PRODUCTION OF PHTHALIC ANHYDRIDE FROM ORTHO XYLENE

AND

REMOVAL OF NaCl FROM TEXTILE WASTE WATER BY

CAPACITIVE DEIONIZATION USING NITRIC ACID MODIFIED
CARBON ELECTRODES

A PROJECT REPORT

Submitted by

JEEVAN M (12CHR019)
GOKUL S (12CHR013)
KARTHIK G (12CHR023)
in partial fulfilment of the requirements
for the award of the degree
of

BACHELOR OF TECHNOLOGY

IN

CHEMICAL ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING
SCHOOL OF CHEMICAL AND FOOD SCIENCES

KONGU ENGINEERING COLLEGE

(Autonomous)

PERUNDURAI ERODE-638 052

MAY 2016
 ii

DEPARTMENT OF CHEMICAL ENGINEERING

KONGU ENGINEERING COLLEGE
(Autonomous)
PERUNDURAI ERODE-638 052
MAY 2016

BONAFIDE CERTIFICATE

This is to certify that the Project report entitled PRODUCTION OF PHTHALIC

ANHYDRIDE FROM ORTHO XYLENE AND REMOVAL OF NaCl FROM TEXTILE
WASTE WATER BY CAPACITIVE DEIONIZATION USING NITRIC ACID MODIFIED
CARBON ELECTRODES is the Bonafide record of project work done by JEEVAN M
(12CHR019), GOKUL S (12CHR013), KARTHIK G (12CHR023) in partial fulfilment of
the requirement for the award of the Degree of Bachelor of Technology in CHEMICAL
ENGINEERING of Anna University Chennai during the year 2015-2016.

SUPERVISOR HEAD OF THE DEPARTMENT

(Signature with Seal)

Date:
Submitted for the end semester viva voice examination held on__________________

INTERNAL EXAMINER EXTERNAL EXAMINER

 iii

DEPARTMENT OF CHEMICAL ENGINEERING

KONGU ENGINEERING COLLEGE

(Autonomous)

PERUNDIRAI ERODE-638 052

MAY 2016

DECLARATION

We affirm that the project report titled PRODUCTION OF PHTHALIC ANHYDRIDE

FROM ORTHO XYLENE AND REMOVAL OF NaCl FROM TEXTILE WASTE
WATER BY CAPACITIVE DEIONIZATION USING NITRIC ACID MODIFIED
CARBON ELECTRODES being submitted in partial fulfilment of the requirements for
the award of Bachelor of Technology is the original work carried out by us. It has not
formed part of any other project report or dissertation on the basis of which a degree
or award was conferred on an earlier occasion on this or any other candidate.

Date: JEEVAN M (12CHR019)

GOKUL S (12CHR013)

KARTHIK G (12CHR023)

I certify that the declaration made by the above candidates is true to the best of my
knowledge.

Date: Name and Signature of the supervisor with seal

 iv

ABSTRACT

PRODUCTION OF PHTHALIC ANHYDRIDE FROM ORTHO XYLENE

Phthalic anhydride, a versatile organic intermediate, is used in the production

of plastics from vinyl chloride, phthalate esters, alkyd resins and insect repellents. It
is bifunctional and cheaply available. The conventional method for the production of
phthalic anhydride involves the usage of O-xylene as raw material. In our project we
focused on the development of modified flow sheet which replaces the switch
condenser with a conventional condenser and single stage distillation instead of two
stage distillation and also we focused on design of distillation column and packed bed
reactor for specific operating conditions.

REMOVAL OF NaCl FROM TEXTILE WASTE WATER BY CAPACITIVE

DEIONIZATION USING NITRIC ACID MODIFIED CARBON ELECTRODES

Capacitive Deionization (CDI) has significant potential for energy-efficient water

desalination over other technologies. In CDI, porous carbon electrodes are used for
removal of salt ions from effluents and brackish water. In our project, graphite is used
as porous carbon electrode material, on which modified activated carbon is coated.
The modified activated carbon coated graphite electrode has many advantages than
other porous carbon electrodes due to its high desalination efficiency, high wettability
and also increase the lifetime of the electrode. The main objective of this project is to
evaluate the desalination performance based on different operational parameters like
Concentration of Feed, Cell Voltage and time. The salt removal efficiency is directly
proportional to the applied voltage, deionization time interval and inversely
proportional to the initial concentration. At higher voltage (8V), the salt removal
efficiency is high. The energy consumption is less when compared to other
conventional technologies. In this project, the evaluation of the desalination
performance based on different operational parameters of the CDI system was
performed and it is verified that this desalination technique using modified carbon
electrodes contributes to the possibility of using it for Textile effluent desalination
 v

ACKNOWLEDGEMENT

First of all we thank almighty, who is behind all our endeavours and
blessed us in completing the project successfully. We thank our beloved
correspondent Thiru.V.K.Muthusamy B.A., B.L., and all the members of Kongu Vellalar
Institute of Technology Trust at this high time of providing us with plethora of facilities
to complete our project successfully. It is our privilege to express our profound thanks
to our beloved principal Prof. S.Kuppuswami B.E.,MSc.,Dr.Ing(France) who has
been a bastion of moral strength and a source of incessant encouragement to us.

We express our sincere thanks to beloved Head of the Chemical Engineering

Department Dr.K.Saravanan, M.Tech.,Ph.D.,(Tech) for his valuable guidance and
suggestion.

We would like to express our heartfelt thanks to our project guide

Mr.G.Mugaishudeen, M.Tech., Asst.Professor for his valuable and constant
support provided all through the course of the project.

We take immense pleasure to express our heartfelt thanks to

Mr.C.Gomadurai, M.Tech., Asst.Professor, our project coordinator and other
officials and staffs of their suggestion, excellent guidance and constant support
provided all through the course of the project.

We also thank the non-teaching staff members of Chemical Engineering

Department and all our fellow students who stood with us to complete our project
successfully. We also extend our warm thanks to our beloved parents.
 vi

TABLE OF CONTENTS

CHAPTER NO TITLE PAGE NO

ABSTRACT iv

LIST OF TABLES x

LIST OF FIGURES xi

LIST OF GRAPHS xii

PRODUCTION OF PHTHALIC ANHYDRIDE FROM ORTHO XYLENE

1 INTRODUCTION 01
1.1 SYNTHESIS AND PRODUCTION 01
1.2 PHTHALIC ANHYDRIDE – APPLICATIONS 02
1.3 PHTHALIC ANHYDRIDE – PROPERTIES 02

2 MSDS (MATERIAL SAFETY DATA SHEET) 04

2.1. OCCUPATIONAL HEALTH HAZARDS 04
2.2. EMERGENCY AND FIRST AID MEASURE 04
2.3. STORAGE 05
2.4. PRECAUTIONS IN HANDLING AND USE 05
2.5 FIRE HAZARD 06
2.6 LABELING PROCEDURE 06
2.7 SPILL OR LEAK PROCEDURE 06

3 PROCESS DECRIPTION 08

4 MATERIAL BALANCE FOR PHTHALIC ANHYDRIDE

MANUFACTURING UNIT 10
4.1 BASIS 10
4.2 REACTIONS 10
4.3 MATERIAL BALANCE FOR REACTOR 10
4.3.1 BALANCE BY REACTION 1 10
4.3.2 BALANCE BY REACTION 2 10
 vii

4.4 MATERIAL BALANCE FOR CONDENSER 11

4.4.1 FRACTIONS LEAVING IN THE OFF-GAS 11

4.5 MATERIAL BALANCE FOR THE

DISTILLATION COLUMN 12
5 ENERGY BALANCE FOR THE PHTHALIC

ANHYDRIDE UNIT 14

5.1 AIR PRE-HEATER 14

5.2 O-XYLENE PRE-HEATER 14
5.3 ENERGY BALANCE FOR REACTOR 15
5.4 ENERGY BALANCE FOR CONDENSER 16
5.5 ENERGY BALANCE FOR DISTILLATION 16

6 DESIGN OF PACKED BED CATALYTIC REACTOR 18

6.1 CALCULATION FOR REACTOR BED DIMENSIONS 18

6.2 CALCULATION FOR HEAD DESIGN 22
6.3 DESIGN OF GASKET 23
6.4 GASKET WIDTH 23
6.5 CALCULATION FOR NUMBER OF BOLTS 24
6.6 CALCULATION FOR THICKNESS OF FLANGE 25
6.7 SUPPORT DESIGN 26
6.8 RESULTS 26

