Production of 30 000 Tons Per Year of Hydrogen Peroxide From Methanol by Enzymatic Conversion

PRODUCTION OF 30,000 TONS PER YEAR OF
HYDROGEN PEROXIDE FROM METHANOL

BY ENZYMATIC CONVERSION
Session: 2012-2016
Project Supervisor: Prof. Dr. Shahid Raza Malik
Co-Supervisor: Engr. Muhammad Awais Ashraf
Group Members
Ahmad Mukhtar 2012-UET-IEFR/CHEM/FD-92
Mehar U Nisa 2012-UET-IEFR/CHEM/FD-83
Muhammad Waqar 2012-UET-IEFR/CHEM/FD-46
Muhammad Zain Feroz 2012-UET-IEFR/CHEM/FD-44
Rana M. Adeem Habib 2012-UET-IEFR/CHEM/FD-73
DEPARTMENT OF CHEMICAL ENGINEERING

National Fertilizer Corporation-Institute of Engineering and
Fertilizer Research (NFC-IEFR)
FAISALABAD, PAKISTAN
PRODUCTION OF 30,000 TONS PER YEAR OF HYDROGEN
PEROXIDE FROM METHANOL BY ENZYMATIC CONVERSION
This project is submitted to the Department of Chemical Engineering,
NFC-IEFR Faisalabad, PAKISTAN
for the partial fulfillment of the requirements for the
Bachelor’s Degree
in
CHEMICAL ENGINEERING
Internal Examiners:
Project Supervisor Co-Supervisor
Prof. Dr. Shahid Raza Malik Engr. Muhammad Awais Ashraf

Director Lecturer,
NFC-IE&FR-Faisalabad, PAKISTAN Department of Chemical Engineering
NFC-IE&FR-Faisalabad, PAKISTAN
External Examiners:
Dr. Muhammad Jamil

Head, Department of Chemical Engineering
The University of Faisalabad, PAKISTAN
DEPARTMENT OF CHEMICAL ENGINEERING

National Fertilizer Corporation-Institute of Engineering and Fertilizer
Research (NFC-IEFR)
FAISALABAD, PAKISTAN
DEDICATION
This Project Report is dedicated to the

Lord, Designer, and Builder of the most Complex Processing Plant;
The Human Body,
It’s accurate and Sophisticated Fluid Transportations, Gas Absorption, Filtration, Chemical
Reactions, and Electronic Control Systems, with Practical, Mechanical, and Structural
capabilities are a product of his engineering skills that we strive to understand and duplicate.
We should also not forget our Loving Parents whose utmost Love, Grave, and Struggle brought
us to Height of Knowledge
and all those who Love, Care, and Pray for us.
ACKNOWLEDGEMENT
All praises with our deepest gratitude to Almighty ALLAH, whose uniqueness, oneness and
wholeness is unchallengeable. All the respects to His Holy Prophet Hazrat Muhammad (PBUH),
who’s enlightened us to understand the mysteries of life.
We acknowledge the depth of our gratitude and heart full thanks to highly learned and respected
Project Supervisor Prof. Dr. Shahid Raza Malik and Co-Supervisor Engr. Muhammad Awais
Ashraf for their constructive suggestions, guidance and encouragement during our research
project.
We are also thankful to Prof. Dr. Shahid Raza Malik, Director, NFC Institute of Engineering and
fertilizer Research Faisalabad, Pakistan for providing us all the necessary facilities, guidance and
moral support to accomplish this work.
We are also thankful to Dr. Waqar Ali Khan, Head, Department of Chemical Engineering, NFC
Institute of Engineering and fertilizer Research Faisalabad, Pakistan and all other department
faculty and staff for their encouraging attitude and kind help for completing this process.
We cannot remain without expressing our heartiest gratitude to our parents who made great
devotion to our studies and prayed for our success.
Authors
ABSTRACT
Hydrogen peroxide is a chemical compound with the formula H2O2. In its pure form, it is a
colorless liquid, slightly more viscous than water; however, for safety reasons it is normally used
as an aqueous solution. Hydrogen peroxide is the simplest peroxide (a compound with an
oxygen–oxygen single bond) and finds use as a strong oxidizer, bleaching agent and disinfectant.
Concentrated hydrogen peroxide, or "high-test peroxide", is a reactive oxygen species and has
been used as a propellant in rocketry.
The process uses the enzyme, methanol oxidase, to convert alcohol and oxygen to formaldehyde
and hydrogen peroxide. The goal is to produce 30,000 tons/y of hydrogen peroxide and using an
enzymatic process. Formaldehyde, methanol, and hydrogen peroxide are considered carcinogenic
and/or hazardous materials. In light of this, a process design was made that minimizes the waste
and emissions generated.
The enzyme, methanol oxidase, catalyzes the reaction in the continuous-stirred tank fermenter.
HFMs were used in an ultrafiltration unit off of the continuous-stirred tank fermenter to recover
the enzyme for recycle.
Table of Contents
List of Tables i
List of Figures iii
List of Symbols iv
Chapter No. 1: INTRODUCTION 01
1.1 Discovery 01
1.2 Physical Properties 02
1.3 Chemical Properties 04
1.4 Uses of Hydrogen Peroxide 06
1.5 Storage 09
1.6 Formaldehyde 10
Chapter No. 2: MANUFACTURING PROCESSES FOR HYDROGEN 12

PEROXIDE
2.1 The Barium Peroxide Process 11

2.2 Electrolytic Method 12
2.3 Direct Combustion of Hydrogen and Oxygen 12
2.4 Autoxidation Processes 12
2.5 Nitrogen Compound Autoxidation 13
2.6 Hydrocarbons Autoxidation 13
2.7 Ethyl-Anthraquinone Autoxidation Process 14
2.8 Enzymatic Process 15
Chapter No. 3: PROCESS DESCRIPTION 17
3.1 Background 17
3.2 Process Description 17
3.3 Process Flow Diagram 18
Chapter No. 4: ENZYME PREPARATION AND PURIFICATION 20
4.1 Introduction 20
4.2 Growth of Hansenula Polymorpha and Enzyme Induction 20
4.3 Enzyme Purification 20
4.4 Enzyme Productivity 21
4.5 Stability of Methanol Oxidase in the Presence of Methanol 21
4.6 Enzyme Activity as a Function of Enzyme Concentrations 22
4.7 Activity of Methanol Oxidase and Products Stability in the 22
Presence of High Concentration reaction Products 22
4.8 Introduction of Oxygen into Reaction Zone 22
Chapter No. 5: MATERIAL BALANCE 25
5.1 Introduction 25
5.2 Material Balance on Distillation Column (T-101) 26
5.3 Material Balance on Flash Column (V-103) 27
5.6 Material Balance on Flash Column (V-101) 32
5.7 Material Balance on Fermenter (R-101) 33
5.8 Overall Balance on the Plant 35
Chapter No. 6: ENERGY BALANCE 36
6.1 Specific Heat Capacities 36

6.2 Energy Balance on Heat Exchanger (E-101) 38
6.3 Energy Balance on Fermenter (R-101) 39
6.4 Energy Balance on Flash Column (V-101) 41
6.5 Energy Balance on Distillation Column (T-101) 43
6.6 Energy Balance on Flash Column (V-103) 46
6.9 Overall Energy Balance on the Plant 54
Chapter No. 7: FERMENTER DESIGN 56
7.1 Introduction 56
7.2 Reactor Selection 56
7.3 Design Steps and Calculations 57
7.4 Specification Sheet for Fermenter 66
7.5 Specification Sheet for Agitator 66
7.6 Specification Sheet for Cooling Jacket 67
Chapter No. 8: MULTICOMPONENT DISTILLATION COLUMN DESIGN 68
8.1 Introduction 68
8.2 Types of Distillation Column 68
8.3 Column Selection 68
8.4 Selection Criteria for Trays 69
8.6 Specification Sheet for Multicomponent Distillation Column 92
Chapter No. 9: FLARE DESIGN 93
9.1 Introduction 93
9.2 Applicability 93
9.3 Factors Affecting Efficiency 94
9.5 Specification Sheet for Flare 100
Chapter No. 10: HEAT EXCHANGER DESIGN 101
10.1 Introduction 101

10.2 Selection Criteria 101
10.4 Specification Sheet Shell and Tube Heat Exchanger 108
Chapter No. 11: FLASH DRUM DESIGN 109

11.2 Design Steps and Procedure 109
11.3 Specification Sheet for Flash Drum 112
Chapter No. 12: INSTRUMENTATION AND PROCESS CONTROL 113

12.2 Instrumentation and Control Objectives 113
12.3 Components of Control Systems 114
12.4 Controllers 114
12.5 Classification of Controllers 115
12.6 Modes of Control 115
12.7 Control Schemes for Distillation Column 116
12.8 Process Instrumentation Diagram of Plant 117
Chapter No. 13: HAZOP STUDY 118

13.2 Objectives of HAZOP Study 118
13.3 Keywords used in HAZOP Study 118
13.4 How to Conduct a HAZOP Study 120
13.5 The HAZOP Study Report 122
13.6 HAZOP Study of Shell and Tube Heat Exchanger 123
Chapter No. 14: ENVIRONMENTAL IMPACTS 125

14.2 Air Pollution 125
14.3 Ozone Depletion 126
14.4 Greenhouse Effect 127
14.5 Biodiversity 129
14.6 Sustainability 130
14.7 Hydrogen Peroxide Environmental Impacts 134
14.8 Methanol Environmental Impacts 134
14.9 Formaldehyde Environmental Impacts 135
Chapter No. 15: COST ESTIMATION 136

15.2 Purchased Equipment Cost 138
15.3 Direct Cost 138
15.4 Indirect Cost 139
15.5 Total Capital Investment 139
15.6 Product Cost 139
15.7 Manufacturing Cost 140
15.8 General Expenses 140
15.9 Gross Earnings/Incomes 141
15.10 Rate of Return 141
15.11 Payback Period 141
Appendix 142
References 171
List of Tables
Table 1.1: Properties of Hydrogen Peroxide 02

Table 2.1: Comparison of Hydrogen Peroxide Manufacturing Processes 15
Table 5.1: Mole Fractions of Components in the Streams of Multicomponent 26
Distillation Column (T-101)
Table 5.2: Overall and Component Material Balance on Multicomponent 27
Table 5.3: Mole Fractions of Components in the Streams of Flash Column 28
(V-103)
Table 5.4: Overall and Component Material Balance on Flash Column (V-103) 28
Table 5.9: Mole Fractions of Components in the Streams of Flash Column 32
(V-101)
Table 5.10: Overall and Component Material Balance on Flash Column (V-101) 33
Table 5.11: Mole Fractions of Components in the Streams of Fermenter (R-101) 33
Table 5.12: Overall and Component Material Balance on Fermenter (R-101) 34
Table 6.1: Shomate Constants for Different Components 36
Table 6.2: Heat Capacities of Components at Different Temperatures 36
Table 6.3: Antoine Constants for Components 37
Table 6.4: Latent Heat of Vaporization of Components 37
Table 6.5: Overall and Component Energy Balance on Fermenter (R-101) 41
Table 6.6: Overall and Component Energy Balance on Flash Column (V-101) 43
Table 6.7: Overall and Component Energy Balance on Multicomponent 46
Table 6.8: Overall and Component Energy Balance on Flash Column (V-103) 48
Table 7.1: Specification Sheet for Fermenter (R-101) 66
Table 7.2: Specification Sheet for Agitator 66
Table 7.3: Specification Sheet for Cooling Jacket 67
Table 8.1: Equations of Bottom Operating Lines (BOL) 73
Table 8.2: Equations of Top Operating Lines (TOL) 74
Page | i
Table 8.3: Specification Sheet for Multicomponent Distillation Column (T-101) 92
Table 9.1: Specification Sheet for Flare 100
Table 10.1: Specification Sheet for Shell and Tube Heat Exchanger (E-101) 108
Table 10.2: Thermal Conductivities of Liquids 142
Table 10.3: Thermal Conductivities of Gasses and Vapors 143
Table 10.4: Thermal Conductivities of Gasses and Vapors (Continued) 144
Table 10.5: Specific Gravities and Molecular Weights of Liquids 147
Table 10.6: Viscosities of Liquids 149
Table 10.7: Viscosities of Gasses 151
Table 10.8: Approximate Overall Design Coefficients 159
Table 10.9: Tube Sheet Layouts 160
Table 10.10: Tube Sheet Layouts (Continued) 161
Table 10.11: Heat Exchangers and Condensers Tube Data 162
Table 10.12: Dimensions of Steel Pipe (IPS) 163
Table 11.1: Specification Sheet for Flash Column (V-101) 112
Table 13.1: Primary Keywords for HAZOP Study 119
Table 13.2: Secondary Keywords for HAZOP Study 119
Table 13.3: HAZOP Study of Shell and Tube Heat Exchanger 123
Table 14.1: Environmental Impacts Indicators of Metropolitan Air Quality 125
Table 14.2: Environmental Impacts Indicators of Ozone Depletion 126
Table 14.3: Environmental Impacts Indicators of Greenhouse Effect in NSE and 127
ACT
Table 14.4: Environmental Impacts Indicators for Water Resources in Key River 128
Sites
Table 14.5: Environmental Impacts Indicators of Biodiversity 129
Table 14.6: Environmental Impacts Indicators of Sustainability 132
Table 15.1: Agitator Cost Estimation (S. M. Walas) 164
Table 15.2: Distillations and Absorption Towers Cost Estimation 165
Table 15.3: Distillations and Absorption Towers Cost Estimation (Continued) 166
Table 15.4: Heat Exchangers Cost Estimation 167
Table 15.5: Pumps Cost Estimation 168
Table 15.6: Pumps Cost Estimation (Continued) 169
Table 15.7: Vessels Cost Estimation 170
Page | ii
List of Figures
Figure 1.1: Phase Diagram of Hydrogen Peroxide and Water 03

Figure 1.2: Activity Co-Efficient of Hydrogen Peroxide and Water Solutions 04
Figure 8.1: Liquid Flow Arrangement 81
Figure 8.2: Relation Between Downcomer Area and Weir Length 83
Figure 8.3: Flooding Velocity, Sieve Plates 84
Figure 8.4: Entrainment Correlation for Sieve Plates 85
Figure 8.5: Weep Point Correlation 86
Figure 8.6: Discharge Co-Efficient, Sieve Plates 88
Figure 10.1: Design Procedures for Shell and Tube Heat Exchangers 102
Figure 10.2: Specific Heats of Liquids 145
Figure 10.3: Specific Heats of Gasses 146
Figure 10.4: Latent Heats of Vaporization 148
Figure 10.5: Viscosities of Liquids 150
Figure 10.6: Viscosities of Gasses 152
Figure 10.7: Caloric Temperature Factor 153
Figure 10.8: LMTD Correction Factor 154
Figure 10.9: Tube Side Heat Transfer Curve 155
Figure 10.10: Tube Side Friction Factor 156
Figure 10.11: Shell Side Heat Transfer Curve 157
Figure 10.12: Shell Side Friction Factor 158
Figure 12.1: Process Instrumentation Diagram of Plant 117
Figure 13.1: How to Conduct HAZOP Study 121
Page | iii
List of Symbols
A, B Antione Constants
A, B, C Shomate Equation Constants
Aa Active Area
Aap Area under Apron
Ac Column Area
AD Downcomer Area
Ah Area of Hole
AN Net Area
B Baffle Spacing
Bv Heating Value
C Clearance
CP Specific Heat Capacity
Cs Concentration of Sugar
D Diameter
Da Impeller Diameter
Dc Diameter of Column
De Equilent Diameter
Dh Diameter of Hole
Di Inside Diameter
Do Outside Diameter
E Height of Impeller
Eo Column Efficiency
Ej Joint Efficiency
FLV Flow Parameter
Fs Safety Factor
g Gravitational Acceleration
G Gravitational Constant
Gs Mass Velocity
H Height
Hi Inside Heat Transfer Co-Efficient
Ho Outside Heat Transfer Co-Efficient
Hw Weir Height
ID Inside Diameter
Ip Hole Pitch
J Wall Thickness
Jh Jh Factor (Constant)
Km Turnover Number
L Length
Lw Weir Length
M 1 , M2 , … Material Balance Streams
Page | iv
N Actual Number of Plates
NB Number of Plates below the Feed Plate
ND Number of Plates above the Feed Plate
Nm Minimum Number of Plates
Ns Rotational Speed
OD Outside Diameter
P Pressure
Q1, Q2, … Energy Balance Streams
Qc Condenser Duty
QR Re-Boiler Duty
Qref Heat Removed by Refrigerant
R Actual Reflux Ratio
RD Dirt Factor
Re Reynolds’s Number
Rmin Minimum Reflux Ratio
S Stress
S1, S2, … Shape Factors
T Temperature
tR Residence Time
Uc Clean Overall Co-Efficient
UD Overall Design Co-Efficient
Uf Flooding Velocity
Umin Minimum Design Vapor Velocity
Vm Volume of Mixture
VR Volume of Reactor
VT Volume of Tank
W Width of Impeller
X Conversion of Reaction
Page | v
Chapter No. 1 Introduction
Chapter 1
INTRODUCTION
Hydrogen peroxide is a chemical compound with the formula H2O2. In its pure form, it is a
colorless liquid, slightly more viscous than water; however, for safety reasons it is normally used
as an aqueous solution. Hydrogen peroxide is the simplest peroxide (a compound with an
oxygen–oxygen single bond) and finds use as a strong oxidizer, bleaching agent and disinfectant.
Concentrated hydrogen peroxide, or "high-test peroxide", is a reactive oxygen species and has
been used as a propellant in rocketry.
Hydrogen peroxide is often described as being "water but with one more oxygen atom", a
description that can give the incorrect impression of significant chemical similarity between the
two compounds. While they have a similar melting point and appearance, pure hydrogen
peroxide will explode if heated to boiling, will cause serious contact burns to the skin and can set
materials alight on contact. For these reasons it is usually handled as a dilute solution (household
grades are typically 3–6% in the U.S. and somewhat higher in Europe). Its chemistry is
dominated by the nature of its unstable peroxide bond.
1.1 Discovery:
Hydrogen peroxide was first described in 1818 by Louis Jacques Thénard, who produced it by
treating barium peroxide with nitric acid. An improved version of this process used hydrochloric
acid, followed by addition of sulfuric acid to precipitate the barium sulfate byproduct. Thénard's
process was used from the end of the 19th century until the middle of the 20th century.
Pure hydrogen peroxide was long believed to be unstable, as early attempts to separate it from
the water, which is present during synthesis, all failed. This instability was due to traces of
impurities (transition-metal salts), which catalyze the decomposition of the hydrogen peroxide.
Pure hydrogen peroxide was first obtained in 1894 almost 80 years after its discovery by Richard
Wolffenstein, who produced it by vacuum distillation.
Determination of the molecular structure of hydrogen peroxide proved to be very difficult. In
1892 the Italian physical chemist Giacomo Carrara (1864–1925) determined its molecular mass
by freezing-point depression, which confirmed that its molecular formula is H2O2. At least half a
dozen hypothetical molecular structures seemed to be consistent with the available evidence. In
1934, the English mathematical physicist William Penney and the Scottish physicist Gordon
Sutherland proposed a molecular structure for hydrogen peroxide that was very similar to the
presently accepted one.
Production of 30,000 Tons Per Year of H2O2 from CH3OH by Enzymatic Conversion Page | 1
1.2 Physical Properties:

The boiling point of H2O2 has been extrapolated as being 150.2 °C, approximately 50 °C higher
than water; in practice hydrogen peroxide will undergo potentially explosive thermal
decomposition if heated to this temperature. It may be safely distilled at lower temperatures
under reduced pressure.
Table 1.1: Properties of Hydrogen Peroxide
Properties
Chemical Formula H2O2
Molar Mass 34.0147 g/mol
Appearance Very light blue color; colorless in solution
Odor slightly sharp
Density 1.11 g/cm3 (20 °C, 30% (w/w) solution )

1.450 g/cm3 (20 °C, pure)
Melting Point −0.43 °C (31.23 °F; 272.72 K)
Boiling Point 150.2 °C (302.4 °F; 423.3 K) (decomposes)

Solubility in Water Miscible
Solubility soluble in ether, alcohol

insoluble in petroleum ether
Vapor Pressure 5 mmHg (30 °C)
Acidity (pKa) 11.75

Refractive Index(nD) 1.4061
Viscosity 1.245 cP (20 °C)

Dipole Moment 2.26 D
Thermochemistry
Specific Heat Capacity (C) 1.267 J/(g·K) (gas)
2.619 J/(g·K) (liquid)
Standard Enthalpy of Formation (ΔfHo298) −187.80 kJ/mol
In aqueous solutions hydrogen peroxide differs from the pure material due to the effects
of hydrogen bonding between water and hydrogen peroxide molecules. Hydrogen peroxide and
water form a eutectic mixture, exhibiting freezing-point depression; pure water has a melting
point of 0 °C and pure hydrogen peroxide of −0.43 °C, but a 50% (by volume) solution of the
two freezes at −51 °C. The boiling point of the same mixtures is also depressed in relation with
the mean of both boiling points (125.1 °C). It occurs at 114 °C. This boiling point is 14 °C
greater than that of pure water and 36.2 °C less than that of pure hydrogen peroxide.
Figure 1.1: Phase diagram of H2O2 and water: Area above blue line is liquid. Dotted lines
separate solid + liquid phases from solid + solid phases.
Figure 1.2: Activity Coefficients of Hydrogen Peroxide-Water Solutions
1.3 Chemical Properties:
Classification of Reaction of Hydrogen Peroxide:
Four categories may be established for classifying the reaction of Hydrogen peroxide. These deal
only with the net or overall result of reactions.
Decomposition Process:
A reaction with became evident almost coincident with the discovery of Hydrogen peroxide was
2H2O2 2H2O + O2
However except at high temperature this reaction does not occur without the action of other
substance. Fortunately Hydrogen peroxide may react in more orderly fashion than just indicated.
Oxidation or Reduction Reactions of Hydrogen Peroxide:
These are the reaction in witch reactant and the oxygen of Hydrogen peroxide both undergoes a
change in valence. As example of a net oxidation by Hydrogen peroxide is
2H2O2 + 2Fe++ + 2H+ 2Fe++ + 2H2O
Similarly, as an example of reduction by Hydrogen peroxide there may be cited
2KMnO4 + 5H2O2 + 3H2SO4 2MnSO4 + K2SO4 + 8H2O + 5O2
It has been pointed out by Steinbach that an infinite number of sets of compatible coefficients
may be chosen for the reduction reaction of Hydrogen peroxide.
Dual Nature of Hydrogen Peroxide:
Hydrogen peroxide can be acted as oxidizing and reducing agent. This is known as dual nature of
Hydrogen peroxide. This property which contributes so much to the variety and complexity of
Hydrogen peroxide chemistry In a larger sense this is only a reflection of intermediate position
of Hydrogen peroxide between water and molecular oxygen in the oxidation reduction scale.
Peroxide Group Transfer:
No change in the valency of Oxygen in Hydrogen peroxide is involved when this peroxide group
is transferred to another molecule. An example of such mathematical reaction is
3H2O2 + Ba(OH)2 BaO2 + 2H2O
It may be pointed out that transfer of the peroxide group intact from molecule to molecules much
the same as formation of Hydrogen peroxide, even though valence change is assumed to occur in
one case and not in the other.
Additional Compound Formation:
The Hydrogen peroxide molecule as a whole may be attached to another molecule to form an
addition compound or “hydroperoxidates” witch are analogous to hydrate, is an example of such
reaction.
3H2O2 + 2Na2CO2 2Na2CO2.3H2O2
Formation of Peroxide Compounds:

