1

CHAPTER 1




INTRODUCTION: PROJECT CONCEPTION AND LITERATURE
REVIEW




Butadiene is a versatile raw material used in the production of a wide
variety of synthetic rubbers and polymer resins as well as a few chemical
intermediates. The largest uses for butadiene are the production of styrene
butadiene rubber (SBR) and polybutadiene rubber (BR), which are used mainly in
tire products.[ Anonymous, (February 2009),Butadiene Uses and Market Data ]


Butadiene is one of the components used in the manufacture of
acrylonitrile-butadiene-styrene (ABS), styrene-butadiene (SB) copolymer latex,
styrene-butadiene block copolymers and nitrile rubbers. 1, 3-Butadiene ranks 36
th

in the most produced chemicals in the United States. Three billion pounds per
year are produced in the United States and 12 billion globally. World butadiene
consumption in the synthetic rubber and latex applications is forecast to grow at
an average rate of about 2%/year.[ Anonymous, (February 2009),Butadiene Uses
and Market Data]


The region seeing the strongest performance has been Asia due to
increased production of finished goods in the electronics, automobile and tire
2

sectors. The major source of butadiene is as a byproduct in the steam cracking of
naphtha and gas oil to make ethylene and propylene. The butadiene is extracted
from the C4 cracker stream using extractive distillation. Butadiene is a colorless,
non corrosive liquefied gas with a mild aromatic or gasoline-like odor. Butadiene
is both explosive and flammable because of its low flash point.[ Anonymous,
(February 2009),Butadiene CAS No: 106-99-0]




1.1) History and Background


1.1.1) History

- In 1863, a French chemist isolated a previously unknown
hydrocarbon from the pyrolysis of amyl alcohol. This hydrocarbon
was identified as butadiene in 1886, after Henry Edward
Armstrong isolated it from among the pyrolysis products of
petroleum. In 1910, the Russian chemist Sergei Lebedev
polymerized butadiene, and obtained a material with rubber-like
properties. This polymer was, however, too soft to replace natural
rubber in many roles, especially automobile tires.[ Anonymous,
(February 2009),History Butadiene]

- The butadiene industry originated in the years leading up to World
War II. Many of the belligerent nations realized that in the event of
war, they could be cut off from rubber plantations controlled by the
British Empire, and sought to remove their dependence on natural
rubber. In 1929, Eduard Tschunker and Walter Bock, working for
IG Farben in Germany, made a copolymer of styrene and
butadiene that could be used in automobile tires. Worldwide
3

production quickly ensued, with butadiene being produced from
grain alcohol in the Soviet Union and the United States and from
coal-derived acetylene in Germany.[ Armstrong, H.E. Miller, A.K.
(1886).]


1.1.2) Background

- 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.[ Sun, H.P. Wristers, J.P. (1992).]

- The name butadiene can also refer to the isomer, 1,2-butadiene,
which is a cumulated diene. However, this allene is difficult to
prepare and has no industrial significance.

- In the United States, western Europe, and Japan, butadiene is
produced as a byproduct of the steam cracking process used to
produce ethylene and other olefins. When mixed with steam and
briefly heated to very high temperatures (often over 900 C),
aliphatic hydrocarbons give up hydrogen to produce a complex
mixture of unsaturated hydrocarbons, including butadiene. The
quantity of butadiene produced depends on the hydrocarbons used
as feed. Light feeds, such as ethane, give primarily ethylene when
cracked, but heavier favor the formation of heavier olefins,
butadiene, and aromatic hydrocarbons.

4

- Butadiene is typically isolated from the other four-carbon
hydrocarbons produced in steam cracking by extraction into a
polar aprotic solvent such as acetonitrile or dimethylformamide,
from which it is then stripped by distillation.

- Butadiene can also be produced by the catalytic dehydrogenation
of normal butane. The first such commercial plant, producing
65,000 tons per year of butadiene, began operations in 1957 in
Houston, Texas.

- In other parts of the world, including eastern Europe, China, and
India, butadiene is also produced from ethanol. While not
competitive with steam cracking for producing large volumes of
butadiene, lower capital costs make production from ethanol a
viable option for smaller-capacity plants. Two processes are in use.

- In the single-step process developed by Sergei Lebedev, ethanol is
converted to butadiene, hydrogen, and water at 400450 C over
any of a variety of metal oxide catalysts:

- This process was the basis for the Soviet Union's synthetic rubber
industry during and after World War II, and it remains in limited
use in Russia and other parts of Eastern Europe. In the other, two-
step process, developed by the Russian chemist Ivan
Ostromislensky, ethanol is oxidized to acetaldehyde, which reacts
with additional ethanol over a tantalum-promoted porous silica
5

catalyst at 325350 C to yield butadiene:[ Beychok, M.R. and
Brack, W.J, June 1957]

- 2 CH
3
CH
2
OH CH
2
=CH-CH=CH
2
+ 2 H
2
O + H
2










Figure 1.1: Structural Chemical Reaction of Ethanol


- CH
3
CH
2
OH + CH
3
CHO CH
2
=CH-CH=CH
2
+ 2 H
2
O










Figure 1.2: Structural Chemical Reaction of Ethanol by react
With tantalum-promoted porous silica

6

- This process was used in the United States to produce government
rubber during World War II, and remains in use today in China and
India.

1.1.3) Butadiene Synonyms and Abbreviations
- Biethylene
- Buta-1,3-diene
- Butadieno
- Divinyl
- Erythrene
- Vinylethylene

1,3-Butadiene


1.1.4) Chemical-Physical Properties product and raw material

- Molecular formula C
4
H
6

- Molar mass 54.09 g mol
1

- Appearance Colorless gas or refrigerated liquid
- Density 0.64 g/cm at -6 C, liquid
- Melting point -108.9 C, 164 K, -164 F
- Boiling point -4.4 C, 269 K, 24 F
- Solubility in water 735 ppm
- Viscosity 0.25 cP at 0 C





7

1.1.5) Importance of Butadiene production

The 1,3-butadiene is the simplest member of the series of
conjugated dienes, which contain the structure C=CC=C, the C being
carbon. The wide variety of chemical reactions peculiar to this system
makes butadiene important in chemical synthesis. Under the influence of
catalysts, butadiene molecules combine with each other or with other
reactive molecules, as acrylonitrile or styrene, to form elastic, rubberlike
materials. In uncatalyzed reactions with reactive unsaturated compounds,
such as maleic anhydride, butadiene undergoes the Diels-Alder reaction,
forming cyclohexene derivatives. Butadiene is attacked by the numerous
substances that react with ordinary olefins, but the reactions often involve
both double bonds (e.g., addition of chlorine yields both 3,4-dichloro-1-
butene and 1,4-dichloro-2-butene). At atmospheric conditions, 1,3-
butadiene exists as a colourless gas, but it is liquefied either by cooling to
-4.4 C (24.1 F) or by compressing to 2.8 atmospheres at 25C.
[Kirshenbaum, I. (1978)]




1.2) Application of Products


Nearly all (96%) of the butadiene produced globally is as a co-product of
the steam cracking of naphtha and gas oil to make ethylene and propylene. After
ethylene and propylene are extracted from the cracker, a C4 stream is separated
from the process which contains predominately hydrocarbons containing four
carbon atoms, e.g. butadiene and butenes.


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
8

automobile tyres. SBR is also used in adhesives, sealants, coatings and in rubber
articles like shoe soles. Polybutadiene is also used in tyres and can be used as an
intermediate in the production of acrylonitrile-butadiene-styrene (ABS). ABS is
widely used in items such as telephones, computer casings and other appliances.[
Anonymous, (June 21, 2007),Product Safety Assessment, Butadiene]


Other polymers made from butadiene include styrene-butadiene latex,
used for example in carpet backings and adhesives; nitrile rubber, used in hoses,
fuel lines, gasket seals, gloves and footwear; and styrene-butadiene block
copolymers which are used in many end-uses ranging from asphalt modifiers
(road and roofing construction applications), to adhesives, footwear and toys.[
Anonymous, (June 21, 2007),Product Safety Assessment, Butadiene]]


Chemical intermediates made from butadiene include adiponitrile and
chloroprene which are used, respectively, in the manufacture of nylon and
neoprene.











Figure 1.3: Chart of uses 1,3 Butadiene



9

1.2.1) Synthetic Elastomer


The synthetic elastomers of the invention have incorporated therein from
about 11-50%, preferably from about 20-40%, of a liquid, high vinyl 1,2-
polybutadiene resin having a pendant vinyl group for every other chain carbon
which is capable of crosslinking to a very high degree. The preferred liquid, high
vinyl 1,2 polybutadiene has from about 80-95 mole %, most preferably from
about 90-95 mole % 1,2 vinyl structure. [Anonymous, (1987), Synthetic
elastomeric with improved chemical, aging and oil resistance]

In the method of the invention, the previously polymerized, liquid, high
vinyl content 1,2-polybutadiene is incorporated into an elastomer selected from
the group consisting of ethylene-propylene copolymer rubbers and ethylene-
propylene-nonconjugated diene terpolymer rubbers. The previously polymerized
liquid, high vinyl content 1,2-polybutadiene is incorporated during the
polymerization of the elastomer to provide additional cure sites on the resulting
elastomer. Rather than attempting to directly polymerize the polybutadiene onto
the backbone of the ethylene-propylene chain, the polybutadiene is solution
blended after catalysis and prior to separating and drying the polymerized
elastomer. The polybutadiene is added prior to precipitating and drying the
polymerized elastomer. The resulting elastomer is peroxide cured to produce an
insulating material exhibiting excellent electrical characteristics, ease of
compounding, and improved performance at extreme temperatures and pressures
when exposed to solvents, oil and aqueous environments.[ Anonymous, (1987),
Synthetic elastomeric with improved chemical, aging and oil resistance]


10

Synthetic olefin polymers are popular as electrical insulating materials
because of their ease of compounding, good extrudability and excellent electrical
characteristics. These polymers also find use as valve seats, and in other
applications. In particular, ethylene-propylene copolymer rubbers, known as EPR,
and ethylene-propylene-nonconjugated diene terpolymer rubbers, known as
EPDM have been widely employed as the primary insulating materials for
electrical wire and cable. These materials have the characteristics of flowing
and/or distorting at elevated temperatures and under extreme pressures and are
sensitive to swelling and dissolving in various hydrocarbon solvents and oils.
Where insulated wire and cable is needed for extreme conditions, EPR and EPDM
elastomers have been physically blended with low molecular weight
polybutadiene in a roll mill, Banbury mixer, or the like. The physical blending or
incorporation of the polybutadiene into the EPR/EPDM rubber provides
additional cure sites for greater cross link density. An increase in cross link
density has been found to enhance the chemical aging and oil resistance of the
elastomer, improving the performance of the elastomer in extreme environmental
conditions. U.S. Pat. No. 3,926,900 to Guzy et al., issued Dec. 16, 1975, discusses
the physical blending of liquid 1,2 polybutadiene with EPDM polymers.
[Anonymous, (1987), Synthetic elastomeric with improved chemical, aging and
oil resistance]




1.2.2) Polymer and Resin


Engineering resins is the term for a group of polymer plastics which
exhibit a greater tendency to form crystals in their solid state than their more
amorphous cousins. The additional level of long-range order at the molecular
11

scale produces a different set of physical properties which suit the engineering
plastic resins to a wide variety of applications that amorphous resins cannot fill. In
general, engineering plastic resins are physically stronger and less flexible than
amorphous resins and show greater resistance to fatigue, friction and wear.
[Anonymous, (2007), Engineering Resin]




1.2.3) Polybutylene Terephthalate (PBT)

PBT engineering plastic resins are used to fabricate components found in
computer keyboards, appliances, fluid handling systems, cars and trucks,
electrical connectors, and industrial systems and controls. This product list is a
testament to the versatility of the compound and is a direct result of its many
outstanding characteristics. Stability and resistance to temperature extremes,
along with a superior ability to be molded into complex or fine shapes makes PBT
one of the most important engineering polymers.[ Anonymous, (2007),
Engineering Resin]




1.2.4) PC/ABS
A true industrial thermoplastic, this engineering resins blend combines the
most desirable properties of both materials; excellent features of ABS and the
superior mechanical properties and heat resistance of polycarbonate. PC-ABS
blends are widely used in automotive, electronics and telecommunications
applications. This engineering plastic resins blend is ideal for the rapid production
12

of prototypes, tooling and the direct (tool-less) manufacturing of production
parts.[ Anonymous, (2007), Engineering Resin]




1.2.5) Nylon 66 (Polyamide 66) resin

A thermoplastic resin with excellent mechanical, thermal and electrical
properties will use as raw materials of fiber, film and engineering plastic.
Engineering plastic resins are replacing the previous metals at a rapid pace. Nylon
has a proven record of outstanding service in a wide range of applications for all
industries.[ Anonymous, (2007), Engineering Resin]




1.2.6) Styrene Butadiene Rubber (SBR)

Styrene butadiene rubber (SBR) is the outcome of synthetic rubber
research that took place in the United States and Europe under the impact of the
shortage of natural rubber, a German chemist developed a series of synthetic
elastomers by copolymerization of two compounds (styrene and butadiene) in the
presence of a catalyst. The first step involved in the process is to let styrene and
butadiene react together. The new synthetic rubber that was formed consists of
about 25% styrene, with butadiene making up the rest, which in principle had the
same properties as natural rubber. This rubber is considered to be the highest
volume general purpose and the most common type of synthetic rubber.
[Anonymous, (2007), Types of Synthetic Rubber]
13

1.2.7) Properties of Styrene Butadiene Rubber


- This type of rubber is usually very weak unless reinforcing fillers are
incorporated. With suitable fillers, this becomes a strong rubber.
- It has similar chemical and physical properties like natural rubber.
- It has better abrasion resistance.
- It has poorer fatigue resistance.
- Heat resistance is better than natural rubber.
- Low temperature flexibility and tensile strength are less than that of
natural rubber.




1.2.8) Chemical used

Chemical intermediates manufactured from butadiene include adiponitrile
and chloroprene. Adiponitrile is used to make nylon fibres and polymers.
Chloroprene is the monomer to make polychloroprene, better known as Neoprene,
which has a wide variety of uses such as wet suits, electrical insulation, car fan
belts, gaskets, hoses, corrosion-resistant coatings and adhesives.[ Anonymous,
(February 2009),Butadiene Uses and Market Data]




1.2.9) Other applications


Elastomers, 61% (styrene-butadiene rubber (SBR), 32%; polybutadiene,
23%; polychloroprene, 4%; nitrile, 2 percent); styrene-butadiene latex, 12%;
adiponitrile for HMDA, 11%; ABS resins, 5 percent; miscellaneous, 11%
14

Anonymous, (November 1996),Locating and Estimating Air Emissons From
Source]


Other polymers made from butadiene include styrene-butadiene (SB)
copolymer latex, which is used in paper coatings, carpet back coatings, foam
mattresses and adhesives. Styrene-butadiene block copolymers have many
applications ranging from asphalt modifiers in road and roofing construction to
adhesives, footwear and toys.


Nitrile rubbers, made by the copolymerisation of acrylonitrile with
butadiene, are used mainly in the manufacture of hoses, gasket seals and fuel lines
for the automobile industry as well as in gloves and footwear.




1.3. Problem Statement


Butadiene is one of highly demanded products in petrochemical industry.
For many years, its production rate has been increasing. The current production of
butadiene is about 7,000,000 ton per year in USA, Western Europe and Eastern
Asia only, and it does not satisfy the market needs, since yearly increase in
demand is predicted to be 3.9%, whereas increase of production rate is 2-3% only.
The price of the product during 2000 increased by 25%. Butadiene is produced
using n-butane as a raw material in a two stage Gudry vacuum dehydrogenation
process. The output of butadiene in this process is usually about 12%. The project
presents the extremely effective solution for production butadiene the catalyst
that makes it possible to increase output of butadiene from 12 to 25%.[DR.
Talishinsky, (1996),Butadiene production]


15

Besides elastomers will continue to be the largest consumer of butadiene
and should maintain their position of 61 percent of total consumption. However,
they are mature products that are heavily reliant on the automotive industry.
Adiponitrile/ hexamethylenediamine (HMDA), styrene-butadiene (SB) copolymer
latex, acrylonitrile-butadiene-styrene (ABS) resins, styrenic block copolymers and
other smaller polymer applications will grow faster than the elastomers (excluding
polybutadiene), but they each account for only 5-10% of the total butadiene
market. With a projected negative average annual growth of -1.7 during 2000-
2004, the total market for butadiene in 2004 will reach 5.1 billion pounds, or
about about what it was in 1998. This takes into account the big hit in demand in
2001. [Lynne M.Miller, (Dec 1978),Investigate of Selected Potential
Environmental Contaminants : Butadiene and its Oligomers,]


So to recover the quality and maintain the production cause of the high of
demand in Malaysia and the entire world, the selected of this plant design
research title are very suitable.




1.4. Objective and Scope


The objective of this research of plant design is to increase the production of
butadiene with efficient way and to bear an amount of demanding production
especially in Malaysia with the scope of this research are:-


i. To design the plan based on demand of production
ii. To develop a suitable business in Malaysia
iii. To make a profit from the production


16

1.5) MARKET SURVEY


1.5.1) Global Situation


The Global production and consumption of butadiene in 2008 were
approximately 10.6 million metric tons and 11.1 million metric tons, respectively.
Global capacity utilization in 2008 was 88%. Global butadiene consumption is
estimated to have increased by almost 2% in 2008, and is expected to average
growth of 3.8% per year from 2008 to 2013, slowing to 2.3% per year from 2013
to 2018. Global utilization rates are expected to be in the 90s. [Anonymous,
(January 2010),Butadiene]


Styrene butadiene rubber (solid & latex) accounted for more than 30% of
global butadiene consumption in 2008, followed by polybutadiene rubber, for
around 25%. Other applications for butadiene include manufacture of styrenic
copolymers, ABS resins, SB latex, nitrile rubber, and adiponitrile/HMDA.
The following pie chart shows world consumption of butadiene by end use:
[Anonymous, (January 2010),Butadiene]


From the figure 1.4, its shown that butadiene demand is concentrated in
its use in the manufacture of styrene butadiene rubber (SBR) solid and latex
(34.7%), polybutadiene rubber (24.9%), ABS resins (10.2%), SB copolymer latex
(9.4%) and other consumptions about 20.9%.







17












Figure 1.4: World consumption of Butadiene


Table 1.1.0: World Butadiene Supply/Demand Balance (1999-2005)


Demand for butadiene in the production of ABS resins will see the highest
average annual rate growth for all derivatives in the increase in total tons of
butadiene consumed. Demand of butadiene in this application will increase by
more than 500,000 tons during the period. Global demand for butadiene will
increase at an average annual rate of 3.9% during the period from 2001-2006
percent and will outpace capacity additions. This rate is higher than the
18

compounded annual rate of 2.7% from 1996-2001 due to the global decline in
demand that occurred in 2001 following the global economic slowdown.[ Jorg
Wutke, (1996),The petrochemical Industry in China]


Its expected that, in 2008 through 2012 period will experience a
butadiene demand growth rate of just under 3.5 percent per year, slightly higher
than the 3.2 percent annual rate experienced over the past five years. Global
demand for butadiene consumed into ABS resin production is estimated to grow
at a high annual rate of around five percent, due to heavy use of thermoplastics in
the manufacture of computer equipment and other appliances, mainly in China.
Butadiene based nylon production, through adiponitrile, will also grow at about
five percent per year. However, worldwide demand for butadiene in its largest
end use sector, the production of commodity-based synthetic rubber and latex, is
anticipated to average around 3% per year.[ Anonymous, (January,14,2008),
CMAI Completes 2008 World Butadiene Analysis]




1.5.1.1)Styrene Butadiene Rubber (SBR) Demand

The tyre industry consumes 75 percent of the SBR produced globally
followed by the mechanical rubber goods/automotive parts applications (19
percent of the market). Footwear accounts for only around six percent of the SBR
market. The main use of SBR is in the manufacture of tyre tread, and
consumption is forecast to develop in line with the automotive sector.

1. The production of auto tyres is increasingly competitive and cost sensitive.
Consequently, the manufacture of tyres and other rubber goods has tended
19

to migrate to lower labour cost areas, depressing market growth in
developed regions such as Western Europe, the United States and Japan.
Exports of finished rubber goods, primarily tyres, from regions such as
China to the United States and Europe have increased dramatically over
the last five years, leading to the closure of a number of tyre plants in the
importing regions. Flourishing automotive sectors in China, India, and
Thailand have also increased demand in the Asia Pacific region.
[Anonymous, (2008), Butadiene Derivatives Impacted by Automotive
Crisis]



Figure 1.5: Global SBR Capacity Additions/ (Closures)












20

1.5.1.2 Butadiene Rubber (BR)

Approximately two-thirds of BR is consumed in tyre production, with a
further quarter used as an impact modifier in high impact polystyrene (HIPS)
production. Other applications consume only around eight percent of the BR
market. As the main use of BR is in the manufacture of tyres, BR consumption is
forecast to increase in line with the automotive sector.
Asia Pacific, North America and Western Europe are the major consuming
regions for BR, with total consumption in these three regions accounting for more
than 80 percent of the global total. China has surpassed the United States to
become the largest consumer of BR in 2007. The combination of new tyre
manufacturing and high impact polystyrene (HIPS) capacities in China has
boosted demand for BR while some rationalisation of both capacities was seen in
the United States.[ Anonymous, (1996), Butadiene rubber]


Figure 1.6: Global Butadiene Rubber Capacity Additions/ (Closures)


21

1.5.1.3 Acrylonitrile Butadiene Styrene (ABS)

Global ABS demand has been under pressure from inter-polymer
competition, especially from polypropylene and lately polystyrene, which is
competing particularly at the lower specification end of the automotive sector.
Recent development in high gloss polystyrene is a new threat for ABS for
decorative parts. However, ABS remains the material of choice in most
applications in the key electronics/electrical appliance sector, due to its
mechanical properties, high gloss and processability.[ Anonymous, (November
1996),Butadiene Styrene]

Although ABS consumption is forecast to grow at slower rates over 2009-
2018 after the recent economic downturn, it will be one of the key drivers for
styrene market growth during the recovery of the economy, with long term
sustainable growth supported by the electrical appliance and automotive sectors.
Asia Pacific, particularly China will remain the largest consuming region with an
increasing proportion of the global consumption. Central Europe is expected to
grow to balance the slowdown in the Western Europe.

22


Figure 1.7: Global ABS Capacity

In 2008, SBR is the largest end use of butadiene, accounting for slightly
less than one-third of total demand, followed by BR and SBL respectively. ABS,
hexamethylenediamine (adipic acid) HMDA and other butadiene uses made up
the remaining demand, accounting for 30 percent in total. Butadiene consumption
is driven to a great extent by the automotive industry, which tends to give a very
volatile growth pattern. Historically, BR grew faster than SBR, but this will
change in the forecast due principally to the slow growth in HIPS market.
Despite a freefall in the ABS sector last year along with electronics and
automotive industries, ABS is expected to recover and continues to grow at high
rates. Due to a cost advantage over the acrylonitrile process, demand into HMDA
towards butadiene will also grow rapidly as new plants start up in the United
States and China. On the other hand, the growth of the SBL sector is forecast to
moderate as a result of more efficient use in paper and carpet industries.
[Anonymous, (2007),Product overview and market projection of emerging bio]

23


Figure 1.8: Global Butadiene Capacity


Butadiene extraction capacity is concentrated in the major naphtha
cracking regions of Asia Pacific, North America and Western Europe. The
development of ethylene capacity based on heavier feedstocks in the Middle East
will increase butadiene capacity there, although the region is destined to remain
small in terms of overall production. Capacity in Eastern Europe is expected to
remain fairly flat as ethylene capacity in the region remains in excess of demand,
and is not expected to increase significantly.[ Anonymous, (2009),Butadiene
Market Dynamics]
24


Figure 1.9: Global Butadiene Consumption, Operating Rate and Capacity


Global butadiene operating rates remain at well above average levels, but
are expected to decline towards a trough in 2011 as major capacity additions are
made during the forecast period of low demand growth. The increasing
proportion of liquids based cracker developments will increase the availability of
mixed C
4
feedstock for butadiene extraction at a rate greater than that of
butadiene demand growth. This is expected to result in a greater proportion of
mixed C
4
hydrogenation and co-cracking rather than over expansion of butadiene
extraction capacity. The limited amount of naphtha cracker capacity expansion in
North America and Western Europe will govern the level of butadiene capacity
development in these areas. No new derivatives will be based in areas where
there is no additional butadiene availability, leading to a gradual concentration of
activity in butadiene and derivatives in Asia. [Anonymous, (2009),Butadiene
Market Dynamics]


25

Year Price ($/Pound)
2004 0.30
2005 0.26
2006 0.544
2007 0.735
2008 1.360
2009 0.428

Table 1.1.1: World Butadiene Prices (2004-2009)










Figure 1.10: Global Butadiene Prices (2004-2009)










26

Year Demand (-000-Metric Tons)
1999 7,880
2000 8,340
2001 8,634
2002 8,937
2003 9,229
2004 9,507
2005 9,810
2006 10,430
2007 10,878
2008 11,513

Table 1.1.2: World Demand toward Butadiene




Figure 1.11: World Demand toward Butadiene (1998-2010)

27

According to the figure 1.4.5, world demand towards butadiene was
slowly increased from 1999 to 2008. In 2009, global butadiene demand is
expected to grow at a pace lower than the 3.2 percent annual rate experienced
over the past five years. For example, the outlook for worldwide butadiene in its
largest end use sector, the production of commodity based synthetic rubber and
latex, is anticipated to only average around 2 percent per year. A slowing global
economy is also causing slower demand for rubber goods, especially in the
automotive sector. Global butadiene growth has averaged 3.3 percent per year
from 1995-2006, but is expected to average only 3.1 percent over 2006-2015.
Global consumption of butadiene is expected to increase from 10 million tons in
2006 to 13 million tons by 2015.[ Anonymous, (2008),Basic Material: Global
Insights]

From figure 1.4.4, the global prices of butadiene were rapidly increasing
from 2004 to 2008 but the price was drastically decreased in 2009. Actually, the
global economic culture and oil prices were affecting the prices of butadiene in
the market. We believe that the global prices rhythm of butadiene will increased
according to the report that said the global economic will became stable at the end
of 2010. The political instability especially in the Middle East (Iraq and Iran) will
cause the increasing of global oil prices. So, we assumed that when the oil prices
increase, the global prices of butadiene will increased too.


1.5.2 Asia Pacific Situation


The Asian market has been particularly active in building new capacity of
butadiene and butadiene derivatives due to the ongoing development of
automotive and tyre production in the region. The relocation of automotive
industries increased synthetic rubber demand through tyre production, while both
ABS and HMDA will benefit from plastics demand in the Asian automotive
28

sector. Additional global demand for butadiene in recent years was entirely
focussed in Asia Pacific where significant new derivatives capacity built up,
particularly in China and South Korea. In the outlook, the share of Asia Pacific
demand will grow further from 45 percent in 2008 to 53 percent in 2015.

Demand in Asia Pacific accounts for 41 percent of the global total, and the
proportion is forecast to increase. The growth in demand in Asia is driven by
increasing availability, and the rapid growth in demand in derivatives to supply
the booming Asian manufacturing sector.[ Anonymous, (2008),Basic Material:
Global Insights]

The markets for butadiene have emerged from a long period of
oversupply, leading to record prices and margins in 2006. Butadiene prices broke
the $1,500 per ton level in Asia in late 2006, almost six times the lowest prices
seen in the late 1990s. At the same time, margins for West European producers
reached over $400 per ton, despite the prevailing high feedstock prices. The
current high global operating rates are set to last through 2007 and 2008, before
dropping off due to major capacity additions.

The Asian market has been particularly active for butadiene due to the
ongoing development of automotive and tyre production in the region which
drives demand, and the major steam cracker developments which drive supply.
The Asia Pacific region has accounted for over half of global capacity and
demand growth over the past five years, and will account for three quarters over
2007-2011.

29

Major steam cracker developments in Asia will provide more mixed C4s
for butadiene production, leading to a decrease in operating rates. In the long
term, the growth of ethylene production, and therefore the availability of C4s, will
exceed demand growth for butadiene, leading to increased reprocessing of steam
cracker C4s. Countries such as China are expected to extract enough butadiene to
serve their own derivative requirements, and hydrogenate then recycle the
remainder back to the steam cracker.[ Anonymous, (2008),Basic Material: Global
Insights]

The operating rates will remain above 85% until 2009, when major
capacity additions and slower demand growth will cause a decline towards a
trough in 2011. New capacity developments are focussed on conventional
extraction from steam cracker mixed C4 streams. The current high margins on
butane dehydrogenation are expected to be temporary and not likely to encourage
new investment in this technology. The tendency towards heavier cracker slates
in the Middle East is increasing the availability of steam cracker C4s for
butadiene and derivatives. The scale however remains small relative to
expansions in Asia . While currently growing rapidly from a small base, the
Middle East is unlikely to build a major export position for butadiene and
derivatives as it has in the ethylene chain.[ Anonymous, (2008),Basic Material:
Global Insights]




1.5.2.1 Butadiene Market in China
With the increase of domestic butadiene production capacity, China's
butadiene supply will basically meet the rising demand in the coming four years,
according to industry experts.With large scale development of the ethylene
industry, enterprises under the aegis of China's two oil giants PetroChina and
Sinopec are swarming to build or expand butadiene production facilities to
30

produce butadiene, which is in great demand on the domestic market. It is
predicted that Chinas butadiene production capacity is expected to reach 2.7
million tons by 2011. [Anonymous, (2008),Management Discussions]

China had 18 butadiene producers and 26 sets of butadiene production
facilities with an annual production capacity totaling 1.614 million tons by May
2007, accounting for 13.5 per cent of the world's total. Last year, it produced
1.153 million tons of butadiene, an increase of 15.78 per cent over 2005. Its
butadiene output grew at an average annual rate of 12.3 per cent in 2001-2006.
However, its current output cannot satisfy the domestic demand. It has to import
butadiene in bulk. With some production facilities newly built or expanded, the
import volume has declined moderately, from 195,900 tons in 2004 to 147,200
tons in 2005 and 89,200 tons in 2006. With the rapid development of synthetic
rubber industry, the main consumer of butadiene, China's apparent butadiene
consumption has kept growing in recent years, from 782,500 tons in 2001 to
1.0353 million tons in 2004 and 1.2153 million tons in 2006. It is predicted that
the consumption will grow 8.7 per cent annually from 2006 to 2011, topping 1.7
million tons in 2011.[ Anonymous, (Nov 2008),Production from China]




1.5.3 Malaysia Situation
Malaysia has a well-developed oil and gas sector and a growing
petrochemical industry. The petrochemical industry is an important sector in
Malaysia with investments totaling US$7.4 billion in 2004 and US$6.9 billion in
2007. From being an importer of petrochemicals, Malaysia is today an exporter of
major petrochemicals product. A wide range of petrochemicals are produced in
Malaysia such as olefins, polyolefin, aromatics, ethylene oxides, glycols, oxo-
31

alcohols, exthoxylates, acrylic acid, phthalic anhydride, acetic acid, styrene
monomer, polystyrene, ethyl benzene, vinyl chloride monomer and polyvinyl
chloride.[ Anonymous, (2009),Butadiene Market Dynamics]

The rapid growth of the industry is mainly attributed to the availability of
oil and gas as feedstock, a well-developed infrastructure, a strong base of
supporting services, the country's cost competitiveness, as well as Malaysia's
strategic location within ASEAN and its close proximity to major markets in the
Asia Pacific Region. Malaysia has the world's 14th largest natural gas reserves
and 23rd largest crude oil reserves. In 2008, Malaysia produced 5,891 million
standard cubic feet per day of natural gas and 691,600 barrels of oil equivalent per
day of crude oil. Malaysia also has the world's largest production facility at a
single location of liquefied natural gas with production capacity of 23 million
metric tonne per year.[ Anonymous, (2009),Butadiene Market Dynamics]

The long term reliability and security of gas supply ensures the sustainable
development of the country's petrochemical industry. The existence of a trans-
peninsular gas transmission pipeline system and six gas processing plants, has
resulted in a ready supply of gas to the industry. To complement the existing gas
reserves and to ensure further security of gas supply, Malaysia has forged
partnerships with other ASEAN members for the supply of gas such as Vietnam,
Indonesia and the Malaysia-Thailand Joint Development Area (JDA). In addition,
gas supply will be further enhanced with the implementation of the ASEAN gas
grid, a venture to make gas available to all the 10 ASEAN countries. With the full
implementation of AFTA, petrochemical manufacturers in Malaysia will benefit
from a single market. Manufacturers based in Malaysia will also benefit from the
access to a much larger Asia Pacific market. With China being a net importer of
petrochemicals, Malaysia's 'early harvest' Free Trade Agreement with China will
32

open up new business opportunities for petrochemicals manufacturers in
Malaysia.[ Anonymous, (2009),Butadiene Market Dynamics]

The presence of world renowned petrochemical companies, such as Dow
Chemical, BP, Shell, BASF, Eastman Chemicals, Toray, Mitsubishi, Idemitsu,
Polyplastics, Kaneka, Dairen and West Lake Chemical speaks clearly of
Malaysia's potential as an investment location for petrochemical industries. Most
of these companies are working in collaboration with Malaysia's national
petroleum company, PETRONAS. Three major petrochemical zones have been
established in Kertih, Terengganu; Gebeng, Pahang; and Pasir Gudang/Tanjung
Langsat, Johor. Each zone is an integrated complex with crackers, syngas and
aromatics facilities to produce feedstocks for downstream products. There are also
other petrochemical plants in Malaysia such as the ammonia and urea plants in
Bintulu, Sarawak and Gurun, Kedah; acrylonitrile butadiene styrene plant in
Pulau Pinang; methanol plant in Labuan and the nitrile-butadiene rubber plant in
Kluang, Johor.[ Anonymous, (2009),Butadiene Market Dynamics]




1.6) SCREENING OF SYNTHESIS ROUTE IN PRODUCTION OF
BUTADIENE


Butadiene is produced commercially by three processes:

- Steam Cracking of Paraffinic Hydrocarbons
- Catalytic Dehydrogenation of n-Butane and n-Butene (the Houdry process).
- Oxidative Dehydrogenation of n-Butene (the Oxo-D or O-X-D process).


33

1.6.1) Butadiene Production via Steam Cracking of Paraffinic Hydrocarbons



Figure 1.12: Typical Olefin Plant


In this process, butadiene is a co product in the manufacture of ethylene
(the ethylene co-product process).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 1.1 depicts a flow chart for a
typical olefins plant.

The flow path of the C4 components (including butadiene) is indicated by bold
[red] lines.


The indicated feed stocks (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
34

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.[ Anonymous,
(2002),Butadiene product Stewardship Guidance Manual]


While some olefins plant designs will accommodate any of the listed feed
stocks, many olefins plants process only Natural Gas Liquids (NGLs) such as
ethane, propane and sometimes butane. The mixes of feed stocks, the conditions
at which the feed stocks 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. Olefins plants generally produce crude
butadiene streams that contain very few C3 and C5 components, as shown by the
analysis found in Table 1.1. The composition of the crude butadiene stream also
can be altered via recycle blending of various product streams. For example, when
finished butadiene streams (99+ wt% pure) do not meet commercial
specifications, they are often combined with crude butadiene streams in order to
recover the butadiene. In this situation, the resulting stream may not fall into the
example range. Generally, crude butadiene is stored as a liquid under pressure in a
pressure products sphere.[Anonymous, (2002),Butadiene product Stewardship
Guidance Manual]

35


Table1.1.3: Example of a Crude Butadiene Analysis


1.6.2) Butadiene Production via Catalytic Dehydrogenation of 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 1.13. 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.[Anonymous,
(2002),Butadiene product Stewardship Guidance Manual]

36


Figure 1.13: Catadiene Process Plant


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.




