0 0
3 Pentane 0.001 346.38 0.002 346.38 0 0

36
 3.1.4 Mass Balance for Reactor

121861.09 lb/hr C3H8

4 5 123299.61 lb/hr
R-1
+
C3H8
1116.11 lb/hr C4H10 0.991 C3H8
C4H10
346.38 lb/hr C5H12 0.007 C4H10
C5H12
0.002 C5H12
C3H6
C4H8
H2

The percentage of conversion for propane and butane are 86% and 90% respectively and since
the weight percent of pentane is too small, we assume that pentane is remain unreacted.

Stream 4 Stream 5

No. Component Mole Mass Flowrate, Mole Mass Flowrate,

Fraction (lb/hr) Fraction (lb/hr)

1 Propane 0.991 121861.09 0.0747 17060.53

2 Butane 0.007 1116.11 0.0004 111.61
3 Pentane 0.002 346.38 0.0009 346.38
4 Propene 0 0 0.4587 100000
5 Butene 0 0 0.0033 969.58
6 Hydrogen 0 0 0.4620 4811.36

37
3.1.5 Mass Balance for Separation Unit 2

H2 4811.36 lb/hr

6
123299.61 lb/hr
5
S-2
C3H8
7 118488.25 lb/hr
C4H10 C3H8
C5H12 C4H10
C3H6 C5H12
C4H8 C3H6
H2 C4H8

Stream 5 Stream 6 Stream 7

No. Component Mass Mass Mass

Mole Mole Mole
Flowrate, Flowrate, Flowrate,
Fraction Fraction Fraction
(lb/hr) (lb/hr) (lb/hr)

1 Propane 0.0747 17060.53 0 0 0.1388 17060.53

2 Butane 0.0004 111.61 0 0 0.0007 111.61
3 Pentane 0.0009 346.38 0 0 0.0017 346.38
4 Propene 0.4587 100000 0 0 0.8526 100000
5 Butene 0.0033 969.58 0 0 0.0062 969.58
6 Hydrogen 0.4620 4811.36 1 4811.36 - -

38
3.1.6 Mass Balance for Separation Unit 3

117060.68 lb/hr

8
C3H8
C3H6

118488.25 lb/hr 7
S-3
C3H8
C4H10
C5H12 1427.57 lb/hr
C3H6 C4H10

C4H8 9 C5H12
C4H8

Stream 7 Stream 8 Stream 9

No. Component Mass Mass Mass

Mole Mole Flowrate, Mole Flowrate,
Flowrate,
Fraction Fraction (lb/hr) Fraction (lb/hr)
(lb/hr)

1 Propane 0.1388 17060.53 0.1400 17060.53 0 0

2 Butane 0.0007 111.61 0 0 0.08 111.61
3 Pentane 0.0017 346.38 0 0 0.20 346.38
4 Propene 0.8526 100000 0.8600 100000 0 0
5 Butene 0.0062 969.58 0 0 0.720 969.58

39
3.1.7 Mass Balance for Separation Unit 4

100000 lb/hr
11

C3H6

117060.68 lb/hr
8
S-4
C3H8
C3H6

17060.53 lb/hr

10
C3H8

Stream 8 Stream 1 Stream 11

No. Component Mass Mass Mass

Mole Mole Mole
Flowrate, Flowrate, Flowrate,
Fraction Fraction Fraction
(lb/hr) (lb/hr) (lb/hr)

1 Propane 0.140 17060.53 1 17060.56 0 0

2 Propene 0.860 100000 0 0 1 100000

40
 3.2 ENERGY BALANCES

Table 3.1: Table of Data for Heat of Capacities

Cp=A+B*T+C*T^-2+D*T^-3

Cp=A+B*T+C*T^-2+D*T^-3
Average
Molecular ∆Hv Cp for
Compound ∆Hf
Weight Kj/mol liquid
A*10^3 B*10^5 C*10^8 D*10^12 KJ/(mol.K)

-
Propane 44.09 18.77 68.023 22.59 -13.11 31.71 0.10584
103.8

Propene 42.08 20.41 18.42 59.58 17.71 -10.17 24.6 0.1199

-
Butane 58.12 22.306 92.3 27.88 -15.47 34.98 0.13367
124.7

Butene 56.1 1.17 21.916 82.88 25.64 -17.27 50.50 0.09396

-
Pentane 72.15 25.77 114.8 34.09 -18.99 42.26 0.167
146.4

Hydrogen 2.016 0 0.904 28.84 0.00765 0.3288 -0.8698 -

41
Energy Balance

We use heat of vaporization instead of liquid heat capacities to calculate the stream
enthalpy and the value stated in Table 3.1. For a mixed stream, both equations are applied based
on the vapor/liquid fraction involved. If there is no reaction occur in a unit (i.e. initial component
= final component), enthalpy change for the unit is express as below:

Qv  n y k [  C po.k (T )dT  H f ,k ]
T2
(Vapor)
T1
k

QL  n xk [  C po.k (T )dT  H f , k (T2 )  H vap

T2
k
(T1 )] (Liquid)
T 1
k

Where, n is the total molar flow rate of that specific stream

For streams with composition or component change (i.e. reactor), heat of formation must be
included.

3.2.1 Separation Unit 1

2
D1 lb/hr
0.990 C3H8

0.009 C4H10

0.001 C5H12
1
F1 lb/hr S-1
0.80 C3H8

0.18 C4H10

0.02 C5H12
3
B1 lb/hr
0.90 C4H10

0.10 C5H12
42
For Stream 1
Liquid phase
Stream temperature, T = 325.13 K and consider datum at 298.13 K

Flow rate Flow rate ∆H

Component Cp
Ibmole/hr mole/hr KJ/hr

Propane 2376.43 1077948.64 0.10584 3080432.27

Butane 534.69 242535.38 0.13367 875332.014

Pentane 59.41 26948.37 0.167 121510.2

∑ 4077274.484 KJ/hr

For Stream 2
Liquid phase
Stream temperature, T = 320.13 K and consider datum at 298.13 K

Flow rate Flow rate Cp

Component ∆H
Ibmole/hr mole/hr liquid

Propane 2376.43 1077924.884 0.10584 2509926.534

Butane 19.203 8710.288 0.13367 25614.69

Pentane 4.8 2177.23 0.167 7999.14

∑ 2543540.36 KJ/hr

43
For Stream 3
/Stream temperature, T = 377.13 K and consider datum at 298.13 K

Flow rate Flow rate Cp

Component ∆H
Ibmole/hr mole/hr liquid

Butane 8.86 4018.8 0.13367 42438.24

Pentane 0.756 342.91 0.167 4524.011

∑ 46962.25 KJ/hr

∑H=46962.25 +2543540.36 -4077274.484 =-1486771.86 KJ/hr

44
3.2.2 Heat exchanger 1

Stream inlet Stream inlet

20C, liq. 52 C, liq.