Hydrogen peroxide is a weak acid, and it can form hydro peroxide or peroxide salts or
derivatives of many metals. For example, on addition to an aqueous solution of chromic acid
(CrO3) or acidic solutions of dichromate salts, it will form an unstable blue peroxide CrO(O2)2.
In aqueous solution it rapidly decomposes to form oxygen gas and chromium salts. It can also
produce peroxoanions by reaction with anions; for example, reaction with borax leads to sodium
perborate, a bleach used in laundry detergents:
Na2B4O7 + 4 H2O2 + 2 NaOH 2Na2B2O4(OH)4 + H2O
H2O2 converts carboxylic acids (RCOOH) into peroxy acids (RCOOOH), which are they used as
oxidizing agents. Hydrogen peroxide reacts with acetone to form acetone peroxide, and it
interacts with ozone to form hydrogen trioxide, also known as trioxidane. Reaction with urea
produces carbamide peroxide, used for whitening teeth. An acid-base adduct with
triphenylphosphine oxide is a useful "carrier" for H2O2 in some reactions.
1.4 Uses of Hydrogen Peroxide:

Industrial Applications:
About 50% of the world's production of hydrogen peroxide in 1994 was used for pulp and paper-
bleaching. Other bleaching applications are becoming more important as hydrogen peroxide is
seen as an environmentally benign alternative to chlorine-based bleaches. It is highly corrosive to
metal.
Other major industrial applications for hydrogen peroxide include the manufacture of sodium per
carbonate and sodium perborate, used as mild bleaches in laundry detergents. It is used in the
production of certain organic peroxides such as dibenzoyl peroxide, used in polymerizations and
other chemical processes. Hydrogen peroxide is also used in the production of epoxides such as
propylene oxide. Reaction with carboxylic acids produces a corresponding peroxy acid. Per
acetic acid and meta-chloroperoxybenzoic acid (commonly abbreviated mCPBA) are prepared
from acetic acid and meta-chlorobenzoic acid, respectively. The latter is commonly reacted with
alkenes to give the corresponding epoxide.
A combination of a powdered precious metal-based catalyst, hydrogen peroxide, methanol and
water can produce superheated steam in one to two seconds, releasing only CO2 and high
temperature steam for a variety of purposes.
Recently, there has been increased use of vaporized hydrogen peroxide in the validation and bio-
decontamination of half suit and glove port isolators in pharmaceutical production.
Hydrogen Peroxide is also used in the Oil and Gas exploration industry to oxidize rock matrix in
preparation for micro-fossil analysis.
Domestic Use:
 Diluted H2O2 (between 3% and 12%) is used to bleach human hair when mixed with
ammonia, hence the phrase "peroxide blond". It is absorbed by skin upon contact and
creates a local skin capillary embolism which appears as a temporary whitening of the
skin. It is used to whiten bones that are to be put on display. The strength of a solution
may be described as a percentage or volume, where 1% hydrogen peroxide releases 3.3
volumes of oxygen during decomposition. Thus, a 3% solution is equivalent to 10
volumes and a 6% solution to 20 volume, etc.
 3% H2O2 is used medically for cleaning wounds, removing dead tissue, and as an oral
debriding agent. Peroxide stops slow (small vessel) wound bleeding/oozing, as well.
Most over-the-counter peroxide solutions are not suitable for ingestion.
 3% H2O2 is effective at treating fresh (red) blood-stains in clothing and on other items. It
must be applied to clothing before blood stains can be accidentally "set" with heated
water. Cold water and soap are then used to remove the peroxide treated blood.
 The United States Food and Drug Administration (FDA) have classified hydrogen
peroxide as a Low Regulatory Priority (LRP) drug for use in controlling fungus on fish
and fish eggs.
 Some horticulturalists and users of hydroponics advocate the use of weak hydrogen
peroxide solution ("Spanish water") in watering solutions. Its spontaneous decomposition
releases oxygen that enhances a plant's root development and helps to treat root rot
(cellular root death due to lack of oxygen) and a variety of other pests. There is some
peer-reviewed academic research to back up some of the claims.
 Laboratory tests conducted by fish culturists in recent years have demonstrated that
common household hydrogen peroxide can be used safely to provide oxygen for small
fish. Hydrogen peroxide releases oxygen by decomposition when it is exposed to
catalysts such as manganese dioxide.
 Hydrogen peroxide is a strong oxidizer effective in controlling sulfide and organic related
odors in wastewater collection and treatment systems. It is typically applied to a
wastewater system where there is a retention time of 30 minutes to 5 hours before
hydrogen sulfide is released. Hydrogen peroxide oxidizes the hydrogen sulfide and
promotes bio-oxidation of organic odors. Hydrogen peroxide decomposes to oxygen and
water, adding dissolved oxygen to the system thereby negating some Biochemical
Oxygen Demand (BOD).
 Mixed with baking soda and a small amount of hand soap, hydrogen peroxide is effective
at removing skunk odor.
 If a dog has swallowed a harmful substance (e.g. chocolate), small amounts of hydrogen
peroxide can be given to induce vomiting.
 Hydrogen peroxide is used with phenyl oxalate ester and an appropriate dye in glow
sticks as an oxidizing agent. It reacts with the ester to form an unstable CO2 dimer which
excites the dye to an excited state; the dye emits a photon (light) when it spontaneously
relaxes back to the ground state.
 Diluted hydrogen peroxide can be used in a 50/50 mixture with white vinegar in the
removal of accumulated lead and gun powder from a stainless steel firearm suppressor.
The acetic acid is the main reagent, but the bubbling action of the hydrogen peroxide is
used to agitate the mixture and accelerate the reaction. The chemical mixture should be
replaced every 24 hours as it will become ineffective after that period. Responsible care
of the waste mixture is required as the end
 Result is an aqueous solution of lead acetate, which is highly toxic and must be disposed
of through a Hazardous Waste facility. Alternately, the solution may be reacted with salt
water or sulfuric acid to precipitate insoluble lead chloride or lead sulfate, respectively.
The solids may then be removed by mechanical filtration and are safer to dispose of than
aqueous lead acetate. This method should not be used on aluminum suppressors, as acetic
acid will dissolve the aluminum and form aluminum acetate.
Use as Propellant:
H2O2 can be used either as a monopropellant (not mixed with fuel) or as the oxidizer component
of a bipropellant rocket. Use as a monopropellant takes advantage of the decomposition of 70–
98% concentration hydrogen peroxide into steam and oxygen. The propellant is pumped into a
reaction chamber where a catalyst, usually a silver or platinum screen, triggers decomposition,
producing steam at over 600 °C which is expelled through a nozzle, generating thrust. H2O2
monopropellant produces a maximum specific impulse (Isp) of 161 s (1.6 kN-s/kg), which makes
it a low-performance monopropellant. Peroxide generates much less thrust than hydrazine, but is
not toxic. The Bell Rocket Belt used hydrogen peroxide monopropellant.
As a bipropellant H2O2 is decomposed to burn a fuel as an oxidizer. Specific impulses as high as

350 s (3.5 kN-s/kg) can be achieved, depending on the fuel. Peroxide used as an oxidizer gives a
somewhat lower Isp than liquid oxygen, but is dense, storable, non cryogenic and can be more
easily used to drive gas turbines to give high pressures using an efficient closed cycle. It can also
be used for regenerative cooling of rocket engines. Peroxide was used very successfully as an
oxidizer in World-War-II German rockets (e.g. T-Stoff for the Me-163), and for the low-cost
British Black Knight and Black Arrow launchers.
In the 1940s and 1950s the Walter turbine used hydrogen peroxide for use in submarines while
submerged; it was found to be too noisy and require too much maintenance compared to diesel-
electric power systems. Some torpedoes used hydrogen peroxide as oxidizer or propellant, but
this was dangerous and has been discontinued by most navies. Hydrogen peroxide leaks were
blamed for the sinkings of HMS Sidon and the Russian submarine Kursk. It was discovered, for
example, by the Japanese Navy in torpedo trials that the concentration of H2O2 in right-angle
bends in HTP pipe work can often lead to explosions in submarines and torpedoes. SAAB
Underwater Systems is manufacturing the Torpedo 2000. This torpedo, used by the Swedish
navy, is powered by a piston engine propelled by HTP as an oxidizer and kerosene as a fuel in a
bipropellant system. While rarely used now as a monopropellant for large engines, small
hydrogen peroxide attitude control thrusters are still in use on some satellites. They are easy to
throttle, and safer to fuel and handle before launch than hydrazine thrusters. However, hydrazine
is more often used in spacecraft because of its higher specific impulse and lower rate of
decomposition.
Therapeutic Use:
Hydrogen peroxide is generally recognized as safe (GRAS) as an antimicrobial agent, an
oxidizing agent and for other purposes by the US Food and Drug Administration.
Hydrogen peroxide has been used as an antiseptic and anti-bacterial agent for many years due to
its oxidizing effect. While its use has decreased in recent years with the popularity of better
smelling and more readily-available over the counter products, it is still used by many hospitals,
doctors and dentists in sterilizing, cleaning and treating everything from floors to root canal
procedures.
 Like many oxidative antiseptics, hydrogen peroxide causes mild damage to tissue in open
wounds, but it also is effective at rapidly stopping capillary bleeding (slow blood oozing
from small vessels in abrasions), and is sometimes used sparingly for this purpose, as
well as cleaning.
 Hydrogen peroxide can be used as toothpaste when mixed with correct quantities of
baking soda and salt. Hydrogen peroxide and benzoyl peroxide are sometimes used to
treat acne.
 Hydrogen peroxide is used as an emetic in veterinary practice.
1.5 Storage
Regulations vary, but low concentrations, such as 3%, are widely available and legal to buy for
medical use. Higher concentrations may be considered hazardous and are typically accompanied
by a Material Safety Data Sheet (MSDS). In high concentrations, hydrogen peroxide is an
aggressive oxidizer and will corrode many materials, including human skin. In the presence of a
reducing agent, high concentrations of H2O2 will react violently.
Hydrogen peroxide should be stored in a cool, dry, well-ventilated area and away from any
flammable or combustible substances. It should be stored in a container composed of non-
reactive materials such as stainless steel or glass (other materials including some plastics and
aluminum alloys may also be suitable). Because it breaks down quickly when exposed to light, it
should be stored in an opaque container, and pharmaceutical formulations typically come in
brown bottles that filter out light.
1.6 Formaldehyde:
Formaldehyde, CH2O is the first of the series of aliphatic aldehydes. It is also known as formic
aldehvde, exomethane & also methanat according to IUPAC system. It was discovered by
Butlerov in & has been mnuñcwred since the beginning of this century.
Formaldehyde has become an industrial chemical of outstanding importance. The

formaldehyde industry continues to expand. In 1972, world production has reached a probable
volume of at least 7.5 million metric tons (calculated as 37% soin.). Because of its relatively low
cost, high purity and variety of chemical reactions, formaldehyde has become one of the works
most important industrial & research chemical. It is not only an important low cost chemical
intermediate, it is also a synthetic tool like hydrogenation, oxidation, etc. In formaldehyde, the
carbonyl carbon in functional group of aldehyde is directly linked with one hydrogen atom.
Since pure, monomeric formaldehyde is a gas at ordinary temperature & cannot be readily
handled in this state, it is marketed chiefly in the form of aqueous solutions containing 37 to 50
% formaldehyde by weight.
In addition, soln. of formaldehyde in methanol, propanol, butanol are also available

commercially. The standard 37% U.S.P soln. contains sufficient methanol (7-15% by wt.) to
prevent precipitation of polymer under ordinary conditions of transportation & storage. A 40%
aq. soln. of methanol containing about 8% methanol is called “Formalin” used for preservation
of biological specimens.
Commercial forms of formaldehyde also include the polymeric hydrate,

paraformaldehyde, HO(CH2O)nH. This is also known as paraform or some times as
trioxymethylene. This polymer behaves chemically as a solid form of formaldehyde. The cyclic
trimer, s-trioxane (-trioxymethylene) is also commercially available formaldehyde. The
tricyclic derivative, hexamethylene tetramine (CH2)N4 produced by the reaction of
formaldehyde with ammonia, reacts as formaldehyde in many instances, is used commercially as
a special form of formaldehyde. The so called alpha poly oxymethylene, HO(CH20)1H in which
n’ is greater than 100, may be regarded as the end product of the series.
Chapter No. 2 Manufacturing Processes for Hydrogen Peroxide
Chapter 2
MANUFACTURING PROCESSES FOR

HYDROGEN PEROXIDE
Following are the processes for the manufacturing of H2O2:
 The Barium Peroxide Process

 Electrolytic Method
 Direct Combination of Hydrogen and Oxygen
 Autoxidation Processes
 Nitrogen Compound Autoxidation.
 Hydrocarbon Autoxidation.
 Ethyl-Anthraquinone Autoxidation Process.
2.1 The Barium Peroxide Process:

This is the earliest method for the preparation of H2O2. It is based on barium peroxide which is
obtained by air roasting barium oxide with sulphuric acid or phosphoric acid to form H2O2 in 3-
8% concentration but it can be concentrated to higher strengths by distillation process.
BaO2 + H2SO4 BaSO4 + H2O2.
The usual method for the preparation of barium peroxide involves the following steps:
 Ground barrettes mixed with coke is heated in a rotary kiln to give barium sulphide.
 To kill clinker bas is lixiviated with water and barium carbonate is precipitated by the
addition of soda ash.
 Then the barium carbonate is mixed with carbon and heated to 1200C in the furnace to
form barium mono oxide.
 This barium oxide is heated in a stream of purified air and 540C is oxidized to barium
peroxide which is used in the manufacturing of H2O2.
Associated Problems:
 Low concentration of product
 Low reaction rates
 Thus this process requires time and it also requires vacuum distillation for higher
concentration and this increases the cost and thus it is not an economic process.
2.2 Electrolytic Method:

This method is based on the hydrolysis of peroxydisulfates obtained by the anodic oxidation of
acidic, sulfate containing solution as shown below:
2 H2SO4 + Electrical Energy H2SO8 + H2

H2SO8 + H2O H2SO5 + H2SO4
H2SO5 + H2O H2O2 + H2SO4
 This process requires extensive and continuous purification of the electrolyte this
increases the capital cost.
 This will increase the power requirement too thus is uneconomical.
2.3 Direct Combination of Hydrogen and Oxygen:

H2O2 can be formed directly by the thermal, electric discharge, or metal activated reaction of
hydrogen and oxygen.
In electrical discharge method a mixture of H2 and O2 saturated with water vapor at 60C and a
pressure of 1 atm, is passed through an heat exchanger and then to an ionizing chamber
containing a large no of quartz plates.
On one side of each of these plates has an Al coating and other side is etched with HF acid. The
uncoated sides are placed face to face 5mm apart and then metalized sides are electrically
connected in groups of alternate plates placed in parallel.
When the current is passed the H2O2 is produced in the ionizing chamber together with other
gases which is then passed through the heat exchanger and a rectifying column. This column has
a condenser from where 10% of H2O2 solution is withdrawn and concentrated.
 Low concentration of hydrogen peroxide

 Low selectivity thus it requires a large quantity of hydrogen
 Rate of reaction is low
 Hazardous operating conditions (particularly hydrogen partial pressure requirements in
the explosive range) and high acid content.
2.4 Autoxidation Processes:

Autoxidation is any oxidation that occurs in the presence of oxygen or UV radiations to form
peroxides and hydro peroxides.
Following methods are involved in Autoxidation methods for the manufacturing of H2O2.
2.5 Nitrogen Compound Autoxidation:

H2O2 can be prepared commercially by the oxidation and reduction of hydrazobenzene in a
cyclic process. Such processes were developed in US (Mathieson alkali corp.) and Germany
(BASF) during World War II.
 The main problem in this process is that since the conversion is not 100% and NOx are
produced in dangerous quantity depending upon the conditions of the reaction and that
cause pollution.
 The reactants for this process are quite expensive which makes this process
uneconomical.
This process takes place according to the following reactions.
2.6 Hydrocarbon Autoxidation:

H2O2 can be prepared by the partial vapor phase oxidation of hydrocarbons and indirectly from
several hydrocarbon hydro peroxides. Although numerous patents have been guaranteed for
producing H2O2 from hydrocarbon feedstock and only few of them are practiced commercially.
 The vapor phase oxidation processes generate a greater number of by products and thus
complicate recovery, purification, and concentration of hydrogen peroxide.
2.7 Ethyl-Anthraquinone Autoxidation Process:

The Anthraquinone process is a process for the production of hydrogen peroxide, which was
developed by BASF. The industrial production of hydrogen peroxide is based on
the reduction of oxygen, as in the direct synthesis from the elements. Instead of hydrogen itself,
however, a 2-alkyl-anthrahydroquinone, which is generated before from the corresponding 2
alkyl-Anthraquinone by catalytic hydrogenation with palladium. Oxygen and the organic phase
react under formation of the Anthraquinone and hydrogen peroxide. Among other alkyl
groups (R) ethyl- and tert. Butyl are used, e.g., 2-ethylanthraquinone. The hydrogen peroxide is
then extracted with water and in a second step separated by fractional distillation from the water.
The hydrogen peroxide accumulates as sump product.
Advantages:
 A high concentration of hydrogen peroxide is produced in this process comparatively to
the other processes like direct combination of hydrogen and oxygen and barium peroxide
process.
 Reaction rates are high by using proper catalyst however in oxidizer no catalyst is used
but researches are going on to involve a certain catalyst that further increases the
performance of the process by increasing the reaction rate.
 In this process the working solution is regenerated which makes the overall process less
costly as compared to the electrolytic process which involves the continuous purification
of electrolyte which makes it costly.
 No dangerous gases are released which have a bad effect on our environment as
compared to the nitrogen compound Autoxidation process for the manufacturing of
hydrogen peroxide.
 The number of side reactions is very small as compared to the hydrocarbon Autoxidation
process which involves complicated recovery of hydrogen peroxide as compared to the
hydrocarbon Autoxidation process in which vapor phase oxidation takes place due to
which by-products increase and thus complicates the recovery of hydrogen peroxide.
 This process involves hydrogenation of ethyl-Anthraquinone to form
ethylhydroanthraquinine which is then oxidized to form hydrogen peroxide. Thus the
overall reactant cost is comparatively less than that of the reactants (hydrazobenzene)
which are used in the nitrogen compound Autoxidation process for the preparation of the
hydrogen peroxide.
2.8 Enzymatic Process:
In the enzymatic process methanol is converted into the formaldehyde and hydrogen peroxide in
the presence of methanol oxidase and pure oxygen at -22oC temperature. The reaction is follows
as
CH3OH + O2 HCHO + H2O2
Table 2.1: Comparison of Hydrogen Peroxide Manufacturing Processes
Process Advantages Disadvantages
The Barium Peroxide Process Earliest Method Low Concentration

8% Concentrated Low Reaction Rates
Barium Oxide By Product
Electrolytic Method Expensive due to Electricity and
Continuous Purification of
Electrolyte
Direct Method Low Concentration
Low Reaction Rates
Low Selectivity
Hazardous Operation Conditions
Nitrogen Compound Low Conversion
Autoxidation NOx Emissions
Expensive Raw Material
Hydrocarbon Autoxidation Due to large amount of products
Purification, Recovery is difficult
and expensive
Anthraquinone Process Relatively High Reaction Rate
Less Expensive Raw Materials
Less Side Reactions
No Emissions
Enzymatic Process High Conversion74.5%

Less Expensive Raw Material
No Harmful Emissions
High Concentration 50%
High Selectivity
No Side Reaction
Safe Operating Conditions
Less Waste Generated
Enzyme Recovery
Chapter No. 3 Process Description
Chapter 3
PROCESS DESCRIPTION
3.1 Background:
The process uses the enzyme, methanol oxidase, to convert alcohol and oxygen to formaldehyde
and hydrogen peroxide. The goal is to produce 30,000 tons/y of 50 wt% hydrogen peroxide using
an enzymatic process. Formaldehyde, methanol, and hydrogen peroxide are considered
carcinogenic and/or hazardous materials. In light of this, a process design was made that
minimizes the waste and emissions generated. Currently, many hollow fiber membrane (HFM)
technologies are emerging into existing markets, allowing for more cost-effective separations
and reactions. HFMs are becoming more useful in the chemical industry. With the recent growth
in the areas of biochemical and environmental technologies, many potential future markets are
available for the use of HFMs. The enzyme, methanol oxidase, catalyzes the reaction in the
continuous-stirred tank fermenter. HFMs were used in an ultrafiltration unit off of the
continuous-stirred tank fermenter to recover the enzyme for recycle. [1]
3.2 Process Description:
The BFD (Figure 1) and four PFDs (Figures 2-5) show a process to produce formaldehyde and
hydrogen peroxide. Methanol (fresh and recycled) at 49.3°C and 11.49 bars mixes with water
(fresh and recycled) at 203.4°C and 11.49 bars. Together they enter heat exchanger, E-101, at
139°C and 11.49 bars and leave at 50°C and 11.15 bars. Oxygen (fresh and recycled) is sparged
through the liquid mixture of methanol and 2 oxygen. The oxygen must first diffuse into the
water before it can be reacted. The enzyme, methanol oxidase, catalyzes the reaction. The
reaction is a function of the enzyme concentration. The reactor has a conversion of oxygen of
74.5%. The reaction must proceed at -22°C! To reach this temperature, a cooling jacket was
added to the reactor. Refrigerant-134a (R-134a) flows through the cooling jacket. R-134a is sent
through two compressors in series (C-201 A/B, no intercooling) to obtain a pressure of 8 bars. R-
134a condenses and sub cools to 35°C in E-201. It is then flashed to 0.75 bars, which lowers the
temperature of the liquid R-134a to -28°C. The liquid R- 134a is sent through the cooling jacket
and then is recycled back through the same process. This refrigeration loop is illustrated in
Figure 4. The unreacted oxygen, taken from the top of the reactor, is compressed from 8 bars to
11.15 bars in compressor C-101 and is recycled back to Stream 3. The ultrafiltration unit
recovers excess enzyme from the outlet of the reactor. The enzyme is sent back to the reactor for
reuse. Stream 6, composed of formaldehyde, methanol, water, hydrogen peroxide, and oxygen, is
sent to V-101 at -22°C and 11.15 bars. Stream 6 is flashed to remove most of the oxygen along
with trace amounts of the other products. The top, Stream 7, is sent to the incinerator. The
bottom, Stream 8, is sent to T-101. This vacuum distillation column separates almost pure
hydrogen peroxide as the bottom product, Stream 10, at 85°C and 0.35 bars. The top, Stream 9,
is sent to V- 103 at 66.6°C and 0.29 bars. Again, this flash unit separates out the oxygen leaving
anegligible amount of oxygen behind in Stream 12.Stream 12 is pumped to 1.22 bars in P-103
before it enters T-102. This tower removes mostly methanol with some water and small amounts
of formaldehyde in Stream 3 13. P-106 A/B pumps Stream 13 up to 11.15 bars where it is
recycled back to the reactor. The bottom, Stream 14, consists mainly of formaldehyde and water
at 112.9°C and 1.53 bars. P-105 pumps Stream 14 up to 20 bars before entering T-103. In T-103,
water is separated from formaldehyde to produce a 37% by weight formaldehyde in water
solution, Stream 15. This stream is at 207.4°C and 19.97 bars. The bottom of this tower, Stream
16, is mostly water at 239.7°C and 20.36 bars. It is split and some of the water is mixed with
Stream 10 to produce the desired 50% by weight hydrogen peroxide in water in Stream 19. This
stream is at 179.4°C and 20.36 bars. Unit 300 provides the steam used in the distillation columns
and flash vessels. The steam produced in this unit is at 20 bars. The condensate return from the
process was pumped and then sent to H-301. The steam is sent to E-103, E-105, V-101, V-103,
and V-103 at 240°C and 20 bars.
3.3 Process Flow Diagram:
The following is the list of equipment in the Process Flow Diagram.
 Shell and Tube Heat Exchanger (E-101)

