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Department of Chemical Engineering

Indian Institute of Technology Bombay

CL 452: Design Project

Tertiary Butanol

GROUP 2
Om Mihani: 200020085
Samagra Jain: 200020118
Dheer Bhanushali: 200020046
Ananya Dhale: 200020025
Sameer Kanute: 200020119
Kumar Saurabh: 200020071
Md Zishan Khatib: 200020076

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EXECUTIVE SUMMARY
This report explores the feasibility of establishing a Tert-Butyl Alcohol (TBA)
production plant in India utilizing the isobutene hydration process.

Market Analysis:

The global TBA market is projected for steady growth, driven by factors like
demand for high-octane fuels and expansion in key end-use industries. Analyzing
leading players and regional trends identifies potential market opportunities for
Indian-produced TBA.

Production Process:

The report evaluates various TBA production routes, ultimately justifying the
selection of isobutene hydration for its advantages. DWSIM software is used to
simulate the chosen process and perform a sensitivity analysis to optimize
operating parameters. A finalized process flow diagram is presented.

Plant Design and Economics:

Equipment sizing methodology is outlined for critical units like reactors, distillation
columns, and heat exchangers. Total capital investment (TCI) estimation and a
financial analysis including payback period and ROI are presented. Sensitivity
analysis assesses the impact of economic fluctuations.

Detailed Engineering:

The design of the first distillation column, crucial for TBA purification, is presented in
detail. This includes specifications for the column skirt, nozzle placement, gasket
and bolt selection, and tray design for efficient operation.

Environmental Considerations:

Strategies for managing hazardous waste streams generated during production,

adhering to Indian environmental regulations, are outlined. Material selection for
plant construction is discussed, emphasizing factors like compatibility with process
chemicals and corrosion resistance.

Conclusion:

This report demonstrates the feasibility of establishing a TBA production plant in

India using the isobutene hydration process. The analysis provides a strong
foundation for further project development, paving the way for a successful venture
in the growing TBA market.

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ACKNOWLEDGEMENTS
We express our profound gratitude to Prof. Kannan Moudgalya and Prof. K.
Guruswamy from the Department of Chemical Engineering at IIT Bombay for their
constant guidance and invaluable feedback throughout our project. Their
constructive feedback proved instrumental in the successful completion of this
project. They made themselves readily available to assist and guide us whenever
required, steering us in the right direction by providing feedback and
recommending resources.

Special thanks to our teaching assistants, Priyam Nayak and Nikhil Sharma, for
their technical assistance with the DWSIM and Aspen simulations, which were vital
in advancing our project. We are also grateful to Professor R.K. Malik for his
guidance on detailed distillation design, which enhanced our understanding and
application of the process.

We would like to acknowledge Prof. Sanjay Mahajani and Prof. Rahul Nabar for their
insights and assistance concerning industry-related aspects of our project, which
greatly enriched our practical knowledge. We would also like to express our
gratitude to Professor A.K. Suresh for his assistance with alternative modeling
approaches in our project.

We are indebted to all other faculty members and teaching assistants whose efforts
have significantly contributed to making this project a resounding success.

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1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.1. Tert-Butanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
1.2. Raw Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2. Market analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1 Global Market Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11
2.2 End use industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3 Key Players. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11
2.4 Regional Outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.5 Market Drivers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12
3. Production Process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15
3.1 Routes for Tertiary Butanol production. . . . . . . . . . . . . . . . .15
3.2 Pros and Cons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.3 DWSIM Simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .34
3.4 Sensitivity Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.5 Process Flow Diagrams. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4. Equipment Sizing & Costing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.1 Reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2 Pumps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.3 Distillation Column. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .54
4.4 Flash Separator. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.5 Heat Exchangers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.6 Valves. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.7 Storage Vessels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.8 Equipment List. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5. Plant economics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

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5.2 Major Equipment Costing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68

5.3 Total Purchased Equipment Cost. . . . . . . . . . . . . . . . . . . . . . . .68
5.4 Capital Investment Estimation. . . . . . . . . . . . . . . . . . . . . . . . . 69
5.5 Raw Material Cost. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.6 Revenue Generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.7 Total Product Cost. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.8 Payback Period. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .72
[Link] Design: Distillation Column. . . . . . . . . . . . . . . . . . . . . . . . . 71
6.1 Skirt Design. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.2 Nozzles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .78
6.3 Gaskets and Boults. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .80
6.4 Tray Design. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.5 Hold Up and Vapour Gap. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
[Link] Waste Management. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7.1 Pollutants and their adverse effects . . . . . . . . . . . . . . . . . . . 86
7.2 Liquid Effluents Treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
7.3 Gaseous Waste Management. . . . . . . . . . . . . . . . . . . . . . . . . .91
8.. Other Topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
8.1 Material Of Construction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .96
8.2 Safety. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Appendix A. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Appendix B. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

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Ch. 1. INTRODUCTION

1.1 TERT BUTANOL

Tert-butyl alcohol or TBA (C4H10O; IUPAC name: 2-methylpropan-2-ol) is the simplest
tertiary alcohol in organic chemistry. It is a colourless oily liquid with a sharp alcohol
odour. It floats and mixes with water in all proportions. Also miscible in ethanol and
diethyl ether. It is found as a natural product in chickpeas and guava. Commercially
it is obtained as a co-product of propylene oxide.

Figure 1: Structure of tert-butanol

PROPERTY1 VALUE

Molecular Weight 74.12 g/mol

Boiling Point 82.8 °C @ 760.00 mm Hg

Melting Point 25.4 °C

Flash Point 11 °C

Solubility in water ∞

Density 781 kg/m3 @ 25°C

Vapor Pressure 4.1 kPa (at 20 °C)

Henry’s Law Constant 9.05x10-6 atm-cu m/mole at 25 °C

Heat of Vaporization 39.07 kJ/mol

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pKa 19.02

Heat Capacity 215.37 J/ K . mol

Standard Enthalpy of Formation −360.04 to −358.36 kJ/mol

(ΔfH⦵298)

Table 1.1: Properties of t-BuOH

1.1.1 Azeotropes of TBA2

Tert-butanol is often available in its homogeneous azeotropic form with water. This
also causes difficulties in separation on an industrial level. Below is the tabulated
data of all other azeotropes it forms.

Component B.P. of component B.P. of mixture (˚C) % Composition by

(˚C) weight

Water 100.0 79.9 11.8

Benzene 80.2 74.0 63.4

Cyclohexane 81.4 71.3 63.0

Table 1.2: Azeotropes of t-BuOH

1.1.2 USES

 Tert-butanol is used in the production of various flavors and fragrances for food and
cosmetics. It is also used as a solvent for these products
 Tert-butanol is used as a fuel additive to increase the octane rating of gasoline,
which improves engine performance and reduces emissions.
 Serves as an intermediate in the synthesis of various chemicals (MTBE and tert-butyl
hydroperoxide), including pharmaceuticals and agrochemicals.
 It is an important solvent in the pharmaceuticals and paint industry.
 Tert-butanol is used as an adhesion/cohesion promoter, plasticizer, process
regulator, and viscosity modifier.

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1.1.3 Grades of tert-butanol

There are two major commercially available grades of tert-butanol:

1. Pure grade (99.65% minimum purity): This grade is commonly used in research and
industry applications. It is used to manufacture organic peroxides, antioxidants, or
pharmaceuticals. However, pure grade is liquid only above room temperature, hence
causing transportation issues. It is flowable and pumpable only at elevated
temperatures (> 30 °C).

2. Azeotropic grade (87.25% minimum purity): Unlike pure grade, it is liquid and
pumpable over a much wider temperature range, especially at room temperature
and below. Majorly required by cosmetics and plastics producing industry

1.2 RAW MATERIALS

1.2.1 ISOBUTANE (C4H10)

Isobutane is a colorless gas with a faint petroleum-like odor. It is shipped as a
liquefied gas under its vapor pressure. Contact with the liquid can cause frostbite. It
is easily ignited. The vapors are heavier than air.

PROPERTY3 VALUE

Molecular Weight 58.12 g/mol

Boiling Point -11.7 °C @ 760.00 mm Hg

Melting Point -145 °C

Flash Point -117 °C

Solubility in water Insoluble

Density 563 kg/m3 (at 15 °C, boiling liquid)

Vapor Pressure 310 kPa (at 21 °C)

Henry’s Law Constant 8.6 nmol/ Pa . kg

Heat of Vaporization 4.570 kcal/mol at 25 °C

Heat Capacity 96.65 J/ K . mol

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Standard Enthalpy of Formation −134.8 – −133.6 kJ/mol

(ΔfH⦵298)

Table 1.3: Properties of Isobutane

USES

 Isobutane is used as a refrigerant in both domestic and commercial refrigeration

systems. It is considered an environmentally friendly alternative to certain
chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) due to its low
ozone depletion potential.
 It is a common propellant in aerosol products such as deodorants, hairsprays, and
spray paints.
 Isobutane is sometimes used as an additive in gasoline to improve its octane rating.
 Isobutane serves as a feedstock in the production of various chemicals, including
isobutylene.

1.2.2 ISOBUTYLENE (C4H8)

Isobutylene is a colorless gas with a faint petroleum-like odor. For transportation it
may be stenched. It is shipped as a liquefied gas under its own vapor pressure.
Contact with the liquid can cause frostbite. It is easily ignited. Its vapors are heavier
than air and a flame can flash back to the source of leak very easily.

PROPERTY4 VALUE

Molecular Weight 56.11 g/mol

Boiling Point -7.0 °C @ 760.00 mm Hg

Melting Point -140.3 °C

Flash Point -76 °C

Solubility in water Insoluble

Density 589 kg/m3 (at 25 °C, P > 1 atm)

Vapor Pressure 257 kPa (at 20 °C)

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Henry’s Law Constant 0.218 atm-cu m/mole at 25 °C

Heat of Vaporization 395 kJ/kg

Table 1.4: Properties of Isobutene

USES

 Primarily used to produce di-isobutylene, trimers, butyl rubber, and other polymers.
 Used to produce antioxidants for foods, packaging, food supplements, and for
plastics.

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Ch. 2. MARKET ANALYSIS

2.1 Global Market Overview 5, 6, 7

The global Tertiary Butyl Alcohol (TBA) market, totalling 1850 thousand tonnes in
2022, is poised to exhibit a growth rate of 5.4% annually until 2032. Driven by its
versatile applications across industries, the market is anticipated to reach a notable
capacity of nearly 3100 thousand tonnes by the conclusion of the forecast period in
2032.

Applications:

TBA plays a pivotal role in various industries, including fuel additives, solvents,
chemicals, rubber, pharmaceuticals, coatings, adhesives, and the food and
beverage sector.

2.2 End-Use Industries

Flavors and fragrances constitute the largest consumer segment (42%) of the global
TBA market in 2022. Paints and coatings follow, with TBA serving as a preferred
solvent.

2.3 Key Players

Major players in the TBA market include LyondellBasell Industries N.V., Lotte
Chemical Corporation, Kuraray Co. Ltd., Evonik Industries, Sinopec Corp., and
others.

2.3.1 New Developments 8

In March 2023, LyondellBasell commissioned the world's largest Tertiary Butyl

Alcohol (TBA) and Propylene Oxide unit in Texas, with subsequent impacts on the
market. TBA, a multifaceted chemical, experienced price fluctuations in the USA
market in the first half of 2023.
The new facilities in Texas have an annual capacity of 470 thousand tonnes of
Propylene Oxide and 1000 thousand tonnes of TBA. Isobutylene prices' slight
decrease upstream affected TBA production expenses in the US market.

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Purity and Application Insights

TBA purity influences its applications, with >99% purity dominating the market.
Solvents and intermediates constitute the largest application segment.

2.4 Regional Outlook 9

1. Asia Pacific (44.3% Market Share): Driven by rising disposable income, population
growth, industrialization, and increased polyurethane manufacturing in China and
India.
2. Europe (26.3% Market Share): Significant presence due to increased construction
activities and growing demand in chemical synthesis, freeze-drying agents, and
flavors & fragrances applications.
3. North America (18.1% Market Share): U.S. demand rises with economic recovery,
increased government spending on drug delivery and retrofitting, and consumer
preference for luxury personal care products.

Prices as of Dec 2023

 North America:US$2.01/KG, 2.6% up
 Europe:US$0.96/KG, 1.1% up
 Africa:US$1.18/KG, 4.4% up
 Northeast Asia:US$1.35/KG, 1.5% up
 South America:US$1.21/KG, 4.3% up

Prices as of Jan 2024

 North America:US$1.92/KG, 3.8% up
 Europe:US$0.97/KG, 2.1% up
 Africa:US$1.15/KG, 3.6% up
 Northeast Asia:US$1.29/KG, 2.4% up
 South America:US$1.21/KG, 3.4% up

2.5 Market Drivers:

 Construction and Automotive Applications

1. Paints, Coatings, and More: Tert-butanol role as a solvent/co-solvent in
paints, coatings, inks, and adhesives, along with its use in varnishes, resins,
gums, and other applications.
2. Construction Boom: Growing demand in the building & construction sector,
especially in expanding economies like China and India, fueled by rapid
urbanization and industrialization.

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3. Automotive Industry Growth: Increasing demand for tert-butanol in the

automotive sector, driven by its application in rechargeable battery cells,
aligning with the automotive industry's shift towards electric vehicles.

 Flavors and Fragrance Industry

1. Complex Mixtures: Tert-butanol's utilization in fruit essence, perfume
production, and its impact on the flavor of food products.
2. Wide Industry Applications: Flavors and fragrances play a pivotal role in
food, perfumes, toiletries, cosmetics, and chemical industries.
3. Market Boost: Rising demand for traditional scents, branded perfumes, air
fresheners, and deodorizers expected to elevate the global tert-butanol
market share.

