FYP Report - Group 5 (CFinal Report)

Production of Oxalic Acid from Starch
Submitted by:
Miss. Zoya Naeem 2017-CH-13

Mr. Siyar Abdullah 2017-CH-41
Mr. Sufyan Naeem 2017-CH-45
Mr. Haris Akhtar 2017-CH-57
Supervised by: Dr. Humayun Wali

Year: 2017
Department of Chemical Engineering

University of Engineering and Technology Lahore.
The Final Year Project titled, “Production of Oxalic Acid from Starch” is being submitted to
the Department of Chemical Engineering, University of Engineering and Technology Lahore
in partial fulfillment of the requirement for the Degree of
Bachelor of Science in Chemical Engineering
Internal Examiner External Examiner
Chairman

University of Engineering and Technology Lahore
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Declaration
We declare that the work contained in this report has been checked for similarity
and the similarity index is within acceptable limits.
Name Registration No. Signature
Zoya Naeem 2017-CH-13
Siyar Abdullah 2017-CH-41
Abu Sufyan
2017-CH-45
Haris Akhtar
2017-CH-57
Date:
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Contribution Statement
We, members of the FYP group, endorse the level of contribution in the project titled,
“Production of Oxalic Acid from the Oxidation of Carbohydrates” as indicated below.
Registration No. % Contribution Signature
Zoya Naeem 25%
Siyar Abdullah 25%
Abu Sufyan 25%
Haris Akhtar 25%
Date:
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Dedications
We warmly dedicate our project to our beloved parents, teachers and

friends for their love, encouragement and endless support.
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Acknowledgments
We are thankful to Allah Almighty who blessed us in such a way to successfully complete
our project. Secondly, we cordially appreciate the whole efforts of our entire department
faculty who helped us throughout this project and our tenure of four years. A huge shout of
appreciation for our Parents and family members who morally supported us continuously
throughout any thick and thin
We are also indebted to our worthy project advisor Engr. Humayun Wali for his
encouragement, technical and moral guidance, suggestions and remarkable efforts which
enabled us to complete this report.
Lastly, we would like to extend our sincere thanks to everyone who helped and supported us
through their abilities for completion of this project.
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Table of Contents
Declaration...............................................................................................................................iii
Contribution Statement..........................................................................................................iv
Dedications................................................................................................................................v
Acknowledgments....................................................................................................................vi
Table of Contents...................................................................................................................vii
List of Figures..........................................................................................................................xi
List of Tables..........................................................................................................................xii
Abbreviations..........................................................................................................................xv
Abstract................................................................................................................................xviii
CHAPTER 1: INTRODUCTION...........................................................................................1
1.1 Background Information...................................................................................................1

1.2 Literature Survey...............................................................................................................1
1.3 Chemistry and Uses of Desired Product...........................................................................1
1.3.1 Properties of Product..................................................................................................1
1.3.2 Uses of Product...........................................................................................................2
1.4 Commerce Analysis..........................................................................................................3
1.5 Capacity Selection.............................................................................................................4
CHAPTER 2: PROCESS SELECTION................................................................................5
2.1 Introduction.......................................................................................................................5
2.1.1 Synthesis of Product...................................................................................................5
2.1.2 Process Comparison:..................................................................................................9
2.1.3 Process Selection......................................................................................................10
2.2 Process Description.........................................................................................................11
2.2.1 Process Flow Diagram..............................................................................................14
2.3 Plant Location.................................................................................................................15
CHAPTER 3: MATERIAL AND ENERGY BALANCE...................................................16
3.1 Material Balance.............................................................................................................16

3.1.1 Basis of Calculations:...............................................................................................16
3.1.2 Overall Material Balance..........................................................................................16
3.1.3 Material Balance across the Hydrolyzer...................................................................17
3.1.4 Material Balance across the Reactor.........................................................................19
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3.1.5 Material Balance across the Crude Crystallizer and Centrifuge...............................22
3.1.6 Material Balance across the Re-dissolver.................................................................25
3.1.7 Material Balance across the Grease Separator..........................................................26
3.1.8 Material Balance across the Product Crystallizer and Centrifuge............................27
3.1.9 Material Balance across the Dryer............................................................................29
3.1.10 Material Balance across the Evaporator.................................................................29
3.1.11 Material Balance across the Fixed Bed Reactor.....................................................31
3.1.12 Material Balance across the Absorber....................................................................32
3.1.13 Material Balance across the Fixed Bed Reactor (Recycled)..................................34
3.1.14 Material Balance across the Absorber (Recycled)..................................................35
3.3 Energy Balance...............................................................................................................37
3.3.1 Energy Balance across the Hydrolyzer.....................................................................37
3.3.2 Energy Balance across the Reactor...........................................................................38
3.3.3 Energy Balance across the Crystallizer....................................................................40
3.3.4 Energy Balance across the Re-dissolver...................................................................40
3.3.5 Energy Balance across the Product Crystallizer.......................................................41
3.3.6 Energy Balance across the Dryer..............................................................................42
3.3.7 Energy Balance across the Evaporator.....................................................................46
3.3.8 Energy Balance across the Compressor 101.............................................................56
3.3.9 Energy Balance across the Pre-Heater 101...............................................................57
3.3.10 Energy Balance across the Compressor 102...........................................................58
3.3.11 Energy Balance across the Pre-Heater 102.............................................................59
3.3.12 Energy Balance across the Fixed Bed Reactor.......................................................60
3.3.13 Energy Balance across the Cooler 101...................................................................61
3.3.14 Energy Balance across the Pump-101....................................................................62
3.3.15 Energy Balance across the Absorber......................................................................62
3.3.16 Energy Balance across the Pre-Heater 103.............................................................64
CHAPTER 4: DETAILED EQUIPMENT DESIGN..........................................................65
4.1 Fixed Bed Reactor Design..............................................................................................65

4.1.1 Design Steps.............................................................................................................65
4.1.2 Reaction Conditions..................................................................................................65
4.1.3 Process Design Calculations.....................................................................................65
4.1.4 Mechanical Design...................................................................................................68
4.1.5 Pressure Drop Calculations.......................................................................................69
4.1.6 Specification Sheet...................................................................................................70
4.2 Continuous Stirred Tank Reactor Design.......................................................................71
4.2.1 Design Steps.............................................................................................................71
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4.2.2 Reaction Conditions..................................................................................................71
4.2.3 Process Design Calculations.....................................................................................71
4.2.4 Design Equation of CSTR........................................................................................74
4.2.5 Reaction Kinetics......................................................................................................74
4.2.6 Mechanical Design...................................................................................................74
4.2.7 Stress calculations.....................................................................................................75
4.2.8 Agitator Design.........................................................................................................76
4.2.10 Pressure Drop inside Tube......................................................................................78
4.2.11 Specification Sheet.................................................................................................79
4.3 Absorber Design..............................................................................................................80
4.3.1 According to IUPAC................................................................................................80
4.3.2 Types of Absorption:................................................................................................80
4.3.3 Packed and Plate Column:........................................................................................80
4.3.4 Conditions of Absorption Column:..........................................................................81
4.3.5 Design Calculation Steps:.........................................................................................81
4.3.6: Flooding Calculations:.............................................................................................82
4.3.7 Wall Factor & Liquid Holdup:.................................................................................83
4.3.8 Calculations of Transfer Coefficients:......................................................................83
4.3.9 Pressure Drop Calculations:.....................................................................................84
4.3.10 Height of Packed Tower:........................................................................................85
4.3.11 Specification Sheet:................................................................................................86
4.4 Evaporator Design...........................................................................................................87
4.4.1 Evaporator:...............................................................................................................87
4.4.2 Design Calculations:.................................................................................................88
4.4.3 Tube Side Calculations:............................................................................................88
4.4.4 Shell Side Calculations.............................................................................................90
4.4.5 Tube Side Pressure Drop..........................................................................................90
4.4.6 Shell Side Pressure Drop..........................................................................................91
4.4.7 Specification Sheet...................................................................................................92
CHAPTER 5: PROCESS CONTROL AND INSTRUMENTATION...............................93
5.1 Introduction to Process Control:.....................................................................................93

5.2 Objectives of the Control System...................................................................................93
5.3 Components of the Control System................................................................................93
5.4 Selection of the Control System......................................................................................95
5.4 Control Schemes of Reactor............................................................................................96
5.4.1 Objectives:................................................................................................................96
5.4.2 Manipulated Variables..............................................................................................96
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5.4.3 Load or Disturbances................................................................................................96
CHAPTER 6: HAZOP ANALYSIS......................................................................................98
6.1 What is HAZOP?............................................................................................................98

6.2 Objective.........................................................................................................................98
6.3 HAZOP Terminology......................................................................................................98
6.4 OSHA Hazard Communication Standard.....................................................................101
6.4.1 Material Safety Data Sheets....................................................................................101
6.4.2 Labels and other Forms of Warning.......................................................................102
6.5 HAZOP Study Steps.....................................................................................................102
6.6 Characteristics of HAZOP Study..................................................................................104
6.7 Limitation of HAZOP Study.........................................................................................104
6.8 Procedure for HAZOP analysis.....................................................................................104
6.9 HAZOP of CSTR..........................................................................................................105
6.9.1 Failure and Possible Solutions................................................................................105
CHAPTER: 7 COST ESTIMATION.................................................................................107
7.1 Evaporator capital cost:.................................................................................................107

7.2 Absorber capital cost.....................................................................................................108
7.3 Fixed Bed Reactor capital cost:.....................................................................................110
7.4 CSTR Capital Cost:.......................................................................................................111
REFERENCES.....................................................................................................................113
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List of Figures
Figure 2-1 Process Flow Diagram............................................................................................14
Figure 3-1 Hydrolyzer..............................................................................................................18
Figure 3-2 Reactor....................................................................................................................19
Figure 3-3 Crude Crystallizer and Crude Centrifuge...............................................................22
Figure 3-4 Re-dissolver............................................................................................................25
Figure 3-5 Grease Separation Tank..........................................................................................26
Figure 3-6 Product Crystallizer and Product Centrifuge..........................................................27
Figure 3-7 Dryer.......................................................................................................................29
Figure 3-8 Evaporator..............................................................................................................29
Figure 3-9 Fixed Bed Reactor..................................................................................................31
Figure 3-10 Absorber...............................................................................................................32
Figure 3-11 Schematic diagram for the evaporator arrangement.............................................46
Figure 3-12 Compressor 101....................................................................................................56
Figure 3-13 Pre Heater 101......................................................................................................58
Figure 3-14 Compressor 102....................................................................................................58
Figure 3-15 Pre-Heater 102......................................................................................................59
Figure 3-16 Cooler 101............................................................................................................61
Figure 3-17 Pump 101..............................................................................................................62
Figure 3-18 Pre-Heater 103......................................................................................................64
Figure 5-1 Control Schemes across the Reactor......................................................................97
Figure 6-1 HAZOP Scheme...................................................................................................105
Figure 7-1 Evaporator Cost Estimation Graph.......................................................................107
Figure 7-2 Absorber Cost Estimation Graph 1.......................................................................108
Figure 7-3 Absorber Cost Estimation Graph 2.......................................................................109
Figure 7-4 Fixed Bed Reactor Cost Estimation Graph...........................................................110
Figure 7-5 CSTR Cost Estimation Graph...............................................................................111
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List of Tables
Table 1-1 Properties of Oxalic Acid (Anhydrous) and Oxalic Acid Dihydrate.........................1
Table 1-2 Oxalic Acid Import Data............................................................................................3
Table 2-1 Process Comparison...................................................................................................9
Table 3-1 MLR Input to the Hydrolyzer..................................................................................18
Table 3-2 Starch Input to the Hydrolyzer.................................................................................18
Table 3-3 Hydrolyzer Output...................................................................................................18
Table 3-4 MLR Input to the Reactor........................................................................................20
Table 3-5 HNO3 Input to the Reactor.......................................................................................21
Table 3-6 Combined Reactor Input..........................................................................................21
Table 3-7 Reactor Effluent Solution........................................................................................21
Table 3-8 NOx Gases Output from the Reactor.......................................................................22
Table 3-9 Composition of MLR + OAD solution from Crude Crystallizer.............................23
Table 3-10 Composition of MLR from Crude Crystallizer......................................................23
Table 3-11 Composition of MLR1.1 + OAD crystal from Crude Centrifuge..........................24
Table 3-12 Composition of MLR1.12 from Crude Centrifuge................................................24
Table 3-13 Water Addition to the Re-dissolver.......................................................................25
Table 3-14 Re-dissolver Output...............................................................................................25
Table 3-15 Grease Separation Output......................................................................................26
Table 3-16 Composition of OAD crystals + MLR from product crystallizer..........................27
Table 3-17 Composition of MLR from product centrifuge......................................................28
Table 3-18 Composition of OAD crystal solution from product centrifuge............................28
Table 3-19 Composition of OAD crystal dried........................................................................29
Table 3-20 Evaporator Input....................................................................................................30
Table 3-21 Evaporator Output..................................................................................................30
Table 3-22 Fixed Bed Reactor Input Gases..............................................................................31
Table 3-23 Addition of O2 to Fixed Bed Reactor.....................................................................32
Table 3-24 Fixed Bed Reactor Output.....................................................................................32
Table 3-25 Addition of Water to the Absorber........................................................................33
Table 3-26 Absorber Output Gases..........................................................................................33
Table 3-27 Absorber Output HNO3 Aqueous Solution............................................................33
Table 3-28 1st Recycled Feed to the Fixed Bed Reactor.........................................................34
Table 3-29 Fixed Bed Reactor Input Gases (Recycled)...........................................................34
Table 3-30 Addition of O2 to Fixed Bed Reactor (Recycled)..................................................35
Table 3-31 Fixed Bed Reactor Output.....................................................................................35
Table 3-32 Addition of Water to the Absorber (Recycled)......................................................35
Table 3-33 Absorber Output Gases (Recycled).......................................................................36
Table 3-34 Absorber Output HNO3 Aqueous Solution (Recycled)..........................................36
Table 3-35 Final Recycled Feed to the Fixed Bed Reactor......................................................36
Table 3-36 Energy Balance across the Hydrolyzer..................................................................37
Table 3-37 Heat Load of Hydrolyzer.......................................................................................38
Table 3-38 Energy Balance across the Reactor........................................................................38
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Table 3-39 Heat Load of Reactor.............................................................................................39
Table 3-40 Energy Balance across the Crystallizer..................................................................40
Table 3-41 Heat Load of Crystallizer.......................................................................................40
Table 3-42 Energy Balance across the Re-dissolver................................................................40
Table 3-43 Heat Load of Re-Dissolver....................................................................................41
Table 3-44 Energy Balance across the Product Crystallizer....................................................41
Table 3-45 Heat Load of Product Crystallizer.........................................................................42
Table 3-46 Energy Balance across the Dryer...........................................................................42
Table 3-47 Mass balance for each stage for 1st iteration of evaporator....................................47
Table 3-48 Specific heat capacity data for 1st iteration of evaporator......................................49
Table 3-49 Mass balance of each stage for 2nd iteration of evaporator....................................51
Table 3-50 Specific heat capacity data for 2nd iteration............................................................54
Table 3-51 Energy Balance across the Compressor 101..........................................................57
Table 3-52 Energy Balance across the Pre-Heater 101............................................................58
Table 3-53 Energy Balance across the Compressor 102..........................................................59
Table 3-55 Energy Balance across the Fixed Bed Reactor......................................................60
Table 3-56 Heat Load of Fixed Bed Reactor...........................................................................61
Table 3-57 Energy Balance across the Cooler 101..................................................................61
Table 3-58 Energy Balance across the Pump 101....................................................................62
Table 3-59 Energy Balance across the Absorber.....................................................................63
Table 3-60 Heat Load of Absorber...........................................................................................63
Table 4-1 Fixed Bed Reactor Conditions.................................................................................65
Table 4-2 Catalyst Specification..............................................................................................67
Table 4-3 Fixed Bed Reactor Volume Calculations.................................................................68
Table 4-4 Fixed Bed Reactor Tubes Specification...................................................................68
Table 4-5 Fixed Bed Reactor Shell Specification....................................................................69
Table 4-6 Material of Construction for Fixed Bed Reactor.....................................................69
Table 4-7 Fixed Bed Pressure Drop Calculations....................................................................70
Table 4-8 Fixed Bed Reactor Specification Sheet....................................................................70
Table 4-9 Continuous Stirred Tank Reactor Conditions..........................................................71
Table 4-10 Wall thickness Calculations...................................................................................75
Table 4-11 Head Thickness Calculations.................................................................................75
Table 4-12 Longitudinal Stress Calculations...........................................................................75
Table 4-13 Circumferential Stress Calculations.......................................................................75
Table 4-14 Pressure and Axial Stresses...................................................................................76
Table 4-15 Dimensions of Impeller..........................................................................................76
Table 4-16 Power of Impeller..................................................................................................76
Table 4-17 Outside Heat Transfer Coefficient Calculations....................................................77
Table 4-18 Reactor Tube Side Heat Transfer Coefficient Calculations...................................78
Table 4-19 CSTR Specification Sheet......................................................................................79
Table 4-20 Flooding Calculations............................................................................................82
Table 4-21 Calculations of Transfer Coefficients....................................................................83
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Table 4-22 Dry Gas Pressure Drop Calculations.....................................................................84
Table 4-23 Overall Pressure Drop Calculations.......................................................................85
Table 4-24 Height of Packed Tower Calculations...................................................................85
Table 4-25 Absorber Specification Sheet.................................................................................86
Table 4-26 Evaporator Specification Sheet..............................................................................92
Table 6-1 Frequently used words in HAZOP...........................................................................98
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Abbreviations
P Pressure
T Temperature
Q Head Load
Cp Specific Heat Capacity
<Cp> Mean Specific Heat Capacity
Hin Inlet Enthalpy
Hout Outlet Enthalpy
∆H Enthalpy Change
∆Hrex Enthalpy of Reaction
rA Rate of Reaction
K Rate Constant
Α Rhombic Form
Β Monoclinic Form
OAD Oxalic Acid Dihydrate
MLR Mother Liquor Recycle
Β Refractive index
BPE Boiling Point Elevation
∆T Temperature Difference
∆P Pressure Drop
W Actual Work
WS Isentropic Work
Ƞ Efficiency
Favg Average Flowrate of Water
xavg Average composition of Water
FBR Fixed Bed Reactor
Dp Particle Diameter
ρf Fluid Density
∈ Porosity
μf Fluid Viscosity
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G Mass Flux
L/D Length/Diameter
Ds Shell Inner Diameter
T Shell Thickness
nD No of tubes at bundle diameter
d′ Bundle Diameter
NP No of passes
Lt Tube Length
t′ Tube Thickness
nt No of tubes
VC Volume of Catalyst
VB Volume of Bed
V∈ Volume of Voids
VT Total Volume of Reactor
CA Concentration of Reference Component
FA Flowrate of Reference Component
Vo Volumetric Flowrate
F Design Stress
Pi Internal Pressure
Di Internal Diameter
C Corrosion Allowance
Re Reynold Number
UC Overall Heat Transfer Coefficient under Clean
Conditions
FLV Flooding Factor
uvf Flooding Velocity
uv Superficial Vapor Velocity
kw Wall Factor
HETP Height of Packed Tower
A Mass Transfer Surface Area
Ψ Psi Factor
KG Convective Gas Phase Coefficient
KL Convective Liquid Phase Coefficient
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∅ Diffusion Coefficient
HOG Overall Height of Mass Transfer Coefficient
Km Overall Volumetric Mass Transfer Coefficient
KVL Volumetric Liquid Phase Coefficient
KVG Volumetric Gas Phase Coefficient
Ls Shell Length
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Abstract
Oxalic acid is currently being used in Textile and Leather tanning industries in Pakistan.
Unfortunately in Pakistan there is no unit which manufactures oxalic acid. In order to fulfill
the requirement demand of oxalic acid in Pakistan, It is compelled to import oxalic acid at
high price. In order to avert the import of such valuable product at high expenses , we are
providing a better, efficient and inexpensive route “Production of Oxalic acid from starch”,
which not only could fulfill the requirement of Pakistan but also unbolts the new job
opportunities and could play an important role in Pakistan’s economy.
In 1989, an investors tried to run the plant of oxalic acid in Hattar Industrial State. This plant
was shut down after three months. Also in 1990, in BHAI PHERU. Another plant was
installed but this plant was also shut down after few months. Both of these plants were using
the route of ‘Production of oxalic acid from sugar’. The reason of shut down of these plants
was high product cost.
In our view the Oxalic Acid Manufacturing plant could be more feasible if it is produced
from starch instead of glucose and integrated with Nitric Acid Recovery Unit.
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CHAPTER 1: INTRODUCTION
1.1 Background Information

Ethanedioic acid commonly known as oxalic acid, is the simplest dicarboxylic acid. It is an
important industrial chemical which derives its name from the Greek word “oxys”, meaning
sharp or acidic, referring to the acidity common in the leaves of certain plans. It is a weak
acid with a pH = 3.00 and is soluble in water. This acid does not exist in anhydrous form in
nature and is available commercially as a solid di-hydrate (C 2H2O4.2H2O). It is present in
various plants and also in human and animal urine.
The anhydrous form of oxalic acid is odorless and colorless. It exists in two crystal forms the
rhombic or α-form and the monoclinic or β-form. Anhydrous oxalic acid can be efficiently
prepared from the di-hydrate by azeotropic distillation or conversely di-hydrate is carefully
heated to 100°C where it loses its water to give anhydrous oxalic acid. The solubility of the
dihydrate in water increases with temperature. The di-hydrate is very soluble in polar
solvents like ethanol but insoluble in benzene etc.
1.2 Literature Survey