 Fermenter (R-101)
 Compressor (C-101)
 Ultrafiltration Membrane (UF-101A/B)
 Flash Column (V-101)
 Multicomponent Distillation Column (T-101)
 Flash Column (V-103)
Chapter No. 4 Enzyme Preparation and Purification
Chapter 4
ENZYME PREPARATION AND
PURIFICATION
4.1 Introduction:
The alcohol oxidase enzyme may be produced by transcription and translation of an appropriate
gene, such as a Hansenula polymorpha gene that has been cloned and amplified by genetic
engineering techniques. However, the preferred technique is simply the growth of Hansenula
polymorpha and the induction of alcohol oxidase synthesis in that organism.
4.2 Growth of Hansenula Polymorpha and Enzyme Induction:
Growth media for yeast are well known in the art. Hansenula polymorpha and other similar
organisms may be grown in either a glucose or a methanol medium. A suitable glucose medium
may contain, by weight, 0.4% NH4Cl, 0.1% KH2PO4, 0.1% K2HPO4, 0.05%, MgSO4. 7H2O,
0.05% yeast extract, and 1% glucose. A suitable methanol medium would contain the same
nitrogen, potassium, phosphate, and sulfate sources, together with from 0.3% to 3% by volume
methanol.
The growth rates of the yeast on glucose and on methanol are similar. The cell doubling time in
glucose is somewhat less than 12 hours. The cell doubling time in methanol is slightly more than
12 hours. When the yeast is grown in a glucose medium, alcohol oxidase production is induced
by diluting the yeast 1:10 from the glucose medium into a 3% by volume methanol medium and
growing to late log phase, approximately 24 hours at 28° C.
Alternatively, yeast may be grown in a methanol limited chemostat in accordance with the
method of Van Dijken, et al., Arch. Microbial. 111, 137-144 (1976).
In the presence of methanol, the resulting Hansenula polymorpha contains at least 20% of the
protein of a cell-free extract in the form of alcohol oxidase.
4.3 Enzyme Purification:
In the first step of a suitable enzyme purification procedure, the cells are disrupted and
homogenized. A phosphate buffer may be used to adjust the pH prior to homogenization to about
7.5. After cell disruption, cell debris can be removed by centrifugation. The supernatant solution
represents a cell-free enzyme extract.
A particularly preferred purification technique utilizes an ion exchange column to purify alcohol
oxidase from the crude cell-free extract. This purification procedure is a relatively fast,
inexpensive, and efficient method for producing large quantities of protein in a short period of
time. The protein that elutes from a DEAE-cellulose column, for example, is free of cellular
catalase. The alcohol oxidase from Hansenula polymorpha elutes from the DEAE-cellulose,
using a salt-gradient elution, at approximately 0.3 M NaCl. At this stage the enzyme is
approximately 80-90% pure. It is also possible to shorten this procedure further by eluting
alcohol oxidase from the column using a batch wise elution rather than a salt gradient. The
enzyme will be of a lower purity, but since the only contaminant that substantially affects the
reaction is catalase (which catalyzes the reaction 2H2 O2 →2H2 O) and since catalase does not
bind to the DEAE-cellulose under the conditions used, the extraneous contamination will be of
little consequence. Residual catalase may be determined by appropriate assay. See, e.g., Luck,
H., Methods of Enzymatic Analysis 885-894 (H. Bergemeyer ed. 1963).
4.4 Enzyme Productivity:
The methanol oxidase from Hansenula polymorpha ATCC 34438 has a Km for methanol of 2.0
mM and a turnover number of 220 moles products/min./mole active site (i.e., 1 g of enzyme
produces approximately 0.1 g each of CH2O and H2O2 per min.). These values are determined at
dilute enzyme concentrations (<5 ug/ml) where reaction rates are linear with respect to time and
enzyme concentration. At higher enzyme concentrations under normal laboratory conditions,
oxygen becomes rate limiting. This is demonstrated by the fact that when identical reaction
vessels, each containing 1 ug/ml of enzyme are compared, where one of the reaction vessels has
been shaken to increase aeration, and the other has been left stationary, different rates of product
formation are observed. This indicates the desirability of introducing oxygen into the reaction
mixture to obtain maximum reaction rates at high enzyme concentrations.
4.5 Stability of Methanol Oxidase in the Presence of Methanol:
Unlike the methanol oxidase enzymes that have been studied in connection with prior art
processes, the methanol oxidase from Hansenula polymorpha ATCC 34438 exhibits remarkable
stability in the presence of methanol and reaction products. Reaction rates for methanol oxidase
remain linear in the presence of methanol up to a concentration of approximately 10% methanol
(by volume). Eighty percent activity is retained at methanol concentrations as high as 30% (by
volume). Accordingly, commercially viable processes within the scope of the present invention
may use a feedstock concentration of methanol of at least 0.5% by volume, preferably at least
1%, 2%, or 3% by volume, and most preferably at least 4% or 5% by volume. Concentrations of

10% or 20% may also be used with some loss of enzyme activity.
4.6 Enzyme Activity as a Function of Enzyme Concentration:
The preferred methanol oxidase from Hansenula polymorpha is stable over a broad range of
enzyme concentrations at enzyme concentrations from 1 to 1000 ug/ml, reaction rates remain
linear for several hours, even in concentrations of up to 10% methanol by volume.
When using unbound enzyme in the process of the present invention, the concentration of
enzyme in the reaction zone is preferably from 0.1 ug/ml up to 1000 ug/ml. In some applications,
the lower limit of enzyme concentration may be 1 ug/ml or 10ug/ml, and the upper concentration
limit may be 100 ug/ml or 500 ug/ml.
4.7 Activity of Methanol Oxidase and Product Stability in the Presence

of High Concentrations of Reaction Products:
Experiments were conducted to ascertain the stability of the preferred methanol oxidase in high
concentrations of products. All concentrations are on a volume basis. A first reaction was
initiated at 1% methanol and 0% product (0% hydrogen peroxide and 0% formaldehyde) and the
increase in product formed was determined as a function of time. A second reaction was initiated
in the presence of 3% hydrogen peroxide, 3% formaldehyde, and 1% methanol. In the first
reaction, the product concentration rose from 0% to 1% in slightly more than four hours and
remained stable at 1% until termination of the experiment at 20 hours. In the second reaction,
product concentration increased from 3% to 4% in a period of about 5 hours, and remained stable
until the termination of the experiment at 20 hours. This 1% increase in the product
concentration in each experiment is a stoichiometric increase, indicating substantially complete
conversion of methanol into product. This demonstrates that the methanol oxidase enzyme
remains active in product concentrations up to 4% and that the reaction goes to completion and
that the products are stable under these conditions.
4.8 Introduction of Oxygen into the Reaction Zone:
In the enzymatic oxidation of alcohol to aldehyde and hydrogen peroxide of the present
invention, oxygen molecules (O2) are stoichiometrically consumed in the conversion process.
Thus, for every mole of methanol or other alcohol converted into product, one mole of O2 is
consumed from the reaction mixture. Even at enzyme concentrations of as low as 5 ug/ml on a
laboratory scale, the diffusion of oxygen into the reaction mixture becomes rate-limiting.
Accordingly, large-scale production processes utilizing high enzyme concentrations significantly
benefit from aeration of the reaction mixture.
Direct aeration, such as sparging or bubbling air or other oxygen-containing gas through the
reaction mixture, represents one alternative for supplying the necessary oxygen. This process,
however, can result in losses of the relatively volatile aldehyde products. In some applications,
such aldehyde loss may be tolerated because of the relatively greater economic value of the
hydrogen peroxide. However, in most cases expelling aldehydes such as formaldehyde into the
environment is not desirable because they are unhealthful to humans and animals.
One method for avoiding aldehyde loss is oxygen enrichment of the feedstock prior to
introduction into the reaction zone.
In accordance with Charles' law, the amount of gas that may be dissolved in a liquid is directly
proportional to the partial pressure of that gas. Thus, more oxygen becomes dissolved in a liquid
when the gas and the liquid are under pressure, and more oxygen becomes dissolved in the liquid
from aeration with pure oxygen than from aeration with air. The rate of absorption of the gas into
the liquid is also dependent on the surface area of the gas/liquid interface. One technique for
maximizing the surface area is the minimization of the bubble size when the gas is bubbled
through the liquid.
Oxygenation may be accomplished by bubbling a gas containing oxygen through the alcohol
solution. The higher the concentration of oxygen in the aerating gas, the more oxygen becomes
dissolved in the liquid. Large quantities of oxygen may be dissolved by increasing the pressure
of the gas above ambient pressure in the oxygenation step.
For example, in one preferred process, the oxygenation step takes place within a pressurized
chamber. That chamber may be the same as the reaction chamber or the reaction zone. If
oxygenation under pressure takes place outside the reaction zone, it is desirable to also maintain
the reaction zone at an elevated pressure to prevent O2 effervescence of the reaction mixture.
This will also serve to maintain the aldehyde in solution.
Various suitable techniques for oxygenating liquids are disclosed in U.S. Pat. Nos. 4,067,696,
4,182,739, and 4,138,288.
In one embodiment of a continuous process, oxygen-enriched liquid flows continuously into the
reaction zone. The water-alcohol feedstock mixture may be enriched as discussed above. If
substantial dilution of the alcohol feedstock is necessary prior to introduction thereof into the
reaction zone, the diluting water itself may be separately oxygenated.
Similarly, in a batch-type process, the entire batch of methanol and water may be oxygenated
prior to introduction into the pressurized reaction zone or combination with the methanol oxidase
enzyme. Alternatively, a continuous stream of oxygenated water and/or methanol solution may
be introduced into the reaction zone, even in the batch-type process.
Although oxygenation of the reaction mixture outside the reaction zone is possible, the preferred
oxygenation method is direct oxygenation of the reaction mixture in the reaction zone. In
addition to simplifying the apparatus, this also permits the availability of greater amounts of
oxygen because the oxygen consumed in the reaction is continuously replenished. Aldehyde loss
may be avoided by recirculation of the gas leaving the reaction zone, and/or by sending the gas
leaving the reaction zone through a condensation chamber to separate the aldehyde from the
oxygen.
Chapter No. 5 Material Balance
Chapter 5
MATERIAL BALANCE
5.1 Introduction:
A mass balance also called a Material Balance is an application of conservation of mass to the
analysis of physical systems. By accounting for a material entering and leaving a system, mass
flows can be identified which might have been unknown, or difficult to measure without this
technique. The exact conservation law used in the analysis of the system depends upon the
context of the problem but all revolve around the mass conservation, i.e. that matter cannot
disappear or be created spontaneously. [5,10,15,21]
Therefore, mass balances are used widely in engineering and environmental analysis. For
example mass balance theory is used to design chemical reactors, analyze alternative processes
to produce chemicals as well as in pollution dispersion models and other models of physical
systems. Closely related and complementary analyses techniques include the population balance,
energy balance and somewhat more complex entropy balance. These techniques are required for
through design and analysis of systems such as the refrigeration cycles.
Capacity = 30000 tons/year = 100.6817 Kg mole/hr.
5.2 Material Balance on Distillation Column (T-101):
M9
M8
M10
Table 5.1: Mole Fractions of Components in the Streams of Multicomponent Distillation

Column (T-101)
Streams
M8 M9 M10
Units Mole % Mole % Mole %
Components
HCHO 0.032 0.033
CH3OH 0.049 0.050
H2 O 0.886 0.915
H2O2 0.032 0.00039 1.00
O2
By overall material balance we get
M8 = M9 + M10
M8 = M9 + 100.6817
By component balance on H2O we get
0.0324 M8 = 0.00039 M9 + 1 (100.6817)
0.0324 (M9 + 100.6817) = 0.00039 M9 + 1 (100.6817)
M9 = 3043.414558 kg mole/hr.
Now put the value in overall balance equation we get
M8 = 3144.096258 kg mole/hr.
Table 5.2: Overall and Component Material Balance on Multicomponent Distillation Column
(T-101)
Streams
Input Output
M8 M9 M10
Units Kg mole/hr. Kg mole/hr. Kg mole/hr.
Components
HCHO 101.8687 101.6500
CH3OH 154.3751 154.3011
H2 O 2785.6692 2785.6373
H2O2 101.8687 1.1869 100.6817
O2 0
Total 3144.096258 3043.414558 100.6817
Total (Input/Output) 3144.096258 3144.096258
5.3 Material Balance on Flash Column (V-103):
M11
M9
M12
Streams
M9 M11 M12
Components
HCHO 0.033 0.033
CH3OH 0.050 0.25 0.050
H2 O 0.915 0.75 0.915
H2O2 0.00039 0.0039
O2
Table 5.3: Mole Fractions of Components in the Streams of Flash Column (V-103)
M9 = M11 + M12
3043.414558 = M11 + M12
0.9153 (3043.414558) = 0.75 M11 + 0.9153 M12
2785.637345= 0.75 (3043.414558 – M12) + 0.9153 M12
M12 = 3043.414555 kg mole/hr.
M11 = 0.000003 kg mole/hr.
Table 5.4: Overall and Component Material Balance on Flash Column (V-103)
Streams
Input Output
M9 M11 M12
Components
HCHO 101.6500 101.6500
CH3OH 154.3011 0.00000075 154.3011
H2 O 2785.6373 0.00000225 2785.6373
H2O2 1.1869 1.2051
O2
Total 3043.414558 0.000003 3043.414555
M13
M12
M14

Column (T-102)
Streams
M12 M13 M14
Components
HCHO 0.033 0.0023 0.035
CH3OH 0.050 0.741 0.0045
H2 O 0.915 0.2560 0.959
H2O2 0.0039 0.0004
O2
M12 = M13 + M14
3043.41455= M13 + M14
By component balance on HCHO we get
0.0334 (3043.41455) = 0.000023 M13 + 0.0355 M14
0.0334 (3043.41455) = 0.000023 (3043.41455 – M14 + 0.0355 M14
M14 = 2863.266342 kg mole/hr.
M13 = 180.148213 kg mole/hr.
(T-102)
Streams
Input Output
M12 M13 M14
Components
HCHO 101.6500 0.004143 101.6459
CH3OH 154.3011 133.5258 12.8846
H2 O 2785.6373 46.1900 2747.0177
H2O2 1.2051 1.2025
O2
Total 3043.414555 180.148213 2863.266342
M15
M14
M16

Column (T-103)
Streams
M14 M15 M16
Components
HCHO 0.035 0.267
CH3OH 0.0045 0.034
H2 O 0.959 0.698 0.999
H2O2 0.0004 0.00046
O2
M14 = M15 + M16
2863.266342 = M15 + M16
0.9594 (2863.266342) = 0.6984 M15 + 0.9995 M16
0.9594 (2863.266342) = 0.6984 (2863.266342 – M16) + 0.9995 M16
M16 = 2481.941448 kg mole/hr.
M15 = 381.324894 kg mole/hr.
(T-103)
Streams
Input Output
M14 M15 M16
Components
HCHO 101.6459 101.9662
CH3OH 12.8846 13.0031
H2 O 2747.0177 266.3173 2480.7004
H2O2 1.2025 1.1416
O2
Total 2863.266342 381.324894 2481.941448
5.6 Material Balance on Flash Column (V-101):
M7
M6
M8
Table 5.9: Mole Fractions of Components in the Streams of Flash Column (V-101)
Streams
M6 M7 M8
Components
HCHO 0.032 0.04 0.032
CH3OH 0.049 0.16 0.049
H2 O 0.885 0.520 0.886
H2O2 0.032 0.04 0.032
O2 0.00020 0.24
M 6 = M7 + M 8
M6 = M7 + 3144.096258
0.8857 M6 = 0.52 M7 + 0.8860 (3144.096258)
0.8857 (M7 + 3144.096258) = 0.52 M7 + 0.8860 (3144.096258)
M7 = 2.57924 kg mole/hr.
M6 = 3146.675498 kg mole/hr.
Table 5.10: Overall and Component Material Balance on Flash Column (V-101)
Streams
Input Output
M6 M7 M8
Components
HCHO 101.9522 0.1031 101.8687
CH3OH 154.8164 0.4126 154.3751
H2 O 2787.0104 1.3412 2785.6692
H2O2 101.9522 0.1031 101.8687
O2 0.6293 0.6190 0
Total 3146.675498 2.57924 3144.096258
5.7 Material Balance on Fermenter (R-101):

M4 M5
M3 M6
Table 5.11: Mole Fractions of Components in the Streams of Fermenter (R-101)
Streams
M3 M4 M5 M6
Units Mole % Mole % Mole % Mole %
Components
HCHO 0.032
CH3OH 0.084 0.0031 0.049
H2 O 0.915 0.885
H2O2 0.00036 0.032
O2 1.00 0.996 0.00020
M3 + M4 = M5 + M6
M3 + M4 = M5 + 3146.675498
M6 stream contains 3.24% of hydrogen peroxide which is the major product of this process so
H2O2 = 0.324 (3146.675498) = 101.9522 kg mole/hr.
Chemical Reaction is given by
CH3OH + O2 H2O2 + HCHO
From the Reaction Stoichiometry it is clear that
1 mole of H2O2 Produced by = 1 mole of O2
101.9522 mole of H2O2 Produced by = 101.9522 mole of O2
For 90% Conversion
M3 = 101.9522/0.90 = 113.2802 kg mole/hr.
So 10% oxygen is unreacted hence
M5 = 0.010 M3 = 0.10 (113.2802) = 11.32802 kg mole/hr.
Now put the values in overall balance equation we get
M4 = 3044.723318 kg mole/hr.
Table 5.12: Overall and Component Material Balance on Fermenter (R-101)
Streams
Input Output
M3 M4 M5 M6
Units Kg mole/hr. Kg mole/hr. Kg mole/hr. Kg mole/hr.
Components
HCHO 101.9522
CH3OH 256.9746 0.3613 154.8164
H2 O 2786.5307 2787.0104
H2O2 0.1096 101.9522
O2 113.2802 11.2917 0.6293
Total 113.2802 3044.723318 11.32802 3146.675498
5.8 Overall Balance on Plant:

Total mass flow input
Streams Total Mole Flow

(Kg mole/hr.)
M3 113.2802
M4 3044.723318
Total 3158.003518 Kg mole/hr.
Total mass flow output
Streams Total Mole Flow

(Kg mole/hr.)
M5 11.32802
M7 2.57924
M10 100.6817
M11 0.000003
M13 180.148213
M15 381.324894
M16 2481.941448
Total 3158.003518 Kg mole/hr.
Chapter No. 6 Energy Balance
Chapter 6
ENERGY BALANCE
In engineering, Energy Balances are used to quantify the energy used or produced by a system.
[5,10,15,21]
6.1 Specific Heat Capacities:

Specific heat capacities of each component in each stream at different temperatures can be
calculated by busing Shomate Equation as given below.
CP = A + BT + CT2
Where
CP = Specific Heat Capacity at constant Pressure = KJ/kg mole (K)
T = Temperature/1000 = Kelvin
For components in this process the values of Shomate Constants are given below.
Table 6.1: Shomate Constants for Different Components
Components A B C Temperature
Range (K)
HCHO 5.193767 93.23249 -44.85457 298-1500
CH3OH 18.3822 0.1015 0.00002868 298-1500
H2 O 3.470 0.00145 298-1500
H2O2 34.25667 55.18445 -35.15443 298-1500
O2 31.32234 -20.23531 57.86644 298-1500
Now the calculated value of specific heat capacities in all streams at different temperatures by
busing the above data are given below as.
Table 6.2: Heat Capacities of Components at Different Temperatures
Components
Streams Temperatures HCHO CH3OH H2 O H2O2 O2
1 298.15 18.3522 3.470 47.5849
2 298.15 18.3522 3.470 47.5849
3 312.05 30.64266
4 323.15 18.35480 3.4704 48.4184

5 363.35 18.3588 31.6095
6 251.15 25.7798 18.4076 3.4703 45.8988 29.8902
7 341.15 31.7797 18.4618 3.4704 48.9914 31.1537
8 341.15 31.7797 18.4168 3.4704 48.9914
9 339.75 29.9153 18.4221 3.4705 50.5352
10 358.05 49.5086
11 341.25 18.3826 3.4704
12 341.25 31.7859 18.3826 3.4704 48.9945
13 337.95 31.5788 18.4165 3.4704
14 386.05 34.5012 18.4213 3.4705 50.3214
15 480.55 39.6384 18.4309 3.4706
16 512.85 3.4707 53.3118
The specific heat capacities of the components at the top of the distillation columns at the inlet of
the condenser are given below and calculated using the above data as previously above values
are calculated.
Components
Streams Temperatures HCHO CH3OH H2 O H2O2 O2
T-101 343.47 31.9247 18.4170 3.4704 49.0636
T-102 1372.3 48.6663 18.5215 3.4719
T-103 410.05 35.8818 18.4238 3.4705
The values of Antoine Coefficients for these components are given below which are useful in
calculating the boiling point of mixture.
Table 6.3: Antoine Constants for Components
Antoine Constants
Components A B
HCHO 7.15610 957.240
CH3OH 7.24693 1605.615
H2 O 16.3872 3885.70
H2O2 7.96917 1886.76
The values of latent heat of vaporization of different components are given below in the table.
Table 6.4: Latent Heat of Vaporization of Components
Components Latent Heat of Vaporization