1.6.3) 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 feed stocks. 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
37

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 selective can
range from 70-90%, making it unnecessary to recover and recycle feedstock.
(Yield losses can produce the CO2.) In the Oxo-D process shown in Figure 1.3, 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.[Anonymous, (2002),Butadiene product
Stewardship Guidance Manual]


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, and then it is sent to a purification system to recover
the butadiene product.[Anonymous, (2002),Butadiene product Stewardship
Guidance Manual]






38


Figure 1.14: Oxidative Dehydrogenation Process




1.6.4) Butadiene Recovery from Crude Butadiene Streams Via Extractive
Distillation


Since the boiling points of the various C4 components are so close to each
other, separation via simple distillation does not currently suffice to adequately
separate the components; therefore, extractive distillation is used. Several design
options are available, including those listed in Table 1.2. Inclusion here is not
intended as an endorsement. These processes involve one or two extractive
distillation steps followed by one or two distillation steps. The number of
extraction and/or distillation steps can be reduced to one by including an
acetylene hydrogenation step.[Anonymous, (2002),Butadiene product
Stewardship Guidance Manual]
39

Table 1.1.4: Major Butadiene Recovery Process




1.6.5) Butadiene Purification via Acetylene Hydrogenation and Extractive
Distillation Using MOPN/Furfural Solvent


This process contains four sections: 1) acetylene hydrogenation, 2)
extractive distillation, 3) butadiene purification, and 4) solvent purification.


The objective of the acetylene hydrogenation section is to hydrogenate C4
acetylenes that could otherwise contaminate the butadiene product. This is
achieved using a liquid phase reactor system. Butadiene-dimers and trimers
formed in the reactor are removed via distillation in the green oil column located
just downstream of the reactor. The green oil column overhead stream is fed to
the extractive distillation section. The function of the extractive distillation
section is to separate the C4 hydrocarbon stream into a butane/isobutene/trans-
butene-2 stream (C4 Raffinate 1) and a butadiene/cis-butene-2 stream via
extractive distillation and solvent stripping. The green oil column overhead
stream is vaporized then fed to the lower portion of the extraction column where
the vapors are counter currently contacted with the aqueous methoxy-proprio-
nitrile (MOPN)/furfural solvent which are fed into the top of the column. Butane
and the less soluble butenes are concentrated and removed in the overhead stream.


40

The butadiene/cis-butene-2 rich solvent from the bottom of the extraction
column are fed to the extract stripper column, where butadiene, cis-butene-2 and
acetylenes (ppm level) are stripped overhead. The extract stripper column
overhead stream is used to feed the butadiene purification column where
butadiene is concentrated in the overhead product. Then the remaining butene-2
and heavier components are drawn from the bottom of the column and recycled to
the olefins plant cracking furnaces. The purpose of the solvent purification section
is to remove impurities from the lean solvent. The system consists of two
evaporators, a stripping column and a solvent settling drum which are used to
remove furfural-butadiene polymer, acrylonitrile-butadiene codimer, and
vinylcyclohexene compounds. [Anonymous, (2002),Butadiene product
Stewardship Guidance Manual]

Figure 1.15: Process A- Acetylene Hydrogenation/Extractive Distillation Using
MOPN/Furfural






41

1.6.6) Extractive and Conventional Distillation Process Using NMP Solvent


This process, licensed by BASF and illustrated in Figure 1.6, is a
combination of extractive and conventional distillation. The extractive distillation
uses n-methylpyrrolidone (NMP) as the solvent. The highest temperature is
approximately 300 F and the maximum pressure is approximately 100 psig (7
bars g).


The evaporated C4 cut is fed to the extractive distillation section where in
the first stage the butanes and the butenes are separated from the more soluble
1,3-butadiene, 1,2-butadiene, C4 acetylenes, propyne and the C5 hydrocarbons.
The loaded solvent is degassed in a steam heated column where the acetylenes are
withdrawn as a side stream and are fed to a washer where the NMP is recovered.


Crude butadiene leaves the extractive distillation section at the top of the
second stage and is then fed to the propyne distillation column where propyne
(methyl-acetylene) is removed overhead. The bottoms product containing the 1,3-
butadiene, 1,2-butadiene and the C5 hydrocarbons is then distilled in the
butadiene column. Generally, 1,3-butadiene with a purity of >99.6% by weight
leaves the top of the butadiene column. The column bottoms stream usually
contains 1,2-butadiene and heavier hydrocarbons.


The crude butadiene, the top of the propyne column, and the purified
butadiene are typically inhibited with tertiary butyl catechol (TBC) or with other
compounds. Sodium nitrite can be used as an inhibitor during extractive
distillation. The waste hydrocarbon streams can be diluted with naphtha and used
as supplemental feedstock for the olefins plant.[ Anonymous, (November
1996),Produce of Butadiene]

42


Figure 1.16: Process B- Extractive and Conventional Distillation Using NMP




1.6.7) Dimethylformamide (DMF) Solvent Extraction Process


This process, licensed by Nippon Zeon, consists of four sections: 1) first
extractive distillation; 2) second extractive distillation; 3) butadiene purification;
and 4) solvent purification. SeeFigure 1.7. In the first section of the plant, the
hydrocarbon feed (C4 fraction) and the DMF solvent are fed to the first extractive
distillation column, where the C4 stream is separated into two fractions:


1. the C4 raffinate 1 overhead product, which contains less soluble
components (butane/butene); and,
2. The bottoms product, which contains the DMF solvent rich in
butadiene/acetylene components which are the more soluble components.


43

At this stage, the C4 raffinate 1 product stream is available for downstream
processing (MTBE, polyisobutylene, alkylation). The butadiene/acetylene rich
solvent is fed to the first stripper column where the butadiene/acetylenes are
stripped from the solvent and proceed overhead to the second extractive
distillation section. The lean solvent from the stripper is cooled via heat recovery
prior to being sent back to the extractor. In the second extractive distillation
section, the butadiene/acetylene stream from the first section also is separated into
two fractions, again using DMF as the solvent:[ Anonymous, (November
2006),Production of Butadiene]


1) butadiene/methyl acetylene rich overhead fraction; and,

2) bottoms fraction, containing the DMF solvent rich in vinyl
acetylene which is more soluble in the DMF solvent than is
butadiene or methyl acetylene.


The butadiene/methyl acetylene rich overhead fraction is sent on to the
butadiene purification section of the process where the remaining acetylenes are
removed using two distillation columns and a pure 1, 3-butadiene product stream
is produced. The bottoms fraction from the second extractive distillation is fed to
a stripper column where a vinyl acetylene rich stream is stripped from the solvent
and used for fuel.


Since the DMF solvent is continuously circulated to the first and second
extractive distillation columns, butadiene dimer, tar, and any water from the C4
feed stream tend to increase in concentration, thereby decreasing the effectiveness
of the solvent. Therefore a part of the solvent is continuously passed to the solvent
purification section of the plant to remove these impurities.


44


Figure 1.17: Process C- DMF Solvent Extraction Process




1.6.8) Aqueous Separation and Acetonitrile (ACN) Extraction


In this process, licensed by Shell, the hydrocarbon feed (C4 fraction) is
routed to an extractive distillation system. The separation is achieved in an
aqueous solvent environment, where the top product contains the
butanes/butylenes and the bottoms stream contains the butadiene and acetylenes.
Acetonitrile (ACN) is used as the extraction solvent. As illustrated in Figure 1.8,
the butadiene is then stripped from the extraction solvent and may be fed to a
topping column where residual light ends (primarily methyl acetylene) are
rejected. Heavier acetylenes such as vinyl acetylene and ethyl acetylene are
rejected as a side stream from the solvent stripping operation. Bottoms product
from the topping column can be fed to a postfractionator where residual olefins
(cis-2/trans-2 butene) and remaining trace heavy ends (vinyl, ethyl and heavier
acetylenes, 1,2-butadiene, dimer, C5s and heavier) are rejected to the bottoms.
45

The overhead butadiene product is chilled and passed through a coalescer
to remove entrainedwater before being sent to the rundown tanks in the tank farm.
Tertiary butyl catechol (TBC) is added to the butadiene to inhibit the formation of
peroxides. It is also common to use an in process inhibitor that is removed prior to
the addition of TBC.
Hydrocarbon streams exiting the process can be washed with water for the
removal of ACN.The recovered solvent can be concentrated and returned to the
extraction section.[ Anonymous, (November 2006),Production of Butadiene]


Figure 1.18: Process D - Aqueous Separation and ACN Extraction
Process



46

1.7) JUSTIFICATION OF PROCESS CHOSEN


PRODUCTION OF CRUDE BUTADIENE
1

2 3
Temperature 1450-1525 F
(790-830 C)
1100-1260 F
(600-680 C)
930-1110 F
(500-600 C).
Pressure 98-118 kPa 15-20 kPa
Reaction
(exo/endo)
endothermic endothermic exothermic
% of butadiene 2-16% 30% - 50% 70-90%
Side products hydrogen,
ethylene,
propylene, fuel
gas, fuel oil
_

Raw material Ethane, propane,
butane, naphtha,
gas oil
n-butane/n-Butenes n-Butenes
catalysts chromium/alumina bismuth
molybdate

Table 1.1.5: Properties of Crude Butadiene


Among the choices for implementing the production of butadiene
(polymer grade) from C4 fractions, we have chosen to do a coupling of catalytic
dehydrogenation of n-butane and n-butene (the Houdry process) and oxidative
dehydrogenation of n-butene (the Oxo-D or O-X-D process).


We have chosen this route because the coupling of the non oxidative
catalytic dehydrogenation with the oxidative dehydrogenation of the n-butenes
47

formed provides a very much higher yield of butadiene based on n-butane used.
The non oxidative dehydrogenation can also be operated in a gentler manner. This
coupling process features particularly effective utilization of the raw materials.
Thus, losses of the n-butane raw material are minimized by recycling unconverted
n-butane into the dehydrogenation. The isomerization of 2-butene to 1-butene also
yield 1-butene as the product of value. So because of the coupling process
method, we get 1-butene as our byproduct after butadiene as a major production.


For our by product, 1-butene is a linear alpha olefin (alkene), produced
either by separation from crude C4 refinery streams or from the reaction of
ethylene. It is distilled to give a very high purity product.[ Anonymous,
(2007),Butadiene Market Demand]


Butene-1 can be produced directly from C4 cracking and also by
extraction from C4's mixtures out of ethylene crackers. It is used as a copolymer
in polyethylene alkylates gasoline, polybutenes, butadiene; as intermediates for
C4 and C5 aldehydes, alcohols and other derivatives; and in the production of
maleic unhydride by catalytic oxidation.


Demand for 1-butene also has a big contribution in chemical area, like
Japans chemical markets for 1-butenes will grow strongly and for isobutylene
very slowly during 20072012. Since August 2004, 1-butene demand for
propylene production via butylene metathesis quadrupled to 2007, but will slow
over the forecast period.[ Anonymous, (2007),Butadiene Market Demand]


While for application for 1-butene is used in the manufacture of a variety
of other chemical products. It fills an important role in the production of materials
such as linear low density polyethylene (LLDPE). The co-polymerisation of
ethylene and 1-butene produces a form of polyethylene that is more flexible and
more resilient. 1-butene can also help to create a more versatile range of
48

polypropylene resins. It is also used in the production of polybutene, butylene
oxide and in the C4 solvents secondary butyl alcohol (SBA) and methyl ethyl
ketone (MEK).




1.8) SEPARATION OF BUTADIENE BY EXTRACTIVE
DISTILLATION


The C
4
product gas stream is separated by means of extractive distillation
into a stream that consisting substantially of n-butane and 2-butene and a product
stream which is butadiene. To this end, C
4
product gas stream is contacted in an
extraction zone with an extractant, preferably an N-methyl-2pyrrolidone
(NMP)/water mixture. Suitable extractants are butyrolactone, nitriles such as
acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfural,
N-alkyl-substituted cyclic amides (lactams) such as N-alkylpyrrolidones,
especially NMP. In general, alkyl-substituted lower aliphatic amides or N-alkyl-
substituted cyclic arnides are used.[ Anonymous, (1996),Process of Butadiene
production]


The effects of the solvents used will be taken into consideration in the
comparison for the separation of C
4
product to butadiene.









49

Solvent Hazard
Identification
Effect
methoxy-proprio-nitrile
(MOPN)
- Toxic fumes of acrylonitrile and
methanol may be released.
- Uncontrolled burning may also result in
the release of highly toxic hydrogen
cyanide (HCN) vapours.

n-methyl-2pyrrolidone (NMP)

- Stable, but decomposes upon exposure to
light.
- Combustible

Dimethylformamide (DMF)

- Hazardous
- DMF has been linked to cancer in
humans, and it is thought to cause birth
defects

Acetonitrile (ACN)

- Toxic and flammable.
- It is metabolized into hydrogen cyanide
and thiocyanate


Table 1.1.6: Effects of the each solvents


It is noticed that all types of solvents used are hazardous and toxic. MOPN
and ACN are unfavourable in terms of environmental friendly as both of these
solvents will metabolize into hydrogen cyanide (HCN), which causes threat not
only to human health, but also environment. Thus, NMP is the most acceptable
solvent to be used in the process as it causes least harm to the environment.


Therefore Extractive distillation process by using aqueous n-methyl-2-
pyrrolidone (NMP) is the most environmental friendly method to be used as the
solvent (NMP) causes less harm to the environment and provides the process with
a safer mode due to the high autoignitable temperature.



50

1.9) SITE SELECTION & PLAN LAYOUT


There are some factors that should be considered in selecting the suitable
site. This is very important because the characteristics of a site location will have
a market effect on the success or otherwise of a commercial venture. The choice
of the final site should be based on a complete survey of the advantages of various
geographical areas, in addition to the advantages and disadvantages of available
industrial estates.


There are locations designated which have potential to fulfill all the criterion
shows above. The locations is Kerteh Industrial Estate, Terengganu




1.9.1) Plant Location


The basic site selection process takes account the criteria of the economic
geography of the area in which the plant site is placed. Several important criteria
or factors should be considered, such as:











51














Figure 1.19: Map of Plant Location


1.9.1.1) Land price


The first factor to consider is the land price. The cost of a land depends on
the location of the property and may vary between rural district and a highly
industrialized area. [49]


1.9.1.2) Raw Materials


This is particularly important if large volumes of raw materials are
required by plant. The availability of raw material is important due to its location
from plant, transportation and its purity to ensure the least cost is needed.




52

1.9.1.3) Transportation


Water, railroads and highways are the common means of transportation
used by major industrial concerns. These types of connection needed to ensure the
distribution of the product is optimize.


1.9.1.4) Water Supply


The plant should be located where water supply is available for the
purposes of cooling, washing, steam generation and as a raw material.
Temperature, mineral content, purification (treatment) and cost of water ought to
be considered.


1.9.1.5) Energy supply


The location of a plant site should be near to hydroelectric installations if
the plant is using electrolytic process. The local cost of power can help to
determine whether power should be purchased of self-generated.


1.9.1.6) Labors

Type and supply of labors available in the vicinity of a proposed plant site
must be examined. Consideration should be given to prevailing pay scales and
restrictions on number of working hours per week





53

1.9.1.7) Waste management


The site selected for a plant should have adequate capacity and facilities
for correct waste disposal. In choosing a plant site, the permissible tolerance
levels for various methods of waste disposal should be considered carefully, and
attention should be given to potential requirements for additional waste treatment
facilities.[ Anonymous, (November 1996),Produce of Butadiene, Website]


1.9.1.8.1 Availability of raw materials

Location/
Characteristics
Kerteh Industrial Estate, Terengganu

Land Price RM 0.18 -RM5.60 per ft 2

Sources of Raw
Material
(Natural gas
-Petronas LNG Sdn Bhd at Kerteh
- Reserved natural gas until 2007
(53 trillion cubic feet)
Transportation East Coast highway Kemaman
Port
Water Supply Terengganu Water Company (SATU
Electricity Supply Paka power plant

Labor - UMP, UMT, UTM, UiTM, TATIUC<
POLISAS
Area Available 1184.2 hectares
Preferred Industry Type Chemical
Nearest town -15 km from Kemaman
-160 km from Kuantan
-220 km from Kuala Lumpur
Waste management Monthly charges vary for disposal of
toxic waste carried out by Kualiti Alam
according to the type and quantity of
waste.

Table 1.1.7: Characteristics of location
54

1.9.1.8.2 Selected Site


Industrial land is available in all districts in the form of developed, semi
developed as well as raw land. Terengganus industrial land is among the
cheapest in Malaysia, at RM0.18 - RM5.60 or (US$0.06 - $1.75 per square
foot) compared to other states, where land sells from lows of RM2.00 -
RM4.50 psf to highs of RM18.00 - RM22.00 psf.

The location very near with Kemaman and Kuantan town provided local
community factors such as banking, medical, security, housing and
entertainment

Our plant needs the supplier to supply major raw material that is C4

For delivering process of ammonia, Kerteh can be link to Kuala Lumpur
by East Coast highway which can reduce traveling time from four hours to
only two hours by truck also can be export by ships through Kemaman
Port

For the manpower or labor, UMP,TATIUC and POLISAS with quality
educational level and other technical schools can provide skilled and semi
skilled workers to operate and handle our plant

Others universities such as UM, UTM, UTP, UPM, UKM and UiTM also
can provide many graduate students to work in our plant
55

Terengganu employs an integrated environmentally friendly waste
management system for industrial wastes that meets international best
practices.[ Anonymous, (November 1996),Produce of Butadiene, Website]


55

Admininstration Building
Butadiene Plant
N-Butane
Butadiene
N-Butane
Butadiene
Cooling Tower
Utilities Area
Waste
treatment
Mosque
Master Evacuation Area
Control Room
Loading / Unloading Area
Fire Station
Fire
Water
Tank
Laboratory
Fire
Water
Tank
Workshop
Cafeteria
Mosque
Cafeteria
Post Guard
Figure 1.20: Plant Layout
56



CHAPTER 2




PROCESS SYNTHESIS AND FLOWSHEETING




2.1 SYNTHESIS OF PROCESS FLOW DIAGRAM


2.1.1 Introduction


Process synthesis and flow sheeting is the most important in plant design.
In this chapter, it will cover material and energy balance and simulation by using
ASPEN. Generally, the processes that choose in producing butadiene from butane
is catalytic dehydrogenation and oxidative dehydrogenation. This route absolutely
gives an optimum purity of butadiene. Here, 50 000 MT/yr butadiene from butane
will produced.




2.1.2 Process Flow Diagram (PFD)


Process flow diagram in figure 2.1 below described details flow of
butadiene process. Basically for the PFD diagram, the major and minor include
together except the controller system that explained details in process safety
studies. Catalytic dehydrogenation process used 1 basic chemical which is butane
and water and air used as a combustion process to remove hydrogen. Then
produce 1-butene and 2-butene. For second reaction, used Oxidative
57

dehydrogenation process to produce 1-butane, 2-butene to butadiene from
hydrogen removed. To produce butadiene, there are 6 equipments involved. The
equipments are:


a. The Fixed Bed Reactor Reaction occurs here

b. The NMP solvent recovery system that function to recover the
NMP solvent.

c. The distillation for separate light and heavy end which is 1-butane
and butane

d. Heat transfer for maintain the temperature in the process

e. Absorption for separate inert gas and C4 hydrocarbon

f. Extractive distillation for separate butadiene and C4 hydrocarbon







58

P-102A/B C-107A/B
P-104A/B
P-103A/B
P-106A/B
P-105A/B
P-107A/B
C-101A/B
Butane Feed
Compressor
R-101
Fixed Bed Ractor
(BDH)
C-107A/B
Compressor
Stream 9
3
4 1
2
15
12a
13
12
9a 7
6
5
1
4
1
1
C-102A/B
Air Pump
Compressor
C-103A/B
Steam Compressor
R-102
Fixed Bed Reactor
(Oxo-D)
E-101
Heat Exchanger
T-101
Absorption
Tower
Steam
Air
n-Butane
C-104A/B
Compressor
Stream 5
C-105A/B
Compressor
Stream 6
C-106A/B
Compressor
Stream 7
P-101A/B
Pump
Stream 8
P-102A/B
Pump
Stream 11
P-103A/B
Pump
Stream 12
D-101
Extractive Distillation
Column
E-102
Condenser
(Air Cooled)
P-104A/B
Pump
Stream 12b
E-103
D1
Heat Exchanger
P-107A/B
Pump
Stream 14
TK-1
Storage
Tank
(Butadiene)
R-103
Fixed Bed
Reactor
(Isomerization)
P-105A/B
Pump
D-102
Solvent
Recovery
Column
E-106
D2
Heat Exchanger
P-106A/B
Pump
E-105
D2
Reboiler
TK-2
Storage Tank
(1-Butene)
TK-2
1-Butene
12b
Air
7a 9
W
a
te
r
1
2
a
D-103
D-102
E-107
D3
Heat
Exchanger
E-104
D1
Reboiler
NMP
2,000 kg/h
1
6
b
16
NMP Recovery
E-101
3b
8
a
8
1
0
E-108
D3
Reboiler
16a
8
b
E-102
C-101A/B
C-102A/B C-104A/B
C-103A/B
C-105A/B
C-106A/B
P
-
1
0
1
A
/B
TK-1
Butadiene
Reflux Drum
Reflux Drum
Reflux Drum
D-101
E-104
Steam
E-103
E-106
E-107
T-101
Calcium
Oxide
R-101 R-102
R-103
CW
CW
CW
E-105
Steam
Steam
E-108

Figure 2.1.: Process Flow Diagram
95

2.2 Manual Calculation of Materials and Energy Balances


2.2.1 Mass Balance


Plant complete if the amount that targeted is achieved. Here, in order to
achieve the target, the amount needed for each hour need to be known operation
day are assumed 333 days with 32 days shutdown and the plant operation 24
hours per day.


Butadiene will produce 50,000 MT/ year:


50,000 MT 1000 kg 1 year 1 day = 6256.2563 kg/hr

year 1 MT 333 days 24 hours


Therefore, to make sure we could achieve the amount production, the mass flow
rate production must be 6256.2563kg/hr. So below is the assumption that our
group have been made.


Assumptions:
- The processes follow the law of conservation of mass where:
- Material out = Material in + Generation Consumption Accumulation
- Steady-state condition in all equipment
- Pure reactants are used
- No leakage in pipes and vessel in the system.
- All stream flow rate is in unit kg/h.
- Catalyst used in reactor does not contribute in mass.
- The entire components in the system behave as ideal condition.
- The total input of any substance to a pump, valve or mixer is assumed
equal to the total output of the substance where no reaction occurs in that
device.
60



Components involve:

Components Formula Molecular Weight
Butane C
4
H
10
58.12
1-Butene C
4
H
8
56.10
2-butene C
4
H
8
56.10
1,3-Butadiene C
4
H
6
54.09
Water H
2
O 18.016
Carbon dioxide CO
2
44.01
Hydrogen H
2
2.016
Oxygen O
2
32.00
Nitrogen N
2
28.02

Table 2.1.0: Components formulas and Molecular Weight




2.2.2 Energy Balance


2.2.2.1 Enthalpies for Vapor Mixtures


Methods suggested by Biegler et al. in calculating enthalpies for vapor
mixtures are as below:


dT T C y T H y H H y T H
T
T
o
k p
k
k
o
k f k k T f v
) ( ) ( ) , (
2
1
. 1 .
}

+ E = A + A = A


where; H
f.k
(T
1
) is the heat of formation for component k at
T
1

C
p
is heat capacities for component k.






61

2.2.2.2 Enthalpies for Liquid Mixtures


Enthalpies for liquid mixtures are evaluated from the ideal vapor enthalpy
and subtracting the heat of vaporization at the saturated condition.


) ( ) ( ) ( ) , (
2
1
. 1 .
T H dT T C x T H x H H x T H
k
vap
T
T
o
k p
k
k
o
k f k k T f L
EA + E = A + A = A
}

where, H
f.k
(T
1
) is the heat of formation for component k at T
1

C
p
is heat capacities for component k.
AH
vap
is heat of vaporization


For a mixed stream, both equations are applied based on the vapor/liquid
fraction involved. If there is no reaction occur in a unit (i.e. initial component =
final component), enthalpy change for the unit is express as below:


] ) ( [
, .
2
1
k f
T
T
o
k p
k
k v
H dT T C y n Q A + =
}

(vapor)


)] ( ) ( ) ( [
1 2 , .
2
1
T H T H dT T C x n Q
k
vap k f
T
T
o
k p
k
k L
A A + =
}

(liquid)




2.2.2.3 Heat of Vaporization


AH
vap
is heat of vaporization of specific component at specific
temperature. It could be found through the Watson Method:

38 . 0
] )[ ( ) (
b
k
c
k
c
T T
T T
b
k
vap
k
vap
T H T H

A = A


where, T
c
k
is critical temperature for component k.
62

T
b
is the boiling temperature for component k


Component Heat Of Vaporization
(kJ/mole)
Butane 22.305
1-Butene 21.916
2-butene 21.916
1,3-Butadiene -
Water 40.706
Carbon dioxide 15.326
Hydrogen 0.964
Oxygen 6.82
Nitrogen 5.577
(Source: Chemical Engineering, Volume 6)
Table 2.1.1: The Heat Of Vaporization for Each Component at boiling point




2.2.2.4 Heat of Formation


Component Heat Of Formation (kJ/mole)
Butane
-126.9
1-Butene
-0.12558
2-butene
-11.17662
1,3-Butadiene
110,21738
Water
-241.9508
Carbon dioxide
-393.60958
Hydrogen 0
Oxygen 0
Nitrogen 0
(Source: Chemical Engineering, Volume 6)

Table 2.1.2: The Heat of Formation for Each Component








63

2.2.2.5 Heat Capacity


C
P
= A + BT + CT
2
+ DT
3


Components A B C D
Butane 92.30x10
-3
27.88x10
-5
-15.47x10
-8
34.98x10
-12

1-Butene
2-butene
1,3-Butadiene
Water 33.46x10
-3
0.6880x10
-5
0.7604x10
-8
-3.593x10
-12

Carbon dioxide 36.11 x10
-3
4.233 x10
-5
-2.887 x10
-8
7.464 x10
-12

Hydrogen
28.84 x10
-3
0.00765 x10
-5
0.3288 x10
-8

-0.8698 x10
-
12

Oxygen
29.10 x10
-3
1.158 x10
-5

-0.6076 x10
-
8
1.311 x10
-12

Nitrogen
29.00 x10
-3
0.2199 x10
-5
0.5723 x10
-8

-2.871 x10
-
12

(Source: Perry Handbook)
Table2.1.3: The Parameters of Heat Capacity, C
p
(J/mole K) or (J/moleC)





2.3 Mass and Energy Balance


2.3.1. Mass Balance in Fix Bed Reactor (FBR)-BDH reaction

R-101


Stream Description Temperature(
0
C) Pressure(atm)
3b Inlet 200 1.0
2 Inlet 300 2.0
4 Inlet 30 4.5
5 Outlet 550 1.0

Table2.1.4: The Operation Condition of Reactor 1

64

Stream 1
Stream 2
Stream 3b
Stream 5


Function


To be a reaction place among butane, air and steam and create combustion,
then remove hydrogen in dehydrogenation process.


Condition


Phase : Gases phase
Operating Temperature : 550
o
C
Operating Pressure : 1.0 atm
Catalyst : Chromium alumina
Promoter : 1-butene and 2-butene
Conversion : 80 %









65


Table 2.1.5: Input stream of FBR (1
st
reactor)


Input Stream (kg/kg) Output
Component S4 S2 S3b S5
Butane 1.0 0 0 0.1860
1-Butene 0 0 0 0.0614
2-butene 0 0 0 0.1316
1,3-Butadiene 0 0 0 0.0127
Water 0 0 1.0 0.1443
Carbon dioxide 0 0 0 0.0065
Hydrogen 0 0.1429 0 0.2245
Oxygen 0 0.2853 0 0
Nitrogen 0 0.5718 0 0.2330

Table 2.1.6: Composition in FBR




Stream Name
S4 S2 S3b S5
Stream Phase Gas Gas Gas Gas
Pressure 1.0 atm 2.0 atm 1.0 atm 1.0 atm
Temperature
o
C
30
o
C 300
o
C 200
o
C 550
o
C
Total Flow
rate(Kg/hr)
For Initial Feed

6885.37

15084.34 5341.72 -
Total Flow rate
(Kg/hr)
Outlet or
recycle back
- - 37018.14
66


Table 2.1.7: Mass Balance in FBR (1
st
reactor)




2.3.2 Energy Balance in FBR (1
st
reactor)


Catalytic Dehydrogenation of n-butane & n-butene reaction (the Houdry
process)
Butane 1-butene + Hydrogen
Butane 2-butene + Hydrogen
C
4
H
10
C
4
H
8
-1 + H
2

C
4
H
10
C
4
H
8
-2 + H
2






Input Stream (kg/hr) Output
Component S1 S2 S3b S5
Butane 6885.373 0 0 6885.37
1-Butene 0 0 0 2269.21
2-butene 0 0 0 4871.58
1,3-Butadiene 0 0 0 470.13
Water 0 0 5341.72 5341.72
Carbon dioxide 0 0 0 240.62
Hydrogen 0 0 8310.57
Oxygen 0 0 0
Nitrogen 0 15084.34 0 8625.23
TOTAL

6885.37

15084.11

5341.72
37018.14
67

Input Stream
H
1
(25
o
C)
COMPONENT
Inlet FBR
Stream 2
Mole flow rate
H, Enthalpy
(kj/mol) Q= nH (J)
C
4
H
10
0 0 0
C
4
H
8
-1 0 0 0
C
4
H
8
-2 0 0 0
C
4
H
6
0 0 0
H
2
O 0 0 0
CO
2
0 0 0
H
2
1077.78 7894.647 8508693
O
2
134.49 8459.949 1137779
N
2
308.04 8206.952 2528069
TOTAL 12174541
Table 2.1.8: Heat of FBR input


COMPONENT
Inlet FBR
Stream 3b
Mole Rate
H, Enthalpy
(kj/mol) Q= nH (J)
C
4
H
10
0 0 0
C
4
H
8
-1 0 0 0
C
4
H
8
-2 0 0 0
C
4
H
6
0 0 0
H
2
O 296.76 6009.047 1783258
CO
2
0 0 0
H
2
0 0 0
O
2
0 0 0
N
2
0 0 0
TOTAL 1783258
Table 2.1.9: Heat of FBR input







68

COMPONENT
Inlet FBR
Stream 1
Mole Rate
H, Enthalpy
(kj/mol) Q= nH (J)
C
4
H
10
118.71 490.207 58194.08
C
4
H
8
-1 0 0 0
C
4
H
8
-2 0 0 0
C
4
H
6
0 0 0
H
2
O 0 0 0
CO
2
0 0 0
H
2
0 0 0
O
2
0 0 0
N
2
0 0 0
TOTAL 58194.08
Table 2.1.10: Heat of FBR input


Output Stream

H
2
(25
o
C 550
o
C)
Component
Outlet FBR
S5
n, Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
118.7133 62884.548 7465230.69
C
4
H
8
-1 40.52161 54976.598 2227740.11
C
4
H
8
-2 86.9925 54709.397 4759307.22
C
4
H
6
8.706111 50283.658 437775.114
H
2
O 296.7622 15107.457 4483322.51
CO
2
5.468636 18599.423 101713.481
H
2
259.7053 12328.319 3201729.94
O
2
0 0 0
N
2
4312.615 12849.743 55415994.4
TOTAL



78092813.5
Table 2.1.11: Heat of FBR output






69

H
f
((25
o
C 550
o
C)
Component
Heat formation (endothermic reaction)
n, Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
118.7133 -1.2579E+05 -1.49E+07
C
4
H
8
-1 40.52161 -5.4E+02 -2.19E+04
C
4
H
8
-2 86.9925 -5.4E+02 -4.70E+04
C
4
H
6
8.706111 1.0924E+05 9.51E+05
H
2
O 296.7622 -2.42E+04 -7.18E+06
CO
2
5.468636 -3.93509E+05 -2.15E+06
H
2
259.7053 0 0
O
2
0 0 0
N
2
4312.615 0 0
TOTAL -2.34E+07
Table 2.1.12: Heat formation of process


Q For FBR (1
st
reactor) = nH2

+ nHf

- nH
1

= [(H
5
+H
f
)-(H
2
+H
3b
+H
1
]

= [(78092813.5+ -2.34E+07)-(12174541+1783258+58194.08)]

= 6.4E+7 kJ/hr




2.3.3 Mass Balance in Fixed Bed Reactor (2
nd
reactor) - Oxo-D reaction


R-102


Table2.1.13: The Operation Condition of Reactor 2


Stream Description Temperature(
0
C) Pressure(atm)
5 Inlet 550 1.0
6 Inlet 34 1.0
7 Outlet 450 2.0
70


Stream 6
Stream 5 Stream 7





Function


To be a reaction place among 1-butene,2-butene and Oxygen to crack or
remove the hydrogen in oxidative dehydrogenation process


Condition


Phase : Gases phase
Operating Temperature : 450
o
C
Operating Pressure : 1 atm
Catalyst : Bismotmolybidat
Promoter : Butadiene





71


Table 2.1.14: Inlet and Outlet Stream of FBR (2
nd
reactor)






2.3.4 Energy Balance in FBR


COMPONENT
Inlet
S5
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
118.7133 62884.548 7465235.03
C
4
H
8
-1 40.58775 54976.598 2231376.42
C
4
H
8
-2 86.99263 54709.397 4759314.06
C
4
H
6
8.706119 50283.658 437775.486
H
2
O 296.7621 15107.457 4483320.83
CO
2
5.468589 18599.423 101712.593
H
2
259.7054 12328.319 3201730.71
O
2
0 0 0
N
2
4312.614 12849.743 55415975.1
TOTAL 78096440.3

Table 2.1.15: Inlet Stream of FBR (2
nd
reactor)
Component Mass Flow rate (kg/hr)
Inlet Stream Outlet Stream
S5 S6 S7
C
4
H
10
6885.374
0
6885.373
C
4
H
8
-1 2272.914
0
0
C
4
H
8
-2 4871.587
0
3133.268
C
4
H
6
470.1304
0
4292.773
H
2
O 5341.718
0
9797.163
CO
2
240.6179
0
885.9137
H
2
8310.572
0
2605.628
O
2
0
2605.63
29248.18
N
2
8625.227
9802.12
8292.412
TOTAL
37018.14 12407.75 65140.71
72

COMPONENT
Inlet
S6
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
0 0 0
C
4
H
8
-1 0 0 0
C
4
H
8
-2 0 0 0
C
4
H
6
0 0 0
H
2
O 0 0 0
CO
2
0 0 0
H
2
0 0 0
O
2
93.05821 270.038 25129.2541
N
2
4901.06 262.032 1284234.55
TOTAL 165968.1956

Table 2.1.16: Inlet Stream of FBR (2
nd
reactor)


COMPONENT
Outlet
S7
Mole Rate H, Enthalpy (kJ/mol) Q= nH
C
4
H
10
118.7133 62884.548 7465233.947
C
4
H
8
-1 0 0 0
C
4
H
8
-2 55.95121 54709.397 3061057.195
C
4
H
6
79.4958 50283.658 3997339.433
H
2
O 544.2868 15107.457 8222789.93
CO
2
20.1344 18599.423 374488.2647
H
2
81.42588 12328.319 1003844.162
O
2
1044.578 13249.802 13840449.78
N
2
4146.206 12849.743 53277681.53
TOTAL 91242884.24

Table 2.1.17: Outlet Stream of FBR (2
nd
reactor)



Table 2.18: Heat of Formation for the process
COMPONENT n,Mole Rate H
f
Q=nH
C
4
H
10
118.7133 -1.2579E+05 -1.49E+07
C
4
H
8
-1 0 -5.4E+02 0
C
4
H
8
-2 55.95121 -5.4E+02 -3.02E+04
C
4
H
6
79.4958 1.0924E+05 8.68E+06
H
2
O 544.2868 -2.42E+04 -1.32E+07
CO
2
20.1344 -3.93509E+05 -7.92E+06
H
2
81.42588 0 0
O
2
1044.578 0 0
N
2
4146.206 0 0
TOTAL -2.7E+07
73



Q For Condenser (air cooled) = nH
2
+ nH
f
- nH
1

= [(H
7
+H
f
)-(H
5
+H
6
)]

= [(91242884.24-27000) (78096440.3+165968.1956)]

= 1.3E+7 kJ/hr




2.3.5 Mass Balance in Heat Exchanger


E-101

Stream Description Temperature(
0
C) Pressure(atm)
7a Inlet 200 2.0
8 Outlet 40 1.0
9a Outlet 40 0.95

Table2.1.19: The Operation Condition of Heat Exchanger



E-101
Stream 7
Stream, 7a



Function


To remove the water, maintain the temperature and recycle the water into
condenser


Condition


Phase : Liquid phase
Operating Temperature : 160
o
C
Operating Pressure : 1 atm

74

Component


Mass Flow rate(kg/hr)
Inlet Outlet
S7a S8 S9a
C
4
H
10
10052.60487 1.45536686 10052.81368
C
4
H
8
-1 0 0 0
C
4
H
8
-2 4574.5534 994.0155654 3576.481791
C
4
H
6
6267.423474 2.91073372 6274.953413
H
2
O 1430.380107 13534.9118 733.0176645
CO
2
1293.42882 16.00903546 1272.711989
H
2
12106.87418 0 12106.87417
O
2
3804.202412 1.45536686 3818.135967
N
2
42702.17207 2.91073372 42716.40302
TOTAL

Table 2.1.20: Inlet and Outlet Streams




2.3.6 Energy balance for Heat Exchanger


COMPONENT
Inlet
Stream 7
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
172.9539919 21056.087 3641734.301
C
4
H
8
-1 0 0 0
C
4
H
8
-2 81.53266795 18566.496 1513775.953
C
4
H
6
115.8681384 16781.533 1944444.988
H
2
O 79.39939533 6009.047 477114.6983
CO
2
29.38943013 7258.533 213324.1485
H
2
6005.393937 4988.39 29957247.06
O
2
118.8850405 5334.38 634177.9825
N
2
1524.369831 5175.577 7889493.437
TOTAL 46271312.57

Table 2.1.21: Energy balance at inlet stream for Heat Exchanger









75

COMPONENT
Outlet
Stream 7a
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
0.025039431 1491.535 37.34718802
C
4
H
8
-1 0 0 0
C
4
H
8
-2 17.71642692 1340.899 23755.93914
C
4
H
6
0.053811793 1220.147 65.65829835
H
2
O 751.3134498 1125.511 845611.5522
CO
2
0.363759042 598.945 217.8716597
H
2
0 0 0
O
2
0.045481636 450.326 20.48156307
N
2
0.103906533 436.974 45.40445352
TOTAL 869754.2545

Table 2.1.22: Energy balance at Outlet stream for Heat Exchanger


COMPONENT
Outlet
S9a
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
172.9575845 1491.535 257972.2908
C
4
H
8
-1 0 0 0
C
4
H
8
-2 63.7439498 1340.899 85474.19854
C
4
H
6
116.0073471 1220.147 141546.0166
H
2
O 40.68929584 1125.511 45796.25004
CO
2
28.91870004 598.945 17320.7108
H
2
6005.393935 422.643 2538137.709
O
2
119.3204777 450.326 53733.11345
N
2
1524.877843 436.974 666331.9706
TOTAL 3806312.26

Table 2.1.23: Energy Balance at Outlet stream for Heat Exchanger
















76

COMPONENT
Outlet
Heat Vaporization
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
172.9575845 22.305 3857.8189
C
4
H
8
-1 0 21.916 0
C
4
H
8
-2 63.7439498 21.916 1397.012404
C
4
H
6
116.0073471 0 0
H
2
O 40.68929584 40.706 1656.2985
CO
2
28.91870004 15.326 443.2079968
H
2
6005.393935 0.964 5789.199753
O
2
119.3204777 6.82 813.7656579
N
2
1524.877843 5.577 8504.24373
TOTAL 22461.54694

Table 2.1.24: Heat Vaporization at Heat Exchanger


Q For Heat Exchanger = nH
2
+ nH
v
- nH
1

= [(H
8
+H
9a
+H
v
)-(H
7a
)]

=[ (869754.2545+ 3806312.26+ 22461.54694)-
46271312.57]

= -41572784.51 kJ/hr




2.3.7 Mass Balance in Condenser (Air cooled)


E-102


Table2.1.25: The Operation Condition of Condenser (air cooled)


Stream Description Temperature(
0
C) Pressure(atm)
7a Inlet 200 1.0
8 Outlet 30 1.0
9 Outlet 40 1.0
77


E-102
Stream 9 Stream 7a
Stream 8

Function


To recycle back the water to cover another process


Condition


Phase : Liquid phase
Operating Temperature : 100
o
C
Operating Pressure : 1 atm

Table 2.1.26: Inlet and Outlet Stream of Condenser (air cooled)
Component Mass Flow rate (kg/hr)
Inlet Stream Outlet Stream
S7a S8 S9
C
4
H
10
8827.6175
1.2811
8823.9913
C
4
H
8
-1 0
0
0
C
4
H
8
-2 4017.1089
874.9719
3139.3046
C
4
H
6
5503.6896
2.5621
5507.9241
H
2
O 12560.7726
11913.9664
643.4160
CO
2
1135.8145
14.0918
1117.1399
H
2
10631.5582
1.2811
3351.4198
O
2
3340.6310
1.2811
37494.8927
N
2
37498.5832
1.2811
10626.9703
TOTAL
83515.7755 83515.7755
78

2.3.8 Energy Balance in Condenser (air cooled)


COMPONENT
Inlet
S7a
Mole Rate H, Enthalpy (kJ/mol) Q= nH
C
4
H
10
152.2003 497798.8 75765126.7
C
4
H
8
-1 0 0 0
C
4
H
8
-2 71.7341 48081.6 3449090.303
C
4
H
6
101.9202 46364.4 4725468.921
H
2
O 697.8207 15454.8 10784679.35
CO
2
25.8140 37778.4 975211.6176
H
2
5315.7791 1717.2 9128255.871
O
2
106900.192 27475.2 2937104155
N
2
1339.2351 24040.8 32196283.19
TOTAL 137024116

Table 2.1.27: Inlet Stream of condenser (air cooled)


COMPONENT
Outlet
S8
Mole Rate H, Enthalpy (kJ/mol) Q= nH
C
4
H
10
0.0221 7540 166.634
C
4
H
8
-1 0 0 0
C
4
H
8
-2 15.6245 874.972 13671
C
4
H
6
0.04745 7020 333.099
H
2
O 661.887 11913.966 7885699.214
CO
2
0.3203 5720 1832.116
H
2
5315.7791 260 1382102.566
O
2
104.3947 4160 1806612920
N
2
1339.2351 3640 4874815.764
TOTAL 1820771540

Table 2.1.28: Inlet Stream of Condenser













79

COMPONENT
Outlet
S9
Mole Rate H, Enthalpy (kj/mol) Q= nH
C
4
H
10
152.1378 10086.2 1534492.278
C
4
H
8
-1 0 0 0
C
4
H
8
-2 56.0590 9738.4 545924.9656
C
4
H
6
101.9986 9390.6 957828.0532
H
2
O 35.7453 3130.2 111889.9381
CO
2
25.3895 7651.6 194270.2982
H
2
1675.7099 347.8 582811.9032
O
2
1171.7154 5564.8 6520361.858
N
2
379.5347 4869.2 1848030.361
TOTAL 12295609.66

Table 2.1.29: Outlet Stream Condenser (air cooled)



Table 2.1.30: Heat of Formation for the process



Q For Condenser(cooled) = nH
2
+ nH
v
- nH
1

= [(H
9
+H
8
+H
v
)-(H
7a
)]

= [(12295609.66+1820771540+58257.81)(137024116)]

= 1696101291 kJ/h








COMPONENT n,Mole Rate H
v
Q=nH
C
4
H
10
152.1599 22.305 3393.9266
C
4
H
8
-1 0 0 0
C
4
H
8
-2 56.1065 21.916 1229.6301
C
4
H
6
102.0461 171.005 17450.3933
H
2
O 697.6323 40.656 28362.9388
CO
2
25.7098 304.2 7820.9212
H
2
6991.489 0 0
O
2
1276.1101 0 0
N
2
1718.7698 0 0
TOTAL 58257.81
80

2.3.9 Mass Balance in Compressor


C-107A/B

Stream Description Temperature(
0
C) Pressure(atm)
9 Outlet 100 1.50
9a Inlet 40 0.95

Table2.1.31: The Operation Condition of Compressor


E-107
Stream 9
Stream 9a



Component


Mass Flow rate(kg/hr)

Inlet Outlet
S9 S9a
C
4
H
10
8823.9913 8823.9913
C
4
H
8
-1 0 0
C
4
H
8
-2 3139.3046 3139.3046
C
4
H
6
5507.9241 5507.9241
H
2
O 643.4160 643.4160
CO
2
1117.1399 1117.1399
H
2
3351.4198 3351.4198
O
2
37494.8927 37494.8927
N
2
10626.97 10626.97
TOTAL 70705.0584 70705.0584

Table 2.1.32: Mass Balance Inlet and Outlet Stream at Compressor










81

2.4.0 Energy balance for Compressor


COMPONENT
Inlet
S9
Mole Rate H, Enthalpy (kJ/mol) Q= nH
C
4
H
10
172.9575845 1491.535 257972.2908
C
4
H
8
-1 0 0 0
C
4
H
8
-2 63.7439498 1340.899 85474.19854
C
4
H
6
116.0073471 1220.147 141546.0166
H
2
O 40.68929584 1125.511 45796.25004
CO
2
28.91870004 598.945 17320.7108
H
2
6005.393935 422.643 2538137.709
O
2
119.3204777 450.326 53733.11345
N
2
1524.877843 436.974 666331.9706
TOTAL 3806312.26

Table 2.1.33: Energy Balance at Compressor


COMPONENT
Outlet
S9a
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
172.9575845 2122.514 367104.8945
C
4
H
8
-1 0 0 0
C
4
H
8
-2 63.7439498 7189.784 458305.2304
C
4
H
6
116.0073471 6609.026 766695.5734
H
2
O 40.68929584 2543.847 103507.3431
CO
2
28.91870004 3038.834 87879.12892
H
2
6005.393935 2122.514 12746532.7
O
2
119.3204777 2264.693 270224.2507
N
2
1524.877843 2197.475 3350880.938
TOTAL 18151130.06

Table 2.1.34: Energy Balance at Compressor













82

COMPONENT n, MOLE RATE Heat Vaporization, H
v
Q= nH
C
4
H
10
172.9575845 22.305 3857.818922
C
4
H
8
-1 0 21.916 0
C
4
H
8
-2 63.7439498 21.916 1397.012404
C
4
H
6
116.0073471 0 0
H
2
O 40.68929584 40.706 1656.298476
CO
2
28.91870004 15.326 443.2079968
H
2
6005.393935 0.964 5789.199753
O
2
119.3204777 6.82 813.7656579
N
2
1524.877843 5.577 8504.24373
TOTAL


22461.54694


Table 2.1.35: Heat Vaporization at Compressor



Q For Compressor = nH
2
+ nH
v
- nH
1

=
H
9
+H
v
-H
9a

= [(18151130.06+ 22461.54694)-3806312.26]

= 14367279.35 kJ/hr


2.4.1 Mass Balance in Absorption Tower


T-101


Stream Description Temperature(
0
C) Pressure(atm)
9 Inlet 100 1.50
10 Outlet 40 0.95
11 Outlet 40 0.95

Table2.1.36: The Operation Condition of Absorption Tower


83


Stream 10
Stream 9 Stream 11

Function

To remove the water and inert gases

Condition

Phase : Gas phase
Operating Temperature : 60
o
C
Operating Pressure : 1 atm


Component


Mass Flow rate(kg/hr)

Inlet Outlet
S9 S10 S11
C
4
H
10
8823.9913 31.4889 8792.8990
C
4
H
8
-1 0 0 0
C
4
H
8
-2 3139.3046 41.9851 3099.8386
C
4
H
6
5507.9241 20.9926 5485.3111
H
2
O 643.4160 152.1962 493.8602
CO
2
1117.1399 787.2215 326.2029
H
2
10626.9703 10627.4904 0
O
2
3351.4198 3332.5711 16.4013
N
2
37494.8927 37487.4883 9.1118
TOTAL 70705.059 70705.059

Table 2.1.37: Inlet and Outlet Streams
84

2.4.2 Energy balance for Absorption Tower


COMPONENT
Input
Stream 9
Mole Rate H, Enthalpy (kJ/mol) Q= nH
C
4
H
10
172.9575845 2122.514 367104.8945
C
4
H
8
-1 0 0 0
C
4
H
8
-2 63.7439498 7189.784 458305.2304
C
4
H
6
116.0073471 6609.026 766695.5734
H
2
O 40.68929584 2543.847 103507.3431
CO
2
28.91870004 3038.834 87879.12892
H
2
6005.393935 2122.514 12746532.7
O
2
119.3204777 2264.693 270224.2507
N
2
1524.877843 2197.475 3350880.938
TOTAL 18151130.06

Table 2.1.38: Energy balance for Input Absorption Tower


COMPONENT
Output
Stream 10
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
0.617180174 1491.535 920.545831
C
4
H
8
-1 0 0 0
C
4
H
8
-2 0.852475051 1340.899 1143.082943
C
4
H
6
0.442123622 1220.147 539.4558111
H
2
O 9.624373527 1125.511 10832.33827
CO
2
20.37739335 598.945 12204.93786
H
2
6005.417956 422.643 2538147.861
O
2
118.6440757 450.326 53428.51203
N
2
1524.081355 436.974 665983.9262
TOTAL 3283200.66

Table 2.1.39: Energy Balance for Output Absorption Tower













85

COMPONENT
Output
Stream 11
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
172.3704507 1491.535 257096.5602
C
4
H
8
-1 0 0 0
C
4
H
8
-2 62.95073242 1340.899 84410.57415
C
4
H
6
115.5460243 1220.147 140983.1349
H
2
O 31.23550603 1125.511 35155.90563
CO
2
8.445301996 598.945 5058.271404
H
2
0 0 0
O
2
0.584009114 450.326 262.9944883
N
2
0.296492623 436.974 129.5595673
TOTAL 523097.0003

Table 2.1.40: Energy Balance for Output Absorption Tower


COMPONENT n, MOLE RATE Heat Vaporization, H
v
Q= nH
C
4
H
10
10018.68771 22.305 223466.8294
C
4
H
8
-1 0 21.916 0
C
4
H
8
-2 3531.976744 21.916 77406.80232
C
4
H
6
6250 0 0
H
2
O 562.7076412 40.706 22905.57724
CO
2
371.6777408 15.326 5696.333056
H
2
0 0.964 0
O
2
18.68770764 6.82 127.4501661
N
2
8.30564784 5.577 46.320598
TOTAL 329649.3128

Table 2.1.41: Heat Vaporization at Absorption Tower


Q For Absorption Tower = nH
2
+ nH
v
- nH
1

= (H
10
+H
11
+H
V
) -H
9


= (3283200.66+523097.0003+329649.3128)- 18151130.06

= -14015183.09 kJ/hr









86

2.4.3 Mass Balance in Extractive Distillation Column


D-101

Stream Description Temperature(
0
C) Pressure(atm)
11 Inlet 40 1.5
12 Outlet 70 1.0
13 Outlet 50 1.0

Table2.1.42: The Operation Condition of Extractive Distillation Column


D-101
Stream 13
Stream 11
Stream 12
Reflux ratio











87

Function

To remove the water, maintain the temperature and recycle the water into
waste boiler

Condition

Phase : Liquid phase
Operating Temperature : 30
o
C
Operating Pressure : 5 atm


Component


Mass Flow rate(kg/hr)

Inlet Outlet
S11 S12 S13
C
4
H
10
8792.8990 8035.3175 63.1945
C
4
H
8
-1 0 0 0
C
4
H
8
-2 3099.8386 3072.4673 0
C
4
H
6
5485.3111 23.8083 6256.2563
H
2
O 493.8602 452.3586 0
CO
2
326.2029 297.6044 0
H
2
0 0 0
O
2
16.4013 15.4754 0
N
2
9.1118 7.1425 0
TOTAL 18223.6249 18223.6249

Table 2.1.43: Inlet and Outlet Streams


















88

2.4.4 Energy balance for Extractive Distillation Column


COMPONENT
Input
Stream 11
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
172.3704507 1491.535 257096.5602
C
4
H
8
-1 0 0 0
C
4
H
8
-2 62.95073242 1340.899 84410.57415
C
4
H
6
115.5460243 1220.147 140983.1349
H
2
O 31.23550603 1125.511 35155.90563
CO
2
8.445301996 598.945 5058.271404
H
2
0 0 0
O
2
0.584009114 450.326 262.9944883
N
2
0.296492623 436.974 129.5595673
TOTAL 523097.0003

Table 2.1.44 Energy balance for Input Extractive Distillation Column


COMPONENT
Output
Stream 12
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
172.352517 4659.945 803153.25
C
4
H
8
-1 0 0 0
C
4
H
8
-2 62.99014602 4169.698 262649.8859
C
4
H
6
0 0 0
H
2
O 31.34050805 1521.028 47669.79027
CO
2
8.44265989 1810.12 15282.22752
H
2
0 0 0
O
2
0.589654535 1354.907 798.9270577
N
2
0.310872515 1314.716 408.7090693
TOTAL 1129962.79

Table 2.1.45: Energy Balance for Output Extractive Distillation Column













89

COMPONENT
Output
Stream 13
Mole Rate H, Enthalpy (kJ/mol) Q= nH
C
4
H
10
1.0896 209.3 228.0533
C
4
H
8
-1 0 0 0
C
4
H
8
-2 0 0 0
C
4
H
6
115.8566 7251.714 84078.7553
H
2
O 0 0 0
CO
2
0 0 0
H
2
0 0 0
O
2
0 0 0
N
2
0 0 0
TOTAL 84306.8086

Table 2.1.46: Energy Balance for Output Extractive Distillation Column


COMPONENT n, MOLE RATE Heat Vaporization, H
v
Q= nH
C
4
H
10
172.352517 22.305 3844.322892
C
4
H
8
-1 0 21.916 0
C
4
H
8
-2 62.99014602 21.916 1380.49204
C
4
H
6
0 0 0
H
2
O 31.34050805 40.706 1275.746721
CO
2
8.44265989 15.326 129.3922055
H
2
0 0.964 0
O
2
0.589654535 6.82 4.021443929
N
2
0.310872515 5.577 1.733736016
TOTAL 6635.709038

Table 2.1.47: Heat Vaporization at Extractive Distillation Column


Q For Extractive Distillation Column = nH
2
+ nH
v
- nH
1

= (H
13
+H
12
+H
V
)-H
11


=( 83853.36747+1129962.79+6635.709038)- 523097.0003

= 697354.8662 kJ/hr









90

2.4.5 Mass Balance in Solvent Recovery Column


D-102

Stream Description Temperature(
0
C) Pressure(atm)
12 Inlet 70 1.0
12a Outlet 400 3.0
12c Outlet 400 3.0

Table2.1.48: The Operation Condition of Recovery Column


Stream 12 Stream 12a


Function

To recovery the NMP solvent

Condition

Phase : Liquid phase
Operating Temperature : 400
o
C
Operating Pressure : 2 atm









91

Component


Mass Flow rate(kg/hr)

Inlet Outlet
S12 S12a
S12c
C
4
H
10
10017.64535 7368.818521 0
C
4
H
8
-1 0 6158.340946 0
C
4
H
8
-2 3534.188123 452.8405315 0
C
4
H
6
0 0 0
H
2
O 564.5992524 37.73671096 0
CO
2
371.5614618 480.4173588 0
H
2
0 0 0
O
2
18.86835548 13.06270764 0
N
2
8.70847176 5.80564784 0
NMP 0 0 2000 kg/hr
TOTAL 14515.57
14515.57 2000

Table 2.1.50: Inlet and Outlet Streams




2.4.6 Energy balance for Solvent Recovery Column


COMPONENT
Input
Stream 12
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
172.352517 4659.945 803153.25
C
4
H
8
-1 0 0 0
C
4
H
8
-2 62.99014602 4169.698 262649.8859
C
4
H
6
0 0 0
H
2
O 31.34050805 1521.028 47669.79027
CO
2
8.44265989 1810.12 15282.22752
H
2
0 0 0
O
2
0.589654535 1354.907 798.9270577
N
2
0.310872515 1314.716 408.7090693
TOTAL 1129962.79

Table 2.1.51: Energy balance for Input Solvent Recovery Column







92

COMPONENT
Output
Stream 12a
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
126.7797347 53583.913 6793354.275
C
4
H
8
-1 109.7606528 46892.33 5146932.752
C
4
H
8
-2 8.071016656 46698.873 376907.3818
C
4
H
6
0 0 0
H
2
O 2.094738327 13233.507 27720.73431
CO
2
10.9160954 16244.64 177328.0401
H
2
0 0 0
O
2
0.408222371 11639.901 4751.667981
N
2
0.207248343 11289.699 2339.771414
TOTAL 12529334.62

Table 2.1.52: Energy Balance for Output Solvent Recovery Column


COMPONENT n, MOLE RATE Heat Vaporization, H
v
Q= nH
C
4
H
10
126.7797347 22.305 2827.821982
C
4
H
8
-1 109.7606528 21.916 2405.514467
C
4
H
8
-2 8.071016656 21.916 176.884401
C
4
H
6
0 0 0
H
2
O 2.094738327 40.706 85.26841834
CO
2
10.9160954 15.326 167.3000781
H
2
0 0.964 0
O
2
0.408222371 6.82 2.784085702
N
2
0.207248343 5.577 1.155824494
TOTAL 5666.729257

Table 2.1.53: Heat Vaporization at Solvent Recovery Column



Q For Solvent Recovery Column = nH
2
+ nH
v
- nH
1

= (H
12a
+H
V
)-H
12


=[(12529334.62+5666.729257)-1129962.79]

= 11405038.56 kJ/hr








93

2.4.7 Mass Balance in Isomerization Stage in FBR


R-103

Stream Description Temperature(
0
C) Pressure(atm)
12 Inlet 70 1.0
12a Outlet 400 3.0

Table2.1.54: The Operation Condition of Isomerazation Stage in FBR
Stream 12 Stream 12a



Function

To isomerizes 2-butene to 1-butene

Condition

Phase : Liquid phase
Operating Temperature : 40
o
C
Operating Pressure : 2 atm











94

Component


Mass Flow rate(kg/hr)

Inlet Outlet
S12 S12a
C
4
H
10
10017.64535 7368.818521
C
4
H
8
-1 0 6158.340946
C
4
H
8
-2 3534.188123 452.8405315
C
4
H
6
0 0
H
2
O 564.5992524 37.73671096
CO
2
371.5614618 480.4173588
H
2
0 0
O
2
18.86835548 13.06270764
N
2
8.70847176 5.80564784
TOTAL 14515.57
14515.57

Table 2.1.55: Inlet and Outlet Streams


2.4.8 Energy balance for Isomerization Stage in FBR




COMPONENT
Input
Stream 12
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
172.352517 4659.945 803153.25
C
4
H
8
-1 0 0 0
C
4
H
8
-2 62.99014602 4169.698 262649.8859
C
4
H
6
0 0 0
H
2
O 31.34050805 1521.028 47669.79027
CO
2
8.44265989 1810.12 15282.22752
H
2
0 0 0
O
2
0.589654535 1354.907 798.9270577
N
2
0.310872515 1314.716 408.7090693
TOTAL 1129962.79

Table 2.1.56: Energy balance for Input Isomerization Stage in FBR









95

COMPONENT
Output
Stream 12a
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
126.7797347 53583.913 6793354.275
C
4
H
8
-1 109.7606528 46892.33 5146932.752
C
4
H
8
-2 8.071016656 46698.873 376907.3818
C
4
H
6
0 0 0
H
2
O 2.094738327 13233.507 27720.73431
CO
2
10.9160954 16244.64 177328.0401
H
2
0 0 0
O
2
0.408222371 11639.901 4751.667981
N
2
0.207248343 11289.699 2339.771414
TOTAL 12529334.62

Table 2.1.57: Energy Balance For Output Isomerization Stage in FBR


COMPONENT n, MOLE RATE Heat Vaporization, H
v
Q= nH
C
4
H
10
126.7797347 22.305 2827.821982
C
4
H
8
-1 109.7606528 21.916 2405.514467
C
4
H
8
-2 8.071016656 21.916 176.884401
C
4
H
6
0 0 0
H
2
O 2.094738327 40.706 85.26841834
CO
2
10.9160954 15.326 167.3000781
H
2
0 0.964 0
O
2
0.408222371 6.82 2.784085702
N
2
0.207248343 5.577 1.155824494
TOTAL 5666.729257

Table 2.1.58: Heat Vaporization at Isomerization Stage in FBR


Q For Isomerization Stage in FBR = nH
2
+ nH
v
- nH
1

= (H
12a
+H
V
)-H
12


=[(12529334.62+5666.729257)-1129962.79]

= 11405038.56 kJ/hr









96

2.4.9 Mass Balance in Distillation Column



D-103

Stream Description Temperature(
0
C) Pressure(atm)
12a Inlet 400 3.0
14 Outlet 30 4.5
15 Outlet 34 4.0

Table2.1.59: The Operation Condition of Distillation Column


Stream 12a
Stream 15
Stream 14

Function

To separate 1-butene as a byproduct and recycle n-butane back to the catalytic
dehydrogenation column

Condition

Phase : Liquid phase
Operating Temperature : 300
o
C
Operating Pressure : 3.5 atm

97

Component


Mass Flow rate(kg/hr)

Inlet Outlet
S12a S14
S15
C
4
H
10
7368.818521 6899.898631 404.8301001
C
4
H
8
-1 6158.340946 0 6190.556591
C
4
H
8
-2 452.8405315 461.7197582 0
C
4
H
6
0 0 0
H
2
O 37.73671096 37.73671101 0
CO
2
480.4173588 0 500.1679444
H
2
0 0 0
O
2
13.06270764 0 13.51805255
N
2
5.80564784 0 4.98033515
TOTAL 14517.02242
14517.02242

Table 2.1.60: Inlet and Outlet Streams



2.4.10 Energy balance for Distillation Column


COMPONENT
Input
Stream 12a
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
126.7797347 53583.913 6793354.275
C
4
H
8
-1 109.7606528 46892.33 5146932.752
C
4
H
8
-2 8.071016656 46698.873 376907.3818
C
4
H
6
0 0 0
H
2
O 2.094738327 13233.507 27720.73431
CO
2
10.9160954 16244.64 177328.0401
H
2
0 0 0
O
2
0.408222371 11639.901 4751.667981
N
2
0.207248343 11289.699 2339.771414
TOTAL 12529334.62

Table 2.1.61: Energy balance for Input Distillation Column










98

COMPONENT
Output
Stream 14
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
118.7120181 490.207 58193.46228
C
4
H
8
-1 0 0 0
C
4
H
8
-2 8.229271895 441.451 3632.820308
C
4
H
6
0 0 0
H
2
O 2.09473833 168.254 352.4481029
CO
2
0 0 0
H
2
0 0 0
O
2
0 0 0
N
2
0 0 0
TOTAL 62178.73069

Table 2.1.62: Energy Balance for Output Distillation Column


COMPONENT
Output
Stream 15
Mole Rate H, Enthalpy (j/mol) Q= nH
C
4
H
10
6.965058584 887.404 6180.820847
C
4
H
8
-1 110.3348351 780.367 86101.66424
C
4
H
8
-2 0 0 0
C
4
H
6
0 0 0
H
2
O 0 0 0
CO
2
11.36487036 358.833 4078.090524
H
2
0 0 0
O
2
0.422452344 270.038 114.078186
N
2
0.177786569 262.032 46.58577018
TOTAL 96521.23957

Table 2.1.63 Energy Balance for Output Distillation Column


COMPONENT n, MOLE RATE Heat Vaporization, H
v
Q= nH
C
4
H
10
118.7120181 22.305 2647.871564
C
4
H
8
-1 0 21.916 0
C
4
H
8
-2 8.229271895 21.916 180.7148108
C
4
H
6
0 0 0
H
2
O 2.09473833 40.706 85.26841846
CO
2
0 15.326 0
H
2
0 0.964 0
O
2
0 6.82 0
N
2
0 5.577 0
TOTAL 2913.854793

Table 2.1.64: Heat Vaporization at Distillation Column
99

Q For Distillation Column = nH
2
+ nH
v
- nH
1

= (H
14
+H
15
+H
V
)-H
12a


= [(62178.73069+96521.23957+2913.854793)-
12529334.62]

= -12367720.8 kJ/hr


Component Amount of Energy (kJ/hr)

Fixed Bed Reactor
-127740.27
Condenser (air cooled) 1696101291

Extractive Distillation Column
697354.8662

Distillation Column
-962682.24

Compressor
14367279.35

Heat Exchanger
-41572784.51

Absorption Column

-14015183.09

Table 2.1.65: Overall Energy Balance





















100



CHAPTER 3




UTILITIES




3.0 Introductions


Plant utilities are a vital service to the operation of most major
industrial plants. In the chemical industries, power is supplied primarily in
the form of electrical energy. Agitators, pumps, hoists, blowers,
compressors and similar equipment are usually operated by electric
motors, although other prime movers such as steam engines, internal
combustion engines, and hydraulic turbines are sometimes employed
(Peters et. al, 2004).




3.1 Utilities in Plant


3.1.1 Electricity


Power can be transmitted into various forms, such as mechanical
energy, electrical energy, heat energy and pressure energy. In our plant,
electrical is supplied by Paka Power Plant since it is nearest to our plant.
The table 3.1 below shows the consumption of electricity used by our
plant.



101

Equipment Power, kW
C-101A/B 3.2424
C-102A/B 25.7246
C-103A/B 17.0327
C-104A/B 93.6073
C-105 A/B 20.8281
C-106A/B 26.03
C-107 A/B 3908.5

P-101 A/B 3.96
P-102 A/B 2.1303

P-103A/B 0.4235
P-104 A/B 49.56

P-105 A/B 0.697

P-106 A/B 0.697

P-107A/B 0.362

E-101

4842

E-102

4842

Table 3.1: Summary of consumption of electricity used by equipments




3.1.2 Water

Water for industrial purpose can be obtained from one of two general
sources: the plants own source or municipal supply. In our plant, we used water
supply from Terengganu water company (SATU). The table 3.2 below shows the
consumption of water used for operation in plant.


102

Equipment Volume of water,m
3

R-101

E-103 5.0314
E-104 7.8194
E-105 4.67
E-106 2.06
E-107 2.06

Table 3.2: Summary of consumption of water need by equipments




3.1.3 Steam


Steam is supplied at unit boiler or reboiler to heat the hydrocarbon in the
distillation system in our plant. The table 3.3 below shows the consumption of
steam used in the plant.


Equipment Mass of steam, kg/hr
E-101 4 514.0729
E-102 54 603.56

Table 3.3 Summary of consumption of steam used in plant


3.1.4 Air


Air is supplied to catalytic dehydrogenation of n-butane and oxidative
dehydrogenation of 1-butene process. The amount of air used is 12 407.754 kg/hr.



103

3.1.5 Cooling tower


Table 3.4 below shows the amount of cooling water needed for the heat
exchangers.


Equipment Cooling water mass
flow
rate (kg/hr)
Cooling water volume
flowrate (m3/hr)
E-101 25540.2 25.54
E-102 15300.4 15.3
E-103 5022.363 5.02
E-105 15057.033 15.06
E-106 2062.809 2.06
TOTAL 62982.8 62.98

Table 3.4: Summary of consumption of cooling water need by equipments

Cooling towers are a very important part of many chemical plants. They
represent a relatively inexpensive and dependable means of removing low grade
heat from cooling water.

Figure 3.1: Closed Loop Cooling Tower System in Butadiene production
plant
104

The make-up water source is used to replenish water lost to evaporation.
Hot water from heat exchangers is sent to the cooling tower. The water exits the
cooling tower and is sent back to the exchangers or to other units for further
cooling.

Types of Cooling Towers
Cooling towers fall into two main sub-divisions: natural draft and
mechanical draft. Natural draft designs use very large concrete chimneys to
introduce air through the media. Due to the tremendous size of these towers (500
ft high and 400 ft in diameter at the base) they are generally used for water flow
rates above 200,000gal/min. Usually these types of towers are only used by
utility power stations in the United States. Mechanical draft cooling towers are
much more widely used. These towers utilize large fans to force air through
circulated water. The water falls downward over fill surfaces which help
increase the contact time between the water and the air. This helps maximize heat
transfer between the two.
Types of Mechanical Draft Towers

Figure 3.2: Mechanical Draft Figure 3.3: Mechanical
Counterflow Tower Draft Crossflow Tower
105

Mechanical draft towers offer control of cooling rates in their fan
diameter and speed of operation. These towers often contain several areas (each
with their own fan) called cells.


Assumption
- Cooling Tower is in cylindrical shape.
- Ratio of L:D = 3:1
- Volume of cooling tower, V=20m3


Calculation
V=20m3
D2/4 L=20
D2/ 4 3D = 20 (3D=L)
D= 2.91m & L= 8.74m






























106

FILL AREA
WATER
AIR
P-7
AIR INLET
AIR INLET
WATER OUTLET
FAN
AIR OUTLET
WATER INLET








L
=8.74m






















D=2.91m

Fig.3.4: Preliminary design of cooling tower















107



CHAPTER 4




EQUIPMENT SIZING




4.1 DESIGN OF REACTOR


4.1.1 Multitubular Fixed Bed Reactor (R-101)


Characteristic of catalyst and bed:
Catalyst used: Chromia alumina

c
= density of catalyst particle = 5000 kg/m
3

= bed porocity = assumed 0.5

b
= bulk density of bed (
c
[1-]) = 2500 kg/m
3
Sizing Calculation:

a) Total volume inside the tubes, V
t


i) Calculate density of mixture

Component, x
x
(kg/m
3
), Mass flow rate,
(kg/hr), m
x

C
4
H
10
4.2 6885.3731
H
2
0 0.596 5341.7169
O
2
1.308 4303.5621
N
2
1.251 8625.2254
H
2
0.0899 2155.5521
108


mix
= (
x
x m
x
)
m
total

mix
= (4.2 x 6885.3731) + (0.596 x 5341.7169) + (1.308 x
4303.5621) +
(1.251x8625.2254) + (0.0899 x 2155.5521)
37 018.135

mix
= 1.3160 kg/m
3


ii) Calculate volumetric flow rate, v
o


v
o
= mass flow rate
density of mixture

v
o
= 37 018.135 kg/hr
1.3160 kg/m
3
v
o
= 28 129.2819 m
3
/hr


iii) From the handbook of Elements of Chemical Reaction Engineering
4
th
edition, the V exact volume of reaction fluid (not including
catalyst surface) :

- Refer to patent US 7 488 857 B2, GHSV is ranging
between 500/hr-200/hr
So, we decide to choose the best value GHSV = 600/hr

GHSV = Vo/V

V = Vo/ GHSV

= 28 129.2819 m
3
/hr
600/hr
V = 46.8821 m
3

109

iv) By assuming that the void fraction of the catalyst bed as 50% of
the total volume of reactor:

= 0.5


v) Total volume inside the tube, Vt:

= V/Vt

Vt = V

Vt = 46.8821 m
3
/0.5

Vt = 93.7643 m
3


b) Diameter, height and cross section area of reactor:

i) Based on engineering practice, we assume ratio of height to
diameter is 1:3

So, H = 3D


ii) Reactor is in vertical cylindrical shape:

V = d
2
h/4

d =
3
4V/3

d =
3
(4 x 93.7643 m
3
)/ 3

d = 3.4141 m



110

iii) Calculate value of h:

h = 3(3.4141 m)

h = 10.2424 m


iv) Total cross section area of reactor:

Ac = d
2
/4

Ac = ( x 3.4141
2
)/4

Ac = 9.1547 m
2



c) Weight of catalyst:

- Refer to the handbook of Elements of Chemical Reaction
Engineering 4
th
edition,

Wc = (1- )A
c
z x
c

- Since we are more interested in catalyst weight rather than the
distance z down to the reactor, we can say at the end of reactor, z =
L:

Wc = (1-0.5) x 9.1547 m
2
x 10.2424 m x 1.3160 kg/m
3
Wc = 117 207.6241 kg

d) Wall thickness:

- Based on table 12.10 in handbook of Plant Design & Economics
for Chemical Engineering :

111

- Recommended stress values (S, kPa) for SS 304 at 550
o
C is 68
392.1933 kPa

- Ej for spot examined if lap-welded is 0.80
- Corrosion allowance (C
c
) about 3 mm for a 10-year life


t = P
ri
+ Cc
S
ej
0.6 p

0.385 S
ej
= 0.385(68 392.1933 x 0.80)

= 21 064.7955 kPa

Since that, P = 101.325 kPa and P 0.385 S
ej


t = 101.325 x (3.4141/2) + 0.003 m
(68 392.1933 x 0.80) (0.6 x 101.325)

t = 6.1648 x 10
-3
m

For ease the heat transfer, we will use tubes each with the following specification.