7 DESIGN OF DISTILLATION COLUMN 27

7.1 DESIGN SPECIFICATIONS 27
7.2 MOLE FRACTIONS 27
7.3 VAPOUR PRESSURE OF MAELIC ANHYDRIDE 27
7.4 VAPOUR PRESSURE OF PHTHALIC ANHYDRIDE 27
7.5 HEIGHT OF THE COLUMN 28
7.6 OPERATING VELOCITY 28
7.7 THE ALLOWABLE VAPOUR VELOCITY 29
7.8 DIAMETER CALCULATION 29
 viii

7.9 MINIMUM VAPOUR VELOCITY CALCULATION 30

7.10 PRESSURE DROP CALCULATION 32

8 CONCLUSION 33

REFERENCES 34
 ix

TABLE OF CONTENTS
REMOVAL OF NaCl FROM TEXTILE WASTE WATER BY CAPACITIVE
DEIONIZATION USING NITRIC ACID MODIFIED CARBON ELECTRODES

CHAPTER NO TITLE PAGE NO

1 INTRODUCTION 36

2 LITERATURE REVIEW 37

3 CAPACITIVE DEIONIZATION MACHANISM 40

4 EXPERIMENTAL METHODS 40

4.1 FABRICATION OF MODIFIED CARBON

ELECTRODES 41

4.2 EXPERIMENTAL SET-UP 41

4.3 EXPERIMENTAL PROCEDURE 42

5 RESULTS AND DISCUSSIONS 43

5.1 TABULATIONS 43

5.1.1 DEIONIZATION USING MODIFIED

CARBON ELECTRODES (MCE) 43

5.1.2 DEIONIZATION USING NORMAL

CARBON ELECTRODES (NCE) 44

5.2 GRAPHICAL REPRESENTATIONS 46

6 ENERGY CONSUMPTION OF CAPACITIVE

DEIONIZATION 51

7 CONCLUSION 54

REFERENCES 55
 x

LIST OF TABLES

PRODUCTION OF PHTHALIC ANHYDRIDE FROM ORTHO XYLENE

TABLE NO TITLE PAGE NO

1.1 PHYSICAL AND CHEMICAL PROPERTIES OF PA 02

1.2 PHYSICAL PROPERTIES OF LIQUID PA 02
1.3 SOLUBILITIES OF PA 02
1.4 SPECIFICATIONS FOR PA 03
2.1 FLAMMABILITY AND EXPLOSIVITY OF PA 07
4.1 MATERIAL BALANCE FOR REACTOR 11
4.2 MATERIAL BALANCE FOR CONDENSER 12
4.3 MATERIAL BALANCE FOR DISTILLATION 13
5.1 ENERGY BALANCE FOR PRE HEATER 14
5.2 ENERGY BALANCE FOR REACTOR FEED 15
5.3 ENERGY BALANCE FOR REACTOR OUTPUT 15
5.4 ENERGY BALANCE FOR CONDENSER 16
5.5 ENERGY BALANCE FOR DISTILLATION 17
 xi

LIST OF FIGURES

PRODUCTION OF PHTHALIC ANHYDRIDE FROM ORTHO XYLENE

FIGURE NO TITLE PAGE NO

3.1 FLOW SHEET FOR THE PRODUCTION OF PHTHALIC 08

ANHYDRIDE FROM O-XYLENE

3.2 MODIFIED FLOW SHEET FOR THE PRODUCTION OF 09

PHTHALIC ANHYDRIDE FROM O-XYLENE

REMOVAL OF NaCl FROM TEXTILE WASTE WATER BY CAPACITIVE

DEIONIZATION USING NITRIC ACID MODIFIED CARBON ELECTRODES

4.1 SCHEMATIC DIAGRAM OF CDI 42

 xii

LIST OF GRAPHS

REMOVAL OF NaCl FROM TEXTILE WASTE WATER BY CAPACITIVE

DEIONIZATION USING NITRIC ACID MODIFIED CARBON ELECTRODES

GRAPH NO TITLE PAGE NO

5.1 DESALINATION OF 1000PPM FEED USING MODIFIED

CARBON ELECTRODES 46

5.2 DESALINATION OF 2000PPM FEED USING MODIFIED

CARBON ELECTRODES 47

5.3 DESALINATION OF 4000PPM FEED USING MODIFIED

CARBON ELECTRODES 48

5.4 DESALINATION OF 1000PPM FEED USING NORMAL

CARBON ELECTRODES 49

5.5 DESALINATION OF 2000PPM FEED USING NORMAL

CARBON ELECTRODES 50

6.1 CURRENT VS VOLTAGE 52

6.2 ENERGY CONSUMPTION VS VOLTAGE 53

PRODUCTION OF PHTHALIC ANHYDRIDE FROM ORTHO
XYLENE
 1

CHAPTER 1

INTRODUCTION

Phthalic anhydride is the organic compound with the formula C6H4 (CO)2O. It is
the anhydride of Phthalic acid. Phthalic anhydride is a principal commercial form of
Phthalic acid. It was the first anhydride of a dicarboxylic acid to be used commercially.
Phthalic Anhydride is an important aromatic dicarboxylic acid anhydride, which is
widely used in the manufacture of Alkyd Resins for paints, Inks and Coatings,
Unsaturated Polyester Resins, Plasticizers and Pigments. Phthalic anhydride is also
used as an intermediate in the production of the alcoholysis reaction as the basis of
the manufacture of phthalate esters, which are widely used as plasticizers.
CAS NO: 85-44-9, CCCN NO: 2917.35

1.1 SYNTHESIS AND PRODUCTION

Phthalic anhydride was first reported in 1836 by Auguste Laurent. More

contemporary routes include catalytic oxidation of O-xylene and naphthalene ("Gibbs
phthalic anhydride process"), although use of naphthalene has declined. Starting from
o-xylene, the oxidation follows the following stoichiometry:

C6H4(CH3)2 + 3 O2 → C6H4(CO)2O + 3 H2O

The reaction proceeds with about 70% selectivity. About 10% of maleic
anhydride is also produced:

C6H4(CH3)2 + 7.5 O2 → C4H2O3 +4 H2O + 4 CO2

A modified Vanadium Pentoxide (V2O5) serves as the catalysts, being active in

the range 320 - 400 °C. The phthalic anhydride is separated from by-products by a
series of ―switch condensers‖. Phthalic anhydride and maleic anhydride are recovered
by distillation.

Phthalic anhydride can also be prepared from phthalic acid.

The reactant stream of o-xylene and air mixture enters the packed bed reactor at a
 2

temperature of 300-420 ⁰C and a pressure slightly less than 1 atm. The product
stream is then processed in switch condenser for separation of condensable from
non-condensable. Phthalic anhydride sublimes on condensation, so after
condensation a hot fluid is used to melt phthalic anhydride and simultaneously
another condenser in series is used for desired condensation process, switching the
condenser back and forth.

For efficient sublimation of crude phthalic anhydride, the partial pressure of

phthalic anhydride should be more than the triple point of phthalic anhydride. So,
increasing the pressure of reaction would favour more efficient separation in switch
condensers. Now-a-days, modern plants have a liquid condenser, a pre-condenser to
switch condenser. Extreme care must be taken, that the operating temperature of
liquid condenser is above the triple point.

The condensate from this series of condensers is sent to a series of distillation

column for effective separation of phthalic anhydride from water and maleic
anhydride.The most common method for production of phthalic anhydride is by
oxidation of o-xylene. Phthalic anhydride is used in the manufacture of plasticizers
(additives to polymers to give them more flexibility) and polyesters, among other
applications.

1.2 PHTHALIC ANHYDRIDE – APPLICATIONS

In the production of-
1. Phthalate plasticizers like DOP, DEP etc.
2. Unsaturated polyester resins (UPR), which are used to produce fiberglass.
3. Plastics from vinyl chloride as a chemical intermediate.
4. Phthalonitrile and phthalimide for insecticides.