Oxalic acid is one of the first organic acids to have been discovered and studied. Oxalic acid,
for the first time, was first isolated by the German chemist Johann Christian Wiegleb in 1769
and first synthesized by the Swedish chemist Karl Wilhelm Scheele in 1776. Friedrich
Wohler’s synthesis of oxalic acid entirely from inorganic materials was a critical step in
disproving the Vitalistic Theory of chemistry. The theory claimed that compounds found in
living organisms could be produced only by the act of some supernatural being, and not by
human actions
1.3 Chemistry and Uses of Desired Product
1.3.1 Properties of Product
Table 1-1 Properties of Oxalic Acid (Anhydrous) and Oxalic Acid Dihydrate
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Oxalic acid Anhydrous (C2H2O2)
Property Value
Melting point (°C)
𝛼 189.5
𝛽 182
Density (g/mL)
𝛼 1.900
𝛽 1.895
Refractive index (β) 1.540
Heat of combustion at 25°C (kJ/mol) -245.61
Standard heat of formation at 25°C, (kJ/mol) -826.78
Standard free energy of formation at 25°C (kJ/mol) -697.91
Heat of solution in water (kJ/mol) -9.58
Oxalic acid Dihydrate (C2H2O4.2H2O)
Melting Point (°C) 101.5
Density (g/ml) 1.653
Refractive index 1.475
Standard heat of formation at 18°C (kJ/mol) -1422
Heat of solution in water (kJ/mol) -35.5
1.3.2 Uses of Product
1. Catalyst: It is utilized as catalyst for the oxidation and reduction reactions such as for
the production of Maleic Anhydride by catalytic air oxidation of benzene in fixed and
fluidized beds. It is likewise utilized as a catalyst in the accelerated oxidation of
various cellulosic materials by sodium hypochlorite.
2. Bleaching Agent: It is utilized for dying wool, wood and hair. Dark natural kerat
fibers (camel and goat hair) are bleached to high degree of brightness by a bleaching
system involving the utilization of oxalic acid.
3. Metal Cleaning: Oxalic acid is a significant constituent of cleaners utilized for car
radiators, boiler tubes and radioactive contaminants from a reactor fuel plant. It gives
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great pH control and great chelating ability. It form water soluble complexes with
metal ions which prevent the formation of insoluble oxides and hydroxides on the
metal surface during cleaning and rinsing.
4. Textile: It is utilized in fabric cleaning, utilization of dyestuff and altering properties
of cellulosic material. Rust, stains which form on fabric during weaving and finishing,
are taken out by the chelating activity of oxalic acid. The iron oxalate formed is rinsed
from the fabric easily; It likewise neutralized the excess alkalinity in the laundries and
dissolves iron and other metallic salt which could stain fabric
5. Photography: Certain oxalates are sensitive to light which lead to the development of
photographic printing measure for example Blue Print. Blue printing paper contains
ferric ammonium oxalate and potassium ferricynide. On exposing to light, ferric ion is
reduced to ferrous on which reacts with ferricynide to shape a blue pigment.
6. Leather Tanning: Oxalic acid is utilized as a pH modifier in leather tanning by
tanning in basic chromium sulfate. It also acts as a bleaching agent for leather.
7. Separation and Recovery of Rare Earth Metals: Rare earth elements have low
solubility in acidic solutions; oxalic acid is utilized for separation and recovery. In the
decomposition of rare earth phosphates such as monazide and xenotime, sulphuric
acid is employed for decomposition. The rare earth elements are precipitated in the
form of oxalate which are then converted to corresponding oxides.
1.4 Commerce Analysis

In Pakistan, there is currently no plant that is producing Oxalic Acid. Pakistan has been
importing Oxalic Acid since very long from different countries. The commerce data presented
in the table below has been taken by UN COMTRADE and Pakistan Bureau of Statistics
and enlists all the countries that have been exporting Oxalic Acid to Pakistan with their
import values in the units US Dollar Thousand.
Table 1-2 Oxalic Acid Import Data
Imported Imported Imported Imported Imported

Exporters value in value in value in value in value in
2015 2016 2017 2018 2019
World 1,822 1,432 1,158 1,731 1,335
China 839 966 700 1,088 1,249
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India 981 451 452 640 85
Italy 0 0 0 0 1
Spain 0 10 2 0 0
Germany 1 2 3 2 0
Austria 0 1 0 0 0
1.5 Capacity Selection

The smallest plant of Oxalic Acid installed worldwide is in China which almost produces
3700 tons of Oxalic Acid per year. Therefore, on the basis of import data of Oxalic Acid in
Pakistan and for its export worldwide, the selected capacity for the Oxalic Acid Production
Plant is 6000 tons/Year (17000 kg/day)
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CHAPTER 2: PROCESS SELECTION
2.1 Introduction
Many industrial processes have been employed for the manufacture of oxalic acid. The
following processes are in use worldwide:
1. Ethylene Glycol Process
2. Propylene Process
3. Sodium Formate Process
4. Dialkyl Oxalate Process
5. Oxidation of Carbohydrate Process
2.1.1 Synthesis of Product
2.1.1.1 Ethylene Glycol Process

Oxalic acid is also prepared by the nitric acid oxidation of ethylene glycol and the process is
basically the same as in the case of carbohydrates except for the absence of the hydrolyzer. In
this process, ethylene glycol is oxidized in a mixture of 30–40% sulfuric acid and 20–25%
nitric acid in the presence of 0.001–0.1% vanadium pentoxide at 50–70°C to give oxalic acid
at more than 90% yield. An improved process has been developed in Japan by Mitsubishi Gas
Chemical, who produces 12,000 tons/year of oxalic acid by this process. Ethylene glycol is
oxidized in 60% nitric acid at 0.3 MPa, 80°C with oxygen. An initiator, such as NaNO 2, may
be used to help the generation of nitrogen oxides, and a promoter, such as vanadium
compounds or sulfuric acid, also may be employed to accelerate the oxidation reaction. The
yield of oxalic acid is 90%. The reaction proceeds according to the following equations.
Neither nitrogen nor N2O that cannot be recovered as nitric acid is produced in this method.
(𝐶𝐻2𝑂𝐻)2 + 4𝑁𝑂2 → (𝐶𝑂𝑂𝐻)2 + 4𝑁𝑂 + 2𝐻2𝑂
4𝑁𝑂 + 2𝑂2 → 4𝑁𝑂2
2.1.1.2 Propylene Process
Carlson and Gilbert describe proposed a route to produce oxalic acid by the oxidation of
propylene with-mixed acid. However, there are two objectionable features which preclude
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commercial acceptance of this procedure. One objection is that propylene does not react
rapidly with mixed acid of suitable strength. This not only imposes process and equipment
limitations but introduces an element of hazard since unreacted propylene reacts with
liberated nitrogen peroxide Such mixtures of propylene and NO can be violently explosive. A
second objection is that recovery of spent sulfuric acid liquor, after filtration of the oxalic
acid product, entails considerable evaporation because of the formation of large quantities of
water.
Oxalic acid is produced by a two-step process. In the first step, propylene is introduced at 10–
40℃ into nitric acid, the concentration of which is kept at 50–75 wt % and converted into α-
nitratolactic acid. α-Nitratolactic acid is oxidized by oxygen in the second step in the presence
of a catalyst at 45–100℃ to produce oxalic acid dihydrate. The overall yield based on
propylene is greater than 90%.
𝐶𝐻3𝐶𝐻 = 𝐶𝐻2 + 3𝐻𝑁𝑂3 → 𝐶𝐻3𝐶𝐻𝑂𝑂𝐻 + 2𝑁𝑂 + 2𝐻2𝑂
𝑂𝑁𝑂2
5
𝐶𝐻3𝐶𝐻𝑂𝑂𝐻 + 𝑂2 → (𝐶𝑂𝑂𝐻)2 + 𝐶𝑂2 + 𝐻𝑁𝑂3 + 𝐻2𝑂
2
𝑂𝑁𝑂2
2.1.1.3 Sodium Formate Process

It is an important commercial route to oxalic acid. The primary raw materials are NaOH, CO,
lime, H2SO4 and end products are oxalic acid, hydrogen, calcium sulphate. Soda is almost
recycled, minor losses can be made up by adding alkali or sodium formate from outside
where needed. The following reactions occur:
1. The manufacturing of sodium formate from carbon monoxide and sodium hydroxide.
It is a slow step.
𝑁𝑎𝑂𝐻 + 𝐶𝑂 → 𝐻𝐶𝑂𝑂𝑁𝑎
2. Manufacturing of sodium oxalate by thermal decomposition of sodium formate
2𝐻𝐶𝑂𝑂𝑁𝑎 → (𝐶𝑂𝑂𝑁𝑎)2 + 𝐻2
The second reaction requires critical control, the efficiency of the whole process depends
upon the success of this operation. The thermal decomposition of sodium formate always
proceeds with the formation of at least four products, sodium oxalate, sodium carbonate,
hydrogen and
6|Page
carbon monoxide. We are interested in the formation of sodium oxalate. The rate of heating
the formate and the maximum temp attainted in the product are important factors in the yield
of oxalate. The temperature of 300℃ favours the decomposition of sodium formate to sodium
carbonate, hydrogen and carbon monoxide while the temperature of 380℃ favors the
decomposition of sodium formate to sodium oxalate.
3. Recovery of Sodium hydroxide by treatment of sodium oxalate with lime

(𝐶𝑂𝑂𝑁𝑎)2 + 𝐶𝑎(𝑂𝐻)2 → (𝐶𝑂𝑂)2𝐶𝑎 + 2𝑁𝑎𝑂𝐻
The 3rd reaction is the caustacization of sodium oxalate in other words. Sodium oxalate is
added to lime slurry where all the calcium is converted to calcium oxalate
4. (𝐶𝑂𝑂)2𝐶𝑎 + 𝐻2𝑆𝑂4 ↔ (𝐶𝑂𝑂𝐻)2 + 𝐶𝑎𝑆𝑂4

The 4th reaction is the decomposition of calcium oxalate by sulphuric acid to produce oxalic
acid and gypsum as a byproduct.
2.1.1.4 Dialkyl Oxalate Process
Oxalic acid is prepared by the hydrolysis of diesters of oxalic acid prepared by an oxidative
CO coupling reaction. UBE Industries (Japan) commercialized this two‐step process in 1978.
This is the latest manufacturing process of oxalic acid. In the first step dialkyl oxalate is
prepared by oxidative CO. Oxalic acid is prepared by the hydrolysis of diesters of oxalic acid
Dialkyl oxalates can be prepared by oxidative CO coupling coupling in the presence of alkyl
nitrite and a palladium catalyst.
𝑃𝑑/𝐶
2𝐶𝑂 + 2𝑅𝑂𝑁𝑂 →−−→ (𝐶𝑂𝑂𝑅)2 + 2𝑁𝑂
(𝐶𝑂𝑂𝑅)2 + 2𝐻2𝑂 → (𝐶𝑂𝑂𝐻)2 + 2𝑅𝑂𝐻
1
2𝑁𝑂 + 𝑂 + 2𝑅𝑂𝐻 → 2𝑅𝑂𝑁𝑂 + 𝐻 𝑂
2 2 2
The alkyl nitrites employed industrially are n‐butyl nitrite (BN) and methyl nitrite (MN). The
reaction rate is fast. In order to generate BN, n-butanol and HNO 3 are premixed before being
fed to the reactor. The high pressure and low reaction temperature favor greater selectivity of
Dialkyl Oxalates.
7|Page
The oxalate process is generally carried out at a temperature preferably between 75°C and
about 160°C. The reaction pressure is generally atmospheric or super atmospheric pressure,
most preferably between about 1 atmosphere and about 7 atmospheres. The process is
preferably carried out in a tubular reactor with fixed catalyst.
It may be preferable to carry out the oxalate process in the presence of an inert gaseous
diluent to moderate the reaction to preclude the formation of explosive gaseous mixtures and
prevent the formation of excessive amounts of undesirable by-products.
2.1.1.5 Oxidation of Carbohydrates Process

Oxalic acid is prepared by the oxidation of carbohydrates, such as glucose, sucrose, starch,
dextrin, molasses etc. with nitric acid. The choice of the carbohydrate raw material depends
on availability, economics and process operating characteristics. Among the various raw
materials considered, corn starch (or starch in general) and sugar are the most commonly
available. For example, tapioca starch is the Brazilian raw material, and sugar is used in
India.
The oxidation of carbohydrates is the oldest method for oxalic acid manufacture. The reaction
was discovered by Scheele in 1776, but was not successfully developed as a commercial
process until the second quarter of the twentieth century. Technical advances in the
manufacture of nitric acid, particularly in the recovery of nitrogen oxides in a form suitable
for recycle, enabled its successful development.
Monosaccharides such as glucose and fructose are the most suitable as starting materials.
When starch is used, it is first hydrolyzed with oxalic acid or sulfuric acid into a
monosaccharide, mainly glucose. It is then oxidized with nitric acid in an approximately 50%
sulfuric acid solution at 63–85°C in the presence of a mixed catalyst of vanadium pentoxide
and iron (III) sulfate.
𝐹𝑒−𝑉2𝑂5
𝐶6𝐻12𝑂6 + 12𝐻𝑁𝑂3 →−−−−→ 3(𝐶𝑂𝑂𝐻)2. 2𝐻2𝑂 + 3𝑁𝑂 + 3𝐻2𝑂 + 9𝑁𝑂2
The Allied process is a typical example of the oxidation of carbohydrates. However, Allied
Corporation itself has stopped the production of oxalic acid. Oxalic acid manufacture via the
oxidation of carbohydrates is still actively pursued, especially in China. In India, processes
which produce silica and oxalic acid have been developed. The raw materials include
agricultural wastes, such as rice husks, nut shell flour, corn cobs, bagasse, straw etc.
8|Page
2.1.2 Process Comparison:
Table 2-1 Process Comparison
Sodium Oxidation of Ethylene Propylene Dialkyl

format carbohydrates glycol process oxalate
process process process
1. Raw material 1. NaOH 1. Carbohydrate 1. Ethylene 1. Propylene 1. CO
2. CO 2. HNO3 glycol 2. HNO3 2. n-Butyl
3. Ca(OH)2 3. H2SO4 2. NO2 O
3. 2 Nitrate
4. H2SO4 4. H2O 3. O2 3.H2O
4. n-
Butanol
a. Availability NaOH is In countries Ethylene Propylene For CO

easily like Pakistan glycol is is easily care is
available agricultural imported available needed in
but CO is a waste are from gulf found in its
poisonous common. We countries wood and handling.
gas so care can easily so it is a coal gas n-butanol,
is required obtain costly raw HNO3, H2O
in its glucose/starch. material. is easily
handling H2SO4 is Oxygen is available.
Ca(OH)2 required in less very easily
and H2SO4 amount nitric available.
both are acid is
easily required 63-
available 65% which
and not too don’t destroy
much the equipment
costly.
b. Recovery NaOH HNO3 is NO2 is not HNO3 is n-Butanol
regenerated regenerated recovered regenerated is
completely completely. but not recovered
completely. back
almost
completely.
2. Catalyst No catalyst 1.
Fe - V2O5 1.
NaNO2 1. Fe2O3 Palladium
is required 2.
H2SO4 2.
H2SO4
3.
V2O5
a. Availability Both are They are easily Not easily
available easily available available
available and not too and it is
and not too much precious
much costly metal but
costly catalyst can
9|Page
except easily be
V2O5 recycled.
3. By products 1.
H2 1.
H2O 1. NO 1. NO 1.
CO2
2.
CaSO4 2.
NO 2. H2O 2.
H2O
3.
NO2 3. CO2
4.
Grease
H2 gas is Both NO and NO is used NO is used CO2 which

higher than NO2 is used in for for HNO3 may form
air, so HNO3 oxidation recovery is separated
exhaust recovery. to NO2 by flashing.
from above Grease is H2O is
and CaSO4 produced so we separated
is filtered have to by
from redissolve and Azeotropic
bottom grease distillation.
separation tank
is required.
4. Yield 80-90% 50-70% 90% 77.5% 80%
2.1.3 Process Selection
Oxidation of Carbohydrates is the oldest method in the world which is widely used for the
production of oxalic acid. In Pakistan Raw materials for this process is very cheap and easily
available because our country is an agricultural country and rich in carbohydrates. The main
benefit of this process is that, raw materials which we are using is regenerated back and can
be used again, Moreover the conditions of temperature and pressure are very moderate which
makes the process non sensitive and a number of countries using this method for generation
of oxalic acid.
Demerits of other processes
In Sodium formate process CO is a poisonous gas, care is required to handle it. By products
are produced so separation is required for H₂ & CaSO4. Not recommended in developed
countries.
In Ethylene Glycol Process raw materials are imported from gulf countries. Besides, NO2 is
not recovered completely but 90%. Used only in Japan.
10 | P a g
In Propylene process HNO3, is partially recovered, CO₂ is produced as a byproduct. Also,
explosive mixtures are produced in this reaction. This method is widely used only in France
only.
In Dialkyl Oxalate Process a number of raw materials required, it is costly method, in which
precious catalyst is used. Distillation column is required for water separation. High pressure
has to be maintained.
2.2 Process Description

The raw material which we have chosen among the carbohydrates, is starch. Since it is a
polysaccharide so it needs to be hydrolyzed first.
 Oxalic Acid Unit

Hydrolyzer:
Starch is fed into the hydrolyzer along with some part of mother liquor recycle coming from
the mixing tank. The mother liquor recycle majorly carries 49.5% H 2SO4, 3.5% glucose, 4.4%
oxalic acid and soluble catalysts (Fe- V2O5) with 0.4% Fe and 0.001% V2O5. Here the
hydrolysis reaction takes place at 75℃ and 1 atm producing glucose solution.
𝐻2𝑆𝑂4
(𝐶6𝐻10𝑂5)𝑛 + 𝑛𝐻2𝑂 →−−→ 𝑛𝐶6𝐻10𝑂6
Reactor:
The glucose solution goes into the reactor into which nitric acid is fed along with the
remaining part of the mother liquor to dilute the glucose solution and also since, sulphuric
acid is required here to improve the yield. Glucose is oxidized by nitric acid in the presence of
Fe- V2O5 and sulphuric acid. As a result, Oxalic acid solution is produced along with Nitric
oxide and nitrogen dioxide. These gases are sent to the nitric acid recovery unit. As the
reaction is exothermic and temp needs to be maintained at 71℃ so here vertical cooling coils
are used. Pressure here is 1 atm.
𝐹𝑒−𝑉2𝑂5
𝐶6𝐻12𝑂6 + 12𝐻𝑁𝑂3 →−−−−→ 3(𝐶𝑂𝑂𝐻)2. 2𝐻2𝑂 + 3𝐻2𝑂 + 3𝑁𝑂 + 9𝑁𝑂2
Crude Crystallizer and Crude Centrifuge:

The oxalic acid solution is sent to the crude crystallizer for its crystallization. To achieve
super saturation which is the driving force for crystallization to occur, the temperature is
reduced to 20℃ by means of cooling medium circulated through suitable coils. The
cooling produces
11 | P a g
crystals of oxalic acid. The crystals from the mother liquor are separated in the crude
centrifuge on the basis of density difference.
Re-dissolver
For good quality and more purity, the crystals are re-dissolved in water in the re-dissolver.
For re-dissolving heat is required. This heat is supplied by the steam circulating in the steam
jacket. Grease Separation Tank
Further, the hot solution is sent into the grease separation tank where the inert present in the
starch are separated which have converted in the form of grease.
Product Crystallizer and Product Centrifuge
The oxalic acid solution is then again sent into crystallizer and further to the centrifuge where
the same process repeats and crystals are formed and hence separated.
Dryer
These crystals are sent into the dryer where its moisture content is reduced by drying done by
hot air. Finally, oxalic dehydrate crystals are produced which is then sent to the packaging
and bagging section. Drying is done at a temperature of 65℃.
Evaporator
The second mother liquor obtained from the product centrifuge combines with the first
mother liquor obtained from the crude centrifuge is recycled to the evaporator. This solution
contains excessive quantity of water. But since optimum concentration of sulphuric acid of
50% is required in the hydrolyzer and reactor so for that purpose, water is evaporated until
50% sulphuric acid solution is achieved.
 Nitric Acid Recovery Unit

Fixed Bed Reactor
Nitrogen Oxide and Nitrogen Dioxide gases are first compressed to a pressure of 5 atm and
then preheated to a temperature of 350℃. Nitrogen Dioxide gas then undergoes catalytic
oxidation in the presence of Pt/Al2O3 catalyst in a fixed bed reactor. The following reaction
occurs;
𝑃𝑡−𝐴𝐿2𝑂3
2𝑁𝑂 + 𝑂2 →−−−−−→ 2𝑁𝑂2
Absorber
Nitrogen Dioxide so produced is cooled to 25℃ and is then absorbed in water at 5atm by the
following reaction:
12 | P a g
3𝑁𝑂2 + 𝐻2𝑂 → 2𝐻𝑁𝑂3 + 𝑁𝑂
The pressure of aqueous nitric acid so produced is reduced to 1 atm and is sent to the reactor
in the oxalic acid unit. While NOx gases are recycled back to the fixed bed reactor.
13 | P a g
2.2.1 Process Flow Diagram
Figure 2-1 Process Flow
14 | P a g
2.3 Plant Location
The location of a plant has a crucial effect on the profitability of a project and the future
expansion.
Following are the factors considered when selecting a suitable site:
 Raw Material Availability
 Market
 Energy Availability
 Climate
 Transportation
 Water Supply
 Waste Disposal
 Labor Supply
 Taxation and Legal Restrictions
 Site Characteristics
 Flood and Fire Protection
 Community Factors
In Pakistan, the raw material (Starch) is widely produced near Okara city, Sahiwal and other
cities of Punjab. Also, it is majorly utilized in textile and leather tanning industries and a large
number of such industries are located near Faisalabad. So considering the stated factors for
plant location, the most suitable location of the plant would be Samundri (Located near
Faisalabad)
15 | P a g
CHAPTER 3: MATERIAL AND ENERGY
BALANCE
3.1 Material Balance