 Denaturants for Ethyl Alcohol Production

1. Denaturant in Ethyl Alcohol:
 Tert-butanol's role as a denaturant in the production of ethyl alcohol,
contributing to the creation of denatured alcohol.

2. Market Driving Factors:

 Manufacturers' inclination towards effective denaturant alternatives.
 Regulatory push for denatured alcohol in gasoline blending.
 Increasing applications in medical disinfectant, cosmetics, specimen
preservation, sanding, fuel, and pest control.

2.5.1 COMPANIES

COMPANY CAPACITY LOCATION

Alfa Aesar - USA

Evonik Industries Ag 0.21 Million TPA GERMANY

Finar Limited - INDIA

Kuraray Co., Ltd. 0.1 Million TPA JAPAN

Lotte Chemical Titan 0.11 Million TPA MALAYSIA

Corporation

Lyondellbasell Industries 1 Million TPA USA

Holdings B.V.

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Merck Kgaa - GERMANY

Sisco Research - INDIA

Laboratories Pvt. Ltd.

Tiande Chemical Holdings - CHINA

Limited

Tokyo Chemical Industry - JAPAN

Co., Ltd. (TCI)

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Ch. 3. PRODUCTION PROCESSES

3.1 ROUTES
There are 4 major routes of synthesising Tertiary Butanol:

3.1.1 Oxidation of Isobutane

3.1.2 Hydration of Isobutene
3.1.3 Fermentation of Alkanes
3.1.4 Grignard Reagent

There are a few minor routes worth mentioning as well:

1. Cyclic Oxidation
2. Ester alkaline degradation

Let’s discuss each of them in detail.

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3.1.1 OXIDATION OF ISOBUTANE 10, 11, 12

(CH3)3CH + O2 → (CH3)3COOH + (CH3)3COH (1)

C(CH3)3OOH + CH3CHCH2 → CH3CHOCH + C(CH3)OH (2)

The manufacturing process of Tert-butanol involves several key steps:

a. Reaction of Isobutane with Oxygen

This step results in the formation of Tertiary Butyl Hydroperoxide and
Tertiary Butanol (Reaction 1). The proportion of these products can be
modulated by altering the catalyst1,2,3 used.
b. Decomposition of peroxide
In this stage, Propene is employed as a reducing agent to decompose the
peroxide while preserving the Tertiary Butanol. This process unfolds in two
phases, with cooling occurring between the stages.
c. Cooling
The vapor stream is subjected to cooling, facilitating the extraction of a
portion of the Tertiary Butanol.
d. Distillation and Separation
This constitutes the final step, wherein Tertiary Butanol is extracted.

It’s important to note that the primary source of revenue in this process is Propylene
Oxide, which holds a value 100 times greater than that of Tertiary Butanol. However,
the process exhibits considerable inefficiency in terms of energy consumption due to
the overoxidation and subsequent reduction involved.

Because of this inefficiency in production, we are ignoring this route.

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3.1.2 HYDRATION OF ISOBUTENE

[Link] REACTIVE ABSORPTION 13

The process commences with the absorption of isobutylene in concentrated

sulphuric acid, a method that proves highly effective due to the reactive nature of
the absorption. Subsequently, the solution undergoes dilution, facilitating the
conversion of C4H9OSO2H to C4H9OH. It’s noteworthy that distillation at this stage
would result in azeotropic distillation, a less desirable outcome. Thus, separation is
done at a later stage.

The ensuing step involves the extraction of Tertiary Butanol using Diethyl Ether. This
extraction is characterized by its selectivity and the ease with which it can be
further processed via distillation. The details of this process are elaborated upon in
the accompanying figure.

The only drawback of this method is that H2SO4 also causes dimerization of
isobutylene leading to formation of 2,4,4-trimethylpent-2-ene, but this happens at a
lower concentration of acid (around 48% w/w). To ensure dimer formation does not
take place, we shall use 67% H2SO4 (w/w).

(CH3)2CCH2 + H2SO4 → (CH3)2C(OSO2H)CH3 (1)

(CH3)2C(OSO2H)CH3 + H2O → (CH3)3COH + H2SO4 (2)

Because of the simplicity of this process and absence of azeotropes, we initially

selected this route but had to discard it later due to absence of kinetic data.

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Calculations done when this route was initially selected:

Figure 2: Overall PFD for Reactive Absorption process

Table 3.1: Stream Data for Figure 2 PFD

Selection of various unit operations:

1] BUBBLE COLUMN REACTOR

For sulphonation of isobutylene, we use a bubble column reactor, owing to the

reactant’s gaseous phase nature.
 The sulphonated ester is somewhat hydrated in the column itself leading to a
noticeable amount of tert-butanol.
 This is actually beneficial as this increases the solubility of isobutylene in the
acid.

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2] HYDRATION REACTOR

We don’t need a dedicated and specialized reactor for the process, as we are just
diluting the TBA and sulfonated ester mixture. The hydration process is exothermic.
A CSTR with cooling jacket would be preferred.

But why is dilution necessary?

a. The ester, despite being stable, is easily broken down into H2SO4 and TBA
upon gaining more water in its surroundings.
b. Also, during the extraction process, as the solvent (diethyl ether) in this case
is immiscible in water, so it only carries TBA with it hence preventing scope of
any azeotrope formation and making it quite readily extractable.
c. Diethyl ether is soluble with concentrated acid, but as it gets diluted, it splits
into two separate phases.

3] LLE and Suitable SOLVENT SELECTION

It has been observed that TBA can be extracted almost completely from the acid
phase, unlike secondary olefins. Upon reviewing various studies, certain solvents
have demonstrated notable effectiveness in this extraction process. These promising
solvents are highlighted based on the reported results in existing research
 Diluted product extraction with benzene (5 times), achieved a 74% tert-
butanol extraction.
 46% of tert-butanol was extracted with o-dichlorobenzene in the same
condition (5 washes with the solvent).
 Ethyl ether identified as the most suitable solvent giving 100% extraction,
although upon 10 times washing. When extraction was done 5 times, 91% of
tert-butanol was recovered.

Furthermore, why diethyl ether should be the solvent was also emphasized above
while discussing the necessity of dilution.

As 10 times extraction led to complete recovery of all the alcohol, we propose a 10-
stage cross current setup for the LLE module.

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A more simplified view of this process is:

Figure 3: Overall Mass balance for Reactive Absorption process

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[Link] DIRECT HYDRATION OF ISOBUTENE 14, 15, 16, 17, 18, 19, 20

(CH3)2CCH2 + H2O ⇌ (CH3)3COH

In this process, Isobutene is reacted directly with water. Given the reversible nature
of the reaction, it necessitates the continuous removal of the product, thereby
requiring the use of multiple reactors.

It's noteworthy that Isobutene, being a gas, is insoluble in water. Furthermore, the
reaction proceeds too slowly in the vapour phase. Consequently, a solvent is required
to maintain both reactants in the liquid phase. Intriguingly, for this reaction, the
product t-butanol itself serves as the solvent.

Given the reversibility of the reaction, the presence of the product in the reaction
mixture can drive the reaction in the reverse direction. Therefore, a balance must be
struck between the solubility of Isobutene and the forward progression of the
reaction.

The catalyst employed in this process is unique. An acid is required as the catalyst,
but in a liquid medium, an overly dilute acid would not exhibit any activity, while an
excessively concentrated acid would induce corrosion and promote side reactions
such as dimerization and ether formation. As a result, a solid acid catalyst, also known
as a cation exchange resin, is utilized, which greatly simplifies the processes of
recovery and regeneration.

However, this route presents a challenge in the form of an azeotrope formed between
water and butanol. The separation of this azeotrope would necessitate the use of
specialized distillation columns, a requirement which is not present in the previous
method.

After rejecting the previous method, this was the next best possible method.
Hence, we are using this.

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Simplified Block Diagram with mass balances

PFD 1: Reactor Subsystem

Table 3.2: Stream Data for PFD 1: Direct Hydration

22
`

PFD 2: Distillation Subsystem

Table 3.3: Stream Data for PFD 2: Direct Hydration

The conceptualization of this design primarily draws upon the innovative ideas
presented in several patents advocating for a multi reactor setup, as well as the
insights gleaned from a scholarly paper on trickle bed reactors. These sources
collectively served as the inspiration and provided the foundational knowledge
necessary for the development of this design.

The Process Flow Diagram (PFD) elucidates the process under discussion. The three
units depicted on the left constitute the reactor network, while the three units on the
right form the separation network. Several characteristics of this setup warrant
attention.

Water and a stream labelled S116, which contains a mixture of alcohol and water,
flow from left to right. Conversely, Isobutene flows from right to left. Notably, even
within a reactor, the flow is counter current.

23
`

It's also important to observe that a portion of the liquid product from each reactor
is separated and directed to a distillation column. Concurrently, water is added to
the remaining part, which is then sent to the subsequent reactor.
Within the distillation subsystem, the initial step involves obtaining the Tert-butanol
water azeotrope and recycling the remaining water. Subsequently, the azeotrope is
broken down using extractive distillation, and the solvent is recycled.
The rationale behind each of these choices will be expounded upon in the following
section.

1] Reasoning

Choice of Trickle Bed Reactor:

The selection of a trickle bed reactor offers several advantages. It eliminates the
need for an additional piece of equipment to dissolve Isobutene (IB) and allows for
operation at slightly higher temperatures without concerns about solubility.
Compared to a slurry reactor, a trickle bed minimizes liquid side reactions such as
ether formation.

Advantages of Trickle Bed over Bubble Column:

The use of a solid catalyst in the process makes a bubble column unsuitable for this
application. Furthermore, the formation of di-isobutene, a by-product expected from
a competitive second-order reaction, is slowed due to lower dissolved
concentrations of IB and lower operating temperatures, leading to higher selectivity
towards the desired product, Tertiary Butanol (TBA).

Counter Current Flow:

The counter current flow design is energy efficient as it reduces the energy required
to cool the process fluid. The gas heats up from left to right, and the liquid heats up
from right to left, maintaining high solubility at all points. This principle applies both
within a single reactor and across multiple reactors.

Multiple Reactors:

The reaction is reversible and exothermic, necessitating the removal and cooling of
the product before each step, which is facilitated by using multiple reactors.
Alcohol in the Reaction Feed:
The presence of alcohol in the reaction feed helps to keep IB soluble and the
reaction in the liquid phase.

Reaction in the Liquid Phase:

Conducting the reaction in the liquid phase ensures better contact with the solid
catalyst.

24
`

Use of Cold Water:

Cold water is used because it is easier to cool the liquid by mixing than to cool the
vapours. Moreover, direct mixing results in a better heat transfer coefficient.
Each of these choices contributes to the efficiency and effectiveness of the process.
However, it's important to note that these choices are interconnected, and changes
to one aspect of the process may necessitate adjustments to others.

2] Solvent Selection 21

The selection of an appropriate solvent for the separation of compounds

necessitates careful consideration of several key factors. Foremost among these
considerations is the establishment of a significant boiling point differential between
the target compound and the chosen solvent. This characteristic facilitates an
efficacious separation process by capitalizing on the disparity in vapor pressures
between the components.

A second imperative criterion involves the miscibility of the extractive agent with
the tert-butyl alcohol, as failure to achieve miscibility may result in the formation of
a two-phase azeotrope in the recovery column. Such an occurrence would
necessitate the implementation of alternative separation methods. In this context, it
is particularly advantageous for the selected solvent to exhibit miscibility with tert-
butyl alcohol to obviate complications in the separation process.

The third crucial consideration pertains to the economic viability of the chosen
solvent, specifically the cost per kilogram. Cost considerations play a pivotal role in
industrial processes, and selecting a solvent with a judicious balance of efficacy and
economic feasibility is paramount for optimizing the overall efficiency of the
separation procedure.

25
`

Figure 4: Cost vs α for various solvents

(The data of different solvents is given in Appendix)

In alignment with these criteria, ethylene glycol phenyl ether has emerged as the
solvent of choice. Possessing a boiling point of 247 °C, it satisfies the prerequisite of
a substantial boiling point difference from the compound being separated,
facilitating efficient vapor-phase separation. Moreover, its miscibility with water
ensures compatibility with tert-butyl alcohol, mitigating the risk of azeotropic
complications in the recovery column. Finally, with a cost of 100 Rs/Kg, ethylene
glycol phenyl ether not only meets economic considerations but also exhibits the
highest relative volatility, further enhancing its suitability for the designated
separation process. This meticulous solvent selection aligns with the imperative of
balancing technical efficacy, compatibility, and economic prudence in industrial
chemical processes.

Upon further processing, it was found that this solvent wasn’t available on DWSIM.
Thus, we use the next best solvent, which is Triethylene Glycol.

3] Heat Exchanger Selection

The utilization of a shell-and-tube heat exchanger in the context of direct hydration

is underpinned by a series of strategic considerations, driven by the specific
requirements of the isobutene hydration process. Notably, the choice of this heat
exchanger configuration is attributed to the need to compress isobutene (IB) before
its introduction into the reactor, resulting in elevated pressures that render plate
heat exchangers less suitable.

26
`

Other advantages are listed below:

 Exothermic Reaction
 Efficient Heat Transfer
 Temperature Control
 Scalability
 High Heat Transfer Surface Area
 Ease of Maintenance

4] Catalyst Selection a

In the quest for an ion exchange catalyst that boasts high porosity and is
economically viable, two primary contenders emerge:
Amberlyst 15 and DuPont™ Duolite™ A568.