Flow rate Flow rate

Component Cp ∆H
Ibmole/hr mole/hr
Propane 2376.96 1077948.64 0.10584 3650882.69

Butane 534.7 242535.38 0.13367 1037430.53

Pentane 59.41 26948.37 0.167 144012.08

∑ 4832325.3 KJ/hr

45
3.2.3 Furnace

Stream temperature, T = 600 C and consider datum at 47 ˚C

Flow rate Flow rate ∆H

Component ∫CpdT
Ibmole/hr mole/hr KJ/hr

Propane 2376.43 1077948.64 69.62 75046784.32

Butane 534.69 242535.38 90.91 22048891.4

Pentane 59.41 26948.37 112.17 3022798.66

∑ 100118475 KJ/hr

46
3.2.4 Energy balance for Heat Exchanger 2 (HE2)

Stream inlet Stream outlet

600˚C 1˚C
(Gas phase) (Mixture phase)

Stream inlet at 600˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H
(mol/hr)
H2 2393.7 16.8053 40226.84661
C3H8 386.86 71.2935 27580.60341
C3H6 2376.4 59.5563 141529.5913
C4H10 1.9203 93.1652 178.9051336
C4H8 17.283 82.9306 1433.28956
C5H12 4.8009 114.9629 551.9253866
∑ 5180.9642 438.7138 211501.1614

Stream outlet at 1˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H ∆Hv
(mol/hr)
H2 2393.7 -0.6922 -1656.91914 -
C3H8 386.86 -2.5392 -982.314912 18.77
C3H6 2376.4 -2.8776 -6838.32864 18.42
C4H10 1.9203 -3.2082 -6.16070646 22.306
C4H8 17.283 -2.255 -38.973165 21.916
C5H12 4.8009 -4.008 -19.2420072 25.77
∑ 5180.9642 -15.5802 -9541.938571 107.182

Q = n(∆Hout - ∆Hin – (-∆Hv))

=5180.9642(-15.5802–438.7138-(-107.182))
= -1798374.845 kJ/hr

47
3.2.5 Energy Balance for Flash Separator (S2)

Stream 6
1˚C

Stream 5
Flash separator
1˚C

Stream 7
1˚C

Stream 5 (Feed Stream) at 1˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H
(mol/hr)
H2 2393.7 -0.6922 -1656.91914
C3H8 386.86 -2.5392 -982.314912
C3H6 2376.4 -2.8776 -6838.32864
C4H10 1.9203 -3.2082 -6.16070646
C4H8 17.283 -2.255 -38.973165
C5H12 4.8009 -4.008 -19.2420072
∑ 5180.9642 -15.5802 -9541.938571

Stream 6 (Distillate stream) at 1˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H
(mol/hr)
H2 2393.7 -0.6922 -1656.91914

Stream 7 (Bottom stream) at 1˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H
(mol/hr)
C3H8 386.86 -2.5392 -982.314912
C3H6 2376.4 -2.8776 -6838.32864
C4H10 1.9203 -3.2082 -6.16070646
C4H8 17.283 -2.255 -38.973165
C5H12 4.8009 -4.008 -19.2420072
∑ 2787.2642 -14.888 -7885.019431

48
There’s no heat transfer from the flash column:

𝑄 = 𝛥𝐻 = 𝟎
Q = n∆Hout - n∆Hin

=(-7885.019431+ (-1656.91914)) – (-9541.938571)

= 0 kJ/hr

49
3.2.6 Energy balance for heat exchanger 3

Stream Stream
inlet outlet
1˚C 42˚C

Stream inlet at 1˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H
(mol/hr)
C3H8 386.86 -2.5392 -982.314912
C3H6 2376.4 -2.8776 -6838.32864
C4H10 1.9203 -3.2082 -6.16070646
C4H8 17.283 -2.255 -38.973165
C5H12 4.8009 -4.008 -19.2420072
∑ 2787.2642 -14.888 -7885.019431

Stream outlet at 42˚C datum at 25˚C

Flowrate ∫CpdT
Compound (kJ/mol) n∆H
(mol/hr)
C3H8 386.86 1.2825 496.14795
C3H6 2376.4 1.1118 2642.08152
C4H10 1.9203 1.7249 3.31232547
C4H8 17.283 1.5516 26.8163028
C5H12 4.8009 2.1421 10.28400789
∑ 2787.2642 7.8129 3178.642106

Q = n∆Hout - n∆Hin

= 3178.642106– (-7885.019431)

= 63273.40588 kJ/hr

50
3.2.7 Energy Balance for Compressor (C1)

STREAM INLET STREAM OUTLET

1 bar 10 bar
600˚C 600˚C

Inlet (stream 2)

Phase Vapor
Component Mixture
Pressure (bar) 1
Temperature (oC) 600
Total Molar Flow Rate (kmol/hr) 2349.64

Outlet (stream 3)

Phase Vapor
Component Mixture
Pressure (bar) 10
Temperature (oC) 600
Total Molar Flow Rate (kmol/hr) 2349.64

The outlet temperature of a stream by assuming the process is an ideal system.

𝜸−𝟏
𝑷𝟐 ( 𝜸
)
𝑻𝟐 = 𝑻𝟏 ( )
𝑷𝟏
For ideal system, γ = 1.3.

Hence,
𝟏.𝟑−𝟏
10 ( 𝟏.𝟑
)
𝑻𝟐 = 𝟔𝟎𝟎 ( )
𝟏
= 𝟏𝟎𝟐𝟎. 𝟕𝟓˚𝑪
For energy balance,

51
 ̂ 𝒊 − ∑ 𝒏𝒊 𝑯
𝑸 = ∆𝑯 = ∑ 𝒏𝒊 𝑯 ̂𝒊
𝒐𝒖𝒕 𝒊𝒏
𝑻 𝑻
= ∑ 𝒏𝒊 ∫ 𝑪𝒑 𝒅𝑻 − ∑ 𝒏𝒊 ∫ 𝑪𝒑 𝒅𝑻
𝒐𝒖𝒕 𝟐𝟗𝟖.𝟏𝟓 𝒊𝒏 𝟐𝟗𝟖.𝟏𝟓

Since there is no change component flow rate,

1293.9
𝑄 = ∆𝐻 = 𝑛𝑖 [∫ 68.023 × 10−3 + 22.59 × 10−5 𝑇 − 13.11 × 10−8 𝑇 2 + 31.71 × 10−12 𝑇 3 𝑑𝑇
298.15
1293.9
+∫ 59.58 × 10−3 + 17.71 × 10−5 𝑇 − 10.17 × 10−8 𝑇 2 + 24.6 × 10−12 𝑇 3 𝑑𝑇
298.15
1293.9
+∫ 92.3 × 10−3 + 27.88 × 10−5 𝑇 − 15.47 × 10−8 𝑇 2 + 34.98 × 10−12 𝑇 3 𝑑𝑇
298.15
1293.9
+∫ 82.88 × 10−3 + 25.64 × 10−5 𝑇 − 17.27 × 10−8 𝑇 2 + 50.50 × 10−12 𝑇 3 𝑑𝑇
298.15
1293.9
+∫ 114.8 × 10−3 + 34.09 × 10−5 𝑇 − 18.99 × 10−8 𝑇 2 + 42.26 × 10−12 𝑇 3 𝑑𝑇
298.15
1293.9
+∫ 28.84 × 10−3 + 0.00765 × 10−5 𝑇 + 0.3288 × 10−8 𝑇 2 − 0.8698
298.15