3.1.1 Basis of Calculations:
 Plant Capacity : 17000 kg/day
 Reference Temp = 25℃ and Reference Pressure = 1 atm
 Mass Flowrates are in kg/day and Molar Flowrates are in kgmol/day
 Basis = 1 day
3.1.2 Overall Material Balance

Mass of OAD to be produced = 17000.000 kg
Moles of OAD to be produced = 134.921 kgmole
𝐅𝐞−𝐕𝟐𝐎𝟓
𝐂𝟔𝐇𝟏𝟐𝐎𝟔 + 𝟏𝟐𝐇𝐍𝐎𝟑 →−−−−→ (𝐂𝐎𝐎𝐇)𝟐. 𝟐𝐇𝟐𝐎 + 𝟑𝐇𝟐𝐎 + 𝟑𝐍𝐎 + 𝟗𝐍𝐎𝟐
Based on 100% Conversion

Moles of C6H12O6 required = 44.974 kgmol
Mass of C6H12O6 required = 8095.238 kg
Moles of HNO3 required = 539.683 kgmol
Mass of HNO3 Required = 34000.000 kg
Mass of 63% HNO3 Solution required = 53968.254 kg solution
(𝐂𝟔𝐇𝟏𝟎𝐎𝟓)𝐧 + 𝐧𝐇𝟐𝐎 𝐇𝟐𝐒𝐎𝟒

→−−−→ 𝐧𝐂𝟔𝐇𝟏𝟎𝐎𝟔

From Simpson Patent;
Raw Starch = 85.6 % of starch
Mass of Raw Starch = 8511.348 kg
Moles of H2O required = 44.974 kgmol
Mass of H2O required = 809.524 kg
16 | P a g
%Conversion (From Simpson Patent)
Yield of (COOH)2.2H2O Based on Starch = 1.615 kg of (COOH)2.2H2O / kg of C6H10O5
Mass of (COOH)2.2H2O Produced = 11766.429 kg
Moles of (COOH)2.2H2O Produced = 93.384 kgmol
%yield = 70
Based on 70% Conversion

Mass of C6H12O6 unreacted in effluent = 2492.177 kg
Moles of HNO3 required = 373.537 kgmol
Mass of HNO3 required = 23532.857 kg
Mass of HNO3 unreacted in effluent = 10467.143 kg
From Simpson Patent

220 parts of Raw Starch = 1840 parts of MLR
Amount of MLR Stream = 71185.824 kg
The composition of MLR obtained from patent
H2SO4 = 49.5%
(COOH)2.2H2O = 4.4%
C6H12O6 = 3.5%
Fe = 0.4%
V2O5 = 0.001%
 Oxalic Acid Unit
3.1.3 Material Balance across the Hydrolyzer
17 | P a g
Figure 3-1 Hydrolyzer
Table 3-1 MLR Input to the Hydrolyzer
Stream17
Composition for MLR stream going into the Hydrolyzer - Hydrolyzer Input
Components Mass% Mass Moles Mole%
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 49.500 35236.983 359.561 21.701
HNO3 14.704 10467.143 166.145 10.028
H2O 27.495 19572.477 1087.360 65.627
(COOH)2.2H2O 4.400 3132.176 24.859 1.500
C6H12O6 3.500 2491.504 13.842 0.835
Fe 0.400 284.743 5.099 0.308
V2O5 0.001 0.797 0.004 0.000
Total 100.000 71185.824 1656.869 100.000
Table 3-2 Starch Input to the Hydrolyzer
Stream 1
Hydrolyzer Input
C6H10O5 100.000 8511.348 52.539 100.000
Table 3-3 Hydrolyzer Output
Stream 2
Hydrolyzer Output
18 | P a g
C6H10O5 1.538 1225.634 7.566 0.455
H2SO4 44.214 35236.983 359.561 21.603
HNO3 13.134 10467.143 166.145 9.982
H2O 23.543 18762.954 1042.386 62.627
(COOH)2.2H2O 3.930 3132.176 24.859 1.494
C6H12O6 13.284 10586.742 58.815 3.534
Fe 0.357 284.743 5.099 0.306
V2O5 0.001 0.797 0.004 0.0003
Total 100.000 79697.172 1664.435 100.000
3.1.4 Material Balance across the Reactor
Figure 3-2 Reactor
Glucose in the reactor is coming from;

 Glucose from starch (Gs)
 Glucose from MLR (Gr)
Material Balance of Glucose over the Reactor is:
In – Out + Generation – Consumption = Accumulation:
(Gs + Gr) - Gr - 0.7(Gs + Gr) = 0
∵ Gs = 44.974 kgmol
Gr = 19.274 kgmol = 3469.390 kg
19 | P a g
Amount of Glucose coming from MLR in the hydrolyzer = 2491.504 kg
Amount of Glucose coming from MLR in the reactor = 977.886 kg
We know the composition of MLR entering into the hydrolyzer, the MLR of same
composition is entering directly into the reactor.
3.5% of C6H12O6 required in MLR going in the reactor
3.5 kg C6H12O6 = 100 kg MLR
Amount of MLR going into the reactor = 27939.605 kg
Table 3-4 MLR Input to the Reactor
Stream 16
Composition of MLR stream going into the reactor
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 49.500 13830.104 141.124 21.701
HNO3 14.704 4108.231 65.210 10.028
H2O 27.495 7681.969 426.776 65.627
(COOH)2.2H2O 4.400 1229.343 9.757 1.500
C6H12O6 3.500 977.886 5.433 0.835
Fe 0.400 111.758 2.001 0.308
V2O5 0.001 0.313 0.002 0.0003
Total 100.000 27939.605 650.302 100.000
Amount of C6H12O6 entering into reactor = 11564.628 kg

Moles of C6H12O6 entering into the reactor = 64.248 kgmol
Moles of OAD theoretically produced = 192.744 kgmol
Based on Conversion = 70 %
Moles of OAD actually produced = 134.921 kgmol
Mass of OAD actually produced = 17000.003 kg
Moles of C6H12O6 actually required = 44.974 kgmol
Mass of C6H12O6 C actually required = 8095.240 kg
Moles of HNO3 actually required = 539.683 kgmol
Mass of HNO3 actually required = 34000.000 kg
Water coming with it is = 19968.254 kg (HNO3 is 63%)
20 | P a g
Moles of H2O actually produced = 134.921 kgmol
Mass of H2O actually produced = 2428.572 kg
Moles of NO actually produced = 134.921 kgmol
Mass of NO actually produced = 4047.620 kg
Moles of NO2 actually produced = 404.762 kgmol
Mass of NO2 actually produced = 18619.051 kg
Table 3-5 HNO3 Input to the Reactor
Stream 31
HNO3 from Recovery Unit
HNO3 63.000 34000.000 539.683 32.727
H2O 37.000 19968.254 1109.347 67.273
Total 100.000 53968.254 1649.030 100.000
Table 3-6 Combined Reactor Input
Stream 31 + Stream 2 + Stream 16

Reactor Input
C6H10O5 0.758 1225.634 7.566 0.191
H2SO4 30.362 49067.087 500.685 12.632
HNO3 30.058 48575.374 771.038 19.452
H2O 28.720 46413.177 2578.510 65.052
(COOH)2.2H2O 2.699 4361.519 34.615 0.873
C6H12O6 7.156 11564.628 64.248 1.621
Fe 0.245 396.502 7.100 0.179
V2O5 0.001 1.110 0.006 0.0003
Total 100.000 161605.031 3963.767 100.000
Table 3-7 Reactor Effluent Solution
Stream 3
Reactor Output
C6H10O5 0.882 1225.634 7.566 0.207
21 | P a g
H2SO4 35.316 49067.087 500.685 13.721
HNO3 10.491 14575.374 231.355 6.340
H2O 35.154 48841.748 2713.430 74.362
(COOH)2.2H2O 15.375 21361.522 169.536 4.646
C6H12O6 2.497 3469.390 19.274 0.528
Fe 0.285 396.502 7.100 0.195
V2O5 0.001 1.110 0.006 0.0003
Total 100.000 138938.368 3648.952 100.000
Table 3-8 NOx Gases Output from the Reactor
Stream 18
Reactor Output
NO 17.857 4047.620 134.921 25.000
NO2 82.143 18619.051 404.762 75.000
Total 100.000 22666.671 539.683 100.000
3.1.5 Material Balance across the Crude Crystallizer and Centrifuge
Figure 3-3 Crude Crystallizer and Crude Centrifuge
According to requirement, we only crystallize 17000 kg crystals of OAD. All the inert goes
into the OAD Crystal solution.
22 | P a g
From Literature
90 kg of OAD crystals = 100 kg of OAD crystal solution
Crystals Required = 17000 kg
Mass of OAD crystal solution (Crystals + MLR1.1) = 18888.889 kg
MLR 1.1 = 1888.889 kg
Table 3-9 Composition of MLR + OAD solution from Crude Crystallizer
Stream 4
Composition of MLR + OAD solution from Crude Crystallizer
C6H10O5 0.882 1225.634 7.566 0.207
H2SO4 35.316 49067.087 500.685 13.721
HNO3 10.491 14575.374 231.355 6.340
H2O 35.154 48841.748 2713.430 74.362
(COOH)2.2H2O 3.139 4361.519 34.615 0.949
C6H12O6 2.497 3469.390 19.274 0.528
Fe 0.285 396.502 7.100 0.195
V2O5 0.001 1.110 0.006 0.000
OAD Crsytals 12.236 17000.003 134.921 3.698
Total 100.000 138938.368 3648.952 100.000
Table 3-10 Composition of MLR from Crude Crystallizer
(Except 17000 OAD crystals and Inerts)

Composition of MLR from Crude Crystallizer
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 40.648 49067.087 500.685 14.279
HNO3 12.074 14575.374 231.355 6.598
H2O 40.461 48841.748 2713.430 77.384
(COOH)2.2H2O 3.613 4361.519 34.615 0.987
C6H12O6 2.874 3469.390 19.274 0.550
Fe 0.328 396.502 7.100 0.202
V2O5 0.001 1.110 0.006 0.000
Total 100.000 120712.731 3506.466 100.000
23 | P a g
MLR separating in centrifuge = 94267.808 – 1888.889 = 92378.919 kg
Table 3-11 Composition of MLR1.1 + OAD crystal from Crude Centrifuge
Stream 5
Composition of MLR1.1 + OAD crystal from Crude Centrifuge
C6H10O5 6.093 1225.634 7.566 3.834
H2SO4 3.817 767.792 7.835 3.970
HNO3 1.134 228.073 3.620 1.834
H2O 3.800 764.266 42.459 21.514
(COOH)2.2H2O 0.339 68.248 0.542 0.274
C6H12O6 0.270 54.288 0.302 0.153
Fe 0.031 6.204 0.111 0.056
V2O5 0.0001 0.017 0.0001 0.00005
OAD Crystals 84.516 17000.000 134.921 68.365
Total 100.000 20114.523 197.355 100.000
Table 3-12 Composition of MLR1.12 from Crude Centrifuge
Stream 6
Composition of MLR1.12 from Crude Centrifuge
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 40.648 48299.295 492.850 14.279
HNO3 12.074 14347.302 227.735 6.598
H2O 40.461 48077.482 2670.971 77.384
(COOH)2.2H2O 3.613 4293.271 34.074 0.987
C6H12O6 2.874 3415.102 18.973 0.550
Fe 0.328 390.297 6.989 0.202
V2O5 0.001 1.093 0.006 0.000
Total 100.000 118823.842 3451.597 100.000
24 | P a g
3.1.6 Material Balance across the Re-dissolver
Figure 3-4 Re-dissolver
From Simpson Patent, to separate Grease, add equal amount of H2O to OAD crystal solution
Table 3-13 Water Addition to the Re-dissolver
Stream 7
H2O Added
H2O 100.000 20114.523 1117.474 100.000
Table 3-14 Re-dissolver Output
Stream 8
Re-dissolver Output
C6H10O5 3.047 1225.634 7.566 0.575
H2SO4 1.909 767.792 7.835 0.596
HNO3 0.567 228.073 3.620 0.275
H2O 51.900 20878.789 1159.933 88.219
(COOH)2.2H2O 42.428 17068.248 135.462 10.303
C6H12O6 0.135 54.288 0.302 0.023
Fe 0.015 6.204 0.111 0.008
V2O5 0.00004 0.017 0.0001 0.00001
25 | P a g
Total 100.000 40229.046 1314.828 100.000
3.1.7 Material Balance across the Grease Separator
Figure 3-5 Grease Separation Tank
Table 3-15 Grease Separation Output
Stream 9
Grease Separator Output
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 1.969 767.792 7.835 0.599
HNO3 0.585 228.073 3.620 0.277
H2O 53.531 20878.789 1159.933 88.730
(COOH)2.2H2O 43.761 17068.248 135.462 10.362
C6H12O6 0.139 54.288 0.302 0.023
Fe 0.016 6.204 0.111 0.008
V2O5 0.00004 0.01737 0.00010 0.00001
Total 100.000 39003.412 1307.263 100.000
Grease Separated = 40229.046 – 39003.412 = 1225.634 kg
26 | P a g
3.1.8 Material Balance across the Product Crystallizer and Centrifuge
Figure 3-6 Product Crystallizer and Product Centrifuge
From Simpson Patent

Again according to requirement, we only crystallize 17000 kg crystals of OAD. From
Literature, it is known to us that from product centrifuge, OAD crystals solution contains
97% crystals
97 kg of OAD crystals = 100 kg of OAD crystal solution

Crystals = 17000 kg
Mass of OAD crystal solution from product centrifuge = 17525.7732 kg
Mass of MLR from product centrifuge = 21477.63876 kg
Table 3-16 Composition of OAD crystals + MLR from product crystallizer
Stream 10
Composition of OAD crystals +MLR from product crystallizer
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 1.969 767.792 7.835 0.599
HNO3 0.585 228.073 3.620 0.277
H2O 53.531 20878.789 1159.933 88.730
27 | P a g
(COOH)2.2H2O 0.175 68.248 0.542 0.041
C6H12O6 0.139 54.288 0.302 0.023
Fe 0.016 6.204 0.111 0.008
V2O5 0.00004 0.01737 0.00010 0.00001
OAD crsytals 43.586 17000.000 134.921 10.321
Total 100.000 39003.412 1307.263 100.000
Table 3-17 Composition of MLR from product centrifuge
Stream 11
Composition of MLR from product centrifuge
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 3.575 767.792 7.835 0.685
HNO3 1.062 228.073 3.620 0.317
H2O 94.764 20353.016 1130.723 98.914
(COOH)2.2H2O 0.318 68.248 0.542 0.047
C6H12O6 0.253 54.288 0.302 0.026
Fe 0.029 6.204 0.111 0.010
V2O5 0.00008 0.01737 0.00010 0.00001
Total 100.000 21477.639 1143.132 100.000
Table 3-18 Composition of OAD crystal solution from product centrifuge
Stream 12
Composition of OAD crystal solution from product centrifuge
H2O 3.000 525.773 29.210 17.797
OAD crsytals 97.000 17000.000 134.921 82.203
Total 100.000 17525.773 164.130 100.000
28 | P a g
3.1.9 Material Balance across the Dryer
Figure 3-7 Dryer
From Simpson Patent, it is known that the crystals are dried until at outlet, 0.2% moisture is
remaining.
Water removed = (0.03-0.002) x 17525.773 = 490.722 kg
Weight of OAD crystal dried = 17525.773 – 490.722 = 17035.052 kg
Table 3-19 Composition of OAD crystal dried
Stream 14
Composition of OAD Crystal Dried
H2O 0.206 35.052 1.947 1.423
OAD crsytals 99.794 17000.000 134.921 98.577
Total 100.000 17035.052 136.868 100.000
3.1.10 Material Balance across the Evaporator
Figure 3-8 Evaporator
29 | P a g
Table 3-20 Evaporator Input
Stream 13
Composition of Total MLR to evaporator Inlet
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 34.973 49067.087 500.685 10.897
HNO3 10.389 14575.374 231.355 5.035
H2O 48.774 68430.498 3801.694 82.740
(COOH)2.2H2O 3.109 4361.519 34.615 0.753
C6H12O6 2.473 3469.390 19.274 0.419
Fe 0.283 396.502 7.100 0.155
V2O5 0.0008 1.1276 0.0062 0.0001
Total 100.000 140301.498 4594.730 100.000
From Simpson Patent

%comp of H2SO4 = 49.5 %
Quantity of MLR solution = (49067.087/49.5) x 100 = 99125.429 kg
Weight of H2O to be evaporated = 140301.498 - 99125.429 =41176.069 kg
Table 3-21 Evaporator Output
Stream 15
Composition of Total MLR from Evaporator Outlet
C6H10O5 0.000 0.000 0.000 0.000
H2SO4 49.500 49067.087 500.685 21.701
HNO3 14.704 14575.374 231.355 10.028
H2O 27.495 27254.429 1514.135 65.627
(COOH)2.2H2O 4.400 4361.519 34.615 1.500
C6H12O6 3.500 3469.390 19.274 0.835
Fe 0.400 396.502 7.100 0.308
V2O5 0.0011 1.1276 0.0062 0.0003
Total 100.000 99125.429 2307.171 100.000
 Nitric Acid Recovery Unit

Calculations without Recycle
30 | P a g
3.1.11 Material Balance across the Fixed Bed Reactor
Figure 3-9 Fixed Bed Reactor
𝟐𝐍𝐎 + 𝐎𝟐 → 𝟐𝐍𝐎𝟐
Moles of NO produced in Oxalic Acid Unit Reactor = 134.921 kgmol

Moles of NO2 produced in Oxalic Acid Unit Reactor = 404.762 kgmol
Conversion = 95 %
Moles of NO reacted = 128.175 kgmol
Moles of NO unreacted = 6.746 kgmol
Moles of NO2 produced = 128.175 kgmol
Moles of O2 required = 67.460 kgmol
Moles of O2 reacted = 64.087 kgmol
Moles of O2 unreacted = 3.373 kgmol
Table 3-22 Fixed Bed Reactor Input Gases
Stream 20 (Stream 18)

Fixed Bed Reactor Input
31 | P a g
NO 17.857 4047.620 134.921 25.000
NO2 82.143 18619.051 404.762 75.000
Total 100.000 22666.671 539.683 100.000
Table 3-23 Addition of O2 to Fixed Bed Reactor

O2 100.000 2158.731 67.460 100.000
Table 3-24 Fixed Bed Reactor Output

Fixed Bed Reactor Output
NO 0.815 202.381 6.746 1.242
NO2 98.750 24515.084 532.937 98.137
O2 0.435 107.937 3.373 0.621
Total 100.000 24825.402 543.056 100.000
3.1.12 Material Balance across the Absorber
Figure 3-10 Absorber
32 | P a g
𝟑𝐍𝐎𝟐 + 𝐇𝟐𝐎 → 𝟐𝐇𝐍𝐎𝟑 + 𝐍𝐎
Conversion = 66.67%
Moles of NO2 reacted = 355.309 kgmol
Moles of NO2 unreacted = 177.628 kgmol
Moles of HNO3 produced = 236.873 kgmol
Moles of NO produced = 118.436 kgmol
∵ Conc of HNO3 at outlet = 63%
HNO3 in aq. HNO3 solution = 236.873 kgmol
Total aq. HNO3 solution = 394.788 kgmol
Water in aq. HNO3 solution = 157.915 kgmol
Total Water required = 276.351 kgmol
Table 3-25 Addition of Water to the Absorber

Absorber Input
H2O 100 4974.324 276.351 100
Table 3-26 Absorber Output Gases
Stream 29
Absorber Output
NO 31.206 3755.469 125.182 40.885
NO2 67.897 8170.878 177.628 58.014
O2 0.897 107.937 3.373 1.102
Total 100.000 12034.283 306.183 100.000
Table 3-27 Absorber Output HNO3 Aqueous Solution

Absorber Output
33 | P a g
H2O 16.000 2842.471 157.915 40.000
HNO3 84.000 14922.971 236.873 60.000
Total 100.000 17765.442 394.788 100.000
Table 3-28 1st Recycled Feed to the Fixed Bed Reactor
New Feed to the Reactor After 1st Recycle ( Stream 23 + Stream 29 + Stream 20 )
Absorber Output
NO 21.170 7803.089 260.103 28.479
NO2 72.681 26789.929 582.390 63.766
O2 6.149 2266.667 70.833 7.756
Total 100.000 36859.685 913.326 100.000
Calculations with Recycle
3.1.13 Material Balance across the Fixed Bed Reactor (Recycled)
𝟐𝐍𝐎 + 𝐎𝟐 → 𝟐𝐍𝐎𝟐
Moles of NO produced in Oxalic Acid Unit Reactor = 426.065 kgmol

Moles of NO2 produced in Oxalic Acid Unit Reactor = 809.463 kgmol
Conversion = 95 %
Moles of NO reacted = 404.762 kgmol
Moles of NO unreacted = 21.303 kgmol
Moles of NO2 produced = 404.762 kgmol
Moles of O2 required = 217.568 kgmol
Moles of O2 reacted = 206.690 kgmol
Moles of O2 unreacted = 10.878 kgmol
Table 3-29 Fixed Bed Reactor Input Gases (Recycled)

NO 25.555 12781.950 426.065 34.484
34 | P a g
NO2 74.445 37235.298 809.463 65.516
Total 100.000 50017.248 1235.528 100.000
Table 3-30 Addition of O2 to Fixed Bed Reactor (Recycled)