Both of them share similar characteristics in terms of pore volume and diameter. The
specifications are as follows:

Amberlyst 15:

- Total Pore Volume: 0.40 cc/g

- Average Pore Diameter: 300 Å

DuPont™ Duolite™ A568:

- Total Pore Volume: 0.78 – 1 mL/g

- Average Pore Diameter: 300 – 500 Å

While both options present comparable pore volumes and diameters, other factors
come into play when choosing between them. Duolite™ A568, often employed for
enzyme holding, is presumed to be more expensive due to its specialized use.
Additionally, it is a weak ionic resin, which could result in lower activity.
In contrast, Amberlyst 15 is a cost-effective and strong ion exchange resin, making
it a more appealing choice given the requirements. Therefore, Amberlyst 15 emerges
as the preferred option in this context.

27
`

[Link] REACTIVE DISTILLATION 22

This process mirrors the one previously discussed, with the notable exception that
the product, Tertiary Butanol, is continuously removed. The accompanying figure
from a referenced paper provides a more detailed illustration of this process:

The continuous removal of TBA serves to drive the reaction forward. Additionally,
the integration of the reactor and separator results in capital cost savings. However,
it’s important to note that this method necessitates the breaking of the azeotrope
between TBA and water, which in turn requires the use of complex distillation
columns. This is a key consideration when evaluating the feasibility and efficiency of
this process.

Thus, this is the least preferred alternative and not considered further.

Figure 5: PFD for Reactive Distillation

Heat Exchanger Selection

The designated heat exchanger for this process is a Plate Heat Exchanger, selected
for its distinct advantages in facilitating the heat transfer requirements integral to
the operational dynamics.
 Enhanced Heat Transfer Efficiency: The plate heat exchanger excels in
augmenting heat transfer efficiency due to its intricate plate structure,
fostering increased surface area for effective thermal exchange between
fluids.
 Compact Design: Characterized by a compact configuration, the plate heat
exchanger optimizes spatial utilization, making it particularly suitable for
applications where space constraints are a consideration.

28
`

 Flexibility in Temperature Control: The design of the plate heat exchanger

affords a high degree of flexibility in regulating temperature, providing
nuanced control over the thermal conditions of the process.
 Rapid Heat Transfer Response: The inherent characteristics of the plate heat
exchanger contribute to swift heat transfer responses, facilitating dynamic
adjustments to temperature variations within the system.
 Ease of Maintenance and Cleaning: The accessibility of the plate heat
exchanger's components facilitates facile maintenance and cleaning
procedures, ensuring sustained operational efficiency over extended
durations.
 Versatility with Corrosive Fluids: The materials employed in the construction
of plate heat exchangers confer resistance to corrosive fluids, broadening the
applicability of this exchanger in scenarios involving chemically aggressive
media.
 Energy Efficiency: The plate heat exchanger, through its optimized design
and efficient heat transfer capabilities, manifests as an energy-efficient
component, contributing to overall process sustainability by minimizing
energy consumption.

29
`

Other Routes
3.1.3 FERMENTATION OF ALKANES 23

Since Butanol is an alcohol, we can also explore fermentation as a method of

production.

The fermentation reaction that produces t-Butanol is referred to as ABE

fermentation, since the products are Acetone, Butanol, and Ethanol. This has never
been done at industrial scale and has the following steps:

1] Selection of feedstock - there are 4 potential feedstocks to be used for the

reaction:

Starch and sucrose feedstocks made from crops like corn, sugarcane, or beets. They
consist of easily fermentable sugars, which are formed of complex polysaccharides.
Lignocellulosic biomass: This includes forestry waste, crop residues, and crops
grown specifically for energy. Because lignocellulosic biomass is abundant and
inexpensive, it is preferred over the other substrates
Algal Biomass
Syngas: Syngas can also act as a substitute carbon source for the fermentation of
ABE.

2] Preparing the feedstock - The feedstock is prepared for the reaction via 3 steps:

 Breakdown and Size Reduction: To break down complicated structures,

increase surface area, and improve porosity, the feedstock is treated to
physical, chemical and biological processes.
 Hydrolysis of Cellulose: Enzymatic hydrolysis is used to break down the
cellulose molecules into smaller sugars like glucose, making sugars available
for fermentation. This process also produces some inhibitors which need to be
removed.
 Detoxification: Detoxification involves the removal of inhibitors produced in
the hydrolysis of cellulose and uses methods like centrifugation, activated
charcoal treatment, and electrodialysis. This increases the effectiveness of
fermentation.

3] Fermentation - Typically, strains of clostridium bacteria are used for the

fermentation process. They break down the feedstock's carbohydrates into
metabolic byproducts like ethanol, butanol, and acetone. This fermentation happens
through 2 steps. 1st, which involves the production of organic acids, which are then
converted to alcohols (butanol, ethanol) and acetone.

4] Separation - The alcohol, butanol, and ethanol need to be removed from the
fermentation broth. Theoretically, distillation seems like the appropriate choice
(although energy-intensive). This is a small-scale method and not used in large scale

30
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Figure 6: Fermentation Route

3.1.4 VIA GRIGNARD REAGENT

The synthesis of tert-butanol via the Grignard reaction, specifically the reaction
between methyl magnesium bromide and acetone, presents certain drawbacks that
impede its favorability for industrial applications. These limitations primarily stem
from low atom efficiency and high effluent generation.

The Grignard reaction necessitates the use of stoichiometric quantities of

magnesium metal and halogenated organic compounds, both of which are costly
and contribute to a substantial degree of wastefulness. The resulting magnesium
salt of the alcohol byproduct lacks intrinsic value and requires appropriate disposal

31
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measures. The atom efficiency, a crucial metric in evaluating the resource utilization
of a synthetic process, is notably low in this context. The atom efficiency is
computed as the ratio of the molecular weight of the desired product to the sum of
the molecular weights of all reactants. In the synthesis of tert-butanol from
methylmagnesium bromide and acetone, the atom efficiency is merely 40%,
signifying that a significant 60% of the atoms are squandered.

Moreover, the Grignard reaction engenders a considerable volume of effluent,

posing environmental concerns and economic challenges associated with its
treatment. The effluent, characterized by the presence of the magnesium salt of the
alcohol, excess Grignard reagent, solvent, and impurities, necessitates intricate and
resource-intensive disposal procedures. Typically, acidic and corrosive, the effluent
may contain trace amounts of heavy metals, halides, and organic compounds,
further complicating its management. Disposing of the effluent mandates
procedures such as neutralization, filtration, extraction, and incineration, all of which
entail substantial energy consumption and resource utilization.

In light of these considerations, the Grignard reaction's limited atom efficiency and
substantial effluent generation underscore the need for more sustainable and
economically viable alternatives in the industrial synthesis of tert-butanol. Efforts to
optimize synthetic methodologies and develop greener alternatives are imperative
for ensuring the ecological and economic sustainability of chemical manufacturing
processes.

32
`

3.2 PROS and CONS

OF THE METHODS CONSIDERED

Isobutane Oxidation Isobutene Hydration

Reactive Direct Hydration Reactive Absorption
Distillation

Inefficient Need to break Need to break Lot of steps needed

(overoxidation then azeotrope azeotrope
reduction)

Low atom efficiency Very efficient Equilibrium driven, No azeotrope formed

compared to hence needs
others due to multiple reactors
constant
product
removal

Safety concerns are High Atom efficiency

high due to
inflammable material

Propylene oxide is Ion exchange catalyst is easy to All reagents can be

produced recover and doesn’t cause corrosion recovered and
recycled

After considering many factors (and lack of kinetic data etc.) we decided to choose
Direct Hydration as our primary route since kinetic data for Reactive Absorption
was missing.

33
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3.3 DWSIM SIMULATION

3.3.1 MODEL SELECTION

The distillation system consists of 3 main components: Tert-butanol, water and

Triethylene Glycol. All of these have -OH groups and hence are polar. Thus, we need
to use an activity coefficient model. Generally, these 3 models are used:
- UNIQUAC
- NRTL
- Wilson

While NRTL and UNIQUAC are more robust and reliable, Wilson can be used for
homogeneous systems and is a simpler model. All these models use a set of binary
interaction parameters, which are either built into the system or available as
datasets in DECHEMA. Unfortunately, in this case, the parameters are neither
present beforehand nor are found in the databases. The only pair for which the
parameters are available is the TBA-Water pair. Consequently, the Wilson model is a
safe choice until the process reaches the stage of extractive distillation. At this point,
the model of choice becomes UNIFAC, a more generalised model that generates
parameters based on molecular structure. Although this approach may introduce
some errors, it currently provides the best estimate available.

The simulation was done using a mixture of models. The reactor and the first
distillation are modelled using Wilson. The extractive distillation was simulated
using UNIQUAC, and the results matched the UNIFAC results (The only explanation
is that the other parameters were estimated internally). The Flash was done using
UNIFAC.

The reason for doing Distillation using a UNIQUAC instead of UNIFAC is due to the
slightly higher computational cost of UNIFAC and DWSIM not being able to handle
UNIFAC for distillation.

34
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3.3.2 REACTOR SUBSYSTEM

Three options were tested for designing the trickle bed reactor system.

A] Reaction Kinetics 24

The intrinsic isobutene hydration kinetic rate constant using pure water can be
expressed as
𝑘 = 2.34 × 108 × e8323/T

Table 3.1: The intrinsic kinetic reaction constants in the CFFBR using the model of
the micropore and the macropore structure

The reaction rates are proportional to the isobutene partial pressures: r = 𝑘 × PiB

𝑘overall = 𝜂𝑚c𝑘/H = 3.78 × 10-12

35
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B] PFR simulation using CSTR cascade

In the investigation of reactor design, a CSTR

cascade resembling a counter-current flow fixed bed
reactor is under consideration. We have used 8-10
CSTRs. Prior to conducting simulations using DWSIM,
it is imperative to establish key quantities such as
flow rates for the streams. To facilitate this
calculation, a series of assumptions will be made,
and subsequent adjustments will be implemented
gradually.

x1 =IB x2 = Water x3 = TBA

Assumptions:
1. No isobutane
2. K is known
3. Conversion is constant across all reactors
4. The liquid stream leaving(L’) and the gas stream
leaving(G’) are in equilibrium. So we can use henry’s
law.

These are the following equations that we get:

Lx1 + G’ - (L’x1’ + G) - R = 0
Lx2 - R - L’x2’ = 0
Lx3 + R - L’x3’ = 0
x3’ = kP (Henry’s Law) => P is the total pressure
R = (Lx3)X (X = conversion)

The challenge lies in solving these nonlinear equations. Unfortunately, we were not
able to solve these equations.

C] PFR with co-current flow of streams

The main idea behind using a trickle bed reactor was to provide a counter current
flow for the gaseous stream (Isobutene-Isobutane inlet) and liquid stream (Water-
TBA inlet). Since a trickle bed reactor is not available as a preset in DWSIM, we
opted for a PFR which resembles the trickle bed reactor the most (considering
catalyst loading too).
 Initially, the reactor type was ‘Define Outlet Temperature’ and sensitivity
analysis was also performed on it.

36
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 However, we changed the reactor type to ‘Adiabatic’ mode. This had 2 major
benefits: higher conversion and decreased operating expenditure in terms of
energy savings.

For detailed & final values and an in-depth study of the simulation, please refer to
the section 3.4 SENSITIVITY ANALYSIS.

37
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3.3.3 SEPARATION SUBSYSTEM

Modelling for EXTRACTIVE DISTILLATION

Figure 7: RCM for TBA-Water-TEG

Table: RCM - [Link]

hRaBQwsHr32GkI6TowEv-u9JZB_xI/edit?usp=sharing

There are no clear Pinch points. Hence, it lies in our hands to select the end
composition we want for water and TBA. Moreover, we have the freedom to choose
the starting point of the middle section.

Let's work with the following assumptions:

We get 99% pure TBA at the top, with 1% impurity of TEG. (We can add an additional
distillation column/flash vessel to reach that purity later. We can even reach higher
if needed)

Assume that RS is a binary between TBA and TEG.

For SS, we will consider three different curves and three different Middle section
beginnings. This way, we will get the trend so that we can optimise later.

Basic Theory:
[Link]

Actual Equations: Calculations -

[Link]

38
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3.4 SENSITIVITY ANALYSIS

3.4.1 REACTOR SUBSYSTEM

CASE I: When reactor type is ‘Define Outlet Temperature’

Parameter 1: Temperature of reactor inlet stream

Figure 8: Mass flowrate of TBA in outlet stream vs temperature of inlet stream

As temperature increases, mass flowrate of TBA in reactor outlet increases

(basically conversion increases), but we cannot keep temperatures high, i.e., close to
78 °C as it is the boiling point of TBA-water azeotrope.

We cannot even keep it low as we need to heat the stream to provide enough
energy to overcome the threshold energy barrier to ignite the reaction.

By reviewing the patents, we fix the temperature around 50 °C.

Parameter 2: Pressure of the reactor inlet stream

Had to do manually as we were facing problem while performing on DWSIM.

Optimized pressure: 0.62 bar

However, with the current reactor type we observed bit counterintuitive results
upon increasing pressure

39
`

1. Conversion was decreasing, which should not be the case, as the rate law is
directly proportional to partial pressure of isobutene.
2. Higher pressure would lead to higher solubility of isobutene in TBA-water
mixture, but that was not observed.

Parameter 3: Volume of the reactor

Figure 9: Mass flowrate of TBA in outlet stream vs volume of the reactor

Conversion peaked around 73 m3, but we choose 67 m3 as at the former value other
parameters were causing conversion to decrease.

CASE II: When reactor type is ‘Adiabatic’

Parameter 1: Pressure of the reactor inlet stream

In this case higher pressure (as close to 1 bar) gave good conversion which is not
contradictory unlike previous case.

Further increase in pressure, i.e., from 1 bar – 1.5 bar; the increase in mass flowrate
of TBA in outlet stream was negligible (only 0.4 TPH), hence it is meaningless to
increase the pressure as it only increases our operating expenditure and not our
product yield.

40
`

Parameter 2: Volume of the reactor

Figure 10: Mass flowrate of TBA in outlet stream vs volume of the reactor

When the reactor type was ‘Define Outlet Temperature’, the volume chosen was 67
m3 but when the reactor was operated in ‘Adiabatic’ mode, the conversion peaked
around 74 m3, hence we are choosing volume of the reactor to be 74 m3.

Final values of reactor:

1. Length = 10 m
2. Volume = 74 m3
3. Number of tubes = 10
4. Catalyst loading = 419.713 kg/m3
5. Catalyst Particle Diameter = 0.68 mm
6. Catalyst void fraction = 0.65

41
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3.4.2 EXTRACTIVE DISTILLATION SUBSYSTEM

The prescriptions are given below:

S = 1.51, S/F = 4, R = 12.63, N = 40, Nf = 20, Ns = 25, D = 160000 Kg/hr

After substitution and slight modification, this is what Aspen gives us:
R = 12, D = 16E4 Kg/Hr, N = 45, Nf = 30, Ns = 10,
Purity = 99.5% by mole, Reboiler duty = 1.12E12 KJ/Hr
(This is different from conceptual design because Aspen takes care of non-idealities,
too)

After this, we start optimisation:

N: 35-45
Nf: 20-30
R: 2-12
Check the effect on Duty and Purity

Figure 11: Total Energy vs Purity of TBA

42
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Figure 12: Reboiler duty vs Purity of TBA

Observations:
1. High purity and lowest energy consumption happen simultaneously.
2. High purity and lowest reboiler duty also happen simultaneously.
Thus, if we minimise Energy consumption while maximising purity, we will be able to
reach an optimum. Thus, we use the sorting feature of excel to achieve these 3
targets (in the same order):
1. Highest purity
2. Least Energy consumption
3. Min number of stages

This gives us the optima to be:

N = 35
Nf = 30
Ns = 10
R=2
Impurity = 1 ppm
Reboiler Duty = 3.4E8 KJ/hr
Condenser Duty = -2.5E8 KJ/hr

Now, to decrease the energy consumption even further, let’s play with the Pressure:

43
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Figure 13: Purity of TBA vs Pressure

Figure 14: Energy needed vs Pressure

44
`

Figure 15: Temperature vs Pressure

Observations:
1. With increasing Vacuum, the purity increases
2. With increasing vacuum, the reboiler duty decreases, and condenser duty
increases, but the net duty decreases
3. With increasing Vacuum, the Temperatures come down, but the condenser will still
have a delta T of 35 degrees

With the given delta T, we can handle a huge amount of cooling needs. Thus, it is ok
to go to 0.5 bar to reduce the reboiler duty.

Next, we use a flash separation to purify the solvent before reuse. This choice is
made due to the huge boiling point difference between the effluent stream
components (namely water and TEG). We optimise this to in the following range:
T: 115 - 130 degrees, P: 0.1 - 0.5 bar check purity.

As expected, we get the highest purity for 130 degrees at 0.1 bar.

For all the sensitivity data, kindly refer: Sensitivity Study Aspen:
[Link]
R3gxmBWIo/edit#gid=0

45
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3.5 PROCESS FLOW DIAGRAMS

Figure 16: Final simulated PFD Part 1 for Reactor and Gaseous Stream Separation

Table 3.4: Stream Data for Figure 16 PFD

46
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Figure 17: Final simulated PFD Part 1 for Reactor and Gaseous Stream Separation

Table 3.4: Stream Table for Figure 17 PFD

47
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3.5.1 PFDs SUMMARY

The Process depicted here is to generate Tert Butanol by reacting Isobutene with
Water. The Process Flow diagram is divided into two parts. The first part consists of
the Reactor and the first Distillation column.

The process is as follows:

1. Isobutene with impurity of Isobutane (S-101) is taken from the spherical tank
(STR-01), where it is stored as a liquified gas. This forms the gas phase
reactant for the Trickle bed reactor, modelled as a PFR (RX-01)
2. We take water from a cylindrical storage tank (STR-02) and pump it using P-
01
3. Next, we take a small part of the product from the Product Storage tank
(STR-03) and mix it with the water stream (S-106 and S-103, respectively).
This gives us the Liquid phase reactant (S-104) for the reactor.
4. After reacting, the exit stream (S-107) contains isobutane, isobutene, water
and TBA. This stream is sent to the first Distillation column (DC-01), where it
gets separated into the non-condensable gases (S-115) and the Liquid
components (S-118). Note that this was impossible with a simple flash, as
sIsobutane and Isobutene have high solubility in TBA.
5. The Distillate(S-115) is flared before releasing into the atmosphere, and the
Bottoms stream(S-119) is taken to the next Distillation column (in PFD 2)

PFD 2 contains the second Distillation column (DC-02) and a Flash vessel (F-01).

6. The Stream S-119 has water and TBA in a near azeotropic state. Hence, DC-02
is an extractive distillation column, whereas S-219 is the solvent stream that
contains Triethylene Glycol, which can take water with it.
7. The Distillate (S-206) is cooled and stored in STR-03 as this is our final
product. Part of this is used to start the process, as TBA also acts as a solvent
for Isobutene.
8. STR-04 contains fresh solvent used for make up and process startup.
9. The Bottoms stream (S-211) contains water and TEG, which can be separated
by a flash separation (F-01).
10. The vapour from flash contains mainly water, which is liquified and sent to
ETP.
11. The liquid from flash contains mainly TEG which is recycled back to the
column.

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Ch. 4. EQUIPMENT SIZING AND COSTING

4.1 REACTOR

4.1.1 REACTOR SIZING

MoC ⟹ SS304
Reactor Volume = 74.28 m3
Length = 10 m
Tube Diameter (inner) = 50 mm
No. of tubes = 3900
c = 0 mm
m = 12.5%
E = 0.8 (spot welding) ⟹ worst case

Poperating = 1 bar ⟹ Pw
PD = max {1.1 Pw, Pw + 2 atm}
= max {1.08562 atm, 2.986923 atm}
= 2.986923 atm
= 3.0265 bar ⟹ Internal Pressure

Toperating = 35 °C
TD = 55 °C
SY = 205 MPa @ TD
Sa = SY/1.5 = 136.67 MPa

Thickness (Hoope's) obtained from ASME code

𝑃 𝐷
𝑡=
2 (𝑆 𝐸 − 0.6𝑃 )

𝑡 = 0.07014 𝑚𝑚

𝑡 +𝑐
𝑡= 𝑚 = 1.223 𝑚𝑚
1 − 100

Recommended thickness = 4.7625 mm

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Do = Di + 2t

Do = 59.525 mm

4.1.2 REACTOR COSTING

Number of tubes = 3900

Inner diameter of tubes = 50 mm
Outer diameter of tubes = 59.525 mm
Length of each tube = 10 m
Volume of each tube = (π/4) × (Do2 - Di2) × L
Volume of each tube = 8.1934×10-3 m3
Total volume of tubes = 31.954 m3

Density of material (SS 304) = 7930 kg/m3

Mass = Volume × Density

Total weight = 2.53395 × 105 kg
Cost of SS304 = INR 195/kg (2024) 25

Total cost of material for reactor = 4.9412 INR Crores as of 2024

Catalyst cost: 9.2$/kg = 761.944 INR/kg 26

Catalyst void fraction = 0.65

Catalyst volume = Reactor volume × (1 - Catalyst void fraction)
Catalyst volume: 0.35 × 74.28 = 25.998 m3
Catalyst loading = 419.713 kg/m3
Catalyst weight = 10911.698 kg

Catalyst cost = 0.8314 INR Crores as of 2024

Total cost of reactor = Catalyst cost + Material cost

Total cost of reactor = 5.7726 INR Crores = 0.696 million USD

50
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4.2 PUMPS

The plant incorporates a total of nine primary pumps, complemented by an equal

number of standby units, bringing the aggregate to eighteen single-stage
centrifugal pumps. Each pump operates at a rotational speed of 3500 revolutions
per minute. The selection of pump type has been diligently determined by an
evaluation of both the flow rate and the head, utilizing pump characteristic curves
as delineated by Towler et al. for the design process

Calculation for P-02 is shown below:

∆𝑃 ∆𝑃
𝑊= + 𝑔∆𝑧 +
𝜌 𝜌

𝑊𝑚
𝑃=
𝜌

where,

W = work done by pump (J/kg)

ΔP = Difference in pressure = P2 – P1 (N/m2)

Δz = Difference in elevation = z2 - z1 (m)

ΔPf = Pressure drop due friction in pipe fittings (N/m2)

ρ = Density of liquid (kg/m3)

g = Acceleration due to gravity (m/s2)

m = Mass flow rate (kg/s)

ηp = Pump efficiency
P=power required

ΔP = 10000

Δz = 0

ρ = 998 kg/m3
ηp = 0.8 (Pump efficiency is based on the pump capacity and head, Towler et. al.) 27
W = 10.02 J/kg

P = 434.05 W

Total power required = 434.05 W

Similar calculations have been performed for all the pumps. The results are
tabulated in Table 4.1

51
`

Table 4.1: Pumps’ Specifications

Mass Flow
Pump Stre ΔP Head W Power
Type Flow Rate
no. -am (Pa) (m) (J/Kg) (W)
(kg/s) (gpm)

P-01 102 Centrifugal 10000 3.3545 24.2 385.273 10.02 303.8

P-02 105 Centrifugal 10000 4.0664 10.39 200.17 114.06 8268

P-03 107 Centrifugal 10000 4.0664 62.2 1197.64 114.07 8869

P-04 112 Centrifugal 10000 3.0434 5.57 152.834 159.40 8276.7

P-05 114 Centrifugal 10000 0.3062 0.65 17.98 159.40 9617

P-06 118 Centrifugal 10000 4.0664 61.55 1185.01 114.07 87761

P-07 204 Centrifugal 50000 21.432 88.7 1801.62 64.02 64.020

P-08 206 Centrifugal 50000 21.432 44.3 900.81 64.02 44.4

P-09 211 Centrifugal 10000 0.3354 15.91 252.79 1.002 19.94

P-10 216 Centrifugal 91192 27.75 61.55 886.89 82.90 6378.3

P-11 214 Centrifugal 50000 21.43 0.27 5.59 64.02 22.04

P-12 220 Centrifugal 10000 0.304 61.55 886.89 206.7 15903.6

The cost estimation for centrifugal pumps within the project scope employs a set of
relations sourced from Walas et al.

𝐶= 𝐹 𝐹 𝐶

𝐶 = 1.55exp (8.833 − 0.6019 ln 𝑄√𝐻 + 0.0519(ln 𝑄√𝐻) , Q in gpm, H in ft

𝐹 = exp 𝑏 + 𝑏 (ln 𝑄√𝐻 + 𝑏 (ln 𝑄√𝐻)

For single stage 3500 rpm centrifugal compressor:

b1=0.0632, b2 = 0.2744, b3 = -0.0253

MoC factor is as follows: Carbon steel FM = 1.35

Based on the cost relations, the results obtained for centrifugal pump costs in
dollars as of 2002 and 2024 are tabulated below in Table 4.2.

52
`

Table 4.2: Cost Summary for Pumps

Total Cost Cost Cost

Equipment Quantity
(2002) (2024, USD) (2024, INR)
PUMPS 12 99968.43 199835.91 16564398.49
BACKUP
12 99968.43 199835.91 16564398.49
PUMPS

53
4.3 DISTILLATION COLUMN

4.3.1 THEORY

We use the Sinnot Procedure to calculate Diameter :

0.5
𝜌L - 𝜌V
uv = -0.17 lt2 + 0.27 lt - 0.047 * (1)
𝜌V

Here, uv is the max allowable vapour velocity (m / s)

lt is the plate spacing(m) and 𝜌 is density kg / m 3

4V w
Dc = (2)
𝜋𝜌v uv

To calculate thickness of the column, we use the standard code :

P Di
t = (3)
2 [Sa E - 0.6 P]

We will ignore effect of winds here. That will be considered in detailed design

Here, D c is column diameter (m) and Vw is max vapour rate (kg / s)

4.3.2 DISTILLATION COLUMN # 1

Borrowing the values from the simulation, we have :

N = 29
lt = 0.5
P = 1 bar

This gives the u value as

0.977 m / s

Thus, the Diameter becomes

4.02 m

54
 recommended thickness becomes : 0.00245 m

L = 29*0.5 = 14.5 m

4.3.3 DISTILLATION COLUMN #2

N = 35
lt = 0.5 m
Nf = 30
Ns olvent = 10
P = 0.5 bar
R = 2

This is an external pressure vessel and hence the caluclations need to be done accordingly

let's start with a thickness estimate of 4.7625 mm

DC = 3.48 m

Now, D o / t = 793.7
L = 17.5 m
L / Do = 4.62

This gives A = 0.00001

Thus, we get B = 140 (From CS chart becuase that's the best we have)

T = 90°C = 194°F

This gives us Factor B = 160

4B 160*4
Pall = = = 0.26878 psi
3( D o / t ) 3*793.7

But we need, Pext = 0.9 bar ⟹ 0.9 * 1.25 * 14.696 = 16.533 psi

3 Do
B = P* * = 16.533*0.75*793.7 = 9841.68
4 t

Now, we can conter calculate to get A = 0.0006

55
 Let's assume we take no stiffening rings then :

This gives that our thickness is pretty huge. Now, we can have fixed value of t and L
t recommended = 50.8 mm

After removing milling and corrosion correction, we get tmin = 57.06 mm

Also, we have a fixed value of L = 17.5 m

Now, let's see the different intersection values for A = 0.0006

If we still get the same D, we get Do / t = 79

But if we take this, we get A = 0.0003

Clearly, this is not enough even with the thickest available sheet.

Lets say the column is broken into 2 parallel columns. D goes down by 1.414

Thus, D o / t = 55.86

using this, we get Factor A = 0.0006

Thus, we need 2 columns each with thickness of 50.8 mm

But observe that we can simply circumvent this problem by simply including stiffening rings

If we have t = 11.1125 mm

Do = 3.78 m

This gives Do / t = 340.15

Let's first take L = 17.5 m and find A

Factor A is just 0.000003

Clearly, we need stiffening rings

We get L / D = 0.25. This means we would need 18 stiffening rings

Let's try one more t value = 25.4 mm

Do = 3.78 m

56
4.3.4 DISTILLATION COLUMN PRICING

Theory

Cb = 1.218exp 7.123 + 0.1478 (ln W) + 0.02488 (ln W) 2 + 0.0158 (L / D)ln(TB / T(1)

D)

W is in pounds and T in K

Ct = 456.6 exp(0.1739 D) (2)

D in ft

Cp1 = 249.6 D 0.6332 L 0.8016

D and L in ft

ρ of SS 304 is 7930 Kg / m 3

installation factor = 1.7

Cpurchase = 1.218*[f1 Cb + N f2 f3 f4 Ct + C pt ]

Cinstall = f 1 *Cpurchase

Now, lets get the value from our design

Volume Weight in Kg Weight in Lb D L TB TD

Column 1 1.744 m 3 13829.92 30494.97 13.19 47.57 352.83 281.75
3
Column 2 10.557 m 83875.61 184945.72 12.40 57.41 363.15 338.15

Subsititute to get

Cb Ct Cp1 Cpurchase Cinstall

Column 1 99869.75 4525.79 28257.51 241207.95 410053.51
Cloumn 2 354111.88 3944.856 31593.93 771705.47 1311899.3

Thus, the final installed costs are :

Column 1 : 410053.51 USD (2002)
Column 2 : 1311899.3 USD (2002)

57
4.4 FLASH SEPARATOR

4.4.1 THICKNESS

Operating pressure = 0.1 bar

Operating temperature = 120 °C = 393 K
D = 7.87 ft
L = 31.9 ft

Material of construction = SS 304 Yield stress = 205 x 10 6 Pa

Yield stress
Allowable stress = = 136 MPa
1.5

Flash vessel is treated as an external pressure vessel

However, pressure difference during operation = 0.9 bar

∴ PD = 0.9 bar × 1.25 = 1.125 bar

Assume t = 0.1875 inches

L / D = 4.05
D / t = 503

Looking at factor A and factor B chart - factor :

factor B = 250
Pall × D
factor B =
t
Pall = 0.5 psi = 0.03 Bar
Since Pall < PD , we try for a higher thickness

Repeating with commercially available metal plate thicknesses (inches)

0.25 : Pall < PD

0.3125 : Pall < PD
0.375 : Pall < PD
0.4375 : Pall < PD
0.5 : Pall < PD
0.5625 : Pall < PD
0.625 : Pall < PD
0.75 : Pall > PD

∴ treg = 0.75 inch = 19.05 mm

58
 t reg + c 19.05 + 1
t rec = m = = 22.91 mm
12.x5
1 - 100 1 - 100

∴ Taking next commercially available plate thickness,

We get trec = 25.4mm = 1 inch

4.4.2 COSTING

Calculating the material cost formulae from Walas et. al. have been used

Vertical Vessels : C = Fm Cb + Ca
𝐶a = 240 × 𝐷 0.7396 × 𝐻 0.7068 (D, H in m)
𝐶b = 1. 218 × exp 9. 1 − 0. 2889 × 𝑙𝑛(𝑊) + 0. 04576 * 𝑙𝑛(𝑊) 2 (W in lb)
Fm = 3.1 for Stainless Steel
Total purchased cost ($) = Ca + 3.1 × Cb

Material of construction = SS 304

Mass of material used = Volume of material × Density
Do3 - Di3
𝜋 2 4
Volume of material = Do - Di2 l + 𝜋
4 3 8
D = 7.87 ft = 2.40 m
l = 31.9 ft = 9.72 m
t = 1 inch = 0.833 ft
Volume of material = 26 ft 3 = 0.736 m 3
Mass of material (W) = 0.736 × 7930 = 5, 836 kg = 12, 866lbs

Ca = 2, 288$ = INR 1, 89, 625

Cb = 42, 646$ = INR 35, 34, 419
C = INR 1, 07, 92, 882
$ to INR conversions are as of 15 th March 2024

59
 4.5 HEAT EXCHANGERS

4.5.1 HEAT EXCHANGER DESIGN

There are three major heat exchangers needed :

1. To cool down the solvent stream before it goes to Distillation column
2. To cool down the distillate of the 2nd Distillation Column
3. To cool the Liquid Effluent

Heat Exchanger 1

Target : To cool down 880 TPH from 120 °C to 70 °C

Let's say we use Cooling water that goes from 35 degrees to 45 degrees

ΔTLMTD = 52.48 °C

Taking a U value of 500 W / m 2 K

Q = Cp of solvent * m␒ * Temp change

880*1000*1000
Q = 330 J / mol. K * mol / s * 50 K
3600*150

Q = 26.89 MW

Q = UAΔTLMTD

This gives us an Area of 1024.73 m 2

Heat Exchanger 2

Target : To cool down the product of flow 160 TPH from 65.65 to 45°C

Let's say we use Cooling water that goes from 35 degrees to 40 degrees

ΔTLMTD = 16.37 °C

Taking a U value of 500 W / m 2 K

Q = Cp of product * m␒ * Temp change

160*1000
Q = 2949 J / Kg. K * Kg / s * 20 K
3600

60
 Q = 3.93 MW

This gives us an Area of 320.26 m 2

Heat Exchanger 3

Target : To cool 66.83 TPH from 120 °C to 45 °C

Let's say we use Cooling water that goes from 35 degrees to 40 degrees

ΔTLMTD = 32.26 °C

Taking a U value of 413.99 W / m 2 K

Q = Cp of feed * m␒ * Temp change

(56.34*4186 + 5.51*2949 + 5.9*350) 66.83*1000
Q = J / Kg. K * Kg / s * 75 K
66.83 3600

Q = 5.29 MW

This gives us an Area of 271.28 m 2

Summary :

Heat Exchanger Th (°C) Tc (°C) Area m 2

HX - 1 120 - 70 35 - 45 1024.73
HX - 2 65.65 - 45 35 - 40 320.26
HX - 3 120 - 45 35 - 40 271.28

61
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4.5.2 HX COSTING

The cost estimation for heat exchangers within the project scope employs a set of
relations sourced from Walas et al.

We have assumed that all our coolers are shell and tube heat exchangers and fixed
head.

𝐶 = 1.218𝑓 𝑓 𝑓 𝐶

𝐶 = 𝑒𝑥𝑝 [8.821 − 0.30863(𝑙𝑛𝐴) + 0.0681(𝑙𝑛𝐴) ]

𝑓 = 𝑒𝑥𝑝 [−1.156 + 0.0906(𝑙𝑛𝐴)]
𝑓 = 0.7771 + 0.04981(𝑙𝑛𝐴)

𝑓 = 𝑔 + 𝑔 (𝑙𝑛𝐴)

For Stainless Steel 304, g1 = 0.8193 and g2 = 0.15984

Table 4.3: Cost Summary for Coolers

Cost Cost
Equipment Area (m2) Total Cost (2002)
(2024, USD) (2024, INR)

Cooler 1 1024.73 371544.98 742713.9565 61563559.85

Cooler 2 320.26 105322.32 210538.0538 17451499.28

Cooler 3 271.28 89241.96 178393.6071 14787046.1

62
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4.6 VALVES

4.6.1 SAMPLE CALCULATIONS for VALVE 1 for S-113

S-113 is bottoms product for DC-01 and feed for DC-02. It needs to expand to a
pressure of 0.5 bar from 1 bar.

Q = 261.625 m3/hr
Qmax = 1.1Q = 287,79 m3/hr = 1266.276 gpm
ΔP = 0.5 bar = 7.252 psi

‘Fail Close’
Valve type ⟹ Gate (good for strictly maintaining pressure drop)
MoC ⟹ Stainless Steel
T = 80.2 °C
ρ = 848 kg/m3

Design Calculations

1) Maximum allowable pressure:

ΔPw = max {68947.6 Pa , 1.5 Poperating}
= 75000 Pa = 10.877psi

2) Cv calculation:

𝑆
𝐶 =𝑄
∆𝑃

0.848
𝐶 = 1266.276 = 353.567
10.877

Chosen Valve: 6” Equal Percentage, Gate Valve

(Selected by looking at Cv Tables for standard industrial valves) 28

4.6.1 VALVE 2 for S - 121

S-113 is bottoms product for DC-02 and feed for F-01. It needs to expand to a
pressure of 0.1 bar from 0.5 bar.

63
`

The calculations done for this valve are also same as above. It is neatly summarized
in the following table.

Table 4.x: Valve Specs

Valve
Qmax ΔPw
Valve Stream S Cv Size Type
(gpm) (psi)
(inches)
Equal
1 S-113 1266.28 10.88 0.848 353.567 6 Percentage,
Gate
Equal
2 S-112 4032.81 10.00 1.028 1293.017 8 Percentage,
Gate

64
`

4.7 STORAGE VESSELS

In this process we have 4 components which are stored namely: water, isobutene,
tertiary butyl alcohol and makeup TEG (solvent). We have considered 30-day
storage for all the components.

1. 29
Isobutene storage: The isobutene is transported and stored at 1.65 bar and
70 F (21.1 °C) as a liquefied gas. We have used 12 spherical storage tanks to
store isobutene.

The thickness of the vessel is obtained from the following relation:

𝑃𝐷
𝑇 =
4(𝑆 𝐸 + 0.4𝑃)

Here,
P = Design pressure = 3.628 atm = 0.367 MPa
Sa = Allowable stress = 120 MPa (Sa = 180/1.5 = 120 MPa)
E = Weld joint efficiency = 0.85

Total weight of Isobutene that need to be stored = 71412336 kg

Density of liquid Isobutene = 587.9 kg/m3
Total Volume of Isobutene = 1201470.2 m3
Volume of each tank = 10122.02 m3
Diameter of each tank = 28.52 m
Thickness (tregulation) = 25.61 mm

We have considered corrosion thickness of 2 mm and a milling tolerance of

12.5%

trec = 31.75 mm

2. Water storage: The water is taken from Rangmati river near Jamnagar and
stored at 1 bar and 35 °C. We have used 6 cylindrical storage tanks to store
water.
3. TBA storage: The TBA produced is stored at 1 bar and 35 °C. We have used 20
cylindrical storage tanks to store TBA.
4. TEG storage: The solvent required for makeup and startup has been stored in
a single cylindrical storage tank at 1 bar and 35 °C.

𝑃𝐷
𝑇 =
2(𝑆 𝐸 + 0.4𝑃)

The cost of Field Erected Storage Tanks is as follows:

65
`

𝐶 = 1.218𝐹 exp [11.662 − 0.6104 ln(𝑉) + 0.04536(𝑙𝑛𝑉) ]

Where, V - Volume in Gallons

Here, we have used FM = 1 for carbon steel

Corrosion allowance of 2 mm has been considered for carbon steel with 12.5%
milling tolerance.

These relations give cost in $ and are valid for a base year of 2002. These have to
30

be scaled up 2024 using the following index:

CEPCI2002 = 395.6

CEPCI2024 = 790.8

Fc = 1.99898

C = Fc×C2002

Using the above correlations, the following costs of storage tanks have been
tabulated below.

Table 4.x: Storage Tanks’ Specifications

Dimensions ofOperating
each tank conditions Number Total
Process Cost
Tank Type Capacity MoC
L D t T P of tanks fluid ($ in 2024)
(m3)
(m) (m) (mm) (°C) (bar)
STR
Sphere - 28.52 31.75 21.11 1.65 12 121470.20 Isobutene CS 5679742.09
-01
STR
Cylinder 12 23 50.8 35 1 6 29901.53 Water CS 1622066.69
-02
STR
Cylinder 12 25.22 50.8 35 1 20 119812.22 TBA CS 5605530.69
-03
STR TEG
Cylinder 12 20.31 38.1 35 1 1 3885.52 CS 359857.727
-04 (Solvent)

For detailed calculation of each storage tank and cost, please refer to following
spreadsheet:
[Link]
iHfv_McH-evNk/edit?usp=sharing

66
`

4.8 EQUIPMENT LIST

Equipment Number Type

Centrifugal
Compressor 2
compressor
1. Shell and Tube
Heat
Heat Exchangers (Coolers & Heaters) 7
Exchangers
2. Kettle type HX
Distillation Column 1 Distillation Unit

Extractive Distillation Column 1 Distillation Unit

Reactor 1 Trickle Bed Reactor

Storage Tanks 3 Cylinder

Storage Tanks 1 Sphere

Pumps 24 Centrifugal Pump

Flash Tank 1 Vertical Flash Tank

Valves 2 Gate

67
`

Ch. 5. PLANT ECONOMICS

5.1 INTRODUCTION
Till now whatever we did was the costing of different equipment that are being used
in this plant. We haven't looked upon whether our plant is generating enough
revenues to overcome the cost incurred in building and installing equipment. In this
part, we focus on the plant economics, by estimating the plant investments,
production costs and the payback period for the tertiary butyl alcohol.

5.2 MAJOR EQUIPMENT COSTING

The tertiary butyl alcohol plant has many major equipment including reactor,
distillation columns, heat exchangers, pumps, flash tank and storage tanks. We used
costing relations provided by Peter-Timmerhaus and Stanley-Walas 31 to determine
the total purchased cost of each of these equipment.

The following data are used for the cost estimation:

 India location factor w.r.t US = 0.7

 Dollar to INR = 82.89
 Cost Index - Chemical Engineering Plant Cost Index
CEPCI2002 = 395.6
CEPCI2024 = 790.8
30
We have used Dec 2023 data as a proxy for 2024 data due to unavailability.

5.3 TOTAL PURCHASED EQUIPMENT COST

Table 5.1

Equipment Total equipment cost (Million $ in 2024)

Reactor 0.696

Flash Tank 0.1302

Storage Tanks 13.267

Distillation Columns 1.7219

Coolers 1.131

Pumps 0.356

68
`

Valves 0.00011

Total 17.34521

5.4 CAPITAL INVESTMENT ESTIMATION

Total purchased equipment costs calculated in the earlier sections are used to
calculate the total capital investment in the plant. The plant is considered to be a
Vapor-Fluid Processing plant. Working capital is taken to be as 15% of the total
capital investment. The total capital investment is determined using the method of
percentage of delivered equipment cost. India factor is considered to be 0.7.

The results of this analysis are as follows:

Table 5.2

Direct costs Percentage Normalized Cost (million $ as in 2024)

Purchase Equipment Cost 100 0.17 17.35

Equipment Delivery Cost 10 0.02 1.73

Purchased Equipment
37 0.06 6.42
Installation
Instrumentation and
36 0.06 6.24
controls
Piping 68 0.11 11.79

Electrical Systems 11 0.02 1.91

Buildings 18 0.03 3.12

Yard Improvements 10 0.02 1.73

Service Facilities 70 0.12 12.14

Land 5 0.01 0.87

Total direct plant cost 365 0.62 63.31

Indirect cost Percentage Normalized Cost (million $ as in 2024)

Engineering and
33 0.06 5.72
Supervision
Construction Expenses 41 0.07 7.11

Legal Expenses 4 0.01 0.69

69
`

Contractor’s Fee 22 0.04 3.82

Contingency 44 0.07 7.63

Total indirect plant cost 144 0.24 24.98

Fixed Capital Investment 509 0.86 88.29

Working capital (15 % of
89 0.15 15.44
TCI)

TCI (according to USA) 593 1.00 102.86

India factor 0.70

TCI (according to India) 72.00

Since our plant has a flare system, effluent treatment plant and cooling tower
requirement, the percentage for service facilities has been considered to be on the
higher side of the ranges given in Peters et. Al

Total Capital Investment = 72.00 million USD

Using an exchange rate of 1$ = 82.89 INR,

We estimate the final value of Total Capital investment = 596.808 Crore INR

5.5 RAW MATERIAL COST

The estimation of the total product cost comes from raw material cost. We require
isobutene as a raw material, which is acquired from Reliance Jamnagar Refinery
and we also require TEG which is our solvent for makeup in this process which we
are buying. Raw material cost calculation is provided below:

Table 5.3

Amount Cost
Cost (Million $/year)
(tons/year) ($/ton)
Isobutene 785535.69 1235 970.13

TEG 47100.24 1214 57.18

Total cost 1027.31

Hence, our total raw material cost = 1027.31 million USD/year

70
`

= 8515.42 Crores INR/year

5.6 REVENUE GENERATION

The plant revenue is calculated from the price of tertiary butyl alcohol which is
priced at 1.83 USD/kg.

The results are:

Table 5.4

Amount
Cost ($/ton) Price (Million $/year)
(tons/year)
TBA 970777.37 1830 1776.52

Total revenue 1776.52

Hence, our total revenue (at 100% capacity) = 1776.52 million USD/year

= 14725.574 Crores INR/year

5.7 TOTAL PRODUCT COST

Total Product cost is calculated using normalized percentage method from Peters
et. al. Since the plant is setup in India, India factor of 0.7 is applied to Operating
Labour, Supervising Labour and Admin costs.

Table 5.5

Category Factor Normalized Cost Mn $/yr

Raw material 60 0.59 1027.316276

Operating Labour 5.5 0.05 94.17065863

Supervising Labour 2 0.02 34.24387586

Utilities 15 0.15 256.829069

Repairs and Maintenance 1 0.01 17.12193793

Operating supplies 0.5 0.00 8.560968966

Laboratory charges 1 0.01 17.12193793

Patents 1 0.01 17.12193793

71
`

Fixed charges 6 0.06 102.7316276

Plant overhead 5 0.05 85.60968966

Admin costs 1 0.01 17.12193793

Distribution and
1 0.01 17.12193793
marketing
R&D cost 2 0.02 34.24387586

Total product cost 101 1 1729.315731

Hence, our total product cost = 1729.316 million USD/year

= 14334.298 Crores INR/year

5.8 PAYBACK PERIOD

The following assumptions were made while making the payback period
calculations:

 90% of Fixed Capital Investment (FCI) excluding the land costs is considered to
be depreciable over a period of 10 years.
 Average depreciation is calculated using a linear depreciation model.
 Bank interest rate of 6% over the total capital is also used.
 Final Product and Raw Material costs are assumed to be constant for-profit
calculations.

Total FCI = 60.697 million USD/ year

Total Depreciable FCI = 54.627 million USD/ year

Total Depreciation per year = 5.462 million USD/ year

Taxation Rate, including surcharge and education cess = 28.3% = 0.283

Total Product Cost = 1729.316 million USD/ year

Revenue = 1776.52 million USD/ year

Bank Interest Rate = 6%

We are taking a loan of entire TCI for 10 years; with yearly instalments of:

( )
Using =( )

72
 `

We get R = 9.7037 million USD

Gross Profit = Revenue - Total Product Cost

Gross Profit = 47.21 million USD/ year

Net Profit = (Gross Profit – Depreciation – Interest) * (1 - Taxation Rate)

Net Profit = 22.97 million USD/ year

Using 70% production capacity for year 1, 80% for year 2, 90% for year 3, 100% for
year 4 and thereafter, the following cash flow diagram was generated from the
plant production. All values in the following table are in million USD.

Table 5.6

Capacity Gross Net Cash Cumulative

Year Investment Cost Revenue Interest Depreciation
(%) profit Profit flow position
0 -72.00 -72.00 -72.00

1 70 -1,210.52 1,243.57 33.04 9.70 5.46 12.82 8.58 -63.42

2 80 -1,383.45 1,421.22 37.77 9.70 5.46 16.20 11.96 -51.46

3 90 -1,556.38 1,598.87 42.49 9.70 5.46 19.59 15.35 -36.11

4 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 -17.38

5 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 1.35

6 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 20.08

7 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 38.81

8 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 57.55

9 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 76.28

10 100 -1,729.32 1,776.52 47.21 9.70 5.46 22.97 18.73 95.01

73
 `

Figure 18: Cash Flow Projections

Detailed calculation: [Link]

ns8m8ETJDmh1JOjB8wu7kuGHOwB_Pcfk/edit?usp=sharing

Payback period = 5 years

5.9 EFFECT OF VARIOUS PARAMETERS ON PAYBACK

PERIOD
In this section, we estimate the sensitivity of the payback period on the raw
material costs and the product selling price. We have considered last 3-year prices
of both the parameters and the effect on payback period is studied.

Table 5.7

TBA Price
2010 1950 1920 1830 1660 1570 1470 1350
($/ton)
Isobutene
Payback Period (years)
Price ($/ton)
1331 2 8 - - - - - -

1235 1 1.1 1.33 5 - - - -

1115 0.41 0.5 0.58 1 6.3 - - -

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1050 0.33 0.39 0.41 0.5 1.5 6.6 - -

970 0.31 0.33 0.36 0.42 0.75 1.25 4.75 -

880 0.21 0.24 0.25 0.3 0.5 0.7 1.1 4.4

Here:

1. All the bold prices are actual prices of TBA and Isobutene in the last 3 years
2. All the payback period cells which have no value means the economic potential
is negative and no realistic payback period is there

From the above analysis, it can be concluded that the payback period is very
sensitive to the raw material cost and the product selling price.

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Ch. 6. DETAILED DESIGN

Distillation Column 1

6.1 SKIRT DESIGN

6.1.1 COLUMN 1

The design velocity for both columns is taken as 123.031 MPH, this data was taken
from “Wind zones in India”. Based on this velocity, the wind pressure (Pw) exerted
on the columns is calculated using the formula:

Wind Pressure = 0.0025𝑉 = 1449.48 Pa

where 𝑉 is the design velocity in MPH, design velocity = 123.031 MPH

Height = 14.5 m

Area = 14.5 × 4.02 𝑚 = 58.29 𝑚

The force (F) acting on each column due to wind pressure is calculated using the
formula:

F = 𝐺𝐴𝑃 = 1.4 × 1449.48 × 58.29 = 118286.84 N

where the A is area which is the product of the column height and its diameter. The
moment (M) due to this force is determined by:

M = F. = 857579.621 𝑁. 𝑚

Sa = 110316000

The regulated thickness (treg) is then calculated from the moment and the allowable
stress (Sa) as follows:

Regulated thickness,
𝑀
𝑡 =
𝜋𝑅 𝑆

= 0.0006125 m = 0.6125 mm
Recommended thickness (tr) = 4.7625 mm

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The recommended thickness (tr) is determined using the Commercially available

metal plate thicknesses table.

6.1.2 COLUMN 2

The design velocity = 123.031 MPH

Wind Pressure = 0.0025𝑉 = 1449.48 Pa

Height = 17.5 m

Area = 17.5 × 4.02 𝑚 = 70.35 𝑚

F = 𝐺𝐴𝑃 = 1.4 × 1449.48 × 70.35 = 142759.99 N

M = F. = 1249149.864 𝑁. 𝑚

Sa = 110316000

Regulated thickness (treg)

𝑀
𝑡 =
𝜋𝑅 𝑆

= 0.000892 𝑚 = 0.892 mm
Recommended thickness (tr) = 4.7625 mm

The initial thickness calculation for the column skirt was predicated on the premise
of it withstanding internal pressure. However, the actual scenario presents a
condition wherein the column is subjected to external pressure, not internal. We are
considering this because there is a big difference between the regulated thickness
and recommended thickness. Therefore, we proceed with the assumption that the
thickness determined under the assumption of internal pressure will also be
adequate for resisting an equivalent external pressure. This approach ensures that
the skirt's design is robust enough to meet the structural demands imposed by
external forces.

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6.2 NOZZLES

Nozzles are the entry exit of fluids inside the column. These are then connected to
the piping system. There would be nozzles around the inlets and outlets of fluids.

For the distillation column, a total of 4 nozzles will be used:

1. Feed inlet of mixture of isobutene, TBA and water mixture
2. Reflux stream from condenser
3. Vapor inlet to condenser at top
4. Bottoms stream from column

6.2.1 DIAMETER

To attain the required flow rate and pressure drop, you must choose the right
diameter for your nozzle design. In general, the flow rate and pressure drop of a
nozzle can be related using the following equation:

𝑄 = 28.9𝐷 √𝑃

𝑊ℎ𝑒𝑟𝑒 𝑄 = 𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑛𝑜𝑧𝑧𝑙𝑒 (𝑔𝑝𝑚)

𝐷 = 𝐼𝑛𝑛𝑒𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟 (𝑖𝑛)
𝑃 = 𝑁𝑜𝑧𝑧𝑙𝑒 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 (𝑝𝑠𝑖)

Refer table 6.1 for calculated diameters of all nozzles.

6.2.2 THICKNESS

Using ‘Area Compensation Method’

TR = 0.00136 mm (regulation thickness of vessel)

T = 4.7625 mm (recommended thickness of vessel)
Sa = 136.67 MPa
E=1
m = 0.125
PD = 1 bar = 105 Pa

Regulation thickness formula as per ASME codes based on inner diameter

𝑃 𝐷
𝑡 =
2 (𝑆 𝐸 − 0.6𝑃 )

tR would be different for every nozzle

t = 4.7625 mm (recommended thickness of nozzle; this is same for all nozzles)

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MT = mT
Mt = mt
H1 = min (2TR , 2tR)

 Area Lost = AL = TR × (di + 2c)

 AA1 = (T - TR – c – MT) × (di + 2c)
 AA2 = 2H1 × (t - tR – c – mt)
 AA3 = 0, as we assume the nozzles are non-protruding
 AA4 = 0 (assumption)
 AD = Area Deficit = AL – (AA1 + AA2 + AA3 + AA4)

Table 6.1: Nozzle Design Overall Summary

Flowrate Diameter Area Deficit

Nozzle tR (mm)
(gpm) (mm) (mm2)
1 230261.93 1161.78 0.4252 -4838.23
2 28386.75 407.92 0.1493 -1698.78
3 3371.64 140.58 0.0515 -585.48
4 1151.94 82.17 0.0300 -342.23

We can see that the area deficit < 0 for all nozzles, therefore none of them requires a
reinforcement plate.

Refer Appendix B] to view MATLAB code used for calculations.

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6.3 GASKET and BOLTS

6.3.1 GASKET
The steps for designing a gasket are as follows:

1. Identification of the gasket material and determination of the requisite

thickness.
2. Acquisition of the yield stress (y) associated with the chosen gasket material,
as well as the pertinent gasket factor (m).
2. Calculation of the ratio of the gasket's outer diameter (GO) to its inner
diameter (Gi).
3. Selection of an optimal inner diameter (Gi) for the gasket, ensuring there is a
sufficient clearance from the inner perimeter of the vessel.
4. Derivation of the gasket's outer diameter (GO), the mean gasket diameter (G),
and the gasket width (N).

We have selected “Iron Solid Flat metal” as the gasket material

m = 3.75

y = 52.4 MPa

𝐺 𝑦 − 𝑚𝑃
=
𝐺 𝑦 − (𝑚 + 1)𝑃

Putting the values of y and m, we get,

𝐺
= 1.0029 … … … … (1)
𝐺
𝐺 = 𝐷 + 50 𝑚𝑚
𝐷 = 4.02 𝑚
𝐺 = 4.07 𝑚
So, using the result in (1), we get
𝐺 = 4.082 𝑚
Now, the mean gasket diameter
𝐺 +𝐺
𝐺=
2
𝐺 = 4.076 𝑚
The Gasket width,
𝐺 −𝐺
𝑁= = 0.006 𝑚 = 6 𝑚𝑚
2
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6.3.2 BOLTS DESIGN

The gasket area of contact during bolt-up conditions can thus be estimated as ‘πGb’
with b suitably related to N depending on flange surface roughness characteristics.
Gasket seating force during bolt up conditions which will also be the tensile force
acting on the bolts, W2 will thus be as follows.

W2 = πGby
where, b is the effective gasket width (N/2, 3N/8, N/4 etc.)

Here, we will consider both the flange surfaces are corrugated, b is taken as N/4.

From using the value of G and y calculated in the previous section, we get

W2 = 1.017 MN.m

After the gasket has deformed to conform to the surface irregularities of the mating
flanges, it achieves complete contact across its width, designated as N.
Consequently, during normal operational conditions, the actual effective gasket
width is equivalent to its physical width. To maintain a seal and prevent leakage, the
gasket must sustain a minimum compressive stress of mP, where m is the gasket
factor and P is the internal pressure. The resulting compressive force required on
the gasket is therefore expressed by πGNmP, where G is the mean gasket diameter.

Simultaneously, the gasket exerts an equivalent and opposing tensile force on the
bolts. Additionally, the bolts are subjected to a tensile force equivalent to the end
thrust borne by the vessel closure due to the internal pressure. This end thrust force
can be calculated using the formula πG2P/4, which represents the product of the
projected area of the closure and the internal fluid pressure.

The operating load on the bolts, W1, is thus

𝑃
𝑊 = πGNmP + π𝐺 = 4.055 MN. m
4

The governing load W on the bolts is taken as the maximum of these two loads
(gasket seating force and operating load).

W = max {W1, W2}

W = 4.055 MN.m

Minimum total bolt cross-sectional area (A) can thus be calculated as:
𝑊
𝐴=
(𝑆 )

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The bolt here is ASTM A193 B7. The (Sa)bolt is 228 MPa.

𝐴 = 0.017785 𝑚

The Bolt Circle Diameter (BCD) is the diameter of the circle on which the bolt holes
are arranged. With a wrench clearance (c) of 0.02 m added to the vessel's outer
diameter of 4.02 m, the BCD is calculated to be 4.04 m.

For a bolt size of 25 mm with a root area of 355.5 mm², the minimum number of bolts
required is found by dividing the total cross-sectional area by the root area of a
single bolt. We get that we need a total of 50.98 bolts. Rounding this number off to
multiple of 4 gives us 52 bolts.

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6.5 HOLD UP and VAPOUR GAP

LV = Liquid volumetric flow rate = 261.65 m 3 / hr

DV = Vessel Diameter = 4.02 m

Assuming a liquid holdup time of 10 minutes

VL = Volume of liquid holdup = LV × 10 / 60 = 43.6 m 3
Volume of holdup VL × 4
Depth of liquid holdup = =
Vessel cross sectional area 𝜋 × D2
Depth = 3.44 m

Vapour gap can be taken approximately to be the same as liquid holdup = 3.44 m

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Ch. 7. Hazardous Waste Management

7.1 POLLUTANTS AND THEIR ADVERSE EFFECTS 33, 34, 35

Next, we will assess the environmental impact of our TBA manufacturing plant. To
do this, we will look at the effluent streams coming out from our plant - we will
identify the components, evaluate the potential environmental hazards of each, and
other related handling risks. We will also discuss the treatment methods for these
effluent streams.

7.1.1 WASTE STREAMS

Our process has 2 effluent streams, out of which 1 is gas and 1 is liquid. We’ll look at
their treatment individually. The constituents of the streams are as follows

Stream number Components State

Isobutane, Isobutene Gas

TBA, TEG Liquid

7.1.2 SAFETY

To assess the safety risks, we look at the safety diamonds of all effluents from our
plant. The safety diamond is a diagram that summarizes the potential health
hazards, fire hazards, and chemical hazards of a compound. We look at the diagram
for CO2 , H2O, TBA, and TEG since they are the final compounds leaving.

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Carbon Dioxide Water Vapour

TBA TEG

7.2 LIQUID EFFLUENT TREATMENT

7.2.1 CHARACTERIZATION OF THE TERT-BUTANOL PRODUCTION

PLANT EFFLUENT

Industrial wastewater treatment plays a crucial role in protecting our water

resources. This section outlines the treatment process designed for the effluent
stream generated by a tert-butanol production plant. The effluent stream from the
tert-butanol production process is a complex mixture with a flow rate of 146
kmol/hr. The primary component is water (56.34 TPH), but it also contains
concerning organic compounds, including tert-butanol (TBA) (5.51 TPH) and
triethylene glycol (TEG) (5.9 TPH).

The presence of these organics is a significant environmental concern. TBA and TEG
can contribute to eutrophication, a process where excess nutrients stimulate

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excessive plant growth in bodies of water. This rapid plant growth can deplete
oxygen levels, harming aquatic life.

Disposing of hot effluent streams into waterways is another environmental concern.

Hot water can disrupt natural temperature cycles, impacting fish spawning and
other aquatic life processes. Therefore, it's important to cool the effluent stream
before treatment.

7.2.2 INDUSTRY STANDARDS FOR WASTEWATER DISCHARGE

Discharges of industrial wastewater are subject to regulations to protect water

resources. Two key metrics that regulate wastewater quality are chemical oxygen
demand (COD) and biological oxygen demand (BOD).

 Chemical Oxygen Demand (COD): COD measures the oxygen required to

chemically oxidize all organic and inorganic matter in a water sample. A high
COD indicates a high concentration of pollutants that can deplete oxygen
levels in waterways.
 Biochemical Oxygen Demand (BOD): BOD measures the amount of oxygen
required by microorganisms to decompose organic matter in water over a
specific time period (typically 5 days at 20°C). A high BOD indicates a high
concentration of biodegradable organic matter that can deplete oxygen
levels as microorganisms decompose it.

BOD is generally considered a more specific indicator of the potential impact of

wastewater on aquatic life compared to COD, as it only considers biodegradable
organic matter. However, BOD analysis is a laboratory test, whereas COD can be
determined more rapidly.

Industrial wastewater regulations utilize COD and BOD to assess water quality.
BOD, typically limited to 30 ppm, reflects the impact on aquatic life. Additionally,
regulations limit effluent temperature to prevent thermal shock. A common
standard restricts discharge temperature to 7°C above the receiving water body's
ambient temperature. This safeguards aquatic ecosystems.

7.2.3 BOD ESTIMATION

We can’t calculate BOD directly as experiments determine it. However, we can

calculate COD, which is a good estimate of the BOD value. The following are the
reactions to be considered:

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C4H9OH + 6O2 -> 4CO2 + 5H2O

C6H14O6 + 9O2 -> 6CO2 + 7H2O

Converting mass flow rates to molar flow rates, we get TBA = 73.5 Kmol/hr and TEG
= 33.5 kmol/hr.

Oxygen needed = 742.5 kmol/hr = 23.76 TPH

This gives a COD of 518777.3 ppm

Clearly, this indicates that BOD is also a very high value (of the order 106 PPM), and
the stream needs to be treated before discharging.

7.2.4 ACTIVATED SLUDGE PROCESS: A BIOLOGICAL SOLUTION 36

The high COD in the effluent stream from the tert-butanol production plant
necessitates treatment to reduce its organic content before discharge. A biological
treatment method, the activated sludge process, is well-suited for this purpose.

The activated sludge process is a

widely used and effective biological
wastewater treatment technology that
utilizes microorganisms to remove
organic pollutants from
wastewater. Here's a breakdown of
the key stages involved:

Figure 19: Activated Sludge Process

1. Equalization: The raw effluent stream first enters an equalization tank. This tank
serves to homogenize the flow rate and composition of the influent stream over
time. Fluctuations in flow rate and organic content are common in industrial
wastewater. The equalization tank helps to ensure a more consistent stream
entering the biological treatment stage, optimizing treatment efficiency.

2. Biological Treatment in an Aeration Tank: After equalization, the effluent

stream flows into the aeration tank, the heart of the activated sludge process. The
aeration tank is a large tank that houses a mixture of wastewater and activated
sludge, a suspension of microorganisms (bacteria and protozoa) that have been
clumped together into flocs. The aeration tank is continuously aerated to provide a
constant supply of dissolved oxygen for the microorganisms.

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The microorganisms in the activated sludge consume the organic pollutants (TBA
and TEG) in the wastewater stream as food for their growth and reproduction. This
biological process is called biodegradation. As the microorganisms feed on the
organic pollutants, the COD of the wastewater is significantly reduced.

3. Solids Separation in a Secondary Clarifier: Following biological treatment in

the aeration tank, the effluent stream containing the treated wastewater and the
activated sludge mixture flows into a secondary clarifier. The secondary clarifier is a
large settling tank that allows the heavier activated sludge to settle out of the
wastewater due to gravity. The settled sludge, with a high concentration of
microorganisms, is then recycled back to the aeration tank through a recycle
stream. This recycled sludge maintains a high concentration of microorganisms in
the aeration tank, ensuring efficient biodegradation of incoming pollutants.
The treated wastewater exiting the secondary clarifier, with a significantly reduced
organic content, can then be discharged to a publicly owned treatment works
(POTW) or reused in the tert-butanol production process, depending on regulatory
requirements and water quality standards.

The activated sludge process offers several advantages, including its effectiveness
in removing a wide range of organic pollutants, its relatively simple operation, and
its ability to handle fluctuating organic loads. However, maintaining optimal
conditions in the aeration tank, such as dissolved oxygen concentration and solids
concentration, is crucial for efficient treatment.

7.2.5 SIZING THE AERATION TANK: CONSIDERATIONS AND

CHALLENGES

The activated sludge process relies on maintaining a sufficient population of

microorganisms within the aeration tank to effectively biodegrade pollutants. A key
factor in achieving this is the aeration tank volume.

One common formula used to estimate the required aeration tank volume (V) is:

V = (SRT × Q × Influent SS) / (MLSS)

Where:
V = Aeration tank volume (m³)
SRT = Solids Retention Time (h) - This represents the average amount of time solids
(microorganisms) spend in the aeration tank system.
Q = Influent wastewater flow rate (m³/hr) [Conversion needed!*]
Influent SS = Influent suspended solids concentration (kg/m³)

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MLSS = Mixed liquor suspended solids concentration (kg/m³)

Values used in our case:
SRT: 10 hours
Q: 57.21 Tonnes/hr (Calculated below)
Influent SS: 3 kg/m³
MLSS: 0.3 kg/m³

We know that the density of water is 1 Tonne / m3, and the stream is mostly water.
Hence, the flow rate becomes 57.21 m3/hr.

Substituting the values, we get V = 57.21 m3.

7.2.6 COMPLETE FLOW OF TREATMENT

STEPS:

 Liquify the stream by cooling it to 40 °C

 Pump up to bring the pressure back to 1 atm
 Use the activated sludge method to bring down the organic content
 Check temperature and cool to 37 °C before releasing

7.3 GASEOUS WASTE MANAGEMENT

7.3.1 ADVERSE IMPACTS

Next, we will look at how we will manage the gaseous waste. We have already seen
earlier that the gaseous effluents are isobutene and isobutane, and they are used as
fuel. We also look at the potentially hazardous effects of these compounds on the
environment and health in case of leakage.

Isobutene

Health effects Result

Acute Toxicity Low acute inhalation toxicity

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Oral / inhalation / dermal High vapor concentrations may produce narcosis or

cause asphyxia by reducing the available concentration
of oxygen

Genotoxicity / Not mutagenic/genotoxic. Low concern for repeated

Mutagenicity exposure toxicity.
Carcinogenicity

Environmental effects Result

Aquatic Toxicity Not expected to be toxic to aquatic life

Biodegradation, Rapidly biodegradable and not expected to accumulate

Bioaccumulation

Isobutane

Health effects Result

Acute Toxicity Inhaling Isobutane can irritate the nose and throat

Oral / inhalation / Exposure to high concentrations can cause dizziness,

dermal lightheadedness, irregular heartbeat and passing out Very
high levels can cause suffocation from lack of Oxygen with
loss of consciousness, convulsions, coma and death

Genotoxicity / Genetic defects and cancer has been observed but no strong
Mutagenicity conclusive evidence
Carcinogenicity

Environmental Result
effects

Aquatic Toxicity Toxic for aquatic life

Biodegradation, Low potential for bioconcentration in aquatic organisms

Bioaccumulation

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7.3.2 GASEOUS STREAM AND ITS TREATMENT

Major effluent gaseous stream is S-115 leaving from top of first distillation column.
The components of the gaseous stream are isobutane and isobutene. We have 2
options to process this stream.