1.3 PHTHALIC ANHYDRIDE - PROPERTIES

Table 1.1. Physical and chemical properties of PA
Property PA
Melting point( ˚C) 131
Boiling Point(˚C) 284.5
 3

Heat of vaporization at 65.3

131˚C (KJ/mol)
Specific gravity at 4˚C 1.527
Specific heat(J/Kg.K) 1009

Table 1.2. Physical properties of liquid PA

Temperature(˚C) Vapor Density(g/cc) Viscosity(CP)
pressure(kPa)
135 0.9 1.215 1.19
160 2.7 1.188 1.02
200 10.7 1.145 0.94

Table 1.3. Solubilities of PA

Solvent PA

Water at 25˚c 0.6

Water at 100˚C 16.5

Water at 150˚C 147

Table 1.4. Specifications for PA

Property & content name Specification Test method

Freezing point(˚C) 130.9 Cryoscopy

Phthalic anhydride (%) 99.7 Gas chromatography

Phthalic acid (%) 0.2 Titration

Maleic acid (%) 0.05 Gas chromatography

Naphthoquinone (%) 0.0002 Gas chromatography

 4

CHAPTER 2
MSDS (MATERIAL SAFETY DATA SHEET)

2.1. OCCUPATIONAL HEALTH HAZARDS

Threshold limit value: 1 PPM (OSHA & ACGIH)

Short term effects: Dust forms flammable mixture with air and can develop static
charges. Minimum explosion limit for dust is 12 gs/m

In contact with skin: Mild irritant

In contact with eyes: Strong irritant

Inhaled: Inhalation of dust, vapour or fumes irritates nose, throat and upper
respiratory tract and may result in coughing, sneezing, increased mucous secretion
and sometimes cabocered breathe.

Ingested: Harmful, causes sour throat, abdominal pain, diarrhea

Long term effects of over exposure: If proper precaution not taken, repeated
exposure of dust may cause conductivities bronchitis, chlorine congestion of nasal
mucous, membrane & dermatitis.

2.2. EMERGENCY AND FIRST AID MEASURE

Skin: The exposed area must be washed with soap and water. If irritation persists
consult a doctor.

Eyes: Eyes must be washed immediately with copious amount of water. If irritation
persists consult a doctor.

Inhalation: The victim must be moved to fresh air immediately. Irritation of throat, nose
may be relieved by gargling with water, if necessary ad mister oxygen, perform
artificial respiration. Get medical attention immediately.
 5

Ingestion: Medical help must be insisted. If the patient is conscious, vomiting must be
induced by giving large quantities of salt solution. Keep the patient comfortable and
warm.

2.3. STORAGE

The PA must be stored in a cool, dry place, well ventilated and in a fire
protected area. The building where it is stored must be detached from other areas and
must be of non-combustible type. Open flame, potential sources o ignition and
smoking must be strictly forbidden. Incompatible materials like strong oxidizers must
be kept well away.

Flash point: Open cup = 165° C

Close cup = 152°C

Auto ignition temperature = 580°C

Flammable limits (% by volume in air): lower = 1.7, upper = 10.5

Fire extinguishing media: Dry powder or Carbon dioxide for small fire must be used.
Water spray and alcohol type aqua film forming foam for large fires. Special fire
protecting procedures: Self contained breathing apparatus and complete personal
protective equipments must be wore when potential for exposure to vapors or
products of combustible exists. Water can be sprayed to cool fire exposed structure
and vessels.

2.4. PRECAUTIONS IN HANDLING AND USE

General precautions: PA must be kept away from heat, naked flame, sparks and
potential sources o ignition. Contact with skin and eyes must be avoided. Vapors
should not be inhaled. Hands should be thoroughly washed after handling. Generation
of dusts should be avoided. Food stuffs should be kept away. Drinking, smoking,
eating in the work area must be avoided.

Ventilation requirements: Adequate ventilation should be provided

Respiratory requirements: Approved respirators should be used

 6

Protective clothes: Rubber, PVC, Neoprene

Eye protection: Close fitting safety goggles

2.5 FIRE HAZARD

Combustible material may burn but does not ignite readily. Substance
will react with water (some violently) releasing flammable, toxic or corrosive gases
and runoff. When heated, vapors may form explosive mixtures with air: indoors,
outdoors and sewers explosion hazards. Most vapors are heavier than air. They will
spread along ground and collect in low or confined areas (sewers, basements, tanks).
Vapours may travel to source of ignition and flash back. Contact with metals may
evolve flammable hydrogen gas. Containers may explode when heated or if
contaminated with water.

2.6 LABELING PROCEDURE

No label is required as per IMDG code.

Packaging group III and the package to be marked class-8, packaging code: 6F.

The labeling requirements of section- 7 and the packaging performance tests

referred to in section-10 of the general introduction to this code inn IMDG should not
apply to this substance due to its low degree of danger(IMDG).

Classification: Class 8 (corrosive), as per IMDG code and DOT.

2.7 SPILL OR LEAK PROCEDURE

Steps to be taken in event of spill or release:

 Eliminate ignition source

 Spilled materials should be swept and it must be collected in a dry container
 The container should be moved to a safer place
 The spills should not be allowed into drains, water sources etc.
 Raising dust must be avoided. The remaining few amount of spills should be
flushed away with plenty of water.
 If necessary, consulting an expert is recommended
 7

Neutralizing chemicals: Soda or sodium bicarbonanate.

Waste disposal: The waste should be disposed with local regulations. It may be
disposed off by dumping in a special area isolated from all operations and where no
contaminations of drinking water supply will be involved. Preferred method is
inclination in federal provincial approved facility.

Table 2.1. Flammability and explosivity of PA

Property Value

Explosibility index >10

Ignition sensitivity 13.8

Minimum ignition energy(J) 0.015

Minimum explosive concentration(g/,L) 0.015

By furnace ignition >90

By spark ignition 90

By furnace ignition 11

By spark ignition 14

Explosive severity 1.6

0.1 g/L dust concentration 269

0.5 g/L dust concentration 496

 8

CHAPTER 3

PROCESS DESCRIPTION

Figure3.1 Flow sheet for the production of phthalic anhydride from o-xylene

The conventional flowsheet contains O-xylene as the raw material. It has

a switch condenser (a type of condenser where the sublimation reaction takes place
for the conversion of maleic and phthalic anhydride from solid to vapour state). It has
two distillation columns. One for the separation of maleic anhydride and the other to
obtain phthalic anhydride (the desired product). This process consumes a lot of
energy.
 9

Figure3.1 Modified flow sheet for the production of phthalic anhydride from o-
xylene

Preheated o-xylene is introduced into a stream of hot air. Ortho xylene–Air mixture is
passed through a tubular reactor where the exothermic oxidation takes place on a
highly selective VANADIUM pentoxide catalyst. The heat of reaction is used to
produce steam, only part of which is utilized in the plant itself and the remaining
steam is used for power generation. The gases emerging from the reactor are fed into
condenser.After cooling the phthalic anhydride it is purified in a distillation chamber.
 10

CHAPTER 4

MATERIAL BALANCE FOR PHTHALIC ANHYDRIDE MANUFACTURING UNIT

4.1 BASIS

O-Xylene: 50 kmols and Oxygen: 150 kmols.

Percentage Conversion: 80% and Yield: 90%.

4.2 REACTIONS
Primary

C8H10 + 3O2 C8H4O3 + 3H2O

Secondary

C8H10 + 7.5O2 C4H2O3 + 4H2O + 4CO2

Moles of C8H10 Converted : 40 kmols.

Moles of C8H10 reacted in reaction 1: 36 kmols.

Moles of C8H10 reacted in reaction 2: 4 kmols

4.3 MATERIAL BALANCE FOR REACTOR

4.3.1 BALANCE BY REACTION 1

36 Kmols of O-Xylene = 36 Kmols of Phthalic Anhydride.

36 Kmols of O-Xylene = 108 Kmols of Water.

36 Kmols of O-Xylene ≡ 108 Kmols of Oxygen.

4.3.2 BALANCE BY REACTION 2

4 Kmols of O-Xylene = 4 Kmols of Maleic Anhydride.

4 Kmols of O-Xylene = 16 Kmols of Water.

4 Kmols of O-Xylene = 16 Kmols of Carbon-di-Oxide.

4 Kmols of O-Xylene = 30 Kmols of Oxygen.

 11

Table 4.1 Material balance for Reactor

Feed
Streams Kmols MW weight (Kg) mole% weight%
O-xylene 50 106.16 5308.00 6.54 20.48
Oxygen 150 32.00 4800.00 19.63 18.53
Nitrogen 564.29 28.00 15800.12 73.83 60.99
TOTAL 764.29 166.16 25908.12 100.00 100.00
Product
Streams Kmols MW weight (Kg) mole% weight%
O-xylene 10 106.16 1061.60 1.30 4.09
Oxygen 12 32.00 384.00 1.57 1.48
Nitrogen 564.29 28.00 15800.12 73.64 60.99
PA 36 148.12 5332.32 4.70 20.58
MA 4 98.00 392.00 0.52 1.51
C02 16 44.00 704.00 2.09 2.72
Water 124 18.00 2232.00 16.18 8.62
Total 766.29 474.28 25906.04 100.00 99.99