O2 100.000 6962.176 217.568 100.000
Table 3-31 Fixed Bed Reactor Output

Fixed Bed Reactor Output
NO 1.124 639.098 21.303 1.709
NO2 98.263 55854.339 1214.225 97.418
O2 0.612 348.109 10.878 0.873
Total 100.000 56979.424 1246.406 100.000
3.1.14 Material Balance across the Absorber (Recycled)
𝟑𝐍𝐎𝟐 + 𝐇𝟐𝐎 → 𝟐𝐇𝐍𝐎𝟑 + 𝐍𝐎
Conversion = 66.67%
Moles of NO2 reacted = 809.524 kgmol
Moles of NO2 unreacted = 404.701 kgmol
Moles of HNO3 produced = 539.682 kgmol
Moles of NO produced = 269.841 kgmol
∵ Conc of HNO3 at outlet = 63%
HNO3 in aq. HNO3 solution = 539.682 kgmol
Total aq. HNO3 solution = 856.639 kgmol
Water in aq. HNO3 solution = 316.956 kgmol
Total Water Required =586.798 kgmol
Table 3-32 Addition of Water to the Absorber (Recycled)
35 | P a g
Absorber Input
H2O 100.000 10562.356 586.798 100.000
Table 3-33 Absorber Output Gases (Recycled)
Stream 29
Absorber Output
NO 1.124 639.098 21.303 1.709
NO2 98.263 55854.339 1214.225 97.418
O2 0.612 348.109 10.878 0.873
Total 100.000 56841.545 1246.406 100.000
Table 3-34 Absorber Output HNO3 Aqueous Solution (Recycled)

Absorber Output
H2O 14.369 5705.214 316.956 37.000
HNO3 85.631 33999.993 539.682 63.000
Total 100.000 39705.207 856.639 100.000
Table 3-35 Final Recycled Feed to the Fixed Bed Reactor
New Feed to the Reactor (Recycled) ( Stream 23 + Stream 29 + Stream 20 )

Absorber Output
NO 22.296 12781.953 426.065 29.103
NO2 64.952 37235.299 809.463 55.292
O2 12.752 7310.285 228.446 15.605
Total 100.000 57327.537 1463.975 100.000
36 | P a g
3.3 Energy Balance
 Plant Capacity : 17000 kg/day
 Reference Temp = 25℃ and Reference Pressure = 1 atm
 Mass Flowrates are in kg/day and Molar Flowrates are in kgmol/day. Cp is in
KJ/kgmol
 Basis = 1 day operation
3.3.1 Energy Balance across the Hydrolyzer

 Isothermal Reaction
 Operating Temp = 348.15 K
 Operating Pressure = 1 atm
 Reference Temp = 298.15 K
𝐇𝟐𝐒𝐎𝟒
(𝐂𝟔𝐇𝟏𝟎𝐎𝟓)𝐧 + 𝐧𝐇𝟐𝐎
→−−−→ 𝐧𝐂𝟔𝐇𝟏𝟎𝐎𝟔
Table 3-36 Energy Balance across the Hydrolyzer
Hydrolyzer Input
Stream 1 Stream 17
Components
T= 298.15 K T= 333.9 K
Moles Mole% Cp<mix> Moles Mole% Cp<mix>
C6H10O5 52.539 100.000 205.700 0.000 0.000 0.000
H2SO4 0.000 0.000 0.000 359.561 21.701 31.441
HNO3 0.000 0.000 0.000 166.145 10.028 11.413
H2O 0.000 0.000 0.000 1087.360 65.627 49.280
(COOH)2.2H2O 0.000 0.000 0.000 24.859 1.500 1.723
C6H12O6 0.000 0.000 0.000 13.842 0.835 2.046
Fe 0.000 0.000 0.000 5.099 0.308 0.000
V2O5 0.000 0.000 0.000 0.004 0.000 0.000
Total 52.539 100.000 205.700 1656.869 100.000 95.903
Hydrolyzer Output
Stream 2
Components
T = 348.15 K
Moles Mole% Cp<mix>
C6H10O5 7.566 0.455 1.115
H2SO4 359.561 21.603 31.665
37 | P a g
HNO3 166.145 9.982 11.572
H2O 1042.386 62.627 47.050
(COOH)2.2H2O 24.859 1.494 1.769
C6H12O6 58.815 3.534 9.020
Fe 5.099 0.306 0.000
V2O5 0.004 0.0003 0.000
Total 1664.435 100.000 102.192
Table 3-37 Heat Load of Hydrolyzer
ΔHrxn ΔHin ΔHout Q = ΔHout - ΔHin + ΔHrxn

-13593883.598 5680651.021 8504632.394 -10769902.225 -124.652
KJ KJ KJ KJ/day KW
Cp of water ΔT m
Cooling Jacket Q=mCpΔT 4.184 15 171686.63
KJ/kg.K K kg/day
3.3.2 Energy Balance across the Reactor

𝐂𝟔𝐇𝟏𝟐𝐎𝟔 + 𝟏𝟐𝐇𝐍𝐎𝟑 →−−−−−→ (𝐂𝐎𝐎𝐇)𝟐. 𝟐𝐇𝟐𝐎 + 𝟑𝐇𝟐𝐎 + 𝟑𝐍𝐎 + 𝟗𝐍𝐎𝟐
Table 3-38 Energy Balance across the Reactor
Component Reactor Input

s Stream 16 Stream 31 Stream 2
T = 333.9 K T = 298.15 K T = 348.15 K
Moles Mole Cp<mi Moles Mole Cp<mi Moles Mole Cp<mi
% x> % x> % x>
C6H10O5 0.000 0.000 0.000 0.000 0.000 0.000 7.566 0.455 1.115
H2SO4 141.1 21.70 31.441 0.000 0.000 0.000 359.56 21.60 31.665
24 1 1 3
HNO3 65.21 10.02 11.413 539.68 32.72 64.694 166.14 9.982 11.572
0 8 3 7 5
38 | P a g
H2O 426.7 65.62 49.280 1109.3 67.27 15.906 1042.3 62.62 47.050
76 7 47 3 86 7
(COOH)2.2 9.757 1.500 1.723 0.000 0.000 0.000 24.859 1.494 1.769
H2O
C6H12O6 5.433 0.835 2.046 0.000 0.000 0.000 58.815 3.534 9.020
Fe 2.001 0.308 0.000 0.000 0.000 0.000 5.099 0.306 0.000
V2O5 0.002 0.000 0.000 0.000 0.000 0.000 0.004 0.000 0.000
3 3
Total 650.3 100.0 95.903 1649.0 100.0 80.601 1664.4 100.0 102.19
02 00 30 00 35 00 2
Reactor Output
Stream 3 Stream 18
Components
T= 344.15 T=344.15
C6H10O5 7.566 0.207 0.502 0.000 0.000 0.000
H2SO4 500.685 13.721 20.048 0.000 0.000 0.000
HNO3 231.355 6.340 7.310 0.000 0.000 0.000
H2O 2713.430 74.362 55.846 0.000 0.000 0.000
(COOH)2.2H2O 169.536 4.646 5.457 0.000 0.000 0.000
C6H12O6 19.274 0.528 1.333 0.000 0.000 0.000
Fe 7.100 0.195 0.000 0.000 0.000 0.000
V2O5 0.006 0.0003 0.000 0.000 0.000 0.000
NO 0.000 0.000 0.000 134.921 25.000 7.495
NO2 0.000 0.000 0.000 404.762 75.000 29.385
Total 3648.952 100.000 90.495 539.683 100.000 36.880
Table 3-39 Heat Load of Reactor

-4.356E+07 1.073E+07 1.611E+07 -38187499.942 -441.985
KJ KJ KJ KJ/day KW
Cp of water ΔT M
KJ/kg.K K kg/day
39 | P a g
3.3.3 Energy Balance across the Crystallizer
Table 3-40 Energy Balance across the Crystallizer
Crystallizer Input Crystallizer Output

Stream 3 Stream 4
Components
T= 344.15 T= 293.15
C6H10O5 7.566 0.207 0.502 7.566 0.207 0.418
H2SO4 500.685 13.721 20.048 500.685 13.721 19.100
HNO3 231.355 6.340 7.310 231.355 6.340 7.006
H2O 2713.430 74.362 55.846 2713.430 74.362 56.277
(COOH)2.2H2O 169.536 4.646 5.457 34.615 0.949 0.992
C6H12O6 19.274 0.528 1.333 19.274 0.528 1.139
Fe 7.100 0.195 0.000 7.100 0.195 0.000
V2O5 0.006 0.0003 0.000 0.006 0.000 0.000
OAD Crsytals 0.000 0.000 0.000 134.921 3.698 3.866
Total 3648.952 100.000 90.495 3648.952 100.000 88.799
Table 3-41 Heat Load of Crystallizer
ΔHcrys ΔHin ΔHout Q = ΔHout - ΔHin + ΔHcrys

3455587.972 1.519E+07 -1.620E+06 -13354353.056 -154.564
KJ KJ KJ KJ/day KW
Cp of water ΔT M
KJ/kg.K K kg/day
3.3.4 Energy Balance across the Re-dissolver
Table 3-42 Energy Balance across the Re-dissolver
Re-dissolver Input Re-dissolver Ouput

Stream 5 Stream 7 Stream 8
Component
T = 293.15 K T = 298.15 K T = 338.15 K
s
Moles Mole Cp<mi Moles Mole Cp<mi Moles Mole Cp<mi
% x> % x> % x>
C6H10O5 7.566 3.834 7.736 0.000 0.000 0.000 7.566 0.575 1.366
40 | P a g
H2SO4 7.835 3.970 5.526 0.000 0.000 0.000 7.835 0.596 0.866
HNO3 3.620 1.834 2.027 0.000 0.000 0.000 3.620 0.275 0.314
42.45 21.51 16.282 1117.4 100.0 75.550 1159.9 88.21 66.244
H2O
9 4 74 00 33 9
(COOH)2.2 0.542 0.274 0.287 0.000 0.000 0.000 135.46 10.30 11.944
H2O 2 3
C6H12O6 0.302 0.153 0.330 0.000 0.000 0.000 0.302 0.023 0.057
Fe 0.111 0.056 0.000 0.000 0.000 0.000 0.111 0.008 0.000
0.000 0.000 0.000 0.000 0.000 0.000 0.0001 0.000 0.000
V2O5
1 05 01
OAD 134.9 68.36 71.420 0.000 0.000 0.000 0.000 0.000 0.000
Crsytals 21 5
197.3 100.0 103.60 1117.4 100.0 75.550 1314.8 100.0 80.791
Total
55 00 8 74 00 28 00
Table 3-43 Heat Load of Re-Dissolver
ΔHsol ΔHin ΔHout Q = ΔHout - ΔHin + ΔHsol

1649971.380 -102237.358 4249064.796 6001273.533 69.459
KJ KJ KJ KJ/day KW
ΔH M
Steam Jacket Q = m∆H 2256.900 2659.078
KJ/kg kg/day
Assumption: Steam is entering at 100C at 1atm as saturated vapour and leaving as saturated
liquid
3.3.5 Energy Balance across the Product Crystallizer
Table 3-44 Energy Balance across the Product Crystallizer
Crystallizer Input Crystallizer Output

Stream 9 Stream 10
Components
T= 338.15 T= 293.15
C6H10O5 0.000 0.000 0.000 0.000 0.000 0.000
H2SO4 7.835 0.599 0.871 7.835 0.599 0.834
HNO3 3.620 0.277 0.316 3.620 0.277 0.306
41 | P a g
H2O 1159.933 88.730 66.627 1159.933 88.730 67.151
(COOH)2.2H2O 135.462 10.362 12.013 0.542 0.041 0.043
C6H12O6 0.302 0.023 0.057 0.302 0.023 0.050
Fe 0.111 0.008 0.000 0.111 0.008 0.000
V2O5 0.00010 0.00001 0.000 0.00010 0.00001 0.000
OAD Crsytals 0.000 0.000 0.000 134.921 10.321 10.793
Total 1307.263 100.000 79.885 1307.263 100.000 79.177
Table 3-45 Heat Load of Product Crystallizer
ΔHcrys ΔHin ΔHout Q = ΔHout - ΔHin + ΔHcrys

3455587.302 4177221.461 -517523.133 -1239157.292 -14.342
KJ KJ KJ KJ/day KW
Cp of water ΔT m
J/Kg.K K Kg/day
3.3.6 Energy Balance across the Dryer
Table 3-46 Energy Balance across the Dryer
Drier Input and Output

Stream 12 Stream 14
Components
T= 293.15 K T= 338.15 K
H2O 29.210 17.797 13.468 1.947 1.423 1.068
OAD crystals 134.921 82.203 85.960 134.921 98.577 114.281
Total 164.130 100.000 99.429 136.868 100.000 115.349
In dryer liquid water is removed from solid crystal by evaporation. To transfer the water from
feed stream to air latent heat of evaporation must be supplied
Qv, min (Js−1) = Wv∆Hv
ṁ g = air flow rate, kg dry air /hr.
ṁ P = Product flow rate, kg dry solid /hr.
W = Absolute humidity, kg water/ kg dry air
w = Product moisture content, dry basis kg water/ kg dry solid
42 | P a g
The material balance for the dryer is:
ṁ gW2 + ṁ Pw1 = ṁ gW1 + ṁ Pw2

The latent heat of evaporation at ambient temperature of 20℃ or 293.15K is:
∆Hv = 2400 kJ kg−1
The total water that will remove via drier is
Wv = Water in feed − water in product
Wv = 526.36 − 35.08 = 491.28 kg of H2O
kJ
Heat supply rate = Qv, min = Wv∆Hv = (491.28 kg of H2O ) (2400 )
kg of H2O
Heat supply rate = Qv, min = 1179072 kJ
ṁ g(W1 − W2) = Wv = ṁ p(win − wout) (1)
win = moisture content in feed = kg of water 526.36 kg of water

kg of kg
dryofsolid = 17000 = 0.0309 kg of dry
wout = moisture content in product = water 35.08
=
kg of dry solid 17000
kg of water
= 0.0021
kg of dry solid
Assume the air inlet at 110℃, from the psychrometric chart the saturated temperature of the
air is about 35℃, and the ambient humidity of 0.0075 kg/kg.
Inlet Absolute humidity = W2 = 0.0075 kg/kg
Substitute all the parameters of equation (1)
ṁ g(W1 − 0.0075) = (17000 kg of dry solid)(0.0309 − 0.0021) kg of water

kg of dry solid
489.6
ṁ g = (2)
W1 − 0.0075
The relationship in between the inlet humidity to the outlet humidity for direr is:
ṁ v 491.28 kg of H2O
W1 = W2 + = 0.0075 +
gout mg + 491.28
m
491.28
W = 0.0075 +
ṁ g+491.28 (3)
1
From equation 3,
W1ṁ g + 491.28 W1 = 0.0075 ṁ g + 494.9646
From equation (2) and (3).
43 | P a g
491.28 W12 − 9.049 W1 + 0.038 = 0
The possible root of the above quadratic equation is 0.012.
Outlet Absolute humidity = W1 = 0.012 kg/kg
From equation (2) the flow rate of air.
489.6 489.6
ṁ g = = = 108800 kg of air
W1 − 0.0075 0.012 − 0.0075
From the psychrometric chart the corresponding temperature of the air is

Ta1 = 78℃
The enthalpy balance for the dryer is:
ṁ gHg2 + ṁ PHP1 = ṁ gHg1 + ṁ PHP2
Here
Hg = Cs(Tg − T0) + WhL
Cs = 1.005 + 1.88 W
And
HP = CPP(TP − T0) + wCpw(TP − T0)
Hg = Thermal energy of air, kJ/kg dry air.
HP = Thermal energy of solid, kJ/kg dry solid.
CPP = Specific heat of dry solid, kJ/kg. K.
CPw = Specific heat of water, kJ/kg. K.
hL = Latent heat of vaporization, kJ/kg.
The enthalpy of feed

HP1 = CPP(TP − T0) + w1Cpw(TP − T0)
kJ
HP1 = (0.8050 ) (293.15 − 273.15)
kg. K
kg of water kJ
+ (0.0309 ) (0.1259 ) (293.15 − 273.15)
kg of dry solid kg.
kJ K
HP1 = 16.18
kg of dry solid
The enthalpy of product
HP2 = CPP(TP − T0) + wCpw(TP − T0)
44 | P a g
kJ
HP2 = (0.9181 ) (338.15 − 273.15)
kg. K
kg of water kJ
+ (0.0021 ) (0.0088 ) (338.15 − 273.15)
kg of dry solid kg.
kJ K
HP2 = 59.68
kg of dry solid
For inlet air
kg water kJ
Cs = 1.005 + 1.88 W2 = 1.005 + 1.88 (0.0075 ) = 1.0191
kg of dry air kg of dry air. K
Hg2 = Cs(Ta2 − T0) + W2hL
kJ
Hg2 = (1.0191 ) (383.15 − 273.15)
kg of dry air. K
kJ
+ (0.0075 kg water ) (1905.52 )
kg of dry air kg. K
kJ
Hg2 = 126.39
kg of dry air
For Outlet air
kg water kJ
Cs = 1.005 + 1.88 W1 = 1.005 + 1.88 (0.012 ) = 1.0276
kg of dry air kg of dry air. K
Hg1 = Cs(Ta1 − T0) + W1hL
kJ
Hg1 = (1.0276 ) (351.15 − 273.15)
kg of dry air. K
kJ
+ (0.012 kg water ) (2963.01 )
kg of dry air kg. K
kJ
Hg1 = 115.71
kg of dry air
Total heat enters to the drier:
ṁ gHg2 + ṁ PHP1
kJ
= (108800 kg of air) (126.39 )
kg of dry air
kJ
+ (17000 kg of solid) (16.18 )
kg of dry solid
Inlet Enthalpy = 14026292 kJ = 14026.29 MJ
Total heat leaves to the drier:
45 | P a g
ṁ gHg1 + ṁ PHP2
kJ
= (108800 kg of air) (115.71 )
kg of dry air
kJ
+ (17000 kg of solid) (59.68 )
kg of dry solid
Outlet Enthalpy = 14026292 kJ = 14026.29 MJ
3.3.7 Energy Balance across the Evaporator

Assume Steam from the boiler area at the thermodynamic conditions of:
Ts1 = 121℃ = 394.16 K and Ps = 1.04 bar
Figure 3-11 Schematic diagram for the evaporator arrangement
Assume that the evaporator produce water at pressure of 13.4 kPa, from the steam table the
saturated temperature of the water produce is.
T3 = 51.67 ℃ = 324.83 K
Overall water removes:
3801.7 moles − 1514.13 moles = 2287.57 moles
Assume equal amount of water remove in each stage then.
2287.57 moles
V1 = V2 = V3 = = 762.52 moles
3
The material balance for each stage is given:
46 | P a g
Table 3-47 Mass balance for each stage for 1st iteration of evaporator
Compone Evaporator inlet Stage 1 Stage 2 Stage 3

nts Stream 13
Moles Composit Moles Composit Moles Composit moles Composit
ion ion ion ion
H2SO4 500.68 10.8969 500.6 0.1307 500.6 0.1631 500.6 0.2170
46 8 8 8
HNO3 231.35 5.03523 231.3 0.0604 231.3 0.0754 231.3 0.1003
51 6 6 6
H2O 3801.6 82.7403 3039. 0.7931 2276. 0.7417 1514. 0.6563
94 18 66 14
OAD 34.615 0.75337 34.61 0.0090 34.61 0.0113 34.61 0.0150
23 5 5 5
C6H12O6 19.274 0.41949 19.27 0.0050 19.27 0.0063 19.27 0.0084
39 4 4 4
Fe 7.1000 0.15453 7.1 0.0019 7.1 0.0023 7.1 0.0031
4
V2O5 0.0062 0.00013 0.006 0.0000 0.006 0.0000 0.006 0.0000
2 2 2
Overall temperature change of evaporator is calculated by the expression:

∆T = Ts1 − T3 − (BPE1 + BPE2 + BPE3)
Where BFE is the boiling point elevation which is calculated by the correlation that relates
boiling point elevation to the composition.
BPEi = 1.80 xi + 6.22 xi2
Boiling point elevation in first stage is
BPE1 = 1.80 xi + 6.22 xi2 = BPEi = 1.80(0.2369) + 6.22 (0.2369)2 = 0.78 ℃
Boiling point elevation in 2nd stage is
BPE2 = 1.80 xi + 6.22 xi2 = BPEi = 1.80(0.2583) + 6.22 (0.2583)2 = 0.88 ℃
Boiling point elevation in 3rd stage is
BPE3 = 1.80 xi + 6.22 xi2 = BPEi = 1.80(0.3437) + 6.22 (0.3437)2 = 1.35 ℃
∆T = Ts1 − T3 − (BPE1 + BPE2 + BPE3) = 121 − 51.67 − (0.78 + 0.88 + 1.35)
= 66.32 ℃
47 | P a g
Overall heat transfer coefficient in each effect is calculated by the correlation
𝐔 ∆𝐓 𝐅𝐚𝐯𝐠
𝐱𝐚𝐯𝐠 𝐜
𝐝
𝐛
= 𝐚( ) ( ) ( )
𝟐𝟎𝟎𝟎 𝟒𝟎 𝟎. 𝟔𝟎 𝟐𝟓
Where a, b and c are constant 𝐱𝐚𝐯𝐠 is average value of composition and 𝐅𝐚𝐯𝐠 is the
average water flow rate from inlet and outlet parameters.
Overall heat transfer coefficient in first stage with constant a = 0.0604, b = − 0.3717, c =
− 1.227 and d = 0.0748, x 0.8274 + 0.7931
avg
= = 0.81 similarly F avg =
2
2534.47 moles of water
U1 66.32 −0.3717 0.81 −1.227 2534.47 0.0748
200 = 0.0604 ( 40 ) ( ) ( )
0.60 25
0
W
U1 = 97.85 2
m .℃
For 2nd stage with constant a = 0.0604, b = − 0.3717, c = − 1.227 and d = 0.0748,
xavg = 0.7674 similarly Favg = 2026 moles of water
U2 66.32 −0.3717 0.7674 −1.227 2026 0.0748
200 = 0.0604 ( 40 ) ( ) ( )
0.60 25
0
W
U2 = 102.82 2
m .℃
For 3rd stage with constant a = 0.1396, b = − 0.7949, c = 0.0 and d = 0.1673, xavg =
0.699 similarly Favg = 1517.77 moles of water
U3 66.32 −0.7949 0.699 0.0 1517.77 0.1673
200 = 0.1396 ( 40 ) ( ) ( )
0.60 25
0
W
U3 = 371.29 2
m .℃
Temperature drops in each effect is calculated as
U11 1
97.85
∆T1 = ∆T ( ) = (66.32℃) ( ) = 29.94℃
1 1 1 1 1 1
+ + + +
U1 U2 U3 97.85 102.82 371.29
48 | P a g
U12 1
102.82
∆T2 = ∆T ( ) = (66.32℃) ( ) = 28.49 ℃
1 1 1 1 1 1
+ + + +
U1 U2 U3 97.85 102.82 371.29
U13 1
371.29
∆T3 = ∆T ( ) = (66.32℃) ( ) = 7.89 ℃
1 1 1 1 1 1
+ + + +
U1 U2 U3 97.85 102.82 371.29
T1 = Ts − ∆T1 = 121 − 29.94 = 91.06 ℃

