Project Report On

“PRODUCTION OF 1,3-BUTADIENE”

Submitted in partial fulfilment of requirement for the award of degree

of B. Tech. – Chemical Engineering

Department of Chemical Engineering

Sardar Vallabhbhai National Institute of Technology – Surat

Year: 2023 – 24

Prepared By Guided by
Prit Kansagara (U20CH014) Dr. Alka A. Mungray
Rajat Govani (U20CH015) Associate Professor – DoChE, SVNIT
 CERTIFICATE

Department of Chemical Engineering

Sardar Vallabhbhai National Institute of Technology – Surat

This is to certify that the Project entitled “PRODUCTION OF 1,3-BUTADIENE” submitted

by Prit Kansagara (U20CH014), Rajat Govani (U20CH015) in the partial fulfilment of the
requirement for the award of degree B. Tech. in Chemical Engineering, Sardar Vallabhbhai
National Institute of Technology, Surat is the record of their work carried out by them under
the guidance of Dr. Alka A. Mungray, Associate Professor – DoChE, SVNIT.

Dr. Alka A. Mungray Head, DoChE

Associate Professor – DoChE, SVNIT Dr. Mousumi Chakraborty
Professor – DoChE, SVNIT

Place: SVNIT, Surat

Date: 08/12/2023

2
 EXAMINER’S CERTIFICATE OF APPROVAL

Department of Chemical Engineering

Sardar Vallabhbhai National Institute of Technology – Surat

This is to certify that the Project entitled “PRODUCTION OF 1,3-BUTADIENE” has been
submitted by Prit Kansagara (U20CH014) and Rajat Govani (U20CH015) in the partial
fulfilment of the requirement for the award of degree B. Tech. in Chemical Engineering, Sardar
Vallabhbhai National Institute of Technology, Surat is hereby approved.

Examiners:

1. Dr. Mousumi Chakraborty

Professor – DoChE, SVNIT

2. Dr. Jignasa V. Gohel

Associate Professor – DoChE, SVNIT

3. Dr. Jogender Singh

Assistant Professor – DoChE, SVNIT

4. TA5

Place: SVNIT, Surat

Date: 08/12/2023

3
 ACKNOWLEDGEMENT

We would like to take the opportunity to express our gratitude towards all the people who have
been involved in successful completion of this project, without them this project would have
never achieved the success it has.

With deep gratitude, We would like to acknowledge the invaluable time, work, advice, and
moral support that our project guide, Dr. Alka A. Mungray, Associate Professor –
Department of Chemical Engineering, SVNIT, has provided. By giving us the chance to
work on this project, her constant direction and assistance made it possible for it to be
completed successfully.

Prit Kansagara (U20CH014)

Rajat Govani (U20CH015)

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 Table of Contents

Table of Contents ....................................................................................................................... 5

List of Tables ............................................................................................................................. 8

List of Figures ............................................................................................................................ 9

Introduction .............................................................................................................................. 10

Market Analysis ....................................................................................................................... 12

Butadiene market in India .................................................................................................... 13

Preliminary Process Synthesis ................................................................................................. 14

Butadiene via Steam Cracking ............................................................................................. 14

Ethanol-to-Butadiene ........................................................................................................... 15

Process Description .................................................................................................................. 17

Overview .............................................................................................................................. 17

Section 100: Dehydrogenation of Ethanol ........................................................................... 18

Section 200: Separation of Hydrogen .................................................................................. 19

Section 300: Catalysis of Acetaldehyde-Ethanol ................................................................. 20

Section 400: Recovery of Butadiene.................................................................................... 22

Material Safety Data Sheets (MSDS) ...................................................................................... 24

Ethanol ................................................................................................................................. 24

1,3-Butadiene ....................................................................................................................... 29

Hydrogen.............................................................................................................................. 34

Acetaldehyde........................................................................................................................ 40

Material Balance ...................................................................................................................... 46

Material balance on Section 100 (Reactor 1): - ................................................................... 48

Material balance on Section 200 (H2 separation unit): - ...................................................... 49

Material balance on Section 300 (Reactor 2): - ................................................................... 50

Material balance on Section 400 (Recovery unit): - ............................................................ 52

Energy Balance ........................................................................................................................ 55

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 Energy balance on Reactor and Heater (Recovery unit): - .................................................. 55

Energy balance on Distillation column: - ............................................................................ 58

Thermodynamics and kinetics ................................................................................................. 63

Thermodynamic ................................................................................................................... 63

Kinetics ................................................................................................................................ 65

ASPEN PLUS Simulation........................................................................................................ 67

Section 100........................................................................................................................... 67

Section 200........................................................................................................................... 68

Section 300........................................................................................................................... 70

Section 400A........................................................................................................................ 71

Section 400B ........................................................................................................................ 73

Equipment Design .................................................................................................................... 76

Reactor Sizing Calculations (R-301) ................................................................................... 77

Flowrate Calculation ........................................................................................................ 77

Tube Internal Volume Calculation ................................................................................... 77

Number of Tubes Calculation .......................................................................................... 77

Tube Superficial Velocity Calculation ............................................................................. 77

Volume of Catalyst Calculation ....................................................................................... 77

Tube-side Pressure Drop Calculation .............................................................................. 78

Shell Sizing Calculation ................................................................................................... 78

Surface Area Heat Transfer Calculation .......................................................................... 79

Heat Transfer Coefficient Calculation ............................................................................. 79

Mechanical Design of Reactor (R-301) ............................................................................... 79

Shell Thickness Calculation ............................................................................................. 80

Design of Head ................................................................................................................ 82

Inlet and outlet Nozzle Design ......................................................................................... 82

Bolt Loading and Flange Thickness Calculations............................................................ 83

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 Design of Support ............................................................................................................ 86

Cost Estimation ........................................................................................................................ 88

Basic Data for Cost Calculation ........................................................................................... 89

Section 100........................................................................................................................... 90

Section 200........................................................................................................................... 92

Section 300........................................................................................................................... 93

Section 400........................................................................................................................... 94

Dowtherm Utility Section .................................................................................................. 101

REFERENCES ...................................................................................................................... 105

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 List of Tables
Table 1 Material Balance on R-301 ......................................................................................... 49
Table 2 Material Balance on F-201 .......................................................................................... 50
Table 3 Material Balance on R-301 ......................................................................................... 51
Table 4 Material Balance on D-401 ......................................................................................... 52
Table 5 Material Balance on D-402 ......................................................................................... 53
Table 6 Material Balnce on D-403 ........................................................................................... 53
Table 7 Material Balance on D-404 ......................................................................................... 54
Table 8 Material Balance on D-405 ......................................................................................... 54
Table 9 Enthalpy at different Temperature............................................................................... 55
Table 10 Section 100 Simulation Data..................................................................................... 67
Table 11 Section 200 Simulation Data ..................................................................................... 68
Table 12 Section 300 Simulation Data..................................................................................... 70
Table 13 Section 400A Simulation Data .................................................................................. 71
Table 14 Section 400B Simulation Data .................................................................................. 74
Table 15 R-301 Data Sheet for Design Calculation ................................................................. 76
Table 16 Section 100 Cost Summary ....................................................................................... 91
Table 17 Section 200 Cost Summary ....................................................................................... 92
Table 18 Section 300 Cost Summary ....................................................................................... 93
Table 19 Section 400 Cost Summary ..................................................................................... 100
Table 20 Dowtherm Heating Cost Summary ......................................................................... 102
Table 21 Total Product Cost From Table 27 of CEPDE Book ............................................... 103
Table 22 Whole Plant Cost Analysis ...................................................................................... 104

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 List of Figures
Figure 1 Butadiene Market ...................................................................................................... 12
Figure 2 Raw Material vs Production of Butadiene................................................................. 15
Figure 3 Block Flow Diagram of Plant .................................................................................... 17
Figure 4 Section 100 PFD ........................................................................................................ 19
Figure 5 Section 200 PFD ........................................................................................................ 20
Figure 6 Section 300 PFD ........................................................................................................ 21
Figure 7 Section 400A PFD ..................................................................................................... 22
Figure 8 Section 400B PFD ..................................................................................................... 23
Figure 9 Reinforcing Pad Limits for Nozzle............................................................................ 82
Figure 10 Effective Gasket Seating Width ............................................................................... 84
Figure 11 Vessel Support on Brackets ..................................................................................... 86
Figure 12 Table 17 of CEPDE Book ........................................................................................ 88
Figure 13 Table 6 from CEPDE Book ..................................................................................... 88

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 Introduction

1,3-Butadiene is a chemical compound that is crucial in producing synthetic materials. It is

commonly used as a monomer in creating styrene-butadiene rubber (SBR). Additionally, it is
utilized to manufacture adiponitrile, a precursor to nylon, and acrylonitrile-butadiene-styrene
(ABS). Other applications include the production of vinyl cyclohexene, cyclooctadiene,
cyclododecatriene, cycloalkanes, cycloalkenes, polybutadiene, hexamethylene diamine,
styrene-butadiene latex, chloroprene, and nitrile rubbers.

The primary method of butadiene production is through the extraction from an unsaturated
hydrocarbon mixture, which is a by-product of steam cracking of saturated hydrocarbons. This
process is predominantly carried out in the United States, western Europe, and Japan. However,
this method requires large-scale plants and thus involves a significant capital investment.

In recent times, the use of ethane as a feedstock in steam cracking has increased due to its lower
cost and availability. This shift has led to a decrease in butadiene production rates, subsequently
causing an increase in the price of butadiene from $0.60/lb to over $1.60/lb today.

Because of its numerous applications, rising costs, and decreased manufacturing, butadiene is
in high demand. As a result, it may be highly beneficial to develop an alternate large-scale
method of producing this chemical. The two-step Ostromislensky procedure involved oxidizing
ethanol to acetaldehyde and then reacting it with more ethanol over a tantalum-promoted silica
catalyst to produce butadiene. It was a common way to produce butadiene during World War
II.

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → C𝐻3 CHO + 𝐻2

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻2 + 2𝐻2 𝑂

The Ostromislensky process, which was widely used in the United States and the Soviet Union
during and before World War II, offers an alternative method for producing butadiene.
Although it is not as economical as the hydrocarbon extraction route, it is still employed in
certain regions of the world, including China and India. One of the key advantages of this
process is its use of ethanol, a renewable resource, as a feedstock. This could potentially reduce
our reliance on fossil fuels, a pressing issue for our generation.

This report aims to explore the feasibility of implementing the Ostromislensky process on an
industrial scale, given the recent surge in butadiene prices. However, it’s important to note that

10
most of the detailed research on this process was conducted shortly after World War II, with
little subsequent investigation. The limited data available from the Mellon Institute for the
Carbide and Carbon Chemicals Corporation serves as the foundation for our design.

The Ostromislensky process, despite the lack of recent research, presents potential profitability
and environmental benefits that make it a compelling area for further exploration and
implementation. The process involves two key steps. In the first step, ethanol reacts over a
heterogeneous catalyst to produce acetaldehyde and hydrogen. This endothermic reaction
requires a heat source to maintain operational conditions. The Carbide and Carbon Chemicals
Corporation reports a reaction selectivity of 92%, with the remaining 8% attributed to
unspecified byproducts. The catalyst type and conversion are not specified and are considered
design parameters for process optimization. This reaction also generates a significant amount
of hydrogen, necessitating a separation and purification process. In the second step,
acetaldehyde and additional ethanol react over a tantalum-silica catalyst-packed bed to produce
butadiene and water. This endothermic reaction also requires a heat source. The Carbide and
Carbon Chemicals Corporation specifies a conversion of 44.5% and a selectivity of 55%. The
remaining 45% is assumed to be associated with by products, including diethyl ether, acetic
acid, ethyl acetate, n-butanol, 1-butene, ethylene, and hexadiene. Given the significant
production of unwanted by-products, it is crucial to separate butadiene from these by products
and recycle the unreacted ethanol and acetaldehyde.

The primary objective is to design a plant utilizing the Ostromislensky reaction capable of
producing and purifying 200,000 tonnes of butadiene annually, with a focus on minimizing
capital investment and maximizing profit. The proposed plant design includes two reactor
sections, purification processes for each reactor’s effluent, and heat supply systems for each
reactor, when sugarcane and ethanol production ceases. The plant is expected to operate 330
days per year.

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 Market Analysis

Butadiene is a highly adaptable raw material utilized in the creation of synthetic rubbers,
polymer resins, and numerous other chemical intermediates. The majority of butadiene
produced, over 75%, is used in synthetic rubber products. Its primary uses include the
production of styrene-butadiene rubber (30% to 35%), polybutadiene rubber (20% to 22%),
adiponitrile (12% to 15%), styrene-butadiene latex (10%), neoprene rubber (5% to 6%),
acrylonitrile-butadiene-styrene resins (5% to 6%), and nitrile rubber (3%). It’s also used in the
production of specialty polymers.

The main products that contain styrene-butadiene and polybutadiene are tires. Other products
include latex adhesives, seals, hoses, gaskets, various rubber products, nylon carpet backings,
paper coatings, paints, pipes, conduits, appliance and electrical equipment components,
automotive parts, and luggage. The only significant non-polymer use is in the production of
adiponitrile, a nylon intermediate

There are no direct substitutes for butadiene. However, the process we use to produce butadiene
competes with the current industrial production process. In this process, butadiene is isolated
by distillation or extraction from crude butadiene, which is a by-product of hydrocarbon
cracking.

Buatadiene Market Size, 2022-2032 (USD Billion)

30

25

20
USD Billion

15

10

0
2022 2023 2024 2025 2026 2027 2028 2029 2030 2031 2032
Year

Figure 1 Butadiene Market

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The global butadiene market is expected to grow significantly in the coming years, driven by
a number of factors, including increasing demand from the automotive industry, rising demand
for water-based solvents and coatings, and the growing popularity of synthetic rubber. The
market is expected to reach a value of USD 25.43 billion by 2032, growing at a CAGR of 9.3%
from 2023 to 2032. Asia Pacific is expected to be the largest market for butadiene, followed by
North America and Europe.
The butadiene market is intricately linked to the automotive and ethylene industries. The
automotive industry's demand for synthetic rubbers, which are heavily reliant on butadiene,
significantly impacts butadiene market demand. Simultaneously, the supply of butadiene is
contingent on the ethylene industry, as ethylene is a crucial component in the steam cracking
process used to produce butadiene. This interdependence renders the butadiene industry
susceptible to supply-demand fluctuations in other markets. Despite these challenges, the
global butadiene market is projected to grow steadily, driven by the development of eco-
friendly polymer emulsion production methods, increasing demand for water-based solvents
and coatings, and the expansion of consumer durables and automotive sectors.
Butadiene market in India

Production The total installed production capacity of butadiene in India is estimated to be

around 150,000 metric tons per year (MTPA). However, actual production is typically lower
than this due to a number of factors, including plant maintenance and supply chain disruptions.
In 2022, India produced an estimated 120,000 MT of butadiene. Imports India is a net importer
of butadiene, and its imports have been increasing in recent years. In 2022, India imported an
estimated 180,000 MT of butadiene. The top three sources of butadiene imports for India are
South Korea, Singapore, and Russia. Demand The demand for butadiene in India is driven by
the growth of the automotive and construction industries. In 2022, the demand for butadiene in
India is estimated to have been around 300,000 MT.

Future Outlook The demand for butadiene in India is expected to continue to grow in the
coming years. As a result, India is expected to continue to import a significant amount of
butadiene. However, there are also plans to increase domestic production capacity. In addition,
India is investing in research and development of alternative sources of butadiene, such as from
biomass. Our plant has a production rate of approximately 2,00,000 tonnes per year, which
would increase total production of butadiene globally by 1.0%, which is within the rate of
increased demand. As will be shown, at these production levels, a significant profit is obtained.

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 Preliminary Process Synthesis

Figure 2: Process Development Over Time Period

Butadiene via Steam Cracking

Butadiene is primarily derived from ethylene production via steam cracking of naphtha, a C6–
11 petroleum distillate. The process is a highly endothermic pyrolysis conducted in the presence
of steam. A vaporized hydrocarbon feed is heated to more than 1073 K at low pressure in a
pyrolysis chamber. Cracking lasts less than one second to prevent product degradation through
secondary reactions. The addition of steam reduces the partial pressure of hydrocarbons,
inhibiting the problematic formation of coke. Refineries generally address this issue by using
extractive distillation, which operates using selective organic solvents to decrease the volatility
of target compounds, thereby enabling their separation by distillation. Consequently, crackers
may seek to maximize ethylene output at the expense of butadiene and other by-products by
using lighter raw materials.

Due to its ties with ethylene production, recent trends in the petrochemical industry threaten
the supply of butadiene. Ethylene-producing steam cracking plants are moving toward lighter
feedstocks, yielding less butadiene for the same amount of ethylene.

If this these trends continue, butadiene shortages and the ensuing price increase can be
expected. In addition, butadiene production via Steam Cracking is unsustainable. Due to the
highly endothermic pyrolysis step, steam cracking is the most energy-consuming process used
by the chemical industry. Because of its prevalence, the process generates yearly 180–200
million tons of CO2, which is the most significant long-lived greenhouse gas (GHG).

14
 Figure 2 Raw Material vs Production of Butadiene

In summary, butadiene is predominantly obtained by the steam cracking of naphtha, which is

primarily used to produce ethylene. However, the emergence of lighter alternative feedstocks
threatens the supply of butadiene by favouring ethylene yield at expense of the former. As a
result, meeting the butadiene demand, which is expected to grow with the increase of car
ownership, may not be achieved with Steam cracking process. Hence, we suggest an alternative
process which uses renewable feedstock i.e. ethanol.

Ethanol-to-Butadiene

Ethanol-sourced butadiene Ethanol production. The numerous advantages of ethanol make it a

potential feedstock for sustainable on-purpose production of butadiene. In contrast to other
ascendant renewable feedstocks, ethanol is already an important global commodity. Due to
government incentives to promote biofuels, the global ethanol supply is already at the industrial
scale. It ranges in 100s of billions of litres annually and is projected to grow in the coming
years.

Butadiene can be produced from ethanol using two main methods. During World War II, the
United States exclusively employed the two-step Ostromislensky process, which involves first

15
dehydrogenating ethanol to acetaldehyde and then converting the resulting ethanol-
acetaldehyde mixture into butadiene. In contrast, Russia also utilized a one-step process for
butadiene production. This one-step method involves using a silicon-magnesium-chromium or
silicon-magnesium tantalum catalyst, over which ethanol undergoes a specific reaction
mechanism to produce butadiene.

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → C𝐻3 CHO + 𝐻2

2 C𝐻3 CHO → 𝐶𝐻3 (𝐶𝐻)3 𝑂 + 𝐻2 𝑂

𝐶𝐻3 (𝐶𝐻)3 𝑂 + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻2 𝑂 + C𝐻3 CHO

C𝐻3 CHO + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 + 2𝐻2 𝑂

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻2 + 2𝐻2 𝑂

Analysis of both processes reveals that they share similar intermediate reactions. Consequently,
the multi-step approach appeared more suitable, as the intermediate reactions require distinct
conditions for optimal performance. Employing the two-step reaction method allows for
optimizing conditions that maximize ethanol dehydrogenation, followed by a separate set of
conditions that optimize the reaction between acetaldehyde and ethanol. Moreover, research
conducted at the Mellon Institute in the 1950s demonstrated that the one-step process achieved
a maximum laboratory yield of 56%, while the two-step process yielded 64%.

Based on the limited information known about the two processes, it was decided to use the
two-step process. The two-step process provided a higher yield, and the by-products were
similar in both reactions, so it was assumed that the separation sections, and thus equipment
costs, would remain the same. Furthermore, the dehydrogenation reaction of the two-step
process utilizes relatively cheap catalysts. Therefore, it was assumed that the additional cost of
purchasing two catalysts would be minimal.

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 Process Description

Overview

The production process is divided into four primary stages, as depicted in Figure . The initial
stage (100) involves the dehydrogenation of ethanol, where ethanol reacts to produce
acetaldehyde and hydrogen. This is followed by a separation sequence (200), comprising a
series of pressure and temperature adjustments to isolate the light components, primarily
hydrogen, from the heavy components. The second stage also incorporates a hydrogen
purification system to ensure its suitability for sale. The third stage (300) encompasses the
second reaction, utilizing the heavy products from the first reaction as feedstocks to generate
butadiene and water. Subsequently, a distillation train (400) separates the final product,
butadiene, along with by products and recyclable feeds, namely ethanol and acetaldehyde,
which are recycled to the second reactor. The process block diagram is reproduced below for
reference.

Dowtherm
Heating
System
Ethanol (95%)

155000 lb/hr

Dehydrogenation Hydrogen Catalysis of

of Ethanol Separation Acetaldehyde – Ethanol
System
595 °F, 35 psi 662°F, 93 psi
Acetaldehyde – Ethanol Recycle

100 200 300

144000 lb./hr.

Butadiene Butadiene (98%)

Separation 56000 lb/hr
System
400

Figure 3 Block Flow Diagram of Plant

17
Section 100: Dehydrogenation of Ethanol

The initial section of the process receives a single feed stream, a liquid mixture of 95% ethanol
and 5% water (by mass), which enters at atmospheric pressure and a temperature of 80 °F. The
feed rate is 155,000 lb/hr, determined by the conversion and selectivity of the two reactions
and the target production of 200,000 tonnes of butadiene per year.

The liquid feed stream is initially pressurized to 50 psi (P-101) to ensure it reaches the first
reactor at its optimal inlet pressure of 35 psi after passing through subsequent process
equipment. Next, the liquid stream is heated to 226 °F and partially vaporized in a heat
exchanger (E-101), which utilizes the effluent from the first reactor as the heating fluid. The
resulting vapor/liquid stream then enters a pressurized vessel (F-101) for phase separation into
two distinct streams. Both streams are then fed to a single heat exchanger (E-102), where they
are further heated to the first reactor's optimal inlet temperature of 595 °F, at which point both
streams are fully vaporized. E-102 is divided into two sections, an upper section for the inlet
vapor stream and a lower section for the inlet liquid stream. This separation ensures that both
phases receive equal contact with the heating fluid.