(KJ/Kg)
HCHO 24.5
CH3OH 35.3
H2 O 40.65
H2O2 48.5
H2 O 3.4099
6.2 Energy Balance on Heat Exchanger (E-101):
Q2 Q4
Q1 Qs
Q2 = Liquid Stream = mCP∆T
Component mCP∆T Q2
CH3OH 256.9746 × 18.3522 ×(298.15-273.15) 117901.2314
H2 O 2786.5307 × 3.4704 ×(298.15-273.15) 241731.5382
H2O2 0.1096 × 47.5849 ×(298.15-273.15) 130.382626
Total 359763.1522 KJ/hr.
CH3OH 256.9746 × 18.3548 ×(323.15-273.15) 235835.8694
H2 O 2786.5307 × 3.4704 ×(323.15-273.15) 483518.8071
H2O2 0.1096 × 48.4184 ×(323.15-273.15) 265.332832
Total 719620.0093 KJ/hr.
So heat provided by the high pressure steam is
QS = 719620.0093 – 359763.1522 = 359856.8571 KJ/hr.
High pressure steam at 20 bar pressure is 4885.511 K
Now
Q = mCP∆T + mλ
m = Q/CP∆T + mλ
Put the values we get
m = 595.6833 kg mole/hr.
6.3 Energy Balance on Fermenter (R-101):
Q4 Q5
Q3 Q6
The mass balance over the fermenter is given below in the table.
Streams
Input Output
M3 M4 M5 M6
Components
HCHO 101.9522
CH3OH 256.9746 0.3613 154.8164
H2 O 2786.5307 2787.0104
H2O2 0.1096 101.9522
O2 113.2802 11.2917 0.6293
Total 113.2802 3044.723318 11.32802 3146.675498
Q4 = 719620.0093 KJ/hr.
Q3 = Vapor Stream = mCP∆T + mλ
Component mCP∆T+ mλ Q3
O2 113.2802 × 30.64266 ×(312.15-273.15) + (113.2802 × 3.4099) 135416.213
Total 135416.213 KJ/hr.
So total heat input = 719620.0093 + 135416.213 = 855036.2223 KJ/hr.
Now heat output
Q5 = Vapor Stream = mCP∆T + mλ
CH3OH 0.3613 × 18.3588 ×(363.35-273.15) + (0.3613 × 35.3) 611.0535965
O2 11.2917 × 31.6095 ×(363.35-273.15) + (11.2917 × 3.4099) 32233.13777
Total 32844.19137 KJ/hr.
Heat of Reaction
CH3OH + O2 H2O2 + HCHO
-∆HR = (-187.8-108.7) – (-238.4-0) = -58.1 KJ/mole
HCHO 101.9522 × 25.7798 ×(251.15-273.15) -57822.7611
CH3OH 154.8164 × 18.4076 ×(251.15-273.15) -62695.56402
H2 O 2787.0104 × 3.4703 ×(251.15-273.15) -212778.7682
H2O2 101.9522 × 45.8988 ×(251.15-273.15) -102948.64
O2 0.6293 × 29.8902 ×(251.15-273.15) -413.8178629
Total -436659.5512 KJ/hr.
So total heat in output = 32844.19137 + 58.1 + 436659.5512 = 469561.8426 KJ/hr.
So heat removed the Refrigerant (R-134a) 1,1,1,2 Tetrafuoro Ethane
Inlet Temperature = -28 oC = 245.15 K
Outlet Temperature = 35 oC = 308.15 K
Temperature Difference = ∆T = 63 K
So heat removed by the Refrigerant is
QRef. = 385474.3797 KJ/hr.
Heat Capacity of Refrigerant is 1.418376 KJ/Kg moles (K)
Now
Q = mCP∆T + mλ
m = Q/CP∆T + mλ
m = 4313.835646 kg mole/hr.
The overall energy balance on the fermenter is given below.
Table 6.5: Overall and Component Energy Balance on Fermenter (R-101)
Streams
Input Output
Q3 Q4 Q5 Q6
Units KJ/hr. KJ/hr. KJ/hr. KJ/hr.
Components
HCHO -57822.7611
CH3OH 235835.8694 611.0535965 -62695.56402
H2 O 483518.8071 -212778.7682
H2O2 265.332832 -102948.64
O2 135416.213 32233.13777 -413.8178629
Total 135416.213 719620.0093 32844.19137 -436659.5512
6.4 Energy Balance on Flash Column (V-101):
Q7
Q6
Q8
The mass balance over the flash column is given below in the table.
Streams
Input Output
M6 M7 M8
Components
HCHO 101.9522 0.1031 101.8687
CH3OH 154.8164 0.4126 154.3751
H2 O 2787.0104 1.3412 2785.6692
H2O2 101.9522 0.1031 101.8687
O2 0.6293 0.6190 0
Total 3146.675498 2.57924 3144.096258
Q6 = Liquid Stream = 436659.5512 KJ/hr.
Q7 = Vapor Stream = mCP∆T+ mλ
HCHO 0.1031 × 31.7777 × (341.15-273.15) + (0.1031 × 24.5) 225.3270708
CH3OH 0.4126 × 18.4168 × (341.15-273.15) + (0.4216 × 35.3) 531.2812542
H2 O 1.3412 × 3.4704 × (341.15-273.15) + (1.3412 × 40.65) 371.0258126
H2O2 0.1031 × 48.9914 × (341.15-273.15) + (0.1031 × 48.5) 348.4692571
O2 0.6190 × 31.1537 × (341.15-273.15) + (0.6190 × 3.4099) 1313.432269
Total 2789.535664 KJ/hr.
HCHO 101.8687 × 31.7777 × (341.15-273.15) 220140.2573
CH3OH 154.3751 × 18.4168 × (341.15-273.15) 193330.4832
H2 O 2785.6692 × 3.4704 × (341.15-273.15) 657382.2746
H2O2 101.8687 × 48.9914 × (341.15-273.15) 339366.9356
Total 1410219.951 KJ/hr.
So total heat in output = 1413009.486 KJ/hr
QS = 1413009.486 – 436659.5512 = 976349.9351 KJ/hr.
Now
Q = mCP∆T + mλ
m = Q/CP∆T + mλ
m = 1413.222902 kg mole/hr.
The overall energy balance on the flash column is given below
Table 6.6: Overall and Component Energy Balance on Flash Column (V-101)
Streams
Input Output
Q6 Q7 Q8
Units KJ/hr. KJ/hr. KJ/hr.
Components
HCHO -57822.7611 225.3270708 220140.2573
CH3OH -62695.56402 531.2812542 193330.4832
H2 O -212778.7682 371.0258126 657382.2746
H2O2 -102948.64 348.4692571 339366.9356
O2 -413.8178629 1313.432269
Total -436659.5512 2789.535664 1410219.951
Total (Input/Output) -436659.5512 1413009.486664
6.5 Energy Balance on Distillation Column (T-101):
Q9
Q8
Q10
The mass balance over the distillation column is given below in table.
Streams
Input Output
M8 M9 M10
Components
HCHO 101.8687 101.6500
CH3OH 154.3751 154.3011
H2 O 2785.6692 2785.6373
H2O2 101.8687 1.1869 100.6817
O2 0
Total 3144.096258 3043.414558 100.6817
Q8 = Liquid Stream = mCP∆T = 1410219.951 KJ/hr.
HCHO 101.6500 × 29.9153 × (339.75-273.15) 202523.2903
CH3OH 154.3011 × 18.4221 × (339.75-273.15) 189313.8496
H2 O 2785.6373 × 3.4705 × (339.75-273.15) 643859.113
H2O2 1.1869 × 50.5352 × (339.75-273.15) 3994.683243
Total 1039690.936 KJ/hr.
Condenser Duty:
Before calculating the condenser duty we will estimate the top column temperature using
Antoine’s Equation
ti = Bi / Ai – ln (Pi)
Pressure of stream is 0.29 bar = 217.5543 mmHg
Components xi × Pressure Pi (mmHg)

HCHO 0.0333 × 217.5543 7.244
CH3OH 0.0506 × 217.5543 11.008
H2 O 0.915 × 217.5543 199.062
H2O2 0.000388 × 217.5543 0.0844
By putting the value of Antoine Co-Efficient and partial pressure calculated above in the Antoine
Equation we will get the individual temperatures and boiling point of mixture can be calculated
by multiplying individual temperatures with their mole fraction and finally add them.
Components ti (K)
HCHO 7.244
CH3OH 11.008
H2 O 199.062
H2O2 0.0844
T = (184.9408 × 0.0333) + (331.1701 × 0.0506) + (350.2655 × 0.915) + (180.7006 × 0.000385)
T = 343.47 K
And ∆T = 343.47 – 273.15 = 70.32 K
Now we calculate the Vapor phase heat duty at the condenser inlet we get
HCHO 101.6500 × 31.9247 × (343.47-273.15) + (101.6500 × 24.5) 230689.0745
CH3OH 154.3011 × 18.4170 × (343.47-273.15) + (154.3011 × 35.3) 205279.6282
H2 O 2785.6373 × 3.4704 × (343.47-273.15) + (2785.6373 × 40.65) 793038.9825
H2O2 1.1869 × 49.0636 × (343.47-273.15) + (1.1869 × 48.5) 4152.550477
Total 1233160.236 KJ/hr.
So heat removed by the condenser
QC = 1233160.236 – 1039690.936 = 193469.2997 KJ/hr

H2O2 100.6817 × 49.5086 × (358.05-273.15) 423193.3901
Total 423193.3901 KJ/hr.
Now by applying the overall heat balance on the Distillation Column
Q8 + QR = Q9 + Q10 + QC
1410219.915 + QR = 1039690.936 + 423193.393 + 193469.2997
QR = 246133.7137 KJ/hr
The overall energy balance on the distillation column is given below
Table 6.7: Overall and Component Energy Balance on Multicomponent Distillation Column
(T-101)
Streams
Input Output
Q8 Q9 Q10
Components
HCHO 220140.2573 230689.0745
CH3OH 193330.4832 205279.6282
H2 O 657382.2746 793038.9825
H2O2 339366.9356 4152.550477 423193.3901
O2
Total 1410219.951 1233160.236 423193.3901
6.6 Energy Balance on Flash Column (V-103):
Q11
Q9
Q12
The mass balance over the flash column is given below in the table.
Streams
Input Output
M9 M11 M12
Components
HCHO 101.6500 101.6500
CH3OH 154.3011 0.00000075 154.3011
H2 O 2785.6373 0.00000225 2785.6373
H2O2 1.1869 1.2051
O2
Total 3043.414558 0.000003 3043.414555
Q9 = 1039690.936 KJ/hr
Q11 = Vapor Stream = mCP∆T+ mλ

CH3OH 0.00000075 × 18.3826 × (341.25-273.15) + (0.0000075 × 35.3) 0.0009653
H2 O 0.00000225 × 3.4704 × (341.25-273.15) + (0.00000225 × 40.65) 0.0006232
Total 0.0015885 KJ/hr.

HCHO 101.6500 × 31.7859 × (341.25-273.15) 220033.6017
CH3OH 154.3011 × 18.43826 × (341.25-273.15) 193162.6128
H2 O 2785.6373 × 3.4704 × (341.25-273.15) 658341.4742
H2O2 1.2051 × 48.9954 × (341.25-273.15) 4020.84862
Total 1075558.536 KJ/hr.
So total heat in output = 1075558.537 KJ/hr
QS = 1075558.537 – 1039690.936 = 35867.6011 KJ/hr.
Now
Q = mCP∆T + mλ
m = Q/CP∆T + mλ
m = 51.91674 kg mole/hr.
The overall energy balance on the flash column is given below.
Table 6.8: Overall and Component Energy Balance on Flash Column (V-103)
Streams
Input Output
Q9 Q11 Q12
Components
HCHO 230689.0745 220033.6017
CH3OH 205279.6282 0.0009653 193162.6128
H2 O 793038.9825 0.0006232 658341.4742
H2O2 4152.550477 4020.84862
O2
Total 1233160.236 0.0015885 1075558.536
Q13
Q12
Q14
Streams
Input Output
M12 M13 M14
Components
HCHO 101.6500 0.004143 101.6459
CH3OH 154.3011 133.5258 12.8846
H2 O 2785.6373 46.1900 2747.0177
H2O2 1.2051 1.2025
O2
Total 3043.414555 180.148213 2863.266342

HCHO 0.004143 × 31.5788 × (337.95-273.15) 8.477846752
CH3OH 133.5258 × 18.4165 × (337.95-273.15) 159348.2476
H2 O 46.1900 × 3.4704 × (337.95-273.15) 10387.29588
Total 169744.0213 KJ/hr.
Condenser Duty:

HCHO 0.000023 × 915.2248345 0.02105
CH3OH 0.7412 × 915.2248345 678.3673
H2 O 0.2564 × 915.2248345 234.6645
Components ti (K)
HCHO 86.8878
CH3OH 2207.8165
H2 O 335.5389
T = (0.000023 × 0.02105) + (0.7412 × 678.3673) + (0.2564 × 234.6645)
T = 1645.5477 K
And ∆T = 1645.5477 – 273.15 = 1372.3977 K

HCHO 0.004143 × 48.6663 × (1372.39-273.15) + (0.004143 × 24.5) 276.8104774
CH3OH 133.5258 × 18.5215 × (1372.39-273.15) + (133.5258 × 35.3) 3398787.612
H2 O 46.1900 × 3.4719 × (1372.39-273.15) + (461900 × 40.65) 221965.0092
Total 3621029.432 KJ/hr.
QC = 3621029.432 – 169744.0213 = 3451285.411 KJ/hr

HCHO 101.6459 × 34.5012 × (386.05-273.15) 395929.6338
CH3OH 12.8846 × 18.4213 × (386.05-273.15) 26796.93716
H2 O 2747.01777 × 3.4705 × (386.05-273.15) 1076334.964
H2O2 1.2025 × 50.3214 × (386.05-273.15) 6831.746487
Total 1505893.281 KJ/hr.
Q12 + QR = Q13 + Q14 + QC
1075558.536 + QR = 169744.0213 + 1505893.281 + 3451285.411
QR = 4051364.177 KJ/hr
The overall energy balance on the distillation column is given below
(T-102)
Streams
Input Output
Q12 Q13 Q14
Components
HCHO 220033.6017 276.8104774 395929.6338
CH3OH 193162.6128 3398787.612 26796.93716
H2 O 658341.4742 221965.0092 1076334.964
H2O2 4020.84862 6831.746487
O2
Total 1075558.536 3621029.432 1505893.281
Q15
Q14
Q16
Streams
Input Output
M14 M15 M16
Components
HCHO 101.6459 101.9662
CH3OH 12.8846 13.0031
H2 O 2747.0177 266.3173 2480.7004
H2O2 1.2025 1.1416
O2
Total 2863.266342 381.324894 2481.941448

HCHO 101.9662 × 39.6384 × (480.55-273.15) 838264.5544
CH3OH 13.0031 × 18.4309 × (480.55-273.15) 49705.24254
H2 O 266.3173 × 3.4706 × (480.55-273.15) 191695.8424
Total 1079665.639 KJ/hr.
Condenser Duty:

HCHO 0.2674 × 14981.23921 4005.9833
CH3OH 0.0341 × 14981.23921 510.8602
H2 O 0.6984 × 14981.23921 10462.8974
Components ti (K)
HCHO -840.0936
CH3OH 1588.4061
H2 O 544.855
T = (0.2674 × 4005.9833) + (0.0341 × 510.8602) + (0.6984 × 10462.8974)
T = 683.2 K
And ∆T = 1645.5477 – 273.15 = 410.05 K

HCHO 101.9662 × 35.8818 × (410.05-273.15) + (101.9662 × 24.5) 1502760.734
CH3OH 13.0031 × 18.4238 × (410.05-273.15) + (13.0031 × 35.3) 98693.25841
H2 O 266.3173 × 3.4705 × (410.05-273.15) + (266.3173 × 40.65) 389816.2287
Total 1991270.221 KJ/hr.
QC = 1991270.221 – 1079665.639 = 911604.5821 KJ/hr

H2 O 2480.7004 × 3.4707 × (512.85-273.15) 2063761.121
H2O2 1.1416 × 53.3118 × (512.85-273.15) 14588.32199
Total 2078349.443 KJ/hr.
Q14 + QR = Q15 + Q16 + QC
1505893.281 + QR = 1079665.639 + 2078349.443 + 911604.5821
QR = 2563726.383 KJ/hr
The overall energy balance over the distillation column is given below.
(T-103)
Streams
Input Output
Q14 Q15 Q16
Components
HCHO 395929.6338 1502760.734
CH3OH 26796.93716 98693.25841
H2 O 1076334.964 389816.2287 2063761.121
H2O2 6831.746487 14588.32199
O2
Total 1505893.281 1991270.221 2078349.443
6.9 Overall Energy Balance on Plant:

Total energy flow input
Streams Energy Flow (KJ/hr.)

Q2 359763.1522
E-101 359856.8571
Q3 135416.213
QR-101 246133.7137
QR-102 21051364.177
QR-103 2563726.383
QV-101 976349.9351
QV-102 35867.6011
Total 8728478.032 KJ/hr.
Total energy flow output
Streams Energy Flow (KJ/hr.)

Q5 32844.19137
QRef. 58.1
∆HR 385474.3797
Q7 2789.535664
Q11 0.0015885
Q13 169744.0213
Q15 1079665.639
Q16 2078349.443
Q10 423193.3901
QC-101 193469.2997
QC-102 3451285.411
QC-103 911604.5821
Total 8728477.995
Chapter No. 7 Fermenter Design
Chapter 7
FERMENTER DESIGN
7.1 Introduction:
Most fermenter can be modeled as batch reactors and hence we are going to design our fermenter
on the basis of batch reactor. [2-3,6-9,18]
Reactor is the heart of chemical process industry. Chemical reactors are vessels that are designed
for a chemical reaction in occur inside them. Our reactor is a stirred tank reactor. The operation
mode of a stirred tank reactor may be continuous, batch or semi batch. A stirred tank reactor
consists of a vessel to contain the reactants, a heat exchanger, a mixer, and baffles to prevent
vortex formation and to increase turbulence, enhancing mixing.
 Fermenter modeled as batch reactor.

 Batch reactor consists of an agitator and a cooling jacket around it.
 Reactants are filled in and allowed to react for a certain period of time without them
exciting.
 Jacket consists of agitation nozzles for providing higher turbulence and hence better heat
transfer.
7.2 Reactor Selection:

Our system is gas-liquid system. We select a batch continuous stirred tank reactor. This is due to
the following reasons.
 We need to have made a long time contact between reactants and enzymes.
 Need to mix the reaction mixture.
 In order to maintain the uniform concentration and temperature of reaction mixture.

M4 M5
M3 M6
The mole fraction data for these four streams is given below in table.
Streams
M3 M4 M5 M6
Units Mole % Mole % Mole % Mole %
Components
HCHO 0.032
CH3OH 0.084 0.0031 0.049
H2 O 0.915 0.885
H2O2 0.00036 0.032
O2 1.00 0.996 0.00020
The mass balance over the column is given below in the table.
Streams
Input Output
M3 M4 M5 M6
Components
HCHO 101.9522
CH3OH 256.9746 0.3613 154.8164
H2 O 2786.5307 2787.0104
H2O2 0.1096 101.9522
O2 113.2802 11.2917 0.6293
Total 113.2802 3044.723318 11.32802 3146.675498
7.3 Design Steps and Calculations:

 Residence Time
 Volume of Reactor
 Height and Diameter of Reactor
 Wall Thickness
 Agitator Design
 Agitator Speed
 Power Consumption
 Baffle Design
 Jacket Design
 Outside Film Co-Efficient
 Inside Film Co-Efficient
 Clean Overall Co-Efficient
 Design Overall Co-Efficient
Residence Time:
As we know that
� ��
�� = ( )−
�� −� ��
Where
Km = 0.4 mM
Vmax = 0.3137 mM/min
X = 90% = 0.9
CSugar = 0.08
Put these values we get
Residence Time = t = 2.8449 min
Volume of Reactor:
×�
=
For this purpose we required the density of mixture and mass flow rate.
For the mass flow rate multiply the molar flow rate with the mass of liquid mixture. The mass of
liquid mixture can be calculate by multiplying the mass of individual component with its mole
fraction and then simply add them.
Mass of mixture = (1×32) + (0.08×32.04) + (0.91×18) + (0.000036×34.0147)
Mass of mixture = 50.944 Kg/Kgmole
Now the mass flow rate will be.
Mass flow rate = 3158.0035 × 50.944
Mass flow rate = 160881.3303 Kg/hr.
If one reactor is used than it has very large dimensions so we use 5-reactors in parallel.
So mass handled by the one reactor will be
Mass flow rate = 160881.3303 / 5 = 32176.226 Kg/hr.
The density of liquid mixture can be calculated by following these steps
1. Calculate volume of each component from its density and molecular weight
2. Calculate the total volume of mixture by multiplying each individual volume of a
component with its mole fraction and finally add them in order to get the volume of total
mixture.
3. Calculate the volume fraction
4. Multiply the volume fraction of each component with its density and finally add them in
order to get the density of liquid mixture.
By following these steps we find out the density of feed mixture is to be.
Density of fluid = ρL = 5.1185 Kg/m3
Residence time = t = 2.8449 min = 0.0474 hr
Now put all of these values in above equation for the volume of reactor we have
. × .
=
.
VR = 297.696 m3
We allow 30% volume of free space in the fermenter so we have.
VT = 1.30 × 297.696
VT = 387.3597 m3
Height and Diameter of Reactor:

For reactor a rule of thumb for its sizing is
L/D = 1.5
So
L = 1.5D
Now as we know that the volume of the reactor is
VT = Area × Length
Where
�� = ( )
Put this value in above equation we get
= ( )× .
Put the values we get the diameter of reactor
DT = 6.90 m
So put this value in rule of thumb we will get the height of reactor
H = 10.358 m
Now from literature is has been noted that the height of dished bottom = 1 m
So the total height of the reactor will be
H = 11.35 m
Wall Thickness:
In order to find out the wall thickness we have to calculate the total pressure first
Static pressure = ρgh = 5.1185 × 9.81 × 10.35 = 0.5196 KPa
Operating pressure = 11.15 bar = 1115 KPa
Total pressure = 115.5196 KPa
In order to safety purposes we add 30% extra pressure so
Maximum allowable pressure = 1.33 (1115.5196) = 1483.641 KPa
Material of Construction = carbon steel
For carbon steel
S = 94408 KN/m2
EJ = 0.85
Shell thickness = tm
As we know that
�
�� = +
(� �− . )
Put all the values we get
. × .
�� = +
× . − . × .
�� = . +
Corrosion allowance = Cc = 2 mm
So the shell thickness will be
�� = .
Now the outside diameter will be
Do = Di + 2tm = 6.90 + 2×0.0665
Do = 7.03 m
Agitator Design:
Da = Dt/3 = 2.3 m
E = Da = 2.3m
L = Da/4 = 0.575 m
W = Da/5 = 0.46 m
J = Dt/10 = 0.69 m
Number of impellers = 3
Number of blades = 6
Distance between 2 consecutive impellers = 2.3 m
Shape Factors:
S1 = Da/Dt = 1/3
S2 = E/Dt = 1/3
S1 = L/Da = 0.25
S4 = W/Da = 1/5
S5 = J/Dt = 1/10
S6 = H/Dt = 1/3
Agitator Speed:
From literature
Tip Velocity = πDaN = 3-6 m/sec
We select
Tip velocity = 5 m/sec
Speed of Impeller is
=( )×
�
NSpeed = 42 RPM
Power Consumption:
Power number = NP = 6
NSpeed = 42 RPM = 0.7 rev/sec
As we know that
� × × � ×
�� =
�
× . × . × .
�� =
.
Power = 21.07 hp
Assume that impeller is 85% efficient
Actual Power = 21.07/0.85 =24.788 hp
Power = 25 hp
Baffle Design:
Number of baffles = 4
Width of 1 baffle = Dt/10 = 0.69 m
Height of baffle = 10.35 m
Jacket Design:
The following is the design of cooling jacket which is used in order to maintain the temperature.
Cooling fluid used = R-134a
R-134a inlet temperature = 245.15 K
R-134a outlet temperature = 308.15 K
∆T = 63 K
So heat removed by the R-134a
QRef. = 385129.7091 KJ/hr
CP = 1.418376 KJ/Kg
As we know that
Q = mCP∆T
m = 4309.9784 Kgmole/hr
Outside Film Co-Efficient:

As we know that
. /
� �
= ( )( ) ( )
�
Where
CP = 1.4188376 KJ/kgmole.K
K = 5.52 J/m.K
µ = 0.00027108 Pa.s
FS = 1.6 (Safety Factor)
ao = 0.33
Di = 6.90 m
Do = 7.033 m
Deq. = (D22 – D12)/D1 = 0.2685 m
A = 0.70πDL + π/4(D)2
L = H = Height of Reactor
A = 0.70 × 3.14 × 7.033 × 10.35 + 3.14/4 (7.033)2
A = 198.8242 m2
G = 439747.0962/198.8242 = 2211.73829 Kg/m2.hr
Put all the values in above equation in order to calculate the outside film co-efficient
. /
× . . . × . . × .
=( )( ) ( )
. . . .
Ho = 2397.1028 KJ/hr.m2.K
Inside Film Co-Efficient:

As we know that
/ /
� � × × ×ℎ � . �
= . ( ) ( )
� ��
Where
Di = 6.90 m
K = 0.6 J/m.K
ρ = 5.1185 Kg/m3
µ w = 0.1212 cp
now we have to find out the viscosity of mixture using this formula
/
�� = [∑ � �� ]
So by using above formula the viscosity of liquid mixture is found to be
µ mixture = 0.1212 cp
the specific heat capacity of mixture can be calculated using this formula
(Cp)mixture = x1Cp1 + x2Cp2 + x3Cp3 + ………………..
So by using above formula the heat capacity of mixture is found to be
CP = 35.2707 KJ/Kgmole.K
Length of Blade = L = 0.575 m
N = 42 RPM = 07 RPH
Now put all these values in above equation we get the inside film co-efficient
/ . /
� × . . × . × . × . . . × .
= . ( ) ( )
. . . .
Hi = 1584.2975 KJ/hr.m2.K
Clean Overall Co-Efficient:

As we know that
ℎ� × ℎ
� =
ℎ� + ℎ
Where
.
ℎ� = ℎ� × = . ×
.
Hio = 1554.1958 KJ/hr.m2.K
Put these values in above equation in order to calculate the clean overall co-efficient
. × .
� =
. + .
UC = 942.8715 K J/hr.m2.K
Design Overall Co-Efficient:

Let us assume that
Dirt factor = RD = 0.001
So as we know that
1/UD = 1/UC + RD
So put the values we get
UD = 485.4368 KJ/hr.m2.K
7.4 Specification Sheet for Fermenter

Equipment Fermenter
Number of Equipment 5
Function To Convert Methanol into Hydrogen Peroxide and Formaldehyde
Operation Continuous
Type Cooling Jacketed Stirred Tank Reactor
Residence Time 2.8449 min
Volume of Reactor 387 m3
Height of Reactor 11.35 m
Diameter of Reactor 6.90 m
Static Pressure 0.5196 KPa
Operating Pressure 1115 KPa
Total Pressure 1115.5196 KPa
Material of Construction Carbon Steel
Shell Thickness 0.0662 m
Outside Diameter 7.033 m
Table 7.1: Specification Sheet for Fermenter (R-101)
7.5 Specification Sheet for Agitator

Item Agitator
Type Three 6-Bladed Flat Turbine
Impeller Diameter 2.3 m
Impeller height above the Vessel Floor 2.3 m
Length of Impeller Blade 0.575 m
Width of Impeller Blade 0.46 m
Width of Baffle 0.69 m
Number of Impellers 3
Number of Impellers Blades 6
Distance between 2 Consecutive Impellers 2.3 m
Speed of Impeller 42 RPM
Power Required 25 hp
Table 7.2: Specification Sheet for Agitator
7.6 Specification Sheet for Cooling Jacket

Item Cooling Jacket
Cooling Fluid R-134a
Inlet Temperature 245.15 K
Outlet Temperature 308.15 K
Refrigerant Flow Rate 4309.9784 Kgmole/hr.
Outside Film Co-Efficient 2397.1028 KJ/hr.m2.K
Inside Film Co-Efficient 1584.2975 KJ/hr.m2.K
Clean Overall Co-Efficient
Overall Design Co-Efficient 485.4368 KJ/hr.m2.K
Table 7.3: Specification Sheet for Cooling Jacket
Chapter No. 8 Multicomponent Distillation Column Design
Chapter 8
MULTICOMPONENT DISTILLATION
COLUMN DESIGN
8.1 Introduction:
In industry it is a common practice to separate a liquid mixture by distilling the components,
which have lower boiling points when they have in pure conditions from those having higher
boiling points. This process is accomplished by partial vaporization and subsequent
condensation. [11,14,15]
Distillation is defined as
“Process in which a liquid or vapor mixture of two or more substances is separated into its
component fractions of desired purity by the application and removal of heat”
8.2 Types of Distillation Columns:

There are many types of distillation columns, each designed to perform specific types of
separation, and each design differs in terms of complexity.
Batch Columns:
In batch operations, the feed to the column is introduced in batch wise. That is the column is
charged with a batch and then the distillation process is carried out. When the desired task is
achieved a next batch of feed is introduced.
Continuous Columns:
In contrast, continuous columns process a continuous feed stream. No interruption occurs unless
there is a problem with the column or surrounding process units. They are capable of handling
high throughputs and are the more common of two types. We shall concentrate only on this class
of columns.
8.3 Column Selection:

Comparison between Packed Column and Plate Column:
 Plate column can be designed to handle a wide range of liquid and gas flow rates than
packed columns.
 Packed columns are suitable for high liquid flow rates.

 Plate column can be designed with more assurance than packed columns. There is always
come doubt that good liquid distribution can be maintained throughout a packed column
under all operating conditions, particularly in large columns.
 It is easier to make provision for cooling in a plate column; coils can be installed on the
plates.
 It is easier to make provision for the withdrawal of side-streams from plate column. The
efficiency of a plate can be predicted with more certainty than the Equilent term for
packing.
 If the liquids cause fouling or contains solids it is easier to make provision for cleaning in
plate’s column.
 For corrosive liquids a packed column will be economical as compared to plate column
 Packed columns are suitable for handling foaming systems.
 Packed columns are always considered for low pressure drop and low diameter.
8.4 Selection Criteria of Trays:

The principal factors to consider when comparing performance of three types of plates i.e. sieve
plate, valve tray and bubble-cap plates are as follows.
Cost:
Sieve Plate : Valve Plate : Bubble-Cap Plate
3 : 1.5 : 1.0
Capacity:
Sieve Plate > Valve Plate > Bubble-Cap Plate
Pressure Drop:
Bubble-Cap Plate > Valve Plate > Sieve Plate
M9
M8
M10
The feed top and bottom composition in the form of mole fraction are given below.
Streams
M8 M9 M10
Components
HCHO 0.032 0.033
CH3OH 0.049 0.050
H2 O 0.886 0.915
H2O2 0.032 0.00039 1.00
O2
Streams
Input Output
M8 M9 M10
Components
HCHO 101.8687 101.6500
CH3OH 154.3751 154.3011

H2 O 2785.6692 2785.6373
H2O2 101.8687 1.1869 100.6817
O2 0
Total 3144.096258 3043.414558 100.6817

 Minimum Reflux Ratio
 Actual Reflux ratio
 Minimum Number of Stages
 Theoretical Number of Stages
 Location of Feed Plate
 Column Efficiency
 Actual Number of Trays
 Diameter of Column
 Provisional Plate Design
 Calculation of Entrainment
 Estimation of Weeping
 Tray Pressure Drop
 Backup in Down Comer
 Check Residence Time
 Height of Column
 Hole Pitch
Minimum Reflux Ratio:

A relationship for the minimum reflux ration for multicomponent mixtures distillation is given
by.
� � =
[ � .{ � . − }]
Where
Rmin = minimum reflux ratio
(XFLK)eff. = XFLK / (XFLK + HFHK) = 0.049 / (0.049 + 0.0323) = 0.6027
Where the relative volatility of light key is 1.517
Light key: Methanol
Heavy Key: H2O2
Put all these values in above equation we get
Rmin = 3.2154
Actual Reflux Ratio:

For actual or optimum reflux ratio a rule of thumb is given in “Chemical Process Equipment
Selection and Design”
R = 1.5 (Rmin) = 1.5 (3.2154) = 4.823
Minimum Number of Stages:

The minimum numbers of plates are calculated by stage to stage calculation using the Lewis-
Matheson Method.
The feed top and bottom composition in the form of mole fraction are given below.
Streams
M8 M9 M10
Components
HCHO 0.032 0.033
CH3OH 0.049 0.050
H2 O 0.886 0.915
H2O2 0.032 0.00039 1.00
O2
Where
F = 3144. 096 Kgmole/hr.
D = 3043.4145 Kgmole/hr.
W = 100.6817 Kgmole/hr.
Now above the feed point we have
Ln = Rm (D) = 3.2154 (3043.4145) = 9785.794 Kgmole/hr.
Vn = 4.9 (D) = 4.9 (3043.4145) = 14912.73 Kgmole/hr.
Now below the feed plate we have
Lm = Ln + F = 9785.794 + 3144. 096 = 12929.89 Kgmole/hr.
Vm = Lm – W = 12929.89 - 100.6817 = 12829.2083 Kgmole/hr.
Now we have to derive the equations of operating lines we have.
Below the feed plate the equation of operating line is
=( ) + −( )
Put the we get
. .
=( ) + −( )
. .
= . + − .
Now the Equations of Bottom Operating Line (BOL) are given below
Table 8.1: Equations of Bottom Operating Line (BOL)
Component Equations of Bottom Operating Line (BOL)
HCHO = . + −
CH3OH = . + − .
H2 O = . + −
H2O2 = . + − .
Now above the feed plate the equation of operating line is
=( ) + +( )
Put the we get
. .
=( ) + +( )
. .
= . + + .
Now the Equations of Top Operating Line (TOL) are given below
Table 8.2: Equations of Top Operating Line (TOL)
Component Equations of Top Operating Line (TOL)
HCHO = . + + .
CH3OH = . + + .
H2 O = . + + .
H2O2 = . + + .
Now we start to calculate the composition of mixture by stage to stage calculation. As we know
that
�
=
∑�
Component Xs Relative Volatility × Xs Ys

HCHO 0 0 0
CH3OH 0.00001152 0.00000063 0.0022
H2 O 0 0 0
H2O2 0.007828 0.000284 1
Total 0.000284 1.0022
Component X1 Relative Volatility × X1 Y2

HCHO 0 0 0
CH3OH 0.00199 0.00011 0.00299
H2 O 0 0 0
H2O2 1.0008 0.0366 0.9970
Total 0.999

HCHO 0 0 0
CH3OH 0.00298 0.00016 0.00438
H2 O 0 0 0
H2O2 0.9978 0.0363 0.9956
Total 0.03646 0.999

HCHO 0 0 0
CH3OH 0.00438 0.000241 0.0066
H2 O 0 0 0
H2O2 0.9964 0.03626 0.9933

Total 0.036501 0.9999

HCHO 0 0 0
CH3OH 0.00656 0.000362 0.0099
H2 O 0 0 0
H2O2 0.9941 0.03618 0.9900
Total 0.036542 0.9999

HCHO 0 0 0
CH3OH 0.00984 0.000544 0.014
H2 O 0 0 0
H2O2 0.9998 0.0363 0.986
Total 0.0368 0.999

HCHO 0 0 0
CH3OH 0.0139 0.000768 0.0209
H2 O 0 0 0
H2O2 0.9869 0.3592 0.9814
Total 0.0366 0.999

HCHO 0 0 0
CH3OH 0.0207 0.00114 0.0309
H2 O 0 0 0
H2O2 0.9823 0.0357 0.9690
Total 0.03684 0.9999

HCHO 0 0 0
CH3OH 0.0306 0.00169 0.0453
H2 O 0 0 0
H2O2 0.9700 0.0356 0.9546
Total 0.03729 0.9999

HCHO 0 0 0
CH3OH 0.0526 0.002908 0.077
H2 O 0 0 0
H2O2 0.9557 0.03478 0.921
Total 0.03776 0.999
So there are approximately 10 plates below the feed plate.
Now for the number of plates above the feed plate we use the Equations of Top Operating Line
(TOL) we have.

HCHO 0 0 0
CH3OH 0.0533 0.00294 0.0526
H2 O 0 0 0
H2O2 1.4546 0.0529 0.947
Total 0.05584 0.999
So there only 1 plate is required above the feed plate.
Theoretical Number of Plates:

By using Gilliland Relationship we can estimate the Theoretical number of stages.
.
− � �−� �
= . [ −( ) ]
+ �+
Where
N = theoretical number of stages
Nmin = minimum number of stages = 11
R = actual reflux ratio = 4.8231
Rmin = minimum reflux ratio = 3.2154
Put all these values in above equation we get the theoretical number of stages
.
− . − .
= . [ −( ) ]
+ . +
N = 18.5 = 19
Location of Feed Plate:

Kirk-Bride Method is used for the estimation of feed plate location
�
�� ( )= . [( ) ( ) { } ]
� �
Where
ND / NB = ratio between top and bottom plates
B = total flow rate in bottom = 100.6817 Kgmole/hr.
D = total flow rate in top = 3043.414558 Kgmole/hr.
(XHK)F = mole fraction of heavy key in feed = 0.0323
(XLK)F = mole fraction of light key in feed = 0.049
(XLK)B = mole fraction of light key in bottom= 0.00147
(XHK)D = mole fraction of heavy key in top = 0.000389
Put all these values in above equation we get
. . .
�� ( )= . [( )( ) { } ]
. . � .
ND / NB = 1.158 = 1
So 9th plate from the top is feed plate
Column Efficiency:
By using the following relation we can calculate the column efficiency
− .
= . [� . −� .]
Where
Eo = column efficiency
the average viscosity of mixture is calculated by using this formula at average column
temperature that is
average column temperature = (339.75 + 358.05) / 2 = 348.9 K
µ avg. = [ €Xi (µ i)1/3 ]3
µ avg. = viscosity of feed mixture = 0.9732 mN/m2
αavg. = relative volatility of light key = 1.517
put all of these values in above equation we get
Eo = 43.32 %
Actual Number of Trays:

Actual number of trays can be found as
Actual Number of Trays = NTheoretical / Eo
Actual Number of Trays = 19/0.4332
N = 44 Plates
Tray Dynamics
Flow Parameter:
The flow parameter can be calculated as
�
=( )( )
�
Where
FLV = flow parameter
LN = liquid flow rate at bottom = 100.6817 Kgmole/hr.
LV = vapor flow rate at bottom = 3043.414558 Kgmole/hr.
The densities of liquid and vapor mixtures can be calculated by using the following methodology
 Calculate volume of each component using (Vi = mi/ρi)

 Calculate mixture volume (Vmixture = V1X1 + V2X2 + V3X3 + …….)
 Calculate the volume fraction (V1-fraction = Vi / Vmixture)
 Calculate the mixture density (ρmixture = ρ1 V1-fraction + ρ2 V2-fraction + ρ3 V3-fraction + ……)
ρV = density of vapors = 960.1240 Kg/m3
ρL = density of liquid = 1031.378 Kg/m3
put all of these values in above formula we get the flow parameter value
. .
=( )( )
. .
FLV = 0.02859
Capacity Parameter
Assume tray spacing = 0.46 m
From figure 15-5 (b) “Plant Design and Economics for Chemical Engineers” we have
Sieve tray flooding capacity = Csb = 0.054 m/sec
The surface tension of the mixture can be calculated as follows
�
� � =( )
� � �
By putting values we get the surface tension of the system is
αmin = 4.1 × 106 N.m/sec.
Now net vapor velocity at flooding can be calculated as
� − .
�
= ( )

.
. × . − .
= . ( )
.
Vnf = 0.1698 m/sec
Actual vapor velocity = Vn = 0.80 × Vnf = 0.80 × 0.1698 = 0.135m/sec
Volumetric flow rate of vapors = 58173.441 / vapor density × 3600 = 0.01683 m3/sec
Net area = An = vapor flow rate / Vn = 0.01683/0.135= 0.1246 m2
Assume that down comer occupies 15% of cross-sectional area Ac of the column
So
Ac = An + Ad
Ac = An + 0.15(Ac)
Ac = An / 0.85 = 0.1246/0.85 = 0.1465 m2
Diameter of Column:
As we know that
− /
= (− . � + . � − . )( )
Where
lt = plate spacing = 0.46 m

/
. − .
= − . . + . × . − . ( )
.
UV = 0.0111 m/sec
Now the diameter of the column can be found by using the formula
=√
Where
VW = vapor flow rate = 58173.441 Kg/hr = 16.1592 Kg/sec
× .
=√
. × . × .
DC = 1.9315 m
Now
Liquid Flow Arrangement:

In order to find out the liquid flow arrangement in the column it is necessary to find out the
volumetric flow rate of liquid.
Liquid volumetric flow rate = 3424.3417 / 1031.378× 3600 = 0.0009222 m3/sec
From figure 8.1 given below “Chemical Engineering Design Coulson and Richardson’s Volume
6, 3rd Edition”
Figure 8.1: Liquid Flow Arrangement
We have selected single pass plate.
Provisional Plate Design:

Dc = column diameter = 1.9315 m
Ac = Column cross-sectional area = 0.1465 m2
Ad = down comer area = 0.15 (Ac) = 0.0438 m2
AN = net area = Ac – AD = 0.1246 m2
Aa = active area = Ac – 2 (Ad) = 0.1027 m2
For hole area
Ah = take 5% of Aa = 0.05 × 0.1027 = 0.005135 m2
Weir Length:
For Weir length
Ad / Ac = 0.0438 / 0.1465= 0.1494
6, 3rd Edition”
Lw / Dc = 0.81
Lw = 0.81 × 1.9315 = 1.549 m
Weir length should be 60.5 to 85% of the column diameter so which is satisfactory.
Now
Take weir height = hw = 50 mm
Hole diameter = dh = 5 mm
Plate Thickness = 5 mm
Flooding Check:
Un = actual velocity (based on net area)
Un = maximum volumetric flow rate at base / An = 0.0009222 / 0.1246= 0.007401 m/sec
Velocity at flooding condition can be calculated using this formula
−
= √
6, 3rd Edition”
at
FLV = 0.2859
Tray spacing = 0.46 m
We have to find out from above graph
Figure 8.2: Relation between Downcomer Area and Weir Length
Figure 8.3: Flooding Velocity, Sieve Plates
K1 = 0.08
Put the values in above formula we get
. − .
= . √
.
Uf = 0.02179 m/sec
Percent flooding = (Un /Uf ) × 100 = (0.007401 / 0.02179) × 100 = 33.96%
Calculation of Entrainment:
6, 3rd Edition”
Figure 8.4: Entrainment Correlation for Sieve Plates
As
FLV = 0.02859
F = 33.96%
We have find out that
Fractional entrainment = 0.007 ≤ 0.1
So process is satisfactory.
Estimation of Weep Point:

The weep point can be estimate by using the following formula
−{ . . − �ℎ }
� = .
Where
Umin = minimum design vapor velocity

/
ℎ = ( )
×

/
.
ℎ = ( )
. × .
how = 39.84 mm
hw = 50 mm
so
how + hw = 50 + 39.84 = 89.84 mm
From figure 8.5 “Chemical Engineering Design Coulson and Richardson’s Volume 6, 3rd
Edition” we have
Figure 8.5: Weep Point Correlation
K2 = 30.9
Put all these values in above equation in order to calculate the minimum design vapor velocity
. −{ . . − . }
� = .
.
Umin = 0.1313 m/sec
Maximum volumetric flow rate of vapors = 3043.414558 / 960.1240 × 3600 = 0.01683 m3/sec
At 80% turn down ratio we have
Actual minimum vapor velocity = vapor volumetric flow rate / Aa
Actual minimum vapor velocity = 0.01683 / 0.1027= 0.1638 m/sec
So
Actual minimum vapor velocity > Umin
So there is no weeping and process is satisfactory.
Tray Pressure Drop:

The tray pressure drop can be calculated by calculating the total head.
Ht = Hd + ( Hw + How ) + Hr
Dry Tray Pressure Drop:

Dry tray pressure drop can be calculated as follows
= ( ) ( )
Where
Un = hole velocity = Qv /Aa = 0.01683 / 0.1027 = 0.1638 m/sec.
Tray thickness = 5 mm (for carbon steel)
Hole diameter = 5 mm (for carbon steel)
Perforated or active area = Aa = 0.1027 m2
Ah /Ap = 0.005135 / 0.1027= 0.0207 = 2.07%
From figure 8.6 “Chemical Engineering Design Coulson and Richardson’s Volume 6, 3rd
Edition”
We have for
plate thickness / hole diameter = 5/5 = 1.00
Co = 0.77 (from graph)
Figure 8.6: Discharge Coefficient, Sieve Plates
Put all the values in above equation we get
. .
= ( ) ( )
. .
Hd = 2148.2 mm liquid
Residual Head:
Hr = 12.5 × 103 / ρL = 12.5 × 103 / 1031.378 = 12.1197 mm liquid
Now we have to find the total head by putting the vales in above equation
Ht = 2148.2 + 89.84+ 12.1197 = 2250.1597 mm liquid
Total Pressure Drop:

∆Pt = 9.81 × 10-3 × Ht × ρL
∆Pt = 9.81 × 10-3 × 2250.1597 × 1031.378= 0.22419 atm per tray = 3.2946 Psi per tray
Backup in Down Comer:

The backup in down comer can be found as follows
Hb = Hw + How + Ht + Hdc
Where
=
×
Where
Aap = Hap × Lw
Where
Hap = Hw – (5 to 10 mm)
Hap = 50 – 10 = 40 mm
So area under apron is
Aap = 40 × 0.9512 = 36.608 m2
Now put all the values in above equation we get
.
= ( )
. × .
Hdc = 0.00418 mm liquid
So
Hdc < Ad that is 0.02
So tray spacing is acceptable
Total Number of Holes:

Total number of holes = Ah / ah
Where
Ah = area of hole = 0.005135 m2
And
ah = π4 (Dh)2 = 3.14/4 (0.005)2 = 0.000019625 m2
so put the values in above equation we get
Total number of holes: 0.005135 / 0.000019625 = 261.656051 = 262 holes
Check Residence Time:

The residence time can be calculated by using the following formula as follows
ℎ
�� =
. × . × .
�� =
.
tR = 73.0 sec = 1.706 min > 3.00 sec.
so process is satisfactory.
Height of Column:
The height of column can be calculated by using the following formula as follows
Hc = (Nact – 1)Hs + ∆H + thickness of trays
Where
Nact = number of actual plates = 44
Hs = 0.46 m
∆H = 0.1125 m
Thickness of trays = plate thickness × Nact = 0.005 × 44 = 0.22 m
Put all the values in above equation we get the height of column
Hc = (44 - 1)0.46 + 0.1125 + 0.22
so
Total height of column = 20.1125 m
For a satisfactory design we prefer that
L/D should be less than 30 and we prefer that it should be less than 20
So
L/D = 20.1125/1.9315 = 10.4128
So design is acceptable.
Hole Pitch:
The hole pitch can be calculated by using this formulas follows
ℎ �ℎ
( )= .
Put all the values we get the hole pitch
. .
( )= .
.
Ip = 21.32 mm
8.6 Specification Sheet for Multicomponent Distillation Column

Identification Item Multicomponent Distillation Column
Tray Type Sieve Tray
Function Recovery of H2O2 from Methanol
Design Data
No. of Trays 44 Hole Area 0.0.005135 m2
Pressure 0.35 Bar Weir Length 1.549 m
Height of Column 20.1125 m Reflux Ratio 4.8231
Diameter of Column 1.9315 m Hole Size 0.005 m
Tray Spacing 0.46 m Down Comer Area 0.0219 m2
Tray Thickness 0.52 m Hole Area 0.005135 m2
Flooding 33.96 % Active Area 0.1027 m2
Entrainment 0.007 Pressure Drop 0.22419 atm
Table 8.3: Specification Sheet for Multicomponent Distillation Column (T-101)
Chapter No. 9 Flare Design
Chapter 9
FLARE DESIGN
9.1 Introduction:
Flaring is a volatile organic compound (VOC) combustion control process in which the VOCs
are piped to a remote, usually elevated, location and burned in an open flame in the open air
using a specially designed burner tip, auxiliary fuel, and steam or air to promote mixing for
nearly complete (> 98%) VOC destruction. Completeness of combustion in a flare is governed
by flame temperature, residence time in the combustion zone, turbulent mixing of the
components to complete the oxidation reaction, and available oxygen for free radical formation.
Combustion is complete if all VOCs are converted to carbon dioxide and water. Incomplete
combustion results in some of the VOC being unaltered or converted to other organic compounds
such as aldehydes or acids. [12,15]
The flaring process can produce some undesirable by-products including noise, smoke, heat
radiation, light, SO , NO , CO, and an additional source of ignition where not desired. However,
by proper design these can be minimized.
9.2 Applicability:
Flares can be used to control almost any VOC stream, and can handle fluctuations in VOC
concentration, flow rate, heating value, and inerts content. Flaring is appropriate for continuous,
batch, and variable flow vent stream applications. The majority of chemical plants and refineries
have existing flare systems designed to relieve emergency process upsets that require release of
large volumes of gas. These large diameter flares designed to handle emergency releases, can
also be used to control vent streams from various process operations. Consideration of vent
stream flow rate and available pressure must be given for retrofit applications. Normally,
emergency relief flare systems are operated at a small percentage of capacity and at negligible
pressure. To consider the effect of controlling an additional vent stream, the maximum gas
velocity, system pressure, and ground level heat radiation during an emergency release must be
evaluated. Further, if the vent stream pressure is not sufficient to overcome the flare system
pressure, then the economics of a gas mover system must be evaluated, If adding the vent stream
causes the maximum velocity limits or ground level heat radiation limits to be exceeded, then a
retrofit application is not viable.
Many flare systems are currently operated in conjunction with base load gas recovery systems.
These systems recover and compress the waste VOC for use as a feedstock in other processes or
as fuel. When base load gas recovery systems are applied, the flare is used in a backup capacity
and for emergency releases. Depending on the quantity of usable VOC that can be recovered,
there can be a considerable economic advantage over operation of a flare alone. Streams
containing high concentrations of halogenated or sulfur containing compounds are not usually
flared due to corrosion of the flare tip or formation of secondary pollutants (such as SO2). If
these vent types are to be controlled by combustion, thermal incineration, followed by scrubbing
to remove the acid gases, is the preferred method.
9.3 Factors Affecting Efficiency:

The major factors affecting flare combustion efficiency are vent gas flammability, auto-ignition
temperature, heating value (Btu/Scf), density, and flame zone mixing.
The flammability limits of the flared gases influence ignition stability and flame extinction. The
flammability limits are defined as the stoichiometric composition limits (maximum and
minimum) of an oxygen-fuel mixture that will burn indefinitely at given conditions of
temperature and pressure without further ignition. In other words, gases must be within their
flammability limits to burn. When flammability limits are narrow, the interior of the flame may
have insufficient air for the mixture to burn. Fuels, such as hydrogen, with wide limits of
flammability are therefore easier to combust.
For most vent streams, the heating value also affects flame stability, emissions, and flame
structure. A lower heating value produces a cooler flame that does not favor combustion kinetics
and is also more easily extinguished. The lower flame temperature also reduces buoyant forces,
which reduces mixing.
The density of the vent stream also affects the structure and stability of the flame through the
effect on buoyancy and mixing. By design, the velocity in many flares is very low; therefore,
most of the flame structure is developed through buoyant forces as a result of combustion.
Lighter gases therefore tend to burn better. In addition to burner tip design, the density also
directly affects the minimum purge gas required to prevent flashback, with lighter gases
requiring more purge.
Poor mixing at the flare tip is the primary cause of flare smoking when burning a given material.
Streams with high carbon-to-hydrogen mole ratio (greater than 0.35) have a greater tendency to
smoke and require better mixing for smokeless flaring. For this reason one generic steam-to-vent
gas ratio is not necessarily appropriate for all vent streams. The required steam rate is dependent
on the carbon to hydrogen ratio of the gas being flared. A high ratio requires more steam to
prevent a smoking flare.
M11
M9
M12
Streams
M9 M11 M12
Components
HCHO 101.6500 101.6500
CH3OH 154.3011 0.00000075 154.3011
H2 O 2785.6373 0.00000225 2785.6373
H2O2 1.1869 1.2051
O2
Total 3043.414558 0.000003 3043.414555
The overall mass balance over the flare is given below.
Streams
Input Output
M9 M11 M12
Components
HCHO 101.6500 101.6500
CH3OH 154.3011 0.00000075 154.3011
H2 O 2785.6373 0.00000225 2785.6373
H2O2 1.1869 1.2051
O2
Total 3043.414558 0.000003 3043.414555

 Total Heat Value
 Flare Tip Diameter
 Flare Height
 Purge Gas Requirements
 Pilot Gas Requirements
 Steam Requirements
 Knock Out Drum Specifications
Total Heat Value:

BV = (868 × 0.16) + (0.70 × 0.03)
BV = 138.901 Btu/Scf
As the heating value of vent stream is less than 300 Btu/Scf so auxiliary fuel is required
Q × BV + F × BF = (Q + F) × 300 Btu/Scf
Where
Q = 12.69 Scfm
Where
F = Q (300-BV /BF – 300)
Where
BF = 1000 Btu/Scf
Put the values in above equation we get
F = 2.92 Scfm
The annual auxiliary fuel requirement is
Fa = F × 60 min/hr ×8760 hr/year
Fa = 526 × F
Fa = 1535.92 Mscf/year
Flare Tip Diameter:

As we know that
Log10 (Vamx) = (BV + 1214) / 852
Log10 (Vamx) = (138.9 + 1214) / 852
Vmax = 65.08 ft/sec
Now
Qtotal = Q + F
Qtotal = 12.698 + 2.92
Qtotal = 15.618 Scfm
Now as we know that
Dmin = 1.95 (Qtotal / Vmax)1/2
Dmin = 1.95 (15.618 / 65.08)1/2
Dmin = 0.999 inch = 1.00 inch
Flare Height:
As we know that
L2 = f × R / 4K
Where
f = friction heat radiant = 0.2
K = allowable radiations = 500 Btu/hr.ft2
R = net heat value
R = W × BV
R = 180.07 × 110537
R = 1897419.198 Btu/hr
Now put all the values in above equation we get
L2 = (0.2 × 1897419.198) / (4 × 500)
L2 = 189.74 ft2
L = 14 ft
Minimum height of flare should be 30 ft.
So
L = 30 ft
Purge Gas Requirements:

As we know that
FPV = 6.88 D2
FPV = 6.88 (1)2
FPV = 6.88 Mscf/year
Pilot Gas Requirements:

From the table given below we have
For the 1 inch flare tip diameter required number of burners is 1.
Annual pilot gas consumption is given by
FPi = 613 × N
FPi = 613 × 1
FPi = 613 Mscf/year
Steam Requirement:
Steam required for methanol = 0.4 lb. of steam / lb. of methanol
Steam required for methanol = 3500 × W
Steam required for methanol = 3500 × 180.071
Steam required for methanol = 630245 lb. /year
Knock Out Drum Specifications:

As we know that
U = G (ρL – ρV / ρV)1/2
Where
G = 0.17 taken from GPSA Engineering Data Book
U = 0.17 (62.04 – 0.1278 / 0.1278)1/2
U = 3.763 ft/sec.
Now
Area = A = QA / U
Area = A = 12.698 / 60 × 3.763
Area = A =0.0562 ft2
Now
Diameter = Dmin = 12 (4 × A)1/2
Diameter = Dmin = 12 (4 × 0.0562)1/2
Diameter = Dmin = 13.202 inch
In accordance to standard head pressure and increment of 6 inch is considered and thickness of
vessel for Dmin less than 36 inch is 0.25 inch.
D = 13.202 + 6 + 0.25
D = 19.452 inches
Now
L/D = 3 for light volatile organic compounds
Now
L/19.452 = 3
L = 58.356 inch = 4.863 ft = 5 ft
9.5 Specification Sheet of Incinerator

Equipment Incinerator
Function To Burn VOC
Type Flare Type
Flare Tip Diameter 1 inch
Flare Height 30 ft
Table 9.1: Specification Sheet for Flare
Chapter No. 10 Heat Exchanger Design
Chapter 10
HEAT EXCHANGER DESIGN

10.1 Introduction:
A heat exchanger is a heat transfer device that is used for the transfer of internal thermal energy
between two or more fluids available at different temperatures. In most heat exchangers, the
fluids are separated by a heat transfer surface, and ideally they do not mix. Heat exchangers are
used in process, power, petroleum, transportation, air conditioning, refrigeration, cryogenic, heat
recovery, alternate fuels, and other industries. Common examples of heat exchangers familiar to
us in day-today use are automobile radiators, condensers, evaporators, air pre-heaters, and oil
coolers. [16,18,19,23]
10.2 Selection Criteria:

 Cost --- wish to have a heat exchanger with least cost.
 Efficiency --- wish to have a heat exchanger that operates most efficiently, with
minimum loss of energy in the heat transfer, and minimum pressure drops of the fluids.
 Space --- wish to have a heat exchanger that is small.
 Materials --- wish to have a heat exchanger which is built from such materials that are
compatible with the process streams and don’t cost a load.
 Maintenance --- wish to have a heat exchanger that can be easily cleaned.
 Ease of Construction --- wish to have a heat exchanger that can be easily constructed.
Shell and Tube Heat Exchangers:

In process industries, shell and tube heat exchangers are used in great numbers, far more than
any other type of heat exchanger. More than 90% of heat exchangers used in industry are of the
shell and tube heat exchangers type. They are produced in the widest variety of sizes and styles.
There is virtually no limit on the operating temperature and pressure.
Figure 10.1: Design Procedure for Shell and Tube Heat Exchangers
298.15 K 325.15 K
350.511 K 485.511 K

The outlet temperature of hot stream can be determined by a method given in “Chemical Process
Equipment Selection and Design” given below.
. −
=
. − .
. −
=
. − .
− . − . − .
∆ =
− .
. − .
Now we suppose the temperature by hit and trial and try to satisfy this equation.
− ∆ ≅
We try 455.15 K, 400 K, 350 K, 300 K, 325 K, and 335 K and finally at 325.512 K above
equation are satisfied with the value of ∆ 49.06. So outlet temperature of the hot stream is
found to be 350.511 K which was initially unknown.
Heat Balance:
For liquid stream
The total flow rate is to be 43251.500 Kgmole/hr so we use 4 heat exchangers in parallel in order
to design optimum heat exchanger with low pressure drop.
Q = mCp∆T = 3043.614 × 1.5782× (325.15– 298.15) = 129248.8947 KJ/hr
For steam
Q = mCp∆T
129248.8947 = m × 3.4706 × (485.15 – 325.51)
M = 232.782 Kgmole/hr
Overall Heat Transfer Co-efficient:

Let suppose
UD = 198.739 J/m2.K.hr
Now as we know that
Q = UD A ∆T
A = 13.277 m2 = 142.8586 ft2
Tube Layout and Sizing:

Length: 15 ft
OD, BWG, Pitch: 0.75, 16, 1 triangular pitch
Passes: 2
Outside surface area per linear ft, a = 0.3271 / linear ft
Number of tubes: 30
Shell ID: 8 in
Corrected Co-efficient:
Corrected Area (A): 30 in × 15× 0.3271= 147.195 ft2
Now by using again this formula with new Area (A) values we have
Q = UD A ∆T
UD = 192.901 J/m2.K.hr
This values is 97.06% correct to the assume value so this is the final value of Overall Design Co-
efficient.
Tube Side Calculation Shell Side Calculation
Flow Area: Flow Area:

a/ = 0.985 in2 /
× ×
� =
×
× �/
� =
× Where
Put the values we get C/ = 1 – 0.75 = 0.25
× . B = 10 in
� =
×
� = = .
× . ×
� =
Mass Velocity: ×
� � = . = .
=
�
Mass Velocity:
�
. =
= �
.
= . .
ℎ .
=
.
Reynolds Number:
= .
µ = 0.6280 Pa.s ℎ .
Di = 1.12/12 = 0.0933 ft = 0.0284 m Reynolds Number:

. × . µ = 0.10 Pa.s
� =
.
from graph Equilent Diameter will be
� = . ≅
De = 0.95 in = 0.079 ft = 0.0021 m
JH Factor:
JH = 70
. × .
� =
.
(CP µ/K)1/3: � = .
CP = 1.5728 KJ/Kgmole. K JH Factor:

K= 0.2 Btu/hr.ft2.F = 0.3459 J/hr.m2.oC JH = 10
µ = 0.6280 Pa.s (CP µ/K)1/3:

now put the values and we get CP = 3.4706 KJ/Kgmole. K
(CP µ/K)1/3 = 1418 K= 0.12 Btu/hr.ft2.F = 0.20754 J/hr.m2.oC
Inside Heat Transfer Co-efficient: µ = 0.101 Pa.s
× . × . now put the values and we get
ℎ� =
.
(CP µ/K)1/3 = 1.418
ℎ� = .
ℎ . . Outside Heat Transfer Co-efficient:
ℎ� = . × . × .
ℎ . . ℎ� =
.
hio Co-Efficient: ℎ� = .
ℎ . .
ℎ�� = ℎ� ×
.
ℎ�� = . ×
.
ℎ�� = .
ℎ . .
Clean Overall Co-Efficient:

As we know that
h ×h . × 8.
U = hio +ho = = .
io o . + 8. hr.ft2 .F
Dirt Factor:
As we know that
− . − . ℎ . .
= = = .
× . × .
Hence the Dirt Factor is in the range of 0.001 so design is satisfactory.
Pressure Drop Calculations

Shell Side Calculation Tube Side Calculation
Re = 396.61 Re = 14642.55
f = 0.001 ft2/in2 f = 0.0002 ft2/in2
N + 1 = (15 × 12)/10 × × ×
∆ =
. × × × ×�
N = 18
ρL = 1278 Kg/m3
∆ = . � = . �
ρw = 1000 Kg/m3
G = 66317.068 lb/ft2.hr
S = ρL / ρw = 1.27
From graph we have
DE = 0.0021 m
V2/2g = 0.001
× � × � +
∆ =
. × × � × ×� �
∆ = × × ×
∆ = . � = . �
∆ = . �
Allowable pressure drop = 10 psi
Now
So design is satisfactory
∆ � � =∆ +∆
∆ � � = . �
Allowable pressure drop = 10 psi
So design is satisfactory
10.4 Specification Sheet for Shell and Tube Heat Exchanger

Identification Unit Heat Exchanger
Item No. E-101
Type Forced Circulation
Function To Heat The Reactor Feed
Heat Duty 129248.8947 Kj/hr
Heat Transfer Area 13.674 m2
Overall Heat Transfer Co- 192.901 J/m2.K.hr
Efficient
Dirt Factor 0.0032 hr.ft2.F/BTU
Shell Side Tube Side
Fluid Circulated Steam Fermenter Feed Mixture
Flow Rates 19075.409 Kgmole/hr. 323788.29 Kgmole/hr.
Temperature Inlet: 485.511 K Inlet: 298.15 K
Outlet: 325.5 K Outlet: 325.15 K
Pressure
Pressure Drop 0.00144 psi 0.539 psi
Material of Construction Carbon Steel Carbon Steel
Specifications ID: 8 inch OD:0.75 inch
C/: 025 Pitch: 1
B: 10 inch Arrangement: Triangular
Length: 15 ft
Nt: 30
Table 10.1: Specification Sheet for Shell and Tube Heat Exchanger (E-101)
Chapter No. 11 Flash Drum Design
Chapter 11
FLASH DRUM DESIGN

11.1 Introduction:
If we say that Chemical Engineering is nothing but the combination of art and science to design
and control the separation equipment, it won’t be a lie. In the chemical industry, more than the
70% of total capital investment is incurred on separation and purification equipment’s. These
stats might highlight the importance of separation equipment in chemical industry.
Let’s carry out the process of elimination o to justify our choice. We can simply rub aside the
choice of knock out drum as it is used for where gas is in the feed stream. In our stream there are
no gases. We have only liquid phases. So we will not go for the knock out drum. Now we are left
with the horizontal, spherical and vertical flash drums. Horizontal drums are used when we have
to handle a large liquid flow rate. But in our case we will see that the liquid flow rate would not
be huge. Instead we will have to deal with a high amount of vapor flow rate. Also Walas carried
out a survey in his book “Chemical Process Equipment Selection and Design” writes that out of
every 10 chemical industries seven are making use of vertical flash drums. The choice is made
due to the economy and the ease with which we can handle the flow rates. A design engineer is
required to start designing a vertical flash drum by default and then after the design is complete
we have to look at the (L/D) ratio to decide which configuration is to be use. So we will follow
the same procedure. We will design and vertical flash tank and would analyze the (L/D) ratio
obtained to determine that which configuration is to be used. Just remember one rule of thumb;
for large liquid flow rates we will use horizontal flash drums and for small liquid flow rate s we
will go for a vertical flash drums. You can start designing any one of these and then final
decision would rest upon the (L/D) ratio of the drum. So don’t bother. Just start your computer
software and begin designing any configuration. Let’s start the design of vertical flash drum.
[11,14,15]

Total mass flow rate = 61747.9 Kg/hr
Total vapor flow rate at outlet stream = 82.05 Kg/hr
Total volumetric flow rate of liquid stream = 62.77 m3/hr
The densities of liquid and vapor mixtures can be calculated by using the following methodology
 Calculate volume of each component using (Vi = mi/ρi)

 Calculate mixture volume (Vmixture = V1X1 + V2X2 + V3X3 + …….)
 Calculate the volume fraction (V1-fraction = Vi / Vmixture)

 Calculate the mixture density (ρmixture = ρ1 V1-fraction + ρ2 V2-fraction + ρ3 V3-fraction + ……)
Average density of liquid stream = 983.38 Kg/m3
Total volumetric flow rate of vapor stream = 17.96 m3/hr
Average density of vapor stream = 6.06 Kg/m3
Now by using the Souder-Brown Equation the maximum gas velocity can be found as
� − �
��− �� = �� √
�
Where Ks = 0.35 for vertical vessel operation at pressure of 0 Bar or low suggested by Wanket in
his book Separation Process Engineering.
Now put the all values in above equation we get
. − .
��− �� = . √
.
VG-max = 4.44 m/sec.
Now for diameter
As we know that
��
� � =√
��
Where
FG = 1.00
QV = 17.96 m3/hr
VG = 4.44 m/sec
Put all of these values in above equation we get
× .
� � =√
. × . × .
Dmin = 2.2 m
Add 6 inch allowance for corrosion in the diameter so actual diameter
D = 2.2 + 0.154 = 2.354 m
Now the liquid height can be calculated as follows
Volume of the liquid = QL × Residence Time
Volume of the liquid = 62.77/60 × 4
Volume of the liquid = 4.18 m3
Now
Liquid Height = LH = VL / A
Liquid Height = LH = 4.18 / (3.14/4) ×2.354
Liquid Height = LH = 1.42
H. Silla and Coulson suggested following formula for vapor height
VH = 1.5D + 0.4
VH = 1.5 (2.2) + 0.4
VH = 3.7
So now the height of vessel will be
L = LH + VH
L = 1.42 + 3.7
L = 5.137 m
Now
L/D = 5.137 / 2.2 = 2.335
11.3 Specification Sheet for Flash Drum

Equipment Flash Drum
Function To separate unreacted gases from product of Fermenter
Type Vertical Flash Drum
Residence Time 4 min
Maximum Gas Velocity 4.44 m/sec
Diameter 2.354 m
Height 5.137 m
Table 11.1: Specification Sheet for Flash Drum (V-101)
Chapter No. 12 Instrumentation and Process Control
Chapter 12
INSTRUMENTATION AND
PROCESS CONTROL
12.1 Introduction:
Instruments are provided to monitor the key process variables during plant operation. They
may be incorporated in automatic control loops or used for the manual monitoring of the
process operation. They may also be part of an automatic computer data logging system.
Instruments monitoring critical process variables will be fitted with automatic alarms to alert
the operators to critical and hazardous situations. [15]
It is desirable that the process variable to be monitored can be measured directly; often,
however, this is impractical and some dependent variable that is easier to measure is monitored
in its place. For example, in the control of distillation columns the continuous on-line, analysis
of the over-head product is desirable but difficult and expensive to achieve reliably, so
temperature is often monitored as an indication of composition. The temperature instrument
may form part of a control loop controlling, say, reflux flow; with the composition of the
overheads checked frequently by sampling and laboratory analysis.
12.2 Instrumentation and Control Objectives:

The primary objective of the designer when specifying instrumentation and control schemes
are:
 Safer Plant Operation

 To keep the process variables within known safe operating limits.
 To detect dangerous situations as they develop and to provide alarms and
automatic shut-down systems.
 To provide inter locks and alarms to prevent dangerous operating procedures.
 Production Rate
 To achieve the design product output.
 Product Quality
 To maintain the product composition within the specified quality standards.
 Cost
 To operate at the lowest production cost, commensurate with the other
objectives.
These are not separate objectives and must be considered together. The order in which they are
listed is not meant to imply the precedence of any objective over another, other than that of
putting safety first. Product quality, production rate and the cost of production will be
dependent on sales requirements. For example, it may be a better strategy to produce a better
quality product at a higher cost.
In a typical chemical processing plant these objectives are achieved by a combination of

automatic control, manual monitoring and laboratory analysis.
12.3 Components of the Control System:

Process:
Any operation or series of operations that produces a desired final result is a process. In this
discussion the process is the cracking of naphtha.
Measuring Means:
Of all the parts of the control system the measuring element is perhaps the most important. If
measurements are not made properly the remainder of the system cannot operate satisfactorily.
The measured available is dozen to represent the desired condition in the process.
Variables to be Measured:
 Pressure measurements
 Temperature measurements
 Flow Rate measurements
 Level measurements
Variables to be Recorded:
 Indicated temperature,
 Composition,
 Pressure,
12.4 Controller:
The controller is the mechanism that responds to any error indicated by the error detecting
mechanism. The output of the controller is some predetermined function of the error. In the
controller there is also and error-detecting mechanism which compares the measured variables
with the desired value of the measured variable, the difference being the error. The final control
element receives the signal from the controller and by some predetermined relationships
changes the energy input to the process.
12.5 Classification of Controllers:
In general the process controllers can be classified as:
 Pneumatic controllers
 Electronic controllers
 Hydraulic controllers
In the ethylene manufacturing from naphtha the controller and the final control element may be
pneumatically operated due to the following reasons:
 The pneumatic controller is vary rugged and almost free of maintenance. The
maintenance men have not had sufficient training and background in electronics, so
basically pneumatic equipment is simple.
 The pneumatic controller appears to be safer in a potentially explosive atmosphere

which is often present in the petro-chemical industry.
 Transmission distances are short. Pneumatic and electronic transmission system are
generally equal upto about 250 to 300 feet. Above this distance, electronic systems
begin to offer savings.
12.6 Modes of Control:
The various type of control are called "modes" and they determine the type of response
obtained. In other words these describe the action of the controller that is the relationship of
output signal to the input or error signal. It must be noted that it is error that actuates the
controller. The four basic modes of control are:
 On-off Control
 Integral Control
 Proportional Control
 Rate or Derivative Control
In industry purely integral, proportional or derivative modes seldom occur alone in the control
system. The On-off controller in the controller with very high gain In this case the error signal
at once off the valve or any other parameter upon which it sits or completely sets the system.
12.7 Control Schemes for Distillation Column
General Considerations:
In distillation column control any of following may be the goals to achieve
 Over head composition.

 Bottom composition
 Constant over head product rate. .
 Constant bottom product rate.
Manipulated Variables:
Any one or any combination of following may be the manipulated variables
 Steam flow rate to reboiler.

 Reflux rate.
 Overhead product withdrawn rate.
 Bottom product withdrawn rate
 Water flow rate to condenser
Load or Disturbances:
Following are typical disturbances
 Flow rate of feed

 Composition of feed.
 Temperature of feed.
 Pressure drop of steam across reboiler
 Inlet temperature of water for condenser.
Control Schemes:
Overhead product rate is fixed and any change in feed rate must be absorbed by changing
bottom product rate. The change in product rate is accomplished by direct level control of the
reboiler if the stream rate is fixed feed rate increases then vapor rate is approximately constant
& the internal reflux flows must increase.
12.8 Process Instrumentation Diagram of Plant:
Figure 12.1: Process Instrumentation Diagram of Plant
Chapter No. 13 HAZOP Study
Chapter 13
HAZOP STUDY
13.1 Introduction:
The Hazard and Operability Study (or HAZOP Study) is a standard hazard analysis technique
used in the preliminary safety assessment of new systems or modifications to existing ones. The
HAZOP study is a detailed examination, by a group of specialists, of components within a
system to determine what would happen if that component were to operate outside its normal
design mode. The effects of such behavior is then assessed and noted down on study forms. The
categories of information entered on these forms can vary from industry to industry and from
company to company. [13]
13.2 Objectives of HAZOP Study:
 To identify the potentials

 To identify and study features of the design that influence the probability of a hazardous
incident occurring.
 To familiarize the study team with the design information available.
 To ensure that a systematic study is made of the areas of significant hazard potential.
 To identify pertinent design information not currently available to the team.
 To provide a mechanism for feedback to the client of the study team’s detailed
comments.
13.3 Keywords used in HAZOP Study:
Keywords are used to focus the attention of the team upon deviations and their possible causes.
These keywords are divided into two sub-sets:
Primary Keywords: which focus attention upon a particular aspect of the design intent or an
associated process condition or parameter.
Secondary Keywords: which, when combined with a primary keyword, suggest possible
deviations.
Primary Keywords:
These reflect both the process design intent and operational aspects of the plant being
studied. Typical process oriented words might be as follows. The list below is purely
illustrative, as the words employed in a review will depend upon the plant being studied.
Table 13.1: Primary Keyword for HAZOP Study
Flow Temperature
Pressure Level
Separate (settle, filter, centrifuge) Composition
React Mix
Reduce (grind, crush, etc.) Absorb
Corrode Erode
Secondary Keywords:
As mentioned above, when applied in conjunction with a Primary Keyword, these suggest
potential deviations or problems. They tend to be a standard set as listed below:
Table 13.2: Secondary Keyword for HAZOP Study
Word Meaning
No The design intent does not occur (e.g. Flow/No), or the operational aspect is not
achievable (Isolate/No)
Less A quantitative decrease in the design intent occurs (e.g. Pressure/Less)
More A quantitative increase in the design intent occurs (e.g. Temperature/More)
Reverse The opposite of the design intent occurs (e.g. Flow/Reverse)
Also The design intent is completely fulfilled, but in addition some other related
activity occurs (e.g. Flow/Also indicating contamination in a product stream, or
Level/Also meaning material in a tank or vessel which should not be there)
Other The activity occurs, but not in the way intended (e.g. Flow/Other could indicate a
leak or product flowing where it should not, or Composition/Other might suggest
unexpected proportions in a feedstock)
Fluctuation The design intention is achieved only part of the time (e.g. an air-lock in a
pipeline might result in Flow/Fluctuation)
Early Usually used when studying sequential operations, this would indicate that a step
is started at the wrong time or done out of sequence
Late As for Early
13.4 How to Conduct a HAZOP Study:

HAZOP study is conducted in following steps:
Specify the purpose, objective, and scope of the study. The purpose may be the analysis of a new
plant or a review of the risk of unexisting unit. Given the purpose and the circumstances of the
study, the objectives listed above can more specific.
 Select the HAZOP study team. The team who will conduct the HAZOP study should
consist of personnel with a good understanding of the process and plant to be
reviewed. The group should ideally contain about six members, with perhaps an absolute
upper limit being set at nine. In a study in which both contractor and client are
participating, it is desirable to maintain a balance between the two in terms of team
membership so that neither side feels outnumbered.
 Make a preparatory work. It is most important that, before a study commences, work that
can be conveniently done beforehand is carried out. This is not only essential in some
respects for the proper structuring of the study and the team, but will also greatly increase
the efficiency of the HAZOP and thus retain the interest and enthusiasm of the
participants.
Figure 13.1: How to Conduct HAZOP Study
 This preparatory work will be the responsibility of the Chairman, and the requirements
can be summarized as follows:
 Assemble the data
 Understand the subject
 Subdivide the plant and plan the sequence
 Mark-up the drawings
 Devise a list of appropriate Keywords
 Prepare Node Headings and an Agenda
 Prepare a timetable.
 Select the team.
13.5 The HAZOP Study Report:
The HAZOP Report is a key document pertaining to the safety of the plant. The number of man-
hours spent on the study is usually considerable. It is crucial that the benefit of this expert study
is easily accessible and comprehensible for future reference in case the need arises to alter the
plant or its operating conditions.
The major part of such a report is of course the printed Minutes, in which is listed the team
members, meeting dates, Keywords applied, and of course every detail of the study teams
findings. However, it is usual to include with this a general summary. The contents of such a
summary might typically be:
1. An outline of the terms of reference and scope of the study.
2. A very brief description of the process which was studied.
3. The procedures and protocol employed. The Keyword combinations applied should be
listed, together with the explanatory meanings given to the team at the start of the
study. Also the fact that Action Sheets have been produced and responses will be
recorded should be explained. A brief description of the Action File (described in the
following section) should be included.
4. General comments. If, for example, the team were assured that high point vents and low
point drains would be universally provided, mention that statement and its source. If
certain details of vendor packages were not available, explain and list the items which
were not reviewed.
5. Results. This usually states the number of recommended actions.
6. Also included in the HAZOP Report would be an Appendix containing:
7. Master copies of the drawings studied.
8. Copies of technical data used.
9. Cause and Effect charts (i.e. matrices showing the executive action of safety related
instruments and trips).
10. Any calculations produced.
11. Relevant correspondence between departments, from contractor to vendor, or client to

contractor.
13.6 HAZOP Study of Shell and Tube Heat Exchanger:

Table 13.3: HAZOP Study of Shell and Tube Heat Exchanger
Guide Word Deviation Causes Consequences Action

Less Less flow of cooling Pipe Temperature of High
water blockage process fluid Temperature
remains constant Alarm
More More cooling flow Failure of Temperature of Low
cooling process fluid Temperature
water valve decrease Alarm
More of More pressure on Failure of Bursting of tube Install high

tube side process pressure alarm
fluid valve
Contamination Contamination of Leakage of Contamination of Proper
process fluid line tube and process fluid maintenance
cooling and operator
water goes alert
in
Corrosion Corrosion of tube Hardness of Less cooling and Proper

cooling crack of tube maintenance
water
Chapter No. 14 Environmental Impacts
Chapter 14
ENVIRONMENTAL IMPACTS
14.1 Introduction:
A 1996 national survey of attitudes to environmental issues revealed that three of the top five
issues about which people were extremely concerned were related to the atmosphere. In Sydney,
50 per cent of those surveyed were extremely concerned about air pollution, 50 per cent about
harm to the ozone layer and 36 per cent about the greenhouse effect. [13,15]
14.2 Air Pollution:

Air quality is a major environmental issue for the population centers of Sydney, the Central Coast,
the Illawarra and lower Hunter regions, which together represent 73.5 per cent of the NSW
population. The concentration of population and of human activities, including high volume road
traffic and industry, result in substantial quantities of pollutants. Measuring air quality is complex
because pollutants interact with each other and impacts vary with meteorological, seasonal and
geographical factors.
Core indicators of metropolitan air quality are:
The level of ground level ozone, since this indicates photo-chemical smog and since elevated
concentrations can cause a range of health effects in humans and can damage vegetation and
building materials; Concentration of nitrogen dioxide in the air, since high concentrations cause
respiratory irritation and have been linked to both mortality and hospital admissions for asthma
and heart disease;
Concentration of fine particles in the air, since long-term exposure to even low levels has been
linked to chronic health effects and increased mortality; and Concentration of benzene in the air,
since long-term exposure to benzene can have carcinogenic effects and cause direct damage to
genetic material.
Table 14.1: Environmental Impact Indicators of Metropolitan Air Quality

Ground level ozone Between 1980 and 1996 the amount of ground level ozone in
the atmosphere exceeded the goal recommended by the
World Health Organization on at least six days per year and
up to 45 days per year. In general terms the number of days
the goal was exceeded has fallen during this period, however
the 1994 result was the worst since 1983 because of the
extensive bushfires that summer and associated weather
conditions.
Nitrogen dioxide Between 1980 and 1996 levels of nitrogen dioxide have
exceeded the goal recommended by the WHO between two

and 47 days each year with no clear trend. A lower peak
measured over the last four years may be the result of
weather conditions.
Fine particles Between 1988 and 1996 annual average concentrations have
remained below goals set for the UK and the USA, although
annual averages for individual sites sometimes exceed these
goals.
Benzene During the period May 1995 to October 1996, the average
benzene concentration was similar to levels measured in
overseas cities in the UK, Canada and California. As is the
case overseas, higher concentrations were recorded in the
more densely trafficked city sites.
Notes: 1 WHO has so far declined to set a goal for fine particles. 2 WHO states that, given it is a
proven human carcinogen; there is no safe concentration of benzene in ambient air. Source:
Environment Protection Authority, State of the Environment Report 1997.
Air quality in Sydney and other urban centers compares well with many world cities. In fact,
studies show that air quality has improved during the last 20 years. However, we do have
unacceptable levels of both smog and brown haze.
14.3 Ozone Depletion:

The stratospheric ozone layer absorbs much of the harmful UV radiation penetrating the earth’s
atmosphere. Increased levels of UV radiation are associated with increased incidence of skin
cancers and eye disorders, damage to the immune system, and adverse effects on plant
development and phytoplankton growth. Ozone depletion has been detected at all latitudes, except
the tropics, and is greater near the poles.
Ozone depleting substances (ODS) are used in domestic, commercial, industrial and agricultural
activities. While the use and manufacture of these substances has declined since the introduction
of international control measures, full restoration of the ozone layer is dependant on the
elimination of all ODS emissions.
The core indicators of ozone depletion are the percentage changes in both stratospheric ozone
layer depletion and ultraviolet radiation increase across New South Wales.
Table 14.2: Environmental Impact Indicators of Ozone Depletion

Stratospheric ozone change Between 1979 and 1992 New South Wales has averaged
a depletion of stratospheric ozone of 1.2 per cent per
decade.
Ultraviolet radiation During the same period New South Wales has averaged
increase an increase in UV radiation of about 1.2 per cent per
decade. However, the level of uncertainty in the measure
is too great for the increase to be considered statistically
significant.
14.4 Greenhouse Effect:

Release of greenhouse gases into the atmosphere as a result of human activities may be affecting
the global climate. Changes in climate have significant implications for the environment and
human well being, by affecting such things as water availability, biodiversity and the capability of
the land to produce food and other resources.
Greenhouse gas emissions are intricately linked to energy production and use, agriculture, land
use, the relationship between population growth and form, and transport provision and usage
patterns.
The core indicator of the greenhouse effect is the annual total amount of greenhouse gas
emissions expressed as an equivalent amount of carbon dioxide (million tons). This measure
accounts for the different global warming potential of each gas. The two most significant
greenhouse gases are carbon dioxide and methane, which together contribute over 90 per cent of
emissions.
Table 14.3: Environmental Impacts Indicators of Greenhouse Effect in NSW and the ACT
1990 1995 % change
Sector Mill. % Mill. Tons %
Tons
Energy1 83.0 49.6 82.7 51.1 -0.4
Agriculture 24.7 14.8 23.5 14.5 -4.9
Transport 20.2 12.1 22.1 13.6 9.4
Industrial processes 4.2 2.5 3.5 2.2 -16.7
Waste 5.2 3.1 5.7 3.5 9.6
Land use change and forestry -10.3 -6.2 -10.5 -6.5 -1.9
(excluding land clearing) 2
Subtotal 126.9 - 127.1 - 0.2
Land clearing 40.4 24.1 34.7 21.4 -
Total 167.3 100.0 161.8 100.0 -
Notes: 1 Includes stationary energy and fugitive emissions but excludes transport, which is
reported separately.
2. Emissions estimates from land clearing are subject to large uncertainties and so have been
reported separately. Source: Australian Greenhouse Office, Australia’s State and Territory
Greenhouse Gas Inventory 1990 and 1995, 1998.
Data for New South Wales (including the ACT) are only available for 1990 and 1995. During this
period an increase in 0.2 per cent in the amount of greenhouse gas emissions was recorded,
excluding emissions due to land clearing which are subject to a large degree of uncertainty.
The energy sector makes the largest contribution to greenhouse gas emissions in New South
Wales, accounting for around 50 per cent of all emissions. The land use change and forestry
sector (excluding land clearing) is a net sink for greenhouse gases as the removal of carbon
dioxide from the atmosphere due to forest growth and pasture improvement exceeds the
greenhouse emissions due to forest harvesting and prescribed burning and wildfires. Land
clearing, however, adds substantially to total greenhouse emissions.
Increases in the amount of greenhouse emissions were recorded in the waste (9.6 per cent) and
transport sectors (9.4 per cent), while decreases were recorded in the industrial processes (-16.7
percent), agriculture (-4.9 per cent) and energy (-0.4 per cent) sectors.
Available core indicators for NSW water resources are:
The level of dissolved salts in river water, since this impacts on the sustainability of aquatic
ecosystems and is a key parameter determining the suitability of river water for such purposes as
irrigation and town water supply;
The level of phosphorus concentrations in river water, since high levels of phosphorus destroy
aquatic ecosystems and stimulate nuisance algal growth; and
river turbidity, which indicates the amount of suspended solid particles in river water. High
turbidity alters aquatic habitats, limiting plant growth, fish movements and the ability of predatory
fish and birds to see their prey. High levels of suspended solids can make water unsuitable for a
range of environmental needs and human uses.
River salinity, phosphorus levels and river turbidity are monitored as part of the Department of
Land and Water Conservation Key Sites Program, in which 89 representative river sites
throughout New South Wales are sampled.
Other core indicators which are being developed include the development of biological criteria to
assess the health of aquatic ecosystems, indicators of river flows, and indicators for groundwater
including changes in watertable level and ambient concentrations of salinity, nitrates and
toxicants (SoE pp.249, 291).
Table 14.4: Environmental Impact Indicators for Water Resources in Key River Sites
1993-94 1994-95 1995-96
River salinity Good % 43 47 53
Fair % 46 45 40
Poor % 11 8 7
Phosphorus levels Good % 22 19 23
Fair % 38 42 32
Poor % 40 39 45
River turbidity Good % 38 36 30
Fair % 49 36 50
Poor % 13 13 20
Indicators are classified according to the good-fair-poor categories used in the DLWC Window on
Water Report.
River salinity appears to be improving, with an increase in the percentage of sites rated as good
and a decrease in the percentage rated as poor. This is the only indicator in which a majority of
sites were rated as good in 1995-96. In contrast, only 23 per cent of sites were rated as good in
terms of phosphorus levels and the data indicate an increase in the percentage of sites rated as
poor. While 30 per cent of sites were rated as good in terms of river turbidity, the percentage of
such sites has declined, while the percentage of sites rated as poor has increased.
14.5 Biodiversity:
Biodiversity is the total variety of life on earth. It includes all species of plants, animals and
micro-organisms, the genetic variety within each species and the variety of habitats in which they
live.
The conservation of biodiversity is necessary to sustain healthy functioning ecosystems, which in

turn sustain the quality of the atmosphere, climate, fresh water, soil formation, cycling of
nutrients and disposal of wastes. Biodiversity can be beneficial by providing the raw materials for
new foods, clothing and medicines, and natural environments for aesthetic appreciation,
recreation and tourism.
The key biodiversity issue for New South Wales is the continuing loss of habitat for ecological
communities caused by native vegetation clearance. What is lost cannot be restored and the rate of
loss far exceeds the rate of evolutionary adaptation. The implementation of sustainable natural
resources management as represented by the activities discussed in other sections of this report
will, by definition, contribute to biodiversity conservation.
Table 14.5 : Environmental Impact Indicators of Biodiversity

Total area of the State 4,522,650 hectares of protected areas in national parks, nature
included in protected reserves and State recreation areas had been properly mapped
areas by 1997. This included 290,567 hectares of enclosed waters
and marine and estuarine extensions to terrestrial national
parks and nature reserves. This area represents about 5.5 per
cent of the total area of the State.
In addition, another 874,000 hectares of protected land is

included in national parks and reserves, crown reserves and
State Forest flora reserves or is land covered by voluntary
conservation agreements, which has not been properly
assessed for protection status or digitally mapped for
accuracy. Including this land, protected lands cover about 6.6
per cent of the State.
Extent to which New South Wales reserves are concentrated in steeper, less
bioregions are fertile country, dominated by rugged and highly scenic
represented in landscapes. They lack attraction for commercial uses and
protected areas meet a community perception equating beauty and wilderness
with conservation value.
In 1997, around 10 per cent of the coastal and alpine regions

of NSW were represented in reserves, while only 2.5 per cent
of central and western regions were represented.
The Australian Alps has the highest level of reservation, with

over 90 per cent of its area protected, while the Murray and
Darling Riverine plains have the lowest representation, with
only 0.4 per cent and 0.9 per cent respectively.
It has been estimated that 27 per cent of environmental

domains are not represented at all in the reserve system, while
domain classes represented at a level of between zero and 2.5
per cent covered 54 per cent of NSW1 .
While there has been a rapid expansion of the network of national parks and reserves in New
South Wales over the past three decades, protected areas in New South Wales do not compare in
scale with other countries with similarly vast land areas such as Canada (8.9 per cent) or the US
(10.6 per cent).
The North Coast, Sydney Basin, South-eastern Highlands and South-eastern Corner bioregions of
the state have exceeded the 10 per cent level of reservation recommended by the World
Conservation Union. The bioregions of the Western and Central divisions of New South Wales
remain poorly represented.
14.6 Sustainability:
Ecologically sustainable development (ESD) means using, conserving and enhancing natural
resources in a way that the ecological processes on which life depends are maintained, and the
total quality of life, now and in the future, is improved. Without attention to ESD the ability of
ecosystems to provide life sustaining functions, such as nutrient cycling of soils, can be depleted.
Because human activities and their effects increasingly transcend national or state borders there is
a need for a global approach to many environmental sustainability issues, such as greenhouse gas
emissions. Recent events, such as the Third Conference of Parties to the UN Framework
Convention on Climate Change held in Kyoto in December 1997, at which 160 countries
hammered out an agreement which requires industrialized countries to reduce greenhouse gas
emissions, show how widely this belief has been accepted. Other environmental issues require a
more local approach but one which is defined in terms of environmental boundaries rather than
political ones. An examination of the sustainable level of water that can be extracted from river
systems, for example, needs to be approached on a catchment area basis.
While the issues involved in determining sustainable development in each context are complex,
there is substantial agreement within the scientific community that current Western consumption
levels are not sustainable in world terms. At present, 20 per cent of the world’s population
consumes more than 80 per cent of available natural resources and produces over 75 per cent of
the waste. If current trends continue, the world’s population will almost double and output will
quadruple over the next 50 years. For this to be sustainable, most scientists agree that resource use
in high-income countries would have to be reduced by up to 90 per cent.
Predicting the future is difficult: changes in the rate of growth of population and economic output,
technological advances, substitution effects and improved waste management and conservation
behavior may all alter the sustainability of current practices and the level of reduction in resource
consumption required by the developed world. However, the above forecasts show that while we
do not know the magnitude of the reduction required, we do know that our current practices are
unsustainable and that drastic reductions must occur. The scale of the reduction required and the
conservative assumptions underpinning it underscore the size of the task.
In light of the uncertainty surrounding forecasts it is not surprising that there is very little
agreement on sustainability measures or performance indicators – particularly at the global level.
Because it is widely accepted that we are some way from sustainable levels of consumption,
efforts in this area have been largely directed into programs that aim to reduce consumption of
key environmental resources, while the more complex issues involved in determining what is a
sustainable level of consumption are developed and debated.
Prominent sustainability issues for New South Wales are listed below.
Extractive resource use and consumption — NSW residents are high consumers of resources by
world standards. Key resources include timber, fish and water.
Waste generation — NSW industry and residents generate comparatively high levels of waste
because of high consumption and limited waste avoidance, reuse and recycling.
Energy production and use — NSW energy requirements are largely met by non-renewable fossil
fuels, which are not sustainable sources of energy. There are opportunities for increased
efficiency in the use of energy and the generation of power from renewable energy sources.
Urbanization — Urbanization exerts pressure on atmosphere, water, land and biodiversity. The
two most significant urbanization problems in New South Wales are the growth of Sydney and
the rapid growth in the population along the coastal strip, particularly the northern coast.
Transport use — the car is the most widely used form of transport in New South Wales. Cars
consume significant amounts of non-renewable fuels, contribute to air and noise pollution, limit
pedestrian movement and, through road accidents, are a serious cause of mortality.
Integration — of social, economic and environmental considerations to achieve sustainable

decision-making needs to be achieved in New South Wales.
In the absence of agreed outcome measures for sustainability, Table 53 summarizes available
information about the trend in resource use in New South Wales related to each of these issues. A
major assumption is that the over-riding need is to reduce consumption or usage of non-renewable
environmental resources in the medium to longer term.
Table 14.6: Environmental Impact Indicators of Sustainability

Resource use and Timber: Per capita consumption of timber products in New South
consumption Wales shows no clear trend between 1989-90 and 1995-96,
although there does seem to be some reduction in consumption
between 1993-94 and 1995-96. In 1995-96, per capita consumption
was 223 kg, about half of which was imported. Timber from native
forests decreased as a percentage of total supply from 58 per cent
in 1989-90 to 42 per cent in 1995-96.
Fish: Domestic production of fish products has remained

moderately stable at 2.5 to 3 kg per capita between 1991-92 and
1995-96. Per capita consumption of fish products increased from
4.8 kg in 1991-92 to 9.9 kg in 1993-94 and then declined to eight
kg in 1995-96; the variation in consumption was met by imported
fish.
Water: Per capita water usage increased between 1988-89 to 1991-

92, then declined dramatically in 1992-93 (coinciding with a
period of drought). In the following years per capita consumption
again increased to reach the 1991-92 level, around 1.06 megalitres,
in 1995-96.
It has been estimated that up to 6.75 hectares of productive land

and water per person is required to produce all the resources
consumed by the Australian population.
Waste generation The total amount of per capita waste disposed in the Sydney
metropolitan area has been steadily increasing from the early
1970s, apart from a period of decrease between 1989 and 1992. In
spite of the NSW Government’s target to reduce waste by 60 per
cent between 1990 and 2000, by 1995 waste disposal levels were
only 16 per cent less than in 1990 and had been increasing since
1992. In 1995, the annual rate of waste disposal was 859 kg per
person. Around 27 per cent of municipal waste is recycled, but the
percentage of industrial and building waste recycled is unknown.
Energy The total amount of energy produced in New South Wales grew by
production and 75 per cent between 1980-81 and 1994-95, while total energy
use consumption grew by 21 per cent. The disparity in the increase was
mainly due to an increase in the exports of coal (which accounts
for 98.5 per cent of the energy produced) and to improvements in
energy efficiency. During the same period energy use per dollar of
Gross State Product decreased by about 14 per cent, which
indicates a less-energy intensive and more-energy efficient

economy in New South Wales. The amount of energy produced
which is lost through conversion to electricity, coal washeries and
distribution has remained around 21 per cent over the same period.
In 1996, 93.7 per cent of the 60,006 GWh of electricity generated

in New South Wales was produced by coal fired power stations,
with the remaining 6.3 per cent supplied by hydro generation.
While renewable energy sources such as landfill gas and other
biomass power stations supplied only 100 to 200 GWh in 1996,
renewable energy generators installed during 1997-98 are capable
of producing a further 130 GWh of electricity1 .
Urbanization There are no agreed estimates of the size of population that the
NSW ecosystem can sustain without damaging its essential
functions, nor is there a State target for urban population growth.
Most urban centers show growth over the last 25 years, with the
highest annual growth rates (six to seven per cent) occurring in
Gosford-Wyong and Canberra conurbation in the early 1970s.
Strong growth has occurred along the coastal strip. While the
population growth of inland statistical divisions has been slight,
there has been a trend towards population increases in strategically
positioned provincial towns at the expense of the population in the
surrounding areas. The annual growth rate in the Sydney
metropolitan region, at considerably less than one per cent is lower
than the growth rate in the State as a whole (just over one per cent),
but because of the large population base Sydney absorbs about half
the annual total population increase in the State.
Transport use Between 1976 and 1995, the total annual distance travelled by cars
(excluding buses) registered for use in New South Wales increased
by 43.6 per cent to 48.4 billion kilometers. During the same period
total distance travelled in the Sydney Statistical Division increased
by 57 per cent, and by 1995 travel in Sydney accounted for 59 per
cent of total NSW vehicle kilometers travelled.
Passenger vehicles regularly accounted for about 77 per cent of the

total distance travelled and freight–carrying vehicles 23 per cent.
In Sydney, the percentage of total trips made by cars for weekday

travel increased between 1981 and 1991 from 65 to 67 per cent,
while the percentage of trips made by train, bus and walking all
decreased.
Surveys taken in 1991 indicate that 78 per cent of person

kilometers travelled are travelled by car, 10 per cent by train and
four per cent by bus.
Integration of In 1992, New South Wales along with other Australian

social, economic governments, endorsed a National Strategy for Ecologically
and Sustainable Development and signed the Intergovernmental
environmental Agreement on the Environment 1992.
considerations in
decision-making In surveys conducted by the EPA, people consistently rank the
environment as a major issue for the State government now but as
the most or second most important issue (after unemployment) in
10 years time. Over 90 per cent of people reported having engaged
in behaviors to protect the environment over the past 12 months.
14.7 Hydrogen Peroxide Environmental Impacts:

Hydrogen Peroxide is mainly used for pulp bleaching (48%) and manufacture of other chemicals
(38%) such as sodium perborate, per carbonate and per acetic acid. The remaining 15% of the
total volume consumed in Europe is used for different applications including textile bleaching,
environmental applications, metal etching, sanitisation of chemical instruments and surfaces,
metal semiconductor chips manufacturing, disinfection of drinking water, disinfectant in aseptic
packaging and bleaching of certain foodstuffs. Less than 1- 4% of the production volume is for
personal and domestic use e.g. hair bleaching, dying or fixing of hair perm, household cleaning,
tooth bleaching, food processing, disinfection of wounds and mouth and disinfection of eye
contact lenses. Also cosmetics, toothpastes and deodorants contain or have contained hydrogen
peroxide (European Commission, 2003).
14.8 Methanol Environmental Impacts:

When burned as fuel, methanol cuts emissions of nitrogen oxides and volatile organic compounds
that form ground-level ozone or “smog.” Methanol is much less reactive than gasoline in the
atmosphere, with the only toxic component of the emissions being formaldehyde, as compared to
dozens of carcinogenic components of gasoline emissions, which also contains formaldehyde.
The use of heated catalytic converters has shown that methanol-fueled auto emissions meet and
exceed California’s stringent Ultra Low Emission Vehicle (ULEV) emission targets for
formaldehyde. Methanol fuel also does not contain the toxic BTEX additives found in gasoline—
benzene, toluene, ethyl benzene, and xylenes. These compounds are highly carcinogenic, do not
readily biodegrade in the environment, and are capable of contaminating groundwater supplies.
Methanol is readily biodegradable in both aerobic and anaerobic environments, with a half-life in
surface and groundwater of just one to seven days, compared to a half-life for benzene in
groundwater of 10-730 days. A report prepared for the Methanol Institute by the environmental
consulting firm Malcolm Pirnie concluded that relative to conventional gasoline and diesel fuel,
methanol is a safer and more environmentally benign fuel. In the United States, more than 200
municipal wastewater treatment plants inject methanol into the treatment system to reduce
nitrogen levels in plant effluent that can harm sensitive aquifers.
14.9 Formaldehyde Environmental Impacts:

Typical releases of Formaldehyde are unlikely to affect plants and wildlife in the vicinity. It is
very quickly removed from the air by reaction with other species in the atmosphere and is broken
down in water and soil within days. As a VOC, Formaldehyde may be involved in the formation
of ground level of ozone, which can damage crops and materials. It is not considered likely that
Formaldehyde pollution has any effects on the global environment. Formaldehyde can enter the
body either by inhalation of air containing formaldehyde, ingestion of contaminated food or by
dermal contact with formaldehyde. Inhalation of formaldehyde can cause irritation of the eyes,
nose and throat. Exposure to high levels may cause throat spasms, accumulation of fluid in the
lungs and in extreme cases death. Repeated exposures can lead to respiratory problems such as
asthma and bronchitis. Individuals with asthma may be more sensitive to the effects of inhalation
of formaldehyde. Ingestion of formaldehyde can cause vomiting, severe pain and in extreme cases
coma and death. Dermal contact with formaldehyde can cause skin irritation and burns. Eye
contact may cause severe burns. The effects of dermal and eye contact may appear hours after
exposure. The International Agency for Research on Cancer has designated formaldehyde as a
carcinogen. However, exposure to formaldehyde at normal background levels is unlikely to have
any adverse effect on human health.
Chapter No. 15 Cost Estimation
Chapter 15
COST ESTIMATION
15.1 Introduction:
An acceptable plant design must present a process that is capable of operating under conditions
which will yield a profit. It is essential that chemical engineer be aware of many different types
of cost involved in manufacturing processes. Capital must be allocated for direct plant expenses
such as those for raw materials, labor, and equipment’s. Besides direct expenses, many other
indirect expenses are incurred, and these must be included if a complete analysis of the total cost
is to be obtained. Some examples of these indirect expenses are administrative salaries, product
distribution costs and cost for interplant communication.
Elements of the Cost of Processing:

The cost of processing is made up of three different and distinct elements.
 Charges related to the total capital investment of the plant

 Operating costs, exclusive of fuel, vary with the production rate
 The cost of operating labor and supervision plus charges normally classified overhead
Capital Related Charges:

The total capital cost of olefins plants per annual ton of ethylene produced prevailing in the U.S.
Gulf Coast is 700 U.S. $/ton.year of ethylene, which is the cost reference location of the
petrochemical industry.
The investment that is represented accounts for the cost of Inside Battery Limits (ISBL) process
facility as well as the cost of the Offsite Battery Limits (OSBL) support facilities.
Depreciation represents the annual rate at which the plant investment is to be written off or
retired as a result of wear, age and obsolescence. For petrochemical facilities the allowable rate
typically ranges from 7% to 12% for ISBAL and from 4% to 7% for OSBL facilities.
Maintenance is another capital related charge. Obviously the plant must be maintained in
operating order, whether or not it is operated. Permanently engaged maintenance crews must be
on hand to service all parts of the plant. These charges nominally range from about 3% to 5% of
the total capital investment annually.
Still other capital related charges are insurance and property taxes. Insurance cost vary somewhat
over the life of plant and depend upon whether the plant owner-operator is self-insured i.e. he
assumes the risks of losses due to accidents, or he contracts with insurance companies, local
property tax rate varies with location and tends to increase with time.
The actual return on investment over the life of the plant will vary with the gross margin realized
and the operating rate. The cash flow associated with the operation of a plant may vary
sustainably with time as is often the case with very large plants which may reach full capacity
only several years after start-up. In these cases the discounted cash flow method of economic
analysis, which takes into account the time-dependent value of money, will yield a more realistic
picture of profitability of the venture than would the return on investment based on full capacity
utilization.
The return on investment is used as the measure of profitability in this section. The desired
pretax annual rate of return for a facility producing commodity petrochemicals is typically in the
range of 20% to 30% of the investment. The total of the annual capital-0related charge as
described above will thus be in the range of 30% to 50% of the investment cost.
Variable Operating Costs:

Variable operating costs are processing expenses that vary with the rate of production, they
comprise the cost of electric power, chemicals, catalysts, desiccants, fresh water, and steam to
the extent that the latter is imported rather than internally generated. Variable operating costs
represent only a relatively small fraction of the total cost of processing. They are typically in the
range of 10% to 15% of the cost of processing.
Labor, Supervision and Overhead Costs:

The operation of an olefins plant requires crades of skilled plant operators and technical
supervisors. A typical naphtha based 500,000 tons/years ethylene plant requires approximately
15 to 20 operators per shift for the operation of the process facilities and support systems.
Supervision and overhead costs cover a variety of expenses including the cost of the plant
management (both technical and administrative), technical. And laboratory services as well as
corporate charges.
Applications of the Cost of Processing Method:

It is realistic to assume that the cost of processing will increase proportionally with inflation of
the cost of capital goods. Given a product yield pattern and the projected prices of the products
and feed stocks, the gross margin can be calculated and compared with the cost of processing,
calculated as necessary, to estimate the economic feasibility of a planned olefins manufacturing
facility.
By product values were calculated on the value of by-product components. For the example, the
value of C4-stream is based on the amount of butadiene that it contains less extraction costs plus
fuel value of C4-components other than butadiene. The value of gasoline fraction in reference to
the recovery of aromatics is calculated in a similar manner. The value ranges, do reflect the
different yields obtained from different quality of feed stocks.
On the basis of assumed product values and yields, these results indicate that full range naphtha
seems presently to be the most attractive feed stock. Revenues could shrink by the Equilent of 15
$/tons of feed stock or conversely the price of feed stock could rise by 15 $/tons without this
change having an effect on the stipulated return on investment. Propane would appear to be at
least desirable feedstock. All other seems grouped together within a range that borders the
estimated accuracy of this analysis so that conclusions can only be drawn on a case to case basis.
To some minor degree this also holds for vacuum gas oil as the technology of producing olefins
from vacuum gas oil has not as yet fully matured.
Extraneous factors not here considered, such as long term feed stock availability, stable
consumer contracts, and the energy situation in general, and the economic feasibility of the
olefins manufacture from different feed stocks.
15.2 Purchased Equipment Cost:

Sr. No. Equipment Unit Cost ($) No. of Total Cost
Equipment’s
01 Distillation 8366.439 3 25099.2927
02 Fermenter 1797.16602 5 8985.8301
03 Compressor 538.1495 1 538.1495
04 Heat Exchanger 11144.698 7 78012.886
05 Reboiler 14685.78 3 44057.34
06 Refrigeration 20151.6402 1 2015164.02
07 Flash Drum 1797.16602 2 3594.33204
08 Pumps 4882.48 7 34177.36
09 Incinerator 10641.0652 2 21282.1304
Total Purchased Cost 2230911.526
Total purchased equipment cost = E = 2300000 $
15.3 Direct Cost:

Sr. No. Direct Cost Percentage of (E) Total Cost ($)
01 Installation Cost 40 920000
02 Instrumentation and Control Cost 13 299000
03 Piping Cost 10 230000
04 Electric Cost 10 230000
05 Building Cost (including Services) 29 667000

06 Yard Improvement Cost 10 230000
07 Land Cost 06 138000
Total Direct Cost 2714000
15.4 Indirect Cost:

Sr. No. Indirect Cost Percentage of (E) Total Cost ($)
01 Engineering and Supervision Cost 32 736000
02 Construction Expenses 30 690000
03 Contractor Fee 18 414000
04 Contingency Cost 30 690000
Total indirect Cost 2530000
15.5 Total Capital Investment:

Fixed capital investment = F.C.I = Direct cost + indirect cost
Fixed capital investment = F.C.I = 2714000 + 2530000
Fixed capital investment = F.C.I = 5244000 $
Now
Working Capital = 18% of Fixed capital investment
Working Capital = 0.18 (5244000)
Working Capital = 943920 $
Now
Total capital investment = T.C.I = F.C.I + Working Capital (W.C)
Total capital investment = T.C.I = 5244000 + 943920
Total capital investment = T.C.I = 6187920 $
15.6 Product Cost:

Assume that the fixed capital investment is depreciated by straight line method for 20 years.
Assuming 5% salvage value at the end of the plant life.
Depreciation = D = (V-VS)/N
Where
V = F.C.I = 5244000
VS = 0.05 (F.C.I) = 262200
N = number of years = 20
Put the values in above equation we get
Depreciation = D = (5244000 – 262200)/20
Depreciation = D = 249090 $
Now
Total Product Cost = T.P.C = T.C.I – D
Total Product Cost = T.P.C = 6187920 – 249090
Total Product Cost = T.P.C = 5938830 $
15.7 Manufacturing Cost:

Sr. No. Manufacturing Cost Percentage of (T.P.C) Total Cost ($)
01 Fixed Charges 12 712659.6
02 Direct Product Cost 55 3266356.6
03 Plant Overhead Charges 10 596883.0
Total manufacturing Cost 4575899.2
15.8 General Expenses:

Usually general expenses are the sum of following expenses given in table as follows.
Sr. No. General Expenses Percentage of (T.P.C) Total Cost ($)

01 Administrative Cost 5 296941.5
02 Distribution and Selling Cost 15 890824.5
03 Research and Development Cost 5 296941.5
04 Finance (Interest) 5 296941.5
Total General Expenses 1781649
Now the total product cost will be
Total Product Cost = Manufacturing Cost + General Expenses
Total Product Cost = 4575899.2 + 1781649
Total Product Cost = 6357548.2 $
15.9 Gross Earnings/Incomes:

Selling price of H2O2 per ton = 500 $
So
Total Income = selling price × quantity of product
Total Income = 500 × 30000
Total Income = 1.5 × 107
Now
Gross Income = Total income – Total product cost
Gross Income = 1.5 × 107 – 0.635 × 107
Gross Income = 0.87 × 107
Let the tax rate is 40%
Taxes = 0.4 × 0.87 × 107 = 0.336 × 107
So
Net Profit = Gross Income – Taxes
Net Profit = 0.87 × 107 – 0.336 × 107
Net Profit = 0.534 × 107
15.10 Rate of Return:

Rate of Return = (Net profit/Total Capital Investment) × 100
Rate of Return = (0.534 × 107/0.6187 × 107) × 100
Rate of Return = 86.31%
15.11 Payback Period:

Payback Period = Total Capital Investment/Net Profit
Payback Period = 0.6187 × 107/0.534 × 107
Payback Period = 1.158 years

Appendix
APPENDIX
Table 10.2: Thermal Conductivities of Liquids
Appendix
Table 10.3: Thermal Conductivities of Gasses and Vapors
Appendix
Table 10.4: Thermal Conductivities of Gasses and Vapors (Continued)
Appendix
Figure 10.2: Specific Heats of Liquids
Appendix
Figure 10.3: Specific Heats of Gasses
Appendix
Table 10.5: Specific Gravities and Molecular Weights of Liquids
Appendix
Figure 10.4: Latent Heats of Vaporization
Appendix
Table 10.6: Viscosities of Liquids
Appendix
Figure 10.5: Viscosities of Liquids
Appendix
Table 10.7: Viscosities of Gasses
Appendix
Figure 10.6: Viscosities of Gasses
Appendix
Figure 10.7: The Caloric Temperature Factor
Appendix
Figure 10.8: LMTD Correction Factor
Appendix
Figure 10.9: Tube Side Heat Transfer Curve
Appendix
Figure 10.10: Tube Side Friction Factor
Appendix
Figure 10.11: Shell Side Heat Transfer Curve
Appendix
Figure 10.12: Shell Side Friction Factor
Appendix
Table 10.8: Approximate Overall Design Coefficients
Appendix
Table 10.9: Tube Sheet Layouts
Appendix
Table 10.10: Tube Sheet Layouts (Continued)
Appendix
Table 10.11: Heat Exchanger and Condenser Tube Data
Appendix
Table 10.12: Dimensions of Steel Pipe (IPS)
Appendix
Table 15.1: Agitator Cost Estimation (S. M. Walas)
Appendix
Table 15.2: Distillation and Absorption Towers Cost Estimation
Appendix
Table 15.3: Distillation and Absorption Towers Cost Estimation (Continued)
Appendix
Table 15.4: Heat Exchangers Cost Estimation
Appendix
Table 15.5: Pumps Cost Estimation
Appendix
Table 15.6: Pumps Cost Estimation (Continued)
Appendix
Table 15.7: Vessels Cost Estimation
References
REFERENCES
1. G. Wesley Hatfield, Dane A. Hoiberg, “Enzymatic Process for Manufacturing
Formaldehyde and Hydrogen Peroxide”, US Patents 52348274 A, 10 August, 1993.
2. Rase, H. F., “Fixed Bed Reactor Design and Diagnostics’, Butterworth Publishers
London, 1990.
3. Rase, H. F., “Chemical Reactor Design for Process Plants’, Vol. 1, Willey, 1977.
4. Silla, H., “Chemical Process Engineering Design and Economics’, Marcel Dekker, Inc.
New York, 2003.
5. Turton, R., Bailie, R. C., Whiting, W. B., & Shaeiwitz, J. A., “Analysis, Synthesis and
Design of Chemical Processes’, Prentice hall International, 1998.
6. Levenspiel, O., “Chemical Reaction Engineering’, 3rd Edition, John Wiley and Sons Inc.,
1999.
7. Walas, S. M., “Chemical Process Equipment Selection and Design”, Butterworth
Heinemann, 1990.
8. Charles, G., Hill, J. R., “The Introduction to Chemical Engineering Kinetics and Reactor
Design” John Wiley and Sons Inc., 1977.
9. Fogler H. S., “Elements of Chemical Reaction Engineering” 2nd Edition, Prentice hall
International, 1997.
10. Bhattacharyya, B. C., “Introduction to Chemical Engineering Design”
11. Ludwig, E. E., “Applied Process Design”, 3rd Edition, Vol. 2, Gulf Professional
Publishers.
12. Ludwig, E. E., “Applied Process Design”, 3rd Edition, Vol. 3, Gulf Professional
Publishers, 2002.
13. Peters, M. S., and Timmerhaus, K. D., “Plant Design and Economics for Chemical
Engineers”, 5th Edition, McGraw Hill, 1999.
14. Coulson, J. M. and Richardson, J. F., “Chemical Engineering”, 4th Edition, Vol. 02,
Butterworth Heinemann, 1991.
15. Sinnot R. K., “Coulson and Richardson’s Chemical Engineering”, 3rd Edition, Vol. 06,
Butterworth Heinemann, 1999.
16. Kern, D. Q., “Process Heat Transfer”, McGraw Hill, 2000.
17. McCabe, W. L., Smith, J. C., and Harriot, P., “Unit Operations of Chemical
Engineering”, 5th Edition, McGraw Hill, 1993.
18. Perry, R. H. and D. W. Green: Perry’s Chemical Engineering Handbook, 7th Edition,
McGraw Hill, 1997.
19. Branan, C. R., “Rules of Thumbs for Chemical Engineers”, Gulf Publishing Company,
1994.
References
20. George T. Austin, Shreve’s Chemical Process Industries”, 5th Edition.

21. Himmelblau David M., Basic Principles and calculations in Chemical Engineering”, 6 th
Edition.
22. McKetta, J. J., “Encyclopedia of Chemical Processing and Design”, Executive Edition,
Vol. 01, Marcel Dekker Inc. New York, 1976.
23. Kuppan, T., “heat Exchanger Design Handbook”, Marcel Dekker Inc. New York, 2000.
Winston Churchill
Now this is not the End.

It is not even the Beginning of the End.
But it is, perhaps, the End of the Beginning.

Production of 30 000 Tons Per Year of Hydrogen Peroxide From Methanol by Enzymatic Conversion

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Production of 30 000 Tons Per Year of Hydrogen Peroxide From Methanol by Enzymatic Conversion

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PRODUCTION OF 30,000 TONS PER YEAR OF

HYDROGEN PEROXIDE FROM METHANOL

DEPARTMENT OF CHEMICAL ENGINEERING

Prof. Dr. Shahid Raza Malik Engr. Muhammad Awais Ashraf

Dr. Muhammad Jamil

DEPARTMENT OF CHEMICAL ENGINEERING

This Project Report is dedicated to the

List of Figures iii

Chapter No. 1: INTRODUCTION 01

Chapter No. 2: MANUFACTURING PROCESSES FOR HYDROGEN 12

2.1 The Barium Peroxide Process 11

Chapter No. 3: PROCESS DESCRIPTION 17

Chapter No. 4: ENZYME PREPARATION AND PURIFICATION 20

Chapter No. 5: MATERIAL BALANCE 25

Chapter No. 6: ENERGY BALANCE 36

6.1 Specific Heat Capacities 36

Chapter No. 7: FERMENTER DESIGN 56

Chapter No. 8: MULTICOMPONENT DISTILLATION COLUMN DESIGN 68

Chapter No. 10: HEAT EXCHANGER DESIGN 101

10.1 Introduction 101

Chapter No. 11: FLASH DRUM DESIGN 109

11.1 Introduction 109

Chapter No. 12: INSTRUMENTATION AND PROCESS CONTROL 113

12.1 Introduction 113

Chapter No. 13: HAZOP STUDY 118

13.1 Introduction 118

Chapter No. 14: ENVIRONMENTAL IMPACTS 125

14.1 Introduction 125

Chapter No. 15: COST ESTIMATION 136

15.1 Introduction 136

Table 1.1: Properties of Hydrogen Peroxide 02

Figure 1.1: Phase Diagram of Hydrogen Peroxide and Water 03

1.2 Physical Properties:

Molar Mass 34.0147 g/mol

Appearance Very light blue color; colorless in solution

Odor slightly sharp

Density 1.11 g/cm3 (20 °C, 30% (w/w) solution )

Melting Point −0.43 °C (31.23 °F; 272.72 K)

Boiling Point 150.2 °C (302.4 °F; 423.3 K) (decomposes)

Solubility soluble in ether, alcohol

Vapor Pressure 5 mmHg (30 °C)

Acidity (pKa) 11.75

Viscosity 1.245 cP (20 °C)

Figure 1.2: Activity Coefficients of Hydrogen Peroxide-Water Solutions

1.3 Chemical Properties:

Classification of Reaction of Hydrogen Peroxide:

Oxidation or Reduction Reactions of Hydrogen Peroxide:

2H2O2 + 2Fe++ + 2H+ 2Fe++ + 2H2O

Similarly, as an example of reduction by Hydrogen peroxide there may be cited

2KMnO4 + 5H2O2 + 3H2SO4 2MnSO4 + K2SO4 + 8H2O + 5O2

Dual Nature of Hydrogen Peroxide:

Peroxide Group Transfer:

3H2O2 + Ba(OH)2 BaO2 + 2H2O

Additional Compound Formation:

3H2O2 + 2Na2CO2 2Na2CO2.3H2O2

Formation of Peroxide Compounds:

Na2B4O7 + 4 H2O2 + 2 NaOH 2Na2B2O4(OH)4 + H2O

1.4 Uses of Hydrogen Peroxide:

As a bipropellant H2O2 is decomposed to burn a fuel as an oxidizer. Specific impulses as high as

Formaldehyde has become an industrial chemical of outstanding importance. The

In addition, soln. of formaldehyde in methanol, propanol, butanol are also available

Commercial forms of formaldehyde also include the polymeric hydrate,

MANUFACTURING PROCESSES FOR