T2 = T1 − BPE1 − ∆T2 = 91.06 − 0.78 − 28.49 = 61.79 ℃
Ts2 = T1 − BPE1 = 91.06 − 0.78 = 90.28 ℃
T3 = T2 − BPE2 − ∆T3 = 53.02 ℃

Ts3 = T2 − BPE3 = 60.44 ℃
From the steam table latent heat of vaporization are:
kJ J
@Ts1 = 121℃ λs1 = 2242.3 = 40361.4
kg mol
kJ J
@Ts2 = 90.28 ℃ λs2 = 2281.84 = 41073.12
kg mol
kJ J
@Ts3 = 60.44 ℃ λs3 = 2356.62 = 42419.16
kg mol
From the steam table enthalpy of water are:
kJ J
@T1 = 91.06℃ H1 = 2661.25 = 47902.5
kg mol
kJ J
@T2 = 61.79 ℃ H2 = 2611.96 = 47015.28
kg mol
kJ J
@T3 = 53.02 ℃ H3 = 2596.63 = 46739.34
kg mol
Table 3-48 Specific heat capacity data for 1st iteration of evaporator
Stage 1 @91.06 ℃ Stage 2 @61.79 ℃ Stage 3 @53.02 ℃

Components Composition 𝐂𝐏 Composition 𝐂𝐏 composition 𝐂𝐏
< mix > < mix > < mix >
H2SO4 0.1307 19.3441 0.1631 23.6514 0.2170 31.2277
HNO3 0.0604 7.1771 0.0754 8.5891 0.1003 11.3194
H2O 0.7931 59.7492 0.7417 55.6910 0.6563 49.2993
49 | P a g
OAD 0.0090 1.1067 0.0113 1.2981 0.0150 1.6940
C6H12O6 0.0050 1.3412 0.0063 1.5430 0.0084 2.0003
Fe 0.0019 0.0000 0.0023 0.0000 0.0031 0.0000
V2O5 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Enthalpy balance on first effect with 0 ℃ as datum
FCP𝐹 (Tf − 0) + S λs1 = L1CPL1 (T1 − 0) + V1H1
Substitute all the parameters,
kJ J
(4594.73 mol) (85.04 ) (20 − 0) + S (40361.4 )
kmol. K mol
kJ J
)
= (L1) (88.7182 ) (91.06 − 0) + (4594.73 − L1) (47902.5 mol
kmol. K
Rearranging and simplifying,
S + 0.99 L1 = 5259.59 (𝟏)
Enthalpy balance on 2nd effect with 0 ℃ as datum.
L1CPL1 (T1 − 0) + V1 λs2 = L2CPL2 (T2 − 0) + V2H2
(L1) (88.7182 kJ ) (91.06 − 0) + (4594.73 − L1 )(41073.12 J )

kmol. K mol
kJ J
= (L2) (90.7726 ) (61.79 − 0) + (L1 − L2) (47015.28 )
kmol. K mol
L1 − 0.52 L2 = 2358.71 (𝟐)
Similarly, enthalpy balance on 3rd effect with 0 ℃ as datum.
50 | P a g
(L2) (90.7726 kJ ) (61.79 − 0) + (L1 − L2) (42419.16 J )
kmol. K mol
kJ
= (2307.1752 moles) (95.5408 ) (53.02 − 0)
kmol. K
J
+ (L2 − 2307.1752) (46739.34 )
mol
L1 − 1.97 L2 = −2266.63 (𝟑)
Simultaneously solve equation (2) and (3)
L1 = 4017.45 moles and L2 = 3189.89 moles
From equation (1), the flow rate of steam will be.

S + 0.99(4017.45 moles) = 5259.59 ⟹ S = 1282.32 moles
The flow rate of water as vapor recover from each stage will be.
V1 = 4594.73 − 4017.45 = 577.28 moles
V2 = L1 − L2 = 4017.45 − 3189.89 = 827.56 moles
V3 = L2 − 2307.1752 = 3189.89 − 2307.1752 = 852.72 moles
Now for the 2nd iteration, value of vapor form in each stage uses as a guess point and the
material balance for the evaporator all stages are given in table 4.
Table 3-49 Mass balance of each stage for 2nd iteration of evaporator
Evaporator inlet Stage 1 Stage 2 Stage 3

Components
Stream 12
Moles Compos moles composi moles Composi Moles Composi
ition tion tion tion
𝐇𝟐𝐒𝐎𝟒 500.68 10.8969 500.68 12.46 500.68 15.70 500.68 21.42
46
𝐇𝐍𝐎𝟑 231.35 5.03523 231.36 5.76 231.36 7.25 231.36 9.90
51
𝐇𝟐𝐎 3801.6 82.7403 3224.4 80.26 2396.8 0.75.14 1514.1 66.07
94 1 5 3
𝐎AD 34.615 0.75337 34.615 0.86 34.615 1.09 34.615 1.48
23
51 | P a g
𝐂𝟔𝐇𝟏𝟐𝐎𝟔 19.274 0.41949 19.274 0. 48 19.274 0. 60 19.274 0. 82
39
𝐅𝐞 7.1000 0.15453 7.1 0. 18 7.1 0. 22 7.1 0. 30
4
𝐕𝟐𝐎𝟓 0.0062 0.00013 0.0062 0.00 0.0062 0.00 0.0062 0.00
Overall temperature change of evaporator is calculated by the expression:

∆T = Ts1 − T3 − (BPE1 + BPE2 + BPE3)
BPEi = 1.80 xi + 6.22 xi2
Boiling point elevation in first stage is
BPE1 = 1.80 xi + 6.22 xi2 = BPEi = 1.80(0.1974) + 6.22 (0.1974)2 = 0.60 ℃
Boiling point elevation in 2nd stage is
BPE2 = 1.80 xi + 6.22 xi2 = BPEi = 1.80(0.2486) + 6.22 (0.2486)2 = 0.83 ℃
Boiling point elevation in 3rd stage is
BPE3 = 1.80 xi + 6.22 xi2 = BPEi = 1.80(0.3393) + 6.22 (0.3393)2 = 1.33 ℃
∆T = Ts1 − T3 − (BPE1 + BPE2 + BPE3) = 121 − 51.67 − (0.60 + 0.83 + 1.33)
= 66.57 ℃
Overall heat transfer coefficient in each effect is calculated by the correlation
𝐔 ∆𝐓 𝐅𝐚𝐯𝐠
𝐝
𝐛 𝐱𝐚𝐯𝐠 𝐜
= 𝐚( ) ( ) ( )
𝟐𝟎𝟎𝟎 𝟒𝟎 𝟎. 𝟔𝟎 𝟐𝟓
Overall heat transfer coefficient in first stage with constant a = 0.0604, b = − 0.3717, c =
− 1.227 and d = 0.0748, xavg = 0.815 similarly Favg = 2534.47 moles of water
U1 66.57
−0.3717 0.81 −1.227 2534.47 0.0748
200 = 0.0604 ( 40 ) ( ) ( )
0.60 25
0
W
U1 = 99.42 2
m .℃
For 2nd stage with constant a = 0.0604, b = − 0.3717, c = − 1.227 and d = 0.0748, xavg =
0.777 similarly Favg = 2149 moles of water
U2 66.57 −0.3717 0.777 −1.227 2149 0.0748
200 = 0.0604 ( 40 ) ( ) ( )
0.60 25
0
W
U2 = 1597.9 2
m .℃
52 | P a g
For 3rd stage with constant a = 0.1396, b = − 0.7949, c = 0.0 and d = 0.1673, xavg =
0.706 similarly Favg = 1597.90 moles of water
U3 66.57 −0.7949 0.706 0.0 1597.90 0.1673
200 = 0.1396 ( 40 ) ( ) ( )
0.60 25
0
W
U3 = 373.38 2
m .℃
Temperature drops in each effect is calculated as
U11 1
99.42
∆T1 = ∆T ( ) = (66.57℃) ( ) = 29.65 ℃
1 1 1 1 1 1
+ + + +
U1 U2 U3 99.42 101.57 373.38
Similarly,
∆T2 = 29.02 ℃
∆T3 = 7.89 ℃
T1 = Ts − ∆T1 = 121 − 29.65 = 91.35 ℃
T2 = T1 − BPE1 − ∆T2 = 91.35 − 0.60 − 29.02 = 61.73 ℃
Ts2 = T1 − BPE1 = 91.35 − 0.60 = 90.75 ℃
T3 = T2 − BPE2 − ∆T3 = 60.9 ℃

Ts3 = T2 − BPE3 = 60.4 ℃
From the steam table latent heat of vaporization are:
kJ J
@Ts1 = 121℃ λs1 = 2242.3 = 40361.4
kg mol
kJ J
@Ts2 = 90.75 ℃ λs2 = 2280.63 = 41051.34
kg mol
kJ J
@Ts3 = 60.4 ℃ λs3 = 2356.71 = 42420.78
kg mol
From the steam table enthalpy of water are:
kJ J
@T1 = 91.35℃ H1 = 2661.72 = 47910.96
kg mol
kJ J
@T2 = 61.73 ℃ H2 = 2611.85 = 47013.3
kg mol
kJ J
@T3 = 60.9 ℃ H3 = 2510.41 = 46987.38
kg mol
The specific enthalpy data for each component at desire temperature is.
53 | P a g
Table 3-50 Specific heat capacity data for 2nd iteration
Stage 1 @91.06 ℃ Stage 2 @61.79 ℃ Stage 3 @60.9 ℃
Components 𝐂𝐏 𝐂𝐏 𝐂𝐏
Composition composition composition
< mix > < mix > < mix >
H2SO4 0.1307 19.3441 0.1631 23.6514 0.2170 31.2277

HNO3 0.0604 7.1771 0.0754 8.5891 0.1003 11.3194
H2O 0.7931 59.7492 0.7417 55.6910 0.6563 49.2993
OAD 0.0090 1.1067 0.0113 1.2981 0.0150 1.6940
C6H12O6 0.0050 1.3412 0.0063 1.5430 0.0084 2.0003
Fe 0.0019 0.0000 0.0023 0.0000 0.0031 0.0000
V2O5 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Enthalpy balance on first effect with 0 ℃ as datum
FCP𝐹 (Tf − 0) + S λs1 = L1CPL1 (T1 − 0) + V1H1
kJ J
(4594.73 mol) (85.044 ) (20 − 0) + S (40361.4 )
kmol. K mol
kJ J
)
= (L1) (88.1508 ) (91.35 − 0) + (4594.73 − L1) (47910.96 mol
kmol. K
S + 0.99 L1 = 5260 (1)
Enthalpy balance on 2nd effect with 0 ℃ as datum.
(L1) (88.1508 kJ ) (91.35 − 0) + (4594.73 − L1 )(41051.34 J )

kmol. K mol
kJ J
= (L2) (90.1794 ) (61.73 − 0) + (L1 − L2) (47013.30 )
kmol. K mol
L1 − 0.52 L2 = 2357 (2)
Similarly, enthalpy balance on 3rd effect with 0 ℃ as datum.
54 | P a g
(L2) (90.1794 kJ ) (61.73 − 0) + (L1 − L2) (42420.78 J )

kmol. K mol
kJ
= (2337.1652 moles) (95.6351 ) (60.90 − 0)
kmol. K
J
+ (L2 − 23037.1652) (46987.38 )
mol
L1 − 1.98 L2 = −2267.92 (3)
Simultaneously solve equation (2) and (3)
L1 = 4004.23 moles and L2 = 3167.75 moles
From equation (1), the flow rate of steam will be.

S + 0.99(4004.23 moles) = 5260 ⟹ S = 1295.81 moles
The flow rate of water as vapor recover from each stage will be.
V1 = 4594.73 − 4004.23 = 590.50 moles
V2 = L1 − L2 = 4004.23 − 3167.75 = 836.48 moles
V3 = L2 − 2337.1652 = 830.58 moles
Overall steam economy:

V1 + V2 + 590.5 + 836.48 + 830.58
V3 = = 1.74
steam economy = 1295.81
S
Enthalpy of feed enter to the evaporator:
kJ
Qf = mCP𝐹∆T = (4594.73 moles) (85.04 ) (293.3 − 0) = 114485600 J
mol. K
Qf = 114.49 MJ
Enthalpy of steam enter to the evaporator:
J
Qs = SHs = (1295.81 moles) (39588.33 ) = 51273974.39 J
mol
Qs = 51.27 MJ
Total enthalpy of inlet streams.
QTotal, In = Qf + Qs = 114.49 + 51.27 = 165.76 MJ
55 | P a g
Enthalpy of product leaving to the evaporator:
kJ
Qp = mCPP∆T = (2337.1652 moles) (95.6351 ) (333.9 − 0) = 74631667.72 J
mol. K
Qp = 74.63 MJ
Enthalpy of water recover in last effect of the evaporator:
J
Q3 = V3H3 = (830.58 moles) (46987.38 ) = 39026778 J
mol
Q3 = 39.03 MJ
Enthalpy of outlet condense water in third
effect.
J ) = 35484134 J
Qsout = V2λs3 = (836.48 moles) (42420.78
mol
Qsout = 35.5 MJ
Enthalpy of outlet condense water in 2nd effect.
J
Q2 = (836.48 moles) (4583.16 ) = 3833721.68 J
mol
Q2 = 3.83 MJ
Enthalpy of outlet condense water in first effect.
J
Q1 = (1295.18 moles) (9144.648 ) = 12843965.19 J
mol
Q1 = 12.84 MJ
Total enthalpy of outlet streams.
QTotal, out = Qp+ Q3 + Qsout + Q2 + Q1 = 165.76 MJ
QTotal, out = 74.63 + 39.03 + 35.5 + 3.83 + 12.84 = 165.76 MJ
3.3.8 Energy Balance across the Compressor 101
Figure 3-12 Compressor 101
56 | P a g
 Inlet Temp (T1) = 348.15 K
 Inlet Pressure (P1) = 1 atm
 Discharge Pressure (P2) = 5 atm
 Efficiency = (Ƞ) = 75 %
 Single Stage Compressor
 Equations: T2' (K) =T1*((P2/P1)^(R/<Cp>s))
Ws(isentropic)= <Cp'>H (T2'-T1)
T2 = T1 + H/<CpH>
Table 3-51 Energy Balance across the Compressor 101
Compressor 101
T2'
Ws
Components Moles Mole% Cp<mix> through <Cp'>s <Cp'>H
(isentropic)
iteration
NO 426.065 34.484 10.338
491.288 37.592 39.176 5764.263
NO2 809.463 65.516 25.669
Total 1235.528 100.000 36.007 K KJ/kgmol KJ/kgmol KJ/kgmol
Compressor 101
T2
Ws
through Components Cp<mix> Q=W W
(actual)
iteration
7685.684 606.685 NO 10.773 9495852.942 109.906
NO2 18.502
KJ/kgmol K Total 29.275 KJ/day KW
3.3.9 Energy Balance across the Pre-Heater 101

 Efficiency = 80%
 Inlet Temp (T1) = 606.85 K
 Outlet Temp (T2) = 623.15 K
57 | P a g
Figure 3-13 Pre Heater 101
Table 3-52 Energy Balance across the Pre-Heater 101
Pre-Heater 101
Stream 19 Stream 20
Components T= 606.85 T= 623.15 K
NO 426.065 34.484 10.773 426.065 34.484 10.814
NO2 809.463 65.516 18.502 809.463 65.516 31.244
Total 1235.528 100.000 29.275 1235.528 100.000 42.059
Pre-Heater 101
ΔHin ΔHout W= Q = ΔHout – ΔHin
11159698.731 16888523.883 7161031.439 82.882
KJ KJ KJ/day KW
3.3.10 Energy Balance across the Compressor 102
Figure 3-14 Compressor 102
 Inlet Temp (T1) = 298 K

58 | P a g
 Discharge Pressure (P2) = 5 atm
 Single Stage Compressor
 Equations: T2' (K) =T1*((P2/P1)^(R/<Cp>s))
Ws(isentropic)= <Cp'>H (T2'-T1)
T2 = T1 + H/<CpH>
Table 3-53 Energy Balance across the Compressor 102
Compressor 102
T2'
Cp<mix> Ws
Components Moles Mole% through <Cp'>s <Cp'>H
at T1 (isentropic)
iteration
O2 217.568 100.000 29.463 464.986 30.109 30.756 5131.114
Total 217.568 100.000 29.463 K KJ/kgmol KJ/kgmol KJ/kgmol
Compressor 102
T2
W Cp<mix>
through Components Q=W W
(actual) at T2
iteration
6841.485 517.218 O2 31.230 1488488.136 17.228
KJ/kgmol K Total 31.230 KJ/day KW
Figure 3-15 Pre-Heater 102
 Inlet Temp (T1) = 512.218 K
59 | P a g
Pre-Heater 102
Stream 19 Stream 20
Components T= 512.218 K T= 623.15 K
O2 217.568 100 31.23 217.568 100 32.210
Total 217.568 100 31.23 217.568 100 32.210
Pre-Heater 102
1488487.548 2277556.216 986335.835 11.416
KJ KJ KJ/day KW
3.3.12 Energy Balance across the Fixed Bed Reactor

𝑃𝑡−𝐴𝐿2𝑂3
2𝑁𝑂 + 𝑂2 →−−−−−−→ 2𝑁𝑂2
Table 3-55 Energy Balance across the Fixed Bed Reactor
Fixed Bed Reactor Input Fixed Bed Reactor Output

Stream 20 Stream 23 Stream 24
Components
T = 623.15 K T = 623.15 K T = 623.15 K

Moles Mole Cp<mix Moles Mole Cp<mix Moles Mole Cp<mix
% > % > % >
NO 426.065 34.484 10.814 0.000 0.000 0.000 21.303 1.724 0.541
1214.22
NO2
809.463 65.516 31.244 0.000 0.000 0.000 5 98.276 46.868
217.56 100.00
O2
0.000 0.000 0.000 8 0 32.209 10.878 0.873 0.281
Tota 1235.52 100.00 42.059 217.56 100.00 32.209 1246.40 100.00 47.276
l 8 0 8 0 6 0
60 | P a g
Table 3-56 Heat Load of Fixed Bed Reactor

-46296648.965 19166009.389 19150573.491 -46312084.863 -536.020
KJ KJ KJ KJ/day KW
3.3.13 Energy Balance across the Cooler 101
Figure 3-16 Cooler 101
 Inlet Temp (T1) = 623.15 K
Table 3-57 Energy Balance across the Cooler 101
Cooler 101
Stream 24 Stream 25
Components
T= 623.15 K T= 298.15 K
NO 21.303 1.709 0.536 21.303 1.709 0.512
NO2 1214.225 97.418 46.459 1214.225 97.418 36.853
O2 10.878 0.873 0.281 10.878 0.873 0.257
Total 1246.406 100.000 47.276 1246.406 100.000 37.623
Cooler 101
19150573.491 0.000 -23938216.864 -277.063
KJ KJ KJ/day KW
61 | P a g
3.3.14 Energy Balance across the Pump-101
Figure 3-17 Pump 101
 Inlet Temp (T1) = 298 K

 Outlet Pressure (P2) = 5 atm
 Equations: Ws (isentropic) = (ΔH)s = mV(P2-P1)
ΔH = (mCpΔT) + (mV(1-BT)ΔP)/(10^9)
Table 3-58 Energy Balance across the Pump 101
Pump 101
Specific Volume
Components Moles Mole% Cp<mix> Volume Cp mCp Expansivity
(V) (B)
H2O 586.7976 100 75.55 1000 4.197 0.513 0.000255
Total 586.7976 100 75.55 kg/cm3 cm3/kg KJ/K K-1
Pump 101
Ws ΔH =
Ws = ΔH ΔT T2
(isentropic ΔHs/n
0.129
0.050 0.066 0.066 298.150
(Negligible)
KJ KJ KJ K K
3.3.15 Energy Balance across the Absorber