- Outside diameter, d
o
= 1 ! inch = 0.0318 m
- Inside diameter, d
i
= 1 inch = 0.0254 m
- Maximum height of tube is 6 m


Maximum weight of catalyst fills able into a single tube:
W
m
= ( x 0.0254
2
)/4 m
2
x 6m x 5000 kg/m
3
= 15.2012 kg/tube
No of tube required = 117 207.6241 kg/ 15.2012 kg/tube = 7710.4068 tubes
7710 tubes


112

Reactor heat transfer coefficient:


a) Tube inside heat transfer coefficient :

Condition of tube region:
- T = 550
O
C
- P = 1 atm
Component, x Mass flow
rate, m
x

(kg/hr)
Viscocity,
x

(kg/s.m)
Thermal
conductivity,
k
x
(W/m.K)
Heat capacity,
C
px
(kJ/kg.K)
C
4
H
10
6885.3731 6.82 x 10
-8
0.0160 0.096
H
2
0 5341.7169 1.295 x 10
-5
0.025 1.888
O
2
4303.5621 0.0206 x 10
-3
0.0266 0.9192
N
2
8625.2254 0.0177 x 10
-3
0.0258 1.038
H
2
2155.5521 8.9060 x 10
-3
0.1790 14.26

i) Fluid velocity at bulk temperature, :

= (
x
x m
x
)/m
total

= 5.2699 x 10
-4
kg/s.m


ii) Fluid thermal conductivity, k:
k = (k
x
x m
x
)/m
total

k = 0.0261 W/m.K


iii) Heat capacity, C
p
:
C
p
= (C
px
x m
x
)/m
tota

C
p
= 1.4694 kJ/kg.K


113

iv) Mass velocity for each tube, Gt (kg/m
2
.s)
Gt = mass flow rate in tubes/area inside per tube
Gt = 37 018.135 kg/hr / ( x 0.0254
2
/4 x 7710 tubes) x 1/3600 s
Gt = 2.6321 kg/m
2
.s


v) Pranditl number, Pr = C
p
/k
Pr = (1.4694 kJ/kg.K x 5.2699 x 10
-4
kg/s.m) / 0.0261 W/m.K
Pr = 29.6689


Reynold number = Gtd
i
/
N
Re
= (2.6321 kg/m
2
.s x 0.0254 m) / 5.2699 x 10
-4
kg/s.m
N
Re
= 126.8626

Refer to Couldson & Richardsons Chemical Engineering Design Vol. 6
Handbook:
Since N
Re
< 2100, the flow is laminar.
Nu = 1.86 (RePr)
0.33
(d/l)
0.33
(/
w
)
0.14

Assume that =
w,
Nu = 1.86 x (126.8626 x 29.6689)
0.33
x (0.0254/6)
0.33
= 4.6374


viii) Tube side heat transfer coefficient:
h
i
= Nuk/d
h
i
= (4.6374 x 0.0261 W/m.K) / 0.0254 = 4.7652 W/m
2
.K


b) Tube side pressure drop:

i) Refer to figure 12.4 in Couldson & Richardsons Chemical
Engineering Design Vol. 6 Handbook:

j
f
= 0.0055

114

ii) Fluid velocity:

t
= Gt/ = 2.6321 kg/m
2
.s /1.3160 kg/m
3

t
= 2.0000 m/s

iii) Assume that tube side velocity is 2-passes

iv) Pressure drop:

Pdrop = Np [8 j
f
(l/d) (/
w
)
-m
+ 2.5] x
t
2
/2
Assume that =
w,
Refer to Couldson & Richardsons Chemical Engineering Design
Vol. 6 Handbook, m for laminar flow = 0.25

Pdrop = 2[2(0.0055) (6/0.0254) + 2.5] x (1.3160 kg/m
3
x 2
2

m
2
/s
2
)/2

Pdrop = 67.8724 N/m
2
= 6.6985 x 10
-4
atm

Since the value is very small, it can be neglected











115

c) 2- shell side heat transfer coefficient

i) By assuming 2 passes and triangular pitch:

Pt = 1.25d
o
= 1.25 x 0.0318 = 0.03975

ii) Refer to Couldson & Richardsons Chemical Engineering Design
Vol. 6 Handbook, from table 12.4 fore 2 passes:

- k
1
= 0.249
- n
1
= 2.207

iii) bundle diameter, D
B
:

D
B
= d
O
(Nt/ k
1
)
1/ n1
= 0.0318 x (7710/0.249)
1/2.207
= 3.4455 m

Jacketed Reactor


Because of this reaction is isothermal, jacket is needed to make sure
no temperature change in this reactor. Water is chosen as the cooling
medium.









Figure 4.1: Jacketed reactor

116


i) Jacketed Reactor Diameter
Assume diameter of jacketed reactor is 20 cm more than diameter
of reactor.




ii) Height of Jacketed
Assume jacket only cover of height of reactor.




iii) Jacketed Reactor Volume
Assume jacketed reactor also in a cylindrical type.


.
Therefore, the reactor volume is calculated as:






iv) Volume of Water in Jacketed Reactor
In order to make sure temperature no change in reactor, water as a
cooling medium must be located in between jacket and reactor.
Quantity of water needed is as follow:

m
3

117

m
3

4.1.2 Multitubular Fixed Bed Reactor (R-102)


Heat release of the reactor = 10"10
3
kW
Cp (average) = 0.0433848 kJ/molK
10"10
3
kJ/s = 0.0433848 kJ/molK x 10371.09 x10
3
/3600s x (Tad 450)
Tad = 618.0 C
If all heat release goes to heating the reaction products, the temperature of the
outlet fluid would be 618.0 C which is way too high from the desired 450C.
To keep isothermal operation, we must release the heat. Simple packed does not
provide efficient heat removal. A multi tube packed bed reactor is a better choice
in light of heat removal. A multi tube packed bed reactor is a reactor shell
consisting of many parallel tubes in which the catalyst is packed. Reactant gases
flows from one end into the shell, then into the tubes, get reacted; flow out from
the tubes, and the reactor shell.


Reactor design


(A) General aspects
Component

Molecular
weight
Mol flow rate (kmol/hr)
input Output
C
4
H
10
58.12 246.3758717 172.9539919
C
4
H
8
-1 56.10 84.11562543 0
C
4
H
8
-2 56.10 180.5810164 81.53266795
C
4
H
6
54.09 18.0764008 115.8681384
H
2
O 18.016 616.6877427 79.39939533
CO
2
44.01 11.37091046 29.38943013
H
2
2.016 8573.518106 6005.393937
O
2
32.00 0 118.8850405
N
2
28.02 640.3678968 1524.369831

118


Flow rate in, F = 10371.09 kmol/h
Gas hourly space velocity, = 600 h-1(298K and 1 atm)
Superficial velocity, v = 1m/s

Step by step approach

[Reference : Martyn S. Ray and Martin G Sneesby, Chemicl engineering Design
Project-A case study approach, 2nd edition, Gordon and Breach Science
publishers, 1998.]

1) Density of inlet gas (298K and 1 atm),
= = 40.9 mol/m3= 0.0409kmol/m

2) Volumetric flow rate (298k and 1atm),
V
s
= =2.5363 "10m /h

3) Volume of catalyst needed, VB = = 422.72 m
3

4) Density of feed gas at operating conditions,
= 16.86mol/m
3

= 16.86 mol/m
3
x 0.058123kg/mol
= 0.9798 kg/m3

5) Volume of gas at operating conditions, Vg
= = 6.1513 "10 m3/h

6) Weight of catalyst required, WB = VBB=422.72 m
3
x 1440kg/m3 = 608716.8
kg
It is desired to use multi tube packed bed rector.
119

The maximum height of tube is 6m.
7) For ease of heat transfer, we will use tubes each with the following
specification.
Outside diameter, Do=0.0318 m,
Inside diameter, Di=0.0254m,
H=6m

Maximum weight of catalyst fills able into a single tube,
" 6m "1440 = 4.378 kg/ tube
Number of tubes required, Nt = = = 139040 tubes
To keep the reactor diameter less than 6m, we use 4 parallel reactors, each will
take
= 34760 tube per reactor. For a single reactor, the packing efficiency
can be assumed to be 99% due to many tubes.
The tubes are to be arranged in a square pitch with a tube pitch (tube centre to
tube centre) of 0.0397m.
0.99Ds
2
/4 m
2
= 0.0397m
2
x 34760 tubes.
The reactor shell diameter, Ds = 6.49m.
We will allow 1m above and below the tube bundle. Therefore the reactor will be
8m high and with internal diameter 6.49m.


The average values of the properties of fluid in the reactor:
inlet Outlet Average

Heat capacity,
Cp(kJ/molK)

0.04365772 0.04311188 0.0433848

Viscosity, (Pas) 2.9452e-5 2.912e-5 2.9286e-5

Density, (kg/m3) 694.9 682.3 688.6
120


Thermal conductivity of air k air = 0.05644W/mK
Thermal conductivity of steam, k steam = 0.05705W/mK

Inlet molar ratio: = = 0.9373
Outlet molar ratio: = = 0.9898

Steam and air are the major components in feed and product gas, take their
individual thermal conductivities to find an average conductivity.
Thermal conductivity of feed, k
in
= 0.9373 x 0.05644 + 0.0627 x 0.05705 =
0.05648 W/mK
Thermal conductivity of outlet gas, k
out
= 0.9898 x 0.05644 + 0.0102 x 0.05705
= 0.05645 W/mK

Prantl number:
Prair = 0.688;
Pr steam= 1.0075
Bed void fraction, = 0.40
Mass flux of feed, G = = = 0.3035

8) Tube side pressure drop,
Dp = catalyst pellet diameter = 6.0mm

)( )

)(
)

= 17.74Pa/m

121

L = 6m
Pt = 0.1064 kPa which is negligible
9) Tube side heat transfer coefficient




Kreith and Bohn(1986) provide a correlation for tube side flow based on Nusselt
Number

Nu = 0.203(Re"Pr)
0.33
+0.22Re
0.8
Pr
0.4

= 0.203(263.23 x 0.02251)
0.33
+0.22(263.23
0.8
x 0.02251
0.4
)
= 4.5304

hi = Nuk/D = 4.5304 x 0.05645/0.0254 = 10.07 W/m2K


Shell side properties
Heat transfer salt Hitec is used to cool the tubes from the shell side.
Hitec inlet temperature: 144C
Hitec outlet temperature: 600C
Tube pitch = 0.0397m
P = baffle pitch = 1 m
(Five 25% baffles are used in the 6m tube height)
Cp = 1.3395 kJ/kgC

(600C) = 1.2x10
-3
Pas
(144C) = 20x10
-3
Pas
(average) =10.6 x10
-3
Pas
Nb = the number of tubes in the baffle window
Fb= fraction of cross sectional area of shell occupied by baffle window
Ds = inside diameter of reactor shell
122

Do=outside diameter of tube

10) Shell side heat transfer coefficient
Nb = fb x Nt=0.1955x34760 tubes

-

- =1.0701 m2

Sc = PDs(1-Do/p)=1x6.49(1-0.0318/0.0397)=1.2915m
2


4.9958kg/ms
2

Ge = (G
b
G
c
)= (4.1394 "4.9958) =4.5475 kg / (m
2
s)
(144 C) =20"10

3
Pas ;
w
at wall = (500 C) =1.2"10
-3
Pas

McCabe and Smith 2005 gives
0.6 0.33
)
0.14
0.6 0.33 0.14

0.6 0.33 0.14

= 39.848 W/m
2
K


11) Shell side pressure drop
De = effective outside diameter of tube=0.99Do=0.99x0.0318=0.03148 m
Gs =mass flux of salt
N = number of baffles
s= average salt density = m
Gs = 5.446kg/s (0.01x6.49mx1m) =83.91 kg/m
2
s
123

= = 242.31Pa
12) Overall heat transfer coefficient
ks = thermal conductivity of 1 % chromium steel
r = radius of tube
Heat transfer coefficient through the wall,

= = 2.183" 10

Assume no fouling,

U

8.04 W/ (m
2
K)


(B) Reactor shell design

(1)Operating and design conditions

Temperature :
Normal = 450oC
Peak = 500oC
Tensile strength of chromium steel = 500MPa

Pressure:
Normal = 2atm
Peak = 3atm
Design pressure = (2+18 atm)x1.1 = 22 atm
[18 atm is the maximum internal explosion pressure expected]
Joint efficiency :
Longitudinal joints and end joints : 90%
Circumferential joints : 90%


124


Wall thickness

= 0.01611m = 16.11mm

P = design pressure = 22atm
t = minimum wall thickness required
Ds = shell inside diameter
F = tensile strength of wall material(chromium steel) = 500MPa
= joint efficiency = 90%

Corrosion allowance for Hitec salt is 0.2mm/year for 20 years and 25% safety
factor are considered. Therefore the actual minimum thickness required for
reactor wall

= 16.11mm +20(0.2) +0.25x16.11mm =24.1425 mm


(2)Ends

Torispherical ends are not suitable at the required working pressure. Either
ellipsoidal or spherical ends could be used but ellipsoidal ends are preferred to
minimize the overall height of the reactor and material cost. The minimum
thickness for 2.5:1 ellipsoidal ends is given by

= 22.04mm

K=1.37 for 2.5 : 1 ends, P = design pressure = 22 atm

Use a safety factor of 20%, t = 1.2x17.52 = 21 mm



125


The MAWP for the ellipsoidal ends is

=2.2321"10 Pa = 22.03atm

The MAWP for ellipsoidal ends coincide with the cylindrical section of the
reactor.


(3) Tube plate design


A tube plate is required to hold the multi parallel tubes in place at the bottom of
the tube bundle. The method recommended in the British Standard BS5500 uses:
CD
t p
= 0.456.49 = 0.2023m= 20.23mm
Incorporate 30% safety factor, the installed tube plate will be 25 mm thick. The
tube plate can be supported by 6 right angled triangular plates, equally spaced at
the circumference of the reactor wall. The non-hypotenuse sides of the triangular
plate are each welded to the internal shell wall and to the the bottom of the tube
plate. The detailed dimensions and joining methods are subject to detailed
mechanical analysis.(eg force sustained, etc)


(4) Reactor openings


The reactor openings are pipes connected to the reactor for fluid flow. The Harker
equation (1978),

[(76982.11) ^0.45]

= 1492mm
W = mass flow rate(kg/h)
Dopt = optimum pipe diameter (mm)
126

= average fluid density in the inlet and outlet pipes(kg/m3) = 0.6886 kg/m3
Insulation


Insulation is selected based on the type and size of vessel, the operating
conditions, safety considerations, and insulation cost.
Without insulation, the heat loss from the cylindrical section is

Q = UAT = 25( DsL)(T) = 25( x 6.49x6)( 0.5(144 + 600) -30) =1062kW

Q = overall heat transfer coefficient for ambient conditions = 25W/m2K

A= heat transfer area= inner circumferential area of shell

T = temperature difference between surrounding and inside the reactor shell
The inside shell temperature is taken to be the average salt temperature
=372oC
The ambient temperature is 30oC.

As calculated, the heat loss is a considerable amount of energy. By insulation, this
heat loss can be integrated into the process line. Mineral wool blankets are
typically used for large diameter vessel. They are as effective as they are
economical. We will use two blankets of mineral wool, each 75mm thick to cover
both the walls and the ellipsoidal ends.










127





End Thickness Air Inlet
= 21mm
Gas
Outlet
Wall Thickness
= 20mm


Salt Inlet

34760Tubes
I.D= 25.4mm
O.D= 31.8mm

Salt Outlet





Gas Inlet


Tube Plate (25mm)
And Supports





128


4.1.3 Fixed Bed Reactor for Isomerazation process (R-103)


Characteristic of catalyst and bed:Catalyst used: Zeolite

c
= density of catalyst particle = 2.32 kg/m
3

= bed porosity = assumed 0.5


b
= bulk density of bed (
c
[1-]) = 1.16 kg/m
3


The isomerazation of 2-butene

Sizing Calculation:

e) Total volume inside the tubes, V
t


vi) Calculate density of mixture

Component, x Mole fraction
x
@ 200
o
C and
3 atm, (kg/m
3
),
Mass flow rate,
(kg/hr), m
x

C
4
H
10
0.0536 4.2 821.2040
C
4
H
8
-2 0.8777 2.07 13447.215
CO
2
0.0662 1.420 1014.2481
O
2
0.0018 1.308 27.5777
N
2
0.0007 1.251 10.72467


mix
= (
x
x m
x
)
m
total

mix
= (4.2 x 821.2040) + (2.07 x 13447.215) + (1.42 x 1014.2481)
+
(1.308x27.5777) + (1.251 x 10.72467)
15346.9695

mix
= 2.00 kg/m
3







129


vii) Calculate volumetric flow rate, v
o


v
o
= mass flow rate
density of mixture

v
o
= 15346.9695kg/hr
2.14 kg/m
3
v
o
= 7673.4848 m
3
/hr


viii) From the handbook of Elements of Chemical Reaction Engineering
4
th
edition, the V exact volume of reaction fluid (not including
catalyst surface) :

- Refer to patent US 7 488 857 B2, GHSV is ranging
between 500/hr-200/hr
So, we decide to choose the best value GHSV = 600/hr

GHSV=Vo/V

V= Vo/ GHSV

= 7673.4848 m
3
/hr
200/hr

V= 38.36 m
3




ix) By assuming that the void fraction of the catalyst bed as 50% of
the total volume of reactor:

= 0.5


x) Total volume inside the tube, Vt:

= V/Vt

Vt = V

Vt = 38.36 m
3
/0.5

Vt = 76.73 m
3



130


f) Diameter, height and cross section area of reactor:


v) Based on engineering practice, we assume ratio of height to
diameter is 1:3

So, H = 3D


vi) Reactor is in vertical cylindrical shape:

V = d
2
h/4

d =
3
4V/3

d =
3
(4 x 76.73 m
3
)/ 3

d = 3.19 m


vii) Calculate value of h:

h = 3(3.19 m)

h = 9.58 m


viii) Total cross section area of reactor:

Ac = d
2
/4

Ac = ( x 3.19
2
)/4

Ac = 7.992 m
2



g) Weight of catalyst:

- Refer to the handbook of Elements of Chemical Reaction
Engineering 4
th
edition,

Wc = (1- )A
c
z x
c


131

- Since we are more interested in catalyst weight rather than the
distance z down to the reactor, we can say at the end of reactor, z =
L:

Wc = (1-0.5) x 7.992 m
2
x 9.58 m x 2.00 kg/m
3
Wc = 7656336 kg


h) Wall thickness:

- Based on table 12.10 in handbook of Plant Design & Economics
for Chemical Engineering :

- Recommended stress values (S, kPa) for SS 304 at 350
o
C is 76
800 kPa

- Ej for spot examined if lap-welded is 0.80

- Corrosion allowance (C
c
) about 3 mm for a 10-year life


t = P
ri
+ Cc
S
ej
0.6 p

0.385 S
ej
= 0.385(76 800x 0.80)

S
ej
= 61 440 kPa

Since that, P = 303.975 kPa and P 0.385 S
ej


t = 303.975 x (3.4141/2) + 0.003 m
(61 440 ) (0.6 x 303.975)

t = 0.0114 m


For ease the heat transfer, we will use tubes each with the following specification.

- Outside diameter, d
o
= 1 ! inch = 0.0318 m
- Inside diameter, d
i
= 1 inch = 0.0254 m
- Maximum height of tube is 6 m


132

Maximum weight of catalyst fills able into a single tube:
W
m
= ( x 0.0254
2
)/4 m
2
x 6m x 2320 kg/m
3
= 7.053 kg/tube
No of tube required = 7656.336 kg/ 7.053 kg/tube = 1085.543 tubes
1085 tubes

Reactor heat transfer coefficient:


d) Tube inside heat transfer coefficient :

Condition of tube region:
- T = 350
O
C
- P = 3 atm
Component, x Mass flow
rate, m
x

(kg/hr)
Viscocity,
x

(kg/s.m)E-4
Thermal
conductivity,
k
x
(W/m.K)
Heat capacity,
C
px
(kJ/kg.K)
C
4
H
10
821.2040 5.852 0.05169 0.096
C
4
H
8
-2 13447.215 5.323 0.04774 4.46
CO
2
1014.2481 6.41 0.03721 0.98651
O
2
27.5777 2.977 0.04709 1.01
N
2
10.72467 1.582 0.04254 1.06


vi) Fluid velocity at bulk temperature, :

= (
x
x m
x
)/m
total

= 5.026E-4 kg/s.m


vii) Fluid thermal conductivity, k:
k = (k
x
x m
x
)/m
total

k = 0.04717 W/m.K


viii) Heat capacity, C
p
:
C
p
= (C
px
x m
x
)/m
tota

C
p
= 3.9808 kJ/kg.K

133

ix) Mass velocity for each tube, Gt (kg/m
2
.s)
Gt = mass flow rate in tubes/area inside per tube
Gt = 15346.9695kg/hr / ( x 0.0254
2
/4 x 1085 tubes) x 1/3600 s
Gt = 7.7541 kg/m
2
.s


x) Pranditl number, Pr = C
p
/k
Pr = (3.9808 kJ/kg.K x 5.026E-4 kg/s.m) / 0.04717 W/m.K
Pr = 42.416


Reynold number = Gtd
i
/
N
Re
= (7.7541 kg/m
2
.s x 0.0254 m) / 5.026E-4 kg/s.m
N
Re
= 357.9


Refer to Couldson & Richardsons Chemical Engineering Design Vol. 6
Handbook:

Since N
Re
< 2100, the flow is laminar.
Nu = 1.86 (RePr)
0.33
(d/l)
0.33
(/
w
)
0.14

Assume that =
w,

Nu = 1.86 x (357.9 x 42.416)
0.33
x (0.0254/6)
0.33
= 3.9503


viii) Tube side heat transfer coefficient:
h
i
= Nuk/d
h
i
= (3.9503x 0.04717 W/m.K) / 0.0254 = 7.336 W/m
2
.K


e) Tube side pressure drop:


v) Refer to figure 12.24, pages 667 in Couldson & Richardsons
Chemical Engineering Design Vol. 6 Handbook:

j
f
= 0.023


vi) Fluid velocity:

t
= Gt/ = 7.7541 kg/m
2
.s /2.0 kg/m
3

t
= 3.877 m/s

134

vii) Assume that tube side velocity is 1-passes


viii) Pressure drop:


Pdrop = Np [8 j
f
(l/d) (/
w
)
-m
+ 2.5] x
t
2
/2
Assume that =
w,
Refer to Couldson & Richardsons Chemical Engineering Design
Vol. 6 Handbook, m for laminar flow = 0.25


Pdrop = 1[8(0.023) (6/0.0254) + 2.5] x (2.00 kg/m
3
x 3.877
2

m
2
/s
2
)/2

Pdrop = 690.9 N/m
2
= 0.0069 atm

Since the value is very small, it can be neglected


f) 2- shell side heat transfer coefficient


iv) By assuming 1 passes and triangular pitch:

Pt = 1.25d
o
= 1.25 x 0.0318 = 0.03975


v) Refer to Couldson & Richardsons Chemical Engineering Design
Vol. 6 Handbook, from table 12.4 for 1 passes:

- k
1
= 0.319
- n
1
= 2.142


vi) bundle diameter, D
B
:

D
B
= d
O
(Nt/ k
1
)
1/ n1
= 0.0318 x (1085/0.319)
1/2.142
= 1.4164 m




135

4.2 DESIGN OF MASS TRANSFER EQUIPMENT



4.2.1 Extractive Distillation (D-101)


Equilibrium stage
Component Relative
volatility,
at
(53 ,
5atm)
Feed
amount
(kg/hr)
Feed
amount
(kmol/hr)
Feed
fraction
Distillate
(di)
Bottom
(bi)
C
4
H
10
(HK) 0.88 10496.55 180.975 0.4825 0.003 0.665
C
4
H
8-2
1.38 3700.44 66.0790 0.1880 0.010 0.033
C
4
H
6
(LK) 1.53 6578.56 121.825 0.3295 0.980 0.002


Multicomponent distillation
Using Fenske Equation,
N
min
=
=
= 15.37 plates 16 plates


Minimum Reflux Ratio,
= 1-q
For liquid feed, q=1.0
=
136

By using trial and error method, "#$% &'()*
= -2.032+0.8915+1.143
= 0.0025 0
must lie between the values of the HK and LK, HK LK
0.88 1.53. By trial and error, = 1.089
Rmin + 1 =

=
= 3.435

So, Rmin = 3.435 1 = 2.435
Number of equilibrium stages,
R = Operational reflux ratio = 3.0

= 0.75
= 0.75
= 0.5023


N= 33.16 33 stages


With,
= 9.267 kg/m
= 540.3 kg/m
=
=
= 0.098
137

Use a tray spacing of 0.31 m,
From Figure 15.5, (Plant Design and Economic for Chemical Engineers, page
778)
At = 0.098, C
sb
= 7.50 10
-1
m/s
The surface tension of 1,3-butadiene, = 4.34 dyne/cm
V
nf
= C
sb

= 7.50"10
-2
= 0.4188 m/s
Assume 80% of flooding,
V
n
= 0.8 V
nf

= 0.8(0.4188)
= 0.3351 m/s
The net column area, A
n
= = =
= 2.236 m
2

Assume that the downcomer occupies 15% of the cross sectional area of the
column. Thus,
Area of column, A
c
=
=
= 2.6306 m
2

Diameter of column, D =
=
= 1.830 m

138

Number of plates = 33 1
= 32 plates


Functional height = (32-1) "0.31
= 9.61 m


Column Height

The column height is the functional height(between top and bottom plate) plus the
base and vapor space at the bottom and top of column. Assign 30% of the
functional height to the column base and top mass flow.


Actual column height = 9.61 m " 1.3
= 12.493 m



4.2.2 Extractive Distillation Column D-102


Equilibrium stage
Component Relative
volatility,
at
(53 ,
5atm)
Feed
amount
(kg/hr)
Feed
amount
(kmol/hr)
Feed
fraction
Distillate
(di)
Bottom
(bi)
C
4
H
10
(LK) 1.17 165.8981 2.8544 0.0107 0.926 0.0076
C
4
H
8-
2
(HK)
1.00 14.4192 0.257 0.00093 0.0731 0.0095
NMP - - - - - -

Multicomponent distillation
Using Fenske Equation,
N
min
=
139

=
= 17.59 plates 18 plates
Minimum Reflux Ratio,
= 1-q
For liquid feed, q=1.0

= = 0


By using trial and error method,
When 1.02
= -2.032+0.8915+1.143
= 0.0025 0

must lie between the values of the HK and LK, HK LK
1.00 1.173. By trial and error, =1.02
Rmin + 1 =
=
= 3.345

So, Rmin = 3.435 1 = 2.345


Number of equilibrium stages,

Method used Gilliland Correlation (Plant Design & economic for Chemical
Engineers, Max S.Peter Klaus D. Timmerhaus, Ronald, pages 772)
R = Operational reflux ratio = Rule of thumb= 1.2 (2.345)= 2.814


= 0.75
= 0.75
140

= 0.521


N = 37.578 38 stages

Determining Actual trays Plant Efficiency
Rule of thumb
Tray efficiency for distillation of light hydrocarbon and aqueous solution are 60%
-90%

N act = = = 41.75 42 trays


With,
= 10.455 kg/m
= 591.5 kg/m
Assume = =
=
=
= 0.09971
Use a tray spacing of 0.31 m,

From Figure 15.5, (Plant Design and Economic for Chemical Engineers, page
778)

At = 0.098, C
sb
= 7.50 10
-1
m/s
The surface tension of 1,3-butadiene, = 4.34 dyne/cm
V
nf
= C
sb

= 5.59"10
-2
= 0.39586 m/s
141

Assume 80% of flooding,
V
n
= 0.8 V
nf

= 0.8(0.39586)
= 0.3167 m/s
The net column area, A
n
= = =
= 5.1413 m
2


Assume that the downcomer occupies 15% of the cross sectional area of the
column. Thus,

Area of column, A
c
=
=
= 6.048 m
2


Diameter of column, D =
=
= 2.7750 m


Number of plates = 35 1
= 34 plates

Functional height = (34-1) "0.31
= 10.23 m


Column Height


The column height is the functional height(between top and bottom plate) plus the
base and vapor space at the bottom and top of column. Assign 30% of the
functional height to the column base and top mass flow.

Actual column height = 10.23 m " 1.3
= 13.299 m
142

4.3 DESIGN OF DISTILLATION COLUMN




4.3.1 Distillation Column D-103




Design basis:

- The feed into the conventional distillation column T-102 with total mass
flow rate of
15504.4987kg/hr at 116C and 4.0 atm.
- Distillation is done under 3.5 atm and 115C at the top of the column
while 4.5 atm and 144C at the bottom of the column.

Design parameters:

- Reflux ratio, R
- Number of tray, N
- The feed stage
- Height of the column, H
- Internal diameter of the column, D


Design criteria:

Distillation is done under moderate pressure condition as the boiling points of C4-
fractions are very low.

Design calculation:

1-butene is being chosen as the light key with the overhead and
n-butane is being chosen as the heavy key.

143

Determining Minimum Trays:
Method used: Fenskes equation
Source: James M. Douglas, Conceptual Desin of Chemical Process, pg 441





Determining Minimum Reflux Ratio:
Method used: Underwoods equation
Source: James M. Douglas, Conceptual Desin of Chemical Process, pg 442


Due to the concentration of n-butane and 1-butene is very less compared to
others, thus, they are not taken into account during the calculation. As the light
key enters at its boiling point, therefore, the q value is 1.




By solving the equation, = 2.9390



Rule of thumb : R=1.2Rmin

Determining Number of Equilibrium Trays:
Method used: Gilliland Correlation
Source: Max S. Peter, Klaus D. Timmerhaus, Ronald E. West, Plant Design and
Economics for Chemical Engineer, pg 772



144







N = 18.44


Determining Actual Trays-Plate Efficiency

Rule of thumb:Tray efficiency for distillation of light hydrocarbons and aqueous
solutions are 60-90%.



Determining the Net Vapor Velocity at Flooding Conditions and the Diameter of
Distillation Column

Source: Max S. Peter, Klaus D. Timmerhaus, Ronald E. West, Plant Design and
Economics for Chemical Engineer, pg 777-778
**Note:

- The net vapor velocity will be obtained at both ends of the column to
determine the maximum allowable vapor velocity and hence maximum
column diameter that will be required.

- The properties for vapor and liquid phases in the distillation column are
obtained by using ASPEN PLUS.

- As the multi-component stream consists of C4 fractions, acetone and
sulfolane, thus, average values of properties such as densities and surface
tensions will be estimated based on the mole fraction of each component
presents in the stream.
145

For top of the column :


=0.9495


Taking tray spacing as 0.91m, Csb obtained = 0.13 m/s. [From figure 15.5,
Plant Design and Economics for Chemical Engineer, pg 778]





= 0.73 m/s


Assuming 80% flooding, Vn = 0.8Vf
= 0.8(0.73)
=0 .58


Net Area,




Assume downcomer occupies 15% of the cross sectional area of the column,


=3.24
So, the top column diameter, D=

146

It is shown that the maximum column diameter happens at the top of the column.
Therefore, the diameter of column D-103 = 2.13 m.

Determining the height of the column:
Source: Max S. Peter, Klaus D. Timmerhaus, Ronald E. West, Plant Design and
Economics for Chemical Engineer, pg 779.

Height of the column,
= (31-1)(0.91)
=27.30 m
Additional height of 15% excess space is required for vapor-liquid disengaging
space at the top of the column and for liquid sump at the bottom of the column.
Therefore, the actual height of the column, Hc=1.15H
=1.15(27.30) m
=31.40 m.



























147

4.4 DESIGN OF ABSORPTION TOWER




4.4.1 Absorption tower (T-101)


Stream 10
Stream 9 Stream 11




Stream 11: 21754.4987 kg/hr
Stream 9: 22219.17 kg/hr
Stream 10: 464.6718 kg/hr
Component


Mole Fraction

Inlet Outlet
S9 S10 S11
C
4
H
10
0.1248 0.0006 0.4825
C
4
H
8
-2 0.0444 0.0008 0.1701
C
4
H
6
0.0779 0.0004 0.3010
H
2
O 0.0091 0.0029 0.0271
CO
2
0.0158 0.0150 0.0179
O
2
0.0474 0.0635 0.0009
N
2
0.5303 0.7143 0.0005
H
2
0.1503 0.2025 0.0000
148


Total: 2661.004 kmol/hr


Step 1: Selecting Type of Packing:
We select the Ceramic Intalox Saddles as our packing material. The size of the
packing material is 1 inch (38mm). Therefore, the packing factor Fp = 170m-1.
(Adapted from Table 11.2, Coulson & Richardsons, Chemical Engineering
Design Volume 6, page 591)


Step 2: Determine the Tower Cross-Sectional Area, AT and Diameter, DT
(CORNELLS Method)
Firstly, we assume the ratio of molar liquid flow rate to molar gas flow rate about
10. Thus, the molar flow rate required is 10 x 2661.004 = 26610.04 kmol/hr.
Molar Gas Flow Rate, Vw* = 2661.004kmol/hr =6.1721kg/s
Molar Liquid Flow Rate, Lw* = 26610.04kmol/hr =61.721kg/s
Gas Density at 40C,v = 0.03698kmol/m3=1.035kg/m3(From Aspen Properties)
Liquid Density at 40C, L= 11.2167kmol/m3 =314.07kg/m3(From Aspen
Properties)
Liquid Viscosity at 40C,L = 3.58x10-4Ns/m2 (From Aspen Properties)


F
LV
= = = 0.574

Component

GAS STREAM
Input
kg/hr kmol/hr kg/s
C
4
H
10
2772.95 47.809 0.7703
C
4
H
8
-2 986.53 17.617 0.2740
C
4
H
6
1730.86 32.053 0.4808
H
2
O 202.19 11.233 0.05617
CO
2
351.06 7.979 0.09752
O
2
1053.19 32.912 0.2926
N
2
11782.83 841.631 3.273
H
2
3339.541 1669.77 0.9277
149

By using the F
LV
value, from the figure 11.44 (Coulson & Richardsons,
Chemical Engineering Design Volume 6), we get the K4 value. We design for a
pressure drop of 20mm H2O/m packing. K4 = 0.6. At flooding K4 = 1.3. From
figure 11.41 and 11.42 (Coulson & Richardsons, Chemical Engineering Design
Volume 6, page 599 and 600)

So, Percentage of Flooding =
The Vw* value =



= 0.54kg/m
2
.s

The column area required, A =
= 11.4298m
2




D =
=
= 3.815 m


Step 3: Determine the Tower Height, H. (CORNELLS Method)

Kinematics Viscosity for liquid, D
L
= 3.19x10-7 m
2
/s
Kinematics Viscosity for gas, D
V
= 4.97x10-6m
2/
s
150

Viscosity for gas,
v
= 1.839 x 10-5 Ns/m
2

Gas Schmidt Number , (Sc)
v
= = 1.839x10
-5
/1.035(4.97x10
-6
)
= 3.58

Liquid Schmidt Number, (Sc)
L
= = 3.58x10
-4
/314.07(3.19x10
-7
)
= 3.573

Liquid mass flow rate per unit area column cross sectional area, kg/m2.s

From figure 11.43, n = 0.1. ( Coulson & Richardson, Chemical Engineering
Design, Vol 6)
For 68% flooding, from Figure 11.41 and 11.42, K
3
= 0.8 and n = 50
H
OG
can be expected to be around 1m, so we estimate of Z=20 m . For gas, f1 =
f2 = f3
= 1.


Height of Liquid Phase Transfer Unit, H
L
=
H
L
= 0.305 n(Sc)
L
. K
3
= 0.305(0.1)(3.573)
0.5
. 0.8
= 0.06115 m


Height of a Gas Phase Transfer Unit, H
G
=

H
G
= 0.011 n (Sc)
v
= = = 2.40568 m


H
OG
= H
G
+m H
L

= 2.40568 + 0.8(0.06115)
= 1.331725 m
151

Height of Column = N
OG
x H
OG estimated

= 8 x 2.4546
= 19.637 m
This value is close enough to the estimated value

" 100% = " 100%
= 1.815%


Where:
K3 = percentage flooding correction factor

n
= HL factor from figure 11.43
Dc = Column Diameter, m
Z = Column Height, m
n = HG factor from figure 11.42

f1 = Liquid viscosity correction factor =
f2 = Liquid density correction factor =
f3 = Surface tension correction factor =

So, the packed bed height is 19.367 m and diameter of column is 3.815 m.















152

4.5 DESIGN OF HEAT EXCHANGER




4.5.1 Heat Exchanger (E-101)




Stream A
T=20C
P=2 atm
=26540.2 kg/hr
Stream B
T=100C
P=2 atm
= 26540.2kg/hr
Stream 7
T=450C
P=2 atm
=65140kg/hr
Stream 7a
T=200C
P=2 atm
=65140kg/hr



- Hot fluid mixture of reaction stream- 7
- Cold fluid water
- Q = Mc
P
t
- Mass flow of liquid mixture, m = 18.09 kg/sec
- Specific heat of liquid mixture, C
p
= 0.5399 KJ/Kg.K
- Outlet temperature = 200
o
C
- Inlet temperature = 450
o
C
- Total amount of heat to be removed, Q = 2441.7 KJ/sec
- Let inlet temperature of water = 20
o
C
- Outlet temperature = 100
o
C
153

Specific heat of water = 4.14 KJ/Kg.K

Mass flow rate of water = 2441.7 / (4.14X80)
= 7.372Kg/sec @ 26540.2 Kg/hr


Routing of fluids :
Water which has the high flow rate is taken in tube side.
Liquid mixture which has viscosity higher than water is taken in shell side.
LMTD:

Liquid mixture Water t
T
hi
= 450
o
C T
co
= 100
o
C 350
o
C
T
ho
= 200
o
C T
ci
= 20
o
C 180
o
C

LMTD = {[(T
hi
T
co
) (T
ho
T
ci
) ] / ln [(T
hi
T
co
) (T
ho
T
ci
) ] }
LMTD = (350 180)/ln(350/180) = 255.65
o
C

R = (T
hi
T
ho
)

/ (T
co
T
ci
)
= (450 200) / (100 20)
= 3.125

S = (T
co
T
ci
)

/ (T
hi
T
ci
)
= ( 100 - 20) / (450 20)
= 0.186

For R = 3.125and S = 0.186

From figure 12.20, correction factor F
T
Coulson and Richardsons Chemical
Engineering Design Vol. 6.
For two shell pass; four or multiple of four tube passes,
F
T
= 0.92


154

(LMTD)
cor
= 0.92 x 255.65
= 207.6

Assumption: (Table 12.1, Chem.Eng, Vol.6)
Overall heat transfer coefficient, U = 200 W/m
2
.
o
C (average typical coefficient
from Table 12.1: Coulson and Richardsons Chemical Engineering Design Vol.
6.)

Area = Q/ (LMTD x U)
= (2441.7 x 10
3
)/ (200 x 207.6)
= 58.8 m
2

Layout and tube size

Using a split-ring floating head for ease of cleaning and can operate in
high differential temperature. High viscosity fluid should circulate on shell side;
steam has higher viscosity than steam, so put air through the tube and steam in
shell. High temperature steam may cause corrosive, so choose stainless steel as
the material of construction for both tubes and shells.

Use 19.05 mm as outside diameter, 14.83 mm as inside diameter and 4.88
meter long tubes on a triangular 23.81 mm pitch (pitch/diameter = 1.25).
(Coulson and Richardsons Chemical Engineering Design Vol. 6)

Calculate number of tubes

Area of one tube (neglecting thickness of tube sheets)
A
tube

= (outside diameter)(length)
= (19.05x10
3
)(4.88)
= 0.2921 m
2
So, number of tubes = A / A
tube

= (58.8 m
2
) / (0.2921 m
2
)
= 201 tubes
For four passes, tubes per pass is 50 tubes
155

Calculate bundle and shell diameter

From Table 12.4: Coulson and Richardsons Chemical Engineering Design Vol. 6
For 4 passes, K
I
= 0.175, n
I
= 2.285
So,
Bundle diameter, D
b
= d
o
(N
t
/K
I
)
1/ nI


Where;
d
o
= outside diameter
N
t
= number of tubes

D
b
= 19.05(201/0.175)
1/ 2.285

= 416.04mm @ 0.416m

For a split-ring floating head exchanger the typical shell clearance from Figure
12.10: Coulson and Richardsons Chemical Engineering Design Vol. 6 is 58 mm,
so shell inside diameter,

Shell diameter, Ds = 416.04mm + 58 mm
= 474 mm (0.474 m)












156

4.5.2 Heat Exchanger (E-102)


Stream B
T=20C
P=2 atm
=15300.4 kg/hr
Stream B
T=100.8C
P=2 atm
= 15300.4kg/hr
Stream 7a
T=200C
P=2 atm
=65140kg/hr
Stream 9
T=40C
P=2 atm
=65140kg/hr



- Hot fluid mixture of reaction stream- 7a
- Cold fluid water
- Q = Mc
P
t
- Mass flow of liquid mixture, m = 18.09 kg/sec
- Specific heat of liquid mixture, C
p
= 0.5399 KJ/Kg.K
- Outlet temperature = 200
o
C
- Inlet temperature = 40
o
C
- Total amount of heat to be removed, Q = 1563.07 KJ/sec
- Let inlet temperature of water = 20
o
C
- Outlet temperature = 100.8
o
C


Specific heat of water = 4.14 KJ/Kg.K

Mass flow rate of water = 2441.7 / (4.14X80)
= 4.25Kg/sec @ 15300.4 Kg/hr
157

Routing of fluids :

Water which has the high flow rate is taken in tube side.
Liquid mixture which has viscosity higher than water is taken in shell side.
LMTD:

Liquid mixture Water t
T
hi
= 200
o
C T
co
= 100.8
o
C 99.2
o
C
T
ho
= 40
o
C T
ci
= 20
o
C 20
o
C

LMTD = {[(T
hi
T
co
) (T
ho
T
ci
) ] / ln [(T
hi
T
co
) (T
ho
T
ci
) ] }
LMTD = (200 100.8) ln (200/100.8) = 144.78
o
C

R = (T
hi
T
ho
)

/ (T
co
T
ci
)
= (200 40) / (100.8 20)
= 1.98

S = (T
co
T
ci
)

/ (T
hi
T
ci
)
= ( 100.8 - 20) / (200 20)
= 0.449

For R = 1.98and S = 0.449

From figure 12.20, correction factor F
T
Coulson and Richardsons Chemical
Engineering Design Vol. 6.
For two shell pass; four or multiple of four tube passes,
F
T
= 0.85

(LMTD)
cor
= 0.85 x 144.78
= 123.06

Assumption: (Table 12.1, Chem.Eng, Vol.6)
158

Overall heat transfer coefficient, U = 200 W/m
2
.
o
C (average typical coefficient
from Table 12.1: Coulson and Richardsons Chemical Engineering Design Vol.
6.)

Area = Q/ (LMTD x U)
= (1563.07 x 10
3
)/ (200 x 123.06)
= 63.5 m
2

Layout and tube size

Using a split-ring floating head for ease of cleaning and can operate in
high differential temperature. High viscosity fluid should circulate on shell side;
steam has higher viscosity than steam, so put air through the tube and steam in
shell. High temperature steam may cause corrosive, so choose stainless steel as
the material of construction for both tubes and shells.


Use 19.05 mm as outside diameter, 14.83 mm as inside diameter and 4.88
meter long tubes on a triangular 23.81 mm pitch (pitch/diameter = 1.25).
(Coulson and Richardsons Chemical Engineering Design Vol. 6)
Calculate number of tubes

Area of one tube (neglecting thickness of tube sheets)
A
tube

= (outside diameter)(length)
= (19.05x10
3
)(4.88)
= 0.2921 m
2


So, number of tubes = A / A
tube

= (63.5m
2
) / (0.2921 m
2
)
= 217.4 tubes
For four passes, tubes per pass is 54 tubes



159

Calculate bundle and shell diameter

From Table 12.4: Coulson and Richardsons Chemical Engineering Design Vol. 6
For 4 passes, K
I
= 0.175, n
I
= 2.285
So,
Bundle diameter, D
b
= d
o
(N
t
/K
I
)
1/ nI


Where;
d
o
= outside diameter
N
t
= number of tubes

D
b
= 19.05(217.4 /0.175)
1/ 2.285

= 430.6mm @ 0.43m

For a split-ring floating head exchanger the typical shell clearance from Figure
12.10: Coulson and Richardsons Chemical Engineering Design Vol. 6 is 58 mm,
so shell inside diameter,

Shell diameter, Ds = 430.6 mm + 58 mm
= 488 mm (0.488 m)


















160

4.5.3 Heat exchanger (E-103)




Step 1: Specification


Stream 13
T=40C
P=4 atm
=6250 kg/hr
Stream 13a
T=30C
P=4 atm
= 6250kg/hr
Stream 1
T=20C
P=4 atm
=5022.363kg/hr
Stream 2
T=24C
P=4 atm
=5022.363kg/hr


Q
S13
= Q
S1
= cT = 83853.36747 kJ/hr
(cT)
water
= 83853.36747 kJ/hr
=
= 5022.363 kg/hr of cooling water


Step 2: Overall Coefficient
For this type of heat exchanger for overall coefficient will be in the range 20-300
W/m.K which is from (Table 12.1), (Coulson & Richardson, Chemical
Engineering Design, Vol 6). So, we start with average value at 150 W/m.K.



161

Step 4: Exchanger Type and Dimensions
With,
Th
1
= 40 C
Th
2
= 30 C
Tc
1
= 20 C
Tc
2
= 24 C

T
m
=
=
= 12.77 C

R =
=
= 2.50

S =
=
= 0.20


Heat duty,Q = 83853.36747kJ/hr X 1hr/3600s
= 23.293 kW
From Table 12.19, (Coulson & Richardson, Chemical Engineering Design, Vol
6), at S=0.20 and R=2.5, F
T
=0.96 which is acceptable.

162

Tm= F
T
T
lm
= 0.96(12.77)
= 12.26 C


Step 5: Heat Transfer Area
Heat transfer area = A
0
=
=
= 12.666m
2


Step 6: Layout and tube sizes

Neither fluid is corrosive and the operating pressure is not high, so a plain carbon
steel can be used for shell and tubes.
The hot stream has large flowrate, so let put it in the tube side and cold stream in
the shell side and then
Use ,

Outside diameter, d0 = 19.05 mm
Inside diameter, di = 16.56 mm Table 12.3, (Coulson &
Richardson, Chemical
Engineering Design, Vol 6)

Length, L = 5.00 m
Tube pitch = square for easy cleaning, 1.25do
= 1.25(19.05)
= 23.8125 mm




163

Step 7: Number of Tubes
Area of one tubes (neglecting thickness of tube sheets) = d
0
L
= (19.05mm)(5.0mm)
= 0.2992 m
2


Total number of tube required =
= 42 tubes

So for 1 passes, total number of tubes required per pass = 42 tubes
Check the tube side velocity at this stage:
Tube cross sectional area = = 0.0002154 m
So, the area per pass = 42"0.0002154
= 0.0090468 m
Volumetric flow rate = "
= 0.002778 m /s
Tube side velocity, u
t
=
=
= 0.3071 m/s








164

Step 8: Bundle and Shell diameter

From Table 12.4, for 1 tube passes K1=0.215, n1=2.207
Source: Table 12.4 page 649
Chemical Engineering Design, Vol 6, Coulson & Richardsons
Constant for use in the heat exchanger calculation

So,
Tube bundle diameter,D
b
= do
= 19.05
= 207.91 mm
= 0.208 m

For a fixed-U tube heat exchanger, the typical shell clearance from Figure 12.10,
(Coulson & Richardson, Chemical Engineering Design, Vol 6, page 663) is 10
mm. So, the shell diameter,

Shell inside diameter, D
s
= (207.91 mm + 10 mm)
= 217.91 mm
= 0.218 m

















165

4.5.4 Condenser (E-106)




Step 1: Specification
























Q
S12b
= cT =942720.8361 kJ/hr

(cT)
water
= 942720.8361 kJ/hr

=
= 15057.033 kg/hr of cooling water
Heat duty, Q

= x 2.38 x (60-40)
= 202.5773KW




166

Step 2: Physical properties

Properties Unit Inlet Mean Outlet
Hot stream
Flow kg/hr 15320.96963
Temperature
0
C 60 50 40
Specific heat kJ/kg.K 2.42 2.38 2.34
Thermal
Conductivity
W/m.K
0.090505 0.09491 0.099315
Density Kg/m
3
418 504.75 591.5
Viscosity M.Ns/m
2
0.26022 0.20317 0.14612
Cold Stream 15057.033
Flow kg/hr 20 27.5 35
Temperature
0
C 27.5 4.185 4.18
Specific heat kJ/kg.K 0.1813 0.179195
Thermal
Conductivity
W/m.K
4.19 4.185 4.18
Density Kg/m
3
1000 1000 1000
Viscosity M.Ns/m
2
0.83547 0.74244 0.64941


Step 3: Overall Coefficient

For this type of heat exchanger for overall coefficient will be in the range 350-900
W/m.K which is from (Table 12.1), (Coulson & Richardson, Chemical
Engineering Design, Vol 6). So, we start with average value at 350 W/m.K.


Step 4: Exchanger Type and Dimensions
With,

Th
1
= 60 C
Th
2
= 40 C
Tc
1
= 35 C
167

Tc
2
= 20T
m
=
=
= 22.407 C

Then,
R =
=
= 1.33

S =
=
= 0.375

From Table 12.19, (Coulson & Richardson, Chemical Engineering Design, Vol
6),pages 657 at S=0.375. and R=1.33, F
T
=0.90 which is acceptable.

Tm= F
T
T
lm
= 0.90(22.407)
= 20.17 C



168

Step 5: Heat Transfer Area


Heat transfer area = A
0
=
=
= 28.7m
2


Step 6: Layout and tube sizes


Neither fluid is corrosive and the operating pressure is not high, so a plain carbon
steel can be used for shell and tubes.
The hot stream has large flowrate, so let put it in the tube side and cold stream in
the shell side and then
Use ,
Outside diameter, d0 = 19.05 mm
Inside diameter, di = 14.83 mm Table 12.3, (Coulson &
Richardson, Chemical
Engineering Design, Vol 6)

Length, L = 5.00 m
Tube pitch = square for easy cleaning, 1.25do
= 1.25(19.05)
= 23.8125 mm


Step 7: Number of Tubes
Area of one tubes (neglecting thickness of tube sheets) = d
0
L
= (19.05mm)(5.0mm)
= 0.2992 m
2


169

Total number of tube required =
= 95.98 tubes ~ 96 tubes

So for 1 passes, total number of tubes required per pass = 96 tubes
Check the tube side velocity at this stage:
Tube cross sectional area = = 0.00017273 m

So, the area per pass = 95"0.00017273 m
= 0.016582 m

Volumetric flow rate = "
= 0.002778 m /s

Tube side velocity, u
t
=
=
= 0.508 m/s







170

Step 8: Bundle and Shell diameter
From Table 12.4, for 1 tube passes K1=0.215, n1=2.207
Source: Table 12.4 page 649
Chemical Engineering Design, Vol 6, Coulson & Richardsons
Constant for use in the heat exchanger calculation
So,
Tube bundle diameter,D
b
= do
= 19.05
= 302.3738 mm
= 0.3023 m

For a fixed-U tube heat exchanger, the typical shell clearance from Figure 12.10,
(Coulson & Richardson, Chemical Engineering Design, Vol 6, page 663) is 10
mm. So, the shell diameter,

Shell inside diameter, D
s
= (0.3023 + 0.053 m)
= 0.3553 m


Step 9: Tubes side heat transfer coefficient

Re =
=
=18716.37

Prandt Number

Pr =
171

=
= 5.0947

L/d
i
=
= 337.154

From figure 12.23 (Coulson & Richardson, Chemical Engineering Design, Vol 6,
page 665)

Re =18716.37 and L/d
i
= 337.154

j
h
= 0.0040


Nu = j
h
x Re x Pr
1/3


= 0.0040 x 18716.37 x (5.0947)
1/3

= 128.8213

h
i
=

=

= 824.439





172

Step 10: Shell side heat transfer coefficient

Kerns method will be used
Db = 0.3023 m refer step 8 same equation
Ds = 0.3553 m


Baffle spacing, lb


b
=
=
= 0.07106 m

Tube pitch
P
t
= 1.25 do
= 1.25 x 0.01905 m
= 0.0238125 m

Cross sectional,As
As =

=
= 5.0495x 10
-3
m
2


Equivalent diamater for square pitch :-
de =

=
= 0.01881 m



173

Volumetric flowrate on shell side :-

V = x x
= 0.0043075 m
3
/s


Shell side velocity

=
=
= 0.85305 m/s


Re =
=
= 21612.3465


Prandt Number

Pr =
=
= 17.3393

Choose 25% battle cut

From figure 12.29 (Coulson & Richardson, Chemical Engineering Design, Vol 6,
page 672)

Re =21612.3465
174

j
h
= 0.0014

Neglecting viscosity correction item

hs= x j
h
x Re x Pr
1/3


= x 0.0014 x 21612.3465 x 17.3393
1/3

= 746.0666 m
2
/K


Step 11: Overall coefficient

= + + + +

= + 0.0005 + + +


= = 244.8514 W/m
2
.K













175

4.5.5 Condenser (E-107)




Step 1: Specification


Q
S13
= Q
S1
= cT = 83853.36747 kJ/hr

(cT)
water
= 83853.36747 kJ/hr

=
= 5022.363 kg/hr of cooling water


Step 2: Overall Coefficient

For this type of heat exchanger for overall coefficient will be in the range 20-300
W/m.K which is from (Table 12.1), (Coulson & Richardson, Chemical
Engineering Design, Vol 6). So, we start with average value at 150 W/m.K.


Step 3: Exchanger Type and Dimensions
With,
Th
1
= 40 C
Th
2
= 30 C
Tc
1
= 20 C
Tc
2
= 24 C



176

T
m
=
=
= 12.77 C

R =
=
= 2.50

S =
=
= 0.20

Heat duty,Q = 83853.36747kJ/hr X 1hr/3600s
= 23.293 kW

From Table 12.19, (Coulson & Richardson, Chemical Engineering Design, Vol
6), at S=0.20 and R=2.5, F
T
=0.96 which is acceptable.

Tm= F
T
T
lm
= 0.96(12.77)
= 12.26 C

177

Step 5: Heat Transfer Area

Heat transfer area = A
0
=
=
= 12.666m
2


Step 6: Layout and tube sizes

Neither fluid is corrosive and the operating pressure is not high, so a plain carbon
steel can be used for shell and tubes.
The hot stream has large flowrate, so let put it in the tube side and cold stream in
the shell side and then
Use ,
Outside diameter, d0 = 19.05 mm
Inside diameter, di = 16.56 mm Table 12.3, (Coulson &
Richardson, Chemical
Engineering Design, Vol 6)
Length, L = 5.00 m
Tube pitch = square for easy cleaning, 1.25do
= 1.25(19.05)
= 23.8125 mm


Step 7: Number of Tubes

Area of one tubes (neglecting thickness of tube sheets) = d
0
L
= (19.05mm)(5.0mm)
= 0.2992 m
2


178

Total number of tube required =
= 42 tubes
So for 1 passes, total number of tubes required per pass = 42 tubes
Check the tube side velocity at this stage:
Tube cross sectional area = = 0.0002154 m
So, the area per pass = 42"0.0002154
= 0.0090468 m

Volumetric flow rate = "
= 0.002778 m /s
Tube side velocity, u
t
=
=
= 0.3071 m/s


Step 8: Bundle and Shell diameter
From Table 12.4, for 1 tube passes K1=0.215, n1=2.207
Source: Table 12.4 page 649
Chemical Engineering Design, Vol 6, Coulson & Richardsons
Constant for use in the heat exchanger calculation
So,

Tube bundle diameter,D
b
= do
= 19.05
= 207.91 mm = 0.208 m
179


For a fixed-U tube heat exchanger, the typical shell clearance from Figure 12.10,
(Coulson & Richardson, Chemical Engineering Design, Vol 6, page 663) is 10
mm. So, the shell diameter,

Shell inside diameter, D
s
= (207.91 mm + 10 mm)
= 217.91 mm
= 0.218 m




4.6 DESIGN OF REBOILER




4.6.1 Reboiler (E-104)


- This is a kettle reboiler using U-tube
- Do = 30mm, Di = 25mm
- Nominal tube length = 10.4 m
- Inlet temperature of bottom product = 34
- Desired temperature for vapor = 110
- Heating medium = Downtherm A, 160

Step 1: Specification


The heat dutys calculated from energy balance (Stream 12)
Heat duty = 1129962.79 kJ/hr + 5% heat loss
= 1186460.93 kJ/hr
1186460.93 kJ/hr " 1hr/3600s = 329.572 kW






180

Step 2: Physical Properties

Component Mole
fraction,x
Surface
tension,
(dyne/cm)
at 34
Liquid
density,
L
(kg/m!)
at 34
Vapor
density,
v
(kg/m!)
at 110
Latent
heat
(kJ/kg)
C
4
H
10
0.675 10.27 510.13 1.241 408.726
C
4
H
8-2
0.323 11.59 533.25 1.133 417.5014
C
4
H
6
0.002 12.78 565.29 1.069 523.71


Average surface tension,
ave
= 11.55 dyne/cm
Average liquid density,
L ave
= 536.22 kg/m
Average vapor density,
v ave
= 1.148 kg/m
Average latent heat,
ave
= 449.98 kg/m


Step 3: Overall Coefficient

U
0
is 1000 W/ .m which is estimated from Figure 12.1 Coulson &
Richardsons, Chemical Engineering Design Volume 6 .


Step 4: Exchanger Type and Dimension

Tm = True mean temperature difference
= 155 - 110
= 45


Step 5: Heat Transfer Area

A = Q/U Tm
=
= 7.324 m

181

Step 6: Layout and Tube Side

This is a kettle reboiler design using U-tube.
Neither fluid is corrosive nor operating pressure is too high, plain carbon
steel can be used for the shell and tube.
Saturated dowtherm A will flow inside the tube while the bottom products
from distillation column will flow in the shell.
Outside diameter of the tube is chosen as 30mm while inside diameter of
the tube is chosen as 25mm.
Use square pitch arrangement = 1.5 " (D
o
of tube)
= 1.5(30mm)
= 45mm
The nominal length of the tube is 10.2m on a square 45mm pitch.


Step 7: Number of Tubes

Area of one tube (neglecting the thickness of tube sheet)
A = DL = (30"10
-3
)(4.8)
= 0.4524 m

Number of tubes =
=
= 16.2 16 tubes

Take minimum bend radius = 1.5 d
o

= 1.5(30) = 45 mm

Total number of tube, Nt= 2"16
= 32 tubes

182

Step 8: Heat Flux, Pool Boiling Coefficent and Overall Heat Transfer
Coefficent

Heat flux, q=
=
= 44.999 kW/m

Checking for maximum allowable heat flux,
For square arrangement, K
b
= 0.44

qcb = Kb
= 0.44

= 156.963kW/m

Applying a factor of 0.7, maximum flux should not exceed 0.70"156.963 =
109.87kW/m
Actual flux of 44.999 kW/m is well below maximum allowable.
Operating pressure: 4.5 bar, Critical pressure = 48.2 bar
By using Mostinskis Equation, pool boiling coefficient,

h
nb
= 0.104(Pc)
0.69
(q)
0.7

=
0.104(48.2)
0.69
(0.044999)
0.7
= 3912.823 W/m .



183

Taking downtherm A condensing coefficient as 6000 W/m .
Downtherm A fouling as 5000 W/m .
Bottom product fouling coefficient as 5000 W/m .
Conductivity of plain carbon steel ,k
w
as 45 W/m .

Calculating Overall Heat Transfer Coefficient

= + + + " + "
= + + + " + "
U
0
= 1032.01 Wm .


Error = " 100%
= " 100%
= 3.20%


Therefore, the overall heat transfer coefficient calculated is close enough to the
original estimated one for the design to stand.


Step 9: Bundle Diameter and Shell Diameter
From Table 12.4, Coulson & Richardsons, Chemical Engineering Design
Volume 6, for two-tubes passes, K
1
= 0.156, n
1
= 2.291




184

Db = d0
= 30
= 306.407 mm

Taking shell diameter as twice bundle diameter, D
s
= 2 306.407
= 612.814 mm


Step 10: Layout and Vapour Velocity
Taking liquid level as 400 mm from base, freeboard = 612.814 400
= 212.814 mm (satisfactory)

Surface area of liquid =
= 0.6837 m




4.6.2 Reboiler (E-105)



- This is a kettle reboiler using U-tube
- Do = 30mm, Di = 25mm
- Nominal tube length = 10.4 m
- Inlet temperature of bottom product = 110
- Desired temperature for vapor = 200
- Heating medium = Downtherm A, 240




185

Step 1: Specification

The heat dutys calculated from energy balance (Stream 16a)
Heat duty = 1252933.62 kJ/hr + 5% heat loss
= 1315580.35 kJ/hr
1186460.93 kJ/hr " 1hr/3600s = 365.43892 kW

Step 2: Physical Properties

Component Mole
fraction,x
Surface
tension,
(dyne/cm)
at 40
Liquid
density,
L
(kg/m!)
at 40
Vapor
density,
v
(kg/m!)
at 200
Latent
heat
(kJ/kg)
C
4
H
10
0.575 15.57 579 10.64 408.726
C
4
H
8-2
0.425 13.98 604 10.27 417.5014

Average surface tension,
ave
= 14.775 dyne/cm
Average liquid density,
L ave
= 591.5 kg/m
Average vapor density,
v ave
= 10.455 kg/m
Average latent heat,
ave
= 413.11 kg/m


Step 3: Overall Coefficient

U
0
is 1000 W/ .m which is estimated from Figure 12.1 Coulson &
Richardsons, Chemical Engineering Design Volume 6 .


Step 4: Exchanger Type and Dimension

Tm = True mean temperature difference
= 240 - 200
= 55
186

Step 5: Heat Transfer Area
A = Q/U Tm
=
= 9.13 m


Step 6: Layout and Tube Side

This is a kettle reboiler design using U-tube.
Neither fluid is corrosive nor operating pressure is too high, plain carbon
steel can be used for the shell and tube.
Saturated dowtherm A will flow inside the tube while the bottom products
from distillation column will flow in the shell.
Outside diameter of the tube is chosen as 30mm while inside diameter of
the tube is chosen as 25mm.
Use square pitch arrangement = 1.5 " (D
o
of tube)
= 1.5(30mm)
= 45mm
The nominal length of the tube is 10.2m on a square 45mm pitch.


Step 7: Number of Tubes

Area of one tube (neglecting the thickness of tube sheet)
A = DL = (30"10
-3
)(4.8)
= 0.4524 m


Number of tubes =
=
= 20.2 20 tubes
187

Take minimum bend radius = 1.5 d
o

= 1.5(30) = 45 mm
Total number of tube, Nt= 2"20
= 40 tubes

Step 8: Heat Flux, Pool Boiling Coefficent and Overall Heat Transfer
Coefficent

Heat flux, q=
=
= 40.026 kW/m
Checking for maximum allowable heat flux,
For square arrangement, K
b
= 0.44

qcb = Kb
= 0.44
= 432.6kW/m

Applying a factor of 0.7, maximum flux should not exceed 0.70"432.6.63 =
302.82kW/m

Actual flux of 40.026 kW/m is well below maximum allowable.

Operating pressure: 4.5 bar, Critical pressure = 40.2 bar

By using Mostinskis Equation, pool boiling coefficient,
h
nb
= 0.104(Pc)
0.69
(q)
0.7

= 0.104(40.2)
0.69
(0.040026)
0.7
= 4758.823 W/m .

188

Taking downtherm A condensing coefficient as 6000 W/m .
Downtherm A fouling as 5000 W/m .
Bottom product fouling coefficient as 5000 W/m .
Conductivity of plain carbon steel ,k
w
as 45 W/m .
Calculating Overall Heat Transfer Coefficient
= + + + " + "
= + + + " + "

U
0
= 1032.01 Wm .

Error = " 100%
= " 100%
= 3.20%

Therefore, the overall heat transfer coefficient calculated is close enough to the
original estimated one for the design to stand.


Step 9: Bundle Diameter and Shell Diameter
From Table 12.4, Coulson & Richardsons, Chemical Engineering Design
Volume 6, for two-tubes passes, K
1
= 0.156, n
1
= 2.291

Db = d0
= 30
= 337.75 mm

Taking shell diameter as twice bundle diameter, D
s
= 2 337.75
= 675.5 mm
189

Step 10: Layout and Vapour Velocity
Taking liquid level as 400 mm from base, freeboard = 675.5 400
= 275.85 mm (satisfactory)

Surface area of liquid =
= 0.3376 m




4.7 DESIGN OF PUMP




4.7.1 P-102A/B


Calculation Power of Pump
Average density = 600 kg/m
We take, = 0.8

(Ref, Mc Cabe Smith Harriot,Unit Operation of Chemical Engineering Sixth
Edition)

Mass flow rate = 21754.4987 kg/hr

Volume flow rate,v =
=
= 36.2575 m /hr



190

P (shaft Power) =
=
= 2.1303 kW

Power delivered to liquid = 0.8 2.1304
= 1.7042 kW

By assuming no velocity difference,
Head = = 5m = 22.21 m




4.7.2 P-103A/B




Calculation Power of Pump

Average density = 600 kg/m
We take, = 0.8

(Ref, Mc Cabe Smith Harriot,Unit Operation of Chemical Engineering Sixth
Edition)

Mass flow rate = 2419.26 kg/hr

Volume flow rate,v =
=
191

= 9.0353 m /hr


P (shaft Power) =
=
= 551.459 kW

Power delivered to liquid = 0.8 2.1304
= 441.1675 kW
By assuming no velocity difference,
Head = = 7m = 45. m




4.7.3 P-104A/B




Calculation Power of Pump

Average density = 3615.22 kg/m
We take, = 0.8

(Ref, Mc Cabe Smith Harriot,Unit Operation of Chemical Engineering Sixth
Edition)

Mass flow rate = 2073.86 kg/hr

Volume flow rate,v =
=
= 10.3563 m /hr
P (shaft Power) =
192

=
= 608.4784 kW

Power delivered to liquid = 0.8 608.4784 kW
= 486.7828 kW

By assuming no velocity difference,
Head = = 7m = 11.98 m




4.8 DESIGN OF COMPRESSOR




4.8.1 Compressor (C-101A/B)




T=20C T=25C
P
inlet
= 0.95 atm P
outlet
= 1 atm









Component, x Mole fraction @ 25
o
C and 1
atm, (kg/m
3
),
Mass flow rate,
(kg/hr), m
x

C
4
H
10
1.0 4.2 6885.3731


Design criteria:

The function of this compressor (C-101A/B) is to move n- butane gases stream to
the reactor.

193

Design basis:
The type of compressor that we used is centrifugal compressor

i) Calculate volumetric flow rate, V (m
3
/s):

= 6885.3731 kg/hr 4.2 kg/m
3

0.4554 m
3
/s

ii) Calculate the poly tropic efficiency of centrifugal compressor:
The equation is referring to Chemical Process Design and Integration
Handbook by Robin Smith, 2005 (ms274):
,
Where,
= poly tropic efficiency
volumetric flow rate, (m
3
/s)

= 0.017 ln ( ) + 0.7
= 0.6866

iii) Calculate poly tropic coefficient:
n= / ( + 1),
Where,
= Cp/Cv = ratio of heat capacity
Refer to Chemical Process Design and Integration Handbook by
Robin Smith, 2005 (ms274):
From table 13.8, typical value of for polyatomic gas is 1.30
n = (1.30 x 0.6866)/ (1.30 x 0.6866) 1.30 +1
n= 1.5063

iv) Calculate the power of centrifugal compressor, W (kW):

W=
194


W=


W= 0.0320 atm.m
3
/s
W=3242.4 J = 3.2424 kW




4.8.2 Compressor (C-102A/B)




T=20C T=25C
P
inlet
= 0.95 atm P
outlet
= 1 atm








Component, x Mole fraction
x
@ 25
o
C and
1 atm, (kg/m
3
),
Mass flow rate,
(kg/hr), m
x

O
2
0.2853 1.308 4303.5621
N
2
0.5718 1.251 8625.2254
H
2
0.1429 0.0899 2155.5521


Design criteria:

The function of this compressor (C-102 A/B) is to move air stream to the reactor.






195

Design basis:
The type of compressor that we used is centrifugal compressor

i) Calculate volumetric flow rate, V (m
3
/s):

mix
= 1.1013 kg/m
3
V= 15084.3396 kg/hr 1.1013 kg/m
3
V= 3.8047 m
3
/s

ii) Calculate the poly tropic efficiency of centrifugal compressor:
The equation is referring to Chemical Process Design and Integration
Handbook by Robin Smith, 2005 (ms274):

,
Where,
= poly tropic efficiency
volumetric flow rate, (m
3
/s)

= 0.017 ln (3.8047 m
3
/s) + 0.7
= 0.7229

iii) Calculate poly tropic coefficient:
n= / ( + 1),
Where,
= Cp/Cv = ratio of heat capacity
Refer to Chemical Process Design and Integration Handbook by
Robin Smith, 2005 (ms274):
From table 13.8, typical value of for diatomic gas is 1.40
n = (1.40 x 0.7229/ (1.40 x 0.7229) 1.40 +1
n= 1.6535

iv) Calculate the power of centrifugal compressor, W (kW):

W=
196

W=


W= 0.2539 atm.m
3
/s
W=25724.6116 J = 25.7246 kW




4.8.3 Compressor (C-103A/B)




T=97C T=100C
P
inlet
= 0.95 atm P
outlet
= 1 atm







Component, x Mole fraction

@ 100
o
C and
1 atm, (kg/m
3
),
Mass flow rate,
(kg/hr), m
x

H
2
0 1.0 0.596 5341.7169


Design criteria:

The function of this compressor (C-103 A/B) is to move steam stream to the
reactor.







197

Design basis:
The type of compressor that we used is centrifugal compressor


i) Calculate volumetric flow rate, V (m
3
/s):

= 0.596 kg/m
3
V= 5341.7169 kg/hr 0.596 kg/m
3
V= 2.4896 m
3
/s

ii) Calculate the poly tropic efficiency of centrifugal compressor:
The equation is referring to Chemical Process Design and Integration
Handbook by Robin Smith, 2005 (ms274):
,
Where,
= poly tropic efficiency
volumetric flow rate, (m
3
/s)

= 0.017 ln (2.4896 m
3
/s) + 0.7
= 0.7155

iii) Calculate poly tropic coefficient:
n= / ( + 1),
Where,
= Cp/Cv = ratio of heat capacity
Refer to Chemical Process Design and Integration Handbook by
Robin Smith, 2005 (ms274):
From table 13.8, typical value of for polyatomic gas is 1.30
n = (1.30 x 0.7155/ (1.30 x 0.7155) 1.30 +1
n= 1.4761

ii) Calculate the power of centrifugal compressor, W (kW):

W=
198

W=


W= 0.1681 atm.m
3
/s
W = 17032.7325 J = 17.0327 kW




4.8.4 Compressor (C-104A/B)




T= 550C T=560C
P
inlet
= 1 atm P
outlet
= 1.10 atm







Component, x Mole fraction
x
@ 550
o
C and 1
atm, (kg/m
3
),
Mass flow rate,
(kg/hr), m
x

C
4
H
10
0.1860 4.2 6885.3731
C
4
H
8-1
0.0614 2.38 2272.9135
C
4
H
8-2
0.1316 2.417 4871.5857
C
4
H
6
0.0127 2.36 470.1303
H
2
O 0.1443 0.314 531.7169
CO
2
0.0065 1.977 240.6179
O
2
- 1.308 -
N
2
0.2370 1.251 8773.2980
H
2
0.2245 0.0899 8310.5713



199

Design criteria:

The function of this compressor (C-104A/B) is to move mixture of gases stream
to the reactor.

Design basis:
The type of compressor that we used is centrifugal compressor
i) Calculate volumetric flow rate, V (m
3
/s):

mix
= 1.4229 kg/m
3

= 37018.135 kg/hr 1.4229 kg/m
3

7.2265 m
3
/s

ii) Calculate the poly tropic efficiency of centrifugal compressor:
The equation is referring to Chemical Process Design and Integration
Handbook by Robin Smith, 2005 (ms274):
,
Where,
= poly tropic efficiency
volumetric flow rate, (m
3
/s)

= 0.017 ln ( ) + 0.7
= 0.7336

iii) Calculate poly tropic coefficient:
n= / ( + 1),
Where,
= Cp/Cv = ratio of heat capacity
Refer to Chemical Process Design and Integration Handbook by
Robin Smith, 2005 (ms274):
From table 13.8, typical value of for polyatomic gas is 1.30
n = (1.30 x 0.7336)/ (1.30 x 0.7336) 1.30 +1
n= 1.4589

200

iv) Calculate the power of centrifugal compressor, W (kW):

W=

W=


W= 0.9238 atm.m
3
/s
W=93607.3413 J = 93.6073 kW




4.8.5 Compressor (C-105 A/B)




T= 20C T=25C
P
inlet
= 0.95 atm P
outlet
= 1.0 atm







Component, x Mole fraction
x
@ 25
o
C and
1 atm, (kg/m
3
),
Mass flow rate,
(kg/hr), m
x

O
2
0.21 1.308 2605.6283
N
2
0.79 1.251 9802.1257


Design criteria:

The function of this compressor (C-105A/B) is to move oxygen gases stream to
the reactor.

201

Design basis:
The type of compressor that we used is centrifugal compressor

i) Calculate volumetric flow rate, V (m
3
/s):

=
1.1854 kg/m
3


= 12407.754 kg/hr 1.1854 kg/m
3

2.9075 m
3
/s

ii) Calculate the poly tropic efficiency of centrifugal compressor:
The equation is referring to Chemical Process Design and Integration
Handbook by Robin Smith, 2005 (ms274):
,
Where,
= poly tropic efficiency
volumetric flow rate, (m
3
/s)

= 0.017 ln ( ) + 0.7
= 0.7181

iii) Calculate poly tropic coefficient:
n= / ( + 1),
Where,
= Cp/Cv = ratio of heat capacity
Refer to Chemical Process Design and Integration Handbook by
Robin Smith, 2005 (ms274):
From table 13.8, typical value of for diatomic gas is 1.40
n = (1.40 x 0.7181)/ (1.40 x 0.7181) 1.40 +1
n= 1.6608



202

iv) Calculate the power of centrifugal compressor, W (kW):

W=

W=


W= 0.2056 atm.m
3
/s
W= 20828.0861 J = 20.8281 kW





4.8.6 Compressor (C-106A/B)




T=450C T=470C
P= 1 atm P= 2 atm






Component


Mass Flow
rate(kg/hr)

Outlet
7
C
4
H
10
10052.60487
C
4
H
8
-1 0
C
4
H
8
-2 4574.5534
C
4
H
6
6267.423474
H
2
O 1430.380107
CO
2
1293.42882
H
2
12106.87418
O
2
3804.202412
N
2
42702.17207
203

Design criteria

The function of this compressor (P-106) is to compress the nitrogen, hydrogen,
carbon dioxide and oxygen.
Design basis
- We know that a pressure drop (P) of 1 atm in the pipeline from the
compressor to the discharge point.
- The pressure of the fluid at the inlet, P1 = 1atm and pressure of the fluid at
the compressor outlet, P2 = 2 atm
- The inlet temperature is 450 C, the calculated outlet temperature is
470C.

Design Calculations
Tout =470 C

- For this stream, we assume for diatomic gases which compression ratio =
4, because the specific heat ratio is 1.4 (heuristic rules). Thus, number of
stage, n

(2/1)
1/n
= 4
n= 0.5 1
- The mixture of the stream is assume to be diatomic, thus K = 1.4
A= (1.4-1)/1.4
= 0.2857

Power, P
P = (3804.202412+42702.17207) kmol /hr "8.314 " 373K"1.0
"
=1170273.04 kJ/ hr
=1170.27 kW

- From the heuristic, assuming efficiency of 80%. Thus, actual power of the
compressor, P
actual


P
actual
=
=1170.27 / 0.80
= 1462.84kW
204

4.8.6 Compressor (C-107A/B)




T=500C T=510C
P
inlet
= 1 atm P
outlet
= 1.5atm









Component, x Mole fraction
x
(kg/m
3
), Mass flow rate,
(kg/hr), m
x

C
4
H
10
0.1057 2.48 6885.37
N2 0.4490 1.251 29248.18
H2 0.1273 0.0899 8292.41


Design criteria:

The function of this compressor (C-106) is to move gases stream to the heat
exchanger.

Design basis:
The type of compressor that we used is centrifugal compressor

i) Calculate volumetric flow rate, V (m
3
/s):

= 44425.96 kg/hr 2.48m
3
/kg
4.976 m
3
/s

ii) Calculate the poly tropic efficiency of centrifugal compressor:
The equation is referring to Chemical Process Design and Integration
Handbook by Robin Smith, 2005 (ms274):

,
205

Where,
= poly tropic efficiency
volumetric flow rate, (m
3
/s)

= 0.017 ln ( ) + 0.7
= 0.7273

iii) Calculate poly tropic coefficient:
n= / ( + 1),
Where,
= Cp/Cv = ratio of heat capacity
Refer to Chemical Process Design and Integration Handbook by
Robin Smith, 2005 (ms274):
From table 13.8, typical value of for polyatomic gas is 1.30
n = (1.30 x 0.7273/ (1.30 x 0.7273) 1.30 +1
n= 1.4648

iv) Calculate the power of centrifugal compressor, W (kW):

W=

W=

W= 0.260304 atm.m
3
/s
W=26030 W= 26.03 kW







206

4.9 DESIGN OF STORAGE TANK




4.9.1 Storage Tank TK-1




Design criteria

To collect butadiene from the separation process before it goes to consumer. The
tank is design for the volume of 2 hours for the inlet mass flow.

Design Parameter
Volume of the storage tank
Diameter and height of the tank
Type of the tank

Design Basis
Total inlet flow rate : 6250 kg/hr
Temperature : 30
Pressure : 1.0 atm

Design Calculation

butadiene
= 54 kg/m
Volumetric flow rate =
=
= 115.74 m /hr


207

Retention time = 2 hours
Volume of the product for 2 hours = 115.74 m /hr " 2h
= 231.48 m

The storage tank is designed as 25% bigger than the product volume.
V= (1.25) " (231.48)
= 289.35 m

Assume L/D = 3


= "
= " 3
D = 122.8
D = 4.97 m
L = D " 3
= 4.97 " 3
= 14.91 m

So, the diameter of storage tank is 4.97m and height is 14.91m.
The storage tank is designed as horizontal tank on concrete supports.


4.9.2 Storage Tank TK-2
Design criteria
To collect 1-butene from the separation process before it goes to consumer. The
tank is design for the volume of 2 hours for the inlet mass flow.

Design Parameter
Volume of the storage tank
Diameter and height of the tank
Type of the tank
208

Design Basis
Total inlet flow rate : 7117.66732 kg/hr
Temperature : 34
Pressure : 1.0 atm

Design Calculation

1-Butene
= 600 kg/m
Volumetric flow rate =
=
= 11.863 m /hr

Retention time = 2 hours
Volume of the product for 2 hours = 11.863 m /hr " 2h
= 23.726 m

The storage tank is designed as 25% bigger than the product volume.
V= (1.25) " (23.726)
= 29.656 m

Assume L/D = 3


= "
= " 3
D = 12.58
D = 2.33 m
L = D " 3
= 2.33 " 3
= 6.978 m
209

So, the diameter of storage tank is 2.33m and height is 6.978m.
The storage tank is designed as horizontal tank on concrete supports.



















210



CHAPTER 5




PROCESS SAFETY STUDIES




5.1 Introduction


Safety has to be an integral part of any process plant. Safe facilities that
meet performance and economic requirements are in the best interest of all
concerned parties. Unless personnel know and understand the principles behind
process and plant safety, there is an increased risk of accidents that could result in
injuries, illness, fatalities and loss property. The importance of a safety review is
being recognized as an important risk management tool. Failure to identify risks
to safety, and the according inability to address or "control" these risks, can result
in massive costs, both human and economic. The multidisciplinary nature of
safety engineering means that a very broad array of professionals is actively
involved in accident prevention or safety engineering. The majority of those
practicing safety engineering are employed in industry to keep workers safe on a
day to day basis All manufacturing processes are to some extent hazardous but in
chemical processes, there are additional, special hazards associated with the
chemicals used and the process condition. It is very important to ensure the risks
and hazards of chemical processes are reduced to acceptable level. Therefore
identifying all potential hazards can control accidents and hazards.


In this chapter, general process safety will be discussed. Hazard and
operability (HAZOP) studies also discussed to identify the potential hazards
associated with operation of the plant and consequently, the appropriate actions to
be taken. Appraisals of plant safety should be prepared as long before construction
211

is started. This mean, the safety aspects should be considered as soon as new plant
is conceived or design begun. The plant safety is managed by taken many parties
into consideration. Generally, it is conducted by plant safety personnel, safety
committee members, and plant or department managers and together with other
related department or agencies include fire prevention personnel, insurance
company engineers or municipal, state, or federal agency representatives.
Checklists are often used to evaluate many safety features in industrial plants
which represented as question asking the specific requirements in the standards. It
can be prepared from numerous sources concern on to determine whether or not a
plant can comply with Occupational Safety and Health Act (OSHA) standards.


The chemical industry has traditionally dedicated considerable attention to
safety, beginning with the research and development new processes through plant
design and construction. In chemical plant, the main hazards are toxic and
corrosive chemicals, explosions, fires and accidents common to all industrial
activities. The Health and Safety at Work (Act 1947) provided a new legal
administrative framework to promote, simulate and encourage even higher
standards of health and safety at work.


It has been found that after many years of improvements in technical
safety methods and process design, many organizations have found that accident
rates, process plant losses and profitability have reach a level beyond which
further improvements seem impossible to achieve. Another findings are that
even in organizations with good general safety records, occasional large scale
disasters occurs which shake public confidence in the chemical process industry
(Guidelines for preventing human error in Process Safety, 1994).


Besides, some hazardous in chemical plant processes are still to be avoided
by all the manufacturing process (R.K Sinnott et el, 1983). In this chapter of
process safety studies as well as special hazards of chemicals shall be reviewed.
Also in this chapter the procedure to start-up and shutdown in general will be
considered.

212

5.2 Identification of Hazard


The hazard identification methods include process hazard checklist,
hazards surveys, HAZOP and safety review. One of the major characteristics of
the HAZOP study is to identify potential hazards such as the corrosive and
toxicity. This is essential to identify the hazards and reduce the risk well in
advance of an accident as well as a guideline to protect the worker.




5.2.1 Corrosive


A Corrosive material is one which causes damage to skin, eyes or other
parts on the body on contact. The technical definition is written in terms of
"Destruction or irreversible damage to living tissue at the site of contact"


Often this damage is caused directly by the chemical, but the action of
some corrosive materials is a consequence of inflammation which they may cause.
Concentrated acids are obvious examples of corrosive materials, but even dilute
solutions of bases such as sodium or ammonium hydroxide may also be very
corrosive, particularly in contact with the eyes.




5.2.2 Toxicity


The potential hazard will depend on the inherent toxicity of the material
and the frequency and duration of any exposure. The inherent toxicity of a
material is measured by tests on animals which are usually expressed as the lethal
dose (LD
50
) at which 50% of the test animals are killed. These definitions apply
only to the short-term effects. Another symbol describing toxicity is Threshold
Limit Value (TLV) for controlling long-term exposure of workers to
contaminated air. Toxicity is often subdivided into:
213

- Acute toxicity adverse effects are observed within a short time of exposure to
the chemical. This exposure may be a single dose, or a short continuous
exposure, or multiple doses administered over 24 hours or less.

- Subacute (subchronic) toxicity adverse effects are observed following
repeated daily exposure to a chemical, or exposure for a significant part of an
organism's lifespan (usually not exceeding 10%). With experimental animals,
the period of exposure may range from a few days to 6 months.

- Chronic toxicity adverse effects are observed following repeated exposure to a
chemical during a substantial fraction of an organism's lifespan (usually more
than 50%). For humans, chronic exposure typically means several decades; for
experimental animals, it is typically more than 3 months. Chronic exposure to
chemicals over periods of 2 years using rats or mice may be used to assess the
carcinogenic potential of chemicals.




5.2.3 Flammable


The flammability term is to describe materials that will burn. Flammable
material depends on a number of factors:




5.2.3.1 Flash point


The flash-point is a measure of the ease of ignition of the liquid. It is a
function of the vapor pressure and the flammability limits of the material.




214

5.2.3.2 Flammability limits


The flammability limits of a material are the lowest and highest
concentrations in air, at normal pressure and temperature, at which a flame will
propagate through the mixture. It is differ widely for different materials.




5.3 Control of Hazard Analysis


5.3.1 1,3-Butadiene


1,3-Butadiene is a product that we get from oxidative dehydrogenation of
n-butene which is colorless gas with a mild, aromatic, gasoline-like odor. The
vapor is heavier than air and commercially available as a liquefied gas (under
pressure) with a stabilizer added for shipment. It is an important industrial uses as
monomer in the production of synthetic rubber. It is colorless gas or refrigerated
liquid with boiling point -4.4C. It needs to be storage in area below 40C. 1,3-
butadiene always be marketed and transported as a liquefied gas under pressure.


Health Concerns:

- At acute exposure, damage to the central nervous system will occur.
Symptoms such as distorted blurred vision, vertigo, general tiredness,
decreased blood pressure, headache, nausea, decreased pulse rate and fainting
may be witnessed. Several studies show that 1,3-Butadiene exposure
increases risk in cardiovascular diseases and cancer. It also can cause
irritation with redness to skin and eyes. Exposure to liquid may cause
frostbite.

- While handling this substance, we need to take precaution step as protections.
Whenhandling the substance, the person in-charged needs to use chemical
protective clothing(CPC) like polyvinyl chloride gloves to prevent contact
215

with chemicals that can injure or be absorbed through the skin. The level of
protection selected should be based on the potential butadiene concentration
and likelihood of contact.

Safety concerns:

- 1,3-Butadiene is non-corrosive but highly flammable substance and can forms
explosive mixtures with air and oxidizing agents. It also sensitive to impact,
so container should be avoid from impact. Its extinguish media are CO2, dry
chemical, water spray or fog. As precautions, the substances need to be store
and use with adequate ventilation. The storage vessel should be enclosed
within fire banks.

- All vessels for storage and handling liquefied the substances should meet
recognized code requirements, such as ASME Code for Unfired Pressured
Vessels. The vessels and pipes should be the quality of solid masonry,
concrete or steel. If steel is used, it should be protected against fire exposure.
All parts of the storage system should be electrically connected to one another
and to a common ground in a way that will prevent the accumulation of static
electrical charge.

- Pressure relief valves should be connected to a burning stack or flare system
provided with a positive means of ignition. Totally enclosed gauging devices
generally should be used.

Environmental concerns:

- 1,3-butadiene is an unstable chemical substance and spontaneously
flammable or explosive peroxides when exposure to air. Thermal
decomposition or burning may produce carbon monoxide or carbon dioxide.

216

- No adverse ecological effect is expected. This product does not contain any
Class I or Class II ozone-depleting chemicals. The components of this
mixture are not listed as marine pollutants by TDG Regulations too.




5.3.2 n-Butane


n-butane which is consists of 1-butene, cis-2-butene and trans-2-
butene are being used as raw material in the oxidative dehydrogenation process to
produce 1,3-butadiene. However, only 1-butene is being discussed. Its boiling
point is 20.8C (-6.25F) with vapor pressure 263.3 kPa at 20C.

Health Concerns:

- At overexposure, it can cause asphyxiant and death due to the lack of
oxygen. Moderateconcentration of 1-butene may cause headaches,
drowsiness, dizziness, excitation, excess salivation, vomiting and
unconsciousness. It also can cause frostbite to skin and eyes when it is in
liquid phase.

- Precaution should be taken when handling the substance. Handler should
use respirable fume respirator or air supplied respirator when working in
confined space or where local exhaust or ventilation does not keep exposure
below TLV. They also need to wear safety gloves and glasses when
handling cylinders that contain 1-butene.

Safety concerns:

- The substances are flammable and high pressure gas. It may form explosive
when mixing with air. The cylinders should be protected from damage by
using suitable hand truck to move the cylinders; do not drag, roll, slide or
217

drop it. Never attempt to lift a cylinder by its cap; the cap is intended solely
to protect the valve.

- Never insert an object into cap openings; doing so may damage the valve
and cause a leak. Precautions should be taken also in storage the substance.
The cylinders should be separated from oxygen, chlorine, and other
oxidizers material. Firmly secure cylinders upright to keep them from
falling or being knocked over. There must be no sources of ignition and all
electrical equipment in storage areas must be explosion proof. Storage
areas must in temperature below 52C.
Environmental concerns:

- 1-butene does not contain any Class I or Class II ozone-depleting chemicals.

- The components of this mixture are not listed as marine pollutants by TDG
Regulations.




5.3.3 n-methyl-2-pyrrolidone


n-Methyl-2-Pyrrolidone (NMP) is a solvent that is being used in
purification process ofcrude butadiene. It is colorless hygroscopic liquid with
characteristic odor. Its boiling point is 202C and flash point is 96C.


Health Concerns:

- NMP also can cause dry, redness and maybe absorbed to skin. As
precaution, useprotective gloves and clothing. When handling the substance,
safety spectacles should be used to prevent eyes from redness, pain and
blurred vision. Avoid from eating, drinking or smoking during work.

218

Safety concerns:

- Because of it is flammable substance, storage area should be separated from
oxidants, rubber, plastics, aluminium and light metal.

- Make sure it place in dry and ventilation along the floor. Above 96C,
explosive vapor/air mixture may be formed.

- Therefore, open flames are prohibits and use a closed system with ventilation
when handle it in temperature above 96C.


Environmental concerns:

- It will turn yellow on exposure to heat. This substance decomposes on heating
or onburning producing toxic fumes including nitrogen oxides, carbon
monoxide. NMP is combustible substance and can give off irritating or toxic
fumes in fire.




5.3.4 Dow Fire and Explosion Index


The hazard classification guide developed by the Dow Chemical Company
and published by the American Institute of Chemical Engineering, Dow (1994)
(www.aiche.org), gives a method of evaluating the potential risk from a process,
and assessing the potential loss. A numerical Fire and explosion index (F & EI)
is calculated, based on the nature of the process and the properties of the process
materials. The larger the value of the F & EI, the more hazardous the process, see
Table 5.1.




219







Table 5.1: Assessment of hazard
(Adapted from the Dow F & EI guide 1994)

To assess the potential hazard of a new plant, the index can be calculated
after the Piping and Instrumentation and equipment layout diagrams have been
prepared. In earlier versions of the guide the index was then used to determine
what preventative and protection measures were needed, see Dow (1973). In the
current version the preventative and protection measures that have been
incorporated in the plant design to reduce the hazard are taken into account when
assessing the potential loss; in the form of loss control credit factors. It is
worthwhile estimating the F & EI index at an early stage in the process design, as
it will indicate whether alternative, less hazardous, process routes should be
considered.


Only a brief outline of the method used to calculate the Dow F & EI will
be given in this section. The full guide should be studied before applying the
technique to a particular process. Judgment, based on experience with similar
processes, is needed to decide the magnitude of the various factors used in the
calculation of the index, and the loss control credit factors.




5.3.4.1 Calculation of the Dow F & EI


The first step is to identify the units that would have the greatest impact on
the magnitude of any fire or explosion. The index is calculated for each of these
units. The basis of the F & EI is a Material Factor (MF). The MF is then
multiplied by a Unit Hazard Factor, F3, to determine the F & EI for the process
220

unit. The Unit Hazard factor is the product of two factors which take account of
the hazards inherent in the operation of the particular process unit: the general and
special process hazards.




5.3.4.2 Material factor


The material factor is a measure of the intrinsic rate of energy release from
the burning, explosion, or other chemical reaction of the material. Values for the
MF for over 300 of the most commonly used substances are given in the Figure
5.1. The Figure5.1 also includes a procedure for calculating the MF for substances
not listed: from knowledge of the flash points, (for dusts, dust explosion tests) and
a reactivity value, Nr. The reactivity value is a qualitative description of the
reactivity of the substance, and ranges from 0 for stable substances, to 4 for
substances that are capable of unconfined detonation. Some typical material
factors are given in Table 5.2. In calculating the F & EI for a unit the value for the
material with the highest MF, which is present in significant quantities is used.
221


Figure 5.1: Procedure for calculating the fire and explosion index
and other risk analysis information.













222



Table 5.2: Some typical material factors




5.3.4.3 General process hazards


The general process hazards are factors that play a primary role in
determining the magnitude of the loss following an incident. Six factors are listed
on the calculation form, Figure5.2.

A. Exothermic chemical reactions: the penalty varies from 0.3 for a mild
exothermic, such as hydrogenation, to 1.25 for a particularly sensitive
exothermic, such as nitration.

B. Endothermic processes: a penalty of 0.2 is applied to reactors, only. It is
increased to 0.4 if the reactor is heated by the combustion of a fuel.

C. Materials handling and transfer: this penalty takes account of the hazard
involved in the handling, transfer and warehousing of the material.

D. Enclosed or indoor process units: accounts for the additional hazard where
ventilation is restricted.
223

E. Access of emergency equipment: areas not having adequate access are
penalized. Minimum requirement is access from two sides.

F. Drainage and spill control: penalizes design conditions that would cause
large spills of flammable material adjacent to process equipment; such as
inadequate design of drainage.
224



Figure 5.2: Dow Fire and Explosion Index Calculation Form

225

5.3.4.4 Special Process Hazards


The special process hazards are factors that are known from experience to
contribute to the probability of an incident involving loss. Below are twelve
factors taking consideration on the calculation:


A. Toxic materials: the presence of toxic substances after an incident will
make the task of the emergency personnel more difficult. The factoapplied
ranges from 0 for non-toxic materials, to 0.8 for substances that can causedeath
after short exposure.

B. Sub-atmospheric pressure: allows for the hazard of air leakage into
equipment. It is only applied for pressure less than 500 mmHg.

C. Operation in or near flammable range: covers for the possibility of air
mixing with material in equipment or storage tanks, under conditions where the
mixture will be within the explosive range.

D. Dust explosion: covers for the possibility of a dust explosion. The degree
of risk is largely determined by the particle size. The penalty factor varies from
0.25 for particles above 175m, to 2.0 for particles below 75m.

E. Relief pressure: this penalty accounts for the effect of pressure on the rate
of leakage, should a leak occur. Equipment design and operation becomes more
critical as the operating pressure is increased. The factor to apply depends on the
relief device setting and the physical nature of the process material.

F. Low temperature: this factor allows for the possibility of brittle fracture
occurring in carbon steel, or other metals, at low temperatures.

G. Quantity of flammable material: the potential loss will be greater the
greater the quantity of hazardous material in the process or in storage. The factor
226

to apply depends on the physical state and hazardous nature of the process
material, and the quantity of material. It varies from 0.1 to 3.0.

H. Corrosion and erosion: despite good design and materials selection, some
corrosion problems may arise, both internally and externally. The factor to be
applied depends on the anticipated corrosion rate. The severest factor is applied if
stress corrosion cracking is likely to occur.

I. Leakage joints and packing: this factor accounts for the possibility of
leakage from gaskets, pump and other shaft seals, and packed glands. The factor
varies from 0.1 where there is the possibility of minor leaks, to 1.5 for processes
that have sight glasses, bellows or other expansion joints.

J. Use of fired heaters: the presence of boilers or furnaces, heated by the
combustion of fuels, increases the probability of ignition should a leak of
flammable material occur from a process unit. The risk involved will depend on
the sitting of the fired equipment and the flash point of the process material.

K. Hot oil heat exchange system: most special heat exchange fluids are
flammable and are often used above their flash points; so their use in a unit
increases the risk of fire or explosion. The factor to apply depends on the quantity
and whether the fluids are above or below its flash point

L. Rotating equipment: this factor accounts for the hazard arising from the
use of large pieces of rotating equipment: compressors, centrifuges, and some
mixers.




5.3.5 Potential loss


The first step is to calculate the Damage factor for the unit. The Damage
factor depends on the value of the Material factor and the Process unit hazards
factor. An estimate is made of the area (radius) of exposure. This represents the
227

area containing equipment that could be damaged following a fire or explosion in
the unit being considered. An estimate of the replacement value of the equipment
within the exposed area is then made, and combined with by the damage factor to
estimate the Base maximum probable property damage (Base MPPD). The
Maximum probable property damage (MPPD) is then calculated by multiplying
the Base MPPD by a Credit control factor. The Loss control credit control factors,
allow for the reduction in the potential loss given by the preventative and
protective measures incorporated in the design. The MPPD is used to predict the
maximum number of days which the plant will be down for repair, the Maximum
probable days outage (MPDO). The MPDO is used to estimate the financial loss
due to the lost production: the Business interruption (BI). The financial loss due to
lost business opportunity can often exceed the loss from property damage.
(Chemical Process Safety, Daniel A. Crowl/Joseph F. Louvar, 2002)




5.3.6 Basic Preventative and Protective Measures


The basic safety and fire protective measures that should be included in all
chemical process designs are listed below. This list is based on that given in the
Dow Guide, with some minor amendments.


1. Adequate, and secure, water supplies for fire fighting.
2. Correct structural design of vessels, piping, steel work.
3. Pressure-relief devices.
4. Corrosion-resistant materials, and/or adequate corrosion allowances.
5. Segregation of reactive materials.
6. Earthing of electrical equipment.
7. Safe location of auxiliary electrical equipment, transformers, switches gear.
8. Provision of back-up utility supplies and services.
9. Compliance with national codes and standards.
10. Fail-safe instrumentation.
11. Provision for access of emergency vehicles and the evacuation of personnel.
228

12. Adequate drainage for spills and fire-fighting water.
13. Insulation of hot surfaces.
14. No glass equipment used for flammable or hazardous materials, unless no
suitable alternative is available.
15. Adequate separation of hazardous equipment.
16. Protection of pipe racks and cable trays from fire.
17. Provision of block valves on lines to main processing areas.
18. Protection of fired equipment (heaters, furnaces) against accidental explosion
and fire.
19. Safe design and location of control rooms.




5.4 Major Equipment Control


This plant consist six major equipments. There are three reactor and three
distillation columns. Each of these equipments has their own hazard. Below is the
equipment process control for each equipment. The primary objectives of the
instrumentation and control schemes are:-

(i) Safety of plant operation:

To keep the process variables within known safe operating limits
To detect dangerous situations as they develop and to provide alarms and
automatic shut-down system.

(ii) Production rate: -To achieve the design product output

(iii) Product Quality: - To maintain the product within the specified quality
standards.

(iv) Cost: - To operate at the lowest production cost, commensurate with the
other objectives.
229

5.4.1 Reactor Control System

E-1
FT
GAS INLET
OUTLET
FIC
PIC
PT
P-31
COLD WATER
HOT WATER
TT
TIC

Figure 5.3: Control System of Reactor (R-101)


The control of chemical reactor is the most important in chemical
engineering and must be carefully consent, since the chemical reactor is the main
of the processes. The stability efficiency of reaction operation is very important to
the entire plant. The reaction employed in the plant is exothermic and runaway
operation cause explosion. Thus, it requires an effective, well-designed control
system to assure stable operation. The control system objectives are defined as:

(i) To maintain the reactor operation at optimum temperature and pressure.

230

(ii) To sustain the product quality in order to make sure the maximum
production rate can be maintained at the annual production rate of
50,000 metric ton per year.

(iii) Provide the safeguards against the unexpected process runaway and
maintain the safe operation.

(iv) To maintain optimum feed condition and composition in order to ensure
high production rate.


Objective Control
Variable
Manipulat
ed
Variable
Disturbanc
e
Type of
Control
Set Point
To maintain
the flow rate
of inlet and
outlet
Inlet flow
rate valve
Inlet flow
rate
Outlet flow
rate
Cascade
(master)
37 018.135
kg/hr
To maintain
the pressure
in the reactor
Inlet flow
rate valve
Inlet flow
rate
Outlet flow
rate
Cascade
(slave)
1 atm
To maintain
the
temperature
of the reactor
Input of
cold
water
valve
Input of
hot water
Outlet flow
rate
Feedback
controller
Not below
or exceed
than 10% of
temperature
set point
which is
550C

Table 5.3: Control Mechanism of Multi-tube Fixed bed Reactor

231

5.4.2 Distillation Column Control System


LIC
LT
PT
PIC
LIC
TT
TIC
Steam
FIC
FT
NMP
Stream 13
Stream 11
Stream 12
D-101
E-103
TK-1
E-104
P-113A/B
Reflux Drum
LT
AT
AIC
AT
AIC

Figure 5.4: Control System of Extractive Distillation Column (D-101)


The control system of distillation column has three main factors to consider:

- Material balance control.
- Product quality control.
- Satisfaction of constraints.







232

5.4.2.1 Material Balance Control


The column control system must cause the average sum of the product
streams (bottom and top product) to be exactly equal to the average feed rate,
keeping the column in material balance. Although the plant is usually designed for
a nominal production rate, a design tolerance is always incorporated because the
market condition and demand may require an increase or decrease from the
current state. The control system is then called to ensure a smooth and safe
transition from the old production level to the newly desired production level. Its
purpose is to direct the control action in such a way as to make the inflows equal
to the outflows and achieve a new steady-state material balance for the plant.




5.4.2.2 Product Quality Control


The purpose of this control is to maintain the desired concentration of
products at bottom and top stream.




5.4.2.3 Satisfaction of Constrains


For safety purposes, satisfactory operation of the column and
certain constraints must be understood and followed, for example, the column
shall not flood. Column pressure drop should be high enough to maintain effective
column operation, that is, to prevent serious weeping or dumping. The
temperature difference in the reboiler should not exceed the critical temperature
difference. Avoid shock loading to the column to avoid overload reboiler or
condenser heat-transfer capacity.

233

Column pressure should not exceed a maximum permissible value. The
main purpose of this distillation column, is to separate acetic acid from the rest of
the feed, and it withdraws from the bottom. Objectives:


Control the top pressure in the column
Control the top temperature in the column
Control the temperature in the condenser
Control the liquid level in the condenser
Control the liquid level in the column
Control the product purity

Table 5.4: Control Mechanism of Extractive Distillation Column
Control
Variables
Measured
Variables
Manipulated
Variables
Disturbances Type of
Controller
Column
Pressure
Pressure at the top
tray
Stream 11
flow rate
Change in
pressure column
Feedback
Temperature in
column
Temperature at the
top tray
Stream flow
to the boiler
Change in
temperature
column
Feedback
Liquid level in
condenser
Liquid level in
reflux drum
Flow rate of
reflux stream
Change in liquid
level in the
condenser
Feedback
Flow rate of
streams
Flow rate of
1) Stream 13
2) Stream NMP
Stream 11
flow rate
Change in flow
rate of streams
1) Feedback
2) Feedback
Liquid level at
the bottom
Liquid level at the
bottom tray
Flow rate of
Stream12
Change of liquid
level at the
bottom
Feedback
Qualitity of
composition in
the product
(Stream 13)
Composition in
Stream 13
Flowrate of
Stream 13
Change of
composition in
the strean of
product
Cascade
234

5.5 Hazard and Operability Studies (HAZOP)


The Hazard and Operability Study is a procedure for the systematic,
critical, examination of the operability of a process. When applied to a process
design or an operating plant, it indicates potential hazards that may arise from
deviations from the extended design conditions. HAZOP include forms of study,
systemic inspection for process plant to determine the danger, probability of
failure and problem that occur and consequences if failure occur. HAZOP studies
are performed by a team consisting of plant operators, engineers, managers and
others, some of whom should be intimately familiar with the facility being
studied.




5.5.1 HAZOP Concept


The HAZOP process is based on the principle that a team approach to
hazard analysis will identify more problems than when individuals working
separately combine results. The HAZOP team is made up of individuals with
varying backgrounds and expertise. The expertise is brought together during
HAZOP sessions and through a collective brainstorming effort that stimulates
creativity and new ideas, a thorough review of the process under consideration is
made.




5.5.2 HAZOP objectives


HAZOPs concentrate on identifying both hazards as well as operability problems.
The objectives of HAZOP study are:

235

- To identify areas of the design that may possess a significant hazard
potential.
- To familiarize the study team with the design information available.
- To ensure that a systematic study is made of the areas of significant hazard
potential.
- To determine all deviations that most might happen and make suggestion
to minimize it.


5.5.3 Important Equipments for HAZOP

- Process diagram and instrumentation (P&ID)
- Mass and energy balances
- Safety procedures documents
- Involved chemicals
- Piping specification
- Previous HAZOP report


5.5.4 HAZOP planning

- Time available
- Time assumption needed
- Available of team members
- Available of P&IDs
- Report of record
- Actions that should be take
- Last report and date
236

5.5.5 HAZOP Team


Ideally, the team consists of five to seven members, although a
smaller team could be sufficient for a smaller plant. If the team is too large, the
group approach fails. On the other hand, if the group is too small, it may lack the
breadth of knowledge needed to assure completeness. The team leader should
have experience in leading a Hazop. The rest of the team should be experts in
areas relevant to the plant operation. A team might include:


a) Design engineer
b Process engineer
c) Operations supervisor
d) Instrument design engineer
e) Chemist
f) Maintenance supervisor
g) Safety engineer (if not Hazop leader)


The team leaders most important job is to keep the team focused on the
key task: to identify problems, not necessarily to solve them. There is a strong
tendency for engineers to launch into a design or problem-solving mode as soon
as a new problem comes to light. Unless obvious solutions are apparent, this mode
should be avoided or it will detract from the primary purpose of Hazop, which is
hazard identification. In addition, the team leader must keep several factors in
mind to assure successful meetings: (1) do not compete with the members; (2)
take care to listen to all of the members; (3) during meetings, do not permit
anyone to be put on the defensive; (4) to keep the energy level high, take breaks as
needed.



237

5.5.6 HAZOP Procedure


Use the following steps to complete an analysis of HAZOP:


a) Begin with a detailed flow sheet and break the flow sheet into a number of
process units. After that select a unit to study
b) Choose a study node (vessel, line, operating instruction).
c) Describe the design intent of study node.
d) Pick a process parameter (level, flow, temperature, pressure, volume,
reaction, and component)
e) Apply a guide word to the process parameter to suggest possible deviation
f) Determine possible causes and note any protective systems.
g) Evaluate the consequences of the deviation (if any)
h) Recommend action
i) Record all information.
Guidewords Meanings Comments
No or not The complete negation of
these intentions
No part of the intentions
is achieved but nothing
else happens
More (more of, higher) Quantitative increases These refer to the
quantities and properties
such as flow rates and
temperatures as well as
activities such as heat and
react.
Less (less of, lower) Quantitative decreases These refer to the
quantities and properties
238


Table 5.5: List of HAZOP Guide Words












such as flow rates and
temperatures as well as
activities such as heat and
react.
As well as A qualitative increase All the design and
operating intentions are
achieved together with
some additional activities.
Part of A qualitative decrease Only some of the design
intentions are achieve;
some are not
Reverse The logical opposite of
the intention
This is mostly applicable
to activities for example
reverse flow or chemical
reactions.
Other than Complete substitution No part of the original
intention is achieved.
Something quite different
happens.
239

5.5.7 HAZOP on Storage Tank

Deviation Causes Consequences Existing
Provision
Actions,
Questions, or
Recommend
ations
More flow - Control
valve
failure
- Settling of the
liquid phase
not
effective
- Flooding in
the tank
- Flow
indicator and
control
- High flow
alarm,
HFA
- Sufficient
provision
Less flow - Pipe line
leakage
- Control
valve
partially
closed
- Loss of
production
yield
- Flow
indicator and
control
- Low flow
alarm,
LFA
- Sufficient
provision
No Flow - Pipeline
rupture
- Blocking in
inlet
pipeline
- Control
valve
fails to open
- Settling tank
dries
up
- Separation
between
products fail
- Flow
indicator and
control
- Low flow
alarm,
LFA
- Sufficient
provision

Table 5.6: HAZOP Studies on Storage Tank





240

5.5.8 HAZOP on Heat Exchanger

Deviation Causes Consequences Existing
Provision
Actions,
Questions, or
Recommendations
Cold Flow -Pipe leakage
-Pump not
function
-Desire
temperature
not
accomplished
-Effect further
process
-Install a filter at
the
Coolant
-Install flow
indicator
-Install temperature
indicator
Excess flow
of the
coolant
-Valve not
Functioning
-The coolant
pump
cannot be
control,
hence the
capacity
rate increase
-The coolant
pipe
rupture
Same as Cold
Flow
-Install an orifice
plate
-Install a cooling
water
flow meter
-Install flow
indicator
Change new valve
Less flow of
the coolant
-Control
valve
malfunction
-Flow pipe of
the
coolant
plugged
Same as Cold
Flow
-Install a less flow
warning device
-Change a new
control
valve
241

Higher
Temperature
-Heat
exchanger is
malfunction
-Temperature
of the hot
fluid is too
high
-Fire beside
the heat
exchanger
-Pressure
increase
-Explosion can
occur
-Failure of the
equipment
-Install high
temperature
warning device at
the out flow of hot
fluid stream
-Repair the damage
of
the heat exchanger
Lower
temperature
-No
temperature
Change
-
Condensation
happen at the
tube of
heat
exchanger
Breakdown of
next
equipment
-Install temperature
low
alarm at the out
flow
-Clean the tube of
the
heat exchanger to
removes deposit

Table 5.7: HAZOP Studies on Heat Exchanger












242

5.5.9 HAZOP on Multi-tube Fixed Bed Reactor
Deviation Causes Consequences Existing
Provision
Actions,
Questions, or
Recommendation
s
No No flow i. Tube leakage
and blocking
ii. Valve fails or
malfunctioning
iii. No flow from
previous
equipment
i. No reaction
ii. No
production
iii Disturbing
others process

i. Emergency
shutdown
ii. Install flow
indicator in inlet
flow
iii. Checking
stream condition
More Higher feed
flow
i. Valve cannot be
controlled
normally
ii. Sudden
increment in fresh
feed

. Rise in
bottom liquid
level and
pressure
ii. Causes
flood in the
reactor
iii. Reduce
conversion
i. Install flow
indicator
ii. Regular
inspection

Higher
pressure
and
temperature

i. Less process
fluid flow into the
heater
ii. More Steam
entering heater

i. Fracture in
transfer line
due by
overload
temperature
ii. Coke
deposits form
on the
catalyst
iii. Reduce
the
i. Install
temperature alarm
high indicator
ii. Proper process
control at heater

243

conversion
Less Less flow

i. Less flow from
previous
equipment
ii. Leakage or
blockage at piping

i. Less
production
ii.Temperatur
e drops,
causing less
or no
iii. Reactions
occurs
iv. Causing
reversible
flow to
reactor
i. Install low flow
alarm and leakage
alarm
ii. Regular
inspection


Low
pressure
and
temperature
i. The reactor
pressure and
ii. temperature
iii.malfunctioning
i. Yield and
efficiency of
products
decreases
ii. Backflow
from reaction
i. Check TIC and
PIC controller
ii. Install alarm
iii. Monitor
pressure at feed
inlet
Reverse Reverse
flow either
to reactor
or to feed
storage

i. High pressure in
column
ii. Failure in PIC
iii. Pipe leakage

i. No
operation
ii. No
production
iii. Plant
break down
Install check
valve'

As well
as
Other flow
of
substances
detected for
example
contaminati
on of cool
water
i. Contaminants
detected
ii. Non-pure feed
iii. Leakage in
cooling system
Quality of
product
decreases


i. Check the

pureness of feed
ii. Check the

composition
controller
244


Table 5.8: HAZOP Studies on Reactor
























Other
than
Production
of
substances
other than
the product.

i. Leakage of
ii. Heat exchanger
and
its substances
entered the reactor
Affect the
reaction

Check and correct
the reactor
internals

245

5.5.10 HAZOP on Extractive Distillation Column


HAZOP for Feed Stream

Deviation Possible
cause
Possible
consequences
Existing
provision
Action
required
No Feed
flow
-Blockage of
leakage
-Control
system
damage
-Level decrease in
the column
-Loss in
production
-Install flow
indicator
controller (FIC)
-Check and
recheck/
maintenance
More feed
flow
-Control
damage
failure
-Damage/broken
of column
-High pressure
flow thus increase
level in column
-Install flow
indicator
controller (FIC)
More
pressure
-Pressure
valve failure
-Thermal
expansion in
stream line
-Stream line
fracture
-Pressure
indicator
controller
-Place valve at
critical
instrument list
More
temperature
-Temperature
built up in
stream line
-Line fracture -
Temperature
indicator
controller
(TIC)
-Sufficient
provision
Less flow Same as NO
or NOT
Same as NO or
NOT
Same as NO or
NOT
Less
pressure
-Unstable
flow
condition in
-Sudden change in
pressure drop
-Same for
MORE for
pressure
246

column condition
Less
temperature
-Temperature
decrease in
column
system
-Loss product in
upstream
-Same for
MORE
condition

HAZOP for Top Upstream


No flow
-Control system
damage
-Loss in
production
-Install
flow
indicator
controller
(FIC)
More flow -Control
damage failure
-Damage/
broken of
column
-Install
flow
indicator
controller
(FIC)
Less flow Same as NO or
NOT
Same as NO or
NOT
Same as
NO or
NOT

HAZOP for Bottom Stream

No flow

-Control system
damage
-Loss in
production
-Install
flow
indicator
controller
(FIC)
More flow -Control
damage failure
- Damage/
broken of
-Install
flow
247

column indicator
controller
(FIC)
Less Same as NO or
NOT
Same as NO or
NOT
Same as
NO or
NOT






































Table 5.9: HAZOP Studies on Distillation Column

248



CHAPTER 6




WASTE MANAGEMENT




6.0 Introduction




Waste management is the collection, transport, processing, recycling or
disposal, and monitoring of waste materials (Anonymous, 2009). The term
usually relates to materials produced by human activity and is generally
undertaken to reduce their effect on health, environment or aesthetics. Waste
management is also carried out to recover resources from it. Furthermore, waste
management can be involving solid, liquid, gaseous or radioactive substances,
with different methods and fields of expertise of each.


Waste management practices differ for developed and developing nations,
for urban and rural areas, and also for residential and industrial producers.
Management for non-hazardous residential and institutional waste in metropolitan
areas is usually the responsibility of local government authorities, while
management for non-hazardous commercial and industrial waste usually the
responsibility of the generator.


There are a number of concepts about waste management which vary in
their usage between countries or regions. Some of the most general, widely used
concepts include:
249

Waste hierarchy: The waste hierarchy refers to the "3
Rs" reduce, reuse and recycle, which classify waste management strategies
according to their desirability in terms of waste minimization. The waste
hierarchy remains the cornerstone of most waste minimization strategies. The
aim of the waste hierarchy is to extract the maximum practical benefits from
products and to generate the minimum amount of waste.

Extended producer responsibility: Extended Producer Responsibility
(EPR) is a strategy designed to promote the integration of all costs associated
with products throughout their life cycle (including end of life disposal costs)
into the market price of the product. Extended producer responsibility is
meant to impose accountability over the entire lifecycle of products and
packaging introduced to the market. This means that firms which
manufacture, import and/or sell products are required to be responsible for the
products after their useful life as well as during manufacture.

Polluter pays principle: The Polluter Pays Principle is a principle where
the polluting party pays for the impact caused to the environment. With
respect to waste management, this generally refers to the requirement for a
waste generator to pay for appropriate disposal of the waste.




6.1 Waste Management

Since the amount of gaseous produced by our plant is not too high, we
have decided to release the gaseous to the atmosphere since it is not harmful to
environment. The four main gas wastes are CO
2,
N
2
, H
2
and O
2
and all the gases
are safe to be release. Few options have been taken into considerations such as
recycling; reuse it or reducing the amount of these waste gasses release. Extra
precaution and detailed planning is needed to successfully control and manage the
waste from our plant as it is in the form of gas such as comparing the air of our
plant to air quality standard.
250

6.2 Air Quality Management Concepts


Air quality management is a term used to describe all the functions
required to control the quality of the atmosphere (Anonymous, 1975). Among the
essential elements of such a program are control regulations and a control
strategy, legal authority to implement the control strategy, emission inventories,
an atmospheric surveillance network, a data management system, agency staffing
and funding, a system for analysis of complains and stack sampling production.




6.2.1 Air Quality Index


The Clean Air Act requires the EPA to establish National Ambient Air
Quality Standards (NAAQS) for six pollutants considered harmful to public
health and the environment: carbon monoxide, lead, nitrogen dioxide, ozone,
particulate matter, and sulfur dioxide. The standards were set at the level required
to provide an ample margin of safety to protect the public health (Peavy, 1985).


The Clean Air Act established two types of national air quality standards.
Primary standards are intended to protect public health, including the health of
"sensitive" populations such as asthmatics, children, and the elderly. Secondary
standards set limits to protect public welfare, including protection against
decreased visibility, damage to animals, crops, vegetation, and buildings.



251

National Ambient Air Quality Standards
POLLUTANT STANDARD
VALUE
STANDARD
TYPE

Carbon Monoxide (CO)
8-hour Average 9 ppm 10 mg/m
3
Primary
1-hour Average 35 ppm 40 mg/m
3
Primary

Lead (Pb)
Quarterly Average 1.5 g/m
3
Primary & Secondary

Nitrogen Dioxide (NO
2
)
Annual Arithmetic Mean 0.053 ppm 100 g/m
3
Primary & Secondary

Ozone (O
3
)
1-hour Average* 0.12 ppm 235 g/m
3
Primary & Secondary
8-hour Average 0.08 ppm 157 g/m
3
Primary & Secondary

Particulate < 10 micrometers (PM-10)
Annual Arithmetic Mean 50 g/m
3
Primary & Secondary
24-hour Average 150 g/m
3
Primary & Secondary

Particulate < 2.5 micrometers (PM-2.5)
Annual Arithmetic Mean 15 g/m
3
Primary & Secondary
24-hour Average 65 g/m
3
Primary & Secondary

Sulfur Dioxide (SO
2
)
Annual Arithmetic Mean 0.03 ppm 80 g/m
3
Primary
24-hour Average 0.14 ppm 365 g/m
3
Primary
3-hour Average 0.50 ppm 1300 g/m
3
Secondary
* The ozone 1-hour standard applies only to areas that were designated nonattainment
when the ozone 8-hour standard was adopted in July 1997.
Figure 6.1: National Ambient Air Quality Standards (NAAQS)





252


CHAPTER 7




ECONOMIC ANALYSIS




7.1 Introduction


The economic analysis that involves the computation of the monetary
investment that needs to poured into the plant should comes before, because its
one of the most essential parts of the entire process design. It also the
determination of the relationship of income and expense to the material welfare of
the company The calculation involves the economic potential for the selected
plant was just a rough estimation in which the calculation does not involve in
counting in other factors such as depreciation, plant lifetime and so on.


Economic evaluation of this project is done by estimating the fixed
capital investment, total capital investment, total production cost and revenue
from sales. Equipments costing have been calculated in Chapter V with the
estimated Chemical Engineering Plant Index in 2009, which are 597.1. Most of
the equipments quotations are obtained by employing the bare module method.
Finally, the profitability analysis is performed by analyze the discounted cash
flow. Payback period (PBP), discounted break-even period, net present value
(NPV) and discounted cash flow rate of return (DCFRR) will be determined.









253


7.2 Grass-roof Capital


Equipment sizing has been carried out before and the cost for each of the
equipment used in the plant is being estimated and because the gross root capital
cost is the major portion of total fixed capital cost, its has been done first. Cost of
equipment, cost of installation, contingency and fees are all includes in the gross
root capital cost part.




7.2.1 Equipment Costs and Grass Roof Capital


EQUIPMENT COST ($)
Compressor
29 026.75
Compressor
27580.74
Compressor
157 559.35
Compressor
738 559.58
Compressor
187 101.75
Multi Tubular Fixed Bed Reactor 890960.73
Catalytic Tubular Fixed Bed Reactor 802244
Isomerazation Process Reactor
12552.41
Heat Exchanger
73500
Heat Exchanger
68250
Heat Exchanger
10080
Heat Exchanger
106 122.8245
Heat Exchanger
39480
Heat Exchanger
135,000.00
Pump 82469.84
Pump
61152
Pump
61152
Pump
61152
254

Pump 94393.84
Pump
94393.84
Pump 33948.42
Pump 10 120.2709
Absorption Tower 782656.5445
Distillation Column
726493.46
Distillation Column 893575
Distillation Column
2 474 200.972
Reboiler
193 585.4067
Reboiler
5460
Cooling Tower
17662.8
Storage Tank
551645.775
Storage Tank 157500
Total Bare Module Cost, C
tbm
$ 9479580.5
Total Bare Module Cost, Ctbm
RM 30457892.15

Table 7.1: Equipment Cost and Grass Root Capital


ITEMS FORMULA PRICE (RM)
Contingency and Fees CC + CF = 0.08CTBM 2436631.37
Total Module Cost CC + CF + CTBM
=CBM
32894523.52
Auxiliary Facilities 0.10CTBM 3045789.22
Gross-roof Capital
(GRC)
38376944.1

Table 7.2: Grass Root Capital









255


7.3 Fixed and Total Capital Investment Cost


Fixed Capital is the total cost for installed the process equipment with
some auxiliaries that completed the operation of the process. It includes the cost
of direct and indirect cost for the set up of the plant.

Total Capital = Fixed Capital Investment + Working Capital + Start Up Cost
Investment


Then, the working capital is the additional investment needed, in order to
start up. The plant and operate to it point when income is earned. Working cost is
most likely to be recovered at the end of the plant.


Specification Cost (RM)
Onsite
Purchased equipment
installation
15%GRC 5,756,541.62
Instrumentation and
control (installed)
10%GRC 3,837,694.41
Piping (installed) 10%GRC 3,837,694.41
Electrical and material
(installed)
5%GRC 1,918,847.21

Offsite
Building 12%GRC 4,605,233.29
Yard improvements 3%GRC 1,151,308.32
Service facilities 8%GRC 3,070,155.53
Land 1%GRC 383,769.44
Total 1 24,561,244.23

Indirect cost
256

Engineering and
supervision
8%GRC 3,070,155.53
Legal expenses 1%GRC 383,769.44
Construction expenses 8%GRC 3,070,155.53
Contractors fee 1.5%GRC 575,654.16
Contingency 5%GRC 1,918,847.21
Total 2 9,018,581.87

Total = total 1+ total 2 33,579,826.1
Gross root capital (GRC) 38,376,944.1

Fixed capital investment
(FCI)
71,956,770.2
Working capital 10%FCI 7,195,677.02
Start up cost 5%FCI 3,597,838.51
Total capital investment
(TCI)
82,750,285.73

Table 7.3: Fixed and Total Capital Investment Cost


For the plant capital investment that have been calculated are includes all
equipments cost, waste treatment cost, the direct cost in setting up the plant,
indirect cost and also cost for working and start up cost. The total capital
investment of RM 82,750,285.73 is needed where the calculations are tabulated in
the Table 6.3.




7.4 Manufacturing Cost and Total Production Cost


Operating cost, the cost of producing the product with the estimation of
raw materials cost, operating labor cost and also estimation of utilities cost for the
plant.

257


7.4.1 Raw Materials Costing and Annual Profit


Raw material Price($/tone) Amount(tonne/yr) Annual cost($/yr)
Butane 607.6 55082.984 33,468,421.08

TOTAL
ANNUAL
COST
RM107,534,036.9
Annual product
credit
Cost Amount Annual cost
1-Butene 475.4 31407.09 14,930,930.59
1,3-Butadiene 943.58 50000 47,179,000
Total $ 62,109,930.59

TOTAL ANNUAL
COST
RM 199,559,207

Table 7.4: Raw Materials Costing and Annual Profit




7.4.2 Estimation of Operating Labor Cost


Equipment type Number of
equipment
Operator per Shift
per Equipment

Operator Required
Per Shift
Compressor 5 0.15 0.75
Reactor 3 0.5 1.5
Heat Exchanger 6 0.5 3
Pump 8 0 0
Absorption Tower 1 0.35 0.35
Distillation Column 3 0.35 1.05
Reboiler 2 0.5 1
Cooling Tower 1 0.35 0.35
Storage Tank 2 0 0
TOTAL 24 8

Table 7.5: Operating Labor Estimation
258

Operating labor = (4.5) (8)
= 15.43 (rounding up to nearest integer yield 16 operators)
= 36 operator/ days
Labor cost in Malaysia = RM 1,500/months
Therefore,
Total labor cost = RM 54,000/month
= RM 648,000/yr


Direct supervision and clerical labor
Assume that supervisory and clerical labor cost is 15% of operating labor cost.
Cost of C
DSCL
= 0.15C
OL

= 0.15 (RM 648,000)
= RM 97,200.00/yr




7.4.3 Manufacturing Cost Summary


Fix capital investment (FCI): RM 71,956,770.2
Working capital: RM 7,195,677.02
Start up cost: RM 3,597,838.51
Total capital investment (TC1): RM 82,750,285.73


MANUFACTURING
EXPENSES
SPECIFICATION COST (RM)
Direct production cost
Raw material:
Butane 107,534,036.9

Utilities:
Electricity RM 0.26/kWh 848,474.40
Water RM 1.20/m
3
190,082.59
Steam RM 14.25/1000 kg 9,845.22
Cooling water RM 0.26/1000 kg 20,149.11
Maintenance and repairs 3%FCI 2,158,703.11
Operating supplies 0.5%FCI 359,783.85
Annual employees wages 745,200
Patents and royalties 1%FCI 719,567.7
259


Indirect production cost
Local taxes 1%FCI 719,567.7
Insurance 0.5%FCI 359,783.85
Plant overhead 50% L. Cost 35,978,380.1
Total manufacturing
expenses, A
ME

114,037,794.4


General Expenses
Administration Cost 5%FCI 3,597,838.01
distribution & selling
expenses
8%FCI 5,756,540.82
Research & development 3%FCI 2,158,703.11
Total general expenses,
A
GE
11,513,081.94

Total production cost,
A
PC
= A
ME
+
A
GE
(Excluding
Depreciation)
125,550,876.3
Depreciation, A
BD
10%FCI 7,195,676.02
Total expenses, A
TE
A
PC
132,746,552.4

Table 7.6: Total Expenses Estimation


Carried out calculation for rate of return,


Revenue from sales, RM 1.05/kg Ethanol = RM 199559207.00

Net annual profit, A
NP
= RM 66812654.68

Income Taxes Of 30% Net Annual Profit = RM 20043796.404
Net Annual Profit After Income Taxes, ANNP = RM 46768858.276
Rate of return (ROR) = Cumulative net cash flow at end of project
(100)
Life of project X original investment
260


= 928497605.1593X 100
20 X 82750285.73

= 56.1%



7.5 Cash Flow Analysis


After all the calculation has been carried out, then the final step to be
determined is the determination of payback period (PBP) and to solve that
particular step, the value can be obtained by using graphical method. For the
plant, the total operating period is 20 year with 3 year at the beginning as the
start-up operation period. The capital investment used in the first year of the plant
is 9 % from Total Capital Investment (TCI) while its increased to 25 % of TCI.
In the third year of operation, capital investment to the plant account of 65 % of
TCI plus the working capital.


To determine the time that must elapse after start up until cumulative
undiscounted cash flow repays fixed capital investment, which is PBP, the cash
flow diagram of undiscounted must be calculated. From the calculated value of
net cash income and refer to cash flow diagram that has been plotted, its clearly
that the Pay-back period (PBP) is estimated of 2 years after 2.5 years of start-up
period.

261


Figure 7.1: Cash Flow Diagram with i= 0%





262


Figure 7.2: Discounted Cash Cumulative


Discounted break-even point is the point in which the time from the
decision to proceed until discounted cumulative cash flow becomes positive
value. And net present value is the final cumulative discounted cash flow value at
project conclusion.


The discounted cash flow rate of return (DCFRR) is the point in which the
rate result a Net present value of zero. In this case, the zero value cannot be
obtained but the value is near the zero compared to other value, so the difference
between the values can be neglected. So, the value of 40 % is selected as the
break-even point. The DCFRR point is the maximum interest rate that counted
after the taxes.







263

7.6 Conclusion


After carried out the economic analysis to the animal feed production
plant, the conclusions that can be makes are:


- The Total Capital Investment is RM 82750285.73

- The Total Production Cost is RM 125,550,876.3

- The plant life is 20 years with the beginning 2.5 years as the start
up period

- From Discounted Cash flow diagram, Pay Back Period is estimated
at 2 years after start up period.

- The rate of returned obtained after the taxes is 56.1%.


















264



CHAPTER 8



CONCLUSION AND RECOMMENDATION



8.0 Conclusion


As a conclusion, the proposed 50 000MT/Year of Butadiene from n-
butane plant is considered to be very profitable plant. It is because only one
existing plant of Butadiene in Malaysia with the cooperation of Titan Company.
Thus, the competition for the product will be less and increase the potential of our
Butadiene plant to expand the plastic and addition rubber market. This plant also
capable to fulfill the demand of Butadiene and 1-butene in Malaysia for the next
20 years because in 2030, it is estimated that about 2.5 millions of Malaysias
company want Butadiene production to produce another stuff like Butadiene
rubber, ABS, SBR and so on. At Global demand for butadiene its also increase at
an average annual rate of 3.9% during the period from 2001-2006 percent and
will outpace capacity additions. This rate is higher than the compounded annual
rate of 2.7% from 1996-2001 due to the global decline in demand that occurred in
2001 following the global economic slowdown


Besides, the Asian market has been also particularly active in building
new capacity of butadiene and butadiene derivatives due to the ongoing
development of automotive and tyre production in the region. The relocation of
automotive industries increased synthetic rubber demand through tyre production.
265

So it is reliable to build Butadiene Plant for the overcome profit and cover for
Malaysia, Asia Pacific and global demanded.



8.1 Recommendation


Based on the proposed plant, Butadiene also has water contamination from
recycling process in the plant. Hence, several strategies need to be sort out to
overcome this problem. Good waste management need to be carried out in order
to protect the environment which is build a small pond of waste water to be
treated in the proposed plant.


Other than that, the energy consumption and manufacturing cost to build
this proposed plant is quite high. In order to minimize the cost, we can reduce it
with develop heat integration using Pinch technology, otherwise to increasing
production rates for maximizing profit. Besides the safety aspect of the plant can
be upgraded



















266



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274








APPENDIX A



MANUAL CALCULATION OF
ENERGY BALANCE































275

Manual Calculation of Energy Balance

Heat Capacity

C
P
= A + BT + CT
2
+ DT
3

Components A B C D
Butane 92.30x10
-3
27.88x10
-5
-15.47x10
-8
34.98x10
-12

1-Butene
2-butene
1,3-Butadiene
Water 33.46x10
-3
0.6880x10
-5
0.7604x10
-8
-3.593x10
-12

Carbon dioxide 36.11 x10
-3
4.233 x10
-5
-2.887 x10
-8
7.464 x10
-12

Hydrogen
28.84 x10
-3
0.00765 x10
-5
0.3288 x10
-8

-0.8698 x10
-
12

Oxygen
29.10 x10
-3
1.158 x10
-5

-0.6076 x10
-
8
1.311 x10
-12

Nitrogen
29.00 x10
-3
0.2199 x10
-5
0.5723 x10
-8

-2.871 x10
-
12



Desired energy = x (H
t
+ H
f
)
Desired energy = x
= + P


Stream 1
N-Butane
desired energy = 118.71 mole/hr x (7540 kJ/mole -124.7 kJ/mole)
= 880270.263 kJ/hr
Total desired energy = 880270.263.kJ/hr
Simulation value for stream 1 = 0.196MMkcal/hr
Percentage error of energy is
Simulation = 0.195x 10
6
kcal/hr x 4.1858j/cal = 816231kJ/hr
Percentage error = x 100%
276

Percentage error = x 100% = 7.27%


Stream 2
Hydrogen:
desired energy = 1077.78 mole/hr x (550.18 kJ/mole)
= 593641.224 kJ/hr
Oxygen
desired energy = 134.49 mole/hr x (88028.8 kJ/mole)
= 11838993.31 kJ/hr
Nitrogen
desired energy = 308.04 mole/hr x (77025.2kJ/mole)
= 23726842.61 kJ/hr
Total desired energy = 593641.224 kJ/hr + 11838993.31 kJ/hr + 23726842.61
kJ/hr
= 36159477.14 kJ/hr
Simulation value for stream 2 = 8.196MMkcal/hr
Percentage error of energy is
Simulation = 8.235x 10
6
kcal/hr x 4.1858j/cal = 34470063kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 4.672%


Stream 3b
Water:
desired energy = 296.76 mole/hr x (50238 kJ/mole-241.83 kJ/mole)
= 14836863.41 kJ/hr
Total desired energy = 14836863.41 kJ/hr
Simulation value for stream 3b = 8.783MMkcal/hr
277

Percentage error of energy is
Simulation = 3.335x 10
6
kcal/hr x 4.1858j/cal = 13959643kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 5.91%


Stream 5
N-butane:
desired energy = 118.7133 mole/hr x (62884.548 kJ/mole-124.7 kJ/mole)
= 7450428.664 kJ/hr
1-butene:
desired energy = 40.52161 mole/hr x (54976.598 kJ/mole + 1.17 kJ/mole)
= 2227787.674 kJ/hr
2-butene:
desired energy = 86.9925 mole/hr x (54709.397kJ/mole + 1.17 kJ/mole)
= 4759409 kJ/hr

1,3 butadiene:
desired energy = 8.706111mole/hr x (50283.658kJ/mole -956 kJ/mole)
= 429452.0166 kJ/hr
Water:
desired energy = 296.7622 mole/hr x (15107.457 kJ/mole 241.83kJ/mole)
= 4411556.173 kJ/hr
Carbon dioxide:
desired energy = 5.468636 mole/hr x (18599.423 kJ/mole 393.5 kJ/mole)
= 99561.5659 kJ/hr
Hydrogen:
278

desired energy = 259.7053 mole/hr x (12328.319 kJ/mole )
= 3201729.784 kJ/hr
Nitrogen;
desired energy = 4312.615 mole/hr x (12849.743kJ/mole)
= 55415994.41kJ/hr
Total desired energy = 7450428.664 kJ/hr + 2227787.674 kJ/hr + 4759409 kJ/hr
+
429452.0166 kJ/hr + 4411556.173 kJ/hr + 99561.5659
kJ/hr
+ 3201729.784 kJ/hr + 55415994.41kJ/hr
= 77995919.29 kJ/hr
Simulation value for stream 3b = 8.783MMkcal/hr
Percentage error of energy is
Simulation = 17.395x 10
6
kcal/hr x 4.1858j/cal = 72811991kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 6.65%


Stream 7
N-butane:
desired energy = 118.7133mole/hr x (62884.548 kJ/mole-147.0 kJ/mole)
= 559606.1638 kJ/hr
2-butene:
desired energy = 55.95121mole/hr x (54709.397kJ/mole + 1.17 kJ/mole)
= 3061122.423 kJ/hr
1,3 butadiene:
desired energy = 79.4958mole/hr x (50283.658kJ/mole - 1127 kJ/mole)
= 3907747.853 kJ/hr

279

Water:
desired energy = 544.2868mole/hr x (15107.457kJ/mole -285.84 kJ/mole)
= 8067210.488 kJ/hr
Carbon dioxide:
desired energy = 20.1344mole/hr x (18599.423kJ/mole 412.9kJ/mole)
= 366174.7287 kJ/hr
Hydrogen:
desired energy = 81.42588 mole/hr x (12328.319kJ/mole-0)
= 1003844.224 kJ/hr
Oxygen:
desired energy = 1044.578 mole/hr x (13249.802kJ/mole )
= 13840451.67 kJ/hr
Nitrogen;
desired energy = 4146.206mole/hr x (12849.743kJ/mole)
= 53277681.53kJ/hr
Total desired energy = 559606.1638 kJ/hr + 3061122.423 kJ/hr + 3907747.853
kJ/hr
+ 8067210.488 kJ/hr + 366174.7287 kJ/hr + 1003844.224
kJ/hr
+ 13840451.67 kJ/hr + 53277681.53kJ/hr
= 84083839.08 kJ/hr
Simulation value for stream 3b = 8.783MMkcal/hr
Percentage error of energy is
Simulation = 18.365x 10
6
kcal/hr x 4.1858j/cal = 76872217kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 8.57%



280

Stream 9a
N-butane:
desired energy = 172.9575845 mole/hr x (2122.514kJ/mole-147.0 kJ/mole)
= 341680.1296 kJ/hr
2-butene:
desired energy = 63.7439498mole/hr x (7189.784kJ/mole + 1.17 kJ/mole)
= 458379.8108 kJ/hr
1,3 butadiene:
desired energy = 116.0073471mole/hr x (6609.026 kJ/mole - 1127kJ/mole)
= 635955.293 kJ/hr

Water:
desired energy = 40.68929584 mole/hr x (2543.847kJ/mole -285.84
kJ/mole)
= 91876.71483 kJ/hr
Carbon dioxide:
desired energy = 28.91870004mole/hr x (3038.834kJ/mole 412.9kJ/mole)
= 75938.5977 kJ/hr
Hydrogen:
desired energy = 6005.393935 mole/hr x (2122.514 kJ/mole 0)
= 12746532.7 kJ/hr
Oxygen:
desired energy = 119.3204777mole/hr x (2264.693kJ/mole )
= 270224.2506 kJ/hr
Nitrogen;
desired energy = 1524.877843 mole/hr x (2197.475/mole)
= 3350880.938 kJ/hr
Total desired energy = 341680.1296 kJ/hr + 458379.8108 kJ/hr + 635955.293
kJ/hr +
281

91876.71483 kJ/hr + 75938.5977 kJ/hr + 12746532.7
kJ/hr
+ 270224.2506 kJ/hr + 3350880.938 kJ/hr
= 17399468.43 kJ/hr
Simulation value for stream 9a = 4.0MMkcal/hr
Percentage error of energy is
Simulation = 4.0x 10
6
kcal/hr x 4.1858j/cal = 72811991kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 3.77%


Stream 11
N-butane:
desired energy = 172.3704507mole/hr x (1491.535kJ/mole-147.0 kJ/mole)
= 231758.1039 kJ/hr
2-butene:
desired energy = 62.95073242mole/hr x (1340.899kJ/mole + 1.17 kJ/mole)
= 84484.2265 kJ/hr
1,3 butadiene:
desired energy = 115.5460243mole/hr x (1220.147kJ/mole - 1127kJ/mole)
= 10762.7655 kJ/hr

Water:
desired energy = 31.23550603 mole/hr x (1125.511kJ/mole -285.84 kJ/mole)
= 26227.5486 kJ/hr
Carbon dioxide:
desired energy = 8.445301996 mole/hr x (598.945 kJ/mole 412.9kJ/mole)
= 1571.20621 kJ/hr
Oxygen:
282

desired energy = 0.584009114mole/hr x (450.326kJ/mole 0)
= 262.9945 kJ/hr
Nitrogen;
desired energy = 119.3204777mole/hr x (436.974kJ/mole )
= 52139.9462 kJ/hr
Total desired energy = 231758.1039 kJ/hr + 84484.2265 kJ/hr + 10762.7655
kJ/hr +
10762.7655 kJ/hr + 26227.5486 kJ/hr + 1571.20621 kJ/hr
+ 262.9945 kJ/hr + 52139.9462 kJ/hr
= 417969.5568 kJ/hr


Simulation value for stream 9a = 2.457MMkcal/hr
Percentage error of energy is
Simulation = 0.095x 10
6
kcal/hr x 4.1858j/cal = 397651kJ/hr
Percentage error = x 100%
Percentage error = x 100% =4.8%


Stream 13
N-butane:
desired energy = 1.0896mole/hr x (209.3kJ/mole-147.0 kJ/mole)
= 67.888kJ/hr
1,3 butadiene:
desired energy = 115.8566mole/hr x (7251.714kJ/mole - 1127kJ/mole)
= 709588.54kJ/hr

Total desired energy = 67.888kJ/hr + 709588.54kJ/hr
= 709656.428 kJ/hr
283

Simulation value for stream 9a = 4.0MMkcal/hr
Percentage error of energy is
Simulation = 0.15x 10
6
kcal/hr x 4.1858j/cal = 627870 kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 11.52%


Stream 15
N-butane:
desired energy = 6.965058584 mole/hr x (887.404kJ/mole-147.0 kJ/mole)
= 5156.9572 kJ/hr
1-butene:
desired energy = 110.3348351mole/hr x (780.367kJ/mole + 1.17 kJ/mole)
= 86230.7559 kJ/hr
Carbon dioxide
desired energy = 11.36487036mole/hr x (358.833kJ/mole - 412.9 kJ/mole)
= -614.4644 kJ/hr


Oxygen:
desired energy = 0.422452344mole/hr x (270.038kJ/mole)
= 114.0782 kJ/hr
Nitrogen
desired energy = 0.177786569mole/hr x (262.032kJ/mole )
= 46.5858 kJ/hr
Total desired energy = 5156.9572 kJ/hr + 86230.7559 kJ/hr -614.4644 kJ/hr +
114.0782 kJ/hr + 46.5858 kJ/hr
= 90933.9127 kJ/hr
Simulation value for stream 15 = 8.783MMkcal/hr
284

Percentage error of energy is
Simulation = 0.02x 10
6
kcal/hr x 4.1858j/cal = 83716kJ/hr
Percentage error = x 100%
Percentage error = x 100% = 7.94%




























285






APPENDIX B









EQUIPMENT SIZING
































286

Reactor specification
Identification number : R-102
Number required : 4 ( parallel)
Date : 2/3/2010
By : Kumaran
Function To convert n-butane feed to1,3butadiene
General
Type of reactor
orientation
operation
catalytic tubular fixed bed
vertical
continuous
Feed (kmol/h)
nbutane
1butene
c2butene
1,3butadiene
steam
carbon dioxide
hydrogen
nitrogen
oxygen
Total flow
Temperature
Pressure
246.3758717
84.11562543
180.5810164
18.0764008
616.6877427
11.37091046
8573.518106
0
640.3678968
10371.09
450(C)
2.0 atm
Catalyst
Type

Volume
Weight
Shape
Conversion of C4mixture :
selectivity of 1,3 butadiene
yield
holding method
Bismuth molybdate(10wt% BiMo3O12
and 90% BiMo2O 12)
422.72 m
3

608716.8 kg
6.0 mm spherical pellets
0.6
2mol C4H6/1molCO2 formed
0.6
wire gauze and clamping ring

Tube
Number
length
catalyst fill height
Inside diameter
Outside diameter
Gauge
Heat transfer area
passes
Tube arrangement pattern
Tube pitch
Pressure drop
Inlet temperature
Outlet temperature
34760
6.0 m
6.0m
25.4 mm
31.8mm
BWG 12(heavy)
7882m
2

1(up flow)
square
39.7 mm
1atm
450C
500C
Shell
Fluid
fluid composition
Flow rate
Hitec heat transfer salt
40% NaNO2. 7%NaNo3, 53%KNO3
10371.09kmol/h
287

Inlet temperature
outlet temperature
Heat removed per tube
Heat transfer coefficient
Inside diameter
Passes
Baffles
Pressure drop
144oC
600oC
253 W
40 W/m2K
6.49m
1
5(segmental)
242.31Pa
Materials of construction
ASTM code

General description
Grade and class
Composition
tensile strength
Yield strength
A387 : Pressure vessel plates, alloy steel,
chromium molybdenum
High alloy chromium steel
stainless steel Type 316
18% Cr, 8% Ni, 2.5% Mo,
500MPa-650MPa
310 MPa
Mechanical design of reactor vessel
Overall height
outside diameter
Total weight(empty)
Design pressure
MAWP
wall thickness
Tube plate
Type of ends ellipsoidal,
end thickness
Gas connection
8.0 m
6.49m
240 T
22 atm
22 atm
20mm
25mm
2.5:1
21mm
1492mm steel pipe

Insulation
Type
Thermal conductivity
Thickness
Mineral fibre double blanket
0.036 W/mK
150 mm(2x75mm)












288

DISTILLATION COLUMN
Identification: Item:
Item Number: D-103
No. Required: 1
Date: 1-Mac-10
By: Wan M. Irman

Function:To recover n-butane and 1-butene
Operation: Continuous

Materials handled:
Feed Overhead Reflux
Bottoms
Quantity (kg/hr) 15504.4987 7117.66732 34323.527
7399.3551
Component (kg/hr)
n-butane 7791.010 404.995 1953.007
899.899
1-butene 6577.008 6190.235 29851.17 -
2-butene 325.594 -
461.719
Water 434.126 -
36.997
Carbon Dioxide 356.603 499.66 2409.51
-
Oxygen 13.954 13.524 65.217
-
Nitrogen 6.202 9.253 44.621
-
Temperature, C
116 115 115
144

Design Data:
No. of trays: 31
Feed stage (from bottom):3
Pressure, atm: Top of the column: 3.5
Bottom of the column: 4.5
Reflux ratio: 4.82
Functional height, m: 31.40
Tray spacing, m: 0.91
Material of construction: Stainless Steel 316
Liquid density, kmol/m : 8.23
Vapor density, kmol/m : 0.11
Maximum allowable vapor velocity (superficial), m/s: 0.64
Maximum vapor flow rate, m /s: 760.06
Recommended inside diameter, m: 2.13
Tray efficincy, %: 60
Utilities: Cooling water, steam
Control: Reflux ratio, column pressure, number of trays
289

Tolerances: Heuristic
Comment and Drawing: Included





CONDENSER
Identification: Item:
Item Number: E-107
No. Required: 1
Date : 1-Mac-10
By : Wan M. Irman
Function: To condense the overhead vapor from distillation column D-103
Operation: Continuous
Type: Shell and Tube Fixed-tube
Tube side: Tubes:
Fluid handled: cooling water Outside diameter: 50 mm
Flow rate: 2062.809 kg/hr Inside diameter: 46 mm
Temperature: 30C to 45C Length: 610 mm
Pressure: 1 atm Pitch: Arrangement
Pressure drop: 0.27 atm Passes: 4
Material of construction: Carbon steel Tube per pass: 86
Shell Side: Shell:
Fluid handled: Overhead vapors Baffle spacing: 1502.81
mm
Flow rate: 11.86 kg/s Inside diameter: 1502.81
mm
Temperature: 115C Pressure: 3.5 atm Passes: 1
Pressure drop: 0.019 atm
Material of construction: Carbon steel
Overall Coefficient: 553.16 W/mC
Utilities: Cooling water
Control: Tubular Exchangers Manufacturers Association (TEMA) Standards
Tolerances: Heuristic
Comment and Drawing: Included








290

REBOILER
Identification: Item:
Item Number: E-108
No. Required: 1
Date : 1-Mac-10
By : Wan M. Irman
Function: To vaporize partial of the bottom product from distillation column D-
103
Operation: Continuous
Type: Shell and Tube U-tube
Tube side: Tubes:
Fluid handled: Dowtherm A Outside diameter: 30 mm
Flow rate: 72108 kg/hr Inside diameter: 25 mm
Temperature: 305C Nominal Length: 10400
mm
Pressure: 1 atm Pitch: Arrangement
Material of construction: Carbon steel Passes: 2
Tube per pass: 340
Shell Side: Shell:
Fluid handled: Overhead vapors Inside diameter: 1502.81
mm
Flow rate: 7117.66732 kg/hr Passes: 1
Temperature: 115C
Pressure: 0.019 atm
Material of construction: Carbon steel
Overall Coefficient: 553.16 W/mC
Utilities: Cooling water
Control: Tubular Exchangers Manufacturers Association (TEMA) Standards
Tolerances: Heuristic
Comment and Drawing: Included















291

PUMP
Identification Item Type : Centrifugal pump Date : 1 Mac 10
Item No : P-105A/B By : Wan M. Irman
No Required : 1
Function Used to move reactant or liquids from one place to another
by mechanical means (lower pressure to higher pressure).
Operation Continuous
Orientation &
Dimension

Mass Flow Rate : 7117.66732 kg/h
Shaft Power : 0.697 kW
Fluid Power : : 0.557 kW
Operating
Condition
Pressure Difference : 1 atm
Temperature : 34C
Material of
Construction
-Alloys including Alloy 20, 317L and Hastelloy.
-Low temperature materials
Utilities The electricity for power requirement is bought from TNB
Controls The volumetric flowrate and pressure required.
Tolerances Based on reference and heuristics rules
Ref , Mc Cabe Smith Harriot,Unit Operation of chemical
engineeringSixth Edition)



















292

PUMP
Identification Item Type : Centrifugal pump Date : 1 Mac
10
Item No : P-106A/B By : Wan M.
Irman
No Required : 1
Function Used to move reactant or liquids from one place to another
by mechanical means (lower pressure to higher pressure).
Operation Continuous
Orientation &
Dimension

Mass Flow Rate :7117.66732 kg/h
Shaft Power : 0.697 kW
Fluid Power : 0.557 kW
Operating
Condition
Pressure Difference : 1atm
Temperature : 34C
Material of
Construction
-Alloys including Alloy 20, 317L and Hastelloy.
-Low temperature materials
Utilities The electricity for power requirement is bought from TNB
Controls The volumetric flowrate and pressure required.
Tolerances Based on reference and heuristics rules
Ref , Mc Cabe Smith Harriot,Unit Operation of chemical
engineeringSixth Edition)

















293

PUMP
Identification Item Type : Centrifugal pump Date : 1 Mac 10
Item No : P-107A/B By : Wan M. Irman
No Required : 1
Function Used to move reactant or liquids from one place to another
by mechanical means (lower pressure to higher pressure).
Operation Continuous
Orientation &
Dimension

Mass Flow Rate :7399.3551 kg/h
Shaft Power : 0.362 kW
Fluid Power : 0.289 kW
Operating
Condition
Pressure Difference : 0.5 atm
Temperature : 115C
Material of
Construction
-Alloys including Alloy 20, 317L and Hastelloy.
-Low temperature materials
Utilities The electricity for power requirement is bought from TNB
Controls The volumetric flowrate and pressure required.
Tolerances Based on reference and heuristics rules
Ref , Mc Cabe Smith Harriot,Unit Operation of chemical
engineeringSixth Edition)





















294

COMPRESSOR
Identification : Item Compressor Date : 1 Feb 2010
Item No. C-106A/B
No. required 1 By : Kumaran
Function : Use to increase the pressure on a fluid to transport it
through a pipe.
Operation : Continuous Flow
Type : Centrifugal Single Stage Compressor
Materials Handled
(kmol/hr)
CO
2
=1293.42882
H
2
=1430.380107
O
2
=3804.202412
N
2
=42702.17207
Design Data Inlet pressure : 1 atm
Outlet pressure : 2 atm
Inlet temperature : 450 C
Outlet temperature : 470C
Pressure change, P : 1 atm
Compressor power : 1462.84kW
Compressor efficiency : 80 %
No. of stages : 1 (single stage)
Compressor ratio : 4
Utilities : Electricity supply
Material of Construction : Stainless steel
Tolerances : Rules of thumb for compressor

Storage Tank TK-2
Identification: storage tank By: Wan M. Irman
Item No: TK-2 Date: 1-Mac-10
No required: 1
Function: to store the 1-Butene
Operation: hold tank
Type: Vertical tank on concrete pad
Temp: 34 C
Design Data
Diameter: 2.33 m
Height: 6.978 m
Volume: 29.656 m
Material of construction: Stainless steel type 302
Insulation: Not provided
Comments and Drawings: Not provided



295


CONDENSER


Identification: Item:
Item Number: E-106
No. Required: 1

Date : 1-Mac-10
By : Wan M. Irman
Function: To condense the overhead vapor from distillation column D-103

Operation: Continuous

Type: Shell and Tube Fixed-tube

Tube side: Tubes:
Fluid handled: cooling water Outside diameter: 50
mm
Flow rate: 2062.809 kg/hr Inside diameter: 46 mm
Temperature: 30C to 45C Length: 610 mm
Pressure: 1 atm Pitch: Arrangement
Pressure drop: 0.27 atm Passes: 4
Material of construction: Carbon steel Tube per pass: 86

Shell Side: Shell:
Fluid handled: Overhead vapors Baffle spacing: 1502.81
mm
Flow rate: 11.86 kg/s Inside diameter:
1502.81 mm
Temperature: 115C Pressure: 3.5 atm Passes: 1
Pressure drop: 0.019 atm
Material of construction: Carbon steel
Overall Coefficient: 553.16 W/mC

Utilities: Cooling water

Control: Tubular Exchangers Manufacturers Association (TEMA) Standards

Tolerances: Heuristic

Comment and Drawing: Included


DISTILLATION COLUMN

Identification: Item:
Item Number: T-102
No. Required: 1

Date: 1-Mac-10
By: Wan M. Irman

Function: To recover n-butane and 1-butene
296

Operation: Continuous

Materials handled:
Feed Overhead Reflux
Bottoms
Quantity (kg/hr) 15504.4987 7117.66732 34323.527
7399.3551
Component (kg/hr)
n-butane 7791.010 404.995 1953.007 6899.899
1-butene 6577.008 6190.235 29851.17 -
2-butene 325.594 - 461.719
Water 434.126 - 36.997
Carbon Dioxide 356.603 499.66 2409.51
-
Oxygen 13.954 13.524 65.217
-
Nitrogen 6.202 9.253 44.621
-
Temperature, C
116 115 115
144

Design Data:
No. of trays: 31
Feed stage (from bottom):3
Pressure, atm: Top of the column: 3.5
Bottom of the column: 4.5
Reflux ratio: 4.82
Functional height, m: 31.40
Tray spacing, m: 0.91
Material of construction: Stainless Steel 316
Liquid density, kmol/m : 8.23
Vapor density, kmol/m : 0.11
Maximum allowable vapor velocity (superficial), m/s: 0.64
Maximum vapor flow rate, m /s: 760.06
Recommended inside diameter, m: 2.13
Tray efficincy, %: 60

Utilities: Cooling water, steam

Control: Reflux ratio, column pressure, number of trays

Tolerances: Heuristic

Comment and Drawing: Included





297




APPENDIX C








EQUIPMENT COSTING


































298

Costing Calculations for Isomerazation Process Reactor R-103


The Chemical Engineering Plant Cost Index (CEPCI) of 2001 = 394
The Chemical Engineering Plant Cost Index (CEPCI) of 2010 = 632.6.

Pressure = 3 barg
Height = 9.58 m
Diameter = 3.19 m

Therefore,
a) Volume = D
2
L/4 = (3.14159)(3.19m)
2
(9.58m)/4 = 76.5661 m
3

From Equation A.1 (refer table A.1)
log
10
C
p
(2001) = K
1
+ K
2
log
10
V + K
3
(log
10
V)
2

= 3.3496 -0.2765 log
10
(76.5661) + 0.0025
[log
10
(76.5661)
2
]
= 2.8192
C
p
(2001) = 10
2.8192
=$659.4775
C
p
(2010) = $659.4775 (632.6/394) = $1 058.8464

b) From Equation 7.10 with P= 3 barg and D=3.19m
F
p,vessel
=
= 1.6969


c) From Table A.3 identification number of stainless steel vertical vessel =
20,
From Figure A.18, F
M
= 3.11

d) From Equation A.3 and Table A.4, F
BM
= [B
1
+ B
2
F
p
F
M
]
F
BM
= [2.25 + 1.82F
p
F
M
]
= [2.25 + 1.82 (1.6969)(3.11)] = 11.8548
299

C
BM
(2010) = $1 058.8464 (11.8548) =
1 USD = RM 3.6996
C
BM
= RM46 439.9046


Cost for Solvent Recovery Distillation Column (NMP)


The costs of the tower and trays are calculated separately and then added together
to
obtain the total cost. All the figures, tables and equations are from Analysis,
Synthesis, and Design of Chemical Processes, 3rd Edition.

The Chemical Engineering Plant Cost Index (CEPCI) of 2001 = 394
The Chemical Engineering Plant Cost Index (CEPCI) of 2010 = 632.6.

For the tower:
a) Volume = D
2
L/4 = (3.14159)(2.8m)
2
( 13.3m)/4 = 81.8949 m
3

From Equation A.1 (refer table A.1)
log
10
C
p
(2001) = K
1
+ K
2
log
10
V + K
3
(log
10
V)
2

= 3.4974 + 0.4485 log
10
(81.8949) + 0.1074
[log
10
(81.8949)
2
]
= 4.7665
C
p
(2001) = 10
4.7665
=$58 406.78
C
p
(2010) = $58 406.78 (632.6/394) = $93 776.9772

b) From Equation A.3 and Table A.4, F
BM
= [B
1
+ B
2
F
p
F
M
]
F
BM
= [2.25 + 1.82F
p
F
M
]

c) From Equation 7.10 with P= 5 bar and D=2.8m
F
p,vessel
=
= 2.08053
300

From Table A.3 identification number of stainless steel vertical vessel =
20,
From Figure A.18, F
M
= 3.11

So, F
BM
= [2.25 + 1.82 (2.08053)(3.11)] = 14.0262
C
BM
(2010) = $93 776.9772(14.0262) = $1 315 334.638

For the trays:


a) Tray (tower) area = D
2
/4 = (3.14159)(2.8m)
2
/4 = 6.1572m
2

From Equation A.1 :
log
10
C
p
(2001) = K
1
+ K
2
log
10
A + K
3
(log
10
A)
2

= 2.9949 + 0.44651 log
10
(6.1572) + 0.3961
[log
10
(6.1572)
2
]
= 3.9727
C
p
(2001) = 10
3.9727
=$9 390.7440
C
p
(2010) = $9 390.7440 (632.6/394) = $15 077.6260

b) From Table A.5,
C
BM
= C
p
NF
BM
f
q
N= 42
f
q
= 1.0 (since number of trays > 20, Table A.5)

c) From Table A.6, SS sieve tray identification number = 61; from Figure
A.19, F
BM
=1.83
C
BM
(2010) = $15 077.6260 (42)(1.83)(1.0) = $1 158 866.334

For the tower plus trays,
C
BM,towe+trays
(2010) = $1 315 334.638 + $1 158 866.334
= $2 474 200.972
1 USD = RM 3.6996
C
BM
= RM9 153 553.916


301

Costing Calculation of Pump (P-104A/B)


Basic operation : 1 hour
Total Mass :15 320.9696 kg/hr
Density, : 25 305.939 kg/m
3

: 80%
The Chemical Engineering Plant Cost Index (CEPCI) of 2001 = 394
The Chemical Engineering Plant Cost Index (CEPCI) of 2010 = 632.6.

Qp = = = 0.00016817 m
3
/s
P = 2 bar 1 bar = 1 bar = 101325 N/m
2

Power = P x Qp x
= 101325 N/m x 0.00016817 x = 0.01363 kW=
0.0183hp
C
BM
= C
p
x (B
1
+ B
2
F
M
F
p
) x UF

C
BM
= Bare Modules Cost
C
p
= Purchase Equipment Cost
(B
1+
B
2
F
M
F
p
) = F
BM
= Bare Modules Cost
UF = Update Factor
UF=
UF= = 1.6056

a) From shaft power 0.01363 kW, From Equation A.1 (refer table A.1)
log
10
C
p
(2001) = K
1
+ K
2
log
10
V + K
3
(log
10
V)
2

= 3.3892 + 0.0536 log
10
(0.01363) + 0.1538
[log
10
(0.01363)
2
]
= 2.7154
C
p
(2001) = 10
2.7154
=$519.2781
C
p
(2010) = $519.2781 (632.6/394) = $833.7445

302

b) From Equation A.3 and Table A.4, F
BM
= [B
1
+ B
2
F
p
F
M
], F
BM
= [1.89 +
1.35F
p
F
M
] ,

At 2 bar, the pressure factor,from Table A.2, F
p
= 1 from Equation A.3
Log
10
F
p
= C
1
+ C
2
log
10
P+ C
3
(log
10
P)
2

c) From Table A.3 identification number of centrifugal pump = 40,
From Figure A.18, F
M
= 4.2

d) So, F
BM
= [1.89 + 1.35 (1.0)(4.2)] = 7.56
C
BM
(2010) = $833.7445 (7.56)(1.6056) = $10 120.2709
1 USD = RM 3.6996
C
BM
= RM37 440.9541



Cost for Heat Exchanger (E-106)

All the figures, tables and equations are from Analysis, Synthesis, and Design of
Chemical Processes, 3rd Edition.

Total heat transfer area, A = 28.7 m
Operating pressure, P = 2 bar
The purchase cost of 1 unit shell and tube heat exchanger with heat transfer area
of
28.7 m , from figure A.7.4,
C
p
(2001) = ($700)(28.7) = $20 090

At 2 bar, the pressure factor, F
p
= 1 from Equation A.3
Log
10
F
p
= C
1
+ C
2
log
10
P+ C
3
(log
10
P)
2

For carbon steel shell and tube side, the material factor, FM = 1.0
Multiply F
p
x F
M
= 1.0

303

The value of B
1
and B
2
for floating-head heat exchanger from Table A.4 is
B
1
= 1.63
B
2
= 1.66

The Chemical Engineering Plant Cost Index (CEPCI) of 2001 = 394
The Chemical Engineering Plant Cost Index (CEPCI) of 2010 = 632.6

So, the bare module cost, C
BM
from equation A.4
C
BM
= C
p
[B
1
+ B
2
F
p
F
M
]
C
BM
(2001) = $20 090 [1.63 + 1.66x1] = $66 096.1
C
BM
(2009) = $ 66 096.1 (632.6/394) = $106 122.8245
1 USD = RM 3.6996
C
BM
= RM392 612


Cost for Reboiler (E-106)


All the figures, tables and equations are from Analysis, Synthesis, and Design of
Chemical Processes, 3rd Edition.

Total heat transfer area, A = 9.13 m
Operating pressure, P = 2 bar
Heat duty = 365.43892 kW
The Chemical Engineering Plant Cost Index (CEPCI) of 2001 = 394
The Chemical Engineering Plant Cost Index (CEPCI) of 2010 = 632.6.
The purchase cost of 1 unit kettle reboiler with heat transfer area of
9.13 m , from figure A.7.4,
C
p
(2001) = ($2500)(9.13) = $22 825
C
p
(2010) = $22 825 (632.6/394) = $36 647.4492

At 2 bar, the pressure factor, F
p
= 1 from Equation A.3
Log
10
F
p
= C
1
+ C
2
log
10
P+ C
3
(log
10
P)
2

For carbon steel kittle reboiler, the material factor, F
M
= 1.0
304

Multiply F
p
x F
M
= 1.0

The value of B
1
and B
2
for kettle reboiler at Table A.4 is
B
1
= 1.63
B
2
= 1.66

So, the bare module cost, C
BM
from equation A.4
C
BM
= C
p
[B
1
+ B
2
F
p
F
M
]
C
BM
(2001) = $36 647.4492 [1.63 + 1.66x1] = $120 570.1079
C
BM
(2009) = $ 120 570.1079 (632.6/394) = $193 585.4067
1 USD = RM 3.6996
C
BM
= RM716 188.5706




Estimation of Utilities Cost


Utilities cost includes electricity, steam for heating and cooling water for
cooling purpose. There are 8000 working hours in this production plant.


Electricity
Price per unit = RM 0.26/kWh (TNB)
Total power required = 3,263,363.062 kWh/yr
Annual electricity cost = 3,263,363.062 kWh/yr X RM 0.26/kWh
= RM 848,474.40/yr


Water
Price per unit = RM 1.20/m
3

Total Water required = 158,402.16 m
3
/yr
Annual water cost = RM 190,082.59


Water cooling
Price per unit = RM 0.26/1000 kg
Amount of water required = 107634.13kg/hr
Water required for one month = 77496573.9 kg/month
Water cost = 77496573.9 kg/month X RM 0.26/1000 kg
= RM 20149.11

305

Steam
Price per unit = RM 14.25/1000 kg
Amount of water required = 690,892.74 kg/hr
Water cost = 690,892.74 kg/hr X RM 14.25/1000 kg
= RM 9845.22/yr


































95

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/0/-1
,23,45,5 64708,
-449-1
,23,45,5 :,3.,76-/604 4,/ 3.0;6/ /-2 <=(>? 3.0;6/ -;/,. /-2
4,/ 7-5@
64708,
5988-/604
4,/ 7-5@
64708,
& ABCCBDED'B&F ABCCBDED'B&F ABCCBDED'B&F
E AE(F)BDB&'C= AE(F)BDB&'C= AE)&=D(*B'&D
= AF(*)==FE'BC AF(*)==FE'BC A)*&&)CD*')*
C &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) ( FFG)&EGFDC'F) BCG(()G==('B( A&D&&(&E*'&*
D &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) ( FFG)&EGFDC'F) BCG(()G==('B( D))*)E(&'D&
F &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) ( FFG)&EGFDC'F) BCG(()G==('B( &=E*(FD=E'E
B &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) ( FFG)&EGFDC'F) BCG(()G==('B( E(F*&C)FE'*
) &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) ( FFG)&EGFDC'F) BCG(()G==('B( E)(*E=&*='F
* &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( ==C))BBEB'*
&( &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( =)))DEEFE'E
&& &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( CCE)&FB*F'D
&E &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( C*FB)&==(')
&= &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( DD(BCD)FD'&
&C &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( F(CB&(=**'C
&D &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( FD)FBC*=='B
&F &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( B&EF=*CF)
&B &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( BFFF(C((E'=
&) &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( )E(DF)D=F'F
&* &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( )BCD==(B('*
E( &**GDD*GE(B'(( &EDGDD(G)BF'=( BG&*DGFBF'(E FFG)&EGFDC'F) E((C=B*F'C CFGBF)G)D)'E) D=G*FCGD=C'=( *E)C*BF(D'E


95

Discounted Cash Cumulative


+,-. 4,/ 3.0;6/ :7;.. <&(>? 798891-/6H,
& AFBB(CBB'*E= AFBB(CBB'*E=
E A&B(*B&FF'CB AE=)FBFCC'C
= ACD)&BB(='(C AF*F)D=CB'C=
C FFG)&EGFDC'F) D(DC)F)D'F) A&*&=FFF&'BF
D FFG)&EGFDC'F) CD*D==D('FE EF)&FF))')F
F FFG)&EGFDC'F) C&BBDBB='E* F)D*ECFE'&C
B FFG)&EGFDC'F) =B*BB*BD'BE &(FDB(C=B'*
) FFG)&EGFDC'F) =CDEDC=E'CB &C&(*D)B('=
* FFG)&EGFDC'F) EE))FE=('CB &F=*)E&((')
&( FFG)&EGFDC'F) E()(DFFC'(B &)CB)BBFC'*
&& FFG)&EGFDC'F) &)*&CEC('(F E(=B(E((C'*
&E FFG)&EGFDC'F) &B&*CBF='F* EE()*FBF)'F
&= FFG)&EGFDC'F) &DF=&F(='=D E=FDE)=BE
&C FFG)&EGFDC'F) &CE&(DC)'D ED(B=)*E('D
&D FFG)&EGFDC'F) &E*&)F)('CF EF=FDBF(('*
&F FFG)&EGFDC'F) &&BCCEDC'*F EBDC(&)DD'*
&B FFG)&EGFDC'F) &(FBFD*D'CE E)F(B)CD&'=
&) FFG)&EGFDC'F) *B(D**D')=F E*DB)CCCB'E
&* FFG)&EGFDC'F) ))E=F=E'DB* =(CF()(B*'B
E( FFG)&EGFDC'F) )(E&C)C'&FE =&EFE*DF='*























308

+,-. 4,/ 3.0;6/ :7;.. <E(>? 798891-/6H,
& AFE(FEB&'C= AFE(FEB&'C=
E A&C=FF=F*'(D AE(DBEFC('C)
= A=DE*&E*B')) ADD)F=*=)'=F
C FFG)&EGFDC'F) =DF*(BCD'* AE(&B=&*E'CF
D FFG)&EGFDC'F) E*BCEE))'ED *DF*(*D'B)B
F FFG)&EGFDC'F) ECB)DEC('E& =C=DC==F
B FFG)&EGFDC'F) E(FDC=FF')C DD(()B(E')C
) FFG)&EGFDC'F) &BE&&*BE'=B BEEE(FBD'E
* FFG)&EGFDC'F) &(CD)F))'E) )EFB*=F='C)
&( FFG)&EGFDC'F) )B&DDB='DFB *&=*C*=B'(D
&& FFG)&EGFDC'F) BEFE*BB'*BE *)FDB*&D'(E
&E FFG)&EGFDC'F) F(DEC)&'FCC &(CB&(=*F'B
&= FFG)&EGFDC'F) D(C=B=C'B(= &(*BDC&=&'C
&C FFG)&EGFDC'F) CE(=&&E'ED= &&=*DBEC='F
&D FFG)&EGFDC'F) =D(ED*='DCC &&BCD*)=B'E
&F FFG)&EGFDC'F) E*&))EB'*D= &E(=B)FFD'&
&B FFG)&EGFDC'F) EC=E=DF'FE) &EE)&&(E&'B
&) FFG)&EGFDC'F) E(EF*F=')DF &EC)=B*)D'F
&* FFG)&EGFDC'F) &F)*&=F'DCB &EFDEB&EE'E
E( FFG)&EGFDC'F) &C(BF&='B)* &EB*=CB=D'*


+,-. 4,/ 3.0;6/ :7;.. <=(>? 798891-/6H,
& ADBE))FD'*=D ADBE))FD'*C
E A&EEC&&FF'D= A&B*B((=E'CB
= AEBBDBDF&'DF ACDBEBD*C'(=
C FFG)&EGFDC'F) ED*&E=B='BF A&*)&DEE('EB
D FFG)&EGFDC'F) &**=ED*D'E &&B=BC'*=DB
F FFG)&EGFDC'F) &D==EBFD'DC &DCD(&C('CB
B FFG)&EGFDC'F) &&B*CC=D'(= EBECCDBD'D&
) FFG)&EGFDC'F) *(BEFCE'==& =F=&BE&B')C
* FFG)&EGFDC'F) D()))=='BC* C&C(F(D&'D)
&( FFG)&EGFDC'F) =*&CC)B'C** CD=E(D=*'()
&& FFG)&EGFDC'F) =(&&&CC'E= C)==&F)='=&
&E FFG)&EGFDC'F) E=&FEFC'B*E D(FCB*C)'&&
&= FFG)&EGFDC'F) &B)&BCE'&C) DECE*F*('ED
&C FFG)&EGFDC'F) &=B(DB('))= D=)((EF&'&C
&D FFG)&EGFDC'F) &(DCE)D'E*D DC)DCDCF'C=
&F FFG)&EGFDC'F) )&(*))'F))E DDFFDD=D'&E
&B FFG)&EGFDC'F) FE=)=B'CDEC DFE)*=BE'DB
&) FFG)&EGFDC'F) CB*)BC'*F=C DFBF*ECB'DC
&* FFG)&EGFDC'F) =F*&=C'D)BE DB&=)=)E'&E
E( FFG)&EGFDC'F) E)=*C*'F)ED DBCEE==&')&

309

+,-. 4,/ 3.0;6/ :7;..<C(>? 798891-/6H,
& AD=&*FF&'EEF AD=&*FF&'E
E A&(DDC))='=) A&D)BCDCC'D)
= AEEEECEDB'DF A=)(*))(E'&C
C FFG)&EGFDC'F) &*EFC*BD'B& A&))==)EF'C=
D FFG)&EGFDC'F) &=BF(F*F'*C AD(B=&E*'C*=
F FFG)&EGFDC'F) *)E*(F*'EC& CBDD*=*'BC*
B FFG)&EGFDC'F) B(E(BF='BCC &&BBFB(='C*
) FFG)&EGFDC'F) D(&C)=&'ECF &FB*&D=C'BC
* FFG)&EGFDC'F) EF&&)*B'=*F &*C(=C=E'&=
&( FFG)&EGFDC'F) &)FDFC('**B E&EF*(B='&=
&& FFG)&EGFDC'F) &==EF(('B&E EEF(&FB=')C
&E FFG)&EGFDC'F) *D&)DB'FD&F E=DD=D=&'D
&= FFG)&EGFDC'F) FB*)*)'=EEF ECE==CE*')E
&C FFG)&EGFDC'F) C)DFC&'FD* ECB&*(B&'C)
&D FFG)&EGFDC'F) =CF))F')**= ED(FD*D)'=)
&F FFG)&EGFDC'F) ECBBBF'=DFF ED=&=B=C'B=
&B FFG)&EGFDC'F) &BF*)='&&&* EDC*(B&B')D
&) FFG)&EGFDC'F) &EFC&F'D()D EDF&B&=C'=D
&* FFG)&EGFDC'F) *(E*B'D(F(F EDB(BC=&')F
E( FFG)&EGFDC'F) FCC*)'E&)FE EDBB&*=('()


+,-. 4,/ 3.0;6/ :7;..<D(>? 798891-/6H,
& AC*FD(&B'&CC AC*FD(&B'&
E A*&*CCBF'&*E A&C&D*C*='E*
= A&)(F*&CC'DE A=EEE)F=B')&
C FFG)&EGFDC'F) &CF&)*E*'DE A&BF(*B()'E*
D FFG)&EGFDC'F) *BCD*D='(&C AB)F=BDD'EBC
F FFG)&EGFDC'F) FC*B=(E'((* A&=FFCD='EFD
B FFG)&EGFDC'F) C==&D=C'FB= E*FD()&'C()
) FFG)&EGFDC'F) E))BF)*'B)E D)DEBB&'&*
* FFG)&EGFDC'F) &C(=BC&'=B* BEDFD&E'DF*
&( FFG)&EGFDC'F) *=D)EB'D)D* )&*E=C('&DD
&& FFG)&EGFDC'F) FE=))D'(DB= ))&FEED'E&E
&E FFG)&EGFDC'F) C&D*E='=B&D *E=E&C)'D)=
&= FFG)&EGFDC'F) EBBE)E'ECBB *D(*C=(')=&
&C FFG)&EGFDC'F) &)C)DC')=&) *F*CE)D'FF=
&D FFG)&EGFDC'F) &E=E=F'DDCD *)&BDEE'E&B
&F FFG)&EGFDC'F) )E&DB'B(=(& *)**FB*'*E
&B FFG)&EGFDC'F) DCBB&')(E(& **DCCD&'BEE
&) FFG)&EGFDC'F) =FD&C'D=CFB ***(*FF'EDB
&* FFG)&EGFDC'F) EC=C='(E=&E &((&D=(*'E)
E( FFG)&EGFDC'F) &FEE)'F)E() &((=&D=B'*F

310

+,-. 4,/ 3.0;6/ :7;..<F(>? 798891-/6H,
& ACFDCB(='DBE ACFDCB(='DB
E A)()&()E'D*& A&EB=DB)F'&F
= A&C)))D&F'= AEBFEC=(E'CF
C FFG)&EGFDC'F) &&E*EBBD'(B A&F==&DEB'=*
D FFG)&EGFDC'F) B(DB*)C'C&* A*EB=DCE'*FB
F FFG)&EGFDC'F) CC&&EC('EFE AC)FE=(E'B(D
B FFG)&EGFDC'F) EBDB(ED'&FC AE&(DEBB'DC&
) FFG)&EGFDC'F) &BE=&C('BEB A=)E&=F')&C&
* FFG)&EGFDC'F) B)DE)B'=E)C C(=&D('D&C=
&( FFG)&EGFDC'F) C*()(C'D)(= )*=*DD'(*CD
&& FFG)&EGFDC'F) =(FBDE')FEB &E((B(B'*DB
&E FFG)&EGFDC'F) &*&BE('D=*E &=*ECE)'C*F
&= FFG)&EGFDC'F) &&*)ED'==B &D&EED=')==
&C FFG)&EGFDC'F) BC)*(')=DF& &D)B&CC'FF*
&D FFG)&EGFDC'F) CF)(F'BBEEF &F==*D&'CC&
&F FFG)&EGFDC'F) E*EDC'E=EFF &FF=E(D'FBC
&B FFG)&EGFDC'F) &)E)=')*DC& &F)&C)*'DF*
&) FFG)&EGFDC'F) &&CEB'C=CF= &F*E*&B'((C
&* FFG)&EGFDC'F) B&CE'&CFFCF &B(((D*'&D&
E( FFG)&EGFDC'F) CCF=')C&FDC &B(CDEE'**E