1. Separate them and sell them

2. Use as fuel

Our production rate for them is 0.991 TPH isobutane and 0.978 TPH isobutene. This is
almost a 50 - 50 mixture of the 2 byproducts and is not a commercial product to be
sold. For us to sell them, we will first have to separate them. The separation costs for
such a small quantity of products is going to be very high, looking at the relatively
smaller revenue from selling them, so it would not make economic sense to do this.

Hence, we use the isobutane and isobutene as fuel in the reactor wherever heating
is needed as utilities. The combustion will produce water and carbon dioxide, both if
which are safe for the environment and do not need to be processed.

7.3.3 REGULATORY STANDARDS

The current regulatory standards for isobutane and isobutene emissions are as
follows:

 NIOSH: The recommended airborne exposure limit (REL) for isobutane is 800
ppm averaged over a 10-hour work shift

 ACGIH: The threshold limit value (TLV) for isobutane and isobutene is 1,000
ppm (as Aliphatic hydrocarbon gasses) averaged over an 8-hour work shift

Since our emissions are way higher than the norms, we flare the stream. The
calorific value of isobutane is also comparable to methane, implying that it is a very
good fuel.

7.3.4 FLUE GAS COMPOSITIONS

We used simple mole balance for combustion reactions for components present in
S115, to calculate oxygen required to completely oxidize them. Upon calculating
oxygen requirement, we accounted for the air needed. Furthermore, we took around
20% excess, to avoid unnecessary coke formation. These are the final compositions
of flue gas.

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Flue gas composition Source (kg/hr) Permissible limit

CO2 (18.67 %) 7251.2 1.08 kg/m3

H2O (8.45 %) 3283.2

N2 (68.66 %) 26664.42

O2 (4.22 %) 1636.48

7.3.5 GAUSSIAN PLUME DISPERSION MODEL

Concentration of the pollutants on the ground is calculated using Gaussian plume

dispersion model since the emissions from the plant are steady state continuous
emissions. The formula for steady state continuous plume dispersion is:

Figure 21: Formula for calculating the concentration through the Gaussian Plume
Dispersion Model

Here,

x,y,z = distance from source (x = downward, y = crosswind, z = vertical)

C = concentration (kg/m3) at location x,y,z;

Gv = vapor emission rate (kg/s)

H = height of source above ground level + Plume rise (m);

U = wind velocity (m/s);

σy, σz = dispersion coefficients (m), the function of downward dispersion

The following considerations have been taken while considering the stack height:

● Pollutant concentration on the ground should be less than emission limits

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● The heat effects due to radiation on the ground should be up to a safe level

Hence, a stack height of 100m is considered (Standard value)

Wind speed (m/s) @ Jamnagar ~ 6m/s

σy = 6.91 m | σz = 8.94 m | y = z = 0

After calculating, C (kg/m3) = 12.20 kg/m3 for CO2 and 1.2 kg/m3 for NO2

7.3.6 TREATMENT OF CO2

Our flue gas has 12.20 kg/m³ of CO2 and the permissible limit is just 1.08 kg/m³. CO2
produced in our plant is more than 10 times the permissible limit. Therefore, treating
it before release is necessary.

We will use the Amine-based Carbon Capture (scrubbing).

It is a regenerative process that uses amine as a solvent, which removes CO2 from
the flue gas. Also, reversing this reaction gives us pure CO2 for capture. Thus, freeing
up the solvent for re-use. This is a well-proven method and a commercially available
technology.

Figure 20: A simple flow diagram of how amine-based carbon recovery system
works

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Ch. 8. Other Topics

8.1 MATERIAL of CONSTRUCTION

Material of Construction chosen is SS 304 since we are dealing with mildly acidic
solutions.

When comparing 304 stainless steel vs 316, they both have pros and cons to consider
when deciding which one to use for different applications. We used the following
parameters:

1. Corrosion Resistance: 316 stainless steel offers superior resistance to salt and
other corrosives compared to 304, making it ideal for products exposed to harsh
chemicals or marine environments.

2. Economical Choice for Less Harsh Conditions: For applications where strong
corrosion resistance is not critical, 304 stainless steel is a more cost-effective option.

3. Interchangeability: In many cases, 304 and 316 stainless steels can be used
interchangeably, depending on the specific environmental conditions and
requirements.

4. Chromium Content: Both 304 and 316 stainless steels have high chromium content,
providing a protective layer against corrosion and rust.

5. Carbon Steel Vulnerability: Unlike stainless steel, carbon steel, which is high in
carbon, is prone to quick corrosion and rust when exposed to moisture.

6. Selection for LLE Method: Given the use of 67% concentrated H2SO4 in the liquid-
liquid extraction (LLE) method, SS 316 is chosen for the bubble column, LLE, and
reactor due to its corrosion resistance, with costs ranging around 240 - 280 Rs/Kg.

7. Distillation Tower Material: For the distillation tower, where corrosion resistance is
less of a concern, either carbon steel or SS 304 can be used, considering cost and
application requirements.

Cost of materials:

37
SS 316: 255 Rs/kg
25
SS 304: 195 Rs/kg

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8.2 SAFETY

A hazard is something which has the potential to cause an accident and every
manufacturing process comes with their own sets of hazards. Some common
hazards in most of the industries are Slips, trips and falls, Electrical Hazard or
Environmental Hazard.

Hazards happen because of actions that aren't safe, the characteristics of materials,
things that are left out, and situations that are not safe. A hazard is something that
can cause harm or danger to health. The best way to avoid accidents and health
problems is to get rid of the hazard or make sure it is well controlled.
The HE is divided into two categories:

1. Qualitative HE Technique
2. Quantitative HE Technique

Among the HE techniques, industries commonly utilise What-If Analysis, What-

If/Checklist Analysis, and HAZOP. Conducting a hazard evaluation study involves
gathering essential information, including the type of chemicals, catalyst properties,
data on reacting chemicals, kinetic data like reaction order and rate constants,
equilibrium considerations, area electrical classification drawings, equipment
electrical classifications, mechanical equipment data sheets, and a diverse range of
material property information and most of the info are provided the material safety
data sheet

Of the various HE techniques we selected HAZOP since it is more comprehensive

than other techniques such as what-if analysis, and suitable for a qualitative study.
HAZOP is commonly used in analysing processes during the design stage or after
the design stage. Different versions of HAZOP Analysis technique is applied in the
chemical industry

The primary objective of HAZOP Analysis is to methodically examine processes or

Plant operations to assess whether deviations in the process could result in
undesirable consequences. This analytical method is suitable for continuous and
batch processes and can be adapted to evaluate documented procedures. The
outcomes of a HAZOP Analysis encompass the identification of hazards and
operational issues. It involves suggesting modifications to the design, making
changes in procedures, etc., to enhance the overall system. Additionally, the analysis
recommends conducting further studies in areas where conclusions are challenging
due to a lack of knowledge about the design.

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The HAZOP procedure uses the following steps to complete an analysis:

a. Defining individual process units
b. Selecting nodes
c. Definition of parameters
d. Application of guide words
e. Identify source
f. Evaluate consequences
g. Recommendations for safety and hazard mitigation

HAZOP STUDY OF DISTILLATION COLUMN

98
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Process Nodes: Parameters Deviations Possible causes Consequences Recommendations

unit

Distillation Reboiler Flow No flow Pipe blockage, Column dry out, Installation of alarms
column Control valve shut, Possible dangerous
Less flow Valve fail, concentration, Installation of
no operation, controllers
Condenser Changes in product
quality Placement of valves
More flow Control valve is fully
opened in case of more Product loss, Emergency shutdown
flow Changes in product options
quality,
Ineffective Instruct operator on
separating process, procedure

Reactive Temperature Low Instrumentation

section temperature failure,
Less steam flow,
Loss of heating

High More steam flow, Separation cannot be

temperature Exchanger tube failure, done,
High steam pressure, Film boiling in
Cooling water in column and reboiler
condenser failure. Phase effect

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Pressure Low Vapour line leakage Low efficiency of

pressure separation,
Loss of products

High High Vapour pressure, Low efficiency of

pressure Pressure indicator separation,
controller fail Rupture of column or
other related
equipment

100
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101
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References

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0(CH3)3COH

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12 Saussine, L., Robine, A., Mimoun, H., & Ifpen, I. E. N. (n.d.). FR2558826A1 - Synthesis
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[Link]

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[Link]

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[Link]

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[Link]

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[Link]

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Isobutylene. III. Separation of Tertiary Butyl Alcohol by the Extraction with Solvents.
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24 Masaharu Katuno, Synthesis of Tertiary Butyl Alcohol by the Hydration of

Isobutylene. III. Separation of Tertiary Butyl Alcohol by the Extraction with Solvents,
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%20flammable%2C%20colorless,of%2024%20psig%20at%2070F

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Datasheet. Tert-Butyl Alcohol. CAMEO Chemicals.
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6%[Link]?v=1632947300283

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105
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Appendix A]

Data for Figure 4: Cost vs α for various solvents

Vapour
Relative Molecular
Solvent Cost (Rs/kg) pressure (in Boiling Point
volatility Weight
Pa at 25 °C)
Polyethylene
1.95 90 200 NA
glycol 200
Polyethylene
1.34 105 300 NA
glycol 300
1,4-Butanediol 1.38 60 90.12 1.9 235
Dipropylene
1.32 180 134.18 2.1331 232
glycol
O Triethylene
2.33 70 150.17 n/a 288
glycol
2-Methyl-1,3-
1.32 250 90.12 5.3328 214
propanediol
Diethylene
1.26 90 106.12 1.3332 245
glycol
Polyethylene
1.92 115 400 1.3332 NA
glycol 400
Methylbenzoa
1.21 245 136.15 53 198
te
Anisole 1.31 174 108.14 468 154
Diisobutyl
1.42 50 142.26 319.9728 216
ketone
n-Butyl
1.14 125 116.16 1999.83 126
acetate
Hexyl alcohol 1.7 589 102.18 133.322 155
isodecanol 1.63 170 170.29 2.7597 257
alpha-Methyl
1.36 1000 122.16 n/a 205
benzyl alcohol
Cyclododecan
1.47 130 182.31 0.050529 272
ol
Diisobutyl
1.94 145 130.22 40.3965 194
carbinol
2-Octanol 1.47 90 130.22 31.9972 180
3-Heptanone 1.7 100 114.19 533.288 157
Dinnethyl
1.51 480 78.13 55.9952 189
sulfoxide
2-
Hydroxyaceto 1.32 3000 136.15 26.6644 180
phenone

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Dimethyl
1.35 70 73.09 493.2914 153
formamide
Isophorone 1.54 199 138.19 40 215
2-Undecanone 1.33 75000 170.29 5.33288 245
Mesityl oxide 1.83 210 136.15 1199.898 140
Benzyl
1.28 270 212.25 0.0298 323
benzoate
Ethylene
glycol 1.23 1800 134.13 10.31912 230
diacetate
Ethyl
1.32 7500 166.21 6.6661 243
salicylate
3-Hexanone 1.97 5000 98.15 1853.176 144
Ethylene
glycol phenyl 2.49 100 162.22 0.9332 247
ether
Isobutylbutyr
1.22 250 130.22 n/a 144
ate
Ethylene
glycol butyl 1.2 85 162.22 n/a 171
ether
Ethylbutyrate 1.62 250 116.16 2066.491 121
Methyl
2 23500 130.22 495.9578 186
caproate
Amyl
1.4 500 144.22 n/a 208
propionate
Ethyl n-
1.38 1000 130.22 626.6134 195
valerate
Dimethyl
1.4 325 194.19 0.4132 282
phthalate
Dimethyl
1.28 124 174.2 n/a 205
adipate

107
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Appendix B]
MATLAB Code for Nozzle Calculations

%% DIAMETER CALCULATIONS

% [Feed Reflux VtoC Boilup]

P = [14.5038 14.5038 14.5038 14.5038]; % in psi

sP = sqrt(P);
Q = 4.403*[52296.6 6447.138 765.76 261.625]; % in gpm

sD = (Q./sP)/28.9;

D = sqrt(sD); % in inches
di = 25.4*D; % in mm

disp(di)

%% THICKNESS CALCULATIONS

Tr = 0.00136; % in mm
T = 4.7625; % in mm
Sa = 136.666667*1000000; % Allowable Stress in Pascal
E = 1;
m = 0.125;
PD = [100000 100000 100000 100000]; % Design Pressure in Pascal

for i = 1:4
tr_m(i) = ((PD(i)*di(i)*0.001)/(2*(Sa*E-0.6*PD(i)))); % in m
end

tr = tr_m*1000; % regulation thickness of nozzles in mm

disp(tr)

t = 4.7625; % in mm

MT = T*m;
Mt = t*m;
ET = T - (Tr + MT); % Extra thickness available in vessel in mm

H1 = 2*Tr;

for i = 1:4
AL(i) = (di(i))*Tr; % Area lost in mm2
A1(i) = ET*(di(i)); % Aa1 in mm2

et(i) = t - (tr(i) + Mt); % Extra thickness available in nozzle in mm

A2(i) = 2*H1*et(i); % Aa2 in mm2

AD(i) = AL(i) - (A1(i) + A2(i)); % Area Deficit in mm

end

disp(AD)

108