 Isothermal
62 | P a g
𝟑𝐍𝐎𝟐 + 𝐇𝟐𝐎 → 𝟐𝐇𝐍𝐎𝟑 + 𝐍𝐎
Table 3-59 Energy Balance across the Absorber
Absorber Input
Stream 25 Stream 27
Components
T= 298.15 K T= 298.15 K
NO 21.303 1.709 0.512 0.000 0.000 0.000
NO2 1214.225 97.418 36.853 0.000 0.000 0.000
O2 10.878 0.873 0.257 0.000 0.000 0.000
H2O 0.000 0.000 0.000 586.798 100.000 75.550
Total 1246.406 100.000 37.623 586.798 100.000 75.550
Absorber Output
Stream 25 Stream 27
Components
T= 298.15 K T= 298.15 K
NO 291.144 41.196 12.351 0.000 0.000 0.000
NO2 404.701 57.264 21.405 0.000 0.000 0.000
O2 10.878 1.539 0.453 0.000 0.000 0.000
H2O 0.000 0.000 0.000 316.956 37.000 27.954
HNO3 0.000 0.000 0.000 539.682 63.000 69.741
Total 706.724 100.000 34.210 856.639 100.000 97.695
Table 3-60 Heat Load of Absorber

-1.099E+08 0 0 - -1271.809
109884300.795
KJ KJ KJ KJ/day KW
63 | P a g
Figure 3-18 Pre-Heater 103
 Inlet Temp (T1) = 298.15 K
Pre-Heater 103
Stream 19 Stream 20
Components T= 298.15 K T= 623.15 K
NO 291.144 41.196 12.351 291.144 41.196 12.919
NO2 404.701 57.264 21.405 404.701 57.264 27.309
O2 10.878 1.539 0.453 10.878 1.539 0.496
Total 706.724 100.000 34.210 706.724 100.000 40.229
Pre-Heater 103
ΔHin ΔHout W= Q = ΔHout – Δhin
0 9239908.039 11549885.049 133.679
KJ KJ KJ/day KW
64 | P a g
CHAPTER 4: DETAILED EQUIPMENT DESIGN
4.1 Fixed Bed Reactor Design
4.1.1 Design Steps

 Process Design Calculations
 Reactor Selection  Mechanical Design Calculations
 Catalyst Selection and Specification  Tube Specification
 Reaction Kinetics  Shell Specification
 Weight of the Catalyst  Pressure Drop Calculations
 Volume of the Reactor  Selection of Material of

Construction
4.1.2 Reaction Conditions
𝟐𝑵𝑶 + 𝑶𝟐 Pt/Al2O3
→−−−−−→ 𝟐𝑵𝑶𝟐
Table 4-1 Fixed Bed Reactor Conditions
Operating Pressure 5 atm
Reaction Temperature 350 °C
Type of Reaction Exothermic
Conversion 95%
Catalyst Used Pt/Al2O3
4.1.3 Process Design Calculations
4.1.3.1 Reactor Selection

Reactor employed for the catalytic conversion of nitric oxide to nitrogen dioxide is a
heterogeneous reactor with gaseous feed flowing through a bed of solid catalyst in the tubes
of reactor. Heterogeneous catalyst can be employed as,
 Fixed bed
65 | P a g
 Fluidized bed
We have selected fixed bed tubular reactor because of following reasons,
 High conversion rate per unit weight of catalyst.
 No regeneration of catalyst required.
 Low operational cost
 Low pressure drop
Fixed bed Reactors can be operated:
 Adiabatically or
 Isothermally
Since reaction is exothermic it will require a cooling source to carry out reaction at reasonable
rate to achieve maximum conversion possible, hence, we will operate it isothermally.
Assumptions
There are following assumptions as,
 Steady State Flow.
 One Dimensional Flow.
 Plug Flow.
 Isothermal Operation.
 No Side reaction is occurring in the system.
4.1.3.2 Catalyst Selection and Specification
Catalyst Selection:
The catalyst: available for the catalytic oxidation of Nitric Oxide to Nitrogen Dioxide are:
1. Noble Metals (e.g. Platinum, Palladium )
2. Metal Oxides (e.g. CuO − MnO2, CuO − Cr2O3)
3. Zeolites (e.g. Fe based zeolites, Cu based zeolites)
The catalyst supports available are:
1. Aluminum Oxide or Alumina (Al2O3)
2. Silicon dioxide or Silica (SiO2)
3. Zirconium dioxide (ZrO2)
Noble metal is selected as a catalyst because these are preferred mainly because of being very
active and operating at low temperature, even at start-up conditions. Among them, Platinum
catalyst is the primary choice for NO oxidation due to its superior activity and life span.
66 | P a g
Pt-based catalysts are the most widely supported in Al2O3, SiO2, ZrO2.The catalytic activity
follows the order:
Pt/SiO2 > Pt/Al2O3 > Pt/ZrO2
Although Silicon Dioxide-supported catalysts present better performance than Aluminum
Oxide and Zirconium dioxide, this performance is strongly crystallite size dependent,
suggesting that alumina support is a better choice among all of these. Hence, Pt/Al 2O3 is the
final selected catalyst.
Catalyst Specification
Table 4-2 Catalyst Specification
Properties Symbol Value

Shape ∅ Spherical
Particle diameter 𝐷𝑃 3.2mm
Bulk Density of particle 𝜌𝐵 1082 kg/m3
Actual Apparent Density 𝜌𝐴 1759 kg/m3
𝜌𝐵
Bed Porosity ∈= 1 − 0.385
𝜌𝐴
4.1.3.3 Reaction Kinetics
4.1.3.3 Catalyst Weight
Reference component:
Boundary Conditions:
Nitric Oxide (NO) X=0 X = 0.95
67 | P a g
Design equation:
X dX
W = FAo ∫0 ( FAo = 426.065 kgmol/day )
−rA
Solved Using Polymath Software;

Weight of the catalyst = W = 8448.35 kg
4.1.3.3 Volume Calculations
Table 4-3 Fixed Bed Reactor Volume Calculations
ρB 0.385
𝐁𝐞𝐝 𝐏𝐨𝐫𝐨𝐬𝐢𝐭𝐲 ∈= 1 −
ρA
Weight of catalyst
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐜𝐚𝐭𝐚𝐥𝐲𝐬𝐭 VC = 7.808m3
Bulk density of catalyst
Volume of catalyst
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐛𝐞𝐝 VB = 12.696 m3
(1-∈)
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐫𝐞𝐚𝐜𝐭𝐨𝐫 Volume of bed

14.107 m3
(with 10% allowance) VB =
0.9
𝐓𝐨𝐭𝐚𝐥 𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐕𝐨𝐢𝐝𝐬 V∈ 5.431m3
𝐓𝐨𝐭𝐚𝐥 𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐑𝐞𝐚𝐜𝐭𝐨𝐫 VT = V + V∈ 19.538 m3
4.1.4 Mechanical Design
4.1.4.1 Tubes Specification
Table 4-4 Fixed Bed Reactor Tubes Specification
𝐓𝐮𝐛𝐞 𝐋𝐞𝐧𝐠𝐭𝐡 (Assume) Lt 10.000 m

𝐓𝐮𝐛𝐞 𝐓𝐡𝐢𝐜𝐤𝐧𝐞𝐬𝐬 (Assume) t′ 0.008 m
Outside 𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫 do 0.102 m
𝐈𝐧𝐬𝐢𝐝𝐞 𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫 di= do − 2(t′) 0.086 m
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐓𝐮𝐛𝐞𝐬 π 2 0.058 m3
Vt = ∗ di ∗ Lt
4
No 𝐨𝐟 𝐓𝐮𝐛𝐞𝐬 VT 242.753 ≈ 243
nt =
Vt
𝐁𝐮𝐧𝐝𝐥𝐞 𝐋𝐚𝐲𝐨𝐮𝐭 (Assume) Triangular -
68 | P a g
𝐏𝐢𝐭𝐜𝐡 p = 1.25 ∗ do 0.128 m
4.1.4.2 Shell Specification
Table 4-5 Fixed Bed Reactor Shell Specification
No of passes (Assume) NP 1.000

nt 1
d′ = do( )
n1
K1
𝐁𝐮𝐧𝐝𝐥𝐞 𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫 2.258 m
k1 = 0.319
n1 = 2.142
𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐭𝐮𝐛𝐞𝐬 𝐚𝐭 4nt − 1 1/2

n = ) 17.982
𝐁𝐮𝐧𝐝𝐥𝐞 𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫
PRs
𝐒𝐡𝐞𝐥𝐥 𝐭𝐡𝐢𝐜𝐤𝐧𝐞𝐬𝐬 t= +C 0.011 m
SE − 0.6P
𝐒𝐡𝐞𝐥𝐥 𝐈𝐧𝐧𝐞𝐫 𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫 Ds = p(nD + 1) 2.420 m
𝐒𝐡𝐞𝐥𝐥 𝐋𝐞𝐧𝐠𝐭𝐡
Ls = Lt + 0.10Lt 0.128 m
(10% safety factor)
𝐋𝐞𝐧𝐠𝐭𝐡/𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫 L/D 4.545 m
4.1.4.3 Material of Construction
Table 4-6 Material of Construction for Fixed Bed Reactor
Material Carbon Steel
ASTM Designation A-285 Gr. C

Joint Efficiency 1
Corrosion Allowance 0.125 in
Allowable Stress 13680 psig
4.1.5 Pressure Drop Calculations
Using Ergun’s Equation
𝐆 𝟏−∈ 𝟏𝟓𝟎(𝟏−∈)𝛍
∆𝐏/𝐋 = + 𝟏. 𝟕𝟓𝐆
𝛒𝐟𝐃𝐩 ( ∈𝟑 )( 𝐃𝐩
69 | P a g e
Table 4-7 Fixed Bed Pressure Drop Calculations
𝐏𝐚𝐫𝐭𝐢𝐜𝐥𝐞 𝐃𝐢𝐚𝐦𝐞𝐭𝐞𝐫 DP 0.0032 m
𝐅𝐥𝐮𝐢𝐝 𝐃𝐞𝐧𝐬𝐢𝐭𝐲 ρf 3.564 kg/m3
𝐏𝐨𝐫𝐨𝐬𝐢𝐭𝐲 ∈ 0.385
𝐅𝐥𝐮𝐢𝐝 𝐕𝐢𝐬𝐜𝐨𝐬𝐢𝐭𝐲 μf 0.0005 Pa. s
𝐌𝐚𝐬𝐬 𝐅𝐥𝐮𝐱 G 0.247 kg⁄m2. s

Pressure D𝐫𝐨𝐩 ∆P 0.026 MPa
4.1.6 Specification Sheet:
Table 4-8 Fixed Bed Reactor Specification Sheet
Reactor Tubular Reactor

Catalyst Pt − Al2O3
Temperature 350°𝐶
Pressure 5atm
Volume of the Reactor 19.538 m3
Volume of catalyst 7.808 m3
Weight of catalyst 8448.35 kg
Tube Length 10.000 m
Tube Thickness 0.008 m
Tube Inside Diameter 0.086 m
Tube Outside Diameter 0.102 m
Volume of Tubes 0.058 m3
No of tubes 243
Pitch 0.128 m
Bundle Layout Triangular
Bundle Diameter 2.258 m
Shell Inside Diameter 2.420 m
Shell Length 0.128 m
Shell Thickness 0.011 m
70 | P a g e
L/D 4.545 m
Pressure Drop 0.026 MPa
Material of Construction Carbon Steel
4.2 Continuous Stirred Tank Reactor Design
4.2.1 Design Steps

 Design of the reactor  Mechanical Design
 Reactor Selection  Wall Thickness of reactor
 Volume of the reactor  Stress Calculations
 Length of the reactor  Vertical Helical Coil Design
 Diameter of the reactor
 Pressure Drop Calculations
4.2.2 Reaction Conditions
𝐂𝟔𝐇𝟏𝟐𝐎𝟔 + 𝐇𝐍𝐎𝟑 →−−−−−→ (𝐂𝐎𝐎𝐇)𝟐. 𝟐𝐇𝟐𝐎 + 𝟑𝐇𝟐𝐎 + 𝟑𝐍𝐎 + 𝟑𝐍𝐎𝟐
Table 4-9 Continuous Stirred Tank Reactor Conditions
Operating Temperature 71◦C

Operating Pressure 1 atm
Type of Reaction Exothermic
Conversion 0.70
4.2.3 Process Design Calculations

4.2.3.1 Reactor Selection
Every industrial chemical process is designed to produce economically a desired product from
a variety of starting materials through a succession of treatment steps. The raw materials
undergo a number of physical treatment steps to put them in the form in which they can be
reacted chemically.
In the next step they pass through the reactor. The products of the reaction must then undergo
further physical treatment separations, purification, etc. For the final desired product to be
obtained.
71 | P a g e
Design of equipment for the physical treatment steps is studied in the unit operations.
Economically this may be an inconsequential unit, perhaps a simple mixing tank. Frequently,
however, the chemical treatment step is the heart of the chemical process, the thing that
makes or breaks the process economically.
4.2.3.2 Classification of Reactor
Classification of chemical reactors can be achieved in two different kinds.
1. Depending upon the nature of reactants and product
(a) Homogeneous Reactors.
(b) Heterogeneous Reactors.
2. Depending upon the mode of operation
(a) Batch Reactor
(b) Continuous Reactors.
4.2.3.3 Comparison of Stirred - Tank and Tubular - Flow Reactors:
The stirred - tank reactor has certain advantages because of the uniform temperature,
pressure, and composition attained as a result of mixing. As. mentioned, it is possible to
operate such a reactor under isothermal conditions even when the heat of reaction is high
impossibility is the usual in the tubular type. Where a small temperature variation is desired,
for example, to minimize side reactions or avoid unfavorable rates, the opportunity for
isothermal operation at the optimum temperature is a distinct advantage. Stirred-tank reactors
by virtue of their large volumes provide a long residence time. This, combined with the
isothermal nature of the reactor, permits operation at the optimum temperature for a long
time. For rate equation of certain type, the selectivity in multiple reactions may be greater in
tank reactors than in tubular residence time. flow reactors for the same.
However, for high-pressure reactions it is usually necessary, because of cost considerations,
to use small - diameter tubular reactors rather than tank types. Tank reactors that are to be
operated at high pressures require a large wall thickness and complex sealing arrangements
for the mixer shaft, factors which increase both initial and maintenance costs.
The rate of heat transfer per unit mass of the reaction mixture is generally lower in the tank
type than in the tubular reactor.
In Summary stirred-tank reactors can be used when the heat of reaction is high, but only if the
temperature level obtained in their isothermal operation is satisfactory from other stand
points. If reactions are endothermic and a high temperature is type, reactors are usually
indicated.
4.2.3.4 Reactor Selection Criteria
1) Conversion
72 | P a g e
2) Selectivity
3) Productivity Yield
4) Heat exchange
5) Mixing
6) Catalyst Distribution
7) Hold-up Time
8) Availability
9) Compatibility with processing
10) Energy utilization
11) Safety
12) Economics
We have selected Continuous Stirred Tank Reactor because of following reasons,
 Mixing of Reactants.
 Good Temperature Control.
 High heat and mass transfer efficiencies.
 Useful for slow reactions requiring large hold up time.
 Uniform Composition throughout the reactor.
 Distribution of Catalyst.
 For Liquid-Liquid system.
 Ease of Automatic Control.
 Less Man power requirements.
Assumptions
There are following assumptions as,
 Liquid phase reaction.
 Single reaction.
 First order reaction.
 Isothermal and non-adiabatic system.
 The feed is well stirred or properly mixed.
 Steady state operation.
 Constant density system.
73 | P a g e
 Cylindrical tank.
4.2.4 Design Equation of CSTR
V/FA0= τ/CA0=(XA/-rA)
4.2.5 Reaction Kinetics

For first order reaction rate constant is,
-rA = kA CA
kA = 1.28×105e-Ea/RT
Ea = 45.65KJ/mol
T = 71◦C
K = 1.28×105e-45659/8.314×344
k = 0.01497 hr-1
-ra = 0.015 CA0 (1-XA)
ρavg = 1187.96 kg/m3
XA = 0.70 FAo/CAo =Vo
Vo = 131 m3
V/FAo=XA/0.015 CAo (1-XA)
V/Vo = XA/0.015 (1-XA)
V=14.1m3
Using the clearance of 10% for head space Ref (Harry Silla, Pg:377)
VT (Total volume of tank) =15.51m3
Using the L/D ratio equal to 1
V= pi/4*D2 L
V= pi/4*D3
D= 2.618m
L=D
L= 2.61m
For 10% volume length Lo
Lo = 2.87m
4.2.6 Mechanical Design

4.2.6.1 Wall Thickness of Reactor
74 | P a g e
Table 4-10 Wall thickness Calculations
Wall Thickness (t) (Pi*Di)/(2f-Pi) Units

Pi (internal Pressure) (kPa) 101.325 KPa
Di (internal diameter) (m) 2.62 m
f (design stress) (KN/m2) 3693 KN/m2
wall thickness t (m) 0.036 m
with 0.002m (CA) 0.038 m
4.2.6.2 Head Thickness
Table 4-11 Head Thickness Calculations
Head thickness (PI*Di)/(2*f*J-0.2Pi) Units

Pi (internal Pressure) 101.325 KPa
Di (internal diameter) 2.61 m
f (design stress) 3693 KN/m2
Joint factor 0.9 J
Head thickness 0.0400 m
with 0.002m CA 0.0420 m
4.2.7 Stress calculations
4.2.7.1 Longitudinal stress
Table 4-12 Longitudinal Stress Calculations
Longitudinal Stress ΩL (P*Di)/4t Units

Pi (internal Pressure) 1.03 bar
Di (internal diameter) 2.618 m
wall thickness (t) 0.038 m
Longitudinal Stress 17.548 (bar) ΩL
4.2.7.2 Circumferential Stress
Table 4-13 Circumferential Stress Calculations
Circumferential Stress (P*Di)/2t Units
75 | P a g e
Pi (internal Pressure) 1.03 Bar
Di (internal diameter) 2.618 M
wall thickness 0.038 M
Circumferential Stress 35.09 Ω (bar)
4.2.7.3 Pressure and Axial Stresses
Table 4-14 Pressure and Axial Stresses
Axial Stress Ω (bar) (P*Di)/(4(ts-CA)) Units
Pi (internal Pressure) 1.03 Bar
Di (internal diameter) 2.618 M
wall thickness t 0.038 M
Corrosion Allowance CA 0.002 M
Axial Stress 18.51 Ω (bar)
4.2.8 Agitator Design

According to our process condition we use pitched blade turbine with 6 blades and 4 baffles.
For this turbine blade standard shape factors are given below.
Table 4-15 Dimensions of Impeller
Dimensions of impeller Shape factors Values Units

Diameter of impeller (Da) S1= Da/Di=0.33 Da=0.863 m
Height of impeller(E) S2= E/Di=0.33 E=0.863 m
Length of impeller (L) S3=L/Da=0.25 L=0.215 m
Width of impeller(W) S4=W/Da=0.2 W=0.17 m
Width of Baffle(J) S5=J/Di J=0.262 m
4.2.8.1 Power of Impeller
Table 4-16 Power of Impeller
Properties Values Units
76 | P a g e
Average viscosity (ս) 0.00256 Kg/m. s
Average density 1187.9 Kg/m3
Radial velocity (N) 1.69 rps
Reynolds Number
Re = (N*p*D2)/ս 584047.5
Power delivered
P = (Np*N3*N*D5)
Np (from table) 6
16468.17 Watt
Power
22.08 hp
Allowing 25% of losses
Power 29.43 hp
4.2.9 Vertical Helical Coil Design
Q (To be removed) = 1755000 KJ/ hr.