The dehydrogenation reaction takes place in a packed-bed reactor with a shell-and-tube design
(R-101). To avoid the expense of purchasing large-diameter reactors, the reactor is divided into
three shells. Additionally, a fourth shell is acquired to ensure uninterrupted operation while one
catalyst undergoes regeneration. A heterogeneous copper-chromite catalyst is employed to
catalyse the endothermic reaction that converts ethanol into acetaldehyde and hydrogen.

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → C𝐻3 CHO + 𝐻2 (92%).

This reaction exhibits a selectivity of 92%. The Carbide and Carbon Chemicals Corporation
did not specify the by-products. Consequently, the remaining 8% was estimated to include the
following by-products: carbon monoxide, carbon dioxide, methane, acetic acid, and ethyl
acetate, diethyl ether, and water. to simulate the reactor in ASPEN using RSTOIC, the
following side reactions were assumed to occur, along with their respective selectivity:

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → CO + 𝐶𝐻4 + 𝐻2 (0.75%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐻2 𝑂 → 𝐶𝑂2 + 𝐶𝐻4 + 2𝐻2 (0.75%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐻2 𝑂 → 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 2𝐻2 (2.5%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 𝑂𝐶𝐻2 𝐶𝐻3 + 2𝐻2 𝑂 (2.5%)

18
 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 → 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 + 𝐻2 𝑂 (1.5%)

Figure 4 Section 100 PFD

Section 200: Separation of Hydrogen

The first reaction generates a sizable amount of hydrogen, which needs to be removed from the
product stream before it enters the second reactor. A heat exchanger (E-201), a multistage
compressor (MSC-201), two pressurised vessels (F-201 and F-203), and two pumps (P-201
and P-202) make up the separation sequence that comes after the first reactor. The procedure
was optimised so that the only resource needed was cooling water. To accomplish the
appropriate separation between the light and heavy components, the reactor effluent's final
temperature was set at 108 °F, which needed a matching pressure of 155 psi. Only a slight
increase in product was seen as the pressure was increased further.

The first reactor's effluent is cooled to 152 °F and slightly condensed before entering E-101.
At the pressure of 22 psi, the mixed stream is split into its two phases in F-201. The vapour
stream is compressed to 155 psi and chilled to 108 °F when it enters MSC-201.

Additionally, using P-201 and P-202, respectively, the liquid stream from F-201 and the
knockout stream from MSC-201 are both pumped to the required pressure of 155 psi. F-201's
liquid stream has a temperature of 153 °F. However, since the stream has a much lower
volumetric flow rate than the other two streams, efforts to chill it to the ideal temperature of
108 °F only slightly increased separation. At a temperature of 121 °F on average, all three

19
streams next enter the pressurised tank F-203, where they are split into two streams: a
hydrogen-rich vapour stream and an ethanol- and acetaldehyde-rich liquid stream.

The hydrogen-rich gas is routed through a number of absorber vessels with separator filters,
where gas molecules attach to the adsorbent material. Due to hydrogen's low polarity,
contaminants in the hydrogen-rich stream can be absorbed, resulting in excellent hydrogen
purity. Following a series of pressure changes, the high purity hydrogen stream exits the
vessel's top and enters the adsorbed vessel. The final vessel's hydrogen product stream is 99%
pure hydrogen that can be sold.

Figure 5 Section 200 PFD

Section 300: Catalysis of Acetaldehyde-Ethanol

The acetaldehyde and ethanol mixture that exits F-203 is routed to the second reactor. The
recycle stream from the distillation train after the second reactor is first combined with it.
Unreacted ethanol, acetaldehyde, and a negligibly small amount of the by-product ethyl acetate
are all present in the recycle stream. By hydrolysing on a tantalum-silica catalyst, ethanol is
easily produced from ethyl acetate.

𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 + 𝐻2 𝑂 → 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐶𝐻3 𝐶𝐻2 𝑂𝐻

20
After mixing, the ethanol and acetaldehyde have reached the requisite molar ratio of 2.75:1,
and the stream temperature and pressure are 150 °F and 108 psi. The recycle stream governed
the total pressure, which was set at 108 psi such that the feed would enter the second reactor at
its optimal input pressure of 93 psi after pressure drops in subsequent process equipment. The
liquid stream is then sent via a heat exchanger (E-301) and vaporised. E-301, like the first
reaction section, uses the effluent from the second reactor as the heating fluid.

The second reaction, like the first, is carried out in a shell-and-tube, packed bed reactor (R-
301). To avoid the costs associated with large-diameter shells, the reactor is divided into three
shells. A fourth shell, like the first, is acquired so that continuous functioning can be maintained
while one shell is being regenerated. The endothermic reaction of ethanol and acetaldehyde to
generate butadiene and water is catalysed by a heterogeneous tantalim-silica catalyst.

𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝐂𝑯𝟑 𝐂𝐇𝐎 → 𝑪𝑯𝟐 = 𝑪𝑯 − 𝑪𝑯 = 𝑪𝑯𝟐 + 𝟐𝑯𝟐 𝑶 (𝟓𝟓%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶2 𝐻9 𝑂𝐻 + 𝐻2 𝑂 (5%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 𝑂𝐶𝐻2 𝐶𝐻3 + 𝐻2 𝑂 (20%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶2 𝐻4 + 𝐻2 𝑂 (10%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶4 𝐻8 + 2𝐻2 𝑂 (5%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + C𝐻3 CHO + 𝐶2 𝐻4 → 𝐶6 𝐻10 + 2𝐻2 𝑂 (5%)

2C𝐻3 CHO → 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (9% 𝐵𝑎𝑠𝑒𝑑 𝑜𝑛 𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒, 𝑛𝑜𝑡 𝑒𝑡ℎ𝑎𝑛𝑜𝑙)

Figure 6 Section 300 PFD

21
The selectivity of this reaction is 55%. Butanol, butene, ethylene, acetic acid, ethyl acetate,
diethyl ether, water, and hexadiene are the most common by products.

Section 400: Recovery of Butadiene

The second reaction generates many by products, which account for a bigger proportion of the
effluent stream than the first. Butadiene is recovered using a distillation train. However, before
the product stream can enter the distillation train, the pressure must be increased to 125 psi.

The second reactor's effluent enters E-301, where it is cooled to 231 °F and partially condensed.
It is then split into two stages in F-401 at 66 psi pressure. The vapour stream enters a second
heat exchanger, E-401, where it is partially condensed and cooled with cooling water to the
appropriate temperature of 200 °F. It is then split into two phases in F-402 at 58 psi pressure.
E-401 is used to reduce flow to the compressor, which is more expensive to run than a pump.
The vapour stream from F-402 is subsequently compressed to 133 psi in C-401. The
compressed vapour then enters E-402, where it is cooled with water to 200 degrees Fahrenheit.
F-401 and F-402 liquid streams are pressurised to 125 psi with P-401 and P-402, respectively,
and then combined. The liquid and vapour streams are then introduced into the distillation train.
The liquid stream from F-401 is 231 degrees Fahrenheit. However, because the stream has a
relatively low flow rate, efforts to cool it to the target temperature of 200 °F only resulted in a
modest decrease in utility demand in D-401.

Figure 7 Section 400A PFD

22
The four distillation columns are designed to recover butadiene with a purity of 98% (by mass)
while also recovering ethanol, acetaldehyde, and ethyl acetate to the greatest extent possible.
Furthermore, each distillation column was optimised to use cooling water in the condensers
and 50 psig steam in the reboilers whenever possible, reducing the need of expensive
refrigerates and high-pressure steam. Initially, the cost and efficiency of two distillation
sequences were examined.

Figure 8 Section 400B PFD

23
 Material Safety Data Sheets (MSDS)
Ethanol
Section 1 – CHEMICAL PRODUCT

Product Name Ethanol

Chemical Formula: C2H5OH

Section 2 – HAZARDS IDENTIFICATION

Precautionary statements

• Obtain special instructions before use

• Do not handle until all safety precautions have been read and understood
• Use personal protective equipment as required
• Wash face, hands and any exposed skin thoroughly after handling Wear eye/face
protection
• Do not breathe dust/fume/gas/mist/vapors/spray
• Do not eat, drink or smoke when using this product Keep away from heat/sparks/open
flames/hot surfaces. No smoking
• Keep container tightly closed
• Ground/bond container and receiving equipment
• Use explosion-proof electrical/ventilating/lighting equipment
• Use only non-sparking tools Take precautionary measures against static discharge.

Hazard statements

• Highly flammable liquid and vapor

• Causes serious eye irritation
• Suspected of causing cancer
• Suspected of damaging fertility or the unborn
• May cause damage to organs
• May cause drowsiness or dizziness
Section 3 – FIRST AID MEASURES
3.1 General advice
• If symptoms persist, call a physic
3.2 Inhalation

24
 • Remove to fresh air. If not breathing, give artificial respiration. Get medical
attention if symptoms occur
3.3 Skin contact
• Wash off immediately with plenty of water for at least 15 minutes. If skin irritation
persists, call a physic.

3.4 Eye contact

• Rinse immediately with plenty of water, also under the eyelids, for at least 15
minutes. Get medical attention
3.5 Swallowing
• Clean mouth with water and drink afterwards plenty of wash.

Section 4 – FIRE FIGHTING MEASURES

4.1 Suitable extinguishing media

• Water spray, carbon dioxide (CO2), dry chemical, alcohol-resistant foam. Water
mist may be used to cool closed con

4.2 Extinguishing media to be avoided

• Water may be ineffective, Do not use a solid water stream as it may scatter and
spread fire.

4.3 Caution about specific danger in case of fire and fire-fighting procedures
• Flammable. Vapors may form explosive mixtures with air. Vapors may travel to
source of ignition and flash back. Containers may explode when heated. Vapors
may form explosive mixtures with air.

4.4 Special protective equipment for fire fighters

• As in any fire, wear self-contained breathing apparatus pressure-demand,
MSHA/NIOSH (approved or equivalent) and full protective gear.

4.5 NFPA

• Health : 3
• Flamability : 3
• Instabilty : 0
• Physical Hazrd : NA

Section 5 –ACCIDENTAL RELEASE MEASURES

5.1 Person-related safety precautions

25
 • Use personal protective equipment as required. Ensure adequate ventilation.

5.2 Precautions for protection of the environment

• Should not be released into the environment

5.3 Recommended methods for cleaning and disposal
• Soak up with inert absorbent material. Keep in suitable, closed

Section 6 –HANDLING AND STORAGE

6.1 Information for safe handling
• Wear personal protective equipment/face protection. Ensure adequate ventilation. Do
not get in eyes, on skin, or on clothing. Avoid ingestion and inhalation.
6.2 Information for storage
• Keep containers tightly closed in a dry, cool and well-ventilated place. Keep away from
heat, sparks and flame. Incompatible Materials. Strong oxidizing agents. Acids. Acid
anhydrides. Acid chlorides. Peroxides. Alkali metals
Section 7 –EXPOSURE CONTROL & PERSONAL PROTECTION
7.1 Occupational Exposure Limits:
Material Source Type ppm mg/m3

Ethyl Alcohol ACGIH STEL 1000

Methyl alcohol ACGIH TWA 200
STEL (Skin) 250
Methyl isobutyl ACGIH TWA 20
ketone STEL 75
Ethyl acetate ACGIH TWA 400
Provide adequate ventilation when using the material and follow the principles of good
occupational hygiene to control personal exposure.

NA: Data not available

7.2 Occupational exposure controls

Respiratory protection: Follow the OSHA respirator regulations found in 29 CFR
1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN
149 approved respirator if exposure limits are exceeded or if irritation or other symptoms
are experience

26
 Eye protection: Wear appropriate protective eyeglasses or chemical safety goggles as
described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or
European Standard EN166.

Body protection: Wear appropriate protective gloves and clothing to preve

Hygiene Measures: Handle in accordance with good industrial hygiene and safety
practice.

7.3 Environmental exposure controls

Proceed in accordance with valid air and water legislative regulations.

7.4 Engineering measures: Ensure adequate ventilation, especially in confined areas. Use
explosion-proof electrical/ventilating/lighting equipment. Ensure that eyewash stations
and safety showers are close to the workstation location.

Section 8 –PHYSICAL AND CHEMICAL PROPERTIES

Appearance Liquid,
Odour Alcohol like
Solubility in water Soluble
Relative Density (H2O=1) 0.785 - 0.792
Boiling Point °C 77.1 °C / 170.8 °F
Melting Point °C < -90 °C / -130 °F
Relative Vapour Density (Air=1) 1.5
Flash point °C 13.9 °C / 57 °F
Auto ignition °C 362.8 °C / 685 °F
Vapour pressure (mmHg) @ 25 °C 48
Explosive limits in air % by volume LEL 1.1% UEL 7.0%
pH NA
Viscosity cP @20 °C NA
Pour point NA
Evaporation rate 3.6 (Butyl acetate = 1.0
% volatile 100
NA: NOT AVAILABLE

27
 Section 9 –CHEMICAL STABILITY AND REACTIVITY INFORMATION
9.1 Conditions to avoid
• Incompatible products. Excess heat. Keep away from open flames, hot surfaces and
sources of ignition
9.2 Material to avoid
• Strong oxidizing agents, Acids, Acid anhydrides, Acid chlorides, Peroxides, Alkali
metal
9.3 Hazardous decomposition products
• Thermal decomposition generates carbon monoxide and carbon dioxide.

Section 10 –TOXICOLOGICAL INFORMATION

10.1 Acute effects

Product irritates eyes and skin. High vapor concentrations irritate respiratory system and
eyes.

Acute toxicity data:

Parameter Route Species Values Exposure period

LD50 Oral Rat 10470 mg/Kg Not applicable

10.2 STOT Single Exposure

• Central nervous system (CNS) Optic nerve Respiratory system
10.3 Sensitization
• No information available.

10.4 CMR effects (carcinogenicity, mutagenicity, toxicity for reproduction)

• Not a CMR. Mutagenic effects have occurred in experiment

10.5 Toxic kinetics, metabolism, distribution

• Not applicable.

Section 11 –ECOLOGICAL INFORMATION

11.1 Eco toxicity data:

Parameter Route Species Values Exposure period

EC50 Inhalation Shrimp 2.0 ppm 96 hours

LC50 Inhalation Fathead minnow 8400 ug/L 96 hours

11.2 Persistence and degradability: Persistence is unlikely based on information

28
11.3 Bio accumulative potential: No information available.

11.4 Mobility : Will likely be mobile in the environment due to its

1,3-Butadiene
Section 1 – CHEMICAL PRODUCT

Product Name 1,3-Butadiene

Chemical Formula: CH2=CH--CH=CH2

Section 2 – HAZARDS IDENTIFICATION

Precautionary statements

Read and follow all Safety Data Sheets (SDS’S) before use. Read label before use. Keep out
of reach of children. If medical advice is needed, have product container or label at hand.
Close valve after each use and when empty. Use equipment rated for cylinder pressure. Do
not open valve until connected to equipment prepared for use. Use a back flow preventative
device in the piping. Use only equipment of compatible materials of construction. Always
keep container in upright position. Approach suspected leak area with caution

Hazard statements

• Extremely flammable gas.

• May form explosive mixtures with air.
• Contains gas under pressure; may explode if heated.
• May cause frostbite.
• May displace oxygen and cause rapid suffocation.
• Harmful if inhaled. May cause genetic defects.
• May cause cancer.
Classification
• FLAMMABLE GASES - Category 1
• GASES UNDER PRESSURE - Liquefied gas
• ACUTE TOXICITY (inhalation) - Category 4
• GERM CELL MUTAGENICITY - Category 1B
• CARCINOGENICITY - Category 1

Section 3 – FIRST AID MEASURES

29
3.1 General advice
• If symptoms persist, call a physic
3.2 Inhalation
• Remove victim to fresh air and keep at rest in a position comfortable for breathing.
If it is suspected that fumes are still present, the rescuer should wear an appropriate
mask or self-contained breathing apparatus. If not breathing, if breathing is
irregular or if respiratory arrest occurs, provide artificial respiration or oxygen by
trained personnel. It may be dangerous to the person providing aid to give mouth-
to-mouth resuscitation. Get medical attention. If necessary, call a poison center or
physician. If unconscious, place in recovery position and get medical attention
immediately. Maintain an open airway. Loosen tight clothing such as a collar, tie,
belt or waistband.
3.3 Skin contact
• Flush contaminated skin with plenty of water. Remove contaminated clothing and
shoes. To avoid the risk of static discharges and gas ignition, soak contaminated
clothing thoroughly with water before removing it. Continue to rinse for at least 10
minutes. Get medical attention. In case of contact with liquid, warm frozen tissues
slowly with lukewarm water and get medical attention. Do not rub affected area.
Wash clothing before reuse. Clean shoes thoroughly before reuse..

3.4 Eye contact

• Immediately flush eyes with plenty of water, occasionally lifting the upper and
lower eyelids. Check for and remove any contact lenses. Continue to rinse for at
least 10 minutes. Get medical attention.
3.5 Ingestion

• Remove victim to fresh air and keep at rest in a position comfortable for breathing.
Get medical attention. Ingestion of liquid can cause burns similar to frostbite. If
frostbite occurs, get medical attention. Never give anything by mouth to an
unconscious person. If unconscious, place in recovery position and get medical
attention immediately. Maintain an open airway. Loosen tight clothing such as a
collar, tie, belt or waistband. As this product rapidly becomes a gas when released,
refer to the inhalation section.

Section 4 – FIRE FIGHTING MEASURES

30
4.1 Suitable extinguishing media
• Use an extinguishing agent suitable for the surrounding fire
4.2 Extinguishing media to be avoided
• Not Known
4.3 Caution about specific danger in case of fire and fire-fighting procedures
• Contains gas under pressure. Extremely flammable gas. In a fire or if heated, a
pressure increase will occur and the container may burst, with the risk of a
subsequent explosion. The vapor/gas is heavier than air and will spread along the
ground. Gas may accumulate in low or confined areas or travel a considerable
distance to a source of ignition and flash back, causing fire or explosion.
4.4 Special protective equipment for fire fighters
• Fire-fighters should wear appropriate protective equipment and self-contained
breathing apparatus (SCBA) with a full face-piece operated in positive pressure
mode. For incidents involving large quantities, thermally insulated undergarments
and thick textile or leather gloves should be worn.

Section 5 –ACCIDENTAL RELEASE MEASURES

5.1 Person-related safety precautions

• Use personal protective equipment as required. Ensure adequate ventilation.

5.2 Precautions for protection of the environment

• Should not be released into the environment
5.3 Recommended methods for cleaning and disposal
• Soak up with inert absorbent material. Keep in suitable, closed

Section 6 –HANDLING AND STORAGE

6.1 Information for storage
• Store in accordance with local regulations. Store in a segregated and approved area.
Store away from direct sunlight in a dry, cool and well-ventilated area, away from
incompatible materials (see Section 10). Eliminate all ignition sources. Cylinders
should be stored upright, with valve protection cap in place, and firmly secured to
prevent falling or being knocked over. Cylinder temperatures should not exceed 52 °C
(125 °F). Store locked up. Keep container tightly closed and sealed until ready for use.
See Section 10 for incompatible materials before handling or us.
Section 7 –EXPOSURE CONTROL & PERSONAL PROTECTION

31
7.1 Occupational Exposure Limits:
Material Source

Ethyl Alcohol ACGIH TLV (United States, 3/2017).

TWA: 4.4 mg/m³ 8 hours.

7.2 Occupational exposure controls

Respiratory protection: Based on the hazard and potential for exposure, select a
respirator that meets the appropriate standard or certification. Respirators must be used
according to a respiratory protection program to ensure proper fitting, training, and other
important aspects of use.

Eye protection: Safety eyewear complying with an approved standard should be used
when a risk assessment indicates this is necessary to avoid exposure to liquid splashes,
mists, gases or dusts. If contact is possible, the following protection should be worn, unless
the assessment indicates a higher degree of protection: safety glasses with side shields

Body protection Safety eyewear complying with an approved standard should be used
when a risk assessment indicates this is necessary to avoid exposure to liquid splashes,
mists, gases or dusts. If contact is possible, the following protection should be worn, unless
the assessment indicates a higher degree of protection: safety glasses with side shields

Hygiene Measures: Wash hands, forearms and face thoroughly after handling chemical
products, before eating, smoking and using the lavatory and at the end of the working
period. Appropriate techniques should be used to remove potentially contaminated
clothing. Wash contaminated clothing before reusing. Ensure that eyewash stations and
safety showers are close to the workstation location.

Environmental exposure controls: Emissions from ventilation or work process

equipment should be checked to ensure they comply with the requirements of
environmental protection legislation. In some cases, fume scrubbers, filters or engineering
modifications to the process equipment will be necessary to reduce emissions to acceptable
levels.

Engineering measures: Use only with adequate ventilation. Use process enclosures, local
exhaust ventilation or other engineering controls to keep worker exposure to airborne
contaminants below any recommended or statutory limits. The engineering controls also

32
 need to keep gas, vapor or dust concentrations below any lower explosive limits. Use
explosion-proof ventilation equipment.

Section 8 –PHYSICAL AND CHEMICAL PROPERTIES

Appearance Gas. [Compressed gas.] Color less

Odour Alcohol like
Solubility in water Characteristic
Relative Density (H2O=1) Not applicable.
Boiling Point °C -4.41°C (24.1°F)
Melting Point °C -108.9°C (-164°F)
Relative Vapour Density (Air=1) 1.9
Flash point °C Closed cup: -85°C (-121°F)
Auto ignition °C 420°C (788°F)
Vapour pressure (mmHg) 21.35 (psig)
Explosive limits in air % by volume Lower: 2% Upper: 12%
pH NA
Viscosity cP @20 °C NA
Pour point NA
Evaporation rate NA
NA: NOT AVAILABLE
Section 9 –CHEMICAL STABILITY AND REACTIVITY INFORMATION
9.1 Conditions to avoid
• Avoid all possible sources of ignition (spark or flame). Do not pressurize, cut, weld,
braze, solder, drill, grind or expose containers to heat or sources of ignition. Do not
allow gas to accumulate in low or confined areas.
9.2 Material to avoid
• Oxidizers
9.3 Hazardous decomposition products
• Under normal conditions of storage and use, hazardous decomposition products should
not be produced.

Section 10 –TOXICOLOGICAL INFORMATION

10.1 Acute effects

33
 Product irritates eyes and skin. High vapor concentrations irritate respiratory system and
eyes.
Acute toxicity data:

Parameter Route Species Values Exposure period

LD50 Oral Rat 128000 ppm 4 hours

10.2 STOT Single Exposure

• Central nervous system (CNS) Optic nerve Respiratory system
10.3 Sensitization
• No information available.

10.4 CMR effects (carcinogenicity, mutagenicity, toxicity for reproduction)

• Not a CMR.

10.5 Toxic kinetics, metabolism, distribution

• Not applicable.

Section 11 –ECOLOGICAL INFORMATION

11.1 Eco toxicity data:

Product/ingredient name logPow BCF Potential

1,3-butadiene 1.99 10 low

11.2 Persistence and degradability: Not available

11.3 Bio accumulative potential: No information available.

11.4 Mobility : Will likely be mobile in the environment due to its

Hydrogen
Section 1 – CHEMICAL PRODUCT

Product Name Hydrogen

Chemical Formula: H2

Section 2 – HAZARDS IDENTIFICATION

2.1 Precautionary statements

34
 General: Read and follow all Safety Data Sheets (SDS’S) before use. Read label before use.
Keep out of reach of children. If medical advice is needed, have product container or label
at hand. Close valve after each use and when empty. Use equipment rated for cylinder
pressure. Do not open valve until connected to equipment prepared for use. Use a backflow
preventative device in the piping. Use only equipment of compatible materials of
construction. Approach suspected leak area with caution. Do not handle until all safety
precautions have been read and understood

Prevention: Keep away from heat, hot surfaces, sparks, open flames and other ignition
sources. No smoking

Response: Leaking gas fire: Do not extinguish, unless leak can be stopped safely. In case
of leakage, eliminate all ignition sources.

Storage: Protect from sunlight. Store in a well-ventilated place.

Disposal: Not applicable

2.2 Hazard statements

• Extremely flammable gas.

• Contains gas under pressure; may explode if heated.
• May displace oxygen and cause rapid suffocation.
• Burns with invisible flame.
• May form explosive mixtures with air

Section 3 – FIRST AID MEASURES

3.1 General advice
• If symptoms persist, call a physic
3.2 Inhalation
• Remove victim to fresh air and keep at rest in a position comfortable for breathing.
If not breathing, if breathing is irregular or if respiratory arrest occurs, provide
artificial respiration or oxygen by trained personnel. It may be dangerous to the
person providing aid to give mouth-to-mouth resuscitation. Get medical attention
if adverse health effects persist or are severe. If unconscious, place in recovery
position and get medical attention immediately. Maintain an open airway. Loosen
tight clothing such as a collar, tie, belt or waistband
.3.3 Skin contact
• Flush contaminated skin with plenty of water. Remove contaminated clothing and
shoes. To avoid the risk of static discharges and gas ignition, soak contaminated
clothing thoroughly with water before removing it. Get medical attention if

35
 symptoms occur. Wash clothing before reuse. Clean shoes thoroughly before reuse.
3.4 Eye contact
• Immediately flush eyes with plenty of water, occasionally lifting the upper and
lower eyelids. Check for and remove any contact lenses. Continue to rinse for at
least 10 minutes. Get medical attention if irritation occurs

3.5 Ingestion
• As this product is a gas, refer to the inhalation section.

Section 4 – FIRE FIGHTING MEASURES

4.1 Suitable extinguishing media

• Use an extinguishing agent suitable for the surrounding fire
.4.2 Extinguishing media to be avoided
• None known.
4.3 Caution about specific danger in case of fire and fire-fighting procedures
• Promptly isolate the scene by removing all persons from the vicinity of the incident
if there is a fire. No action shall be taken involving any personal risk or without
suitable training. Contact supplier immediately for specialist advice. Move
containers from fire area if this can be done without risk. Use water spray to keep
fire-exposed containers cool. If involved in fire, shut off flow immediately if it can
be done without risk. If this is impossible, withdraw from area and allow fire to
burn. Fight fire from protected location or maximum possible distance. Eliminate
all ignition sources if safe to do so.
4.4 Special protective equipment for fire fighters
• Fire-fighters should wear appropriate protective equipment and self-contained
breathing apparatus (SCBA) with a full face-piece operated in positive pressure
mode.

Section 5 –ACCIDENTAL RELEASE MEASURES

5.1 For non-emergency personnel

• Accidental releases pose a serious fire or explosion hazard. No action shall be taken
involving any personal risk or without suitable training. Evacuate surrounding areas.
Keep unnecessary and unprotected personnel from entering. Shut off all ignition
sources. No flares, smoking or flames in hazard area. Avoid breathing gas. Provide
adequate ventilation. Wear appropriate respirator when ventilation is inadequate. Put
on appropriate personal protective equipment.

36
5.2 For emergency responders
• If specialized clothing is required to deal with the spillage, take note of any information
in Section 8 on suitable and unsuitable materials. See also the information in "For non-
emergency personnel.

5.3 Recommended methods for cleaning and disposal

• Soak up with inert absorbent material. Keep in suitable, closed

Section 6 –HANDLING AND STORAGE

6.1 Information for safe handling
• Put on appropriate personal protective equipment (see Section 8). Contains gas under
pressure. Avoid breathing gas. Use only with adequate ventilation. Wear appropriate
respirator when ventilation is inadequate. Do not enter storage areas and confined
spaces unless adequately ventilated. Do not puncture or incinerate container. Use
equipment rated for cylinder pressure.
• Close valve after each use and when empty. Protect cylinders from physical damage;
do not drag, roll, slide, or drop. Use a suitable hand truck for cylinder movement. Use
only non-sparking tools. Avoid contact with eyes, skin and clothing. Empty containers
retain product residue and can be hazardous. Store and use away from heat, sparks,
open flame or any other ignition source. Use explosion-proof electrical (ventilating,
lighting and material handling) equipment.
6.2 Information for storage

• Store in accordance with local regulations. Store in a segregated and approved area. Store
away from direct sunlight in a dry, cool and well-ventilated area, away from incompatible
materials (see Section 10). Eliminate all ignition sources. Cylinders should be stored
upright, with valve protection cap in place, and firmly secured to prevent falling or being
knocked over. Cylinder temperatures should not exceed 52 °C (125 °F). Keep container
tightly closed and sealed until ready for use. See Section 10 for incompatible materials
before handling or use.
Section 7 –EXPOSURE CONTROL & PERSONAL PROTECTION

7.1 Occupational Exposure Limits:

Material Source

37
 Ethyl Alcohol California PEL for Chemical Contaminants ( Table AC-1)
(United States). Oxygen Depletion [Asphyxiant]. ACGIH
TLV (United States, 3/2019). Oxygen Depletion
[Asphyxiant]. Explosive [Link]
NA: Data not available

7.2 Occupational exposure controls

Respiratory protection: Follow the OSHA respirator regulations found in 29 CFR
1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN
149 approved respirator if exposure limits are exceeded or if irritation or other symptoms
are experience

Eye protection: Safety eyewear complying with an approved standard should be used
when a risk assessment indicates this is necessary to avoid exposure to liquid splashes,
mists, gases or dusts. If contact is possible, the following protection should be worn,
unless the assessment indicates a higher degree of protection: safety glasses with side-
shields

Body protection: Personal protective equipment for the body should be selected based
on the task being performed and the risks involved and should be approved by a specialist
before handling this product. When there is a risk of ignition from static electricity, wear
antistatic protective clothing. For the greatest protection from static discharges, clothing
should include anti-static overalls, boots and gloves.

Hygiene Measure Wsash hands, forearms and face thoroughly after handling chemical
products, before eating, smoking and using the lavatory and at the end of the working
period. Appropriate techniques should be used to remove potentially contaminated
clothing. Wash contaminated clothing before reusing. Ensure that eyewash stations and
safety showers are close to the workstation location

7.3 Environmental exposure controls

Emissions from ventilation or work process equipment should be checked to ensure they
comply with the requirements of environmental protection legislation. In some cases, fume
scrubbers, filters or engineering modifications to the process equipment will be necessary
to reduce emissions to acceptable levels.

38
7.4 Engineering measures: Use only with adequate ventilation. Use process enclosures, local
exhaust ventilation or other engineering controls to keep worker exposure to airborne
contaminants below any recommended or statutory limits. The engineering controls also
need to keep gas, vapor or dust concentrations below any lower explosive limits. Use
explosion-proof ventilation equipment.

Section 8 –PHYSICAL AND CHEMICAL PROPERTIES

Appearance Gas
Odour Ordorless
Solubility in water Not aplicalbe
Relative Density (H2O=1) Not applicable.
Boiling Point °C -253°C (-423.4°F)
Melting Point °C -259.15°C (-434.5°F)
Relative Vapour Density (Air=1) 0.07 (Air = 1)
Flash point °C Not available
Auto ignition °C 500 to 571°C (932 to 1059.8°F)
Vapour pressure (mmHg) @ 25 °C 48
Explosive limits in air % by volume Lower: 4% Upper: 76%
pH Not applicable.
Viscosity cP @20 °C Not applicable.
Pour point Not applicable.
Evaporation rate Not applicable.
NA: NOT AVAILABLE

Section 9 –CHEMICAL STABILITY AND REACTIVITY INFORMATION

9.1 Conditions to avoid
• Avoid all possible sources of ignition (spark or flame). Do not pressurize, cut, weld,
braze, solder, drill, grind or expose containers to heat or sources of ignition.
9.2 Material to avoid
• Oxidizers
9.3 Hazardous decomposition products
• Under normal conditions of storage and use, hazardous decomposition products should

39
 not be produced.
Section 10 –TOXICOLOGICAL INFORMATION

10.1 Acute effects Not available.

10.2 STOT Single Exposure Not available.
10.3 Sensitization No available.
10.4 CMR effects (carcinogenicity, mutagenicity, toxicity for reproduction) Not available.
10.5 Toxic kinetics, metabolism, distribution Not applicable.
Section 11 –ECOLOGICAL INFORMATION

11.1 Eco toxicity data: Not available.

11.2 Persistence and degradability: Persistence is unlikely based on information

11.3 Bio accumulative potential: No information available.

11.4 Mobility: Will likely be mobile in the environment due to its

Acetaldehyde
Section 1 – CHEMICAL PRODUCT

Product Name Acetaldehyde

Chemical Formula: CH3CHO

Section 2 – HAZARDS IDENTIFICATION

2.1 Precautionary statements

• Obtain special instructions before use

• Do not handle until all safety precautions have been read and understood
• Use personal protective equipment as required
• Wash face, hands and any exposed skin thoroughly after handling
• Do not eat, drink or smoke when using this product
• Wear eye/face protection Avoid breathing dust/fume/gas/mist/vapors/spray
• Use only outdoors or in a well-ventilated area
• Keep away from heat/sparks/open flames/hot surfaces. –
• No smoking Keep container tightly closed
• Ground/bond container and receiving equipment

40
 • Use explosion-proof electrical/ventilating/lighting equipment
• Use only non-sparking tools
• Take precautionary measures against static discharge
• Keep cool.

2.2 Hazard statements

• Extremely flammable liquid and vapor

• Harmful if swallowed
• Causes serious eye irritation
• May cause respiratory irritation
• Suspected of causing genetic defects
• May cause cancer
Section 3 – FIRST AID MEASURES
3.1 General advice
• If symptoms persist, call a physic
3.2 Inhalation
• Remove to fresh air. If not breathing, give artificial respiration. Get medical
attention if symptoms occur
3.3 Skin contact
• Wash off immediately with plenty of water for at least 15 minutes. If skin irritation
persists, call a physician
3.4 Eye contact
• Rinse immediately with plenty of water, also under the eyelids, for at least 15
minutes. Get medical attention.
3.5 Swallowing
• Clean mouth with water and drink afterwards plenty of water.

Section 4 – FIRE FIGHTING MEASURES

4.1 Suitable extinguishing media

• CO2, dry chemical, dry sand, alcohol-resistant foam. Water mist may be used to
cool closed containers.

4.2 Extinguishing media to be avoided

• Water may be ineffective, Do not use a solid water stream as it may scatter and
spread fire.

4.3 Caution about specific danger in case of fire and fire-fighting procedures

41
 • Extremely flammable. May form explosive peroxides. Risk of ignition. Vapors
may form explosive mixtures with air. Vapors may travel to source of ignition and
flash back. Containers may explode when heated. Thermal decomposition can lead
to release of irritating gases and vapors. Keep product and empty container away
from heat and sources of ignition. Vapors may form explosive mixtures with ai
4.4 Special protective equipment for fire fighters
• As in any fire, wear self-contained breathing apparatus pressure-demand,
MSHA/NIOSH (approved or equivalent) and full protective gear.

4.5 NFPA

• Health : 2
• Flamability : 4
• Instabilty : 2
• Physical Hazrd : NA

Section 5 –ACCIDENTAL RELEASE MEASURES

5.1 Person-related safety precautions

• Use personal protective equipment as required. Ensure adequate ventilation. Remove
all sources of ignition. Take precautionary measures against static discharges

5.2 Precautions for protection of the environment

• Do not flush into surface water or sanitary sewer system
5.3 Recommended methods for cleaning and disposal
• Soak up with inert absorbent material. Keep in suitable, closed containers for disposal.
Remove all sources of ignition. Use spark-proof tools and explosion-proof equipment
Section 6 –HANDLING AND STORAGE
6.1 Information for safe handling
• Wear personal protective equipment/face protection. Do not get in eyes, on skin, or on
clothing. Avoid ingestion and inhalation. Ensure adequate ventilation. Keep away from
open flames, hot surfaces and sources of ignition. Use spark-proof tools and explosion-
proof equipment. Use only non-sparking tools. To avoid ignition of vapors by static
electricity discharge, all metal parts of the equipment must be grounded. Take
precautionary measures against static discharges.
6.2 Information for storage

42
 • Keep containers tightly closed in a dry, cool and well-ventilated place. Flammables
area. Keep away from heat, sparks and flame. Refrigerator/flammables. Store under an
inert atmosphere. Do not freeze. Incompatible Materials. Strong oxidizing agents.
Acids. Bases. Metals. Strong reducing agents. Alcohols. Amines. Halogen

Section 7 –EXPOSURE CONTROL & PERSONAL PROTECTION

7.1 Occupational Exposure Limits:

Material Source Type ppm mg/m3

Acetaldehyde ACGIH Celling 25

Provide adequate ventilation when using the material and follow the principles of good
occupational hygiene to control personal exposure.

NA: Data not available

7.2 Occupational exposure controls

Respiratory protection: Follow the OSHA respirator regulations found in 29 CFR
1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN
149 approved respirator if exposure limits are exceeded or if irritation or other symptoms
are experienced.

Eye protection: Wear appropriate protective eyeglasses or chemical safety goggles as

described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or
European Standard EN166.

Body protection: Wear appropriate protective gloves and clothing to preve

Hygiene Measures: Handle in accordance with good industrial hygiene and safety
practice

7.3 Environmental exposure controls

Proceed in accordance with valid air and water legislative regulations.

Engineering measures: Use only under a chemical fume hood. Use explosion-proof
electrical/ventilating/lighting equipment. Ensure adequate ventilation, especially in
confined areas. Ensure that eyewash stations and safety showers are close to the
workstation location.

43
 Section 8 –PHYSICAL AND CHEMICAL PROPERTIES

Appearance Liquid
Odour Pungent
Solubility in water Soluble
Relative Density (H2O=1) 0.785
Boiling Point °C 21 °C / 69.8 °F
Melting Point °C -123 °C / -189.4 °F
Relative Vapour Density (Air=1) 1.52
Flash point °C -27 °C / -16.6
Auto ignition °C 155 °C / 31
Vapour pressure (mmHg) @ 25 °C 986 m
Explosive limits in air % by volume LEL 4.0% UEL 60.0%
pH NA
Viscosity cP @20 °C NA
Pour point NA
Evaporation rate 49.1
Mw 44.04
NA: NOT AVAILABLE

Section 9 –CHEMICAL STABILITY AND REACTIVITY INFORMATION

9.1 Conditions to avoid
• Excess heat. Exposure to air. Keep away from open flames, hot surfaces and sources of
ignition.
9.2 Material to avoid
• Strong oxidizing agents, Acids, Bases, Metals, Strong reducing agents, Alcohols,
Amines, Halogens
9.3 Hazardous decomposition products
• Thermal decomposition generates carbon monoxide and carbon dioxide.

Section 10 –TOXICOLOGICAL INFORMATION

10.1 Acute effects

Product irritates eyes and skin. High vapor concentrations irritate respiratory system and
eyes.

Acute toxicity data:

44
 Parameter Route Species Values

LD50 Oral Rat 660 mg/Kg

10.2 STOT Single Exposure

Respiratory system Central nervous syndrom

10.3 Sensitization
No information available.

10.4 CMR effects (carcinogenicity, mutagenicity, toxicity for reproduction)

Mutagenic effects have occurred in experimental
Possibly Carcinogenic to Humans

10.5 Symptoms / effects, both acute and delayed

Inhalation of high vapor concentrations may cause symptoms like headache, dizziness,
tiredness, nausea and vomit.

Section 11 –ECOLOGICAL INFORMATION

11.1 Eco toxicity data:

Parameter Route Species Values Exposure period

EC50 Inhalation Microtex 280 mg/L 15 min

LC50 Inhalation Fathead minnow 28.0 - 34.0 mg/L 96 hours

11.2 Persistence and degradability: Persistence is unlikely based on information

11.3 Bio accumulative potential: No information available.

11.4 Mobility : log Pow=0.5

45
 Material Balance
From market analysis we estimated to establish a plant of capacity 200000 MT butadiene per
year.

Let suppose total working day in plant is 330 and 24-hour full working during this period.

Therefore, we require following butadiene production rate-

Production rate = 200000000/(330 ∗ 24)

= 2,52,525.25 Kg/hr

= 556722.879 lb/hr

= 468 𝑘𝑚𝑜𝑙/ℎ𝑟

Main Reactions: -

1. 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → C𝐻3 CHO + 𝐻2 . (R1-Conversion=50%, selectivity=92%)

2. 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + C𝐻3 CHO → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 + 2𝐻2 𝑂 (R2-Conversion=
44.5%, selectivity=55%)
3. 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + C𝐻3 CHO + 𝐶2 𝐻4 → 𝐶6 𝐻10 + 2𝐻2 𝑂 (R2-Conversion=44.5%,
selectivity=5%)

From reaction 2
𝐵𝑢𝑡𝑎𝑑𝑖𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑
𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
Total ethanol reacted
𝐵𝑢𝑡𝑎𝑑𝑖𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑
𝑇𝑜𝑡𝑎𝑙 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 =
𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦
468
𝑇𝑜𝑡𝑎𝑙 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 =
0.55
𝒌𝒎𝒐𝒍
𝑻𝒐𝒕𝒂𝒍 𝒆𝒕𝒉𝒂𝒏𝒐𝒍 𝒓𝒆𝒂𝒄𝒕𝒆𝒅 = 𝟖𝟓𝟏
𝒉𝒓
Total ethanol reacted
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 =
Total ethanol fed
851
0.445 =
Total ethanol fed
𝒌𝒎𝒐𝒍
𝑻𝒐𝒕𝒂𝒍 𝒆𝒕𝒉𝒂𝒏𝒐𝒍 𝒇𝒆𝒅 = 𝟏𝟗𝟏𝟐. 𝟑𝟔
𝒉𝒓

46
Hear we consider recycle stream in reactor 2 , therefore all unreacted ethanol will return to
the reaction.

𝑻𝒐𝒕𝒂𝒍 𝒆𝒕𝒉𝒂𝒏𝒐𝒍 𝒄𝒐𝒏𝒔𝒖𝒎𝒆𝒅 𝒊𝒏 𝒓𝒆𝒂𝒄𝒕𝒐𝒓 𝟐 = 𝟖𝟓𝟏 𝒌𝒎𝒐𝒍/𝒉𝒓

𝑘𝑚𝑜𝑙
𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 2 = 468
ℎ𝑟

𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙
𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 3 = 851 × 0.05 = 42.55
ℎ𝑟 ℎ𝑟

𝒌𝒎𝒐𝒍
𝑻𝒐𝒕𝒂𝒍 𝑨𝒄𝒆𝒕𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆 𝒄𝒐𝒏𝒔𝒖𝒎𝒆𝒅 = 𝟒𝟔𝟖 + 𝟒𝟐. 𝟓𝟓 = 𝟓𝟏𝟎. 𝟓𝟓
𝒉𝒓

510.55
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑓𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 1 =
0.50 × 0.92

𝑘𝑚𝑜𝑙
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑓𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 1 = 1110
ℎ𝑟

𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙
𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 1 = 1110 × 0.5 = 555
ℎ𝑟 ℎ𝑟

Rest of unreacted ethanol will consume in reactor 2

𝑇𝑜𝑡𝑎𝑙 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 2 = 555 𝑘𝑚𝑜𝑙/ℎ𝑟

𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙 𝑘𝑔
𝑇𝑜𝑡𝑎𝑙 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 = (555 + 851) = 1406 = 64676
ℎ𝑟 ℎ𝑟 ℎ𝑟
= 142611 𝑙𝑏/ℎ𝑟

Purity of input stream =0.95%

𝑻𝒐𝒕𝒂𝒍 𝒆𝒕𝒉𝒂𝒏𝒐𝒍 𝒓𝒆𝒒𝒖𝒊𝒓𝒆𝒅 = 𝟏𝟓𝟎𝟏𝟏𝟕 𝒍𝒃/𝒉𝒓

Due to side reactions and small amount of unreacted acetaldehyde we assume surplus feed of
ethanol

𝑻𝒐𝒕𝒂𝒍 𝒆𝒕𝒉𝒂𝒏𝒐𝒍 𝒇𝒆𝒆𝒅 = 𝟏𝟓𝟓𝟎𝟎𝟎 𝒍𝒃/𝒉𝒓

47
Material balance on Section 100 (Reactor 1): -

Acetaldehyde

Hydrogen

Ethanol CO
Reactor -1 CO2

Acetic Acid
(conv.=50%)
Methane

Diethyl Ether

Ethyl Acetate

Reaction

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → C𝐻3 CHO + 𝐻2 (92%).

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → CO + 𝐶𝐻4 + 𝐻2 (0.75%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐻2 𝑂 → 𝐶𝑂2 + 𝐶𝐻4 + 2𝐻2 (0.75%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐻2 𝑂 → 𝐶𝐻3 𝐶𝑂𝑂𝐻 + 2𝐻2 (2.5%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 𝑂𝐶𝐻2 𝐶𝐻3 + 2𝐻2 𝑂 (2.5%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 → 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 + 𝐻2 𝑂 (1.5%)

Material Balance

𝑙𝑏 𝑘𝑔 𝑘𝑚𝑜𝑙
𝑇𝑜𝑡𝑎𝑙 𝐸𝑡ℎ𝑎𝑛𝑜𝑙 𝑓𝑒𝑒𝑑 = 155000 = 70306.82 = 1528.5
ℎ𝑟 ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × 0.92 = 703.07 = 68211.85
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × (0.9925) = 758.52 = 244.314
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐶𝑂 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × 0.0075 = 5.73 = 353.77
ℎ𝑟 ℎ𝑟

48
 𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐶𝑂2 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × 0.0075 = 5.73 = 556
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐶𝐻4 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × (0.0075 + 0.0075) = 11.46 = 404.31
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐴𝑐𝑖𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × 0.01 = 7.64 = 1005.5
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐸𝑡ℎ𝑒𝑟 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × 0.015 = 11.46 = 1873
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑇𝑜𝑡𝑎𝑙 𝐻2 𝑂 𝑓𝑜𝑟𝑚𝑒𝑑 = 1528.5 × 0.5 × 0.035 = 26.75 = 1061.7
ℎ𝑟 ℎ𝑟

Table 1 Material Balance on R-301

Units Feed Product

Ethanol lb/hr 147703 76616.9
Acetaldehyde lb/hr 0 64970.3
Methanol lb/hr 0 207.921
CO lb/hr 0 181.855
CO2 lb/hr 0 284.658
Acetic Acid lb/hr 0 535.183
Diethyl Ether lb/hr 0 786.103
Water lb/hr 7774 7687.99
Ethylene lb/hr 0 0
Hexadiene lb/hr 0 0
N-Butane lb/hr 0 0
1-Butene lb/hr 0 0
1:3-Butadiene lb/hr 0 0
Hydrogen lb/hr 0 3098.82
Ethyl Acetate lb/hr 0 1107.27
Total lb/hr 155477 155477
Material balance on Section 200 (H2 separation unit): -

Hydrogen

d
Feed
Flash

Product

49
d
Table 2 Material Balance on F-201

Units Feed Top Bottom

Ethanol lb/hr 972.442 0 972.442
Acetaldehyde lb/hr 7670.19 0 7670.19
Methanol lb/hr 156.595 0 156.595
CO lb/hr 174.573 0 174.573
CO2 lb/hr 185.681 0 185.681
Acetic Acid lb/hr 1.74808 0 1.74808
Diethyl Ether lb/hr 158.432 0 158.432
Water lb/hr 129.657 0 129.657
Ethylene lb/hr 0 0 0
Hexadiene lb/hr 0 0 0
N-Butane lb/hr 0 0 0
1-Butene lb/hr 0 0 0
1:3-Butadiene lb/hr 0 0 0
Hydrogen lb/hr 3098.82 3067.83 30.9882
Ethyl Acetate lb/hr 35.7054 0 35.7054
Total lb/hr 12583.85 3067.83 9516.02

Material balance on Section 300 (Reactor 2): -

Acetaldehyde

Hydrogen

Ethanol Butanol

1-butene
Reactor -2
Ethylene
Acetaldehyde
(Conversion=44.5%) Methane

Diethyl Ether
Recycle
Ethyl methyl ether
Acetate
Ethyl Acetate

𝑪𝑯𝟑 𝑪𝑯𝟐 𝑶𝑯 + 𝐂𝑯𝟑 𝐂𝐇𝐎 → 𝑪𝑯𝟐 = 𝑪𝑯 − 𝑪𝑯 = 𝑪𝑯𝟐 + 𝟐𝑯𝟐 𝑶 (𝟓𝟓%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶2 𝐻9 𝑂𝐻 + 𝐻2 𝑂 (5%)

50
2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 𝑂𝐶𝐻2 𝐶𝐻3 + 𝐻2 𝑂 (20%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶2 𝐻4 + 𝐻2 𝑂 (10%)

2𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶4 𝐻8 + 2𝐻2 𝑂 (5%)

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + C𝐻3 CHO + 𝐶2 𝐻4 → 𝐶6 𝐻10 + 2𝐻2 𝑂 (5%)

2C𝐻3 CHO → 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 (9% 𝐵𝑎𝑠𝑒𝑑 𝑜𝑛 𝐴𝑐𝑒𝑡𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒, 𝑛𝑜𝑡 𝑒𝑡ℎ𝑎𝑛𝑜𝑙)

From above material balance total ethanol fed to Reactor 2 is 1912 kmol/hr

𝑘𝑚𝑜𝑙 𝑙𝑏
𝐵𝑢𝑎𝑡𝑎𝑑𝑖𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 0.55 × 1912 = 468 = 55725
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝑊𝑎𝑡𝑒𝑟 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 1.42 × 1912 = 1209 = 47954
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝐵𝑢𝑡𝑎𝑛𝑜𝑙 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 0.025 × 1912 = 21.271 = 3471
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝐷𝑖𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑒𝑟 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 0.1 × 1912 = 85.084 = 13883.16
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 0.1 × 1912 = 85.084 = 5253
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝐵𝑢𝑡𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 0.025 × 1912 = 21.271 = 2626.54
ℎ𝑟 ℎ𝑟

𝑘𝑚𝑜𝑙 𝑙𝑏
𝐻𝑒𝑥𝑎𝑑𝑖𝑒𝑛𝑒 𝑓𝑜𝑟𝑚𝑒𝑑 = 0.445 × 0.05 × 19124 = 42.54 = 7880
ℎ𝑟 ℎ𝑟

Butadiene is separated as product and rest are recycled back to reactor

Table 3 Material Balance on R-301

Units Feed Product

Ethanol lb/hr 190875 117584
Acetaldehyde lb/hr 59777.2 10567
Methanol lb/hr 51.3261 51.3261
CO lb/hr 7.2816 7.2816
CO2 lb/hr 98.9766 98.9766
Acetic Acid lb/hr 533.448 1975.39
Diethyl Ether lb/hr 13018.3 23039.9
Water lb/hr 18647.7 63946.4

51
 Ethylene lb/hr 4.10E-11 1841.31
Hexadiene lb/hr 1200.42 5926.68
N-Butane lb/hr 0.9395 2563.37
1-Butene lb/hr 0.00043 1650.81
1:3-Butadiene lb/hr 0.00038 56028.5
Hydrogen lb/hr 0.00044 0.00044
Ethyl Acetate lb/hr 3186.01 2115.55
Total lb/hr 287396 287396

Material balance on Section 400 (Recovery unit): -

D-401

Table 4 Material Balance on D-401

Units Feed Feed Top Top Bottom

Ethanol lb/hr 22961.45 94622.14 0.026792 35.14333 117548.4
Acetaldehyde lb/hr 5381.647 5185.327 10.13108 1080.223 9476.619
Methanol lb/hr 48.25889 3.067253 5.295012 46.03113 3.20E-12
CO lb/hr 7.214105 0.067499 3.367189 3.914414 2.88E-39
CO2 lb/hr 93.55274 5.423849 6.620828 92.35576 1.22E-09
Acetic Acid lb/hr 19.13734 1956.249 8.64E-06 0.043215 1975.343
Diethyl Ether lb/hr 20112.78 2927.14 9.530262 1955.379 21075.01
Water lb/hr 5903.081 58043.33 19.31623 1391.852 62535.24
Ethylene lb/hr 1476.652 364.6572 97.28538 1740.276 3.747356
Hexadiene lb/hr 636.7437 5289.939 0.002043 1.389381 5925.291
N-Butane lb/hr 116.8256 2446.543 1.37E-05 0.087602 2563.281
1-Butene lb/hr 820.1264 830.6875 0.567445 57.28425 1592.962
1:3-Butadiene lb/hr 47757.05 8271.439 1013.123 53585.54 1429.827
Hydrogen lb/hr 0.000441 1.29E-10 0.000441 2.83E-09 5.87E-172
Ethyl Acetate lb/hr 974.9222 1140.623 0.001344 1.042132 2114.502
Total lb/hr 106309.4 181086.6 1165.267 59990.56 226240.2

52
Table 5 Material Balance on D-402

Units Feed Top Bottom

Ethanol lb/hr 35.14333 3.09E-08 35.14333
Acetaldehyde lb/hr 1080.223 1.185704 1079.038
Methanol lb/hr 46.03113 46.03114 1.03E-12
CO lb/hr 3.914414 3.914415 1.12E-38
CO2 lb/hr 92.35576 92.35515 0.000628
Acetic Acid lb/hr 0.043215 5.30E-18 0.043215
Diethyl Ether lb/hr 1955.379 1.13E-05 1955.379
Water lb/hr 1391.852 9.48E-08 1391.852
Ethylene lb/hr 1740.276 1740.137 0.139954
Hexadiene lb/hr 1.389381 9.23E-15 1.389381
N-Butane lb/hr 0.087602 3.42E-19 0.087602
1-Butene lb/hr 57.28425 3.34253 53.94172
1:3-Butadiene lb/hr 53585.54 428.0329 53157.51
Hydrogen lb/hr 2.83E-09 2.83E-09 4.16E-229
Ethyl Acetate lb/hr 1.042132 8.29E-16 1.042132
Total lb/hr 59990.56 2314.999 57675.56

Table 6 Material Balnce on D-403

Units Feed Top Bottom

Ethanol lb/hr 117548.4 115269.4 2279.018
Acetaldehyde lb/hr 9476.619 9476.61 0.0072
Methanol lb/hr 3.20E-12 0 0
CO lb/hr 2.88E-39 0 0
CO2 lb/hr 1.22E-09 1.22E-09 4.09E-38
Acetic Acid lb/hr 1975.343 0.013098 1975.331
Diethyl Ether lb/hr 21075.01 21075 5.69E-17
Water lb/hr 62535.24 11078.24 51457.01
Ethylene lb/hr 3.747356 3.747356 2.36E-13
Hexadiene lb/hr 5925.291 1235.757 4689.536
N-Butane lb/hr 2563.281 0.938986 2562.343
1-Butene lb/hr 1592.962 1592.959 0.002686
1:3-Butadiene lb/hr 1429.827 1429.826 2.00E-16
Hydrogen lb/hr 5.87E-172 0 0
Ethyl Acetate lb/hr 2114.502 2114.502 1.85E-05
Total lb/hr 226240.2 163277 62963.25

53
Table 7 Material Balance on D-404
Units Feed Top Bottom
Ethanol lb/hr 115269.4 11.59431 115257.8
Acetaldehyde lb/hr 9476.61 7000.777 2475.834
Methanol lb/hr 0 0 0
CO lb/hr 0 0 0
CO2 lb/hr 1.22E-09 1.22E-09 2.73E-16
Acetic Acid lb/hr 0.013098 6.11E-10 0.013098
Diethyl Ether lb/hr 21075 8698.424 12376.58
Water lb/hr 11078.24 0.054959 11078.18
Ethylene lb/hr 3.747356 3.747356 4.05E-11
Hexadiene lb/hr 1235.757 36.58709 1199.17
N-Butane lb/hr 0.938986 1.13E-08 0.938986
1-Butene lb/hr 1592.959 1592.959 0.000432
1:3-Butadiene lb/hr 1429.826 1429.826 0.00038
Hydrogen lb/hr 0 0 0
Ethyl Acetate lb/hr 2114.502 0.029592 2114.472
Total lb/hr 163277 18774 144503

Table 8 Material Balance on D-405

Units Feed Top Bottom

Ethanol lb/hr 2279.504 2279.49 2.70E-18
Acetaldehyde lb/hr 13.33762 13.33754 4.53E-40
Methanol lb/hr 0 0 0
CO lb/hr 0 0 0
CO2 lb/hr 2.64E-05 2.64E-05 2.77E-67
Acetic Acid lb/hr 1975.334 0.15824 1975.176
Diethyl Ether lb/hr 1.086522 1.086515 1.37E-74
Water lb/hr 52739.47 1173.652 51565.83
Ethylene lb/hr 0.009022 0.009022 1.03E-83
Hexadiene lb/hr 4689.625 4689.597 1.38E-100
N-Butane lb/hr 2562.343 2562.327 3.61E-22
1-Butene lb/hr 3.607549 3.607527 1.04E-100
1:3-Butadiene lb/hr 17.09673 17.09663 4.19E-97
Hydrogen lb/hr 0 0 0
Ethyl Acetate lb/hr 0.001095 0.001095 7.29E-54
Total lb/hr 64281.41 10740.36 53541.01

54
 Energy Balance
Reference Temperature: (Tr) = 77 ° F
Temperature of Stream = Tp ° F

Cp = A + BT + 𝐶𝑇 2 + 𝐷𝑇 3

Heat capacity data for component at different temperature is taken from aspen plus: -

Table 9 Enthalpy at different Temperature

(BTU/lb mol)

80 ° F 151 ° F 225 ° F 296 ° F 595 ° F 662 ° F

Ethanol -119230 -117050 -114440 -111470 -96783.2 -95674.7
Acetaldehyde -84532.8 -82336 -79737.6 -76870.3 -70961.7 -70058.6
Methanol -35050.4 -35014.6 -35022.5 -35052.3 -35037.7 -34947.6
CO -51494.1 -51912.9 -52385.8 -52846.7 -54533 -54820.4
CO2 -171700 -172040 -171880 -171790 -172690 -173170
Acetic Acid -196470 -195120 -193720 -192330 -179470 -180040
Diethyl Ether -120010 -116960 -113560 -109810 -95838.4 -93376.7
Water -122820 -121540 -120140 -118730 -111260 -108130
Ethylene 19751 19989.9 20361.7 20710.1 21987.4 22250.5
Hexadiene 17743.1 20775.4 24174.1 27733.5 44750.6 47490.3
N-Butane -141140 -137390 -133150 -128800 -105090 -103720
1-Butene -9014.82 -6590.9 -3633.02 5046.91 7748.94 9439.48
1:3- 37949 40199.9 42933.3 48518.9 54155.3 55701.2
Butadiene
Hydrogen -28851.3 -28348.8 -27823.8 -27319.6 -25199.6 -24725.7
Ethyl Acetate -206320 -203240 -199810 -196260 -179220 -176850

Energy balance on Reactor and Heater (Recovery unit): -

E-102

Enthalpy of feed mixture (assuming ideal mixture)

= ∑𝑋𝑖𝐻𝑖

= ∑((0.88 × −114440) + (0.12 × −120140))

𝐵𝑇𝑈
= −115124
𝐿𝑏𝑚𝑜𝑙

Enthalpy of heated product mixture

= ∑𝑋𝑖𝐻𝑖

55
= ∑((0.88 × −96783.2) + (0.12 × −111260))

𝐵𝑇𝑈
= −98520.4
𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 = −98520.4 + 115124 = 16603.58 𝐵𝑇𝑈/𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑑𝑑𝑒𝑑 = 16603.58 × 3637.65 = 60398027.34 𝐵𝑇𝑈

Suppose this heat is provided by dowtherm

60398027.34
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚

𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑎𝑡 600 𝐹 = 114 BTU/lb

60398027.34
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
114

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 529807 𝑙𝑏

R-101

Enthalpy of feed mixture (assuming ideal mixture)

= ∑𝑋𝑖𝐻𝑖

𝐵𝑇𝑈
= −91399.8
𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = −98520.4 × 3637.65 = −332480482.5 𝐵𝑇𝑈/𝐿𝑏

Enthalpy of heated product mixture

= ∑𝑋𝑖𝐻𝑖

𝐵𝑇𝑈
−56044.17
𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = −56044.17 × 5159.86 = −289180071 𝐵𝑇𝑈/𝐿𝑏

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 = −289180071 + 332480482.5 = 43300411.47 𝐵𝑇𝑈/𝐿𝑏

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑑𝑑𝑒𝑑 = 43300411.47 𝐵𝑇𝑈/𝐿𝑏

Suppose this heat is provided by dowtherm

56
 43300411.47
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚

𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 = 114 BTU/lb

43300411.47
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
114

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 379828.17

E-302

Enthalpy of feed mixture (assuming ideal mixture)

= ∑𝑋𝑖𝐻𝑖

𝐵𝑇𝑈
= −93166.73
𝐿𝑏𝑚𝑜𝑙

Enthalpy of heated product mixture

= ∑𝑋𝑖𝐻𝑖

𝐵𝑇𝑈
= −85413.92
𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 = 93166.73 − 85413.92 = 7752.81 𝐵𝑇𝑈/𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑑𝑑𝑒𝑑 = 7752.81 × 6784.06 = 5259528.21 𝐵𝑇𝑈

Suppose this heat is provided by dowtherm

5259528.21
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚

𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑎𝑡 600 𝐹 = 114 BTU/lb

5259528.21
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
114

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 46136.21 𝑙𝑏

R-301

Enthalpy of feed mixture (assuming ideal mixture)

57
= ∑𝑋𝑖𝐻𝑖

𝐵𝑇𝑈
= −85413.9
𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = −85413.9 × 6783.82 = −579432523.1 𝐵𝑇𝑈/𝐿𝑏

Enthalpy of heated product mixture

= ∑𝑋𝑖𝐻𝑖

𝐵𝑇𝑈
−70706.1
𝐿𝑏𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 = −70706.1 × 7964.19 = 56311614.6 𝐵𝑇𝑈/𝐿𝑏

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 = 579432523.1 − 56311614.6 = 𝐵𝑇𝑈/𝐿𝑏

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑑𝑑𝑒𝑑 = 16315708.54 𝐵𝑇𝑈/𝐿𝑏

Suppose this heat is provided by dowtherm

16315708.54
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚

𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 = 114 BTU/lb

16315708.54
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
114

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 143120.25

𝑇𝑜𝑡𝑎𝑙 𝐷𝑜𝑤𝑡ℎ𝑒𝑟𝑚 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 529807 + 379828.17 + 46136.21 +143120.25

= 1500000 𝑘𝑔/ℎ𝑟

Energy balance on Distillation column: -

D-401

𝐹𝑒𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, = 200 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐹𝑒𝑒𝑑, 𝐶𝑝𝑓 = 29.83 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒, 𝐶𝑝𝑑 = 31.73 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

58
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐵𝑜𝑡𝑡𝑜𝑚, 𝐶𝑝𝑏 = 32.25 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑡𝑜𝑝 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑡 = 138 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑏𝑜𝑡𝑡𝑜𝑚 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑏 = 259 ° F

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡𝑜𝑝 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝐷 = 8573.16 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑏𝑜𝑡𝑡𝑜𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝑤 = 11703.52 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙

𝑅𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜, 𝑅 = 1 ∶ 6

𝑉𝑎𝑝𝑜𝑟 𝑟𝑎𝑡𝑒𝑠 𝑓𝑟𝑜𝑚 𝑐𝑜𝑙𝑢𝑚𝑛 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑉 = 𝐷(𝑅 + 1) = 7 ∗ 1187.76 = 8314.32 𝑙𝑏𝑚𝑜𝑙/ℎ𝑟

𝐻𝑒𝑎𝑡 𝑙𝑜𝑎𝑑 𝑜𝑛 𝑟𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑄𝑏 = 𝐹 ∗ 𝐶𝑝𝑓 ∗ (𝑇𝑏 – 𝑇𝑓) + 𝑉 ∗ 𝐻𝐷

𝑅𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑏 = 7964.2 ∗ 28.43 ∗ (259 − 200) + 8314.32 ∗ 8573.16

= 80 𝑀𝑀𝐵𝑇𝑈/ℎ𝑟

𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 𝑉 ∗ 𝐶𝑝𝑑 ∗ (𝑇𝑡 – 𝑇) + 𝑉 ∗ 𝐻𝐷

𝑃𝑢𝑡𝑡𝑖𝑛𝑔 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟𝑠, 𝑄𝑐 = 8314.32 ∗ 31.73 ∗ (138 − 107) + 8314.32 ∗ 7679.46

𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 71763889.08 𝐵𝑇𝑈/ℎ𝑟

D-402

𝐹𝑒𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 138 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐹𝑒𝑒𝑑, 𝐶𝑝𝑓 = 31.77 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒, 𝐶𝑝𝑑 = 10.91 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐵𝑜𝑡𝑡𝑜𝑚, 𝐶𝑝𝑏 = 32.35 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑡𝑜𝑝 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑡 = 16 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑏𝑜𝑡𝑡𝑜𝑚 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑏 = 145 𝐹

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡𝑜𝑝 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝐷 = 9865 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑏𝑜𝑡𝑡𝑜𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝑤 = 8151.89 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙

𝑅𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜, 𝑅 = 1 ∶ 4.8

𝑉𝑎𝑝𝑜𝑟 𝑟𝑎𝑡𝑒𝑠 𝑓𝑟𝑜𝑚 𝑐𝑜𝑙𝑢𝑚𝑛 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑉 = 𝐷(𝑅 + 1) = 5.8 ∗ 75.234 = 436.36 𝑙𝑏𝑚𝑜𝑙/ℎ𝑟

59
𝐻𝑒𝑎𝑡 𝑙𝑜𝑎𝑑 𝑜𝑛 𝑟𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑄𝑏 = 𝐹 ∗ 𝐶𝑝𝑓 ∗ (𝑇𝑏 – 𝑇𝑓) + 𝑉 ∗ 𝐻𝐷

𝑅𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑏 = 1187.76 ∗ 31.77 ∗ (145 − 138) + 9865 ∗ 436.36

= 4568837.346 𝐵𝑇𝑈/ℎ𝑟

𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 𝑉 ∗ 𝐶𝑝𝑑 ∗ (𝑇𝑡 – 𝑇) + 𝑉 ∗ 𝐻𝐷

𝑃𝑢𝑡𝑡𝑖𝑛𝑔 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟𝑠, 𝑄𝑐 = 436.36*9865

𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 4304691.4 𝐵𝑇𝑈/ℎ𝑟

D-403

𝐹𝑒𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, = 259 𝐹

𝐵𝑇𝑈
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐹𝑒𝑒𝑑, 𝐶𝑝𝑓 = 32.25 𝑚𝑜𝑙 ° F
𝐿𝑏

𝐵𝑇𝑈
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒, 𝐶𝑝𝑑 = 36.51 𝑚𝑜𝑙 ° F
𝐿𝑏

𝐵𝑇𝑈
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐵𝑜𝑡𝑡𝑜𝑚, 𝐶𝑝𝑏 = 21.30 𝑚𝑜𝑙 ° F
𝐿𝑏

𝐶𝑜𝑙𝑢𝑚𝑛 𝑡𝑜𝑝 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑡 = 186 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑏𝑜𝑡𝑡𝑜𝑚 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑏 = 261 ° F

𝐵𝑇𝑈
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡𝑜𝑝 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝐷 = 12835.5 𝑚𝑜𝑙
𝐿𝑏

𝐵𝑇𝑈
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑏𝑜𝑡𝑡𝑜𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝑤 = 16881 𝑚𝑜𝑙
𝐿𝑏

𝑅𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜, 𝑅 = 1 ∶ 2

𝑙𝑏𝑚𝑜𝑙
𝑉𝑎𝑝𝑜𝑟 𝑟𝑎𝑡𝑒𝑠 𝑓𝑟𝑜𝑚 𝑐𝑜𝑙𝑢𝑚𝑛 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑉 = 𝐷(𝑅 + 1) = 3 ∗ 3716.5 = 11149.5
ℎ𝑟

𝐻𝑒𝑎𝑡 𝑙𝑜𝑎𝑑 𝑜𝑛 𝑟𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑄𝑏 = 𝐹 ∗ 𝐶𝑝𝑓 ∗ (𝑇𝑏 – 𝑇𝑓) + 𝑉 ∗ 𝐻𝐷

𝑅𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑏 = 226266 ∗ 32.25 ∗ (261 − 259) + 11149.5 ∗ 12835.5

𝐵𝑇𝑈
= 143 𝑀𝑀
ℎ𝑟

𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 𝑉 ∗ 𝐶𝑝𝑑 ∗ (𝑇𝑡 – 𝑇) + 𝑉 ∗ 𝐻𝐷

60
𝑃𝑢𝑡𝑡𝑖𝑛𝑔 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟𝑠, 𝑄𝑐 = 11149.5 ∗ 12835.5

𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 143 𝑀𝑀 𝐵𝑇𝑈/ℎ𝑟

D-404

𝐹𝑒𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, = 186 𝐹

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐹𝑒𝑒𝑑, 𝐶𝑝𝑓 = 36.51 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒, 𝐶𝑝𝑑 = 19.77 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐵𝑜𝑡𝑡𝑜𝑚, 𝐶𝑝𝑏 = 32.40 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑡𝑜𝑝 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑡 = 77 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑏𝑜𝑡𝑡𝑜𝑚 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑏 = 171 ° F

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡𝑜𝑝 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝐷 = 11353.14 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑏𝑜𝑡𝑡𝑜𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝑤 = 14915.1 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙

𝑅𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜, 𝑅 = 1 ∶ 2

𝑉𝑎𝑝𝑜𝑟 𝑟𝑎𝑡𝑒𝑠 𝑓𝑟𝑜𝑚 𝑐𝑜𝑙𝑢𝑚𝑛 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑉 = 𝐷(𝑅 + 1) = 4.8 ∗ 331.5 = 1591.2 𝑙𝑏𝑚𝑜𝑙/ℎ𝑟

𝐻𝑒𝑎𝑡 𝑙𝑜𝑎𝑑 𝑜𝑛 𝑟𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑄𝑏 = 𝐹 ∗ 𝐶𝑝𝑓 ∗ (𝑇𝑏 – 𝑇𝑓) + 𝑉 ∗ 𝐻𝐷

𝑅𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑏 = 3716.5 ∗ 36.51 ∗ (186 − 171) + 1591.2 ∗ 11353.14

= 20.1 𝑀𝑀 𝐵𝑇𝑈/ℎ𝑟

𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 𝑉 ∗ 𝐶𝑝𝑑 ∗ (𝑇𝑡 – 𝑇) + 𝑉 ∗ 𝐻𝐷

𝑃𝑢𝑡𝑡𝑖𝑛𝑔 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟𝑠, 𝑄𝑐 = 1591.2 ∗ 11353.14

𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 18 𝑀𝑀 𝐵𝑇𝑈/ℎ𝑟

D-405

𝐹𝑒𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, = 259 ° F

𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐹𝑒𝑒𝑑, 𝐶𝑝𝑓 = 21.53 𝐵𝑇𝑈/𝐿𝑏 𝑚𝑜𝑙 ° F

𝐵𝑇𝑈
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒, 𝐶𝑝𝑑 = 23.43 𝑚𝑜𝑙 ° F
𝐿𝑏

61
 𝐵𝑇𝑈
𝐻𝑒𝑎𝑡 𝐶𝑎𝑝𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝐵𝑜𝑡𝑡𝑜𝑚, 𝐶𝑝𝑏 = 19.51 𝑚𝑜𝑙 ° F
𝐿𝑏

𝐶𝑜𝑙𝑢𝑚𝑛 𝑡𝑜𝑝 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑡 = 202 ° F

𝐶𝑜𝑙𝑢𝑚𝑛 𝑏𝑜𝑡𝑡𝑜𝑚 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑇𝑏 = 238 𝐹

𝐵𝑇𝑈
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑡𝑜𝑝 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝐷 = 18364.98 𝑚𝑜𝑙
𝐿𝑏

𝐵𝑇𝑈
𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑏𝑜𝑡𝑡𝑜𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑡, 𝐻𝑤 = 17087.44 𝑚𝑜𝑙
𝐿𝑏

𝑅𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜, 𝑅 = 1 ∶ 16

𝑙𝑏𝑚𝑜𝑙
𝑉𝑎𝑝𝑜𝑟 𝑟𝑎𝑡𝑒𝑠 𝑓𝑟𝑜𝑚 𝑐𝑜𝑙𝑢𝑚𝑛 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑉 = 𝐷(𝑅 + 1) = 17 ∗ 188 = 3196 ℎ𝑟

𝐻𝑒𝑎𝑡 𝑙𝑜𝑎𝑑 𝑜𝑛 𝑟𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑤𝑖𝑙𝑙 𝑏𝑒, 𝑄𝑏 = 𝐹 ∗ 𝐶𝑝𝑓 ∗ (𝑇𝑏 – 𝑇𝑓) + 𝑉 ∗ 𝐻𝐷

𝐵𝑇𝑈
𝑅𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑏 = 3108 ∗ 21.53 ∗ (259 − 238) + 3196 ∗ 18364.98 = 61 𝑀𝑀 ℎ𝑟

So, heat load on condenser will be (assuming distillate is at 10 F subcooled)

𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 𝑉 ∗ 𝐶𝑝𝑑 ∗ (𝑇𝑡 – 𝑇) + 𝑉 ∗ 𝐻𝐷

𝑃𝑢𝑡𝑡𝑖𝑛𝑔 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟𝑠, 𝑄𝑐 = 3196 ∗ 18364.98

𝐵𝑇𝑈
𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑦 𝑄𝑐 = 59 𝑀𝑀
ℎ𝑟

𝑀𝑀𝐵𝑇𝑈
𝑇𝑜𝑡𝑎𝑙 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑟 𝑑𝑢𝑡𝑖𝑒𝑠 = 72 + 43 + 143 + 18 + 159 = 435
ℎ𝑟
𝑇𝑜𝑡𝑎𝑙 𝑟𝑒𝑏𝑜𝑖𝑙𝑒𝑟 𝑑𝑢𝑡𝑖𝑒𝑠 = 80 + 46 + 143 + 20 + 61 = 350 𝑀𝑀𝐵𝑇𝑈/ℎ𝑟

For condenser we took cooling water from 90 °F to 120 °F

106 𝑙𝑏
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 435 × = 14.5 × 106
30 × 0.99 ℎ𝑟
For reboiler we took steam at 50 psig
106
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 350 × = 350000 lb/hr
1000

62
 Thermodynamics and kinetics
Thermodynamic
For any reaction to take place, we must check its thermodynamic and kinetic feasibility. If the
reaction is feasible, then one may proceed towards production.

A well-known thermodynamic property, Gibbs free energy (ΔG), gives the feasibility and the
spontaneity of the reaction. Thus, we can evaluate whether or not our reaction is spontaneous
or not by the value of ΔG as follows:

If ΔG < 0 reaction will occur

If ΔG > 0 reaction will not occur

Thus, we will check this thermodynamics feasibility for the guiding chemical reaction:

1.-Dehydrogenation of Ethanol

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → C𝐻3 CHO + 𝐻2

Calculating ΔG and ΔH for this reaction. Below are the thermodynamic properties at 595 F and
32 psi

Components ΔG ΔH
Ethanol -46357.2 -90278.7
Acetaldehyde -46810.2 -64895.9
Hydrogen 279.477 3613.98

Reaction Temperature: - 595 F

Reaction Pressure: - 32 psi

𝛥𝐺 = ∑𝛥𝐺 𝑃 − ∑𝛥𝐺𝑅

= (−46810.2 + 279.477) – (−46357.2)

𝐵𝑇𝑈
= −173.523
𝑙𝑏 𝑚𝑜𝑙

𝛥𝐻 = ∑𝛥𝐻𝑃 − ∑𝛥𝐻𝑅

= (−64859.9 + 3613.98) – (−90278.7)

63
 𝐵𝑇𝑈
= 29032.78
𝑙𝑏 𝑚𝑜𝑙

Applying the Gibbs free energy equation at T= 595F

𝛥𝐺𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝛥𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 – 𝑇 × 𝛥𝑆𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝐵𝑇𝑈
𝛥𝑆𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 49.08
𝑙𝑏 𝑚𝑜𝑙

Since this energy is positive so our reaction is feasible according to thermodynamics

2.1-3, Butadiene

𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + C𝐻3 CHO → 𝐶𝐻2 = 𝐶𝐻 − 𝐶𝐻 = 𝐶𝐻2 + 2𝐻2 𝑂

Calculating ΔG and ΔH for this reaction. Below are the thermodynamic properties at 662 F and
80 psi

Components ΔG ΔH
Ethanol -41435.6 -88501.8
Acetaldehyde -43611.3 -63482.5
Water -90255.7 -99111.5
Butadiene 81332.2 62838.3

Reaction Temperature: - 662 F

Reaction Pressure: - 80 psi

𝛥𝐺 = ∑𝛥𝐺 𝑃 − ∑𝛥𝐺𝑅

= (81332.2 − (2 ∗ 90255.7)) – (−63482.5 − 88501.8)

= −52805.1𝐵𝑇𝑈/(𝑙𝑏 𝑚𝑜𝑙)

𝛥𝐻 = ∑𝛥𝐻𝑃 − ∑𝛥𝐻𝑅

= (62838.3 − (2 ∗ 99111.5) – (−63482.5 − 88501.8)

= 16599.6 𝐵𝑇𝑈/(𝑙𝑏 𝑚𝑜𝑙)

Applying the Gibbs free energy equation at T= 595F

ΔG reaction = ΔH reaction – T × ΔS reaction

64
 𝐵𝑇𝑈
𝛥𝑆𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 104.84
𝑙𝑏 𝑚𝑜𝑙

Since this energy is positive so our reaction is feasible according to thermodynamics.

Kinetics
REACTION ONE

The first step of the process involves the dehydrogenation of ethanol to acetaldehyde. Kinetics
are readily available for this reaction using an unsupported copper-chromite catalyst and were
used to determine optimal conditions for the first reactor. The mechanism involved is a dual-
site surface reaction of the adsorbed ethanol. The mechanism for the reaction was derived first
using a homogenous Hougen-Watson method.

(1) 𝐶𝐻3𝐶𝐻2𝑂𝐻 ↔ 𝐻2 + 𝐶𝐻3𝐶𝐻𝑂

(2) 𝐴 ↔ 𝑅 + 𝑆

(3) 𝑅𝐴 = 𝑘(𝑝𝐴 − ((𝑝𝑅 × 𝑝𝑆)/𝐾𝑒)

The reaction rate was then corrected by a Langmuir-Hinshelwood, dual-site, surface reaction-
controlled mechanism.

(4) 𝑅𝐴 = 𝑘 (𝑝𝐴 − (𝑝𝑅𝑝𝑆)/𝐾𝑒)/(1 + 𝐾𝐴𝑝𝐴 + 𝐾𝑅𝑝𝑅 + 𝐾𝑠𝑝𝑠)2

where RA is the rate of the reaction in mol/L-s, pi is the partial pressure of species i in atm, k
is the reaction rate constant in mol/s-kg cat. -atm, Ki is the adsorption coefficient for species i
in atm-1, and Ke is the equilibrium constant in atm. The corrections to the original homogenous
model were necessary due to the variance of reaction step speeds. The reaction steps were as
follows:

(5) 𝐴 + 𝑐𝐿 → 𝑐𝐴

(6) 𝑐𝐴 + 𝑐𝐿 → 𝑐𝐴2

(7) 𝑐𝐴2 → 𝑐𝑅 + 𝑐𝑆

(8) 𝑐𝑅 → 𝑐𝐿 + 𝑅

(9) 𝑐𝑆 → 𝑐𝐿 + 𝑆

where A, S, and R denote molecules of ethanol, acetaldehyde, and hydrogen, respectively. A2

denotes a reactive intermediate, and L denotes the catalyst surface. The controlling steps of the

65
mechanism are the surface reactions, (6) and (7), which occur in parallel on the catalyst. In this
model, ethanol approaches the catalyst and then adsorbs to its surface which is a fast step (5).
The surface reaction takes place where hydrogen is adsorbed away from acetaldehyde on a
second site of the catalyst surface which are the rate controlling slow steps, (6) and (7). Finally,
desorption of acetaldehyde and hydrogen occurs, freeing both molecules from the catalyst,
which are fast steps, (8) and (9). The following mass balance, based on the above mechanism,
was presented in the literature.

(10) 𝑑𝜉/𝑑𝑧 = 𝑝𝐵 ∗ 𝑆 ∗ 𝑅𝐴 ∗ 𝑛𝐴0

where pB is the catalyst bed density, S is the cross-sectional area of the reactor, nA0 is the
ethanol feed rate, and ξ is the ethanol conversion. The mass balance (10) and reaction rate (4),
in conjunction with the following expressions for K values, were used and manipulated to
calculate the reaction conversion and to determine an optimal operating temperature and
pressure at which to run the reaction. Expressions for K values were determined by fitting
curves to experimental data

(11) ln Ke = 11.82 − 6189.1/Tk

(12) ln k = 17.900 − 5810.5/Tk

where Tk is the reaction temperature, k is the reaction rate constant in mol/s-kg cat.-atm, , and
Ke is the equilibrium constant in atm.

66
 ASPEN PLUS Simulation
For the analysis of the process simulation, the ASPEN PLUS program was used. In order to
simulate the appropriate thermodynamic and transport characteristics of all chemical species
used in the process, data was supplied to ASPEN PLUS using the NRTL-RK property
method. All activities and thermodynamic properties were checked to ensure that the NRTL-
RK property method contained all relevant values.

Section 100

Table 10 Section 100 Simulation Data

Units S1 S2 S3 S4 S5 S6 S7 S8
From P-101 E-101 F-101 F-101 E-102 R-101 E-101
To P-101 E-101 F-101 E-102 E-102 R-101 E-101 F-201
Ethanol lb/hr 147703 147703 147703 63779.7 83923.3 147703 76616.9 76616.9
Acetaldehyde lb/hr 0 0 0 0 0 0 64970.3 64970.3
Methanol lb/hr 0 0 0 0 0 0 207.921 207.921
CO lb/hr 0 0 0 0 0 0 181.855 181.855
CO2 lb/hr 0 0 0 0 0 0 284.658 284.658
Acetic Acid lb/hr 0 0 0 0 0 0 535.183 535.183
Diethyl
lb/hr 0 0 0 0 0 0 786.103 786.103
Ether
Water lb/hr 7774 7774 7774 3392.69 4381.31 7774 7687.99 7687.99
Ethylene lb/hr 0 0 0 0 0 0 0 0
Hexadiene lb/hr 0 0 0 0 0 0 0 0
N-Butane lb/hr 0 0 0 0 0 0 0 0
1-Butene lb/hr 0 0 0 0 0 0 0 0

67
 1:3-
lb/hr 0 0 0 0 0 0 0 0
Butadiene
Hydrogen lb/hr 0 0 0 0 0 0 3098.82 3098.82
Ethyl Acetate lb/hr 0 0 0 0 0 0 1107.27 1107.27
Total lb/hr 155477 155477 155477 67172.4 88304.6 155477 155477 155477

Liquid Liquid Vapor Liquid Vapor Vapor

Phase
Phase Phase Phase Phase Phase Phase
Temperature F 80 80.154 225.21 225.207 225.21 595 595 151.4
Pressure psia 15 50 42 42 42 35 35 22
Mass Vapor
0 0 0.4397 1 0 1 1 0.8775
Fraction
Mass Liquid
1 1 0.5603 0 1 0 0 0.1225
Fraction
Mass -
Btu/lb -2799 -2799 -2527.8 -2320.6 -2690 -1860 -2131.1
Enthalpy 2138.5
Mass Density lb/cuft 50.279 50.272 0.5715 0.25311 43.891 0.1333 0.0935 0.1124

Section 200

Table 11 Section 200 Simulation Data

Units S8 S9 S10 S11 S12 S13 S14 S15

From E-101 F-201 C-201 E-201 F-202 C-202 E-202 F-202
To F-201 C-201 E-201 F-202 C-202 E-202 F-203 P-202
Ethanol lb/hr 76616.9 58301.8 58301.8 58301.8 2228.26 2228.26 2228.26 56073.5
Acetaldehyde lb/hr 64970.3 61889 61889 61889 19740.7 19740.7 19740.7 42148.3

68
Methanol lb/hr 207.921 207.406 207.406 207.406 192.696 192.696 192.696 14.7096
CO lb/hr 181.855 181.795 181.795 181.795 180.017 180.017 180.017 1.77767
CO2 lb/hr 284.658 283.487 283.487 283.487 251.731 251.731 251.731 31.7561
Acetic Acid lb/hr 535.183 207.763 207.763 207.763 2.26811 2.26811 2.26811 205.495
Diethyl Ether lb/hr 786.103 771.685 771.685 771.685 369.824 369.824 369.824 401.861
Water lb/hr 7687.99 5574.37 5574.37 5574.37 299.085 299.085 299.085 5275.28
Ethylene lb/hr 0 0 0 0 0 0 0 0
Hexadiene lb/hr 0 0 0 0 0 0 0 0
N-Butane lb/hr 0 0 0 0 0 0 0 0
1-Butene lb/hr 0 0 0 0 0 0 0 0
1:3-Butadiene lb/hr 0 0 0 0 0 0 0 0
Hydrogen lb/hr 3098.82 3098.82 3098.82 3098.82 3098.82 3098.82 3098.82 7.28E-05
Ethyl Acetate lb/hr 1107.27 988.207 988.207 988.207 106.022 106.022 106.022 882.185
Total lb/hr 155477 131504 131504 131504 26469.5 26469.5 26469.5 105035

Vapor Vapor Vapor Vapor Liquid

Phase
Phase Phase Phase Phase Phase
Temperature F 151.396 150 296.363 108 108 335.015 108 108
Pressure psia 22 22 60 53 53 160 155 53
Mass Vapor
0.87755 1 1 0.20128 1 1 0.65271 0
Fraction
Mass Liquid
0.12245 0 0 0.79872 0 0 0.34729 1
Fraction
Mass
Btu/lb -2131.1 -2017 -1952.4 -2350 -1566.8 -1405.2 -1677 -2547.4
Enthalpy
Mass Density lb/cuft 0.11237 0.09779 0.21606 0.54664 0.11103 0.23882 0.35988 48.4703

Units S16 S17 S18 S19 S20 S21 S22

From P-202 F-201 P-201 F-203 PSA-201 PSA-201 F-203
To F-203 P-201 F-203 PSA-201 MIX
Ethanol lb/hr 56073.5 18315.1 18315.1 972.442 0 972.442 75644.4
Acetaldehyde lb/hr 42148.3 3081.28 3081.28 7670.19 0 7670.19 57300.1
Methanol lb/hr 14.7096 0.51549 0.51549 156.595 0 156.595 51.3261
CO lb/hr 1.77767 0.05985 0.05985 174.573 0 174.573 7.2816
CO2 lb/hr 31.7561 1.17059 1.17059 185.681 0 185.681 98.9766
Acetic Acid lb/hr 205.495 327.42 327.42 1.74808 0 1.74808 533.435
Diethyl Ether lb/hr 401.861 14.4183 14.4183 158.432 0 158.432 627.671
Water lb/hr 5275.28 2113.62 2113.62 129.657 0 129.657 7558.33
Ethylene lb/hr 0 0 0 0 0 0 0
Hexadiene lb/hr 0 0 0 0 0 0 0
N-Butane lb/hr 0 0 0 0 0 0 0
1-Butene lb/hr 0 0 0 0 0 0 0
1:3-Butadiene lb/hr 0 0 0 0 0 0 0
Hydrogen lb/hr 7.28E-05 7.08E-06 7.08E-06 3098.82 3067.83 30.9882 0.00044
Ethyl Acetate lb/hr 882.185 119.062 119.062 35.7054 0 35.7054 1071.56

69
 Total lb/hr 105035 23972.7 23972.7 12583.8 3067.83 9516.02 142893

Liquid Liquid Liquid Vapor Vapor Liquid

Phase
Phase Phase Phase Phase Phase Phase
Temperature F 108.196 150 150.335 121 121 121 121
Pressure psia 155 22 153 155 155 155 155
Mass Vapor
0 0 0 1 1 0.07644 0
Fraction
Mass Liquid
1 1 1 0 0 0.92356 1
Fraction

Mass Enthalpy Btu/lb -2547 -2846.4 -2845.8 -1330.2 152.882 -2058.9 -2545.2

Mass Density lb/cuft 48.4615 47.6834 47.6685 0.17722 0.04984 5.83271 47.903

Section 300

Table 12 Section 300 Simulation Data

Units S22 S23 S24 S25 S26 S27 S50

From F-203 MIX E-301 E-302 R-301 E-301 P-403
To MIX E-301 E-302 R-301 E-301 F-401 MIX
Ethanol lb/hr 75644.4 190969 190969 190875 117584 117584 115258
Acetaldehyde lb/hr 57300.1 59765.2 59765.2 59777.2 10567 10567 2475.83
Methanol lb/hr 51.3261 51.3261 51.3261 51.3261 51.3261 51.3261 0
CO lb/hr 7.2816 7.2816 7.2816 7.2816 7.2816 7.2816 0
CO2 lb/hr 98.9766 98.9766 98.9766 98.9766 98.9766 98.9766 2.73E-16
Acetic Acid lb/hr 533.435 533.448 533.448 533.448 1975.39 1975.39 0.0131
Diethyl Ether lb/hr 627.671 12910.5 12910.5 13018.3 23039.9 23039.9 12376.6
Water lb/hr 7558.33 18676.2 18676.2 18647.7 63946.4 63946.4 11078.2
4.00E-
Ethylene lb/hr 0 4.00E-11 4.10E-11 1841.31 1841.31 4.05E-11
11
Hexadiene lb/hr 0 1202.08 1202.08 1200.42 5926.68 5926.68 1199.17

70
 N-Butane lb/hr 0 0.94158 0.94158 0.9395 2563.37 2563.37 0.93899
1-Butene lb/hr 0 0.00042 0.00042 0.00043 1650.81 1650.81 0.00043
1:3-Butadiene lb/hr 0 0.00038 0.00038 0.00038 56028.5 56028.5 0.00038
Hydrogen lb/hr 0.00044 0.00044 0.00044 0.00044 0.00044 0.00044 0
Ethyl Acetate lb/hr 1071.56 3180.77 3180.77 3186.01 2115.55 2115.55 2114.47
Total lb/hr 142893 287396 287396 287396 287396 287396 144503

Liquid Liquid Vapor Vapor Vapor Liquid

Phase
Phase Phase Phase Phase Phase Phase
Temperature F 121 147.62 296 662 662 231.784 169.537
Pressure psia 155 108 100 93 73 66 108
Mass Vapor
0 0 1 1 1 0.58854 0
Fraction
Mass Liquid
1 1 0 0 0 0.41146 1
Fraction
Mass
Btu/lb -2545.18 -2638.79 -2197.22 -2013.55 -1956.99 -2398.56 -2729.64
Enthalpy
Mass Density lb/cuft 47.903 47.0442 0.55828 0.33367 0.22177 0.67475 46.4061

Section 400A

Table 13 Section 400A Simulation Data

Units S27 S28 S29 S30 S31 S32 S33

From E-301 F-401 E-401 F-402 C-401 E-402 F-402
To F-401 E-401 F-402 C-401 E-402 D-401 P-401
Ethanol lb/hr 117584 57443.7 57443.7 22961.5 22961.5 22961.5 34482.3
Acetaldehyde lb/hr 10567 7469.11 7469.11 5381.65 5381.65 5381.65 2087.46

71
Methanol lb/hr 51.3261 49.6264 49.6264 48.2589 48.2589 48.2589 1.36754
CO lb/hr 7.2816 7.24372 7.24372 7.2141 7.2141 7.2141 0.02962
CO2 lb/hr 98.9766 96.65 96.65 93.5527 93.5527 93.5527 3.0973
Acetic Acid lb/hr 1975.39 202.473 202.473 19.1373 19.1373 19.1373 183.336
Diethyl Ether lb/hr 23039.9 21993.9 21993.9 20112.8 20112.8 20112.8 1881.09
Water lb/hr 63946.4 18477.2 18477.2 5903.08 5903.08 5903.08 12574.1
Ethylene lb/hr 1841.31 1615.23 1615.23 1476.65 1476.65 1476.65 138.576
Hexadiene lb/hr 5926.68 1889.82 1889.82 636.744 636.744 636.744 1253.08
N-Butane lb/hr 2563.37 719.084 719.084 116.826 116.826 116.826 602.258
1-Butene lb/hr 1650.81 1126.59 1126.59 820.126 820.126 820.126 306.465
1:3-Butadiene lb/hr 56028.5 52772.9 52772.9 47757.1 47757.1 47757.1 5015.81
Hydrogen lb/hr 0.00044 0.00044 0.00044 0.00044 0.00044 0.00044 3.87E-11
Ethyl Acetate lb/hr 2115.55 1562.23 1562.23 974.922 974.922 974.922 587.303
Total lb/hr 287396 165426 165426 106309 106309 106309 59116.3

Vapor Vapor Vapor Liquid

Phase
Phase Phase Phase Phase
Temperature F 231.784 231 200 200 279.477 200 200
Pressure psia 66 66 58 58 133 126 58
Mass Vapor
0.58854 1 0.64264 1 1 0.32306 0
Fraction
Mass Liquid
0.41146 0 0.35736 0 0 0.67694 1
Fraction
Mass
Btu/lb -2398.56 -1364.6 -1535.41 -734.676 -703.844 -910.473 -2975.37
Enthalpy
Mass Density lb/cuft 0.67475 0.40196 0.64684 0.41781 0.88881 3.04286 45.5186

Units S34 S35 S36 S37

From P-401 F-401 P-402 MIX-401
To MIX-401 P-402 MIX-401 D-401
Ethanol lb/hr 34482.3 60139.8 60139.8 94622.1
Acetaldehyde lb/hr 2087.46 3097.87 3097.87 5185.33
Methanol lb/hr 1.36754 1.69971 1.69971 3.06725
CO lb/hr 0.02962 0.03788 0.03788 0.0675
CO2 lb/hr 3.0973 2.32655 2.32655 5.42385
Acetic Acid lb/hr 183.336 1772.91 1772.91 1956.25
Diethyl Ether lb/hr 1881.09 1046.05 1046.05 2927.14
Water lb/hr 12574.1 45469.2 45469.2 58043.3
Ethylene lb/hr 138.576 226.081 226.081 364.657
Hexadiene lb/hr 1253.08 4036.86 4036.86 5289.94
N-Butane lb/hr 602.258 1844.28 1844.28 2446.54
1-Butene lb/hr 306.465 524.223 524.223 830.688
1:3-Butadiene lb/hr 5015.81 3255.63 3255.63 8271.44
Hydrogen lb/hr 3.87E-11 9.06E-11 9.06E-11 1.29E-10
Ethyl Acetate lb/hr 587.303 553.32 553.32 1140.62

72
 Total lb/hr 59116.3 121970 121970 181087

Liquid Liquid Liquid Liquid

Phase
Phase Phase Phase Phase
Temperature F 200.33 231 231.274 221.237
Pressure psia 125 66 125 125
Mass Vapor
0 0 0 0
Fraction
Mass Liquid
1 1 1 1
Fraction
Mass
Btu/lb -2974.98 -3815.4 -3815.05 -3540.81
Enthalpy
Mass Density lb/cuft 45.5027 46.8983 46.8853 46.4131

Section 400B

73
Table 14 Section 400B Simulation Data

Units S32 S37 S38 S39 S40 S41 S42

From E-402 MIX-401 D-401 D-401 D-402 D-402 DC-401
To D-401 D-401 D-402 DC-401 E-403
Ethanol lb/hr 22961.45 94622.14 0.026792 35.14333 3.09E-08 35.14333 34.65703
Acetaldehyde lb/hr 5381.647 5185.327 10.13108 1080.223 1.185704 1079.038 1065.707
Methanol lb/hr 48.25889 3.067253 5.295012 46.03113 46.03114 1.03E-12 0
CO lb/hr 7.214105 0.067499 3.367189 3.914414 3.914415 1.12E-38 0
CO2 lb/hr 93.55274 5.423849 6.620828 92.35576 92.35515 0.000628 0.000602
Acetic Acid lb/hr 19.13734 1956.249 8.64E-06 0.043215 5.30E-18 0.043215 0.040429
Diethyl Ether lb/hr 20112.78 2927.14 9.530262 1955.379 1.13E-05 1955.379 1954.292
Water lb/hr 5903.081 58043.33 19.31623 1391.852 9.48E-08 1391.852 109.3986
Ethylene lb/hr 1476.652 364.6572 97.28538 1740.276 1740.137 0.139954 0.130933
Hexadiene lb/hr 636.7437 5289.939 0.002043 1.389381 9.23E-15 1.389381 1.29982
N-Butane lb/hr 116.8256 2446.543 1.37E-05 0.087602 3.42E-19 0.087602 0.087408
1-Butene lb/hr 820.1264 830.6875 0.567445 57.28425 3.34253 53.94172 50.33685
1:3-
lb/hr 47757.05 8271.439 1013.123 53585.54 428.0329 53157.51 53140.41
Butadiene
4.16E-
Hydrogen lb/hr 0.000441 1.29E-10 0.000441 2.83E-09 2.83E-09 0
229
Ethyl Acetate lb/hr 974.9222 1140.623 0.001344 1.042132 8.29E-16 1.042132 1.041056
Total lb/hr 106309.4 181086.6 1165.267 59990.56 2314.999 57675.56 56357.4

Liquid Vapor Liquid Vapor Liquid Liquid

Phase
Phase Phase Phase Phase Phase Phase
Temperature F 200 221.2374 138.2785 138.2785 16.67641 144.9789 139
Pressure psia 126 125 125 125 100 106.3 107
Mass Vapor
0.323061 0 1 0 1 0 0
Fraction
Mass Liquid
0.676939 1 0 1 0 1 1
Fraction
Mass
Btu/lb -910.473 -3540.81 678.2819 427.6039 541.8424 431.0379 589.0221
Enthalpy
Mass Density lb/cuft 3.04286 46.41309 1.067814 35.82932 0.646939 36.19453 35.89387

Units S43 S44 S45 S46 S47 S48 S49

From E-403 DC-401 D-401 D-403 D-403 D-404 D-404
To B30 D-403 D-404 B30 P-403
Ethanol lb/hr 34.65703 0.486298 117548.4 115269.4 2279.018 11.59431 115257.8
Acetaldehyde lb/hr 1065.707 13.33042 9476.619 9476.61 0.0072 7000.777 2475.834
Methanol lb/hr 0 0 3.20E-12 0 0 0 0
CO lb/hr 0 0 2.88E-39 0 0 0 0
CO2 lb/hr 0.000602 2.64E-05 1.22E-09 1.22E-09 4.09E-38 1.22E-09 2.73E-16
Acetic Acid lb/hr 0.040429 0.002786 1975.343 0.013098 1975.331 6.11E-10 0.013098
Diethyl Ether lb/hr 1954.292 1.086522 21075.01 21075 5.69E-17 8698.424 12376.58

74
Water lb/hr 109.3986 1282.454 62535.24 11078.24 51457.01 0.054959 11078.18
Ethylene lb/hr 0.130933 0.009022 3.747356 3.747356 2.36E-13 3.747356 4.05E-11
Hexadiene lb/hr 1.29982 0.089561 5925.291 1235.757 4689.536 36.58709 1199.17
N-Butane lb/hr 0.087408 0.000194 2563.281 0.938986 2562.343 1.13E-08 0.938986
1-Butene lb/hr 50.33685 3.604864 1592.962 1592.959 0.002686 1592.959 0.000432
1:3-
lb/hr 53140.41 17.09673 1429.827 1429.826 2.00E-16 1429.826 0.00038
Butadiene
5.87E-
Hydrogen lb/hr 0 0 0 0 0 0
172
Ethyl Acetate lb/hr 1.041056 0.001076 2114.502 2114.502 1.85E-05 0.029592 2114.472
Total lb/hr 56357.4 1318.162 226240.2 163277 62963.25 18774 144503

Liquid Liquid Liquid Liquid Liquid Vapor Liquid

Phase
Phase Phase Phase Phase Phase Phase Phase
Temperature F 110 139 258.2824 185.8182 260.9775 76.57675 170.0918
Pressure psia 99 107 125 40 46.4 18 20.1
Mass Vapor
0 0 0 0 0 1 0
Fraction
Mass Liquid
1 1 1 1 1 0 1
Fraction
Mass
Btu/lb 571.7087 -6585.66 -3375.52 -2563.47 -5657.84 -1236.21 -2730.14
Enthalpy
Mass Density lb/cuft 37.32839 59.33387 44.12327 44.987 52.36222 0.18271 46.38082

75
 Equipment Design
Table 15 R-301 Data Sheet for Design Calculation

Reactor
Identification: R-301
Function: To react acetaldehyde with excess ethanol to form 1,3-butadiene
Operation: Continuous
Materials Handled:
(lb/hr) In Out
Ethanol 191478 117928
Acetaldehyde 59714 10379
Acetic Acid 533.45 1961.57
Butadiene 0 56199.4
Butanol 1 2571.23
Methanol 51.326 51.326
Butene 0 1655.85
Carbon Dioxide 98.98 98.98
Carbon Monoxide 7.2816 7.2816
Diethyl Ether 12481.8 22493.5
Ethyl Acetate 3162.91 2095.27
Ethylene 0 1846.92
Hexadiene 1199.39 5940.07
Hydrogen 0 0
Methane 0 208
Water 18727.5 64167.6
Total 287396 287396
Design Data
Type Fixed head, Shell & Tube Tube diameter 1.5 in
Material Carbon steel /Stainless Steel Tube Length 16 feet
Catalyst type 2% tanlala, 98% silica Number of tube 2661
Catalyst mass 230000 lbs Shell Diameter 114 in
Temperature 662 °F Number of Shell 4 ( 3 Op.+1 Reg.)
Pressure In 93 psi Residence time 5s
Pressure out 73 psi

76
Reactor Sizing Calculations (R-301)
The following nine calculations step are for rector design

Flowrate Calculation
The first step in sizing the reactor was determining the volumetric flowrate (v) of the
reactants from their corresponding molar flowrates (n). This process is shown below
for Ethanol:
𝑛𝑒𝑡ℎ𝑎𝑛𝑜𝑙 ∗ 𝑀𝑤
𝑣𝑒𝑡ℎ𝑎𝑛𝑜𝑙 =
𝜌𝑒𝑡ℎ𝑎𝑛𝑜𝑙
This expression can be expanded and written as:
𝑛𝑒𝑡ℎ𝑎𝑛𝑜𝑙 ∗ 𝑀𝑤 1887.78 𝑐𝑚3
𝑣𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = = = 17085474510
𝑃𝑎𝑣𝑒𝑟𝑎𝑔𝑒 ∗ 𝑀𝑤 5.65 ℎ𝑟
𝑇𝑟𝑒𝑎𝑐𝑡𝑜𝑟 ∗ 𝑅 623.15 ∗ 82.06

The volumetric flowrates for acetaldehyde, water, and ethyl acetate 5570453888 cm3
/hr, 4270457429 cm3 /hr, and 147526914 cm3 /hr respectively. Total flow rate in
empirical unit was 984564.2294 ft3/hr.

Tube Internal Volume Calculation

The internal volume of the cylindrical tubes can be calculated using the equation:
𝑉 = 𝜋 ∗ (𝑇𝑢𝑏𝑒𝑟 𝐼𝑛𝑛𝑒𝑟 𝑅𝑎𝑑𝑖𝑢𝑠)2 ∗ 𝐿𝑡𝑢𝑏𝑒 = 𝜋 ∗ (0.7 𝑖𝑛)2 ∗ 16 𝑓𝑡 = 296 𝑖𝑛3

Number of Tubes Calculation

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡𝑢𝑏𝑒 296
𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑜𝑛𝑒 𝑡𝑢𝑏𝑒 = =
𝑐𝑜𝑛𝑡𝑎𝑐𝑡 𝑡𝑖𝑚𝑒 5
𝑖𝑛3
= 59.2
𝑠
𝑓𝑡3
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤𝑟𝑎𝑡𝑒 984564.2294
ℎ𝑟
𝑁𝑜. 𝑜𝑓 𝑡𝑢𝑏𝑒𝑠 = 𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑜𝑛𝑒 𝑡𝑢𝑏𝑒 = 𝑖𝑛3
= 7983 𝑡𝑢𝑏𝑒𝑠
59.2
𝑠

Tube Superficial Velocity Calculation

Cross sectional area of a tube = π ∗ (𝑇𝑢𝑏𝑒𝑟 𝐼𝑛𝑛𝑒𝑟 𝑅𝑎𝑑𝑖𝑢𝑠)2 = 1.54 𝑖𝑛2
𝑖𝑛3
59.2 𝑠 𝑓𝑡
Superficial Velocity through a tube = = 3.2
1.54 𝑖𝑛2 𝑠

Volume of Catalyst Calculation

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡 = 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑇𝑢𝑏𝑒𝑠 ∗ 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑜𝑛𝑒 𝑇𝑢𝑏𝑒
7983 ∗ 296 𝑖𝑛3
= = 1367.458 𝑓𝑡 3
123

77
Tube-side Pressure Drop Calculation
150 ∗ µ𝑓𝑙𝑢𝑖𝑑 ∗ (1 − 𝜀)2 ∗ 𝐿𝑡𝑢𝑏𝑒
𝛥𝑃 = ∗ 𝑉𝑠𝑢𝑝𝑒𝑟𝑓𝑖𝑐𝑖𝑎𝑙
𝛷𝑠 2 ∗ 𝐷𝑝2 ∗ 𝜀 3
1.75 ∗ 𝜌𝑓𝑙𝑢𝑖𝑑 ∗ (1 − 𝜀) ∗ 𝐿𝑡𝑢𝑏𝑒
+ 2 3
𝑉𝑠𝑢𝑝𝑒𝑟𝑓𝑖𝑐𝑖𝑎𝑙 2
𝛷𝑠 ∗ 𝐷𝑝 ∗ 𝜀
The superficial velocity was calculated above. Values for the catalyst pellet void fraction,
sphericity, and diameter are taken from report . values have simply been substituted into the
Ergun equation below. To calculate the density of the fluid, the expression: 1/ρ = ∑ yi*ρi
was used, which holds in the case of an ideal mixture, an acceptable assumption given the
temperature and pressure the system was operating at. The viscosity of the fluid was
calculated using the expression: µ = ∑ µi ∗ yi, which again holds in the case of an ideal
mixture. Using these two expressions it was found that:
ρfluid = 0.004389003 g /cm3
µfluid = 0.0000224 kg /m.s
𝑘𝑔
150 ∗ 0.000024 ∗ (1 − 0.38)2 ∗ 16 𝑓𝑡
𝛥𝑃 = 𝑚. 𝑠 ∗ 3.2 𝑓𝑡/𝑠
12 ∗ 0.3175 𝑐𝑚2 ∗ 0.383
𝑔
1.75 ∗ 0.004389003 3 ∗ (1 − 0.38) ∗ 16 𝑓𝑡
+ 𝑐𝑚 (3.2 𝑓𝑡/𝑠)2 = 20 𝑝𝑠𝑖
12 ∗ 0.3175 𝑐𝑚 ∗ 0.383
The process of obtaining these values was iterative. The iterative process was as follows:
i) An average reactor pressure was chosen
ii) Calculations 1) through 6) were performed and a pressure drop was obtained
iii) If the pressure drop calculated was less than 20 psi, the process was repeated, using
the pressure drop just calculated to gauge a new guess for the average reactor
pressure.

The values in the calculations shown above are for the final iteration, where a pressure drop
of 20 psi was obtained.

Shell Sizing Calculation

The formula used to size the reactor shell diameter was:

𝟒
𝑺𝒉𝒆𝒍𝒍 𝑫𝒊𝒂𝒎𝒆𝒕𝒆𝒓 = √𝑵𝒐. 𝒐𝒇 𝒕𝒖𝒃𝒆𝒔 ∗ (𝑺𝒒𝒖𝒂𝒓𝒆 𝑷𝒊𝒕𝒄𝒉)𝟐 ∗ + 𝟐 ∗ 𝑻𝒖𝒃𝒆 𝑶𝑫 + 𝟏
𝝅

𝟒
𝑺𝒉𝒆𝒍𝒍 𝑫𝒊𝒂𝒎𝒆𝒕𝒆𝒓 = √𝟕𝟗𝟖𝟑 ∗ (𝟏. 𝟖𝟕𝟓)𝟐 ∗ + 𝟐 ∗ 𝟏. 𝟓 + 𝟏 = 𝟏𝟗𝟑. 𝟎𝟗𝟑 𝒊𝒏
𝝅

78
 Since the maximum recommended shell diameter was 120 inches, we divided the reactor
into three smaller reactors, each with a third of the number of tubes.

𝟕𝟗𝟖𝟑 𝟒
𝑺𝒉𝒆𝒍𝒍 𝑫𝒊𝒂𝒎𝒆𝒕𝒆𝒓 = √ ∗ (𝟏. 𝟖𝟕𝟓)𝟐 ∗ + 𝟐 ∗ 𝟏. 𝟓 + 𝟏 = 𝟏𝟏𝟑. 𝟏𝟔 𝒊𝒏 ≈ 𝟏𝟏𝟒 𝒊𝒏
𝟑 𝜋

Surface Area Heat Transfer Calculation

The surface area available for heat transfer can be determined as follows:
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑓𝑜𝑟 ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 = 𝑁𝑜. 𝑜𝑓 𝑡𝑢𝑏𝑒𝑠 ∗ 𝐿𝑡𝑢𝑏𝑒 ∗ 𝑇𝑢𝑏𝑒 𝑂𝐷 ∗ 𝜋
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 𝑓𝑜𝑟 ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 = 7983 ∗ 16 𝑓𝑡 ∗ 1.5 𝑖𝑛 ∗ 𝜋 = 50133.24 𝑓𝑡 2

Heat Transfer Coefficient Calculation

𝐵𝑇𝑈
𝑄 1.63 ∗ 107 𝐵𝑇𝑈
𝑈 = = ℎ𝑟 = 78.70
𝐴∆𝑇 2
51,773 𝑓𝑡 ∗ (666˚𝐹 − 662˚𝐹) ˚𝐹. 𝑓𝑡 2 . ℎ𝑟

Mechanical Design of Reactor (R-301)

For the Design we will use some standard data for the carbon steel alloy

Material of Construction IS 2002-1962 Grade I

Modulus of Elasticity 202420 N/mm2
Height of Shell 20 feet 6.096 m
Inside Diameter 114 in 2.8956 m
Shell Side Pressure 86 psi 5.848 atm
Shell Side Deign P 86*1.1=94.6 psi 6.4328 atm
Tube inlet Pressure 93 psi 6.324 atm
Tube Outlet Pressure 73 psi 4.964 atm
Temperature 666 °F 352.22 °C
Poisson Ratio 0.29
Density 7850 kg/m3
Permissible Tensile Stress 37 kgf/mm2 93.157 N/mm2
Corrosion Allowance 2 mm
Here we will use 1 atm = 0.11N/mm2

79
Shell Thickness Calculation
𝑃𝐷𝑖
𝑡𝑠 = + 𝐶𝐴
2𝑓𝐽 − 𝑃

Where, ts = shell thickness

P = design pressure

Di = I.D. of the shell

f = allowable stress

J = joint factor (0.85)

C = corrosion allowance (2 mm)

𝑡𝑠 = 12.98 + 2 = 14.98 𝑚𝑚

As per nearest above market availability we take shell thickness 𝑡𝑠 = 15 𝑚𝑚

Shell thickness ts = 15 mm

Shell outside diameter DO = 2895.6+ (2*15) = 2925.6 mm

Checking combined loading:

For combined loading calculation we will take;

t = ts – C = 15 – 2 = 13 mm

P = 0.707 N/mm2

a) Circumferential stress;
𝑃(𝐷𝑖 + 𝑡)
𝑓𝑡 = = 79.5538 N/mm2 (𝑇)
2𝑡

b) Longitudinal / axial stress;

𝑃𝐷𝑖
𝑓1 = = 39.369 𝑁/𝑚𝑚2 = (𝑇)
4𝑡

Wg
𝑓2 = π(Di + t)∗t

Weight Calculation
Shell Weight 𝑊1 = 𝜋/4 ∗ (𝐷𝑜2 − 𝐷𝑖 2 ) ∗ 𝜌 ∗ ℎ = 6558.86 𝑘𝑔

80
 Taking head weight as 20% of shell weight
Head Weight 𝑊2 = 6558.86 ∗ 0.2 ∗ 2 = 2623.544 𝑘𝑔
Tube Weight 𝑊3 = 2661 ∗ 3.14 ∗ (1.52 − 1.42 ) ∗ 0.02542 ∗ 7800 ∗ 16/4 =
48836.826 𝑘𝑔
Total Weight of Vessel
𝑊𝑇 = 6558.86 + 2623.544 + 48836.826 = 58019.23 𝑘𝑔
Mounting & Pipe weight will be 12-20% we are taking as 12%
Mounting Weight 𝑊3 = 9182.404 ∗ 0.15 = 1377.36 𝑘𝑔

Shell Volume 𝑉1 = 𝜋/4 ∗ (𝐷𝑖 2 ) ∗ ℎ = 39.28 𝑚3

Volume of tubes 𝑉2 = 2661 ∗ .14 ∗ (1.52 − 1.42 ) ∗ 0.02542 ∗ 16/4 = 6.261 𝑚3
We are assuming 12% volume in each head
Total Volume
𝑉𝑇 = 39.28 + 2 ∗ 39.28 ∗ 0.12 − 6.6261 = 42.0811 𝑚3
Weight of liquid 𝑊1 = 𝑉 ∗ 𝜌𝑙 = 42.0811 ∗ 1000 = 42081.1 kg
Total Weight of Vessel 𝑊1 = 58019.23 + 42081.1 + 1377.36 = 101477.69 𝑘𝑔
101477.69∗9.8
f2 = = 8.376𝑁/𝑚𝑚2 ©
π(2895.6+13)∗13

We are taking no wind condition so f3 = 0

fa = f1 + f2 + f3 = 39.369 − 8.376 = 30.993 𝑁/𝑚𝑚2
No torque data is given so we take as T=1000 Nm
2T
fs = = 5.8174 ∗ 10−3 𝑁/𝑚𝑚2
π ∗ Di ∗ (Di + t) ∗ t
Resultant Stress
fr = √(𝑓𝑡 2 − 𝑓𝑡 ∗ 𝑓𝑎 + 𝑓𝑎2 + 3𝑓𝑠 2 = 69.449 𝑁/𝑚𝑚2
c) Permissible stress due to compression
𝐸∗𝑡∗2
𝑓𝑐𝑝𝑒𝑟𝑚𝑖𝑠𝑠𝑖𝑏𝑙𝑒 = = 45.227 𝑁/𝑚𝑚2
12 ∗ √3(1 − 𝜇2) ∗ Do
Here
𝒇𝑹,𝒕𝒆𝒏𝒔𝒊𝒍𝒆 < 𝒇𝒕,𝒑𝒆𝒓𝒎𝒊𝒔𝒔𝒊𝒃𝒍𝒆
𝒇𝒂,𝒕𝒆𝒏𝒔𝒊𝒍𝒆 < 𝒇𝒕,𝒑𝒆𝒓𝒎𝒊𝒔𝒔𝒊𝒃𝒍𝒆
𝒇𝒂,𝒄𝒐𝒎𝒑𝒓𝒆𝒔𝒔𝒊𝒃𝒍𝒆 < 𝒇𝒄,𝒑𝒆𝒓𝒎𝒊𝒔𝒔𝒊𝒃𝒍𝒆
Thus, thickness is 15 mm based on internal pressure.

81
Design of Head
The column should be provided with Tori spherical head on both ends as operating
pressure is 6.438 atm.
For tori spherical head,
RC = Di = 2895.6 mm
RK = 6% of RC = 0.06 x 2895.6 = 173.736 mm

𝑅𝑐
𝑤 = 0.25 ∗ (3 + √ ) = 1.77
𝑅𝑘
𝑃 ∗ 𝑅𝑐 ∗ 𝑤
𝑡ℎ = + 𝐶𝐴 = 24.88 𝑚𝑚
2𝑓𝐽
RC = crown radius
J = joint efficiency (0.85)
f = allowable stress
RK= knuckle radius
C = corrosion allowance
Taking head thickness as 25 mm as per market availability.

Inlet and outlet Nozzle Design

Diameter of Nozzle , dn = 289.56 mm (10% of Reactor Diameter)

Thickness of head = 25 mm

𝑃∗𝑑𝑛
Nozzle Thickness 𝑡′𝑛 = + 𝐶𝐴 = 1.2927 + 2 = 3.927 𝑚𝑚
2𝑓𝐽−𝑃

Figure 9 Reinforcing Pad Limits for Nozzle

82
 As per market availability tn= 5 mm.

Now applying area for area method to see if any compensation is required or not.

AB = 2*di = 2∗289.56= 579.12 mm

AD = = 2.5 th + 3.5 tn = (2.5∗25) + (3.5∗3) = 73 mm

H1 = 2.5 th = 2.5∗25 = 62.5 mm

Area Available for compensation,

1. Area available due to extra shell thickness

As = di ( th – th′- C.A.) = 289.56∗(25-22.88-2) = 34.747 mm2
2. Area available due to extra wall thickness of nozzle
Ao = 2H1 ( tn – tn′- C.A.)
= 2∗ 62.5 ∗(5 -1.927 – 2) =134.125 mm2
3. Area available due to inside projection of nozzle
Ai = 0 (considering no projection of nozzle inside)

A’ = Ah + A0 + Ai = 168.872 mm2

Now the area for which the compensation is required is, A = dn × th’ = 289.56*22.88

= 6625.1328 mm2

As A > A’ compensation is required.

∴ now H1 = 2.5*tn, = 12.5 mm, A’= 61.572 mm2

Area available for compensation = A- A’ = 6563.56 mm2

Which can be added by placing a ring of metal outside nozzle.

Bolt Loading and Flange Thickness Calculations

Inner Diameter of Gasket Load Reaction, Gi = 2896 mm
From the IS Code 4864-487 for the shell of inside diameter approx
For Go = 2936 mm,
Mean Diameter of Gasket Load Reaction, G = 2916 mm
Now
1 𝐺0 − 𝐺𝑖
𝑏0 = ∗( ) = 0.25 ∗ (40) = 10 𝑚𝑚
2 2

83
as b > 6.3 mm 𝑏 = 2.5√𝑏0 = 7.9 𝑚𝑚
let us take data for gasket has with m = 2.75
from the IS 2825 bolt of 1 % Cr V Mn Steel
Permissible Tensile Stress under Atmospheric Condition, fatm = 192.86 N/mm2
Permissible Tensile Stress under Operating Condition, fop = 164.64 N/mm2
Ya = 25.48 N/mm2

Figure 10 Effective Gasket Seating Width

Bolt Load
Under atmospheric condition
𝑊𝑚,𝑎𝑡𝑚 = 𝜋 ∗ 𝑏 ∗ 𝐺 ∗ 𝑌𝑎 = 1844406 𝑁
Under operating condition
𝜋
𝑊𝑚,𝑜𝑝 = 𝜋 ∗ 2𝑏 ∗ 𝐺 ∗ 𝑚 ∗ 𝑃 + ∗ 𝐺 2 ∗ 𝑃 = 5000628 N
4
Area calculation
𝑊𝑎𝑡𝑚
𝐴𝑚,𝑎𝑡𝑚 = = 9563.248 𝑚𝑚2
𝑓𝑎𝑡𝑚
𝑊𝑜𝑝
𝐴𝑚,𝑜𝑝 = = 30373.11 𝑚𝑚2
𝑓𝑜𝑝
2 ∗ 𝜋 ∗ 𝑌𝑎 ∗ 𝐺 ∗ 𝑁
𝑀𝑎𝑥 𝑎𝑟𝑒𝑎 𝑡𝑜 𝑏𝑒 𝑝𝑟𝑜𝑣𝑖𝑑𝑒𝑑 𝐴𝑏 = = 48386.63 𝑚𝑚2
𝑓𝑎𝑡𝑚
No. of Bolt
𝑁𝑏 = 𝐺/2.54 = 292.52/2.54 = 114.93
next nearest number of 4 is 120

84
 Area of One Bolt for M20 Bolt
𝐴𝑜𝑛𝑒 𝑏𝑜𝑙𝑡 = 0.51 ∗ (𝑋)2.09 = 267.13 𝑚𝑚2
𝑇𝑜𝑡𝑎𝑙 𝐵𝑜𝑙𝑡 𝐴𝑟𝑒𝑎 = 𝑁𝑏 ∗ 𝐴𝑜𝑛𝑒 𝑏𝑜𝑙𝑡 = 120 ∗ 267.13 = 32055.61 𝑚𝑚2
Condition Check
𝐴𝑏𝑜𝑙𝑡 > 𝐴𝑚,𝑎𝑡𝑚
𝐴𝑏𝑜𝑙𝑡 > 𝐴𝑚,𝑜𝑝
𝐴𝑏𝑜𝑙𝑡 < 𝐴𝑏,𝑚𝑎𝑥

Bolt Diameter
𝐵 = 𝐺 + 2𝑋 + 12 = 2968 𝑚𝑚
Bolt Pitch

𝜋∗𝐵
𝑃𝑖𝑡𝑐ℎ = = 77.662
𝑁𝑏

Condition Check
𝑃𝑖𝑡𝑐ℎ > 3.5 ∗ 𝑋 = 3.5 ∗ 20 = 70
𝑃𝑖𝑡𝑐ℎ < 5 ∗ 20 = 100

So the condition is satisfied and bolt calculation is accepted.

Flange Plate Thickness Calculation;

𝑃
𝑡𝑓 = 𝐺 × √
𝐾∗𝑓

G = Mean Diameter of Gasket Load Reaction

P = Design Pressure

f = Permissible Tensile Stress

1
𝐾 = 1.5∗𝑊𝑚𝑎𝑥 ∗ℎ𝐺 = 3.18
0.3+
𝐻∗𝐺

where, Wmax = Wop = 5000628N

𝐵−𝐺
hG = Radial Distance from Gasket Load Reaction to Bolt Circle = = 26
2

𝜋
H = Total Hydrostatic End Force = 4 ∗ 𝐺 2 𝑃 = 4719154 𝑁

85
Now after finding K we will find tf ;

𝑡𝑓 = 144.03 𝑚𝑚

Based on market availability 145 mm should be used.

Flange Outer Diameter

𝐷𝑂𝐷,𝐹𝑙𝑎𝑛𝑔𝑒 = 𝐵 + 2 ∗ 𝑋 = 3008 𝑚𝑚

Design of Support
We will be using Bracket Support for the reactor;
The material of construction will be structural steel IS-800
Permissible Stresses for Structural Steel IS-800:-
Tension = 140 N/mm2
Compression = 123.3 N/mm2
Bending = 157.5 N/mm2
Number of Brackets, n = 8
Wind Pressure = 1300 N/m2
Clearance from bottom and foundation = 1000 mm
Diameter of Vessel = 2896 mm

Figure 11 Vessel Support on Brackets

86
 For finding Base Plate Thickness;

𝐵2 𝑎4
𝑓𝑏 = 0.7 ∗ 𝑃𝑎𝑣 ∗ 2 ∗ [ 4 ]
𝑇1 𝑎 + 𝐵4

fb = Permissible Bending Stress

a, B = Base Plate Dimensions

T1 = Thickness of Base Plate Now,

Pav = PFT /(a × B )

For finding Pavg we need;

4 ∗ 𝑓𝑤 ∗ (𝐻 − 𝐹) ∑ 𝑊
𝑃𝐹𝑇 = +
𝑛 ∗ 𝐷𝑏 𝑛

Where, PFT = Total Force

F = Bottom Clearance = 1000mm

H = Height of Vessel above the Foundation = 7000 mm

Db = Diameter of Bolt Circle = 2968 mm

PW = Weight of Vessel with its Contents = 101477.69 𝑘𝑔

n = Number of Brackets = 8

fw = Force due to Wind Load = 0.7 × 𝑝 × ℎ × 𝐷𝑜 = 18855.2 𝑁

𝑃𝑓𝑡 = 31743.20 𝑁

Now for finding base plate thickness we consider base plate dimensions as a = 140 mm &
B = 150 mm.

𝑃𝑎𝑣 = 1.5115 𝑁/𝑚𝑚2

Now using info Plate thickness of base plate

𝑇𝑓 = 8.387 𝑚𝑚

As per standards and market availability we should use 10 mm thick base plate.

87
 Cost Estimation
The cost available to us from reference was of 2012, so it was converted to present value using
Chemical Industries and process industries cost index values of 801.4 for the present and 584.6
for 2012.

Now, using the percentage of purchase equipment cost method, the rest of the data such as
installation cost, piping, electrical, IPC, land, construction, etc. were calculated. This way we
obtained the fixed capital investment for each equipment.

Figure 12 Table 17 of CEPDE Book

Figure 13 Table 6 from CEPDE Book

88
 Due to the high no. of equipment the calculations were done in excel for ease of
calculation. They are shown below for each section.

Basic Data for Cost Calculation

1 pound 0.45359237 kg
No. of days operational in a year 330
Butadiene production 25252.25 kg/hr
Butadiene annual production 200000000 kg/yr
1,3 butadiene selling price 1500 $/1000 kg
Ethanol cost 0.62 $/kg
Ethanol requirement 11550 kg/hr
Hydrogen production 1360 kg/hr
Hydrogen selling price 3.66 $/kg
Nitrogen amount per year 49271232 SCM/yr
Nitrogen cost 1.22 $/SCM
Oxygen cost 0.49 $/SCM
Oxygen for catalyst regeneration 1514.856 SCM/yr
Cooling water 0.038684 $/1000kg
electricity cost 0.11186 $/kWhr
Refrigerant 6.9813 $/1000kg
Steam @ 50 psig 12.33 $/1000kg
Natural gas 0.47 $/SCM
Natural gas consumption 3,60,33,500 SCM/yr
Salaries and Benefits in 2012 4186000 $/yr
Salaries and Benefits in 2021 5452352.94 $/yr

89
Section 100
Equipment No. R101 R102 R103 R104 F101 ST101
Purchase Cost
2287000 2287000 2287000 2287000 23700 1963000
In 2012
Purchase Cost
3135138 3135138 3135138.2 3135138.2 32489.19 2690982.2
In 2023
Installation
1410812 1410812 1410812.2 1410812.2 14620.14 1210942
Cost
IPC 877838.7 877838.7 877838.7 877838.7 9096.973 753475.02
Piping 971892.8 971892.8 971892.85 971892.85 10071.65 834204.49
Electrical 313513.8 313513.8 313513.82 313513.82 3248.919 269098.22
Building 689730.4 689730.4 689730.41 689730.41 7147.622 592016.09
Service
1724326 1724326 1724326 1724326 17869.05 1480040.2
Facilities
Land 188108.3 188108.3 188108.29 188108.29 1949.351 161458.93
Total Direct
9311360 9311360 9311360.5 9311360.5 96492.89 7992217.2
Costs

Eng. And
1003244 1003244 1003244.2 1003244.2 10396.54 861114.31
Supervision
Construct
1065947 1065947 1065947 1065947 11046.32 914933.95
Expense
Total Indirect
2069191 2069191 2069191.2 2069191.2 21442.86 1776048.3
Costs
Total Direct &
11380552 11380552 11380552 11380552 117935.8 9768265.4
Indirect Costs

Contractor
569027.6 569027.6 569027.59 569027.59 5896.788 488413.27
Fee
Contingency 1138055 1138055 1138055.2 1138055.2 11793.58 976826.54

FCI 13087634 13087634 13087634 13087634 135626.1 11233505

Utility (Kg/Hr)
Operating
Cost Per Year

Part of Manufacturing Cost

Maintenance
523505.4 523505.4 523505.38 523505.38 5425.045 449340.21
And Repairs

Part of Fixed Charges

Depreciation 104504.6 104504.6 104504.61 104504.61 1082.973 89699.407

90
 Equipment No. P101 E101 E102
Purchase Cost In 2012 7500 136000 216000
Purchase Cost In 2023 10281.39 186435.9 296104
Installation Cost 4369.59 83896.13 133246.8
IPC 2878.789 52202.04 82909.12
Piping 3187.231 57795.11 91792.24
Electrical 1028.139 18643.59 29610.4
Building 0 41015.89 65142.88
Service Facilities 5654.764 102539.7 162857.2
Land 616.8833 11186.15 17766.24
Total Direct Costs 28016.78 553714.5 879428.9

Eng. and Supervision 3290.044 59659.47 94753.28

Construct Expense 0 63388.19 100675.4
Total Indirect Costs 3290.044 123047.7 195428.6
Total Direct & Indirect Costs 31306.83 676762.1 1074858

Contractor Fee 1565.341 33838.11 53742.88

Contingency 3130.683 67676.21 107485.8

FCI 36002.85 778276.5 1236086

Utility (Kg/Hr)/ Power consumption (kW) 8.6 0 0
Operating Cost Per Year 7619.008 0 0

Part Of Manufacturing Cost

Maintenance And Repairs 1440.114 31131.06 49443.45

Part Of Fixed Charges

Depreciation 685.4259 9321.793 14805.2

Table 16 Section 100 Cost Summary

FCI 65770034.74
Operating Cost Per Annum 7619.00832
Depreciation Per Year 533613.2273
Contract and Contingency 8578700.184
Maintenance and Repairs 2630801.39

91
Section 200
Equipment No. F201 F203 P201 P202 MSC201 PSA201
Purchase Cost
58800 53900 3000 16600 4640000 4410000
In 2012
Purchase Cost
80606 73889 4112.556 22756 6360753 6045457
In 2023
Installation
36273 33250 1747.836 9671.4 7314866 7980003
Cost
IPC 22570 20689 1151.516 6371.7 1781011 1692728
Piping 24988 22906 1274.892 7054.4 1971833 1874092
Electrical 8060.6 7388.9 411.2556 2275.6 636075.3 604545.7
Building 17733 16256 0 0 1399366 1330000
Service
44333 40639 2261.906 12516 3498414 3325001
Facilities
Land 4836.4 4433.3 246.7533 1365.4 381645.2 362727.4
Total Direct
239400 219450 11206.71 62010 23343962 23214554
Costs
Eng. And
25794 23644 1316.018 7282 2035441 1934546
Supervision
Construct
27406 25122 0 0 2162656 2055455
Expense
Total Indirect
53200 48767 1316.018 7282 4198097 3990001
Costs
Total Direct &
292600 268217 12522.73 69292 27542059 27204555
Indirect Costs
Contractor Fee 14630 13411 626.1366 3464.6 1377103 1360228
Contingency 29260 26822 1252.273 6929.2 2754206 2720456
FCI 336490 308449 14401.14 79686 31673368 31285239
Power
consumption 0 0 6.6 19.1 2860
(kW)
Utility (Kg/Hr) 899473.7
Operating Cost 2809342
0 0 5847.146 16921 2000000
Per Year
Part of Manufacturing Cost
Maintenance 1251410
13460 12338 576.0457 3187.5 5425.045
And Repairs
Part of Fixed Charges
Depreciation 2686.86965 2462.964 274.1704 1517.1 1082.973 403030.4

Table 17 Section 200 Cost Summary

FCI 63697633.22
Operating Cost Per Annum 4832109.96
Depreciation Per Year 2525285.335
Contract And Contingency 8308386.942
Maintenance And Repairs 2547905.329

92
Section 300
Equipment No. E301 E302 R-301-A R-301-B R-301-C R-301-D
Purchase Cost
44300 24400 674000 674000 674000 674000
In 2012
Purchase Cost
60728.7 33449 923954 923954 923954 923954.2
In 2023
Installation
27327.9 15052 415779 415779 415779 415779.4
Cost
IPC 17004 9365.7 258707 258707 258707 258707.2
Piping 18825.9 10369 286426 286426 286426 286425.8
Electrical 6072.87 3344.9 92395.4 92395.4 92395.4 92395.42
Building 13360.3 7358.7 203270 203270 203270 203269.9
Service
33400.8 18397 508175 508175 508175 508174.8
Facilities
Land 3643.72 2006.9 55437.2 55437.2 55437.2 55437.25
Total Direct
180364 99343 2744144 2744144 2744144 2744144
Costs

Eng. And
19433.2 10704 295665 295665 295665 295665.3
Supervision
Construct
20647.8 11373 314144 314144 314144 314144.4
Expense
Total Indirect
40081 22076 609810 609810 609810 609809.7
Costs
Total Direct &
220445 121419 3353954 3353954 3353954 3353954
Indirect Costs

Contractor
11022.3 6071 167698 167698 167698 167697.7
Fee
Contingency 22044.5 12142 335395 335395 335395 335395.4

FCI 253512 139632 3857047 3857047 3857047 3857047

Utility (Kg/Hr)
Operating
Cost Per Year
Part of Manufacturing Cost
Maintenance
10140.5 5585.3 154282 154282 154282 154282
And Repairs
Part of Fixed Charges
Depreciation 1366.4 752.6 20789 20789 20789 20789

Table 18 Section 300 Cost Summary

FCI 15821330.58
Operating Cost Per Annum 0
Depreciation Per Year 85274.86837
Contract And Contingency 2063651.815
Maintenance And Repairs 632853.2231

93
Section 400
Equipment No. D 401 D 402 D 403 D 404 D 405
Purchase Cost
467000 341000 445000 144000 877000
In 2012
Purchase Cost
640187.8 467460.5 610029.1 197402.7 1202237
In 2023
Installation
480140.9 350595.4 457521.8 148052 901677.8
Cost
IPC 179252.6 130888.9 170808.1 55272.75 336626.4
Piping 198458.2 144912.8 189109 61194.83 372693.5
Electrical 64018.78 46746.05 61002.91 19740.27 120223.7
Building 140841.3 102841.3 134206.4 43428.59 264492.2
Service
352103.3 257103.3 335516 108571.5 661230.4
Facilities
Land 38411.27 28047.63 36601.74 11844.16 72134.23
Total Direct
2093414 1528596 1994795 645506.7 3931315
Costs

Eng. And
204860.1 149587.4 195209.3 63168.85 384715.9
Supervision
Construct
217663.9 158936.6 207409.9 67116.91 408760.6
Expense
Total Indirect
422524 308523.9 402619.2 130285.8 793476.5
Costs
Total Direct &
2515938 1837120 2397414 775792.5 4724792
Indirect Costs

Contractor Fee 125796.9 91855.99 119870.7 38789.62 236239.6

Contingency 251593.8 183712 239741.4 77579.25 472479.2

FCI 2893329 2112688 2757026 892161.4 5433511

Utility (Kg/Hr)
Part of Manufacturing Cost
Operating Cost
467000 341000 445000 144000 877000
Per Year
Maintenance
115733.2 84507.51 110281.1 35686.45 217340.4
And Repairs
Part of Fixed Charges
Depreciation 21339.59 15582.02 20334.3 6580.089 40074.57

94
Equipment No. P401 P402 P403 P404 P405 P406
Purchase Cost
7500 6200 19000 4800 19000 6400
In 2012
Purchase Cost
10281.39 8499.282 26046.19 6580.089 26046.19 8773.452
In 2023
Installation
4369.59 3612.195 11069.63 2796.538 11069.63 3728.717
Cost
IPC 2878.789 2379.799 7292.932 1842.425 7292.932 2456.567
Piping 3187.231 2634.777 8074.317 2039.828 8074.317 2719.77
Electrical 1028.139 849.9282 2604.619 658.0089 2604.619 877.3452
Building 0 0 0 0 0 0
Service
5654.764 4674.605 14325.4 3619.049 14325.4 4825.399
Facilities
Land 616.8833 509.9569 1562.771 394.8053 1562.771 526.4071
Total Direct
28016.78 23160.54 70975.86 17930.74 70975.86 23907.66
Costs

Eng. and
3290.044 2719.77 8334.779 2105.628 8334.779 2807.505
Supervision
Construct
0 0 0 0 0 0
Expense
Total Indirect
3290.044 2719.77 8334.779 2105.628 8334.779 2807.505
Costs
Total Direct &
31306.83 25880.31 79310.63 20036.37 79310.63 26715.16
Indirect Costs

Contractor Fee 1565.341 1294.016 3965.532 1001.819 3965.532 1335.758

Contingency 3130.683 2588.031 7931.063 2003.637 7931.063 2671.516

FCI 36002.85 29762.36 91207.23 23041.83 91207.23 30722.44

Power
consumption 12.6 8.4 3.3 1.4 16.3 2.9
(kW)
Operating Cost
11162.73 7441.822 2923.573 1240.304 14440.68 2569.2
Per Year
Part of Manufacturing Cost
Maintenance
1440.114 1190.494 3648.289 921.6731 3648.289 1228.897
And Repairs
Part of Fixed Charges
Depreciation 685.4259 566.6188 1736.412 438.6726 1736.412 584.8968

95
Equipment No. P407 P408 C401 E401 E402 E403
Purchase Cost
9600 9800 1030000 27800 16600 892000
In 2012
Purchase Cost
13160.18 13434.35 1411977 38109.68 22756.14 1222800
In 2023
Installation
5593.076 5709.598 635389.8 17149.36 10240.26 550259.9
Cost
IPC 3684.85 3761.618 395353.7 10670.71 6371.719 342384
Piping 4079.655 4164.648 437713 11814 7054.404 379068
Electrical 1316.018 1343.435 141197.7 3810.968 2275.614 122280
Building 0 0 310635 8384.13 5006.351 269016
Service
7238.098 7388.892 776587.6 20960.33 12515.88 672539.9
Facilities
Land 789.6107 806.0609 84718.65 2286.581 1365.368 73367.99
Total Direct
35861.48 36608.6 4193573 113185.8 67585.74 3631716
Costs

Eng. and
4211.257 4298.991 451832.8 12195.1 7281.965 391296
Supervision
Construct
0 0 480072.3 12957.29 7737.088 415752
Expense
Total Indirect
4211.257 4298.991 931905.1 25152.39 15019.05 807047.9
Costs
Total Direct &
40072.74 40907.59 5125478 138338.1 82604.79 4438764
Indirect Costs

Contractor Fee 2003.637 2045.38 256273.9 6916.907 4130.24 221938.2

Contingency 4007.274 4090.759 512547.8 13833.81 8260.479 443876.4

FCI 46083.65 47043.73 5894300 159088.9 94995.51 5104578

Utility
(Kg/Hr)/
Power 21.4 2.9 923 453592.4 303906.9 1179340
consumption
(kW)
Operating Cost
18958.93 2569.2 817714.5 138970.4 93110.17 361323
Per Year
Part of Manufacturing Cost
Maintenance
1843.346 1881.749 235772 6363.555 3799.82 204183.1
And Repairs
Part of Fixed Charges
Depreciation 877.3452 895.6232 94131.83 1905.484 1137.807 61139.99

96
Equipment No. E404 E405 E406 E407 E408 E409
Purchase Cost
238000 66000 13900 11000 207000 241000
In 2012
Purchase Cost
326262.7 90476.2231 19054.84 15079.37 283766.3 330375.3
In 2023
Installation
146818.2 40714.3004 8574.678 6785.717 127694.9 148668.9
Cost
IPC 91353.57 25333.3425 5335.355 4222.224 79454.57 92505.08
Piping 101141.5 28047.6291 5907.001 4674.605 87967.56 102416.3
Electrical 32626.27 9047.62231 1905.484 1507.937 28376.63 33037.53
Building 71777.8 19904.7691 4192.065 3317.462 62428.59 72682.57
Service
179444.5 49761.9227 10480.16 8293.654 156071.5 181706.4
Facilities
Land 19575.76 5428.57338 1143.29 904.7622 17025.98 19822.52
Total Direct
969000.3 268714.382 56592.88 44785.73 842786 981214.6
Costs

Eng. and
104404.1 28952.3914 6097.549 4825.399 90805.23 105720.1
Supervision
Construct
110929.3 30761.9158 6478.646 5126.986 96480.55 112327.6
Expense
Total Indirect
215333.4 59714.3072 12576.2 9952.385 187285.8 218047.7
Costs
Total Direct &
1184334 328428.69 69169.07 54738.11 1030072 1199262
Indirect Costs

Contractor Fee 59216.69 16421.4345 3458.454 2736.906 51503.59 59963.12

Contingency 118433.4 32842.869 6916.907 5473.811 103007.2 119926.2

FCI 1361984 377692.993 79544.43 62948.83 1184583 1379152

Utility (Kg/Hr) 37648.17 257186.874 2041.166 14968.55 2766913 81646.6
Operating Cost
Per Year 3676479 14220349.9 199327.2 4586.023 847719 7973087
Part of Manufacturing Cost
Maintenance
54479.35 15107.7197 3181.777 2517.953 47383.3 55166.07
And Repairs
Part of Fixed Charges
Depreciation 16313.14 4523.81115 952.742 753.9685 14188.32 16518.76

97
Equipment No. E410 E411 E412 E413 E414 DC401
Purchase Cost
28100 22400 62300 110000 20500 24000
In 2012
Purchase Cost
38520.94 30707 85404.1 150794 28102.5 32900.4
In 2023
Installation
17334.42 13818 38431.8 67857.2 12646.1 14805.2
Cost
IPC 10785.86 8598 23913.1 42222.2 7868.69 9212.12
Piping 11941.49 9519.2 26475.3 46746 8711.76 10199.1
Electrical 3852.094 3070.7 8540.41 15079.4 2810.25 3290.04
Building 8474.606 6755.6 18788.9 33174.6 6182.54 7238.1
Service
21186.52 16889 46972.2 82936.5 15456.4 18095.2
Facilities
Land 2311.256 1842.4 5124.24 9047.62 1686.15 1974.03
Total Direct
114407.2 91200 253650 447857 83464.3 97714.3
Costs

Eng. and
12326.7 9826.3 27329.3 48254 8992.79 10528.1
Supervision
Construct
13097.12 10440 29037.4 51269.9 9554.84 11186.2
Expense
Total Indirect
25423.82 20267 56366.7 99523.8 18547.6 21714.3
Costs
Total Direct &
139831 111467 310017 547381 102012 119429
Indirect Costs

Contractor Fee 6991.55 5573.3 15500.8 27369.1 5100.6 5971.43

Contingency 13983.1 11147 31001.7 54738.1 10201.2 11942.9

FCI 160805.7 128187 356519 629488 117314 137343

Utility (Kg/Hr) 1081364 5896.7 1270059 42637.7 100244
Operating Cost
Per Year 59790677 575834 389117 4163723 30712.5
Part of Manufacturing Cost
Maintenance 5493.716
6432.22613 5127.469 14260.77 25179.53 4692.549
and Repairs
Part of Fixed Charges
Depreciation 1926.04687 1535.354 4270.204 7539.685 1405.123 1096.681

98
Equipment No. F401 F402 RA401 RA402 RA403 RA404
Purchase Cost
28700 22600 46000 10400 36300 18800
In 2012
Purchase Cost
39343.4 30981.3 63059.2 14256.9 49761.9 25772
In 2023
Installation
17704.6 13941.6 28376.6 6415.59 22392.9 11597.4
Cost
IPC 11016.2 8674.75 17656.6 3991.92 13933.3 7216.16
Piping 12196.5 9604.19 19548.3 4419.63 15426.2 7989.32
Electrical 3934.34 3098.13 6305.92 1425.69 4976.19 2577.2
Building 8655.56 6815.88 13873 3136.51 10947.6 5669.84
Service
21638.9 17039.7 34682.6 7841.27 27369.1 14174.6
Facilities
Land 2360.61 1858.88 3783.55 855.412 2985.72 1546.32
Total Direct
116850 92014.3 187286 42342.9 147793 76542.9
Costs

Eng. and
12589.9 9914 20178.9 4562.2 15923.8 8247.04
Supervision
Construct
13376.8 10533.6 21440.1 4847.33 16919.1 8762.49
Expense
Total Indirect
25966.7 20447.6 41619.1 9409.53 32842.9 17009.5
Costs
Total Direct &
142817 112462 228905 51752.4 180636 93552.4
Indirect Costs

Contractor
7140.84 5623.1 11445.2 2587.62 9031.79 4677.62
Fee
Contingency 14281.7 11246.2 22890.5 5175.24 18063.6 9355.24

FCI 164239 129331 263241 59515.3 207731 107585

Utility (Kg/Hr)
Operating
Cost Per Year
Part of Manufacturing Cost
Maintenance
6569.57 5173.25 10529.6 2380.61 8309.25 4303.41
And Repairs
Part of Fixed Charges
Depreciation 1311.45 1032.71 2101.97 475.229 1658.73 859.067

99
 Equipment No. RA405 ST401 ST402 ST403
Purchase Cost In 2012 22200 435000 453000 1855000
Purchase Cost In 2023 30432.9 596321 620996 2542930
Installation Cost 13694.8 268344 279448 1144319
IPC 8521.22 166970 173879 712020.5
Piping 9434.2 184859 192509 788308.4
Electrical 3043.29 59632.1 62099.6 254293
Building 6695.24 131191 136619 559444.6
Service Facilities 16738.1 327976 341548 1398612
Land 1825.97 35779.2 37259.8 152575.8
Total Direct Costs 90385.7 1771072 1844358 7552503

Eng. and Supervision 9738.53 190823 198719 813737.7

Construct Expense 10347.2 202749 211139 864596.3
Total Indirect Costs 20085.7 393572 409857 1678334
Total Direct & Indirect
Costs 110471 2164644 2254215 9230837

Contractor Fee 5523.57 108232 112711 461541.8

Contingency 11047.1 216464 225422 923083.7

FCI 127042 2489340 2592347 10615462

Utility (Kg/Hr)
Operating Cost Per Year
Part of Manufacturing Cost
Maintenance And Repairs 5081.69 99573.6 103694 424618.5
Part of Fixed Charges
Depreciation 1014.43 19877.4 20699.9 84764.34

Table 19 Section 400 Cost Summary

FCI 48468144
Operating Cost Per Annum 93344037
Depreciation Per Year 474566.1
Contract And Contingency 6321932
Maintenance And Repairs 1938726

100
Dowtherm Utility Section
Equipment No. P501 P502 P503 ST501 ST502 ST503
Purchase Cost
29300 11100 12700 177000 92800 125000
In 2012
Purchase Cost
40165.96 15216.46 17409.82 242640.8 127215.1 171356.5
In 2023
Installation
17070.53 6466.994 7399.173 109188.4 57246.77 77110.42
Cost
IPC 11246.47 4260.608 4874.749 67939.42 35620.21 47979.82
Piping 12451.45 4717.101 5397.044 75218.64 39436.67 53120.51
Electrical 4016.596 1521.646 1740.982 24264.08 12721.51 17135.65
Building 0 0 0 53380.97 27987.31 37698.43
Service
22091.28 8369.051 9575.4 133452.4 69968.28 94246.07
Facilities
Land 2409.958 912.9873 1044.589 14558.45 7632.903 10281.39
Total Direct
109452.2 41464.84 47441.76 720643.1 377828.7 508928.8
Costs

Eng. and
12853.11 4869.266 5571.142 77645.05 40708.82 54834.07
Supervision
Construct
0 0 0 82497.87 43253.12 58261.2
Expense
Total Indirect
12853.11 4869.266 5571.142 160142.9 83961.93 113095.3
Costs
Total Direct &
122305.3 46334.11 53012.9 880786 461790.6 622024
Indirect Costs

Contractor Fee 6115.267 2316.705 2650.645 44039.3 23089.53 31101.2

Contingency 12230.53 4633.411 5301.29 88078.6 46179.06 62202.4

FCI 140651.1 53284.22 60964.83 1012904 531059.2 715327.6

Power
consumption 25.9 6.7 9.2
(kW)
Operating Cost
22945.62 5935.739 8150.567
Per Year
Part of Manufacturing Cost
Maintenance
5626.046 2131.369 2438.593 40516.16 21242.37 28613.11
And Repairs
Part of Fixed Charges
Depreciation 2677.731 1014.43 1160.655 8088.026 4240.502 5711.883

101
 Equipment No. FH501 FH502
Purchase Cost In 2012 2080000 2376000
Purchase Cost In 2023 2851371.9 3257144
Installation Cost 2423666.1 2768572.4
IPC 798384.13 912000.33
Piping 883925.28 1009714.6
Electrical 285137.19 325714.4
Building 627301.81 716571.69
Service Facilities 1568254.5 1791429.2
Land 171082.31 195428.64
Total Direct Costs 9609123.2 10976575

Eng. and Supervision 912439 1042286.1

Construct Expense 969466.44 1107429
Total Indirect Costs 1881905.4 2149715.1
Total Direct & Indirect Costs 11491029 13126290

Contractor Fee 574551.43 656314.52

Contingency 1149102.9 1312629

FCI 13214683 15095234

Power consumption (kW) 2718720 3200160
Operating Cost Per Year 4521775.1 5322506.1
Part of Manufacturing Cost
Maintenance And Repairs 528587.32 603809.36
Part of Fixed Charges
Depreciation 95045.729 108571.47

Table 20 Dowtherm Heating Cost Summary

FCI 30824108
Operating Cost Per Annum 9881313
Depreciation Per Year 226510.4
Contract And Contingency 4020536
Maintenance And Repairs 1232964

102
Table 21 Total Product Cost From Table 27 of CEPDE Book

Direct production cost In $/yr

1. Raw materials 59677385
2. Labour 5452352.9
3. Utilities 77047390
4. Maintenance & repairs 8983250
5. Patent and royalties 0

Fixed Charges
1. Depreciation 3845249.9
2. Taxes 5419517.8
3. Insurance 1354879.5

Plant Overhead
Buildings & offices 3271411.8

General Expenses
1. Administrative cost 2165340.4
2. Distribution cost 1904713
3. R&D 1904713

TOTAL PRODUCT COST 111348819

103
Table 22 Whole Plant Cost Analysis

FCI of equipment and land 224581250.4 $

Dowtherm A 1544950.51 $
Catalyst 6573234.69 $
Contract and contingency 29293206.57 $
Maintenance and Repairs 8983250.015 $
Total FCI 270975892.2 $

Operating cost per annum 108065079.5 $/yr

Salaries and benefits (Labour) 5452352.941 $/yr
Ethanol 51559200 $/yr
Nitrogen 60110903.04 $/yr
Oxygen 742.27944 $/yr
Natural Gas 16935745.08 $/yr
Working Capital (WC) 242124022.8 $/yr
TCI 513099915

Hydrogen Sale 39422592 $/yr

1,3-butadiene sale 300000000 $/yr
Heat recovery from PSA 3592728.567 $/yr
Gross Revenue/Sales/Turnover 343015320.6 $/yr

Profit per annum before taxes 231666501.8 $/yr

Property taxes (2%) 4633330.036 $/yr

Income tax (33%) 76449945.59 $/yr
Net Profit after taxes 150583226.2 $/yr

ROR before taxes 45.15036838 %

ROR after taxes 29.34773945 %

Depreciation by straight line method 3845249.921 $/yr

Pay out period without interest 1.754701588 years

104
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TWO-STEP PRODUCTION OF 1,3-BUTADIENE FROM ETHANOL.
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dehydrogenation of ethanol to acetaldehyde on unsupported catalysts. The
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105