Production of Butadiene

from n-Butane

By

Saddam firas sami

Fathi
Amer

Guided by,
Dr. Aysar taleb
 CHEMICAL ENGINEERING DEPARTMENT

Production of Butadiene
from Butane

CHEMICAL ENGINEERING DEPARTMENT

COLLEGE OF ENGINEERING (1988)
TIKRIT UNIVERSITY
2018/2019

Prepared By : Sudhanshu S Soman

Guided By : Professor (Dr.) Ranjan Sengupta

 CONTENTS :
CHAPTER 1: INTRODUCTION

1.1 Butadiene Introduction……………………………………………………………………...4

CHAPTER 2 : LITERATURE REVIEW

2.1 Feed Properties………………………………………………………………………………8

2.2 Product Selection……………………………………………………………………………9

2.3 Market Scenario…………………………………………………………………………....13

2.4 Butadiene Manufacturing Process Information………………………………………….15

2.5 Conceptual Design Analysis………………………………………………………………..21

2.6 Input Output Structure…………………………………………………………………….25

2.7 Recycle / Reactor Synthesis………………………………………………………………...25

2.8 Separation Structure……………………………………………………………………….29

CHAPTER 3 : PROCESS DESCRIPTION

3.1 Preprocess Purification Deisobutanizer…………………………………………………...33

3.2 Dehydrogenation Section…………………………………………………………………...34

3.3 Purification Section…………………………………………………………………………36

CHAPTER 4 : MATERIAL & ENERGY BALANCE

4.1 Distillation Unit……………………………………………………………………………..40

4.2 Non-Oxidative Dehydrogenation Reactor………………………………………………...41

4.3 Oxidative Dehydrogenation Reactor………………………………………………………42

4.4 Distillation Unit Energy Balance…………………………………………………………..44

4.5 Non-Oxidative Dehydrogenation Reactor Energy Balance....…………………………...46

4.6 Oxidative Dehydrogenation Reactor Energy Balance……………………………………47

CHAPTER 5 : DESIGN OF EUIPMENTS

5.1 Design of Distillation Column……………………………………………………………...49

5.2 Design of Heat Exchanger………………………………………………………………….58

5.3 Design of Reactor…………………………………………………………………………...65

CHAPTER 6 : PLANT LAYOUT

6.1 Factors in Choosing a Suitable Plant Location…………………………………………...77

6.2 Plant Layout Consideration Factors………………………………………………………80

6.3 Site Layout…………………………………………………………………………………..82

CHAPTER 7 : COST ESTIMATION

7.1 Direct Cost…………………………………………………………………………………..90

7.2 Total Product Cost………………………………………………………………………….93

7.3 Spreadsheet For Estimation of TCI……………………………………………………….97

7.4 Spreadsheet For Estimation of TPC……………………………………………………....98

7.5 Profitability Analysis……………………………………………………………………….99

CHAPTER 8 : MATERIAL SAFETY AND CHEMICAL HAZARD

8.1 Inherent Safety Aspect……………………………………………………..101

8.2 Distillation Column HAZOP Analysis…………………………………………………...105

8.3 Non-Oxidative Dehydrogenation Reactor HAZOP Analysis…………………………...106

CONCLUSION

REFERENCES

APPENDICES
 CHAPTER 1
INTRODUCTION
INTRODUCTION

1.1 Butadiene Introduction :

Butadiene is a noncorrosive flammable, colorless gas at room temperature and atmospheric

pressure with a mild aromatic odor and it is highly reactive. It’s physical Description - Colorless
gas that has a mild gasoline-like odor. Its molecular weight is 54.1 & boiling/melting point 24ºF /
-164ºF(-4.44ºC / -108.88 ºC). Butadiene is slightly soluble in methanol and ethanol and soluble
in organic solvents like diethyl ether benzene and carbon tetrachloride , insoluble in water and
polymerizes readily, particularly if oxygen is present. [14]

One major use of butadiene has been in the making of synthetic rubber (styrene-butadiene and
nitrile butadiene rubbers, to a large extent, CIS-polybutadiene is also an extender and substitute
for rubber, and polymerizations transpolybutadiene is a type of rubber with unusual properties).
Butadiene is also used extensively for various polymerizations for plastics manufacturing.

Butadiene, C4H6 exists in two isomeric forms: 1.3-butadiene CH2==CH---CH==CH2, 1,2

butadiene CH2==C==CH---CH3, 13 Butadiene is commodity product of the petrochemical
industry with a 1989 U.S. production of 3.1 billion pounds (1.4 x 109 kg) according to United
States International Trade Commission USITC. [14]

.Although this is not very different from production in 1971.it represents significant rebound
from the low production in the mid-1988s Elastomers consume the bulk of 1,3butadiene led by
the manufacture of styrene - butadiene rubber SBR, 13-Botadiene is manufactured primarily as a
co-product of steam cracking to produce ethylene in the United States, Western Europe, and
Japan. However, in certain parts of the world (eg, China, India, Poland and the former Soviet
Union) it is still produced from ethanol. The earlier manufacturing processes of dehydrogenation
of n-butane and oxydehydrogenation of n-butenes have significantly declined in importance and
output Efforts have been made to make butadiene from other feedstocks such as other
hydrocarbons coal (2.3), and renewable sources like animal and vegetable oil (5), cellulose,
hemicellulose, and lignin (6,7) but in the United States none of these have moved beyond the
research and development stage. [14]

The other isomer, 1,2-butadiene, a small by-product in 1,3-butadiene production, has no

significant current commercial interests. However, there are anumber of publications and patents
on its recovery and applications, particularly in the specialty polymer area (8,9) and as a gel
inhibitor [14]

1,3-Butadiene was discovered in the nineteenth century and its use in the development of rubber-
like polymers was explored during the early 1900s (Grub and Loser 2005; Sun and Wristers
2002). Large volume production of 1,3-butadiene in the United States began during World War
II. The Russian chemist Sergei Vasilyevich Lebedev was the first to polymerize butadiene in
1910.[19][20] In 1926 he invented a process for manufacturing butadiene from ethanol, and in
1928, developed a method for producing polybutadiene using sodium as a catalyst.
There are two sources of butadiene in world: Extractive distillation from Crude C4 stream
produced as a co-product of ethylene production, and “on-purpose” production by
dehydrogenation of n-Butane or n-Butenes. Leading licensors of technology for Butadiene are
Shell, BASF and Nippon-Zeon.

BASF, Borealis, Equistar Chemical, ExxonMobil, Ineous, Polimeri Europa, Reliance Industries,
Repsol YPF, Sabic, Shanghai Petrochemical, Shell, Sinopec are the leading producers of
Butadiene.

The demand on the global butadiene market is indicating reasonable growth – it is also expected
that it will move upwards by 2-2.5% annually in the coming 5-6 years. The butadiene markets in
the developed countries are not considered as considerable contributors to the demand growth –
the market has already reached its saturation point. However the developing BRIC countries
make up the major driver behind the butadiene industry activity.
The global capacity of Butadiene was 12 MMT in 2011 against demand of 9 MMT. The capacity
is expected to increase to 14 MMT in 2016 with demand reaching 12 MMT. In India total
Butadiene capacity is expected to reach 528 KTA by 2016-17 and IOC has planned capacity
expansion to 138 KTA by 2016-17 followed by OPAL 95 KTA

Up to 50% of the produced volume of butadiene is taken up by SBR and polybutadiene. These
applications are forecast to lead the demand in the near future as they are both set to lavishly
develop through 2017.

Butadiene is used to manufacture rubber for tires, hoses, gaskets, paints and adhesives. It is also
used in the production of nylon clothing, carpets and engineering plastic parts.

It has been the subject of intensive theoretical and experimental studies to understand its physical
and chemical properties. The conjugation of the double bonds makes it 15 kJ/mole (3.6 kcal/mol)
[14] more thermodynamically stable than a molecule with two isolated single bonds. The s-trans
isomer, often called the trans form, is more stable than the s-cis form at room temperature.
Although there is a 20 kJ/mole (4.8 kcal/mol) rotational barrier, rapid equilibrium allows
reactions to take place with either the s-cis or s-trans form [16]

The double-bond length in 1,3-butadiene is 0.134 nm, and the single-bond, 0.148 nm Since
normal carbon-carbon single bonds are 0.154 nm, this indicates the extent of double-bond
character in the middle single-bond. Upon complexing with metal carbonyl moieties like
Fe(CO)3, the two terminal bonds lengthen to 0.141 nm, and the middle bond shortens even more
to 0.145 nm [14][17]

Solubilities of 1,3-butadiene and many other organic compounds in water have been extensively
studied to gauge the impact of discharge of these materials into aquatic systems. Estimates have
been advanced by using the UNIFAC derived method [14], Similarly a mathematical model has
been developed to calculate the vapor - liquid equilibrium VLE for l3-butadiene in the presence
of steam [17]

Table : Properties of 1, 3 Butadiene (Air Liquide MSDS, 2005) &[14]

PROPERTIES VALUES

Physical state at 20 °C Liquefied gas.

Colour Colorless gas.

Odour Poor warning properties at low concentrations.

Molecular weight 54.092 g/mol

Melting point "freezing point" -108.888 ºC

Boiling point -4.5°C at 0.999 atm

Critical temperature 152°C

Critical pressure 4.32 MPa

Critical volume 221 cm3/mol

Heat capacity gas 25°C , 79.538 J/(mol.°K)

Vapour pressure, 20°C 2.4 bar

Viscosity (liq.) at 0°C , 0.25 cP

Solubility in water at 25°C , 735 ppm/L

Relative density, gas (air=1) 1.9

Relative density, liquid (water=1) 0.65

Flammability range [vol% in air] 1.4 to16.3

Auto-ignition temperature [°C] 415

Other data Gas/vapour heavier than air. May accumulate in confined
spaces, particularly at or below ground level

Molecular formula C4H6 , CH2==0.134nm==CH--0.148nm--CH==0.134nm==CH2

Antoine constant A = 15.7727 , B = 2142.66 , C =-34.3

Tmin = -58ºC – Tmax = 17ºC, T(ºK), P(mmhg)[15]

Heat of formation gas , 110.165 kJ/mol

Heat of formation liquid , 88.7 kJ/mol

Free energy of formation, 150.66 kJ/mol

Heat of vaporization at -4.5ºC, 418 J/fg

Flash point -85 ºC

 CHAPTER 2
LITERATURE REVIEW
LITERATURE REVIEW

2.1 Feed Properties :

The main feed supplied to the plant is crude C4 which mainly consisted of butanes (also called
normal butane or n-butane). According to Wikipedia (2018), butane is the unbranched alkane
with four carbon atoms, CH3CH2CH2CH3. Butane is also used as a collective term for n-butane
together with its only other isomer, isobutane (also called methylpropane), CH (CH3)3. Figure
shows the molecular structure of n-butane and isobutane.

Figure : Molecular structure of (a) n-butane and (b) isobutane Butanes are highly flammable,
colorless, easily liquefied gases. The properties of butane as feed are given in Table.

Table : Properties of Butane (Wikipedia 2018 and [15])

PROPERTIES VALUES

Molecular formula C4H10

Molar mass 58.08 g/mol

Appearance Colorless gas

Density 2.52 g/l, gas (15 °C, 1 atm)

Density of liquid Phase 0.584 g/cm3, at 15ºC and 1.8 atm

 Liquid Solubility in water 6.1 mg/100 ml (20 °C)

Melting point −138 °C

Boiling point −0.5 °C

2.2 Product Selection :

The team has been assigned by BCD Chemicals to design a plant which uses butane as the main
feed and to select the most economical butane derivative product. There are four potential
products discussed by the team;

1. Polyisobutylene

2. Maleic Anhydride

3. Propylene Oxide

4. Butadiene

According to Peters and Timmerhaus (1991), before any detailed work is done on the design, the
technical and economic factors of the proposed process should be examined. A feasibility survey
will give an indication of the probable success of the project and will also shows what additional
information is necessary to make a complete evaluation.

2.2.1 Polyisobutylene :

Polyisobutylene, also known as Butyl rubber (C4H8)n is a synthetic rubber, a homopolymer of 2-

methyl-1-propene. Polyisobutylene is produced by polymerization of about 98% of isobutylene
with about 2% of isoprene. Structurally, polyisobutylene resembles polypropylene, having two
methyl groups substituted on every other carbon atom. It has excellent impermeability, and the
long polyisobutylene segments of its polymer chains give it good flex properties.
Polyisobutylene is a colorless to light yellow viscoelastic material. It is generally odorless and
tasteless, though it may exhibit a slight characteristic odor (Wikipedia, 2018).
[https://en.wikipedia.org/wiki/Butyl_rubber]
The formula is for polyisobutylene is shown in Figure :

Figure : Polyisobutylene

Application:

Polyisobutylene is used in making adhesives, agricultural chemicals, fiber optic compounds,

cling film, electrical fluids, lubricants (2 cycle engine oil), paper and pulp, personal care
products, pigment concentrates, for rubber and polymer modification, as a gasoline/diesel fuel
additive, and even in chewing gum. The first major application of butyl rubber was tire inner
tubes. This remains an important segment of its market even today.

Strengths and Weaknesses

One of the strengths of polyisobutylene is the increasing market demand of this product. The
region range for polyisobutlyne consimer is wide too. However, the production process is very
extreme since the feed needed to be heated up to 600oC for dehydrogenation process then later
coolded to -40oC for polymerization. The capital and operting cost of the process will be very
high.

2.2.2 Maleic Anhydride :

Maleic anhydride (cis-butenedioic anhydride, toxilic anhydride, dihydro-2,5-dioxofuran) is an
organic compound with the formula C4H2O3 (C=OCH=CHC=O2).

Figure : Maleic Anhydride

In its pure state, it is a colorless or white solid with an acrid odor. Maleic anhydride is refined
pure white crystal at room temperature and transformed to colorless liquid at heating. It is
sublimate. (Wikipedia, 2018) [https://en.wikipedia.org/wiki/Maleic_anhydride]

Application:

Maleic anhydride is used as a chemical intermediate in the synthesis of fumaric and tartaric acid,
certain agricultural chemicals, resins in numerous products, dye intermediates, and
pharmaceuticals. It is also used as a co-monomer for unsaturated polyester resins, an ingredient
in bonding agents used to manufacture plywood, a corrosion inhibitor, and a preservative in oils
and fats.

Strengths and Weaknesses

Maleic anhydride market is very stable since it has been established for very long. However, it is
very hard for a new player to perform in the competitive environment. The market demand of
maleic anhydride is also slowed down recently.

2.2.3 Propylene Oxide [3]

Propylene oxide is a versatile chemical intermediate used in a wide range of industrial and
commercial products. By volume, it is among the top 50 chemicals produced in the world.

Figure : Propylene Oxide

Application:

Propylene oxide is a highly reactive chemical used as an intermediate for the production of
numerous commercial materials. It reacts readily with compounds containing active hydrogen
atoms, such as alcohols, amines, and acids. Therefore, propylene oxide is used worldwide to
produce such versatile products as:

 Polyether polyols (polyglycol ethers)

 Propylene glycols
 Propylene glycol ethers

Polyether polyols are one of the main components in polyurethane systems and are used in many
consumer applications, such as rigid foam insulation and flexible foam seat cushions. Polyether
polyols make up the largest share of propylene oxide usage, between 60% and 70% of the total
volume. Propylene glycol consumes another 20% of the total volume while propylene-based
glycol ethers comprise about 5%. The remaining share goes into other propoxylated or specialty
organic compounds. Also, other products made using propylene oxide are:

 Flame retardants
 Modified carbohydrates (starches)
 Synthetic lubricants
 Oil field drilling chemicals
 Textile surfactants

Strengths and Weaknesses

Although the market demand is growing, the production process of propylene oxide is very
complicated. Since the main reactant of for propylene oxide production is propylene, and the
feed only consisted of very small portion of propylene, additional process is required to
converted n-butane or isobutane to propylene. Hence, the process might not be economy feasible.

2.2.4 Butadiene :
1,3-Butadiene is a simple conjugated diene. It is an important industrial chemical used as a
monomer in the production of synthetic rubber. When the word butadiene is used, most of the
time it refers to 1,3-butadiene.
 Figure : Butadiene

Application:

The largest single use for butadiene is in the production of styrene- butadiene rubber (SBR)
which in turn is principally used in the manufacture of tires. According to Huntsman (2006),
about half of all butadiene consumption in the United States is for styrene butadiene rubber
(SBR) and polybutadiene (PB), the primary feed to tires manufacturing. Approximately 14% of
the butadiene consumed in the US goes into the production of nylon 6, 6 which is used in making
carpet. About 13 % of the butadiene is used in the manufacture of styrene butadiene latex (SBL)
which is further processed into products such as adhesives and carpet backing. Another
important use for butadiene is the production of acrylonitrile butadiene styrene (ABS) plastic
which is used for pipe, automotive components and housings for electronic equipment such as
telephones and computers.

2.3 Market :

The single largest use for butadiene is in the production of synthetic elastomers including
styrene-butadiene rubber (SBR) and polybutadiene rubber, both of which are consumed in the
manufacture of tires. Other elastomer applications include nitrile rubber hoses, mechanical belts,
carpet backing, footwear, and neoprene products. Butadiene is also copolymerized into plastics,
the largest-volume being acrylonitrile-butadiene-styrene (ABS) resins, which are used in various
applications.

Because of the global nature of butadiene production and its diverse applications, it is impacted
by various dynamics including changes in the production of ethylene, fluctuations in energy
markets, and general economic cycles.

The following pie chart shows world consumption of butadiene:

Since the late 1990s, growing demand for elastomers and other polymers in Asia has led to an
increase in butadiene demand; however, the demand for natural rubber is still strong and
maintains some downward pressure on commodity synthetic rubbers.

In regions where downstream markets are still developing, such as the Middle East and Asia,
demand growth will be robust. Continued economic and demand growth in China will secure the
country’s position as the world’s largest producer and consumer of butadiene. In the more
mature markets of North America, Western Europe, and Japan, growth will be much slower or
even declining over the forecast period. With the rapid development in China, Asia has emerged
as the world’s most active butadiene market, with new capacity being built close to naphtha-fed
steam crackers and downstream derivatives production expanding rapidly. Analysts anticipate
that automobile sales in emerging markets will double or possibly triple over the next 10–15
years, driven by the expanding middle and upper classes. Given the current economic conditions,
however, companies will continue to exercise caution in planning and executing new capacity
buildup, particularly with instability in both naphtha and butadiene pricing.

Elastomer production represents 60–65% of world butadiene demand, with a majority consumed
in tires. Butadiene demand in tires depends on a variety of factors including new vehicle
production, tire design (tread wear, performance, operating conditions, etc.), replacement tire
demand/consumer spending, and the price of competitive elastomers, including natural rubber.
Additional factors that have impacted tire markets in recent years include the development of
renewable materials for use in tire manufacture and a focus on improved energy efficiency, as
required by labeling laws enacted in Europe. The other butadiene-based elastomers, nitrile and
polychloroprene, are not used in tires, but both are used extensively in various other automotive
applications such as hoses, belts, seals, and gaskets, and as impact modifiers for resins used for
automotive parts.

ABS resin production is the largest nonrubber market and the third-largest individual end use for
butadiene, accounting for nearly 14% of total global consumption in 2017. Used in various home
and office appliances, personal electronics, and automotive components, global demand will
likely improve at a rate of 4–5% annually on end-market growth. Demand in SB copolymer
latexes (used in paper products and carpet backing) and adiponitrile (which is predominantly
converted into hexamethylenediamine [HMDA] and used to produce nylon 66 fibers and resins)
will experience 1–2% growth annually. Consumption for other applications, particularly styrenic
block copolymer elastomers, which are consumed in footwear, asphalt, and adhesives/sealants, is
likely to increase as a result of both improved demand in developing regions and producers and
investors looking to improve their return on investment through greater diversification of product
offerings.

Global butadiene demand is expected to grow at an average annual rate of about 2% during
2017–22. ABS resin manufacture is the fastest growing application for butadiene at just over 4%
per year and accounts for about 27% of the total volume growth. Elastomer manufacture is
forecast to grow at a slower rate of about 2% per year, but to account for 61% of the butadiene
volume growth in the next five years. [19]

And old studies say according to CMAI (25 March 1999 18:32pm), global butadiene demand is
expected to grow at just under 3.5%/year through 2012, slightly above the average of 3.2%/year
growth of the past five years. Demand in India will be the largest, growing nearly 15%/year for
the next five years. Demand in Asia is expected to exceed 5%/year, although demand in some
countries, primarily China, will be at more than 10%, analysts say. Demand in North America
and Western Europe is expected to rise at less than 1%.

Most of the capacity will be added in Asia, particularly China, which will account for nearly
75% of new capacity, added before 2012. Operating rates in Asia are expected to be strong at
85%-90%, while operating rates in Europe will be highest, at about 90%, analysts say. Operating
rates in North America are expected to hover in the 70% range, they say. Table 2.3 shows the
butadiene producer and production rate in Asia. Notice that in Malaysia, there is only 100,000 mt
/year production totally.

Production Rate
Country Producers
(in thousands of MT./year)
Yangzi Petrochemical 185
CNOOC Shell Petrochemicals4 155
Maoming Petrochemical 150
Jilin Chemical 140
Qilu Petrochemical 130
China
Lanzhou Petrochemical 120
Shanghai Petrochemical 120
Yanshan Petrochemical 113
Others 395
Total 1508
Reliance Industries 150
India Others 172
Total 322
Japan Synthetic Rubber 268
Chiba Butadiene 177
Japan
Nippon Zeon 150
Okayama Butadiene 140
 Tobu Butadiene 130
Tonen General 105
Nippon Petrochemicals 70
Total 1040
Yeochon Naphtha Cracking Centre 218
Korea Kumho Petrochemical 205
LG Chemical 145
Lotte Daesan Petrochemical 109
Korea Samsung Petrochemicals 99
LG Daesan Petrochemical 98
SK Corp. 72
SK Energy 72
Total 1018
Titan Petchem 100
Malaysia
Total 100
60
Singapore
Total 60
Formosa Petrochemical 373
Taiwan Chinese Petroleum 173
Total 546
Bangkok Synthetics 140
Thailand IRPC5 65
Total 205
Average: 149.96875
 2.4 Butadiene Manufacturing Process Information :

Butadiene is produced commercially by three processes:

1) Steam Cracking of Paraffinic Hydrocarbons: In this process, butadiene is a co- product in the
manufacture of ethylene (the ethylene co-product process).
2) Catalytic Dehydrogenation of n-Butane and n-Butene (the Houdry process).
3) Oxidative Dehydrogenation of n-Butene (the Oxo-D or O-X-D process).

Each of these processes produces a stream commonly referred to as crude butadiene that is rich
in 1,3-butadiene.

2.4.1 Butadiene Production Via Steam Cracking of Paraffinic Hydrocarbons

The steam cracking process is reported to be the predominant method of the three processes of
production, accounting for greater than 91% of the world's butadiene supply. Figure depicts a
flow chart for a typical olefins plant. While this does not represent any particular plant, and there
are certainly many variations among olefins plants, this representation will provide the reader
with a general understanding of the process.

The indicated feedstocks (ethane, propane, butane, naphtha and gas oil) are fed to a pyrolysis
(steam cracking) furnace where they are combined with steam and heated to temperatures
between approximately 1450-1525 °F (790-830 °C). Within this temperature range, the feedstock
molecules "crack" to produce hydrogen, ethylene, propylene, butadiene, benzene, toluene and
other important olefins plant co-products. After the pyrolysis reaction is quenched, the rest of the
plant separates the desired products into streams that meet the various product specifications.
Process steps include distillation, compression, process gas drying, hydrogenation (of
acetylenes), and heat transfer. The focus of this review is 1,3-butadiene;however, since butadiene
is created in the olefins plant pyrolysis furnace, and is present in the crude butadiene product
stream at concentrations up to approximately 75 wt%, the olefins plant process and the crude
butadiene stream are addressed in this publication to a limited degree.
The flow path of the C4 components (including butadiene) are indicated by bold [red] lines.
While some olefins plant designs will accommodate any of the listed feedstocks, many olefins
plants process only Natural Gas Liquids (NGLs) such as ethane, propane and sometimes butane.
The mix of feedstocks, the conditions at which the feedstocks are cracked, and the physical plant
design, ultimately determine the amount of each product produced, and for some of the streams,
the chemical composition of the stream.

2.4.2 Butadiene Production via Catalytic Dehydrogenationof n-Butane and n-Butene (the
Houdry process)

The catalytic dehydrogenation of n-butane is a two-step process; initially going from n-butane to
n-butenes and then to butadiene. Both steps are endothermic.A major butane-based process is the
Houdry Catadiene process outlined in Figure.
In the Houdry process, n-butane is dehydrogenated over chromium/alumina catalysts. The
reactors normally operate at 12-15 centimeters Hg absolute pressure and approximately 1100-
1260 °F (600-680 °C). Three or more reactors can be used to simulate continuous operation:
while the first reactor is on-line, the second is being regenerated, and the third is being purged
prior to regeneration. Residence time for feed in the reactor is approximately 5-15 minutes. As
the endothermic reaction proceeds, the temperature of the catalyst bed decreases and a small
amount of coke is deposited. In the regeneration cycle, this coke is burned with preheated air,
which can supply essentially all of the heat required to bring the reactor up to the desired
reaction temperature.

The reactor effluent goes directly to a quench tower, where it is cooled. This stream is
compressed before feeding an absorber/stripper system, where a C4 concentrate is produced to
be fed to a butadiene extraction system for the recovery of high purity butadiene.
2.4.3 Butadiene Production via Oxidative Dehydrogenation
of n-Butenes (the Oxo-D or O-X-D process)

Oxidative dehydrogenation of n-butenes has replaced many older processes for commercial (on-
purpose) production of butadiene. Several processes and many catalyst systems have been
developed for the oxydehydrogenation of either n-butane or of n-butene feedstocks. Butenes are
much more reactive, however, and they require less severe operating conditions than that of n-
butane to produce an equivalent amount of product. Therefore, the use of n-butane as a feedstock
in this process may not be practical.

In general, in an oxydehydrogenation process, a mixture of n-butenes, air and steam is passed

over a catalyst bed generally at low pressure and approximately 930-1110 °F (500-600 °C). The
heat from the exothermic reaction can be removed by circulating molten heat transfer salt, or by
using the stream externally for steam generation. An alternate method is to add steam to the feed
to act as a heat sink. The heat can then be recovered from the reactor effluent.Reaction yields and
selectives can range from 70-90%, making it unnecessary to recover and recycle feedstock.

Butadiene Production via Oxidative Dehydrogenation

 In the Oxo-D process shown in Figure, a mixture of air, steam, and n-butenes is passed over the
dehydrogenation catalyst in a continuous process. The air feed rate is such that an oxygen/butene
molar ratio of approximately 0.55 is maintained, and the oxygen is totally consumed. A steam to
butene ratio of 10:1 has been reported as necessary to absorb the heat of reaction and to limit the
temperature rise.

The reactor effluent is cooled and the C4 components are recovered in an absorber/degasser/
stripper column combination. The lean oil flows from the bottom of the stripper back to the
absorber, with a small amount passing through a solvent purification area. Crude butadiene is
stripped from the oil, recovered in the overhead of the stripper, then it is sent to a purification
system to recover the butadiene product.

2.4.4 Conclusion of Product Selection :

Comparisons for all four products have been tabulated in Table 2.4. Based on the comparisons,
the team has decided to select butadiene as the butane derivative product. The team decides to
design butadiene production plant because;
 Increasing market demand especially in Asia region. Demand in Asia will grow at a more rapid
rate, at 5% /year, although demand in some countries, particularly China, will be at more than
10%/year (CMAI, 2007).
 High market pricing of USD 0.64/lb which will give higher profit.
 Only one competitor in Malaysia, which is Titan Petchem. (M) Sdn. Bhd.
 Nearby neighbor, Singapore is only producing 60mt/yr.
 Aiming to be the major butadiene supplier in Asia
 Table : Comparison between potential Butane Derivative Product

Polyisobutylene Maleic Anhydride Propylene Oxide Butadiene

Market $1.30 per pound $0.63 per pound $0.64 per pound $0.64 per pound
pricing (1996-2001) (2007) (1995-2000) (2006)
Complexity Copolymerization Oxidation of 2 routes Catalytic
of the of isobutylene aromatic -chlorohydrin dehydrogenation
reactions compound -indirect of normal butane
oxidation
Strengths Tires,tubes the Mature market Price stable and Present market
largest end user rising demand firmed and
accounting for 75- increasing
80% total High market
consumption. potential

Fortunes tied Growth slowed Demand driven by Heavily relied on

heavily to tires down and No automotive, automotive
Weaknesses industry growth housing and industry
agriculture construction
chemical market
and oil
additives

The process which is here described in the project among these three processes is the production
of the n-Butadiene by oxydehydrogenation process.
2.5 CONCEPTUAL DESIGN ANALYSIS

The Hierarchical Decomposition Approach suggested by Douglas (1988) is consisted of 3

hierarchy of decisions, which are:

Level 1: Batch vs. Continuous

Level 2: Input-output Structure
Level 3: Recycle / Reactor Synthesis
Level 4: Separation

2.5.1 BATCH vs. CONTINUOUS

Continuous processes are designed so that every unit will operate continuously for close to a year
at almost constant conditions before the plant shut down for maintenance. On the other hand,
batch processes normally contain several units that are designed to be started and stopped
frequently. During a normal batch operating cycle, the units are filled with material and perform
their desired function for a specified period. After that, the units will be shut down, drained and
cleaned before the cycle is repeated (Douglas J.M, 1988).

According to Douglas (1988), there are a few criteria that needed to be considered when
selecting the type of process, which are:

1. Production rates:
Plant that has a capacity that is greater than 10 x 106 Ib/yr is usually continuous. In contrast,
if the plant’s capacity is less than 1 x 106 Ib/yr, then batch process will be chosen. Batch
process is usually simpler and more flexible. Therefore, a satisfactory product can be
produced with a large uncertainty in the design. Besides that, because of greater flexibility,
batch plants are most common when a large number of products are produced in essentially
the same processing equipment.

2. Market forces:
 Batch plants are often preferred for products with a seasonal demand. Batch process is also
preferred for products with a short life time.

3. Operational problems:
It is very difficult to build continuous processes when a low capacity of slurries must be
handled. This is because it is very hard to pump slurries at low flow rate without having the
solid settling out of the suspension and plugging the equipment problem. Some materials
tend to foul the equipment frequently that the equipment must be shut down and cleaned very
often. Hence, batch process is suitable for this kind of process instead of continuous.

Butadiene demand is not seasonal and it is forecasted to have 3.5 percent growth per year
through 2012 (CMAI, 2007). Besides, the production rate of butadiene plant that is decided is
more than 10 x 106 Ib/yr and no slurry material is involved in the process. Therefore,
continuous process is selected for butadiene production.

2.5.2 Purification of Feed

A decision to purify the feeds before they enter the process is equivalent to a decision to design a
preprocess purification system. Some design guidelines to be considered are as follows (Douglas,
1988):

i. If a feed impurity is not inert and is present in significant quantities, remove it. Otherwise it
will lead to raw-material losses, and usually a much complicated separation system is
required to recover the additional by-products.
ii. If a feed impurity is present in a gas feed, as a first guess process the impurity.
iii. If a feed impurity in a liquid feed stream is also a by-product or a product component, usually
it is better to feed the process through the separation system.
iv. If a feed impurity is present in large amounts, remove it.
v. If a feed impurity is present as an azeotrope with a reactant, often it is better to process the
impurity.
vi. If a feed impurity is inert but is easier to separate from the product than the feed, it is better
to process the impurity.
vii. If a feed impurity is a catalyst poison, remove it.
Table shows the composition of the component in feed. The main component that is to be used
in butadiene production is n-butane. However, the amount of isobutane in the stream is large
(39.3 mole %). If isobutane is not separated from the feed and is processed, additional by product
might be produced and thus complicated the separation process downstream. This will imposed
additional cost (capital and operating) to the plant. Hence, with reference to guideline i and iv,
the team decided to purify the stream first before entering to the reactor.

Table : Composition of the Components in the Feed

Component Formula Mole %

Propane C3H8 9.0

i-Butane (isobutene) C4H10 25.9

n-Butane C4H10 72.2

Other Hydrocarbon C5+ 1.0

Isobutane
Propane

n-butane
Feed Distillation
Column

C5+

Figure : Purification of the feed

Figure shows the schematic diagram of the feed purification section. Distillation column is used
to separate the impurities from the feed. As shown in the diagram, n-butane will be withdrew as
side draw product, while isobutane and propane will be withdrew from the distillation column as
the top product and C5+ as bottom product.

To convert n-butane to butadiene, two stages of dehydrogenation reaction are involved (non-
oxidative and oxidative dehydrogenation). The by product of the processes are hydrogen (H2),
carbon monoxide (CO), carbon dioxide (CO2), short chain hydrocarbon (C1-C3) and steam
(H2O). Figure 4.3 shows the schematic diagram of two stages of dehydrogenation process. Only
approximately 33% of n-butane will be converted to butadiene. Hence the unreacted n-butane
will be recycled.

O2

butenes
n-butane
n-butane Non-Oxidative H2 Oxidative
Dehydrogenation Dehydrogenation
Reactor Reactor butadiene
H2
H2O
C1-C3
CO
CO2
O2
n-butane

Figure : Two Stages Dehydrogenation of n-butane

Since only approximately 33% of n-butane will be converted to butadiene, the unreacted n-
butane will be recycled after separated of the product stream. It is impossible to achieve sharp
separation in the separation process. Hence, the recycle stream will consist of low fraction of
impurities. Hence, part of the recycle stream will be purged to avoid accumulation of the
impurities in the process stream.
2.6 Input Output Structure :

2.7 RECYCLE / REACTOR SYNTHESIS

Good reactor performance is of paramount importance in determining the economic viability of

the overall design and fundamentally important to the environmental impact of the process
(Smith, 2005). Therefore, issues to be addressed for a good reactor design should include;
1. Reactor type
2. Catalyst
3. Size
4. Operating Conditions (Temperature and Pressure)
5. Phase
6. Feed Conditions (Concentration and temperature)

At early stages in design, a kinetic model normally is not available. Thus, material balance
calculations should be based on a correlation of the product distribution (Douglas, 1998). This
type of kinetic analysis is very crude but in most cases the reactor cost is not nearly as important
as the product distribution costs.

2.7.1 Reactor Selection

The selection of reactor is crucially important in order to make sure that the feed operates at its
maximum. For single reaction, the highest rate of reaction is maintained by the highest
concentration of feed (Smith, 2005). Based on the design guidelines for reactors by Douglas,
1998 stated that in order to maximize the conversion, reactor that always maintains the highest
concentration should be selected. The ideal plug flow reactor (PFR) is chosen for all three
reactors because it always maintains higher concentration of the reactant. Beside, all three
reactions is in gas phase and PFR is also suitable for gas phase reaction.

Since the reaction is carried out in gas phase over a selective catalyst, the options for type of
reactor selection for this type of reaction are fixed-bed catalytic reactor and fluidized bed reactor.
The structure of fixed bed catalytic reactor is similar to a shell and tube heat exchanger. It is a
tubular reactor that is packed with solid catalyst particles. It gives the highest conversion per
weight of catalyst of any catalytic reactor. It is suitable to be used for high pressure reaction
where smaller diameter cylinder vessels are used to allow usage of thinner vessel walls. Fixed
bed catalytic reactor is also suitable for process that uses catalyst with a long life time. However,
it has difficulty with temperature control because heat loads vary through the bed. Temperature
in the catalyst might become locally excessive, which may lead to undesired product and catalyst
deactivation. The catalyst is usually troublesome to replace too. Besides, channeling of the gas
flow might occur in the reactor which will result ineffective use of parts of the reactor bed.

On the other hand, fluidized bed reactor is designed to be operated in a well mixed condition
between the gas phase reactant and catalyst, which result in an even temperature distribution
throughout the bed. Since the temperature is relatively uniform throughout the reactor, the
possibility of having hot spots n the reactor can be eliminated. The heat transfer rate is high due
to the rapid motion of the catalyst. It can also handle large amounts of feed and solids and has
 good temperature control. One of the disadvantages of fluidized bed reactor is high operating
cost. Furthermore, the attrition of catalyst can cause generation of catalyst fines which could be
carried over and lost in the system. This may cause fouling in the pipelines or equipment
downstream. Hence, fluidized bed reactor is Preferable for gas-solid non-catalytic reactions. The
advantages and disadvantages of both types of reactors are summarized in Table .

Table : Advantages and Disadvantages of Packed Bed and Fluidized Bed Reactor

Reactor Fixed Bed Catalytic Reactor Fluidized Bed Reactor

 It gives the highest conversion per
weight of catalyst of any catalytic
reactor.
 Used for high pressure reaction where
Advantages smaller diameter cylinder vessels is
used to allow usage of thinner vessel
walls.
 High heat transfer due to rapid
motion of catalyst.
 The temperature is relatively
uniform throughout the catalyst,
thus avoiding hot spots.
 Can handle large amounts of feed
and solids and has good
temperature control.

 Difficult to control the temperature  High cost of the reactor and

because heat loads vary through the
bed.
 Temperature in the catalyst becomes
locally excessive, which may lead to
undesired product and catalyst
Disadvantages
deactivation.
 The catalyst is usually troublesome to
replace.
 Channeling of the gas flow occurs,
resulting in ineffective use of parts of
the reactor bed.
catalyst regeneration equipment.
 Attrition of catalyst can cause
generation of catalyst fines which
could be carried over and lost in
the system, and may cause fouling
in pipelines and equipment
downstream.
 Preferable for gas-solid non-
catalytic reactions.
After comparing both types of reactor, tubular fixed-bed catalytic reactor is chosen for all three
reactors involve in the process. This is due to the:

a. lower capital and operating cost

 The reactions involved in the butadiene production are required to be operated in high
pressure condition.

 The required volume for tubular fixed bed catalytic reactor is smaller compared to
fluidized bed reactor for high pressure operation, and thus lower capital cost.

 The operating cost for fluidized bed reactor is very high because it is more difficult to
maintain the gas phase reactant and catalyst to be in the well mixed condition if it is
operated in high pressure.

b. less losses in catalyst

 There will be losses in catalyst if fluidized bed reactor is selected.

 The losses in catalyst are resulted from:

 catalyst will settle at the bottom of the reactor if it is not well mixed with the gas phase
reactant.

 catalyst fine might be generated during the operation of the reactor when the catalyst hit
on the wall of the reactor or through attrition. The catalyst fine will be brought to the
downstream of the process when together with the product stream.

c. lower maintenance cost

 If fluidized bed reactor is selected, the catalyst that settle at the bottom of the reactor will
foul and plug the reactor while the generated catalyst fine will cause fouling in the
pipeline and equipment downstream

 Plant might need to be shut down often for maintenance.

2.8 SEPARATION STRUCTURE

The core reaction in butadiene production is the dehydrogenation using n-butane as the reactant.
However, the feed stream contains significant amount of i-butane which is up to 39.3%. Thus, in
order to increase yield, we need to convert i-butane into n-butane. The conversion is done in the
Isomerization Reactor.

The deisobutanizer column in pretreatment section employs side draws to yield purified n-
butane. The n-butane stream is drawn as a vapor side product a few trays above the bottom,
leaving a small heavy end stream which is only about 1% of the feed stream to be the bottom
product. Thus, the system consists of two prominent products and we can assume that the small
stream does not exist.

The initial assumption for distillation columns is to have 0.02 mole percent of light key
component in bottom and 0.01 mole percent of heavy key component in the overhead product.
Also, we assume that all the component lighter than the light key leave with overhead and that all
components heavier than the heavy key are taken at the bottoms.

2.8.1 Design of Extractive Distillation Column :

According to Seader (1998), extractive distillation is a partial vaporization process in the
presence of a miscible, high-boiling, non-volatile mass separation agent, normally called the
solvent, which is added to an azeotropic or non-azeotropic feed mixture to alter the volatilities of
the key components without the formation of any additional azeotropes.

2.8.2 Solvent selection:

Since the solvent is the heart of extractive distillation, more attention should be paid on the
selection of potential solvents. The affinity of hydrocarbon to polar solvent depends directly on
their degree of un-saturation. A highly unsaturated hydrocarbon is more soluble in a polar
solvent, and the solvent decreases the volatility of the hydrocarbon.

Based on Perry’s Handbook, several features are essential:

1. The solvent must be chosen to affect the liquid-phase behavior of the key components
differently; otherwise no enhancement in separability will occur.
2. The solvent must be higher boiling than the key components of the separation and must be
relatively nonvolatile in the extractive column, in order to remain largely in the liquid phase.
3. The solvent should not form additional azeotropes with the components in the mixture to be
separated.
4. The extractive column must be a double-feed column, with the solvent feed above the
primary feed; the column must have an extractive section.
From Ullman’s handbook (1985), there are five solvents that are commonly used in industry:
a. n-methyl-2-pyrrolidone (NMP),
b. dimethylformamide (DMF)
c. Dimethylacetamide (DMAC)
d. Acetonitrile (ACN)
e. Furfural
Of all possible solvents that can be used for the separation of butadiene-butane mixture we have
chosen dimethylformamide (DMF). DMF is recommended as a potential entrainer because it
gives great alteration in relative volatility. This in turn will make the separation easier and
cheaper, as the utilities and trays required are lesser. Even though NMP gives greater value, it
costs almost twice the DMF.
 CHAPTER 3
PROCESS DESCRIPTION
Process Description

In this project, butadiene is produced in continuous process. Here the 1,3-butadiene is produced
by oxidative dehydrogenation reaction.
3.1 Preprocess Purification – Deisobutanizer :

E-102

C-101

E-101

Figure : Preprocess Purification Section

The main objective of this pre-treatment unit is to extract n-butane from the feed. The extracted
n-butane will be used as the reactant for the dehydrogenation process in order to produce
butadiene.

The feed omposition is as follows :

Table : Feed Composition

Component Formula Mole %
Propane C3H8 9.0
i-Butane C4H10 25.90
n-Butane C4H10 72.2
Other Hydrocarbon C5+ 1.0

From the table, it can be seen that the feed also contains significant amount of i-butane which is
25.90 %. In order to fully utilize the feed, the separated i-butane will be sent to isomerization
section to undergo the isomerization process that will convert i-butane to n-butane.

The distillation column, C-101 will recover i-butane as the top product. The overhead product of
the column also consists of significant amount of n-butane. For the sake of purity, the overhead
product will enter the vapor recovery system which is the condenser (E-102). The operating
temperature and pressure of E-102 are 40.71oC and 300 kPa. The condensed product which is
mainly n-butane will be recycled back to C-101 while the vapor product which is mainly i-
butane will be sent to the Alkylation Section. N-butane is extracted as the side product. This n-
butane will enter the Reaction Section to undergo the dehydrogenation process. The bottom
product of this column consists of the heavier product which is the condensate (C5+) together
with considerable amount of n-butane. The bottom stream of column will then enter the reboiler
(E-101) to recover the n-butane.
3.2 Dehydrogenation Section
The third section of the plant is the dehydrogenation unit. The main objective of the unit is to
convert the n-butane to the product desired, Butadiene. The section involves two steps of
dehydrogenation processes which are the non-oxidative dehydrogenation and oxidative
dehydrogenation. The processes are represented by Dehydrogenation Reactor (R-301) and
Oxidative Dehydrogenation Reactor (R-302) respectively.

Figure : Dehydrogenation Section

Air

K-401

R-302
R-301

Furnace Fuel

E-303

E-301 E-302

The process gas from Section 1, the preprocess unit enters the furnace (F301) at 42.92 oC. The
furnace will heat up the process gas up to 600oC. The heated process gas will enter the
Dehydrogenation Reactor (R301) where the n-butane will be converted in to butenes. Hydrogen
and other byproduct such as C1 – C3 will also form.The Dehydrogenation Reactor (R301) is a
 fixed bed tubular reactor operating at temperature of 500oC and pressure of 3 bar. The reaction is
an exothermic reaction and the temperature is maintained using molten salt at the shell side of
the reactor. The catalyst used in the reactor is the Pt0.3 Sn0.6Cs0.5K0.5 La3.0 which gives the
conversion of 32.9 % and selectivity of 96%.

The butenes from R301 will be cooled down from 600oC to 420oC by Dehydrogenation Inter-
cooler (E301) before further supplied to Oxidative Dehydrogenation Reactor (R302). The R302
is also a fixed bed tubular reactor and is operating at temperature of 330oC and pressure of 3 bar.
The reaction is an exothermic reaction and the temperature is maintained by molten salt. The
catalyst used in the reactor is the Mo12Bi1Cr3Ni8Zr1Fe0.1K0.2 which gives the conversion of 99 %
and selectivity of 96%.

The Oxidative Dehydrogenation Reaction in R302 will convert the butenes to butadiene and also
byproducts such as C1-C3, Carbon Oxide, Carbon Dioxide (CO2 ), water (H20) , and Hydrogen
(H2 ). The product gases from the reactor need to be cooled down to 24.48oC by two
Dehydrogenation Reactor Coolers which are the E302 and also E303 before can be sent to
Section 3, the purification section.

3.3 Purification Section

The purity of 1,3-butadiene produced is demanded to be at least 99.6%. To achieve the high
purity, purification section is employed to separate 1,3-butadiene from any impurities.

Solvent Top up
From Storage

C4 recycle stream
23

P-401
E-404
C-401

E-402

17 C-402
V-404
2
P-403
Product to Storage
V-403
22

15

P-402

16

E-403
Feed from reactor

18
E-401 21

V-401

14
V-402
K-401

19

Solvent recycle
4
 Figure : Purification Section

The product stream which comes from reactor section contains component as heavy as water and
as light as hydrogen.

Table 2: Product Stream from Reactor

Mole
Component NBP (oC)
Fraction
Hydrogen -252.60 0.0099
CO -191.45 0.00018
Oxygen -182.95 0.0329
CO2 -78.55 0.00028
butenes -6.25 0.0029
1,3-butadiene -4.45 0.3487
n-butane -0.50 0.5815
H2O 100.00 0.0233
TOTAL 1

Due to wide array of component’s boiling point, different method of separation is utilized. First
is by cooling the stream to achieve partial condensation which is happened in the previous
section. The stream is then introduced to flash drum V-401 to separate the liquid phase which is
essentially water from the gaseous phase. The liquid phase is sent to water treatment section
while the gas is fed into compressor K-401 to do partial condensation by compression. The K-
401 outlet stream is sent to a flash drum V-402 to separate off-gas from C4 which is the liquid
phase.
Afterward, liquid C4 stream enter a distillation column C-401. Since the relative volatility is very
low, thus extractive distillation is employed where solvent is introduced at the upper trays and
feed enters the column at lower tray of C-401. The column is equipped with a condenser E-402
at 30oC and 304kPa of operating condition and a reboiler E-403 to supply heat at 70oC and
354kPa of operating condition. The overhead product consists of all the feed but solvent and 1,3-
butadiene. Overhead product is sent back to C-101 Pretreatment Section. On the other hand,
solvent extracts 1,3-butadiene from the feed stream and leave the column as bottom product to
solvent recovery column, C-402.

The C-401 bottom product enters solvent recovery column, C-402. The purpose of C-402
column is to recover solvent and produce 99.7% purity of 1,3-butadiene. The heat to column C-
402 is supplied by a reboiler E-403. The operating condition of E-403 is at temperature 208oC
and pressure 355kPa. The bottom product is the solvent which will be recycled to column C-
401, while overhead of the column is cooled down in a condenser with operating condition is at
27.45oC and 304kPa and collected in a reflux drum. Eventually, final product of 1,3-butadiene
flows from the reflux drum to storage.
CHAPTER 4 : MATERIAL & ENERGY BALANCE
 Material Balance

4.1 Distillation Column :

Isobutane
Propane

n-butane
Feed Distillation
Column

C5+

Light Key Component : i-C4

Heavy Key Component : n-C4

Feed = 3000 kmol/hr

Feed Distillate Bottoms

Components Xf mole % Xd mole% Xb mole%
C3 27 0.009 27 0.03710499 0 0
i-C4 777 0.259 693.084 0.95247676 83.916 0.036929
n-C4 2166 0.722 7.581 0.01041826 2158.419 0.949868
C5+ 30 0.01 0 0 30 0.013202
Total 3000 1 727.665 1 2272.335 1

Split Fractions of LK = 0.892

For Distillate:

LLK C3 : In = Out = 27 kmol/hr

LK i-C4 : 777*0.892 = 693.084 kmol/hr

HK n-C4 : (1 – 0.9965)*2166 = 7.581 kmol/hr

Total : 727.665 kmol/hr

For Bottoms :

LK i-C4 : 777-693.084 = 83.916 kmol/hr

HK n-C4 : 2166-7.581 = 2158.419

HHK C5+ : 30 kmol/hr

4.2 Non-Oxidative Dehydrogenation Reactor :

Dehydrogenation
Reactor 1
n-butane n-butane
1-butene
trans-2-butene
cis-2-butene
butadiene
C1s-C3s

n  C4 H10  C4 H 8  H 2 (1  butene)
n  C4 H10  C4 H 8  H 2 (cis  2  butene)
Reaction : n  C4 H10  C4 H 8  H 2 (trans  2  butene)
1 1 3
n  C4 H10  C4 H 8  C4 H 6  H 2 (butadiene)
2 2 2
Assumption : 35% conversion of n-Butane to (1,cis,trans) Butenes

Components Feed (kmol/hr) (kg/hr) Product (kmol/hr) (kg/hr)

n-C4 2158.419 131339.7962 1402.97235 81544.9619
Butenes 0 0 863.3676 48440.9659
H2 0 0 671.5081333 1353.7604
131339.7962 2937.848083 131339.688

n-C4 : 2158.419-(2158.419*0.35) = 1402.9723 kmol/hr

Butenes : ( 2158.419*0.35)*(4/3.5) = 863.36 kmol /hr

H2 : (2158.419*0.35)*(4/4.5) = 671.50 kmol/hr

4.3 Oxidative Hydrogenation Reactor :

O2

Dehydrogenation
Reactor
n-butane n-butane
1-butene 1-butene
trans-2-butene trans-2-butene
cis-2-butene cis-2-butene
butadiene butadiene
CO
CO2
O2
 C4 H 8  C4 H 6  H 2
Reactions : C4 H 8  4O2  4CO  4 H 2O
C4 H 8  6O2  4CO2  4 H 2O

Amount of O2 added : (863.3676*3/10)*(1.07) = 277.1409996

Conversion : 99.16 % of reacted of Butenes for Butadiene & 50% O2 is reacted.

Components Feed (kmol/hr) (kg/hr) Product (kmol/hr) (kg/hr)

n-C4 1402.97235 81372.3963 1402.97235 81372.3963
Butadiene 0 0 856.1153122 48798.5728
Butenes 863.3676 48348.5856 7.25228784 413.380407
H2 671.5081333 1343.016267 671.5081333 1399.28865
O2 277.1409996 8868.511987 138.5704998 4614.39764
H2O 0 0 173.2131248 3268.53166
CO 0 0 0.90653598 26.1082362
CO2 0 0 0.90653598 40.0054328
139932.5102 139932.681

n-C4 : In = out = 1402.97235

Butadiene : 863.3676*0.9916 = 856.1153122

Butenes : 863.3676 - (863.3676*0.9916) = 7.25228784

H2 : In = Out = 671.5081333

O2 : (277.1409996*0.50) = 138.5704998

H2O : (277.1409996*0.50)*(10/8) = 173.2131248

CO : ((863.3676 - (863.3676*0.9916)) / 2) = 0.90653598

CO2 : ((863.3676 - (863.3676*0.9916)) / 2) = 0.90653598

 Energy Balance :

4.3 Distillation Unit :

Inlet Temperature = 313 K

Overhead Temperature = 510 K

Temperature Difference = 197 K

Distillate Flow Rate Cp Enthalpy

KJ/kmol
Components Xd mole% in Kg/hr K H (KJ/hr)
C3 27 0.037104986 1188 76.701 407972.619
i-C4 693.084 0.952476758 40198.872 101.475 13855147.68
n-C4 7.581 0.010418256 439.698 101.475 151548.5491
C5+ 0 0 0 114.002 0
Total 688.37109 1 41826.57 14414668.85

Q = mCpΔT

Condenser Duty Qc = (Qv- QD-QL)

V = 1.408836 kmol/sec

Cp = 89.72 J/kmol K

Qv = 14.4088*3600*89.72*( 510-273)

Qv = 107845163 KJ/hr

L = 1.206707 kmol/sec

Cp = 119 J/kmol K

QL = 1.206*119*(298-273)

QL = 12916260 KJ/hr
Similarly we can find the QD for distillate in which temperature difference is taken as

( 773-273) K

Reference Temperature is 273 K

QD = 25361268.33 KJ/hr

Hence Condenser Duty Qc = 107845163 – 12916260 - 25361268.33

Qc = 69567634 KJ /hr

For Bottom

Inlet Temperature = 313 K

Bottom Temperature = 773 K

Temperature Difference = 448 K

Bottoms Flow Rate Cp Enthalpy

Components Xb mole% in Kg/hr KJ/kmol K H (KJ/hr)
C3 0 0 0 68.318 0
i-C4 83.916 0.03692941 4867.128 104.766 3938611.6
n-C4 2158.419 0.94986831 125188.3 104.766 101305758
C5+ 30 0.01320228 2100 117.592 1580436.5
Total 2149.629 1 132155.4 106824806

Reboiler Duty QB = QW+QD+QC-QF-QL

Reference Temperature = 273K

For Qw temperature difference = 773-273=500 K

QW = 224598914 KJ/hr
For feed stream Temperature difference = 313-273= 40 K

Qf = 16100760 KJ/hr

Hence Reboiler Duty QB

QB = 224598914 +25361268.33 +69567634 -16100760 – 12916260

QB = 290510796 KJ/hr

4.5 Non-Oxidative Dehydrogenation Reactor :

Inlet Temperature : 773 K

Outlet temperature : 603 K

Temperature Difference : 170 K

Component Mλ ( KJ/hr)
C3H8 18.774
i-C4 21.297

n-C4 22.383
Butenes 68.02
Butadiene 22.468

Components Product (kmol/hr) Cp (KJ/kmol K) Enthalpy H (KJ/hr)

n-C4 1402.97235 197.955 47213338.95
Butenes 863.3676 169.333 24853494.41
H2 671.5081333 30.043 3429600.204
Total 2937.848083 75496433.56

Enthalpy of outlet stream of Non-oxidative dehydrogenation = 75496433.56 KJ/hr

4.6 Oxidative Dehydrogenation Reactor :

Inlet Temperature : 603 K

Outlet Temperature : 295 K

Temperature Difference : 308 K

Components Product Cp (KJ/kmol Enthalpy H

(kmol/hr) K) (KJ/hr)
n-C4 1402.97235 168.927 72995994.71
Butadiene 856.1153122 133.674 35247652.81
Butenes 7.25228784 144.458 322744.527
H2 671.5081333 29.381 6076710.783
O2 138.5704998 31.692 1352605.494
H2O 173.2131248 36.424 1943207.376
CO 0.90653598 31.425 8774.271097
CO2 0.90653598 45.468 12695.26041
Total 3251.44478 117960385.2

Enthalpy of outlet stream of Oxidative Dehydrogenation Reactor = 117960385.2 KJ/hr.

CHAPTER 5 : DESIGN OF EQUIPMENTS
 Design of Equipments

5.1 Design of Distillation Column

Calculation for Rmin

Rmin + 1 = ∑((άi xi)/(άi -φ))

ά X ((άi xi)/(άi -φ))

C3 3.45 0.009 1.473051

i-C4 1.38 0.259 -0.17444

n-C4 1 0.722 -0.29725

C5+ 0.41 0.01 -0.00136

Total 6.427255

By Trial and Error we get the value of φ = 1.228921306

Rmin = 5.427

R/ Rmin =1.1

R= 5.9699 ≈ 6

Calculations for Nmin :

Where xdi and xbi are molefractions light key component in distillate and bottom respectively &
xdj and xbj are molefractions heavy key component in distillate and bottom.

xDi 0.9524768

xBi 0.0369294

xDj 0.0104183

xBj 0.9498683

α 1.375

By evaluating these values we get the minimum no. of trays required ,

Nmin = 23.376606

Calculation for No. of Trays and Feed stage location :

N  N min  1  54.4 x  x  1 
y  1  exp   0.5 
N 1  11  117.2 x  x 
where
 R  R min 
x 
 R 1 

x = 0.077866

y = (N-Nmin)/(N+1) = 0.576719

No. of trays N = 56

Height of the Column = Tray spacing x No. of trays = 56 * 0.5 = 28 m

Feed Stage Location :

0.206
   
2

Z
NRR/Ns = 2.63039 x  B 
N
   *
HK , Fand as weLKknow
,B
 *   56
NR + Ns =
 
N S  Z LK , F   xHK , D   D 
Hence NR = 40 = No. of Trays in Rectifying Section

And NS = 16 = No. of Trays in Stripping Section

COLUMN DIAMETER:

Overall balance: 𝐹 =𝑉+𝐿

Component balance: 𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖

Equilibrium: 𝑦𝑖 = 𝐾𝑖 𝑥𝑖
L= D*R

L =( 727.665/3600)*6 = 2.168681 kmol / sec

V = L +D = 2.168681 + (727.665/3600) = 2.37081 kmol/sec

ΡL = 750 Kg/m3 ρV = 2.3 Kg/m3

0.5
 L   
FLV    v 
 V   L 

Liq-Vap Flowrate FLv = (2.168/2.3708)*(750/2.3)0.5

= 0.050656 m/s

Flooding Velocity

0.5
   V 
U F  K  L 
 v 

For 0.5 m tray spacing K = 0.097

Flooding Velocity Uf = 0.097*((750-2.3)/2.3)0.5

= 1.748926 m/s

Design for 80% Flooding

V = 1.399141 m/s

Flowrate = Vapor velocity*M.W./ Density of Vapor

Net Area = (Flowrate / velocity) = 8.249589 m2

Downcomer Area = 12% of total Area

C/S Area = 9.374533 m2

Column Diameter = 3.4557315 m

Hence Actual Column Diameter = 3.5 m

C/S Area Ac = 9.61625 m2

Downcomer Area Ad = 1.15395 m2

Net Area An= Ac - Ad = 8.4623 m2

Active Area Aa= Ac - 2Ad = 7.30835 m2

Hole Area = 10% of active area = 0.730835 m2

Check for weeping

Weir Length lw = (0.77 x Column Dia)=(0.77*3.5)= 2.695 m

Max how= 750 (Lv / ρL*lw ) =750*(2.168681/(750*2.695)) = 8.72537 mm of Liq

Min how = 750 (V / ρL*lw ) =750*(2.37081/(750*2.695)) = 8.226993 mm of Liq

Assume hw =50 mm

hw+ how = 58.22699 mm

From Graph K= 32

Uh = ((K – 0.9(25.4 - d0))/ ρv0.5 )

= 8.99395 m/s
Actual min Vapor velocity through holes U = (min. vapor rate/ hole area) = 13.81919 m/s

Since U> Uh , there is no chance for weeping

Plate Pressure Drop

Pressure drop for flow of vapor through dry plate hd

hd = (51*(Uh/C0)2*(ρV/ρL) ) = 86.38675 mm of liq

Residual losses hr =( 12.5*103/ ρL ) = 16.66667 mm of liq ρL

hw+ how = 58.22699 mm

ht = hd + (hw+ how) + hr = 86.386 + (58.226) + 16.66 = 161.7788 mm of liq

∆P = ρL ht g =(750*161.778*9.81) = 0.172636 Psi (tolerable)

Downcomer Backup Check

Height of bottom plate of apron hap = 50-10 = 40 mm

Aap = hap*weir length = 0.040*2.695 = 0.1078 m2

Ad = 1.15395 m2 & Aap = 0.1078 m2

Hence select Am = 0.1078 m2

Head loss in downcomer hd = 166*(Lv/ρL Am)2

=166*(2.168/(750*0.1078))2

= 0.119437 mm

hbc = (hw+ how)+ hd+ ht

= (58.226) + 0.119 + 161.77 = 220.6236 mm

Now (0.05+0.5)/2 = 0.275 = 275 mm

220.6236 < 275 , hence Tray sapcing is adequate.

Downcomer residence time tr (From Graph) = 8.804498661 > 3 sec hence it is also satisfactory.

Check for Flooding & Entrainment

Velocity = (Vapor flow rate/ Net area) = 1.329184 m/s

Actual % flooding = ( 1.329184/Floodig velocity) = (1.329 / 1.746) = 76 % which is satisactory

For Entrainment

FLV = 0.050656

ψ ≈ 0.09 < 0.1 (From Graph)

Hence no Entrainment.

Hydraulic Gradient

Fva = (Q/Aa)( ρv)0.5 = (0.8 / 7.30835)*(2.3)0.5= 11.97591 m/s

ǿ = froth density = 0.2

QP = Aeration Factor = 0.8

q = 2.168681*55 / 750 = 0.0981 m3/sec

ha = 0.8 (0.1*hw + how) = 0.8*(0.1*58.22699) = 10.9803 cm

hf = ha/ (2 QP – 1)= 10.9803 / (2*0.8 – 1) = 18.30049 cm

Df = 3.0975 m

Hydraulic Radius Rh = ( hf Df/2 hf + 100 Df )

=( 18.30049*3.0975/2*18.3)+(100*3.0975)

= 0.163666

Velocity of Aerated Mass Uf = (100 q / hf ǿ Df)

=(100*0.0981/ 18.3*0.2*3.09750)

= 1.263771 m/s

Reynolds modulus = ( Rh Uf ρL/ µL ) =

(0.163*1.263*750/4.674*10^-4)

=189179.3

f = 0.090 (from Graph)

∆ =( 10000*f * Uf2 weir length / Rh g )

= (10000*0.090*1.2632*2.695 / 189179.3*9.81) = 24.12745 mm

Tray Layout

Area for unperforated edge strip = 0.243743 m2

Area of Calming Zone = 0.2595 m2

Total Area available for perforations = Active Area – (Area for unperforated edge strip + Area of
Calming Zone)

= 7.3083 – (0.24374 + 0.2595)

= 6.805108 m2

Area of holes = (π*d2/4) = 0.000019625 m2

No. of Holes = (Active area / Area of holes)

= (6.805108/0.000019625)

= 372400
5.2 Design of Heat Exchanger :

Mass Flow Rate Tin (C) Tout (C)

(kg/hr)

Hot Fluid 131339.7 500 330

Cold Fluid 80973.67 160 280

Difference 340 50

Q= 75496433.56 KJ/hr (From Non Oxidtive Rector Energy Balance)

LMTD = ((340-50)/ ln (340/50)) = 151.9269 oC

Assumption : Overall Heat Transfer Co-efficient Uf = 900 W/m2 oC

Q
A
UTLMTD

Area = 75496433.56 / 900*151.9269

=154.0239 m2

Assumptions :

Two pass Heat Exchanger with Square pitch Lay out with tube I.D. 0.016 m & the length of the
Heat Exhanger is assumed to be 11 ft.

CTP= 0.9

CL= 1.0

Pitch Ratio (PR)= P/do

PR= 1.25

do= 0.019 m

P=0.02375

L=3.35 m

A = 154.0239 m2

0.5
 A0 ( PR) 2 d o 
0.5
 CL 
Ds  0.637   
 CTP   L 

Dia. Of Shell (Ds)

= 0.637 * (1/0.9)0.5 * ( 154.0239*(1.25)2*0.019 / 3.35 )

= 0.78447 m ≈ 0.8 m

No. of Tubes

 CTP  Ds 
2
N t  0.785  
 CL  PR d o 
2 2


= 0.785* ( 0.9 / 1.0 )*( 0.82/ 1.252 0.019)

(Nt) = 770 For two pass

= 385 per pass

Baffle Spacing is 60%

B= 0.6 x 0.8 = 0.48 m

Shell Side : Feed from Non-Oxidative Reactor Unit

T = 415 oC

Ρ = 750 Kg/m3 , Cp = 1920 J/Kg K , µ = 4.67 x 10-4 , K = 0.652 W/m K , µw= 6.04 x 10-4

Tube Side : Water

T = 220 oC

Ρ = 1000 Kg/m3 , Cp = 4160 J/Kg K , µ = 4.2 x 10-4 , K = 0.610 W/m K

1
 Cp 3   
0.55 0.14
h0 De DG 
 0.36 e s     
K     K 
  w

Equivalent Diameter (De)

De = 4*( P2 – (π*d02/4))/( π*d0) where P= d0*Pitch Ratio

= 4*(0.023752 – (π*0.0192/4))/( π* 0.019)t

= 0.018818 m

C= P – do

C= 0.00475 m

Area of Flow = (Ds*C*B/P) = 0.07384 m2

Gs = 131339.688/(3600*0.07384) = 494.5716 Kg/s m2

Res= De Gs/ µ = 19907.67

ho= 4283.297 W/m2 K

Now , calculations for hi

m = 80973.67 Kg/hr = 0.037488 m3/s

C/s area of Flow = (Nt * di2 * π / 8) = 0.077449 m2

Um =0.037488/0.07744 = 0.48403 m/s

Rtube = 10088.85

hi di 𝐶𝑝 µ 0.4
As = 0.023(𝑅𝑒)0.8 ( )
K 𝐾

hi = 1759.641 W/ m2 K

1
  r ln ro 
 1 ro  o ri 
Uf    R ff   
 h0 ri hi  K  
  

Hence overall Heat Transfer Coefficient (Uf) = 899.6566 W/ m2 K

Design Summary :

Area = 154.0239 m2

Dia. Of Shell (Ds) = 0.8 m

No. of Tubes

(Nt) = 770 For two pass

= 385 per pass

ho= 4283.297 W/m2 K

hi = 1759.641 W/ m2 K

(Uf) = 899.6566 W/ m2 K
5.2.1 Mechanical design of Heat Exchanger

(a) Shell side details

Material : carbon steel

Number of shell passes: one

Working pressure: 0.1N/mm2

Design pressure : 0.11N/mm2

Permissible stress for Stainless Steel: 95 N/mm2

(b) Tube side details

Number tubes: 770

Number of passes: 2

Outside diameter: 19.05mm

Inside diameter : 15.75

Length: 3.35 m

Pitch triangular: 1 inch

Working pressure: 0.1 N/mm2

Design pressure: 0.11N/mm2

Shell side

(1) Shell thickness

ts= PD/(2fJ+P)

= 0.11*838/(2*95*0.85+0.11)
= 0.57

Minimum thickness of shell must be=6.3 mm

Including corrosion allowance shell thickness is 8mm

(2) Head thickness.

Shallow dished and torispherical

ts=PRcW/2fJ

= 0.11*838*1.77/(2*95*1)

= 0.858

minimum shell thickness should be 10mm including corrosion allowance.

(3) Transverse Baffles

Baffle spacing =0.6*Dc

= 48mm

number of baffles,

Nb+1=L/LS=3350/480=7

Nb = 6

Thickness of baffles, tb=6mm

Nozzles

Tube side nozzles diameter=180 mm

Shell side nozzles diameter = 180 mm

Thickness of nozzles = t =10mm

Saddle support

Material: low carbon steel

Total length of shell: 6.6 m

Diameter of shell: 800 mm

Knuckle radius : 51.24 mm

Total depth of head (H)= (Doro/2)0.5

= (800*51.24/2)0.5

= 143 mm

Weight of the shell and its contents = 11943kg = W

R=D/2=400 mm

Distance of saddle center line from shell end = A =0.5R=200 mm

5.3 Reactor Design :

Reaction for Oxidative Dehydrogenation

3 C4H8 + 10O2 = C4H6 + 4CO + 4CO2 + 8H2O + H2

Flowrate
C4H8 863.3676 kmol/hr
Steam in feed 671.508133 kmol/hr
Air in feed 277.141 kmol/hr
Total Fa 1812.01673 kmol/hr

Pressure Pa = 350 kPa

Conversion Xa = 0.9

r = a/(a + bfo)2 , where

r1 = moles butene converted/ft3 catalyst-hr.

r2 = moles butadiene produced/ft3 catalyst-hr.

f0 = equivalent reciprocal space velocity for zero age catalyst, ft3 catalyst-hr/mol feed.

a and b = constants calculated from equations

In a = -13.03794 + 0.19267 (1 x lo5 )

In b = -4.48793 + 0.09814 (Ix lo5 )

But K value is given by this equation : K = 2.1x104 exp (-63.116/ RT) which is an empirical
equation

Hence K= 20000 kmol/m3reactor/h/(kPa)2

Volume of Reactor V= (Fa/ K Pa)*∫((dXa/(1-Xa)2)

V = (F/K Pa)*((1/(1-Xa)) - 1)
V = (1812.01673/20000*350)*((1/(1 - 0.09)) – 1)

Hence Volume of Reactor V = 2.3297358 m3

Now Volume of Catalyst

Catalyst particle diameter, dp = 5 mm

Catalyst particle density = 2100 kg/m3

Packing void fraction E = 0.45

Volume of catalyst = (1-E )* Volume of reactor

= (1 - 0.45) * 2.3297358

= 1.28135469 m3

Consider length of tube = 5 m

Diameter of tube = 2.5 cm

Volume of one tube = /4 (d)2 (L)

= /4 (2.5 x 10-2)2 (4)

= 0.00245313 m3

Props. Shell Side (Water) Tube side (Butene Feed + H2O)

Cp 5.1865 (KJ/Kg oK) 1.920 (KJ/Kg oK)

 9 x 10-4 (Kg/m.Sec) 4.187 x 10-4 (Kg/m.Sec)

K 0.62 (w/m.oK) 0.54 (w/m.oK)

 995.40 (Kg/m3) 750 (Kg/m3)

No. of tube = ( Volume of reactor / Volume of one tube )

= 2.3297358 / 0.00245313

No. of tubes = 950 tubes

Area of tube per pass:

Atp = (/4) (d) 2 (Ntp)

= (/4) (2.5 x 10-2)2 (950)

At = 0.46609375 m2

Mass flow rate of reacting material = 57217.0976 kg/hr

= 15.8936382 kg/sec

Velocity:

U = m/ Atp

m = 15.8936382 Kg/Sec

U = 15.8936382 / 750*0.46609375

U = 19.3748066 m/sec

NRe = duρ/µ(1-E)

= (2.5 x 10-2) x (19.3748) x (794.09)/ (0.00000784) x (1 -0.45)

NRe = 108736.159

AO = Nt x  x d xL

= (950) x  x (2.5 x 10-2) x (5)

AO = 372.875 m2
Shell diameter:
0.5
 A0 ( PR) 2 d o 
0.5
 CL 
Ds  0.637   
 CTP   L 

Consider the Triangular pitch

CTP = 0.9

CL = 0.7

Take PR = Tube pitch ratio = 1.25

Ds = 0.637 * ( 0.7/ 0.9)0.5 *(409.66 x (1.25)2 x (2.5 x 10-2) / (0.5) )0.5

Ds = 0.95883493 m

 CTP  Ds 
2
N t  0.785  
 CL  PR d o
2 2 


= 0.785* ( 0.9 / 0.7 )*( 0.95882 / ( 1.252 * 0.0252 )

= 1059.10 > Total No of tube that is required.

1
 Cp 3   
0.55 0.14
h0 De DG 
 0.36 e s     
K     K 
  w

De = 4*( P2 – (π*d02/4))/( π*d0) where P= d0*Pitch Ratio

PT = 0.03125 m

De = 4*( ( 0.031252 – ( π*0.0252/ 4 )) / ( π*0.025))

= 0.018 m
C= P – do

= 0.03125 – 0.025

= 0.00625

B = 0.6*Ds

B = 0.6 * 0.95883493

B = 0.38353397

As = Ds*C*B / PT

= ( 0.95883493 x 0.00625 x 0.38353397 ) / ( 0.03125 )

As = 0.07354915 m2

Gs = m/ As

= 8.648 / 0.07354915

Gs = 117.581231 Kg/m2.sec

From the above equation,

0.333
 5.1865 x10 3 x9 x10  4 
0.55
 0.018 x117.5812 
( h0 * 0.018 / 0.62) = 0.36    10.14
 9 x10  4   0.62 

ho = 1725.81167 W/m2K

Tube side H.T.C:

Nu = 0.023 (NRe)0.8 (Pr)0.4

0.8 (Cp ) 0.4

( hi*di/k ) = 0.023( 2905.09) ( )
k
 (4.84 x10 3 x4.187 x10 4 ) 0.4
0.8
( hi*0.025/0.54) = 0.023x(1059.107) ( )
0.254

hi = 280.163 W/m2K

Over all H.T.C

1/U0 = ( (1/h0) + (1/hi) + 0.005 )

 1 1 
=    0.005 
 1725.8116 280.163 

Uo = 39.0939011 W/m2 K

Now,

Total H.T area available = 372.875 m2

Rate of H.T. is given by

Q = UAT

(4713400) = 39.0939011 x A x 30

A = 391.448444 m2 > A available

5.3.1 MECHANICAL DESIGN

Now, Internal design pressure

Pd = 0.1 * 0.375

= 0.0375 N/ mm2

External Design Pressure

Pd = 0.1*0.35
= 0.0375 N/mm2

Material of Construction is stainless steel (SS – 316).

Maximum Allowable Tensile Stress at 30 o C = 98 N / mm2

SHELL DESIGN:

For Internal Design Pressure

P – Design Pressure

D- Mean Diameter

J- Joint Efficiency

f- Design Or Permissible stress at design temperature

Di – Internal Diameter

Do – Out Side Diameter

ts = PDi / (2fJ – P)

= 0.0375*1000 /(2*98*0.85 - 0.11)

(Here Dia = 0.95883493 m ≈ 1000 mm)

= 0.26 mm
= 5.00 mm (Because minimum thickness of the plate available is 5 mm) + C.A.
Use 10 mm Thick Plate For Fabrication.

For External Design Pressure

Pc = 2.42 E ( t/D0 ) 5/2 / ((1-µ2 )3/4 [ ( L / Do ) – 0.45 ( t / Do ) 1/2 ])

= {2.42*190*103*( 5 /1000)5/2}/{( 1-0.32 ) 3/4 [ (2000/1000) – 0.45 (10/1000)1/2]}
= 0.4367 N/mm2
Now, Allowable Pressure

P = Pc/4 = 0.4367/4
P = 0.109 N/mm2 < Pd
Means critical buckling pressure is less than External design pressure.

So, we can use thickness of the shell ts = 5 mm.

HEAD DESIGN:

Here The Design Pressure is 0.0375 N/mm2 so we can use Torrispherical Head.

Let Rc = Crown Radius = internal diameter of shell = 1000 mm

R1 = Knuckle radius

= 6% of Inside Dia. Of Shell

= D * 0.06

= 1000 *0.06

= 60 mm

Torrispherical head:

Thickness of head th= (P*Rc*W ) / 2fJ

Where, P - internal design pressure

Rc - crown radius

W - stress intensification factor

W = 0.25 * (3+ (Rc/R1)0.5)

W = 0.25 * (3+ (1000/60)0.5)

W =1.770
th = 0.11*1000*1.77 /2*98*0.85

th = 1.17 mm

= 5 mm

Thickness of Torrispherical head = 5 mm.

BRACKET SUPPORT DESIGN:-

Let,

Pt = Total force due to wind load acting on vessel

H = Height of vessel above foundation.

F = Vessel clearance from foundation to vessel bottom.

Db = Diameter of bolt circle.

∑W = Maximum weight of vessel with attachments & contents.

n = no. of brackets.

Pw = Wind pressure.

P1 = Wind pressure for the lower part (Below 20m) of the vessel = 400 to 1000 N/m2

Kp = Coefficient depending of the safe factor

Wind pressure = Pw = Kp*h*Do*P1

= 0.7*2.00*1.01*1000

= 1414 N

Density of SS-316 = 7750 kg/m3

Wt. of catalyst = 2000 kg = 20000 N

∑W = wt. of vessel with attachment + wt. of content

Weight of Shell = (3.14*Ds2*L/4)*7750 = 3.683*7750 = 39970 kg =399700 N

Weight of Tube = (3.14*Dt2*L/4)*7750 = 19.0117 kg = 190.11 N

P = ( 4*Pw*(H-F) / n*Db ) + ( ∑w/ n)

= (4*1414*5.00 / 4*1.65) + (419890 / 4)

P = 109257 N

Bracket: Base plate size

a =140 mm, b=150mm

Allowable bending stress for structural steel = f = 157.5 N/mm2

Pav = P / a*b = 109257 / 140*150

Pav = 5.20 N/mm2

f = 0.5 (Pav * b2 / T12 ) * ( a4 / a4+b4 )

= 0.5* (5.20 * (150)2 / T12) *(1404 / 1404+1504)

157.5 = 1689.09 / T12

T1 = 32 mm

So, thickness of base plate = T1= 32 mm = 3.2 cm.

5.3.2 Thickness of the Insulation:

From the heat balance it is clear that there is some amount of heat lost into the atmosphere.To limit the
heat loss to the same figure an insulation is to be given to the reactor. The insulating material can be
chosen as asbestos.
Density of asbestos = 577 Kg/m3
Thermal Conductivity of asbestos = 681.4 x 10-3 W/m2 K
Material of the drier is stainless steel
Thermal Conductivity = 147.6 W/m2 K
Convective Heat transfer Coefficient = 40 W/m2 K
From Heat Balance Heat Loss = 97 KW
D1 = 1 m
D2 = 1.02 m
t1 = 10 mm
Let ‘y’ be the thickness of insulation.
D3 = D2 + 2y = 1.02 + 2y
T1 = 603 ºK , T2 = 295 ºC
We have from the Continuity equation
Q = (T1 – T2)
t1 + t2 + 1
k1 A1 k2 A2 Hc A3

A1 = π (D1+ D2) x L/ 2
= 3.14 (1.0 + 1.02 ) x 7 /2
= 3.79 m2
A2 = π (D2 + D3) x L / 2
= 3.14 (1.02+ 1.02 + 2y) x 7/2
= 22.42 + 21.98 y
A3 = π x D3 x L
= 3.14 x (1.02 + 2y) x 7
= 22.42 + 43.96 y

97x103 = ( 603 – 295)

10 x 10 -3 + y + 1
147.6 x 3.79 681.4 x 10 -3 (22.42 + 21.98 y) 56.8 (22.42+43.96 y)

y = 38.78 mm
Therefore the thickness of the insulation should be 40mm.
CHAPTER 6 : PLANT LAYOUT
 PLANT LAYOUT

A preliminary determination of the plant layout enables consideration of pipe runs and pressure
drops, access for maintenance and repair, access in the event of accidents and spills, location of
the control room and administrative offices. The preliminary plant layout can also help to
identify undesirable and unforeseen problems with the preferred site, and may necessitate a
revision of the site selection.

The proposed plant layout must be considered early in the design work to ensure economical
construction and efficient operation of the completed plant. The plant layout adopted will also
affect the safe operation of the completed plant, and acceptance of the plant (and possibly any
subsequent modification or extension) by the community.

6.1 Factors in Choosing a Suitable Plant Location :

There are several major factors that contribute to the operability and economic aspects of a site
location for a plant, which are the primary factor and specific factor.

Primary Factors :

Availability of Raw Material

A plant with close proximity to the source of the raw material allows a lower cost of
transportation. The cost of shipping raw materials and fuel to the plant site should be considered
along with the cost of transporting the products to market so as to minimize the total
transportation cost as much as possible while balancing that cost against other operating
expenses. A seaport might have to be at a reachable distance from the site location if the raw
material is to be imported.
Reasonable land price

The cost of the land depends on the location itself. An ideal land will provide an economical land
price to the total investment cost. It is then vital to choose a suitable land price when initiating a
new plant in order to gain the highest economic and profit value.

Proximity to market

The plant should be constructed close to the primary market to minimize transportation costs.
Local demand of product should also be taken into account in selecting a proper plant site. It
would add as an extra point if both the raw material supplier and buyers are at a reachable
distance.

Electricity and water

Any chemical plant is in need of large quantities of water supply for cooling and other uses in the
plant. Electricity is needed to run all the machines and equipments. Therefore, sufficient local
water and power supply plants is required to ensure a smooth operation of the plant.

Geographical and Weather :

The climate conditions affect the budget and cost operation. It may be necessary to consider the
yearly weather consideration.

Specific Factors

Availability of low cost labor and services

Any chemical processing plant should be located where sufficient labor supply is adequately
available. The usual practice is to bring non-local, skilled construction workers and ample
number of local, unskilled workers for training of plant operation. The cost of operation will
reduce if inexpensive manpower for plant operation can be gathered from the surrounding area.
Transport facilities

The construction of the plant should be located close to road network, seaport and airport. All
these major facilities will aid to smooth transportation of the raw feed, product, plant personnel
and plant equipment supplies.

Government incentives

To attract investors to place their investment in a state, state governments offer attractive
investments incentives. Some incentives grant partial or total relief from income tax payment for
a specified period, while indirect tax incentives come in the form of exemptions from import
duty, sales tax and excise duty.

Waste and effluent disposal facilities

Site location should also take into account the availability of efficient and satisfactory disposal
system. This is to ensure that the factory waste and industrial effluent will have proper treatment
if those are to be treated off-site.

Plant layout is often a compromise between a numbers of factors such as :

 The need to keep distances for transfer of materials between plant/storage units to a
minimum to reduce costs and risks
 The geographical limitations of the site
 Interaction with existing or planned facilities on site such as existing roadways, drainage and
utilities routings
 Interaction with other plants on site
 The need for plant operability and maintainability
 The need to locate hazardous materials facilities as far as possible from site boundaries and
people living in the local neighbourhood
 The need to prevent confinement where release of flammable substances may occur
 The need to provide access for emergency services
 The need to provide emergency escape routes for on-site personnel
 The need to provide acceptable working conditions for operators
The most important factors of plant layout as far as safety aspects are concerned are:

 Prevent, limit and/or mitigate escalation of adjacent events (domino)

 Ensure safety within on-site occupied buildings
 Control access of unauthorized personnel
 Facilitate access for emergency services

Many factors must be considered when selecting a suitable site with respect to the marketing
area, raw material supply, transport facilities, availability of labor, availability of utilities,
availability of suitable land, environment impact, etc. All these factors play a significant role in
the choice of the site. The overall site layout is shown.

Several factors have been considered in laying out the site. The process units and ancillary
building should be laid out to give the most economical flow of materials and personnel around
the site. In term of safety, process area is located at enough distance from the place where there
are a lot of personnel.

6.2 Plant Layout Consideration Factors

When laying out the plant, these are the factors that we have considered;

1. Inherent Safety
The major principle in Inherent Safety is to remove the hazard altogether. The best method in
achieving this is to reduce the inventory of hazardous substances such that a major hazard is
no longer presented. However, this is not often achievable. Other possible methods to
achieve an Inherently Safer design are;

 Intensification to reduce inventories

 Substitution of hazardous substances by less hazardous alternatives
 Simpler systems/processes to reduce potential loss of containment or possibility of errors
causing a hazardous event
2. Domino Effect
Hazard assessment of site layout is critical to ensure consequences of loss of containment and
chances of escalation are minimized. Domino maybe by fire, explosion (pressure wave and
missiles) or toxic gas cloud causing loss of control of operations in another location.

3. Fire
There are four ways that fire can spread;

 Direct burning
 Convection
 Radiation
 Conduction
The use of vertical and horizontal compartmentation using fire-resisting walls and floors can
prevent the spread of fire from its origin to the other part of the premises. Protection against
domino by convection, conduction and radiation can be achieved by ensuring that the
distances between plant items are sufficient to prevent overheating of adjacent plants
compromising safety of that plant also. If this is not possible due to other restrictions, other
methods such as fire walls, active or passive fire protection may be considered.

4. Explosion :
Explosion propagation may be directly by pressure waves or indirectly by missiles.
Inherently safety methods that should be considered are;

 Arranging separation distances such that damage to adjacent plant will not occur even in
the worst case.
 Provision of barriers e.g. blast walls.
 Protecting plant against damage e.g. provision of thicker walls on vessels.
5. Toxic gas releases
Toxic gas releases may cause domino effects by rendering adjacent plants inoperable and
injuring operators. Prevention of such effects may be affected by provision of automatic
control system using inherently safer principles and a suitable control room.
6. Reduction of consequences of event on and off site
A plant layout design technique is also applicable to the reduction of the risks from release of
flammable or toxic materials include;

 Locating all high-volume storage of flammable/toxic material well outside process area
 Locating hazardous plant away from main road
 Siting of plants in the open air to ensure rapid dispersion of minor releases of flammable
gases and vapors and thus prevent concentrations building up which may lead to flash
fires and explosions.
 Provision of ditches, dykes, embankments, sloping terrain to contain and control releases
and limit the safety and environmental effects.
 Hazardous area classification for flammable gases, vapors and dusts to designate areas
where ignition sources should be eliminated.
7. Positioning of occupied buildings
The distance between occupied buildings and plant buildings will be governed by the need to
reduce the dangers of explosion. Evacuation routes should not be blocked by poor plant
layout, and personnel with more general site responsibilities should be housed in buildings
sited in a non-hazard area near the main entrance. Occupied buildings should not be sited
downwind of hazardous plant areas.

8. Aggregation / trapping of flammable vapors :

To avoid aggregation and trapping of flammable/toxic vapors which could lead to a
hazardous event, buildings should be designed so that all parts of the building are well
ventilated by natural or forced ventilation. Flammable storage should be sited in the open air
so that minor leaks or thermal out breathing can be dissipated by natural ventilation.

6.3 Site Layout : The site layout can be divided into two parts:

 Non-Process area – area where there is no production activity and has low risk hazards to
workers and process units.

 Process Area - consists of all processing equipments, butadiene is produced.

6.3.1 Non-Process Area :

The non-process area usually occupies a smaller fraction of the overall plant site area. All the
facilities in the non-process area should be located in a logical manner that considers site terrain,
accessibility to roads, soil bearing capability and the climate including the wind direction and
other unusual weather condition. This is important to avoid any undesired incident due to
explosion or fire from the process zone will be easily spread to the non-process area. Taking this
into account, the entire process area where the reaction and separation occurs is surrounded with
a buffer zone to ensure that surrounding buildings or sites are not affected in case of an
emergency. Among the buildings or units in the non-process area are: -

a) Guard Post

Guard posts are located at the entrance of the site in order to ensure that only authorized
personnel gets access into the plant. There are 5 guard posts that are situated at the crucial
entrances in the plant:

 Main entrance guard post – to control the flow in and out of personnel or cars between the
site and public area.
 Emergency entrance guard post – security check for emergencies such as ambulance, fire
engine or other special occasions.
 Process entrance guard post – As shown in the layout, there are two different main entrances
to the plant. The first one is for public entrance where only cars and other small vehicles are
allowed to pass through. The second main entrance is only open to trucks. This is to avoid
congestion and at the same time reduce the hazard of material spillage at the plant. With two
different entrances, the public are less exposed to the danger of chemicals exposure or
accidents with the trucks.

b) Administration Building

The administration block is built adjacent to the main entrance. This is to allow the
administration employees to enter their office without passing through the hazardous process
area. As shown in the plant layout, the administration building is place near to the process area.
This location is most strategic as it is aligned with the process area. This arrangement allows the
employees at the administration building to alert on any mishap at the process area that is visible
from the administration building but far enough to ensure that no accidents from the processing
area can affect the administration block.

c) Cafeteria
Canteen provides meals for the employees and visitors. Canteen is located in the public zone and
far away from the process area to avoid contaminant in food and ensure safety of the public.

There are other facilities that should be located in the non-process area including surau,
gymnasium, car park and also fire station.

6.3.2 Process Area

Process zone is an area where all processing equipment is allocated and is deemed as a hazardous
area, thus precaution has to be applied at all times. The buildings or units situated in this process
zone are:

 Process zone guard post

 Control Building

 Laboratory

 Wastewater treatment plant

 Plant Area

 Utilities

 Storage area

 Fire assembly points

 Flare area

a) Process zone guard post

This facility is to ensure no unauthorized personnel will be access into the process area by using
a security pass, to record the personnel activity, such as check-in and check-out between process
zone and public zone. The purpose of this process zone guard post is to ensure that all the
personnel will obey to the plant rule and regulations.

b) Control Building :

All the control valves for the whole process area will be controlled and monitored from this
central control building. The control rooms are designed with blast proof construction and have
emergency backup power and air conditioning. In case of emergency occurs in the plant, control
room will be the assembly point in the process area. At least two escape routes for
operators/personnel must be provided from each level in process buildings.

c) Laboratory
Here the quality of the purity of butadiene is tested to determine whether it meets the
specifications or not. All the result will be sent to the control room and some adjustments in
controlling will be made, if needed. Thus, the distance between laboratory and control room is
not too far. Laboratory staffs will also perform an analysis regarding waste of the process before
being channeled to nearby environment.

d) Wastewater Treatment Plant

The waste stream from Plant Area will first flow into the Wastewater Treatment plant to separate
the impurities from the water. The impurities will be treated before being recycled back to the
process released to the environment. It is located adjacent to the main process unit so that the
wastewater effluents from the process units can be channeled easily.

e) Plant Area

This area is the major processing unit where the butadiene is produced. Safety, economy,
operability and ease of maintenance are considered during the allocation of each equipment
within the area. Adequate spacing between equipment is also considered to minimize the spread
of fire in case it happens. Distances between each unit are also well designed to prevent any
hazards from occurring.
f) Utilities

This unit will supply cooling water, low pressure steam, instrument air and some other utilities to
the main process unit. For this plant, the utilities located near to plant area where all the process
of producing butadiene occurs. Its location is perfectly suitable to give the most economical run
of pipe to and from the process unit. The utilities and control building is situated near to the
utilities for easy monitoring.

g) Storage area

This unit stores vessels containing chemical substance, lubricants, and catalyst used for the
process. It also stores chemicals needed for the waste water treatment plant. It is situated next to
the waste water treatment plant.

h) Warehouse :

Warehouse stores all the equipment’s spare parts. It is placed near to the workshop to ease the
maintenance job and to conduct hot work.

i) Expansion Site
Ample expansion areas are allocated at the process area for future expansion in case the
management decides to increase production rate or other crucial considerations.

j) Fire assembly points

In case of emergency, the assembly point in the plant for public zone will be located in the
nearest car park area and next to the canteen. For process zone; the assembly point will be near
to the QC Laboratory building and next to the Utilities and Control building for personnel
working there. Once gathered, wait for further instruction from Health, Safety and Environment
personnel or from fire department personnel. There are a total of 5 assembly points planned at
the site.
k) Flare Area

Flare is used to burn all excess gas that is emitted from the process units as well as to burn some
of the waste gas from waste treatment area. The flare is located far from the process area and
administration complex

Process Unit :

Table below summarizes the layout consideration for process units

Table : Layout Consideration for Process Unit

PROCESS UNIT LAYOUT CONSIDERATIONS

Process Area  Located in well ventilated area with leak detector to allow
maximum safety if there is leakage or spillage
 Located as far s possible from ignition sources
Instrumentation  Instrumentation control cables are routed underground to
prevent any hazards.
 Fire proofing protection should be considered.
 Consider types of fluid, temperatures, pressures and flow
Pipelines
condition
Reactor/Column/Heat  Isolated from other equipment and from flammable, toxic
Exchanger/Pressure or inert materials.
Vessels  Consider internal refractory of insulation due to
overheating and rupturing.
`

Figure : Plant Layout of Butadiene Production Plant

CHAPTER 7 : COST ESTIMATION
 Cost Estimation

7.1 Direct Cost :

1.) Purchased Equipment

Sr. No. Equipment Name Quantity Price in Rs.

1 Dehydrogenation Reactor 1 3424735
2 OxydativeDehydrogenation Reactor 1 749890
3 Deisobutanizer 1 16352892
4 Extractive Distillation Column 1 26147632
5 Solvent Recovery Column 1 4412826
6 Furnace 1 163076706
7 Flash Drum 1 6528834
8 Dehydrogenation Inter-Cooler 1 3478284
9 Dehydrogenation Reactor Cooler 1 3928860
10 Compressor 1 18602226
11 Deisobutanizer Pump 1 1133838
12 Extractive Pump 1 522756
13 Recovery Pump 1 268740
14 Feed Pump 1 368136
15 Solvent Pump 1 176706
16 Tanks 2 83372220
17 Heat Exchanger 10 40000000

Total Cost of Equipment = 372545281 Rs.

2.) Purchased Equipment Installation

Installation of all the equipments listed, structural supports, paints (Taken as 25% of the
purchased equipment cost)

= 85685414 Rs.

Sr. No. Description Grand Total cost in Rs.

1 Purchased Equipment 372545281
2 Purchased Equipment Installation 85685414
3 Instrumentation and Control (17%) 63332697
4 Piping (20%) 74509056
5 Electrical (10%) 37254528
6 Building (17%) 63332697
7 Yard Improvement (3%) 11176358
8 Service Facilities (9%) 33529075
9 Land (15%) 55881792

Total Direct Cost (D) = 797246902 Rs.

7.1.1 Indirect Cost (I)

1) Engineering and Supervision

Total Engineering and Supervision Cost is taken as 8% of the Total Direct Cost
= 87,697,159.27 Rs.

2) Construction Expenses

Total Construction Expenses cost is taken as 7% of the Total Direct Cost

= 63,779,752.20Rs.
3) Contractor's Fee
Total Contractor's fee is taken as 5% of the Total Direct Cost = 39,862,345.12Rs.

4) Contingency

Total Contingency cost is taken as 8% of the Total Direct and Indirect cost
= 55,807,283.17 Rs.

Sr. No. Description Grand Total cost

1 Engineering and Supervision Cost (11%) 87,697,159.27
2 Construction Expenses (8%) 63,779,752.20
3 Contractor's Fees (5%) 39,862,345.12
4 Contingency (7%) 55,807,283.17

(% of Total Direct Cost)

Total Indirect Cost (I) = 247,146,539Rs

Total Fixed Capital Investment (D + I) = 1,044,393,442 Rs.

Working Capital (WC), 15% of TCI = 184,304,725.10 Rs.

Total Capital Investment (TCI) = 1,228,698,167.31 Rs.

7.2 Total Product Cost

Determination of the necessary Capital Investment is only one part of a complete cost estimate.
Another equally important part is the estimation of costs for operating the plant and selling the
products. These costs can be grouped under the general heading of Total Product Cost.

Basis:

1.) Total cost is calculated on the basis on the Annual Cost Basis

2.) Number of days working per year is taken as 330 days

3.) Plant is running in three shifts i.e. 24 hrs per day

4.) Capacity of the plant per year = 1512939600 Kg/yr

Manufacturing Cost

1.) Direct Production Costs

a.) Raw Material

Sr.
No. Quantity per annum Kg Cost per unit Total annual cost
in Rs. in Rs.
1 LPG 1,512,939,600.00 26.00 39,336,4296

Total Cost of Raw Materials = 39,336,4296 Rs

Total Direct Production Cost :

Sr. No. Description % Cost in Rs.

1 Raw Material 50.00 39,336,4296

2 Operating Labour 15.00 5,900,464,4.40

3 Operating Supervision 15.00 885,069,6.66

4 Utilities 10.00 5,000,000.00

5 Maintainance and Repair 3.50 11176358.45

6 Operating Supplies 15.00 1676453.77

7 Laboratory Charges 0.20 1,180,0928.88

8 Patents and Royalities 0.00 0.00

9 Catalyst (yeast) 2,400,000.00

Total Direct Production Cost = 493273378Rs.

2) Fixed Charges

a) Depreciation

i) Annual cost of Depreciation for Machinery and Equipment is assumed as 10% of the Fixed
Capital Investment = 10,443,934.42 Rs.

ii) Annual cost of Depreciation for buildings is taken as 3% of the Initial Cost of buildings =
1,899,980.94 Rs.

iii) Annual cost of Depreciation for Instrumentation & Controls, piping, Electrical equipment and
Materials is assumed as 5% of FCI = 52,219,672.11 Rs.
b) Taxes : Annual property taxes for plant is assumed as 1% of the Fixed Capital Investment =
10,443,934.42 Rs.

c) Insurance : Annual cost of Insurance is assumed as 1% of the Fixed Capital Investment =

10,443,934.42 Rs

d) Rent Annual cost of Rent for Land and Buildings = 0.00 Rs.

Total Annual Fixed Charges :

S. No. Description Total Annual cost in Rs.

1.00 Depreciation 64563587.47

2.00 Taxes 10,443,934.42

3.00 Insurance 10,443,934.42

4.00 Rent 0.00

Total Fixed Charges = 85451456Rs.

4) Plant Overhead Costs

Annual Plant Overhead Costs is assumed as 30% of the total cost of operating labor, supervision
and maintenance = 2,038,193,918.38 Rs.

Total Manufacturing Cost :

S. No. Description Total Annual cost in Rs.

1 Direct Production Cost 47,319,169,059.24

2 Fixed Charges 50,706,388.08

3 Plant Overhead Cost 2,038,193,918.38

Total Manufacturing Cost = 49,408,069,365.70 Rs.

7.2.1 General Expenses

1) Administrative Expenses [9]

Annual cost of Administrative expenses is assumed as 25% of the total cost of operating labor =
1,475,1161.10 Rs.

2) Distribution and Marketing Expenses

Annual cost of Distribution & Marketing expenses is assumed as 10% of the Total Product Cost
= 49,327,337.82 Rs.

3) Research and Development

Annual cost of Research and Development = 24,663,668.91 Rs.

4) Financing (interest)

Annual cost of Financing (interest) = 0.00 Rs.

Total General Expenses (G)

S. No. Description Total Annual cost

1 Administrative Expenses 1,475,1161.10
2 Distribution and Marketing Expenses 49327337.82
3 Research and Development 24,663,668.91
4 Financing (interest) 0.00

Total Cost of General Expenses = 88,742,167.82 Rs.

Total Product Cost (TPC), M + G = 691,176,512.14 Rs.

7.3 Spreadsheet for Estimation of Total Capital Investment
S. No. Description Cost in Rs. Cost in Rs.
Direct Costs
1 Purchased Equipment 372,545,281.52
Purchased Equipment
2 Installation 85,685,414.75
Instrumentation and
3 Controls 63,332,697.86
4 Piping 74,509,056.30
Electrical Equipment and
5 Materials 37,254,528.15
Buildings (Including
6 services) 63,332,697.86
7 Yard Improvements 11,176,358.45
8 Service Facilities 33,529,075.34
9 Land 55,881,792.23
Total Direct Costs (D) 797,246,902.45
Indirect Costs
Engineering and
10 Supervision 87,697,159.27
11 Construction Expenses 63,779,752.20
12 Contractors Fee 39,862,345.12
13 Contingency 55,807,283.17
Total Indirect Costs (I) 247,146,539.76
Fixed Capital Investment (FCI),
D+I 1,044,393,442.21
Working Capital (WC), 15% of
TCI 184,304,725.10
7.4 Spreadsheet for Estimation of Total Product Cost
S. No. Description Cost in Rs. Cost in Rs.
Manufacturing Costs
Direct Production Costs
1 Raw Materials 393,364,296.00
2 Operating Labor 59,004,644.40
3 Operating Supervision 8,850,696.66
4 Power and Utilities 5,000,000.00
Maintenance and
5 Repairs 11,176,358.45
6 Operating Supplies 1,676,453.77
7 Laboratory Charges 11,800,928.88
8 Patents & Royalties 0.00
9 Catalysts and Solvents 2,400,000.00
Total Direct Production Costs 493,273,378.15
Fixed Charges
10 Depreciation 64,563,587.47
11 Taxes 10,443,934.42
12 Insurance 10,443,934.42
13 Rent 0.00
Total Fixed Charges 85,451,456.31
Plant Overhead Costs
14 Plant Overhead Costs 23,709,509.85
Total Plant Overhead Costs 23,709,509.85
Total Manufacturing Costs (M) 602,434,344.32
General Expenses
Administrative
15 Expenses 14,751,161.10
Distribution &
16 Marketing Expenses 49,327,337.82
 Research &
17 Development 24,663,668.91
18 Financing (Interest) 0.00
Total General Expenses (G) 88,742,167.82
Total Product Cost, M + G 691,176,512.14

7.5 Profitability Analysis

To Calculate Profitability Analysis two methods have been employed based on Fixed Known
Selling Price of the Finished Product API at 75% Capacity

Revenue Through sales

At present the market value of the Finished Product API manufactured under this facility per kg
= 110 Rs. [10]

Annual Revenue through sales at 75% capacity = 1248175170 Rs

Gross Profit = Annual Revenue through sales - Annual Operating Cost

Gross Profit = 556,998,657.86 Rs.

Net Profit = Gross Profit x (1 - tax%)

Assuming tax percent = 30 %

Net Profit = 389899061 Rs.

Pay Back Period = Total Investment / ( Net Profit + Depreciation )

where Total Investment = Fixed Capital Investment

Pay Back Period = 2.298084225 years

Rate of Return = ( Net Profit / Total Investment ) x 100

Rate of Return = 56.410925 %

CHAPTER 8 : MATERIAL SAFETY AND HAZARD
 Material, Safety and Chemical Hazard

8.1 INHERENT SAFETY ASPECT

Inherent safety aspect must be considered to reduce the potential consequences of accident.

Distillation

 In a distillation column, among the potential accident that can happen is flooding. This
circumstance occurs as a result of high pressure in the column. There are also large inventories
of boiling the liquid such as sometimes under pressure, in the distillation column both in the base
and held up.

 To prevent the accident from happened, sequence that tends to minimize the flow rate of nonkey
component can be chose. Dividing wall column can be used to reduce the inventories and also
number of items to lower the potential for leaks. In case of over pressurization, the relief system
can be installed.

Pressure and Temperature

 High temperature condition in a plant can lead to possible rupture of tubes carrying process
fluids. Thermal shock and leaking flanges also can occur due to the loss of cooling medium.
Problem of fluids leaking can become more serious with high pressure operation because when
fluid is flashing, mass flow rate of liquid can increase which can leak through holes.

- In order to overcome the high temperature and pressure condition, relief system must be
installed. Automatic shutdown system also must be installed to prevent overpressure and
temperature. The system must always be operated at normal temperature and pressure condition.

Heat Transfer Operation

 Generally, problems include in heat transfer operation involve tube rupture, leaking,
polymerization and solidification. These problems will influence the pressure and temperature
conditions in heater and also cooler.
- Pressure relief can be used to overcome the overpressure consequences and also to protect
against tube rupture. To prevent thermal shock, the control valve (fail-to-open/fail-to-close) can
be used to control the flow rate of cooling or heating medium.

Chemical storage

 Chemicals which are highly flammable can lead to explosion. Leakage of chemical from the
storage tank can also cause the vapor cloud and toxic cloud to occur. Failure of instrumentation
especially those which indicate the pressure and temperature will also cause the explosion to
happen. Leaking of chemical into the sewage system also can happen in this area.

- Prevention step can be taken to avoid all of these accidents from occurring. To prevent
explosion, the explosion proof motor and switches should be installed. The use of non-sparking
tools and equipment is required. All storage areas must be clearly marked with warning notices
forbidding smoking and open fire. Pressure safety valve should be installed to maintain the
pressure inside the storage tank. The storage area also should have no drain without suitable
cover or water seal to prevent the chemicals from entering the sewage system.

Transportation

 Accident involves in this transportation factor involve spillage of toxic chemicals and also risk of
accident happened. Sometimes, the explosion can also happen due to pressure and temperature
change in the transportation tank.

- In handling the loading and unloading of the chemicals, the workers should wear proper Personal
Protection Environment (PPE). Training should be provided to the driver of the vehicles so that
they can drive carefully and avoid the risk of road accident. To reduce the effect caused by
sudden changes of vehicle speed, baffles should be installed. Other technical requirements such
as gauges, thermometers, safety valve, indicator for maximum and minimum filling and also
device to remove static electricity should be installed to make sure that the tanks are in normal
condition. In case of transportation by sea, tankers with heat-insulated reservoir should be used.
 Plant Layout

 Weaknesses in the arrangement of facilities in the process area can lead to fire (via conduction,
convection and radiation), explosions and toxic gas releases.

- The spread of fire from its origin to the other parts of the premises can be prevented by vertical
and horizontal compartmentation using fire-resisting walls and floors. Fire accident through
convection, conduction and radiation can also be prevented by ensuring that the distances
between plant items are sufficient to prevent overheating of adjacent plants. To prevent
explosions, among inherently safe methods that should be considered are arranging separation
distances such that damage to adjacent plants will not occur, provision of barriers (blast walls),
protecting plant against damage (provision of thicker walls or vessels) and also directing
explosion relief vents away from vulnerable areas. Prevention of toxic gas releases may be
affected by provision of automatic control systems using inherently safer principles and a
suitable control room.

Sitting and Safe Location

 Human health will be affected in case if there is amount of toxic gas release into the
environment. The plant itself will be put into a high risk if it is build at an area which always
being strike by nature disaster such as flooding, earth quake and others.

- The plant area should be located far from the vulnerable area but near the raw materials supplier
so that the transportation can be made effectively. It should also be near the fire station so that
there are no difficulties in case of emergency.

Materials for Construction

 Leakage, corrosion, crack and explosions can happen due to the poor materials used for the
construction purpose. Crack problem can also arise if high pressures occur within the vessels.

- To prevent such incident from happening, stainless steel is recommended to be used for process
stream to prevent corrosion. Electrical equipments used should also be spark resistance to
prevent explosions.
 Toxicology and health hazard

 Most chemicals used in the plant either in process stream or product has contains of several
hazardous materials. When the toxic chemicals come into contact with human being, it can cause
a very bad impact to human’s health. Human being might expose to human mutagenic effect if
they are exposed to the chemicals for such long period.

- In order to prevent all these bad consequences from happening, proper Personal Protection
Equipment (PPE) should be worn by workers when dealing with the toxic chemicals. Handling
procedure of these hazardous materials should also be understood well to avoid the accident.
Supervision from expert personnel during handling chemicals also is useful to prevent any
accident from occurring.

Flammability

 If the chemicals in reboiler or heater are overheated, explosion may occur. In addition, spark can
be produced from tools or vehicles used in the process area which can lead to explosion or fire
accident.

- The vehicles and also the tools with spark resistance can only be used in the process area. All
activity which can lead to the production of sparks must be prohibited in the process area
(especially smoking).

Explosion limit

 If the oxygen content in the reactor and other equipments exceed its normal limit, explosions can
occur.

- To reduce the risk, total oxygen amount content in all these equipments should always be less
than its maximum limit. . A standard practice of ensuring oxygen content less than 2% shall be
employed prior to introduce flammable chemicals.
 Hazop Analysis

8.2 Distillation Column Inlet

Intention: To transport process raw material into the distillation column.
PARAMETER: FLOW

Table : HAZOP Analysis for Node 1 (Flow)

GUIDE POSSIBLE
DEVIATION CONSEQUENCE SAFEGUARDS
WORD CAUSES
NO No flow  Feed pump  No raw material to  Install flow
failure the indicator
 Control valve distillation column.  Install low flow
fails to close alarm
 Install standby
pump
 Install
Emergency
Shutdown (ESD)
valve

LESS Less flow  Cavity in pump  Less raw material  Install flow
 Partially to the distillation indicator
plugged line column  Install low flow
alarm
 Install bypass
line valve
 Install
Emergency
Shutdown (ESD)
valve
MORE More flow  Control valve  More raw material  Install flow
malfunction to the distillation indicator
column.  Install high flow
alarm

REVERSE Reverse Flow  Backflow due  Desired flow could  Install the check
to backpressure not be achieved valve
 Regular
inspection and
maintenance for
valve.

8.3 Heat Exchanger Outlet to the Non-oxidative Dehydrogenation Reactor

Intention: To transport process material from heat exchanger into the reactor.
PARAMETER: FLOW

Table : HAZOP Analysis for Node 2 (Flow)

GUIDE POSSIBLE
DEVIATION CONSEQUENCE SAFEGUARDS
WORD CAUSES
NO No flow  Control valve  No process  Install flow
fails to material to the indicator
close reactor  Install low
 No product from flow alarm
the reactor.  Install bypass
line valve
 Install
Emergency
 Shutdown
(ESD) valve

LESS Less flow  Leakage in  Less process  Install flow

pipeline material to the indicator
 Partially reactor  Install low
plugged  Less product flow alarm
line from the reactor  Install bypass
line valve
 Install
Emergency
Shutdown
(ESD) valve

MORE More flow  Control valve  More process  Install flow

malfunction material to indicator
the reactor.  Install high
 Build up pressure flow alarm
in the  Install release
reactor valve at reactor

REVERSE Reverse Flow  Backflow due  Desired flow  Install the

to could not be check valve.
backpressure achieved.  Regular
from reactor  Less of process inspection and
material maintenance
for valve
 CONCLUSION

The design project of the Butadiene production plant has met its objectives of producing
15,129,39600 tonne / year of Butadiene with a purity of more than 99% and is based on 330
working days and 7920 operating hours per year.

It has been proven conceptually that the setting up of a Butadiene plant in India is feasible and
crucial in order to meet the high demand of Butadiene in the Asian region. From the feasibility
research carried out, the Jamnagar or Hazira are identified to be the best location for a Butadiene
production plant. This is due to the combination of attractive features, incentives and availability
of raw material. Basic utilities such as steam and raw water are obtained easily. Moreover heavy
machinery and raw materials, fuel and all equipments can be directly delivered to Jamnagar Plant
because of Arabian Sea. Furthermore, the product can also be transported easily through marine.

The initial information of product and feed together with the reaction kinetics has been vital in
evaluating the feasibility of the chosen process route. The best method to produce Butadiene so
far has been the non-oxidative dehydrogenation reaction of n-butane to butenes and followed by
oxidative dehydrogenation of butenes to butadiene.

The process is carried out in four stages. In distillation column, the height of distillation column
is 28 m. The no. of actual trays are 56. The diameter of column is 3.5 m. In second stage n-
butane is dehydrogenated to butenes. The butenes are further dehydrogenated in oxidative
dehydrogenation reactor to 1,3 butadiene.In final stage the product 1,3 butadiene is separated
from unreacted n-butane by extractive distillation column.

As far as designing of the reactor is concerned the volume calculated for the reactor is 2.4 m3.
The diameter of the multitubular reactor is 1m. The no, of tubes are 1060.The catalyst used in
Non-oxidative dehydrogenation reactor is Pt0.3 Sn0.6Cs0.5K0.5 La3.0. While the catalyst used in
oxidative dehydrogenation reactor is Mo12Bi1Cr3Ni8Zr1Fe0.1K0.2. The solvent used in extractive
distillation column is DMF (dimethyl formaldehyde).

Finally the cost of the butadiene production plant is also reasonable. The Total Capital
Investment is 1,228,698,167 Rs. The Total Production Cost of the plant is 691,176,512 Rs. The
annual net profit after the income tax paid is 389899061. The payback period of the project is
2.298084225 year & the rate of return of the project is 56.41 %.

Overall, as a conclusion, the project has achieved the overall objectives for preliminary design
stages of the Butadiene production plant. For accurate design purposes, the recommendations
should be taken into consideration and applied into the design project of Butadiene production
plant.
References :

[1] Biegler L.T, Grossmann I.E and Westerberg A.W, Systematic Methods of Chemical
Process Design, Prentice Hall, United States. (1997)

[2] Bhasin M.M et al, “Dehydrogenation and Oxydehydrogenation of Paraffins to Olefins”,

Applied Catalyst A: General 221, 397-419 (2001)

[3] Douglas J.M, Conceptual Design of Chemical Processes, Mc Graw Hill, Singapore. (1988)

[4] Dow , Propylene Oxide, http://www.dow.com/propyleneoxide/app /index.htm (2007)

[5] Geoff Wells, (1996) Hazard Identification and Risk Assessment

[6] Jackson S.D and Rugmini S., “Dehydrogenation of n-butane Over Vanadia Catalysts
Supported on θ Alumina”, Journal of Catalysts 251, 59-68 (2007)

[7] Peters M.S and Timmerhaus K.D., Plant Design and Economics for Chemical Engineers, 4th
Edition, Mc Graw Hill, Singapore.(1991)

[8] Wikipedia , http://en.wikipedia.org/wiki/Butane (2018)

[9] Schindler G.P, Walsdorff C., Harth K. Hibst H., Method for the production of butadiene
from n-butane, United States Patent.(2006)

[10] Chang J.(2006), http://www.icispricing.com/

[11] Introduction to Process Equipment Design By Bhattacharya

[12] Process Equipment Design By M.V. Joshi

[13] Perry's Chemical Engineers' Handbook, Eighth Edition [Don Green, Robert Perry] 8th
Edition

[14] Kirk-Othmer Encyclopedia of Chemical Technology vol 4 butadiene P340 –P354 . Fourth
Edition.

[15] Chemical Engineering Design vol 6 5th Edition by Ray Sinnott and Gavin Towler.

[16] J. G. Aston Szasz H. W. Wooley, and F. G. Brickwedde, J. chem. Phys. 14,67 1946

[17] Faith, Keyes, and Clark's Industrial chemicals. (1975 edition)

[18] PLANT DESIGN AND ECONOMICS FOR CHEMICAL ENGINEERS Fourth Edition
Max S. Peters Klaus D. Timmerhaus.

[19] IHS Markit Chemical Economics Handbook (https://ihsmarkit.com/products/butadiene-

chemical-economics-handbook.html)

APPENDICES