In reactor it is essential to maintain the temperature at 71 ◦C
4.2.9.1 Outside Heat Transfer Coefficient Calculation
Formula
ho dt/k= 0.17(NRe)0.67*(Npr)0.33*(Da/D)0.1*(dt/D)0.5
Table 4-17 Outside Heat Transfer Coefficient Calculations

NRE 584047.5
K 1.64 KJ/hr. m C
Cp 2.32 KJ/kg K
NPr 13.04
Dt 0.034 m
D 2.618
Da 0.863 m
ho 8691.59 KJ/m2 hr. C
4.2.9.2 Reactor Tube Side Heat Transfer Coefficient

Cooling medium: water
Inlet Temperature = 25 ◦C
77 | P a g e
Outlet Temperature = 40 ◦C
Water Temperature = 32.5 ◦C
Table 4-18 Reactor Tube Side Heat Transfer Coefficient Calculations

Cp 4.18 KJ/Kg. K
Density 994 kg/m3
Viscosity 3.23 Kg/m hr.
K 2.22 KJ/hr. m C
m (mass flow rate) 4851.85 Kg/hr.
Npr 6.08
I.D 0.034 M
O. D 0.038 M
Area 0.0009 m2
G (Mass velocity) 5117089 Kg/hr. m2
NRE 55128.31
F 0.00015
Jh 200
hio 21142 KJ/m2 hr C
4.2.9.3 Overall Heat Transfer Coefficient

Uc = 6318 KJ/m2 hr. C
Dirt Factor Recommended=0.000196
Ud = 5621.83KJ/m2 hr. C
Q = Ud *A * LMTD
Area = 6.9 m2
a = 0.19 m2/m
L = 36 m
4.2.10 Pressure Drop inside Tube
Formula
𝑓𝐺𝑡2𝐿𝑛
∆𝑃𝑡 =
(5.22 𝑋 1010)𝐷 ∅
� �
78 | P a g e
Ø=0.994
L= 36 = 118.08 ft
G=1048061.61 lb./hr.ft2
f= 0.00015
I.D=0.11413
After putting values,
Pressure Drop = 3.283 Psi
No. of Turns = 6
4.2.11 Specification Sheet
Identification:
CSTR (Continuous Stirred Tank Reactor)
Function:
Formation of oxalic acid Dihydrate from Glucose and Nitric acid
Operation:
Continuous
Type:
Agitator Cylindrical Vessel
Design Data:
Table 4-19 CSTR Specification Sheet
working volume 14.1 m3

Design Volume 15.51m3
Process Temperature 71 ◦C
Design Temperature 71 ◦C
working pressure 1 atm
Design pressure 1 atm
Length of vessel 2.618 m
Diameter of vessel 2.87 m
wall thickness 0.0384 m
longitudinal stress 17.5 bar
head thickness 0.042 m
Type of Agitator Pitched Blade turbine

No. of Blades 6
No. of Baffles 4
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4.3 Absorber Design
In Engineering, absorption is a physical or a chemical process in which atoms, molecules or
ions enter in the bulk phase liquid or a solid and get absorbed. It is a bulk phenomenon as
atom molecule or ions get absorbed in the volume. The process of absorption means that a
substance captures and transforms energy.
4.3.1 According to IUPAC:
The process of one material (absorbate) being retained by another (absorbent); this may be
physical solution of gas, liquid or solid in a liquid, attachment of molecules of a gas, vapors,
liquid, or dissolved substance to a solid surface by a physical force, etc.
4.3.2 Types of Absorption:

Following are the two types of Absorption:
4.3.2.1 Physical (non-reactive) absorption:
There is just a physical phenomenon of absorption like hydrophilic solids that readily absorbs
water. Polar interactions between water and the molecule of the solid favors partition of the
water into the solids, which can allow significant absorption of water into the solid even in
relatively low humidity
4.3.2.2 Chemical (reactive) absorption:

There is a chemical reaction between the absorbed and the absorbing substances. Sometimes
it combines with physical absorption, but this type of absorption depends upon the
stoichiometry of the reaction and the concentration its reactants. In most cases this can be
carried out in a packed or plate column.
4.3.3 Packed and Plate Column:
The type use to absorb the material highly depends upon the factor that how much absorption
need to be done and ultimately it’s depend upon the type of column you used.
In packed columns there is a need of packing (several numbers of packing are available in the
market) that increases the surface area to increase the contact of liquid and gas as much as
possible that enhances the absorption, it also provides the strength to the column when there
is low pressure inside as compared to outside. Just make sure to calculate the capacity
and
80 | P a g e
efficiency of that packing. It is expensive than plate column. For thermally sensitive material
packed column is used in plate column (several types of plates are available in market) plates
are used and there is no such big difference in it. Pressure drop is dependent on flowrate of
gas and liquid in both cases but in plate column pressure drop is large and if the flowrates are
very high then the efficiencies are about to maximum. Plate column will be preferred when
there is high residence time of liquid is in demand. As a rule of thumb, plates are always used
in columns of large diameters and towers that have more than 20 to 30 stages.
4.3.4 Conditions of Absorption Column:

Temperature of Column =
25℃ Column Pressure = 5 atm
Mass flowrate of gas = Vw = 56494 kg/day
Mass flowrate of Water = Lw = 10562 kg/day
Average molecular weight of gas = Mv = 76 kg/kmol
Molecular Weight of Water = ML = 18 kg/kmol
4.3.5 Design Calculation Steps:

 Absorber Selection
 Selection of Packing
 Hydraulic Parameters
 Flooding Calculations
 Inside Diameter
 Pressure Drop Calculations
 Liquid Holdup & Wall Factor
 Transfer Coefficients
 Height of Packed Column (HETP)
4.3.5.1 Absorber Selection:

Scale: For column diameter of less than approximately 3 ft. It is more usual to employ packed
towers because of high fabrication cost of small trays Rut if the column is very large then the liquid
distribution is problem and large volume of packing and its weight is problem.
Pressure Drop: Pressure drop in packed column is less than the plate column. In plate column
there is additional friction generated as the vapor passes through the liquid on each tray. If there
are large
81 | P a g e
number of plates in the tower, this pressure drop may be quite high and the use of packed column
could affect considerable saving.
Liquid Hold-Up: Because of the liquid on each plate there may be a large quantity of the liquid in
plate column, whereas in a packed tower the liquid flows as a thin film over the packing.
Size and Cost: For diameters of less than 3 ft. packed tower require lower fabrication and material costs
than plate tower with regard to height, a packed column is usually shorter than the equivalent plate
column. Above mentioned criteria helps us to choose Packed Absorber as our Absorber type
selection for our process.
4.3.5.2 Assumptions:
Packing Type = Top Pak
Packing Size = DP = 0.051 m
Packing Factor = FP = 46 m-
1 Surface Area = a = 92 m2
4.3.6: Flooding Calculations:
Table 4-20 Flooding Calculations
Flooding Factor L ML √ ρV
FLV = V M ρ 0.174
V L
Specific Pressure Drop at

0.7
Flooding ∆PFlood = 0.115 FP 1.651 in H2O/ft
Flooding Velocity Fc
uvf = ρ 2.48 ft/sec
Fp0.5 ( ρV) VL0.05
L
Superficial Vapor Velocity 1.742 ft/sec

uv = f uvf
Fraction of Flooding
(Assumed) f = 50-70% 0.5 to 0.7
82 | P a g e
4.3.7 Wall Factor & Liquid Holdup:
For Wall Factor,
𝑘𝑤 = 1
21 𝑑
1+ ( 𝑝
3 1−∈) 𝐷𝑇
Here we have to calculate Diameter dp first so,
1−∈
𝑑𝑝 = 6 ( )
𝑎
So, dp = 0.0015 m
And then in turn Kw will turns out to be,
Kw = 0.972
4.3.8 Calculations of Transfer Coefficients:
Table 4-21 Calculations of Transfer Coefficients
𝐂𝐨𝐧𝐯𝐞𝐜𝐭𝐢𝐯𝐞 𝐆𝐚𝐬 Phase

Coefficient KG 0.0069 Kmol/m2 sec
𝐂𝐨𝐧𝐯𝐞𝐜𝐭𝐢𝐯𝐞 𝐋𝐢𝐪𝐮𝐢𝐝 𝑎 𝑢𝐿
𝐾 = 0.757 𝐶 ( ) 0.5 0.182 m/sec
𝐏𝐡𝐚𝐬𝐞 𝐂𝐨𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐭 𝐿 𝐿
∈ ℎ𝐿
𝐃𝐢𝐟𝐟𝐮𝐬𝐢𝐨𝐧 𝐂𝐨𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐭 ∅ 0.06
𝐕𝐨𝐥𝐮𝐦𝐞𝐭𝐫𝐢𝐜 𝐆𝐚𝐬
𝐏𝐡𝐚𝐬𝐞 𝐂𝐨𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐭 𝐾𝑉𝐺 = 𝐾𝐺 𝑎ℎ
0.391 Kmol/m3 sec
𝐕𝐨𝐥𝐮𝐦𝐞𝐭𝐫𝐢𝐜 𝐋𝐢𝐪𝐮𝐢𝐝
𝐏𝐡𝐚𝐬𝐞 𝐂𝐨𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐭 𝐾𝑉𝐿 = 𝐾𝐿 𝑎ℎ𝐿 𝐶 0.571 Kmol/m3 sec
1
Overall Volumetric 𝐾𝑚 =
1 ∅
Mass Transfer Coefficient +
𝐾𝑉𝐺 𝐾𝑉𝐿 0.275 Kmol/m3 sec
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𝐎𝐯𝐞𝐫𝐚𝐥𝐥 𝐇𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐺𝑀
Mass Transfer Coefficient 𝐻𝑂𝐺 = 2.518 m
𝐾𝑀
4.3.9 Pressure Drop Calculations:
For Pressure drop calculations, there will be different equations for Dry Gas Pressure drop
and then Overall Pressure drop so first for Dry Gas Calculations;
4.3.9.1 Dry Gas Pressure Drop:
For dry gas,
∆𝑃𝑜 𝑎 𝜌𝑔 𝑉𝐺2
=ψ
𝑍 ∈3 2 𝑘𝑤
Table 4-22 Dry Gas Pressure Drop Calculations
Psi Factor Ψ 0.05
𝐌𝐚𝐬𝐬 𝐓𝐫𝐚𝐧𝐬𝐟𝐞𝐫 Surface Area A 92 m
𝐕𝐚𝐩𝐨𝐫 𝐕𝐞𝐥𝐨𝐜𝐢𝐭𝐲 VG 2.48 ft/sec
𝐃𝐞𝐧𝐬𝐢𝐭𝐲 𝐨𝐟 𝐆𝐚𝐬 ρg 15.54 g/L
𝐖𝐚𝐥𝐥 𝐅𝐚𝐜𝐭𝐨𝐫 kw 0.972
∆P
Dry Gas Pressure Drop 132.64 Pa/m
oZ
4.3.9.2 Overall Pressure Drop:

This Pressure drop for Gas is then used in Ergun’s Equation to calculate the overall pressure
drop which will be;
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∆𝑃 ∆𝑃𝑜 1.5 𝑅𝑒
) 𝑒𝑥𝑝 ( )]
∈
= [(
𝑍 𝑍 ∈ −ℎ𝐿 200
Table 4-23 Overall Pressure Drop Calculations
∆P
𝐃𝐫𝐲 𝐠𝐚𝐬 𝐩𝐫𝐞𝐬𝐬𝐮𝐫𝐞 𝐝𝐫𝐨𝐩 132.64 Pa/m
oZ
𝐋𝐢𝐪𝐮𝐢𝐝 𝐇𝐨𝐥𝐝𝐮𝐩 hL 0.0826
𝐑𝐞𝐲𝐧𝐨𝐥𝐝𝐬 𝐍𝐮𝐦𝐛𝐞𝐫 Re 7.39
Overall Pressure D𝐫𝐨𝐩 ∆P/Z 135.29 Pa/m
4.3.10 Height of Packed Tower:
To calculate the height of a Packed Tower we will be using the equation,
1
ln
𝐻𝐸𝑇𝑃 = 𝐻𝑂𝐺 𝐴
(1 − 𝐴)⁄
𝐴
Firstly, we have to calculate the Area which is,
𝐿
𝐴=
𝐾. 𝑉
HOG is already calculated before so using these values we will be calculating the Height of
Packed Column.
Table 4-24 Height of Packed Tower Calculations
𝐇𝐎𝐆 0.690 m
L/V 0.186
K (assumed) 0.10
A 1.86
85 | P a g e
And then HETP will
be,
HETP = 3.38 m
HETP = 11.08 ft
Height of the Packed Column is 11.08ft which turns out to be in range for Packed Column
Absorber.
Table 4-25 Absorber Specification Sheet
Specifications Values
Absorption Column Packed Column
Packing Material Top Pak Rings
Temperature 25 oC
Pressure 5 atm
Flooding Factor 0.174
Flooding Velocity 2.48 ft/sec
Superficial Gas Velocity 1.742 ft/sec
Specific Pressure Drop at Flooding 1.651 in H2O per ft.
Wall Factor 0.972
Liquid Holdup 0.0826
Effective Diameter 0.0015 m
Dry Gas Pressure Drop 132.64 Pa/m
Overall Pressure Drop 135.29 Pa/m
Volumetric Gas Coefficient 0.391 Kmol/m3 sec
Volumetric Liquid Coefficient 0.571 Kmol/m3 sec
Height of Transfer Unit 0.690 m
Height of Packed Column (HETP) 0.925 m or 3.03 ft
86 | P a g e
4.4 Evaporator Design
4.4.1 Evaporator:
All liquids and solids have a characteristic vapor pressure depending on the temperature. In a
closed vessel after a sufficient time has elapsed for equilibrium to be established, as many
molecules leave the liquid surface to form vapors as return to it from vapor phase to form the
liquid. In an open vessel however no equilibrium is set up and if the molecules of vapor
immediately over the liquid surface are removed, further liquid molecules vaporize to take
there place. In this way liquid bulk is continuously diminished and the process of evaporation
occurs. In chemical and process industry the term usually refers to the removal of water from
the solution.
4.4.1.2 Classification of Evaporators:
Evaporators may be classified as follows;
1. Heating medium separated from evaporating liquid by tubular heating surface.
2. Heating medium confined by coils, jackets, double walls, flat plate etc.
3. Heating medium brought into contact with evaporating liquid.
4. Heating by solar radiation.
By far the largest number of industrial evaporators employ tubular heating surfaces.
Chemical evaporators are classified in to two types;
1. Natural circulation Evaporators.
2. Forced circulation Evaporators.
4.4.1.3 Selection of Evaporator

The selection of type of evaporator best suited for a particular service is governed by the
characteristics of the feed & product. Points that must be considered are salting & scaling,
product quality, corrosion & forming.
4.4.1.4 Forced Circulation Evaporator
Forced circulation Evaporators are used for viscous, salting and scale forming solutions.
4.4.1.5 Why to select “Forced Circulation Evaporator”.
 Forced circulation evaporator may not be so economical to operate as natural-
circulation evaporators, but they are necessary where the concentration problem
involves a solution with poor flow, scale & thermal characteristics.
 With very viscous materials there is no alternative but to use this type of evaporator.
87 | P a g e
4.4.1.6 Advantages:
• High heat transfer coefficient
• Positive circulation.
• Relative freedom from salting, scaling & fouling.
• Crystalline product
• Corrosive Solution
4.4.2 Design Calculations:

The range of overall heat transfer coefficients (Ud) for forced-circulation evaporators given in
literature is from 2000 to 5000 W/m2 ℃
We assume
Ud = 3000 W/m2 ℃
Ud = 10800 kJ/m2 ℃ hr
Heat Transfer Area =
𝑄
Ud X LMTD
ΔT1− ΔT2
LMTD = ΔT1
ln( )
ΔT2
ΔT1 = 20
ΔT2 = 60.9
LMTD = 36.7309
Heat Transfer area = 5.38 m2
Heat Transfer area = 57.96 ft2

4.4.3 Tube Side Calculations:
Generally used diameters today ranges from ¾ to 2 inches.
Most generally used length of tubes ranges from 8 ft to more than 12 ft.
Pitch is taken 1.25 to 1.50 D.
Selecting 8ft long, 16 BWG tubes having Outer Diameter 0.75 in & triangular 1 in pitch
OD = 0.75 in = 0.063 ft
Tube Length = 8 ft = 2.44 m
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Therefore,
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ID = 0.62 in = 0.052 ft = 0.016 m
Outside surface area per linear ft = 0.1963 ft
Flow area per tube = at = 0.302 in2 = 0.0021 ft2
Number of tubes required (Nt):
Nt = A/(at x L)
Nt = 37
Corrected Heat Transfer area:
A = Nt x (Outside surface area per linear ft x length of one tube)
A = 58.1048 ft2 = 5.3981 m2
4.4.3.1Corrected Overall Heat Transfer Coefficient
Ud = Q/A (LMTD)
Ud = 10774.06 kJ/m2 ℃ hr
Ud = 2992.79 W/m2 ℃
Tube side flow area = Nt*at/n
Tube side flow area = 0.03885 ft2 = 0.003609 m2
Mass flow rate of Mother Liquor = 5845.893361 kg/hr
Mass velocity = Gt = 1619683.386 kg/hr.m2
Mass velocity = Gt = 331439.3075 lb/hr.ft2
Reynold’s Number (NRe) = DGt/µ
D = 0.016 m
µ = 21.78 kg/hr.m
NRe = 3569.550161
4.4.3.2 In Side Film Coefficient:
𝐿
Inside film coefficient hi= Jℎ ( 𝐶𝑝
0.333
) ∗ (μ ) )
(
𝐷 𝑘
Where,
Cpav = 2.84 kJ/kg.K
L/D = 154.84
Jh = 120
K = 2.05 kJ/hr.m. ℃
hi = 57780.14837 kJ/hr.m2.℃
4.4.3.3 Inside Film Coefficient (based on outer dia):
hio = hi * ID/OD
hio = 48529.2586 kJ/hr.m2. ℃
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4.4.3.4 Outside Film Coefficient:
For Steam ho = 8517.45 W/m2 ℃
ho = 30662.82 kJ/hr.m2. ℃
4.4.3.5 Clean Overall Heat transfer Coefficient (Uc):
Clean Overall Uc= (ℎ𝑖𝑜 ∗ ℎ𝑜)/(ℎ𝑖𝑜 + ℎ𝑜)
Clean Overall Uc = 18790.31269 kJ/hr.m2. ℃
4.4.3.61 Dirt Factor:
Rd= 1
𝑈𝑑 − 𝑈𝑐
Rd = 3.93737 X 10-5 m2 ℃ hr/kJ
4.4.4 Shell Side Calculations
Shell OD = 10.75 in
Shell ID = 10.02 in = 0.835 ft
Pt = 1 in
C = Pt – D
C = 0.25 in
B = 1/5 D
B = 2.004 in = 0.051 m
Mass flow rate of Steam = 961.74 (kg/hr)
Shell Side flow area = 0.035 ft2 = 0.00324 m2
Mass velocity of steam Gs = 296951.1323 kg/hr.m2
Mass velocity of steam Gs = 60765.7512 lb/hr.ft2
Equivalent Diameter for 1 in triangular pitch = De = 0.061 ft = 0.0185 m
µ = 4.96 x 10-2 kg/hr.m
NRe = 1.11 x 105
4.4.5 Tube Side Pressure Drop
fi = 0.046 Re-0.2 for Re > 2100
Friction factor = f = 1.12E-02
Mass velocity = Gt = 1619683.386 kg/hr.m2
Mass velocity = Gt = 331439.3075 lb/hr.ft2
Tube Length = 8 ft = 2.44 m
ID = 0.62 in = 0.052 ft = 0.016 m
Φ=1
vapor density (kg/m3) = 0.28
91 | P a g e
liquid density (kg/m3) = 1315.79
Fluid Density kg/m3) = 658.035
2 𝐵𝑖𝑓𝑖𝐺𝑖^2𝐿𝑛𝑝
ΔPt = 𝑝𝑖𝐷𝑖Φ
ΔPt = 15129.12244 Pa
ΔPt = 2.195440275 psi
According to rule of thumb the allowable pressure drop is 5 psi
4.4.6 Shell Side Pressure Drop

ΔPo = 2Bof/NtrG2/
po Xt = 1.33
0.11
Bo = 0.23 +
(𝑋𝑡−1)1.08
Bo = 0.5903
𝐷𝐺𝑠
f/ = Bo ( µ )-0.15
f/ = 1.03E-01
Ntr = 16
Water density = 1000 kg/m3s
ΔPo = 0.07 psi
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Table 4-26 Evaporator Specification Sheet
Shell Side Tube Side

Mother Liquor (Oxalic
Fluid Circulated Steam
acid)
Flow Rates 961.74 (kg/hr) 5845.893361 kg/hr
Inlet = 20℃
Temperature 121 oC
Outlet = 60.9
Pressure Drop 0.07 psi 2.2 psi
Material of Construction Carbon steel Carbon steel
OD = 0.75 in 16 BWG
OD = 10.75 in Pitch = 1 in
ID = 10.02 in Triangular arrangement
Specifications
C = 0.25 in Tube Length = 8ft
B = 2 in Number of tubes = 37
Heat Duty = 2136250 kJ/hr

Dirt Factor = 3.93737 x 10-5 m2 ℃ hr/kJ
Overall Heat Transfer Coefficient = Ud = 2992.79 W/m2
℃
93 | P a g e
CHAPTER 5: PROCESS CONTROL AND
INSTRUMENTATION
5.1 Introduction to Process Control:

The key variables in the process are monitored and controlled by the instrumentation during
the operation of the plant. The instrumentation can be used to automatically or manually
control the process and its operations. In manual control, an operator may need to periodically
read and adjust the value of the process variable. It is mainly used in non –critical
applications where any process conditions occur slowly and in small increments and where a
minimum of operator attention is required. On the other hand, critical processes and
operations are controlled automatically and hence automatic control is being widely used in
industries due to improvement in product quality, increase in production rate, better safety of
equipment as well as plant personnel.
5.2 Objectives of the Control System

1. To minimize the influence of external disturbances
2. To make sure the process is stable at all times.
3. To optimize the operation of the process.
5.3 Components of the Control System

 The Process: A process is the operation or series of operations whether physical or
chemical that produces a desired final result.
 Measuring Means: Measurement is a fundamental requisite to process control
whether that control is affected automatically, semi automatically or manually. Therefore of
all the parts of the control system, the measuring element perhaps is the most important. If
measurement is not made properly, the remainder of the system cannot operate satisfactorily
and effectively.
 Process Variables: The even operation of a process is dependent upon the control of
the process variables. The different process variables are:
1. Temperature
2. Pressure
3. Flow
4. Level
94 | P a g e
 The Controller: The hardware element that has intelligence is the controller. It is the
unit that logically decides how much to vary the value of the manipulated variable. It has a
comparator that compares the values of the measured variable to its desired value and the
difference is indicated as an error. The output of the controller is some predetermined
function of the error.
 Modes of Controller
There are various modes in which the process can be controlled. The different modes depend
upon the types of controllers and the action it takes to control any process variable.
1. On-Off Control
2. Proportional Control
3. Integral Control
4. Derivative Control
5. Composite Control
It is very rare to find only one of the above control actions in different operations but a
composite control action is more often in practice. Following are the typical composite
control modes:
1. Proportional – Integral Control
2. Proportional – Derivative Control
3. Proportional – Integral – Derivative Control
 Control Loops
For instrumentation and control of different sections and equipments, following control loops
are mainly used:
1. Feedback Control Loop:
A loop in which a measured value of a process variable is compared with the desired value of
the process variable and any necessary action is taken is the feedback control loop. Any
changes from the set point will be sent to the final control element through the controller in
order to adjust the incoming value according to the desired value. In such loop, change has
already occurred and only corrective action can be taken.
2. Feed Forward Control Loop
In feed forward control loop, the value of disturbance is measured and the action is taken to
prevent the disturbance by changing the values of the process variable. This is a control
method designed to prevent errors from occurring in a process variable.
3. Ratio Control Loop
95 | P a g e
A control loop in which the controlling element maintains a predetermined ratio of one
variable to another is ratio control loop. Such loops are used in systems where two different
streams which enter a vessel for reaction are to be maintained in stoichiometric ratios.
4. Cascade Control Loop
A cascade loop is in which there is one manipulated variable and more than one
measurement. This is a control in which two or more control loops are arranged so that the
output of one controlling element adjusts the set point of another controlling element. In this
loop, one is the primary or master controller and the other is the secondary controller.
5. Split Range Loop:
A split range loop is in which there is only one measurement and more than one manipulated
variable. In this loop, controller is per set with different values corresponding to different
action to be taken at different conditions.
 Final Control Element
The decision taken by the controller is transferred to the final control element which
implements the decision by increasing or decreasing the values of the process variable.
 Transducer
Numerous measurements cannot be utilized for control until these are changed to physical
quantities. A transducer is an instrument which is used to convert a mechanical signal to an
electric signal. These signals are then transferred to the controller.
 Transmission Lines
These lines are used to carry measurements signals from measuring device to the controller
and from the controller to the final control element. These can be either pneumatic or
electrical.
5.4 Selection of the Control System