4.4 MATERIAL BALANCE FOR CONDENSER

4.4.1 FRACTIONS LEAVING IN THE OFF-GAS

O-Xylene =1

Oxygen =1

Nitrogen =1

Phthalic Anhydride = 0.05

Maleic Anhydride = 0.10

Water =1

Carbon-di-Oxide =1
 12

Table 4.2 Material balance for Condenser

Off Gas
Streams Kmols MW weight (Kg) mole% weight%
O-xylene 10 106.16 1061.60 1.37 5.03
Oxygen 12 32.00 384.00 1.65 1.82
Nitrogen 564.29 28.00 15800.12 77.46 74.90
C02 16 44.00 704.00 2.20 3.34
Water 124 18.00 2232.00 17.02 10.58
MA 0.4 98.00 59.25 0.05 0.28
PA 1.8 148.12 853.70 0.25 4.05
TOTAL 728.49 474.28 21094.67 100.00 100.00
Liquid
streams Kmols MW weight (Kg) mole% weight% mole fraction
PA 34.2 148.12 5065.70 90.48 93.49 0.9048
MA 3.6 98.00 352.80 9.52 6.51 0.0952
Total 37.8 246.12 5418.50 100.00 100.00 1

4.5 MATERIAL BALANCE FOR THE DISTILLATION COLUMN

Top Product : Maleic Anhydride (Light Key)

Bottom Product : Phthalic Anhydride (Heavy Key)

Top Temperature : 150°C

°
Bottom Temperature : 225 C

The feed to the distillation chamber is the liquid obtained from the Condenser
containing Phthalic Anhydride and Maleic Anhydride.
 13

Table 4.3 Material balance for Distillation

Top Section
Streams Kmols MW weight (Kg) mole% weight% mole fraction
PA 0.68 148.12 100.72 16.15 22.55 0.1615
MA 3.53 98.00 345.94 83.85 77.45 0.8385
TOTAL 4.21 246.12 446.66 100.00 100.00 1
Bottom Section
Streams Kmols MW weight (Kg) mole% weight% mole fraction
PA 33.52 148.12 4964.98 99.79 0.14 0.9979
MA 0.07 98.00 6.86 0.21 99.86 0.0021
TOTAL 33.59 246.12 4971.84 100.00 100.00 1
 14

CHAPTER 5

ENERGY BALANCE FOR THE PHTHALIC ANHYDRIDE UNIT

5.1 AIR PRE-HEATER

Inlet temperature of Air : 33°C.

Outlet temperature of Air: 350° C.

Specific Heat (Cp) : 1.028 KJ/Kg.K.

Flow rate (m) : 0.2397 Kg/s.

QAir = mCp (∆T)

= 0.2397 * 1.028 * (350-33)

= 78.11 KW.

5.2 O-XYLENE PRE-HEATER

Inlet temperature of the feed : 33°C.

Outlet temperature of the feed : 350°C.

Specific heat of O-Xylene (Cp) : 187 KJ/Kmol.K.

Flow-rate of O-Xylene (m) : 5.787x10-4 Kmols/s.

Q O-Xylene = mCp (∆T) = 34.30 KW

Table 5.1 Energy balance for Pre Heater

Pre- inlet outlet Q

heaters temp(k) temp(K) Cp M (KW)
0.2397
Air 306 623 1.028 KJ/Kg.K Kg/s 78.11
187 0.0005787
0-Xylene 306 623 KJ/Kmol.k Kmols/s 34.30
 15

5.3 ENERGY BALANCE FOR REACTOR

Table 5.2 Energy balance for Reactor feed

Feed
Streams temp diff Cp m (Kmol/s) Q (KW)
O-xylene 593 187 KJ/Kmol.k 0.000579 64.17
Air 593 1.028 KJ/Kg.K 0.00086 5.037
69.207

Table 5.3 Energy balance for Reactor output

Product
streams temp diff Cp ( KJ/Kmol.k) m (Kmol/s) Q (KW)
O-xylene 593 187 0.00016 17.74256
Air 593 1.028 0.0066 4.0233864
PA 593 271.46 0.000417 67.12690026
MA 593 0.00004629 0.000046 1.2627E-06
C02 593 0.000185 0.0044 0.000482702
Water 593 0.000185 868 95.22394
184.12

5.4 ENERGY BALANCE FOR CONDENSER

Temperature of the Inlet : 1700C

Temperature of the Inlet : 3200C

Energy input to the condenser : 184.12 KJ/s (Refer Table 5.3)

 16

Table 5.4 Energy balance for Condenser

Off Gas
Cp Temp
Streams (KJ/Kmol.k) m (Kmol/s) difference Q (KW)
O-xylene 187 0.000116 150 3.2538
Oxygen 0.921 0.000139 150 0.01920285
Nitrogen 29.4 0.0065 150 28.665
C02 868 0.000185 150 24.087
Water 4.186 0.00144 150 0.904176
MA 1.65 0.000005 150 0.0012375
PA 271.46 0.000021 150 0.855099
57.79
Liquid
Cp Temp
Streams (KJ/Kmol.k) m (Kmol/s) difference Q (KW)
PA 271.46 0.000396 150 16.124724
MA 1.65 0.000042 150 0.010395
16.14

5.5 ENERGY BALANCE FOR DISTILLATION

Temperature of the Feed : 1100C.

Temperature of the Top Section : 1500C.

Temperature of the Bottom Section : 2250C.

Energy input to the distillation column : 16.95 KJ/s (Refer Table 5.4)
 17

Table 5.5 Energy balance for Distillation

Top Section
Cp Temp
Streams (KJ/Kmol.k) m (Kmol/s) difference Q (KW)
PA 271.46 0.000008 50 0.1086
MA 1.65 0.000041 50 0.0034
0.11
Bottom Section
Cp Temp
Streams (KJ/Kmol.k) m (Kmol/s) difference Q (KW)
PA 271.46 0.000388 125 13.166
MA 1.65 0.000001 125 0.00022
21.28
 18

CHAPTER 6

DESIGN OF PACKED BED CATALYTIC REACTOR

Reactor Type:
Packed bed catalytic reactor:

Mass flow rate of O-Xylene = 221.17 kg/hr

Mass flow rate of Air = 858.34 kg/hr

Total flow rate = 1079.51 kg/hr

Reactor bed thickness = 1.2 cm

Reaction time = 0.13 sec

Catalyst density = 3360 kg/m3

Catalyst void = 0.5

Pressure drop = 45 KPa

Temperature = 723 K

Density of O-Xylene = 0.283 kg/m3

Density of Air = 1.331 kg/m3

Inlet pressure = 303.975 KPa

6.1 CALCULATION FOR REACTOR BED DIMENSIONS:

Reactor bed thickness

Linear velocity = __________________
Reaction time

1.2
Linear velocity = ______________
0.13
 19

Linear velocity = 9.23 cm/s

Volumetric flow rate = {(Mass flow rate of n butane /Density of n butane) +

(Mass flow rate of oxygen/Density of oxygen) }

= {(221.17/0.283*3600)+(858.34/2.48*3600)}

= 0.227 m3/s

Volumetric flow rate

Cross Section Area = __________________
Linear velocity

0.227
Cross Section Area = _______________
9.23 * 10-2 .

Cross Section Area = 2.459 m2

Diameter of the reactor = {(4*CSA)/3.14}0.5

= 1.77 m

Volume of catalyst used = reactor bed thickness * CSA

= 0.012 * 2.459

= 0.0295 m3
Weight of the catalyst used = density of catalyst * volume of the catalyst

= 3360 * 0.0295

= 99.12 kg
 20

Assume residence time = 20 sec

Volumetric flow rate = 0.227 *20

Volume of the reactor based on reactor = 4.54 m3

Porosity = 0.5

Pore volume available in the reactor = volume of the catalyst used * Porosity

= 0.0295 * 0.5

= 0.0148 m3

Total volume of the reactor = (volume of the reactor based on reaction

+ volume of catalyst used ) - pore volume

= (4.54 + 0.0295) – 0.0148

= 4.55 m3

C.S.A = ( 3.14 * D2 ) / 4

= (3.14 *(1.77)2)/4

= 1.38 m2

Total volume of the reactor = (volume of the cylindrical portion + volume of spherical
portion)

Volume of spherical portion = ((2/3)*3.14*(1.77/2)3) = 1.45 m3

 21

Volume of cylindrical portion = CSA * height of cylindrer + 1.45

Height of the cylinder = (4.55-1.45)/ 1.38

= 2.22 m
Design volume of the reactor = 1.1 * working volume

= 1.1 * 4.55

= 5.05 m3

Pressure in the reactor = 3.09968 kg/cm2

Internal diameter = 1.77 m

Assuming Joint efficiency = 0.85

Maximum allowable stress = 1130 kg/cm2

Corrosion allowance = 1.1* 3.09968

= 3.4096 kg/cm2

Thickness of the reactor = {(P*Dt)/(2fj-P)}+C

= {(3.4096 * 177)/((2*1130*0.85)-1.1363}+0.3

= 0.8357 cm
 22

6.2 CALCULATION FOR HEAD DESIGN

Type: Standard shallow dished

head

Crown radius = D-6‖

= 1.77 - 0.1524

Crown radius = 1.6176 m

Knuckle radius = 6% of Crown radius

= 0.06 x 1.6176

Knuckle radius = 0.097 m

Height of dished bottom = Rc - Rc2 - (D2/4) 0.5

=1.6176 - 1.61762 – (1.772/4) 0.5

Height of dished bottom = 0.2649 m

Thickness of the head = {(PRcW) / 2fj}+ C

Where W – Stress intensification factor (W)

Stress intensification factor W = ¼ [3 + (Rc / rk) 0.5]

= ¼ [3 + (1.6176/0.097)0.5]

= 1.7709

Thickness = {(3.4096 x 161.76 x 1.7709) / (2 x 1130 x 0.85)}+0.3

Thickness = 0.8084 cm
 23

6.3 DESIGN OF GASKET

Gasket selected is compressed asbestos which is suitable or high temperature and

pressure conditions.
Thickness of the gasket = 3mm

Gasket factor(m) =2

Gasket yield(Y) = 112 Kg/cm2

Basic gasket sealing width = 30/2

= 15mm

= 1.5 cm

Effective gasket sealing width Wb = ½ (b)0.5

= ½ (1.5)0.5
= 0.6124 cm
= 0.006124 m

6.4 GASKET WIDTH

Consider the forces acting over the gasket;
Gasket sealing force – Hydrostatic pressure force = Residual gasket force
Go/Gi = {(Y - mP) / (Y – P(m+1)) }0.5
= {(112 – 2 x 1.1363) / (112 – 1.1363 x 3)} 0.5

Go/Gi = 1.005218
 24

Where,
Go – outer diameter of the gasket in m
Gi – inner diameter of the gasket in m
Gi= inner diameter of the reactor +( 2 X thickness of the reactor)
= 1770 + (2 x 8.084)
= 1786.17 mm
Go = 1.005218 X Gi
= 1795.48 mm
6.5 CALCULATION FOR NUMBER OF BOLTS
Bolt load due to initial gasket
load reaction, Wm1 = πWb GY
Mean gasket diameter, G = (Gi + Go)/2
= 1790.83 mm
Wm1 = 3.14* 0.6124* 179.08 * 112
= 38568.25 kg
Mean gasket diameter, G = (Gi + Go)/3
= (1786.17+ 1795.488 ) / 2
Bolt load at operating condition :
Wm2 = π/4 {G2 P + πmGP(2Wb)}
=3.14/4{179.082 x 3.4096 +3.14* 2*179.08* 3.4096(2x0.6124)}
= 28864.11 Kg

Higher Wm should be taken to find the area of the bolt

Area of bolts = Wm1 / fb
=38568.25 /1203.99
= 32.03 cm2
Type of Bolt = M20

Bolt area calculated on ¾ of bolt diameter = 3/16 (3.14*0.022)

= 2.349*10-4 m2

Number of Bolts = 3.203*10-3/ 2.349*10-4 =13

 25

Number of bolts should be multiple of 4.

Therefore 12 number of bolts can be used
Bolt circle diameter, B = Go + (12*Db) +12
= 1796.486 + (12*20) + 12
= 2047.438 mm

6.6 CALCULATION OF THICKNESS OF FLANGE

tf = G (P/Kf)0.5
where:
p =design pressure Kg/cm2
K = {1/[(0.3 + 1.5 Wm hG)/H.G]}
Wm = total bolt load Kg
hG = (B-G)/2
H =Hydrostatic load = (3.14/4)G2P
B = bolt diameter
G = mean gasket diameter
hG = (2047.438-1790.83)/2
= 128.30 mm
= 12.83 cm
H = (3.14/4)*(179.083)2*3.4096
= 85838.44 Kg

K = {1/[(0.3+(1.5*67522.36)/(85838.44*179.083)]}
= 11.83
Thickness of flange (tf ) = 179.083[3.4096/(11.83* 1130)]0.5
= 2.8876cm
= 28.87 mm
 26

6.7 SUPPORT DESIGN

Type of support = Bracket support

Diameter of reactor = 1.77 m
Height of the reactor = 2.22 + 0.2649 + 0.7099
= 3.1948 m
Type of support = Bracket support
Height of the reactor = 2.22 + 0.2649 + 0.7099
= 3.1948 m
6.8 RESULTS
Diameter of reactor = 1.77 m
Height of the reactor = 3.1948 m
Thickness of Rector = 8.837 mm
Thickness of Head = 8.084 mm
Gasket inner Diameter = 1786.17 mm
Gasket Outer Diameter = 1795.49 mm
Number of Bolts = 12
Thickness of Flange = 28.87 mm
 27

CHAPTER 7

DESIGN OF DISTILLATION COLUMN

7.1 DESIGN SPECIFICATIONS

Operating pressure :1 atm

Distillate temperature : 150°C

Residue temperature : 225°C

Light key component : Maleic anhydride

Heavy key component : Phthalic anhydride

7.2 MOLE FRACTIONS

 Light key component in distillate : 0.8385

 Light key component in residue : 0.0021
 Heavy key component in distillate : 0.1615
 Heavy key component in residue : 0.9979

7.3 VAPOUR PRESSURE OF MAELIC ANHYDRIDE

 150° C : 156.018 mmHg

 225° C: 760 mmHg

7.4 VAPOUR PRESSURE OF PHTHALIC ANHYDRIDE

 150° C: 20 mmHg
 225° C: 200 mmHg

The average relative volatility can be calculated using the formula

 28

αtop= ⁄ = 7.8

αbottom= ⁄ = 3.8

αav= (αtop x αbottom)

αav= 5.4

Frenskee equation can be used to calculate the minimum number of stages

Nmin+1 =

=log (0.8385/0.1615 x 0.9979/0.0021)/ log (5.4)

Nmin = 4.63

(N-Nmin)/(N+1) =0.60

N = 13

The actual number of plates can be calculated by

Nact=N/0.80 = 16

7.5 HEIGHT OF THE COLUMN

Assuming the stage spacing to be 0.5m

Height = (Number of stages x stage spacing) + (2 x stage spacing )

H = 9m

7.6 OPERATING VELOCITY

L/V x ( v/ l)(0.5)

V= 0.0274 m/s
 29

From the graph between L/V x ( v/ l)(0.5) vs Kv , we get Kv= 0.32 assuming the value of
stage spacing as 19.68 inch.

7.7 THE ALLOWABLE VAPOUR VELOCITY

Uc= 0.32 x ( v/ l)(0.5)x ( 0.5

Uc = 0.20 m/s

7.8 DIAMETER CALCULATION

Diameter at the top

Composition of vapour (Kmoles/day)

 Phthalic anhydride : 0.68

 Maelic anhydride : 3.53

V=nRT/P

n = 0.410 Kmoles/day

R = 0.082 l atm.Mol.k

T = (197+273)= 470° C

P = 1atm

Volumetric flow rate = (0.410 x 0.082 x (197 + 273))/1

V =15.8 m3/ day

Cross sectional area = Volumetric flow rate/Uc

πD2/4 = 15.8/0.20m2

D = 10 m

Diameter At The Bottom

Composition of liquid (Kmoles/day)

 Phthalic anhydride : 33.52

 30

 Maelic anhydride : 0.07

T = (202+273)= 475° C

Volumetric flow rate : V = 15.96 m3/ day

Cross sectional area= 15.96/0.20 m2

D = 10.08 m

Mavg of feed = 142.324

Mavg of distillate = 95.5133

Mavgof residue = 150.360

F = 5418.50/142.32 = 38.06 Kmoles/day

D = 446.66/95.5133 = 4.67 Kmoles/day

L = 4971.84/148.12 = 33.56 Kmoles/day

7.9 MINIMUM VAPOUR VELOCITY CALCULATION

Minimum Vapour Velocity At Top

Minimum vapour velocity through holes

Vhmin = [ K-0.9(25.4-dh)]/( v)0.5

= 11.24 m/sec

v= 0.4269 Kg/m3 l= 1142.796 Kg/ m3

Weir length= Lw= 0.77 m Di = 7.7 m

Lm= 0.7 x L’ x Mavg

L’= L + (F x V)

= 34.998

Lm = 0.7 x L’ x Mavg = 0.55 Kg/s

 31

how= 750 [Lm/( l x Lw)]

= 0.055 m

hw = 50 mm

how + hw = 105 mm

L=R x D

= 7.005 Kmoles/day

V=(R+1) x D ( Eq 6.17 )

=11.675 Kmoles/day

Actual vapour velocity = 0.7(Qh/Ah)

Ac=cross sectional = 78.5 m2

down comer area= Ad= 0.12 Ac = 9.42 m2

Active area Aa= Ac - 2 Ad = 59.66 m2

Ah = 0.1 Aa= 5.9.6 m2

Vhact = 0.7(Qh/Ah) ; Vhact = 0.003218 m/s

Minimum Vapour Velocity At Bottom

Minimum vapour velocity through holes

Vhmin = 0.2089 m/s

Vhact= 0.7(Qh/Ah)

Wier length : Lw = 7.76 m

L’ = 41.51 Kmoles/day
 32

Lm = 0.77 Kg/s

how = 0.6512 m

hw = 50 mm

how + hw =115.12 mm

Down comer area = 9.571 m2

Active area Aa= 60.17m2

Ah= 6.06 m2

Vhact = 0.004455 m/s

7.10 PRESSURE DROP CALCULATION

Pressure drop at top

hd= 51[(Vh/Co)2 x ( v/ l)]

Co=0.84

hd= 51[(11.24/0.84)2 x (0.4269/1142.796)] = 3.411 mmHg

Residual pressure drop

hr = (12.5 x 10-3)/ l = 1.093 x 10-5

 33

CHAPTER 8

CONCLUSION

A flow sheet for the production of Phthalic anhydride from o-xylene was
considered. The conventional flow sheet had two distillation columns and a switch
condenser. The number of distillation columns was reduced to one and the switch
condenser was changed to a conventional condenser. The material and energy
balance was performed for the production system. A distillation column was
theoretically designed with specifications including height, diameter, pressure drop
and vapour velocity. Packed bed reactor was also theoretically designed with
specifications including diameter, height, gasket thickness, number of bolts and
thickness of flange. Phthalic anhydride is being used in the preparation of Phthalate
esters, which function as plasticizers. Phthalate plasticizers are used for the
production of flexible PVC products such as cables, pipes and hoses. The amount of
energy consumed was considerable reduced in the modified flow sheet.
 34

REFERENCES

1. U.S.A. Environmental Protection Agency (7407), Pollution Prevention and

Toxics, December 1994 EPA 749-F-95-016a, Phthalic Anhydride Fact Sheet
(CAS No. 85-44-9).

2. Design of Phthalic Anhydride Production Process by Acacio Mendes and Ana

Rita Seita, Instituto Superior Tecnico – Av. RoviscoPais, 1049-001, Lisboa,
Portugal.

3. Mannsville Chemical Products Corporation. Phthalic Anhydride. Chemical

Product Synopsis, May 1993.

4. NCI. 1979. National Cancer Institute. Bioassay of Phthalic Anhydride for

possible Carcinogenicity. CAS No. 85-44-9. NCI National Institute of Health,
USA DHEW, Bethesda, MD.

5. CHEMFATE . 1994. Syracuse Research Corporation Environmental Fate Data

Base. Retrieved November 1994.

6. ACGIH. 1991. American Conference of Governmental Industrial Hygienists,

Inc. Documentation of the Threshold limit Values and Biological Exposure
Indices, 6th ed. ACGIH, Cincinnati, OH, pp. 1263-1265

7. ACGIH. 1993-1994. Threshold limit Values for Chemical Substances and

Physical agents and Biological Exposure. Indices. ACGIH, Cincinnati, OH, p-
29
 35

REMOVAL OF NaCl FROM TEXTILE WASTE WATER BY

CAPACITIVE DEIONIZATION USING NITRIC ACID MODIFIED
CARBON ELECTRODES
 36

CHAPTER 1

INTRODUCTION

The increase in the groundwater extraction around the globe and industrial
activities has resulted in several impacts over environment. As a consequence, there
is a large interest in the development of economically attractive treatment
technologies. Over the years, a number of methods have been developed among
which distillation, reverse osmosis, and electro dialysis are the most commonly known
and widespread technologies. A common goal for current research is to make these
technologies more energy efficient and cost effective, both for the deionization of
seawater and for industrial effluent water. The effluents from the Industries which
constitute Textile industries, Leather industries, Pulp and paper industries and several
other industries have possibilities to pollute the environment at a larger scale. There is
necessity to use most suitable methodologies and techniques to treat these effluents.
Capacitive deionization technique have significant role in the final stages of treatment.
The energy release during electrode regeneration (ion release, or electrode
discharge) in deionization can be utilized to charge a neighboring cell operating in the
ion electro sorption step and in this way energy recovery is possible. The energy
efficiency of CDI for water with a salt concentration is due to the fact that the salt ions,
which are the minority compound in the water, are removed from the mixture. CDI
applies a basic principle of electro chemistry to purify the brackish water and industrial
effluents. The main objective of our project is to treat the Textile effluents which
contain salts by reducing the TDS of the water using Nitric acid modified carbon
electrodes. In conventional textile waste water treatment process, the RO reject is
taken and desalted using capacitive deionization. In this project, the evaluation of the
desalination performance based on different operational parameters of the CDI
system was performed and it was found that this desalination technique using
modified carbon electrodes can be an alternate for thermal desalination process.
 37

CHAPTER 2

LITERATURE REVIEW

Fenf Daun (2015), Desalination of capacitive deionization using ordered

mesoporous carbon: Effect of oxygen- containing surface groups and pore properties.
This article includes the study of ordered mesoporous carbons and the evaluation of
desalination performance of capacitive deionization during 50 continuous cyclic
adsorption / desorption experiments. The results showed pronounced degradation in
the desalination performance for all materials as the cycle number increased and an
inversion in conductivity appeared at the beginning of the adsorption or desorption
stage after several cycle. Author also studied that the materials which had a very
small surface area and pore size underwent the most remarkable degradation and the
materials which had large surface area and pore diameter were more favorable
towards long term stability.

Rafael L.Zornitta (2015), Effect of Electrode properties and operational

parameters on capacitive deionization using low-cost commercial Carbon. In this
article, inexpensive materials that are commercially available were investigated for
being used as electrodes in Capacitive deionization. In this article author studied how
factorial design of experiments were used investigate the effect of cell potential, mass
and thickness of activated carbon coating over the electrode and porosity of the
activated carbon.

Julio J. Lado (2014), Evaluation of operational parameters for a capacitive

deionization reactor employing asymmetric electrodes. This article is about the study
of capacitive deionization which is potential technology for water softening. This article
is the study of low-cost high surface area carbons coated with two different metal
oxides, SiO2 on the anode and Al2O3 on the cathode. Author also came experimentally
verified that higher efficiency can be achieved by conducting the deionization in higher
voltage.
 38

k.Laxman, (2014), Efficient Desalination of Brackish Ground Water via a Novel

Capacitive Deionization Cell Using Nanoporous Activated Carbon Cloth Electrodes. In
this article the application of capacitive deionization (CDI) for the deionization of
ground water samples from wells in Al-Musanaah Wilayat is proposed and
demonstrated. A CDI cell is fabricated using nanoporous activated carbon cloth (ACC)
as the electrodes and is shown to be power efficient for desalting ground water
samples with total dissolved solids (TDS) of up to 4,000 mg/l. The CDI cell was able
to remove up to 73% of the ionic scaling and fouling contaminants from brackish
water samples. The power consumption for deionization of brackish water was
estimated to be 1 kWh/m3 of desalinated water, which is much lower than the power
required to process water with equivalent TDS by the reverse osmosis processes.

Özgür Arar (2014),Various applications of electrodeionization (EDI) method for

water treatment—Ashortreview. In this article the author has presented examples of
applications have shown that EDI process is very efficient in environmental protection,
production of ultra-pure water, and for the recovery of some valuable species.
Normally, weakly-ionized species, such as carbondioxide and boron are difficult to
remove via such membrane processes as reverse osmosis and electrodialysis
reversal (EDR). The EDI offers the benefit of continuous removal of these species to a
very high degree. The main technological parameters determining the efficiency of an
EDI module are the current strength, flow velocity in the dilute and concentrate
compartments, temperature, and TDS (in both initial and purified water).

Geiong Lu, (2014), Enhanced capacitive deionization performance with carbon

electrodes prepared with a modified evaporation casting method. In this article the
surface and structural properties, as well as the electrochemical behaviors of the
prepared electrode were systematically characterized by digital photo images, contact
angle measurement, scanning electron microscopy (SEM) and cyclic voltammetry
(CV). Capacitive deionization experiments were carried out at various operating
conditions using a CDI cell with the as-prepared carbon electrodes. The specific
capacitance of the carbon electrode and the desalination efficiency of the CDI cell
were14.5 F/g and 50.4% respectively, which are promisingly higher than that obtained
 39

with other carbon electrodes prepared with traditional spray coating and roller coating
methods. Moreover, a regeneration time of 19 min and an electrosorption capacity of
14.4 mg/g were achieved for capacitive deionization in 25 mL NaCl aqueous solution
with an initial conductivity of 2020 μs/cm by using the new carbon electrodes. The
enhanced CDI performance was attributed to the loose structure and favorable
channels of the carbon electrode. Therefore, the prepared electrodes by using this
novel method show promising stability, high porosity, good pore distribution, and
favorable hydrophilic property.
 40

CHAPTER 3

CAPACITIVE DEIONIZATION MACHANISM

CDI desalination technology is a member of the family of electricity based

desalination techniques. The concept of CDI stems from the two words capacitive and
deionization. The term deionization refers to the removal of charged atoms or
molecules in the form of ions and the term capacitive refers to the fact that a capacitor
is used to facilitate this removal. A capacitor is a device made of one or more pairs of
electrodes, oppositely charged. An electric potential is applied to the electrodes
producing positively and negatively charged poles. Salt molecules dissolved in water
exist in the form of positively and negatively charged ions. Positive ions (cations) are
attracted by the electrostatic force to the negative electrode while the negative ions
(anions) are attracted to the positive electrode. CDI works by attracting salt ions to the
surface of porous carbon electrodes where ions are held in electrical double layers
(EDLs). The ions are adsorbed on the electrodes, and thus the deionised water is
obtained from the outlet. When the charge potential is removed or reversing the
voltage, the ions are desorbed from the electrodes and are regenerated, and the ion
containing water is discharged from the cell. A CDI cycle consists of two steps, the
first being an ion electro sorption, or charging; step to purify the water, where ions are
immobilized in porous carbon electrode pairs. In the following step, ions are released,
that is, are desorbed from the electrodes, and thus the electrodes are regenerated. In
this way ions are separated from the water solution. A cycle of purification (ion
removal) and regeneration (ion discharge) is alternated to produce two streams of
desalinated water and brine.
 41

CHAPTER 4

EXPERIMENTAL METHODS

4.1 FABRICATION OF MODIFIED CARBON ELECTRODES

The activated carbon powder used in this work was initially treated with Nitric
acid (HNO3) and Sodium silicate is used as binder material for the coating of activated
carbon over the Graphite sheet. Initially 10 g of raw AC powder and 100 ml of HNO3
solution (10 mol/l) were mixed together and stirred for 4 h at 90 °C. Then, the
activated carbon powder was separated with filtration. The filter cake was washed
with distilled water until the filtrate became neutral. After that, the cake was dried at
60 °C, which was referred as the modified activated carbon. Then the activated
carbon slurry was prepared by mixing the powder with Sodium silicate gel which is
used as the binder in a magnetic stirrer. After that, the slurry was uniformly casted on
a graphite sheet with a blade to form electrodes with the dimensions of 10 × 3.7 cm.
The casted electrodes were dried at 50 °C for 2 h. The weight of the AC electrode
was 6 g.

4.2 EXPERIMENTAL SET-UP

The experiment is conducted in a batch process which consists of CDI reactor

whose dimensions are 30cm x 10cm x 15cm, DC power supply, Total dissolved salts
meter (TDS meter), Multimeter. The CDI reactor consists of Carbon electrodes in
appropriate positions and is connected to DC power supply at appropriate voltage.
The water sample that is to be experimented is kept in the reactor at a particular
voltage for considerable interval of time. The changes in the concentration of the
water from the reactor are noted with the help of TDS meter.
 42

Figure 4.1 Schematic diagram of CDI

4.3 EXPERIMENTAL PROCEDURE

Experiments were conducted to evaluate the desalination performance

based on different operational parameters of the CDI system. The operational
parameters are Concentration of Feed, Applied voltage and time. Deionization
capacity of modified carbon electrode is initially studied and then it is compared
with deionization capacity of normal electrodes. Both studies include same
procedure. Initially Modified carbon electrodes are taken in the CDI reactor. The
concentration of the feed is taken as 1000 ppm, 2000 ppm and 4000 ppm of NaCl
solution. The potential difference of 1.2V, 2V and 4V is applied between electrodes
and the respective change in concentration of the feed with respect to time is
measured. The concentration is measured using a TDS meter. Different
concentrations of the feed solution are taken and the corresponding change in the
total dissolved salts is measured with respect to change in time. Same
experimental procedure is conducted using normal electrodes.
The Salt removal efficiency is calculated by using the formula,
C0 - C
x
Salt Removal Efficiency (%) = 100
C0

where C0 - Concentration of Feed and C - Concentration of Treated Water

 43

CHAPTER 5

RESULTS AND DISCUSSIONS

5.1 TABULATIONS

5.1.1 DEIONIZATION USING MODIFIED CARBON ELECTRODES (MCE)

a. Concentration of the feed = 1000 ppm

Time( min) TDS ( ppm) SRE (%)

1.2 V 2V 4V 1.2 V 2V 4V

5 928 785 585 7.2 21.5 41.5

10 890 668 474 11 33.2 52.6
15 847 616 413 15.3 38.4 58.7
20 816 574 378 18.4 42.6 62.2
25 810 551 351 19 44.9 64.9
30 798 544 343 20.2 45.6 65.7
35 792 536 334 20.8 46.4 66.6
40 786 523 329 21.4 47.7 67.1
45 774 515 322 22.6 48.5 67.8
50 769 488 315 23.1 51.2 68.5
55 765 479 308 23.5 52.1 69.2
60 760 466 303 24 53.4 69.7

b. Concentration of the feed = 2000 ppm

Time( min) TDS ( ppm) SRE (%)

1.2 V 2V 4V 1.2 V 2V 4V

5 1870 1622 1202 6.5 18.9 39.9

10 1776 1416 1002 11.2 29.2 49.9
15 1714 1290 886 14.3 35.5 55.7
20 1666 1178 830 16.7 41.1 58.5
25 1642 1148 802 17.9 42.6 59.9
30 1628 1124 778 18.6 43.8 61.1
35 1616 1116 752 19.2 44.2 62.4
40 1602 1094 736 19.9 45.3 63.2
45 1590 1062 714 20.5 46.9 64.3
50 1574 1038 696 21.3 48.1 65.2
55 1566 1014 670 21.7 49.3 66.5
60 1556 972 652 22.2 51.4 67.4
 44

c. Concentration of the feed = 4000 ppm

Time( min) TDS ( ppm) SRE (%)

1.2 V 2V 4V 1.2 V 2V 4V

5 3764 3332 2528 5.9 16.7 36.8

10 3612 3028 2184 9.7 24.3 45.4
15 3472 2808 1928 13.2 29.8 51.8
20 3376 2572 1764 15.6 35.7 55.9
25 3344 2404 1716 16.4 39.9 57.1
30 3316 2348 1668 17.1 41.3 58.3
35 3284 2304 1612 17.9 42.4 59.7
40 3260 2244 1580 18.5 43.9 60.5
45 3236 2196 1532 19.1 45.1 61.7
50 3208 2144 1496 19.8 46.4 62.6
55 3184 2088 1444 20.4 47.8 63.9
60 3164 2044 1396 20.9 48.9 65.1

5.1.2 DEIONIZATION USING NORMAL CARBON ELECTRODES (NCE)

a. concentration of the feed = 1000 ppm

Time( min) TDS ( ppm) SRE (%)

1.2 V 2V 4V 1.2 V 2V 4V

5 968 897 768 3.2 10.3 23.2

10 907 821 700 9.3 17.9 30
15 868 756 616 13.2 24.4 38.4
20 846 699 568 15.4 30.1 43.2
25 836 677 543 16.4 32.3 45.7
30 825 661 528 17.5 33.9 47.2
35 818 644 513 18.2 35.6 48.7
40 811 628 505 18.9 37.2 49.5
45 805 606 493 19.5 39.4 50.7
50 799 594 483 20.1 40.6 51.7
55 792 581 474 20.8 41.9 52.6
60 787 576 468 21.3 42.4 53.2
 45

b. Concentration of the feed = 2000 ppm

Time( min) TDS ( ppm) SRE (%)

1.2 V 2V 4V 1.2 V 2V 4V

5 1956 1838 1574 2.2 8.1 21.3

10 1852 1706 1436 7.4 14.7 28.2
15 1766 1550 1336 11.7 22.5 33.2
20 1714 1442 1268 14.3 27.9 36.6
25 1682 1396 1174 15.9 30.2 41.3
30 1666 1346 1118 16.7 32.7 44.1
35 1654 1312 1072 17.3 34.4 46.4
40 1638 1288 1054 18.1 35.6 47.3
45 1628 1262 1038 18.6 36.9 48.1
50 1612 1232 1016 19.4 38.4 49.2
55 1598 1206 998 20.1 39.7 50.1
60 1582 1196 982 20.9 40.2 50.9
 46

5.2 GRAPHICAL REPRESENTATIONS

Salt removal efficiency vs Time for 1000 ppm

80
Salt removal efficinecy ( % )

70
60
50
40 1.2 V
30
2V
20
4V
10
0
0 20 40 60 80
Time (min)

Total dissolved salts vs Time for 1000 ppm

1200
Total dissolved salts (ppm)

1000

800

600 1.2 V

400 2V
4V
200

0
0 10 20 30 40 50 60 70
Time (min)

5.1 Desalination of 1000ppm feed using Modified Carbon Electrodes

This graph shows the Impact of voltage and time on salt removal efficiency
for concentration of the feed = 1000 ppm using Modified Carbon Electrodes
 47

Salt removal efficiency vs Time for2000 ppm

80
70
Salt removal efficiency (%)

60
50
40 1.2 V
30 2V
20
4V
10
0
0 20 40 60 80
Time (min)

Total dissolved salts vs Time for 2000 ppm

2500
Total dissolved salts (ppm)

2000

1500
1.2 V
1000 2V

500 4V

0
0 10 20 30 40 50 60 70
Time (min)

5.2 Desalination of 2000ppm feed using Modified Carbon Electrodes

This graph shows the Impact of voltage and time on salt removal efficiency
for concentration of the feed = 2000 ppm using Modified Carbon Electrodes
 48

Salt removal effiecincy vs Time for 4000 ppm

70
Salt removal efficiency (%)

60
50
40
1.2 V
30
2V
20
10 4V

0
0 20 40 60 80
Time (min)

Total dissolved salts vs Time for 4000 ppm

4500
4000
Total dissolved salts (ppm)

3500
3000
2500
Series1
2000
1500 Series2
1000 Series3
500
0
0 20 40 60 80
Time (min)

5.3 Desalination of 4000ppm feed using Modified Carbon Electrodes

This graph shows the Impact of voltage and time on salt removal efficiency
for concentration of the feed = 4000 ppm using Modified Carbon Electrodes
 49

Salt removal efficiency vs Time for 1000 ppm

60

50
Salt removal eiciency (%)

40

30 1.2 V
2V
20
4V
10

0
0 10 20 30 40 50 60 70
Time (min)

Total dissolved salts vs Time for 1000 ppm

1200
Total dissolved salts (ppm)

1000

800

600 1.2 V

400 2V
4V
200

0
0 10 20 30 40 50 60 70
Time (min)

5.4 Desalination of 1000ppm feed using Normal Carbon Electrodes

This graph shows the Impact of voltage and time on salt removal efficiency
for concentration of the feed = 1000 ppm using Normal Carbon Electrodes
 50

Salt removal efficiency vs Time for 2000 ppm

60
Salt removal efficiency (%)
50

40

30
1.2 V
20 2V
4V
10

0
0 20 40 60 80
Time (min)

Total dissolved salts vs Time for 2000 ppm

2500
Total dissolved salts (ppm)

2000

1500
1.2 V
1000 2V

500 4V

0
0 10 20 30 40 50 60 70
Time (min)

5.5 Desalination of 2000ppm feed using Normal Carbon Electrodes

This graph shows the Impact of voltage and time on salt removal efficiency
for concentration of the feed = 1000 ppm using Normal Carbon Electrodes
 51

CHAPTER 6

ENERGY CONSUMPTION OF CAPACITIVE DEIONIZATION

The energy consumption of CDI (kWh) of a purification cycle can be

calculated, based on the equation
W = φ∫ I dt
where
W = total energy Consumption (kWh)
Φ = voltage (V)
I = current (A) supplied
t = time taken for purification cycle (hr)

For 2V,
W = φ∫ I dt
W = (2)∫ (0.28) dt
= (2) (0.3) (60/60)
=0.192 kWh

For 4V,
W = (4)∫ (0.56) dt
=2.24 kWh
For 8V,

W = (8)∫ (1.39) dt
= 2.400 kWh

Similarly for 1V the total energy consumption is 0.192 KWh and for 10V the
total energy consumtion is 21.7 volt using modified carbon electrodes.

The energy consumption of CDI varies from 0.15 to 2.4 kWh, when the voltage
is increased from the 2 to 8 V. The energy consumption for RO is stated as 3-10 KWh
 52

for single equipment. This clearly states that CDI is far more efficient when compared
to RO. The energy spent to pump water is taken as basis and compared.

Energy consumption of capacitive deionization

VOLTAGE CURRENT TIME W (KWh)

MCE NCE MCE NCE

1.2 0.16 0.26 1 0.192 0.312

2 0.28 0.43 1 0.56 0.86
4 0.56 0.87 1 2.24 3.48
8 1.11 1.73 1 8.88 13.84
10 1.39 2.17 1 13.9 21.7

Current vs Voltage
2.5

2
CURRENT (A)

1.5
Modified Carbon
1 Electrode
Normal Carbon
0.5 Electrodes

0
0 5 10 15
VOLTAGE (V)

5.1 CURRENT VS VOLTAGE

This graph shows the relation between Current and voltage Modified and Normal
Carbon Electrodes
 53

Energy consumption vs Voltage

25
Energy consumptiom (KWh)
20

15 Modified carbon
electrodes
10
Normal carbon
electrode
5

0
0 5 10 15
VOLTAGE (V)

5.2 ENERGY CONSUMPTION VS VOLTAGE

This graph shows the Impact of Voltage on Energy Consumption using Modified and
Normal Carbon Electrodes
 54

CHAPTER 7

CONCLUSION

The concept of CDI is mainly revolves around desalination process of brackish

water and industrial. The experiments were conducted for various test conditions. The
two main operational parameters such as time and voltage are studied under various
concentration and applied voltages. The synthetic brackish water is prepared using
hard water producing salts such as sodium chloride. The electrodes are graphite
coated with nitric acid modified carbon electrode. The mechanisms might be attributed
to that the nitric acid treatment increased the amount of oxygen-containing
functionalities on Activated carbon surfaces. The performance of modified carbon
electrodes is better than that of normal carbon electrodes. Salt removal efficiency
decreases with increase in concentration at same pair of electrodes. There is higher
salt removal efficiency at higher voltage and at lower voltage the salt removal
efficiency is considerably low. For higher concentration of feed number of electrodes
can be increased. The best view was studied and justified. And for every aspect, the
efficiency of the process was effectively studied. We evaluated the desalination
performance based on different operational parameters of the CDI system by taking
different concentration of RO reject and proved that this desalination technique using
modified carbon electrodes can contribute to the possibility of using this method for
the Textile effluent desalination by replacing the thermal desalination method.
 55

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