× 10−12 𝑇 3 𝑑𝑇]

= 2349.64 (175.44 + 144.36 + 227 + 197.87 + 278.61 + 30.52)

= 2476050.63 kJ/hr

52
3.2.8 Separation Unit 3 (S3)

117060.68 lb/hr

8
C3H8
C3H6

118488.25 lb/hr 7
S-3
C3H8
C4H10
C5H12
C3H6
C4H8 1427.58 lb/hr

9
C4H10
For Stream 7 C5H12
C4H8
Liquid stream
Stream temperature, T = 315.15 K and consider datum at 298.15 K

Flow rate Flow rate ∫CpdT n∆H

Component Cp
(lbmol/hr) (mol/hr) (kJ/mol) kJ/hr

Propane 386.86 1.75447 х 105 0.10584 1.7993 315681.79

Butane 1.92 870.748 0.13367 2.2724 1978.69

Pentane 4.80 2176.871 0.167 2.8390 6180.14

Propene 2376.43 10.777 x 105 0.1199 2.0383 2196675.91

Butene 17.28 7836.735 0.09396 1.5973 12517.62

∑ 2533034.15

53
For Stream 8
Gas stream
Stream temperature, T = 317.15 K and consider datum at 298.15 K

Flow rate Flow rate ∫CpdT n∆H

Component Cp
(lbmol/hr) (mol/hr) (kJ/mol) kJ/hr

Propane 386.86 1.75447 х 105 0.10584 2.0110 352823.92

Propene 2376.4 1077732.426 0.1199 2.2781 2.45518 х 106

2.8080 x 106
∑

For Stream 9
Liquid stream
Stream temperature, T = 381.55 K and consider datum at 298.15 K

Flow rate Flow rate ∫CpdT n∆H

Component Cp
(lbmol/hr) (mol/hr) (kJ/mol) kJ/hr

Butane 1.9203 870.884 0.13367 11.1481 9708.70

Butene 17.283 7838.095 0.09396 7.8363 61421.66

Pentane 4.80 2176.871 0.1670 13.9278 30319.02

∑ 101449.38

∑H = 101449.38+ 2.8080 x 106 - 2533034.15 = 376415.23kJ/hr

54
3.2.9 Separation Unit 4 (S4)

11
D1 lb/hr
C3H6

8
F1 lb/hr S4
C3H8
C3H6

12
B1 lb/hr
C3H8

For Stream 8
Liquid stream
Stream temperature, T = 318.15 K and consider datum at 273.15 K

Flow rate Flow rate ∫CpdT n∆H

Component Cp
(lbmol/hr) (mol/hr) (kJ/mol) kJ/hr

Propane 386.95 1.75517 х 105 0.10584 4.7628 8.35952 х 105

Propene 2376.43 10.77929 х 105 0.1199 5.3955 58.15965 х 105

66.51917 х 105
∑

55
For Stream 11
Gas stream
Stream temperature, T = 309.15 K and consider datum at 273.15 K

Flow rate Flow rate ∫CpdT n∆H

Component
lbmol/hr (mol/hr) (kJ/mol) (kJ/hr)

Propene 2376.43 10.77929 х 105 2.258 24.33963 х 105

24.33963 х 105
∑

For Stream 12
Liquid stream
Stream temperature, T = 320.15 K and consider datum at 273.15 K

Flow rate Flow rate ∫CpdT n∆H

Component Cp
(lbmole/hr) (mol/hr) (kJ/mol) (kJ/hr)

Propane 386.95 1.75517 х 105 0.10584 4.97448 8.73105 х 105

8.73105 х 105
∑

Q = ∑H = 8.73105 х 105 + 24.33963 х 105- 66.51917 х 105= -33.44849 х 105 kJ/hr

56
3.2.10 Pump (P1)

outlet

inlet

Component Molar Flow Rate Molar Flow Rate, F Molar Fv

(lbmol/hr) (kmol/hr) volume,v(kmol/m3)
C3H8 386.86 1.75476 х 102 21.9375 3849.50
C3H6 2376 10.77734 х 102 23.2486 25055.81
C4H10 1.92 0.00870 х 102 0.09667 0.08410
C4H8 17.28 0.07838 х 102 0.09048 0.70918
C5H12 4.801 0.02178 х 102 0.11452 0.24942
∑Fv = 28906.35

Inlet Stream

Phase Liquid
Pressure (bar) 1
Temperature (oC) -47

Outlet Stream
Phase Liquid
Pressure (bar) 18
Temperature (oC) -47

Q = ∑Fv ( P)
Q = 28906.35 х (18 -1) = 4.91408 х 105 kJ/hr

57
3.2.11 Energy Balance for Reactor

873K (600˚C), 1 bar 873K (600˚C), 1 bar

R-1
4
5 C3H8
121861.09 lb/hr C3H8
0.991 C3H8 C4H10
+
0.007 C4H10 C5H12
1116.11 lb/hr C4H10
0.002 C5H12 C3H6
346.38 lb/hr C5H12
C4H8

H2

1. C3H8 C3H6 + H2 ̂𝑟1

∆𝐻

2. C4H10 C4H8 + H2 ̂𝑟2

∆𝐻

C3H8 (g), 873K (600˚C), 1 bar C3H6 (g), 873K (600˚C), 1 bar

̂𝑅
𝐻 ̂𝑃
𝐻
>
>

>
C3H8 (g), 298K (25˚C), 1 bar C3H6 (g), 298K (25˚C), 1 bar
̂𝑟1
∆𝐻

Reaction path for Propane

̂𝑅1 + 𝑛𝐻
𝑄1 = 𝑛𝛥𝐻 = ∑ 𝑛𝐻 ̂𝑝1 + ∆𝐻
̂𝑟1 (for Propane)

̂𝑅2 + 𝑛𝐻
𝑄2 = 𝑛𝛥𝐻 = 𝑛 ∑ 𝑛𝐻 ̂𝑝2 + ∆𝐻
̂𝑟2 (for Butane)

𝑄 = 𝑄1 + 𝑄2

58
1. Energy balance for Propane

Component ̂𝑅1
𝐻 ̂𝑝1
𝐻 ̂𝑟1
∆𝐻

Flow rate
1253192.74 2330911.57 -
(mol/hr)
Specific
̂
Enthalpy, 𝐻 -91.8 184.72 -
(kJ/mol)
∆H
-115043093.5 430565985.2 140.21
(kJ/hr)

∑ 315523031.9

2. Energy balance for Butane

Component ̂𝑅2
𝐻 ̂𝑝2
𝐻 ̂𝑟2
∆𝐻

Flow rate
8708.84 16547.07 -
(mol/hr)
Specific
̂
Enthalpy, 𝐻 -119.0 240.61 -
(kJ/mol)
∆H
-1036351.96 3981390.5 125.87
(kJ/hr)

∑ 1945164.41

𝑄 = 𝑄1 + 𝑄2

kJ kJ
𝑄 = 315523031.9 + 1945164.41
hr hr
Q = 317.468 x 106 kJ/hr

59
3.3 Simulation Result from ASPEN HYSYS
3.3.1 Material Balance
Mass
Stream no. (lbmole/hr)
(Hysys)
stream 1 3179
stream 2 3179
stream 3 769.4
stream 4 2410
stream 5 2523
stream 6 2523
stream 8 4692
stream 9 4692
stream 10 4692
stream 11 4692
stream 12 2533
stream 13 2159
stream 14 2533
stream 15 2533
stream 16 156.3
stream 17 2377
stream 23 2263
stream 24 113.4
stream 25 113.2

3.3.2 Energy Balance

Energy, kJ/h
Equipment
(HYSYS)
Q-HE00 5.76E+06
Q-HE01 1.79E+08
Q-HE02 1.65E+07
Q-Furnace 9.23E+07
Q-Compressor 6.78E+07
Q-Pump 6.90E+04

60
3.4 Percentage Difference between Manual Calculation and HYSYS Calculation
3.4.1 Mass Balance
Mass Mass
Stream no. (lbmole/hr) (lbmole/hr) % Diff
(manual) (Hysys)
stream 1 2971 3179 6.54
stream 2 2971 3179 6.54
stream 3 721.5 769.4 6.23
stream 4 2400.4 2410 0.40
stream 5 2787.3 2523 10.48
stream 6 2787.3 2523 10.48
stream 8 5181 4692 10.42
stream 9 5181 4692 10.42
stream 10 5181 4692 10.42
stream 11 5181 4692 10.42
stream 12 2787 2533 10.03
stream 13 2393 2159 10.84
stream 14 2787 2533 10.03
stream 15 2787 2533 10.03
stream 16 165.4 156.3 5.82
stream 17 2663.5 2377 12.05
stream 23 2376.4 2263 5.01
stream 24 124.5 113.4 9.79
stream 25 124.5 113.2 9.98

3.4.2 Energy Balance

Energy, kJ/h Energy, kJ/h

Equipment % Diff
(manual) (HYSYS)
Q-HE00 4.83E+06 5.76E+06 16.09
Q-HE01 1.80E+06 1.79E+08 99.00
Q-HE02 6.33E+04 1.65E+07 99.62
Q-Furnace 1.00E+08 9.23E+07 8.46
Q-Compressor 2.48E+06 6.78E+07 96.35
Q-Pump 4.91E+05 6.90E+04 612.70

61
 CHAPTER 4

HEAT INTEGRATION

4.1 PROCESS ENERGY INTEGRATION

∆Tmin = 10˚C

Table 4.1: Steam Table Data

Stream Type Tsupply (˚C) Ttarget (˚C) FCp (MW/K)

C1 Cold 20 50.08 0.053

C2 Cold 43.85 576.30 0.048

H1 Hot 870.7 -137.1 0.049

C3 Cold -136.8 30 0.028

62
4.2 Algorithm Table

∑FCpC -∑FCpH
T (˚C) ∆T (˚C) ∆Hi (MW) 1st Cascade
0.049 (MW/K)

865.70 H1 0
Pinch
h
284.4 -0.049 -13.9356

581.30 13.94

526.22 -0.001 -0.52622

55.08 14.46

6.23 0.052 0.32396

48.85 C2 14.14
0.048
13.85 0.004 0.0554

35.00 14.08

10 0.032 0.3200

25.00 C1 13.76
0.053
156.8 -0.021 -3.2928

-131.80 C3 17.06
0.028
10.3 -0.049 -0.5047
17.56
-142.10
Qc min

Figure 4.1: Algorithm Table

63
4.3 Heat Exchanger Network

T pinch
∆H (MW) FCp(MW/K) (870.7˚C)

1.5942 0.053 C1
50.08 20

25.5576 0.048 C2
576.3 43.85

4.6704 0.028 C3
30 -136.8

49.3822 0.049 H1 E1 E2 E3 C
1 2 -137.1
870.7 25.5576 1.5942 4.6704 17.56

Figure 4.2: Heat ExchangerNetwork

Table 4.2: Summary of Temperature of Heat Exchanger

TH,in (˚C) TH,out(˚C) TC,in (˚C) TC,out (˚C)
E1 870.7 349.12 43.85 576.3
E2 349.12 316.59 20 50.08
E3 316.59 221.28 -136.8 30
C 221.28 -137.1 - -

64
4.4 Process Flow Diagram Heat Exchanger Network

Figure 4.3: Process Flow Diagram Heat Exchanger Network

65
 CHAPTER 5

OPTIMIZATION

Optimization is the tool to maximize our profit by minimizing the supply of raw material
and maximizing the product. In this case, our target that we want to maximize it the production
of propene (100000 Ib/hr) and our supply that we want to minimize it is the propane which is
initially set to 104800 Ib/hr depending on the stoichiometric coefficient of (propane/propene
=1.048) and (Hydrogen/propene= 0.0457).

Propane Propene Hydrogen

Ibmol 1 1 1

MW 44.1 42.08 2.16

+
Ib 44.1 42.08 2.16

Ib/Ib propene 1.048 1 0.0457

USD RM/Ib 0.79 1.96 11.3

66
Step 1:
Define decision variables:
P1= amount of product (Propene)
P2=amount of byproduct (Hydrogen)
R=amount of reactant (Propane)
Z=maximum profit

Step 2:
Define objective function
Maximum profit (Z) = (1.96*P1 +11.3*P2)-(0.79*R)

Step 3:
Defining equality and inequality constraints:
a) Inequality constraints
Propane supply R << 104800 Ib/hr
Propene production P1>> 100000 Ib/hr

b) Equality constraints
R= 1.048*P1
P2=0.0457*P1

c) Non-negativity constraint
R, P1, P2 ≥ 0

67
Step 4
Optimization technique
We used solver add-in in Microsoft excel:
P1=100000 Ib/hr
P2=4789.36 Ib/hr
R=104800 Ib/hr
Z=167327.768 RM/hr
After optimization the maximum profit is close to the manually calculated one= RM
167327.768/hr.

68
 CHAPTER 6

EQUIPMENT SIZING AND COSTING

6.1 Introduction

In this chapter, the equipment sizing is done to all equipment that is involved in the
proposed propylene production plant. Equipment sizing is a very important aspect of process
design as it enables the subsequent analysis that is involved in process design such as
mechanical design and economy analysis. The sizing involves the reactors, distillation
column, compressor, pump, and heat exchangers.

6.2 Reactor

6.2.1 Sizing of Reactor

Parameter SI
Volumetric Flowrate , Q 3517.02 ft3/hr
Retention time (half-full), t 5 min
Reactor Volume, V 586.17 ft3
Vessel Inside Diameter, Di 7.20 ft
Vessel Length, L 14.4 ft
Design Type Vertical
Material of Contruction Low- Alloy Steel SA-387B

69
6.2.2 Costing of Reactor

Cost of vessel, Cv = $ 40, 279

Cost of ladders and nozzles, CPL = $ 10, 264

Cost of purchase CP = $ 58, 599

Total cost with bare-module = 4.16 (58, 599) = $ 243, 772

6.3 Pump

6.3.1 Sizing of Pump

Pressure inlet, P1 = 1000kPa = 145.04psi

Pressure outlet, P2 = 1750kPa = 253.82psi
Pressure drop, ΔP = 750kPa = 108.78psi
Volumetric flow rate, Q = 93.57 m3/hr = 413.09 gpm
𝛥𝑃 (2.31) 𝛥𝑃
Pump head, H = = = 356.82 ft
𝑆𝐺 ρ

6.3.2 Costing of Pump

Cost of pump, CP = $ 6577.78
Cost of motor, CP = $ 4689.90
Total cost with bare-module = (6577.78 + 4689.90) (3.30)
= $ 37,183.34

6.4 Distillation Column

6.4.1 Sizing and costing of the main vessel:

Parameters S1
Domed head wall
13.7 mm
thickness, a
Tray spacing, b 2ft

Column diameter, c 6.05 ft

70
 Column wall thickness,
0.5 in
d

Design type Vertical

Material of Construction Carbon steel

Mineral
Material of insulation
wool,60mm

Column type Plate column

Plate type Sieve

Domed head type Torispherical

Costing in $:

Cost of vessel. Cv= $ 67436

Cost of ladders and nozzles, CPL= $ 21642
Cost of plates, CT= $ 27462

Total cost with bare-module

=4.16 (67436+21642+27462) = $ 484809

6.4.2 Sizing and costing of the reflux drum:

Parameters S1
Domed head wall
13.7 mm
thickness,

Vessel length,L 8.924 ft

vessel diameter, D 17.85 ft

Column wall thickness,

0.562 in
d

Design type Vertical

71
 Material of Construction Carbon steel

Mineral
Material of insulation
wool,60mm

After bare-model:
Cost= $ 223290

6.4.3 Sizing and costing of the condenser:

Parameters S1

Length of tube 20 ft

Area of transfer,Ac 273.1 ft2

Material of Construction Carbon steel

fixed head,
Type of HE shell tube
exchanger

Cp= $ 21721
After bare-module,
Cost= $ 68857

72
6.4.4 Sizing and costing of the re-boiler:

Parameters S1

Length of tube
20 ft

Area of transfer,AR 3.146 ft2

Material of Construction Carbon steel

Type of HE kettle reboiler

CB= $ 65325
With bare-module
$ 3.17(65325) = $ 207080

Total cost for S1:

Vessel or Equipment Cost in $

main vessel 484809

the reflux drum 223290

the condenser 68857

the re-boiler 207080

Total 984036

73
6.5 Compresssor
6.5.1 Main Sizing Parameters

Parameters Compressor
Compressor Type Centrifugal
Drive Type Steam turbine
Material of Construction Stainless steel
Inlet Volumetric Flow Rate, QI 83283.83 ft3/min
Inlet Pressure, PI 14.5 psi
Outlet Pressure, PO 72.52 psi
Specific Heat Ratio, k 1.10

6.5.2 Costing in $:

Purchase cost of compressor = $ 7,328,904

6.6 Heat Exchanger

6.6.1 Sizing of Heat exchanger (HE 2)

Heat exchanger type 2 shell and 4 tubes

Design type Fixed Head
Heat exchanger orientation Horizontal
Tube inlet direction Horizontal
Heat duty (kJ/s) 1594.2
Heat duty (Btu/hr) 5.44x10^6

Hot Cold
Tin (C̊) 870.7 43.85
Tout (C̊) 349.12 576.3

1594.2kJ 0.94782 Btu 3600s

Q x x
s kJ hr
Q  5.44 x10 Btu / hr
6

(349.12  43.85)  (870.7  546.3)

LM 
349.12  43.85
ln( )
870.7  546.3

74
LM  314.74 o F

870.7  349.12
R
576.3  43.85
R  0.98

576.3  43.85
S
870.7  43.85
S  0.644

From Figure 18.15 (a), FT = 0.85 and 2-4 exchanger is used.

Ui = 235.5 Btu/oF.ft2.hr

5.44 x10 6 Btu / hr

Ai 
235.5Btu / oF . ft 2 .hrx 0.85 x314.74 o F
Ai  86.34 ft 2

Velocity of tube-side;

99.59m 3 144in 2 / ft 2 35.3145 ft 3

ui  x x
hr 0.302in 2 m3
u i  1.68 x10 6 ft / hr

Cross section are/pass;

111244.12lb ft 3 hr
Aci  x x
hr 0.421lb 1.68 x10 6 ft
Aci  0.157 ft 2 / pass

By using 0.75 in. O.D. 16 BWG tubing with I.D. of 0.62 in.;

0.302in 2 ft 2
Inside area/tube = x
tube 144in 2
= 2.097x10-3 ft2/tube

75
 0.157 ft 2 / pass
Nt 
2.097 x10 3 ft 2 / tube
N t  75tubes / pass

Area per tube;

86.43 ft 2
=
4 passx 75tubes / pass
= 0.288 ft2/tube

0.288 ft 2 / tube
L
0.62in
x
12in / ft
L = 5.58 ft

6.6.2 Costing of Heat Exchanger (HE2)

Ai  86.34 ft 2

FBM = 3.17

86.34 0.5
𝐹𝑀 = 1.08 + ( )
100
= 2.01

FL = 1.25 (Tube length = 5.58 ft2)

145.04 145.04 2
𝐹𝑃 = 0.9803 + 0.018 ( ) + 0.0017 ( )
100 100

= 1.01

Fixed head:

𝐶𝐵 = exp{11.0545 − 0.9228[𝑙𝑛(86.34)] + 0.09861[𝑙𝑛(86.34)]2 }

= $7,334.88

𝐶𝑃 = (2.01)(1.25)(1.01)(7,334.88)
= $18,613.18

Bare-module cost = 3.17 ( 18,613.18)

= $59,003

76
 CHAPTER 7

TOTAL CAPITAL INVESTMENT AND PAYBACK PERIOD

7.1 Total Capital Investment

By using method 3, which is based on the individual factors method of Guthrie, 1969,
1974 there are few steps to find the total capital investments, CTCI.

Firstly, we need to prepare an equipment list, giving the equipment tittle, label, size,
material of construction, design temperature, and design pressure.

Equipment Label Size Material of Design Design Bare-

Tittle Construction Temp. Pressure (bar) module
(˚C) Cost, CBM

Reactor R1 V=586.17 ft3 Low- Alloy 576 1 $ 243, 772

Di = 7.20 ft Steel SA-387B
L= 14.4 ft
Pump P1 H =356.82 ft Cast Steel -137.1 Pinlet = 10 $ 37,183
Poutlet = 17.5
Distillation S1 D = 6.05 ft Carbon steel 50 15 $ 984,036
Column t = 0.5 in

Compressor C1 Q = 83283.83 Carbon Steel 526 Pinlet = 1 $ 15,757,144

ft3/min Poutlet = 10
Heat HE2 A = 86.34 ft2 Carbon Steel 870.7 10 $ 59,003
Exchanger
CTBM ∑ $17,081,138

After we get the value of total bare module cost, CTBM, we need to find the site
development cost, Csite, building cost, Cbuildings, and offsite facilities cost, Coffsite facilities by
assuming some factor. The calculation of total capital investment cost is shown below:

77
Assume it is grass-roots plant, the value fo CSITE is 10-20% of CTBM. Assume we take
15% of CTBM.
CSITE = 0.15 (17,081,138)
CSITE = $ 2,562,170.75

Assume it is process buildings, the value of CBUILDINGS is 10% of CTBM

CBUILDINGS = 0.10 (17,081,138)
CBUILDINGS = $ 1,708,113.80

The value of COFFSITE FACILITIES is 5% of CTBM

COFFSITE FACILITIES = 0.05 (17,081,138)
COFFSITE FACILITIES = $ 854,056.90

Use factor of 1.18 to cover a contingency and a contractor fee

CTPI = 1.18 ( CTBM + CSITE + CBUILDINGS + COFFSITE FACILITIES)
CTPI = 1.18 (17,081,138+ 2,562,170.75 + 1,708,113.80 + 854,056.90)
CTPI = $ 39,969863.01

The value of CWC can be estimated 17.6% of CTPI

CWC = 0.176 (39,969863.01)
CWC = $ 7,034,695.89

Thus,
CTCI = CTPI + CWC
CTCI = $ 39,969,863.01+ $ 7,034,695.89
CTCI = $ 47,004,558.90

78
7.2 Payback Period

Payback period is the time in which the initial cash outflow of an investment is
expected to be recovered from the cash inflows generated by the investment. It is one of the
simplest investment appraisal techniques.

The formula to calculate payback period of a project depends on whether the cash
flow per period from the project is even or uneven. In case they are even, the formula to
calculate payback period is:

Initial Investment
Payback Period =
Cash Inflow per Period
𝑅𝑀 152,764,816.40
=
RM 167,327.77/hr
𝟏 𝒅𝒂𝒚 𝟏 𝒎𝒐𝒏𝒕𝒉
= 𝟗𝟏𝟐. 𝟗𝟔𝟕 𝒉𝒓 × 𝟐𝟒 𝒉𝒓 × 𝟑𝟎 𝒅𝒂𝒚𝒔

= 1 month 9 days

79
 CONCLUSION

Propylene is one of the highest volume of chemicals produced globally and primarily
used as an intermediate for the production of other chemical raw materials. These chemical
raw materials are then subsequently used to manufacture a large variety of substances and
products. Example of such product is propylene, a widely used plastic where the
manufacturing process consumes more than half of the world’s production of polypropylene.
There are other uses as well, such as manufacture of acrylonitrile, oxo process chemicals,
cumene, isopropanol, polygas chemicals, and propylene oxide. This shows that the
production of propylene has its demand in the global industry, hence a good marketability,
especially in recent years where the price of propylene in the market is expected to continue
rising as the demand increases for the chemical material. Market research report says
worldwide polypropylene capacity increased at a Compound Annual Growth Rate (CAGR)
of 5.2% from 2003, reaching 65 million tons per year (MMTY) in 2013, and is expected to
continue rising to 86 MMTY by 2018, at a slightly higher CAGR of 5.8%. As Malaysia is a
part of the global market, it can be expected that prices in Malaysia to be affected by the
global prices.

In terms of reaction pathways for this particular project, a screening process was done
based on gross profit, economic potential as well as other factors related such as energy
consumption, toxicity, safety and environmental impacts. There are two reaction pathways
suggested for the production of propylene, which are dehydrogenation of propane, and
metathesis reaction of ethylene and butene. From the screening process, it was shown that
dehydrogenation of propane reaction is a better process compared to the metathesis reaction.
Based on the gross profit calculation, a dehydrogenation process would bring in a gross profit
of RM 1.67/lb propylene with 86% conversion compared to only RM 0.46/lb propylene for
metathesis reaction with a 90% conversion yield. Since the calculation was based on gross
profit, further analysis need to be done in order to optimize the production process of
propylene via the dehydrogenation of propane process for a sustainable plant design.

80
 In addition to the reaction pathways and process screening, a process synthesis for the
production of propylene from dehydrogenation of propane was done by following the steps
that was introduced by Rudd, Powers, and Siirola. From these steps, a general overview of
the whole process, starting from the raw materials into products is translated into a process
flow diagram, as well as the operating parameters were obtained. This is an important step in
designing the production process of our desired product before performing a further
optimization of the processes and unit operations involved.

In a nutshell, after we had done a simulation, optimization and process integration,

our total capital investment is $ 47,004,558.90.

81
 APPENDICES A

CALCULATION OF MATERIAL BALANCES

Sample Calculation for Mass Balance

1. Overall mass balance

Number of moles of propylene formed

= (100,000 lb/hr)/42.08

= 2376.43 lbmole/hr C3H6

Assume 100% conversion, the mass flowrate of feed, m1 = 2376.43 x 44.1

= 104800.56 lb/hr

for 86% conversion, the mass flowrate of recycle, R = (1-0.86)/0.86 x 104800.56

R = 17060.53 lb/hr

Mass flowrate of H2 , m3

= (no. of mole) X (molecular weight)

= (2376.43) x (2.01)

= 4776.62 lb/hr

Mass flowrate feed to the reactor, F = m1 + R

= 104800.56 + 17060.53 = 121861.09lb/hr

2. Separation Unit 1

Overall mass balance :

F1 = D1 + B1

82
From the overall mass balance, we know that the mass flowrate of propane at D1 is
104800.56 lb/hr and the composition is assume 0.990 of C3H8, so

0.990 D1 = mass flow rate of C3H8

D1 = mass flow rate of C3H8 / 0.990

= 104800.56 / 0.990

= 106263.1 lb/hr distillate

Propane balance :

0.8 F1 = 0.990 D1

F1 = (0.990 x 106263.1)/0.8

F1 = 140163.6 lb/hr feed

F1 = D1 + B1

B1 = 140163.6 – 106263.1

B1 = 33900.6 lb/hr of bottom product

3. Mixer

Overall mass balance :

F = D1 + R where R is the recycle of propane

from previous calculation, the value of D1 = 106263.1 lb/hr and R = 17060.53 lb/hr. Hence,

F = 106263.1 lb/hr + 17060.53 lb/hr = 123323.6 lb/hr

Propane balance : 0.990 x (106263.1) + 17060.53 x (1.0) = 123323.6 x (a1)

a1 = 0.991

Butane balance : 0.009 x (106263.1) = 123323.6 x (a2)

a2 = 0.007

and the weight percent of pentane

83
 a3 = 1 – 0.991 – 0.007 = 0.002

4. Reactor

For dehydrogenation of propane, 0.86% of propane is converted. The unreacted propane

recycled.

(a) Mass flowrate of propane recycle

R = (1-0.86)/0.86 x 104800.56

R = 17060.53 lb/hr

(b) no of mol of propane recycle

= 17060.53/ 44.1 = 386.9 lbmole/hr

(c) no of mole of propene produce

= (121861.09 / 44.1) x 0.86 = 2376.64 lbmole/hr

(d) no of mole of butene produce

= 1116.106 / 58.12 x 0.9 = 17.28 lbmole/hr

(e) no of mole of hydrogen produce

= no of mole of hydrogen from propane + no of mole of hydrogen from propane

= 2376.4 + 17.28 = 2393.7 lbmole/hr

(f) mass flowrate of hydrogen produce

= 2393.7 x 2.01 = 4811.36 lb/hr

84
 APPENDICES B

CALCULATION OF ENERGY BALANCE

Sample Calculation for Energy Balance

Molar Flow Rate for Propane

𝑙𝑏𝑚𝑜𝑙 1𝑘𝑔𝑚𝑜𝑙 1000𝑚𝑜𝑙
𝑛 = 2763.3 ℎ𝑟
𝑥 2.205𝑙𝑏𝑚𝑜𝑙 𝑥 1𝑘𝑔𝑚𝑜𝑙
= 1253197.28mol/hr

For reaction of propane

298𝐾
𝐻𝑅1 = ∫ Cp(reactant) 𝑑𝑡
873𝐾

298𝐾
𝐻𝑅1 = ∫ (68.023 × 10−3 + 22.59 × 10−5 𝑇 − 13.11 × 10−8 𝑇 2 + 31.71 × 10−12 𝑇 3 ) 𝑑𝑡
873𝐾

𝐻𝑅1 = −91.81𝑘𝐽/𝑚𝑜𝑙
298𝐾
𝐻𝑅1 = ∫ Cp(product) 𝑑𝑡
873𝐾

873𝐾
𝐻𝑝1 = ∫ (68.023 × 10−3 + 22.59 × 10−5 𝑇 − 13.11 × 10−8 𝑇 2 + 31.71 × 10−12 𝑇 3 ) 𝑑𝑡
298𝐾
+ (59.58 × 10−3 + 17.71 × 10−5 𝑇 − 10.17 × 10−8 𝑇 2 + 24.6 × 10−12 𝑇 3 ) 𝑑𝑡
+ (28.84 × 10−3 + 0.00765 × 10−5 𝑇 + 0.3288 × 10−8 𝑇 2 − 0.8698
× 10−12 𝑇 3 )𝑑𝑡

𝐻𝑝1 = 91.79𝑘𝐽/𝑚𝑜𝑙 + 75.75𝑘𝐽/𝑚𝑜𝑙 + 17.18𝑘𝐽/𝑚𝑜𝑙

𝐻𝑝1 = 184.72kJ/mol

̂𝑟1 = ∑ 𝑣𝑖 ∆𝐻
∆𝐻 ̂𝑓 = (1)(∆𝐻
̂𝑓 ) ̂𝑓 )
+ (1)(∆𝐻 ̂𝑓 )
− (1)(∆𝐻
C3H6 H2 C3H8

20.41 𝑘𝐽 (−119.8)𝑘𝐽
̂𝑟1 =
∆𝐻 +0 − = 140.21 𝑘𝐽/𝑚𝑜𝑙
𝑚𝑜𝑙 𝑚𝑜𝑙

85
APPENDICES C

ASPEN HYSYS

86
 APPENDICES D

CALCULATION OF HEAT INTEGRATION

Calculation for temperature of heat exchanger.

E1

Q=FCpH∆T

25.5576 = 0.049 (870.7-T)

T = 349.12˚C

Q=FCpC∆T

25.5576 = 0.048 (T – 43.85)

T = 576.3˚

E2

Q=FCpH∆T

1.5942 = 0.049 (349.12-T)

T = 316.59˚C

Q=FCpC∆T

1.5942 = 0.053 (T-20)

T = 50.08˚C

E3

Q=FCpH∆T

87
4.6704 = 0.049 (316.59-T)

T = 221.28˚C

Q=FCpC∆T

4.6704 = 0.028 (T—136.8)

T = 30˚C

88
 APPENDICES E

CALCULATION OF SIZING AND COSTING

REACTOR

Q = 3517.02 ft3/hr

Retention time =5 min at half full :

5 min×1 ℎ𝑟
Volume, V = (3517.02 ft3/hr) × ( × 2) = 586.17 ft3
60 𝑚𝑖𝑛

Assume L/ D = 2
V = 𝜋 (D/2)2L = (𝜋D3)/2
D = (2V/ 𝜋)1/3 = [2(586.17)/ 𝜋] 1/3 = 7.20 ft
L= 2D = 14.4 ft

Operating Pressure = 1 bar = 14.5 psig :

Pd = exp { 0.60608 = 0.91615 [ln(14.5)] + 0.0015655 [ln(14.5)]2} = 21.48 psig (eqn. 22.61)
S = 10993.86 psi (low – alloy)
E = 1.0
21.48 × 7.2 ×12
tP = 2 (10993.86)(1.0) − 1.2 (21.48) = 0.085 in

Minimum wall thickness, tP = 0.375 in

tS = tP + tC = 0.375 + 0.125 = 0.5 in
W = 3.14 [ 7.2 + 0.0417) (14.4 + 0.8 (7.2)] 0.0417 (490) = 9366.83 lb
Cv = exp { 7.0132 + 0.18255[ ln (9366.83) ] + 0.02297 [ ln (9366.83)]2} = $ 40, 279
CPL = 361.8 ( 7.2 ) 0.73960 (14.4) 0.70684 = $ 10, 264
Cp = FMCv + CPL = 1.2 (40, 279) + 10, 264 = $ 58, 599
Bare-Module cost
= 4.16 ( 58, 599 ) = $ 243, 772

89
PUMP
Pressure inlet, P1 = 1000kPa = 145.04psi

Pressure outlet, P2 = 1750kPa = 253.82psi

Pressure drop, ΔP = 750kPa = 108.78psi

Q = 93.57 m3/hr = 413.09 gpm

𝛥𝑃 (2.31) 𝛥𝑃 1𝑙𝑏/𝑖𝑛2 𝑓𝑡3 144 𝑖𝑛2
H= = = 108.78 psi x x x
𝑆𝐺 ρ 1 psi 43.9 lb 1 ft2

H = 356.82 ft

S = Q (H)0.5 = 413.09(356.82)0.5 = 7803.14 gallon.ft0.5/min

ln S = 8.962

CB = exp [9.7171 - 0.6019(8.962) + 0.0519(8.962)2] = $ 4872.43

FT = 1, FM = 1.35 (Assume cast steel)

CP = FTFMCB = (1)(1.35)(4872.43) = $ 6577.78 for pump

𝑄 𝐻ρ 𝑔𝑎𝑙 43.9 𝑙𝑏 0.1334𝑓𝑡3 1

PT = 33000 = 413.09 min x 356.82 ft x x x
ft3 1 gal 33000

𝑙𝑏.𝑓𝑡
= 26.16 min

ln Q = 6.024

ηp = -0.316 +0.24015 (6.024) – 0.01199(6.024)2

= 0.6956
PT 26.16 𝑙𝑏.𝑓𝑡
PB = ηp = 0.6956 = 37.61 min

ln PB = 3.627
ηm = 0.80 + 0.0319(3.627) – 0.00182(3.627)2
= 0.892
PT 26.16 𝑙𝑏.𝑓𝑡
PC = ηpηm = (0.6956)(0.892) = 42.16 min

ln Pc = 3.741
CB = exp [5.8259+0.13141(3.741)+ 0.053255 (3.741)2 + 0.028628 (3.741)3 –
0.0035549(3.741)4]
= $ 2605.50

90
FT = 1.8 (assume explosion-prof enclosure)
CP = FTCB = 1.8(2605.50) = $ 4689.9 for motor
FBM = 3.30
CPTotal (Pump + Motor) = (6577.78 + 4689.9) (3.30)
= $ 37,183.34

DISTILLATION COLUMN
Distillation column, S1
Main vessel sizing

Diameter, DT
FLG= 0.1345
CSB=0.34
FST=0.757
Assume:
FF=1,FHA=1
C=0.2574
Uf=2.758 ft/s
Ad/AT=0.10378
Assume 80% flooding
425100
4( )
3600
DT=0.8(2.758)(3.14)(1−0.10378)(2.09)=6.05 ft=1.844 m

Purchase costs of the vessel

P0=1500 Kpa=217.55 psig

Pd= 5.582 psig
Di=6.05 ft
L= 50 ft
(5.582)(6.05)(12)
tp=2(15000)(0.85)−(1.2∗5.582)=0.0158 < tabulated data thus tp=0.375 in

ts=0.375+0.125=0.5 in
W= π (Di+ts) (L+0.8Di) ts ρ= 21458 Ib
Cv= $ 67436

91
CPL=300.9 ∗ 6.050.63316 500.8016= $21642
CT= $ 27462

Total cost after bare-module= 4.16(27462+21642+67436)= $ 484806

Cost of the reflux drum

Dvolumetric =3350
Volume flow = (1+3) *(3350) = 13400 ft3/hr
Assume residence time of 5 mins at full capacity and L/D=2
V=13400 ft3/hr * (5 min/ (60 min/hr))
V=116 ft3
D=8.924 ft3
L=17.85 ft3

tp =7/16=0.4375 in
ts =0.4375+0.125=0.562 in
W=π (Di + ts)*(L+0.8*Di)*(ts)*ρ
W=16150 Ib
Cv= $ 733210
After bare-model:
Cost= $ 223290

Condenser

Qc= -0.126*105
Uf=4.402 Btu/ (ft2*hr*F)
TLM= 10.48 F
Ac=273.1 ft2

Assume fixed head, shell tube exchanger and carbon steel, 20 feet long:
FL=1

92
FP=1
TM=2.732
CB= 7950

Cp= $ 21721
After bare-module,
Cost= $ 68857

Re-boiler costing

Heat flux 5000 Btu/hr.ft3

Q=16600 Kj/hr=15733.76 Btu/hr
AR=QR/ Flux
AR=3.146 ft2
Choose kettle reboiler with carbon steel, 20 ft long
FL=FM=FP=1
CB= $ 65325
With bare-module
$ 3.17(65325) = $ 207080

COMPRESSOR
(a) Preliminary estimate of brake horsepower, PB

Inlet volumetric flow rate, QI = 83,283.83 ft3/min

Inlet pressure, PI = 14.5 psi
Outlet pressure, PO = 72.52 psi
Specific heat ratio, k = 1.10
Mechanical efficiency, ηB = 0.4952

93
 1.10−1
1.10 83283.83×14.5 72.52 1.10
𝑃𝐵 = 0.00436 × (1.10−1) × × (( 14.5 ) − 1) = 18430.94 𝐵𝐻𝑝
0.4952

(b) Purchase cost of compressor

Assumption:
Drive efficiency, ηC = 0.75
Material factor, FM = 1.00 (carbon steel)
Drive type factor, FD = 1.15 (steam turbine)

18430.94
𝑃𝐶 = = 24574.59 𝐻𝑝
0.75

Base purchase cost,

𝐶𝐵 = 𝑒𝑥𝑝{7.5800 + 0.80[ln(𝑃𝐶 )]}
𝐶𝐵 = 𝑒𝑥𝑝{7.5800 + 0.80[ln(24574.59)]}
𝐶𝐵 = $ 6,372,960

Total purchase cost,

𝐶𝑃 = 𝐹𝐷 𝐹𝑀 𝐶𝐵
𝐶𝑃 = 1.15 × 1.00 × $ 6,372,960
𝑪𝑷 = $ 𝟕, 𝟑𝟐𝟖, 𝟗𝟎𝟒

94
HEAT EXCHANGER (HE2)
Sizing of Heat exchanger (HE 2)

Heat exchanger type 2 shell and 4 tubes

Design type Fixed Head
Heat exchanger orientation Horizontal
Tube inlet direction Horizontal
Heat duty (kJ/s) 1594.2
Heat duty (Btu/hr) 5.44x10^6

Hot Cold
Tin (˚C) 870.7 43.85
Tout (˚C) 349.12 576.3

1594.2kJ 0.94782 Btu 3600s

Q x x
s kJ hr
Q  5.44 x10 Btu / hr
6

(349.12  43.85)  (870.7  546.3)

LM 
349.12  43.85
ln( )
870.7  546.3

LM  314.74 o F

870.7  349.12
R
576.3  43.85
R  0.98

576.3  43.85
S
870.7  43.85
S  0.644

From Figure 18.15 (a), FT = 0.85 and 2-4 exchanger is used.

Ui = 235.5 Btu/oF.ft2.hr

95
 5.44 x10 6 Btu / hr
Ai 
235.5Btu / oF . ft 2 .hrx 0.85 x314.74 o F
Ai  86.34 ft 2

Velocity of tube-side;

99.59m 3 144in 2 / ft 2 35.3145 ft 3

ui  x x
hr 0.302in 2 m3
u i  1.68 x10 6 ft / hr

Cross section are/pass;

111244.12lb ft 3 hr
Aci  x x
hr 0.421lb 1.68 x10 6 ft
Aci  0.157 ft 2 / pass

By using 0.75 in. O.D. 16 BWG tubing with I.D. of 0.62 in.;

0.302in 2 ft 2
Inside area/tube = x
tube 144in 2
= 2.097x10-3 ft2/tube

0.157 ft 2 / pass
Nt 
2.097 x10 3 ft 2 / tube
N t  75tubes / pass

Area per tube;

86.43 ft 2
=
4 passx 75tubes / pass
= 0.288 ft2/tube

0.288 ft 2 / tube
L
0.62in
x
12in / ft
L = 5.58 ft

Costing of Heat Exchanger (HE2)

96
Ai  86.34 ft 2

FBM = 3.17

86.34 0.5
𝐹𝑀 = 1.08 + ( )
100
= 2.01

FL = 1.25 (Tube length = 5.58 ft2)

145.04 145.04 2
𝐹𝑃 = 0.9803 + 0.018 ( ) + 0.0017 ( )
100 100

= 1.01

Fixed head:

𝐶𝐵 = exp{11.0545 − 0.9228[𝑙𝑛(86.34)] + 0.09861[𝑙𝑛(86.34)]2 }

= $7,334.88

𝐶𝑃 = (2.01)(1.25)(1.01)(7,334.88)
= $18,613.18

Bare-module cost = 3.17 ( 18,613.18)

= $59,003

97
 PROCESS FLOW DIAGRAM
(HEAT EXCHANGER NETWORK)

98
99
100
101
102