The selection of the most appropriate type of controller for any particular environment is a
very systematic procedure. There are many ways and means that how a particular type of
system may be controlled through which type of controller. Usually type of controller is
selected using only quantitative considerations stemming from the analysis of the system and
ending at the properties of that particular controller and the control objective. Following is the
summarized criterion for the selection of appropriate controller or any process:
1. If possible, use a simple proportional controller
Simple P-Controller can be used if we can achieve acceptable off-set with not too high values
of gain. So for gas pressure and liquid level control, usually a simple P-Controller may be
used.
2. If a simple P-Controller is not acceptable, use a PI-Controller
96 | P a g e
A steady state error always remains for proportional controller so in systems where this off-
set is to be minimized, a PI-Controller is incorporated. So in flow control applications,
usually a PI- Controller is found.
3. Use a PID-Controller to increase the speed of closed loop response and retain
robustness
The anticipatory characteristic of the derivative control enables to use somewhat higher
values of proportional gains to that off-set is minimized with lesser deviations and good
response of the system. Also, it adds stability to the system. So this type of control is used for
sluggish multi-capacity processes to control temperature and composition.
5.5 Control Schemes of Reactor

5.4.1 Objectives:
 To maintain the temperature of the reactor
In the oxalic acid unit, the reaction taking place in the Reactor-102 is exothermic and
temperature needs to be maintained at 71℃ in order to avoid dangerous side reactions, to
increase the rate of the reaction and yield of the oxalic acid. For that purpose, cold water is
allowed to circulate through the cooling jacket. A thermocouple is installed to measure the
temperature in the reactor.
5.4.2 Manipulated Variables

 Flowrate of the water in the cooling jacket
The controller is given the set point of 71℃. The controller compares the measured value
coming from the thermocouple with the set point and estimates the error if any. This error is
passed to the pneumatic control valve installed on the inlet of the cooling water which
controls the flow rate of the water in order to maintain the temperature in the reactor.
5.4.3 Load or Disturbances

 Flowrate of feed
 Temperature of feed
 Flowrate of cooling water
 Composition of the feed
 Temperature and Pressure of the reactor
97 | P a g e
Figure 5-1 Control Schemes across the Reactor
98 | P a g e
CHAPTER 6: HAZOP ANALYSIS
The HAZOP is an organized and perilous test by a team of engineering and operational
intentions to evaluate the probability of mismanagement or poor performance of individual
components of equipment and the impact of a facility.
6.1 What is HAZOP?

The HAZOP procedure mainly involves taking a broad description of the process and
systematically questioning each part of the process to govern how deviations from design
intent and consequences can have a negative effect on the safe end and proficient operation of
the plant. If considering the necessary action is then taken to medication the situation. The
hazardous analysis is applied in an organized manner by the HAZOP team and is based on
their imagination to discover the true causes of the deviations. In practice, many causes will
be impartially obvious, such as a pump failure that causes loss of circulation in the above-
mentioned cooling water facility. However, then the type of automatic reference check. The
result is that their good chance is to identify possible failures and problems that have not been
previously experienced in the type of plant being considered.
6.2 Objective
The objectives of a HAZOP study can be categorized as follows:
 To classify (areas of the design that may possess a significant hazard potential
 To classify and study features of the design that influence the probability of a
hazardous incident occurring. To explain the study team with the design
information available.
 To make sure that a systematic study is made of the areas of significant hazard
potential.
 To categorize pertinent design information not currently available to the team.
6.3 HAZOP Terminology

Words frequently arising in HAZOP Studies are defined in this section.
Table 6-1 Frequently used words in HAZOP
Term Definition
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Sections of equipment with certain
boundaries within which process parameters
are examined for deviations. The locations
Process Sections on P&IDs at which the process parameters
are examined for deviations.
Dissimilar actions in a batch process or a

procedure analyzed by a HAZOP analysis
team. May be manual, automatic, or
software implemented actions. The
deviations applied to each step are
Operating steps
somewhat different than the ones used for a
continuous process.
Definition of how the plant is estimated to

operate in the absence of deviation. Take
many forms and can be either expressive
Intention or illustrative (e.g., process description,
flowsheets, line diagrams, P&IDs).
Simple words that are used to qualify the

design intention and to guide and stimulate
the brainstorming process for identifying
Guide Words
process hazards.
Physical or chemical property associated

with the process. Includes general items
such as reaction, mixing, concentration, pH,
Process Parameter and specific items such as temperature,
pressure, phase, and flow.
100 | P a g
Departures from the design intention that
are discovered by systematically applying
the guide words to process parameters
(flow, pressure, etc.) resulting in a list for
Deviations
the team to review (no flow, high
pressure, etc.) for each process section.
Teams often increase their list of
deviations.
Reasons why deviations might occur. Once
a deviation has been shown to have a
credible cause, it can be treated as a
significant deviation. These causes can be
hardware failures, human errors,
Causes
unanticipated process states (e.g., change of
composition), external disruptions (e.g.,
loss of power), etc.
Results of deviations (e.g., release of toxic

materials). Normally, the team assumes
active protection systems fail to work.
Consequences
Minor consequences, unrelated to the study
objective, are not considered.
Engineered systems or executive controls
designed to prevent the causes or temperate
the consequences of deviations (e.g.,
process alarms, interlocks, procedures)
Actions (or Recommendations)
Safeguards
Suggestions for design changes.
Suggestions for design changes, technical

Actions or Recommendations changes, or areas for further study (e.g.,
adding a terminated pressure alarm or
101 | P a g
reversing the sequence of two operating
steps).
6.4 OSHA Hazard Communication Standard

The OSHA is the U.S. Federal regulation requiring chemicals manufacturers, importers and
distributers to evaluate the hazards of their chemical products and convey hazards information
through labels and material safety data sheets to its employees and customers. OSHA
provides the information to its employee about the hazardous chemicals to which they could
be exposed by mean of
1. Material and data sheets.
2. Labels and other forms of warning.
3. A written hazard communication program.
4. Training and information program.
6.4.1 Material Safety Data Sheets

The MSDS requirements fall firstly on chemical manufacturer, importers or distributers. It’s a
requirement by OSHA standard to provide a MSDS for each hazardous chemical they
produce or handle. The MSDS should include the below listed points
➢ Customary and chemical name.
➢ Chemical detail.
➢ Actual and chemical properties.
➢ Physical hazards – Possible reactivity, fire and explosion.
➢ Health related Hazards.
➢ Sign of exposure.
➢ Basic route of doubtless entrance into the body on exposure.
➢ OSHA permissible exposure limit.
➢ Safety precautions.
102 | P a g
➢ Waste ejection.
➢ Protection measurement and instrumentality as well as maintenance.
➢ First- aid procedures of emergency.
➢ Revision and preparation of MSDS.
➢ Emergency contact of manufacturer or distributor.
6.4.2 Labels and other Forms of Warning

There should be a clear large readable tag on all hazardous containers of chemical which has
➢ Address and name of the manufacturer
➢ Chemical Name
➢ List of hazardous warnings supplied by the manufacturer
➢ Labels could also be color coded as
 Orange: Carcinogen Hazards (Benzene)
 Red: Chemical Burn Hazards (Acid, Bases)
 Yellow: Hazard toxic vapor (H2S)

 White: All other
6.5 HAZOP Study Steps

A HAZOP study is conducted in the following steps:
 Identify the purpose and scope of the study. The purpose may be to examine a plant
that has not yet been built or to review the risk of a current unit. Given the present
circumstances of the study, the above objectives can make them more specific. The
scope of the study is the limits of physical unity, as well as the range of events and
variables measured. For example, at one time, HAZOP focused primarily on
endpoints of fires and explosions, while the range now typically includes toxic
releases, invasive smells, and environmental ends. The initial establishment of
purpose, objectives and scope is very important and must be carefully defined so that
it is clear, now and in the
103 | P a g
future, what has been involved in the study and has not been included. These
decisions must be made through a suitable level of responsible management.
 Select the HAZOP study group. The team leader must be skilled at HAZOP and in
personal techniques to facilitate successful team interface. Many other team experts
should be included to cover all aspects of design, operation, process chemistry and
safety. The team leader must guide the team in the HAZOP procedure and confirm
that the ultimate goal of the HAZOP scan is to identify the risks; solutions to the
problems are a discrete effort.
 Collect data. 16 components have listed the following materials that are usually
needed: Process Flow Sheet
Process Flow Diagram
Piping and Instrumentation Diagrams
Data on Chemical, Physical and toxicological properties of all raw materials,

intermediates and Products.
Equipment Piping and Instrument Specification.
Process Control Logic Diagrams.
Layout Drawings.
Operating Procedures.
Maintenance Procedures.
Emergency Response Procedures.
Safety and Training Manuals.
 Conduct the study. Using the information composed, the unit is divided into a
"contract" study and follows the sequence shown in the figure for each node. The
nodes are points in the process where the process parameters (pressure, temperature,
composition, etc.) have known and proposed values. These values vary between nodes
as a result of the operation of different parts of equipment such as distillation columns,
heat exchangers or pumps. Various models and working papers have been developed
to help establish node process parameters and control logic information.
104 | P a g
 When the nodes are documented and the parameters are identified, each node is
studied by applying the specialized guide words to each parameter. These guide words
and their meanings are key elements of the HAZOP procedure.
 The repeated rotation during this process, which takes into account how and why each
parameter differs from the intended and the result, is the principle of the HAZOP
study.
 Type the report. Many details about the events and their results should be recorded as
exposed by the study. Clearly, if HAZOP identifies an improbable sequence of events
that could lead to disaster, appropriate follow-up action must be taken. Thus, although
risk reduction measures are not part of HAZOP, HAZOP may lead to the need for
such a procedure. HAZOP studies are time-consuming and expensive. Just updating
the P & ID in an old factory may be a great engineering effort. However, for high-risk
operations, they are cost-effective when compared to potential loss of life property,
business, and even the future of the enterprise that may result from a maximum
release.
6.6 Characteristics of HAZOP Study

➢ A systematic, more organized judgment depends upon HAZOP guide words and team
hardworking to create a complex study and assure that suitable protection against accidents.
➢ Suitable to any system or process.
➢ Mostly used as a system-level risk judgment technique.
➢ Generates primarily qualitative results
6.7 Limitation of HAZOP Study

➢ Well-defined system or activity is needed
➢ Time taking
➢ Stick on one-event is a causes of deviations
6.8 Procedure for HAZOP analysis

➢ Define items
105 | P a g
➢ Study of system and activity
➢ Main process of analysis
➢ Take reviews about HAZOP
➢ These results are used for decision making
6.9 HAZOP of CSTR

This process is exothermic, which necessitates the use of a cooling mechanism to remove the
surplus energy. When the cooling flow is halted, the reactor temperature rises, causing the
reaction rate and heat production rate to increase. As a result, a runaway reaction might occur,
leading to a rise in vessel pressure and, perhaps, a rupture of the vessel.
Figure 6-1 HAZOP Scheme
A control valve measures the temperature within the reactor and uses it to adjust the
cooling water flow rate.
A full form like the one shown in the Figure would result from doing a HAZOP on
this process with the given job of considering runaway reaction occurrences. Cooling
water line, stirring motor, monomer supply line, and reactor vessel are the four study
nodes.
6.9.1 Failure and Possible Solutions
The results of the HAZOP study would show the following possible process changes:
1. Installation of a cooling water flow metre and low flow alert to detect cooling
loss immediately.
106 | P a g
2. In the case that the cooling function is lost, a high temperature alarm will be
installed to warn the operator.
3. Installation of a high temperature shutdown mechanism that would shut down

the process automatically if the reactor temperature became too high. To allow
the operator to restore cooling before the reactor is shut down, the shutdown
temperature would be greater than the alert temperature.
4. In order to avoid reverse flow, a check valve is installed in the cooling line. A
check valve might be put both before and after the reactor to prevent the
contents of the reactor from flowing upstream and to prevent backflow in the
case of a coil leak.
5. Inspections and maintenance of the cooling coil on a regular basis to ensure its
integrity.
6. Analyze the cooling water source for any potential interruptions or

contamination of the supply.
The high temperature alert and emergency shutdown mechanism prevents a runaway
if the cooling water system fails (independent of the cause of the failure). The HAZOP
review committee determined that the installation of a backup controller and control
valve was not required. In this case, the high temperature alert and shutdown system
prevents a runaway.
Similarly, either the alarm or emergency shutdown system would identify a lack of
cooling water source or a clogged cooling line. All cooling water problems should be
appropriately reported, according to the review committee. If a certain reason happens
on a regular basis, more process changes are required.
107 | P a g
CHAPTER: 7 COST ESTIMATION
7.1 Evaporator capital cost:
Figure 7-1 Evaporator Cost Estimation Graph
Total Area = 58.1 ft2
Using graph cost is:

Heat exchanger cost = $ 4,000
Cost = Bare Equipment Cost*Factor *Module Factor
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Using the above equation for fixed tube sheet, shell and tube with carbon steel construction
material:
C = 4000 * 1.61 * 3.2 = $20608.47
The cost is for in 1987 and to extrapolate it to 2021 using 3% inflation rate.
Cost = $20608.47 ×
(1.03)34
Cost = $ 56300.38
7.2 Absorber capital cost:
Figure 7-2 Absorber Cost Estimation Graph 1
109 | P a g
Total capital cost = bare equipment cost*installation Cost*module factor
Absorber diameter = 2.827 ft
Cost $/ft of column height = 0.58 * 1000 = $580
Column height = 11.08 ft
Capital Cost = 11.08 * 580 = $6426.4
By using total capital cost equation:
Installation cost factor =1.72
Module factor = 4.16
Total capital cost in 1987 = 1.72 * 4.16 * 6426.4 = $45982.17
This cost is calculated using 1987 data so for 2021 the absorber cost with 3 % inflation rate
C1=Total capital cost in 2021 = $45982.17* (1.03)34 = $125618.93
Figure 7-3 Absorber Cost Estimation Graph 2
110 | P a g
Packing size = 2 in.
Material of packing = Pall /Top Pak
Cost $/ft3 = 13.5
Total capital Cost for packing in 1987 = 13.5 × 11.03 = $148.951
C2=Total capital Cost for packing in 2021 = $148.951*(1.03)^34 = $406.79
Total Absorber capital cost = C1 + C= $ 126025.72
7.3 Fixed Bed Reactor capital cost:
Figure 7-4 Fixed Bed Reactor Cost Estimation Graph
Volume = 5610 gallons

So, cost in the above graph is = $38000
And the total cost of equipment will be,
111 | P a g
C= (Bare Equipment Cost) × (Factor) × (Module Factor) =
38000 * 1.2 * 1.8
=$83000.80
This is the cost in year 1987 and for the year 2020 the cost of equipment at the inflation rate
of 3%
C = $ 83000.80 × (1.03)34
C = $ 226750.32
7.4 CSTR Capital Cost:
Figure 7-5 CSTR Cost Estimation Graph
Volume = 4120 gal
112 | P a g
Cost = $ 21000
And the total Capital cost will be = Bare Cost * Material Factor * Module factor
C = 21000 * 1.7 * 2.5
C = $ 89250
This cost was in 1987 so for the year 2021 with 3% inflation rate,
the cost in 2021 will be ,
C = 89250 * (1.03)34
C = $ 243822.54
Total Cost = $ 243822.54 + $ 226750.32 + $ 126025.72 + $ 56300.38 = $ 652,898.96
113 | P a g
REFERENCES
[1] Kirk-Othmer, “Encyclopedia of Chemical Technology”, Volume:16, 2nd Edition
[2] George Stevens Simpson “Method of Producing Oxalic Acid” U.S. Patent
No.2057119, August 9, 1993.
[3] Maxwell J, Brooks, “Manufacture of Oxalic Acid” U.S. Patent No. 2322915, June 29,
1943
[4] McCabe, W.L., Smith J.C., Harriot P., 1993, Unit Operations of Chemical
Engineering, 5th Edition, McGraw Hill, USA.
[5] Max S. Peters, Klaus D. Timmerhaus, Ronald E. West, ‘Plant Design and Economics
For Chemical Engineers,’ Fifth Edition, University of Colorado.
[6] J. M. Smith, Hendrick C Van Ness, Michael Abbott, Hendrick Van Ness,
‘Introduction To Chemical Engineering Thermodynamics,’ Sixth Edition.
[7] Carl L. Yaws, ‘Chemical Properties Handbook’ McGraw-Hill.
[8] Kern, D.Q, 1950, “Process Heat Transfer, McGraw-Hill, USA.
[9] Howard F.Rase, “Fixed Bed Reactor Design and Diagnostics, Gas Phase Reactions ”,
1990
[10] Carlos A. Grande “Process Intensification in Nitric Acid Plants by Catalytic Oxidation
Of Nitric Oxide”, DOI: 10.1021/acs.iecr.8b01483, 2018
[11] J. D. Seader, Ernest J. Henley, D. Keith Roper “Separation Process and Principles”, 4th
Edition
[12] Zhe Hong, Zhong Wang and Xuebing Lia, “Catalytic oxidation of nitric oxide (NO)
over different catalysts: An overview” , DOI: 10.1039/C7CY00760D
114 | P a g

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Production of Oxalic Acid from Starch

Miss. Zoya Naeem 2017-CH-13

Supervised by: Dr. Humayun Wali

Department of Chemical Engineering

Bachelor of Science in Chemical Engineering

Internal Examiner External Examiner

Department of Chemical Engineering

Name Registration No. Signature

Zoya Naeem 2017-CH-13

Siyar Abdullah 2017-CH-41

Registration No. % Contribution Signature

Zoya Naeem 25%

Siyar Abdullah 25%

Abu Sufyan 25%

Haris Akhtar 25%

We warmly dedicate our project to our beloved parents, teachers and

1.1 Background Information...................................................................................................1

3.1 Material Balance.............................................................................................................16

4.1 Fixed Bed Reactor Design..............................................................................................65

5.1 Introduction to Process Control:.....................................................................................93

6.1 What is HAZOP?............................................................................................................98

7.1 Evaporator capital cost:.................................................................................................107

1.1 Background Information

1.2 Literature Survey

1.3 Chemistry and Uses of Desired Product

1.3.1 Properties of Product

Melting point (°C)

Refractive index (β) 1.540

Heat of combustion at 25°C (kJ/mol) -245.61

Standard heat of formation at 25°C, (kJ/mol) -826.78

Standard free energy of formation at 25°C (kJ/mol) -697.91

Heat of solution in water (kJ/mol) -9.58

Oxalic acid Dihydrate (C2H2O4.2H2O)

Melting Point (°C) 101.5

Density (g/ml) 1.653

Refractive index 1.475

Standard heat of formation at 18°C (kJ/mol) -1422

Heat of solution in water (kJ/mol) -35.5

1.3.2 Uses of Product

1.4 Commerce Analysis

Table 1-2 Oxalic Acid Import Data

Imported Imported Imported Imported Imported

1.5 Capacity Selection

2.1.1 Synthesis of Product

2.1.1.1 Ethylene Glycol Process

(𝐶𝐻2𝑂𝐻)2 + 4𝑁𝑂2 → (𝐶𝑂𝑂𝐻)2 + 4𝑁𝑂 + 2𝐻2𝑂

4𝑁𝑂 + 2𝑂2 → 4𝑁𝑂2

2.1.1.2 Propylene Process

𝐶𝐻3𝐶𝐻 = 𝐶𝐻2 + 3𝐻𝑁𝑂3 → 𝐶𝐻3𝐶𝐻𝑂𝑂𝐻 + 2𝑁𝑂 + 2𝐻2𝑂

2.1.1.3 Sodium Formate Process

3. Recovery of Sodium hydroxide by treatment of sodium oxalate with lime

4. (𝐶𝑂𝑂)2𝐶𝑎 + 𝐻2𝑆𝑂4 ↔ (𝐶𝑂𝑂𝐻)2 + 𝐶𝑎𝑆𝑂4

(𝐶𝑂𝑂𝑅)2 + 2𝐻2𝑂 → (𝐶𝑂𝑂𝐻)2 + 2𝑅𝑂𝐻

2.1.1.5 Oxidation of Carbohydrates Process

Table 2-1 Process Comparison

Sodium Oxidation of Ethylene Propylene Dialkyl

a. Availability NaOH is In countries Ethylene Propylene For CO

H2 gas is Both NO and NO is used NO is used CO2 which

4. Yield 80-90% 50-70% 90% 77.5% 80%

2.1.3 Process Selection

2.2 Process Description

 Oxalic Acid Unit

Crude Crystallizer and Crude Centrifuge: