GHG Manual Chlor Alkali Sector

Good Practices
Manual
Green House Gases Emission Reduction
Chlor-alkali Sector
Prepared by Supported by
National Productivity Council Department of Industry and Policy Promotion
Prepared by
National Productivity Council, India
Supported by
Department of Industrial Policy and Promotion
Ministry of Commerce and Industry
Government of India
Copyright 2017 National Productivity Council
This manual is the property of Department of Industrial Policy and Promotion, Ministry of Commerce
and Industry, Government of India. No part of this publication may be reproduced, distributed, stored in
retrieval system, or transmitted in any form or by any means, including photocopying or other electronic
or mechanical methods, without the prior written permission of the Publisher.
TABLE OF CONTENTS
ACKNOWLEDGEMENT............................................................................................... 1
PREFACE .................................................................................................................... 2
STUDY TEAM............................................................................................................... 3
1. INTRODUCTION................................................................................................... 4
1.1 BACKGROUND............................................................................................................. 4
1.2 ABOUT THE PROJECT................................................................................................... 5
1.3 METHODOLOGY .......................................................................................................... 5
1.4 GREENHOUSE GASES AND ITS IMPACT .................................................................. 6
1.5 OUTLINE OF ENERGY SCENARIO IN INDIA ............................................................. 9
1.6 GHG EMISSION FACTORS ........................................................................................ 13
2. CHLOR ALKALI SECTOR PROFILE ..................................................................... 14

2.1 INTRODUCTION .......................................................................................................... 14
2.2 CAPACITY UTILIZATION ............................................................................................. 14
2.3 USES OF CAUSTIC AND CHLORINE ........................................................................ 16
2.4 EXPORTS AND IMPORTS ........................................................................................... 17
2.5 PERFORMANCE AND PRODUCTIVITY INDICATORS ........................................... 17
2.6 BENCHMARKS FOR CHLOR-ALKALI INDUSTRY .................................................... 20
3. CHLOR-ALKALI MANUFACTURING PROCESS .................................................. 22

3.1 OVERVIEW OF CHLOR-ALKALI PRODUCTION .................................................... 22
3.2 BRINE PREPARATION ................................................................................................. 23
3.3 CELL HOUSE................................................................................................................. 24
3.4 CAUSTIC CONCENTRATION .................................................................................... 28
3.5 CHLORINE .................................................................................................................... 34
3.6 HYDROGEN GAS MANAGEMENT ..........................................................................vii
3.7 UTILITIES .........................................................................................................................vii
4. BEST PRACTICES ................................................................................................ xx

4.1 CELL HOUSE................................................................................................................. xx
4.2 CHLORINE LIQUEFACTION AND TAIL GAS TREATMENT .................................. xxv
4.3 HYDROGEN GAS MANAGEMENT ....................................................................... xxvi
4.4 CAUSTIC CONCENTRATION ................................................................................xxvii
4.5 STEAM GENERATION AND DISTRIBUTION .......................................................... xxix
4.6 ENERGY EFFICIENCY IN PUMPING SYSTEM ........................................................ xxx
4.7 ENERGY EFFICIENCY IN TRANSFORMERS AND RECTIFIERS ..........................xxxii
4.8 ENERGY EFFICIENCY IN LIGHTING SYSTEM ......................................................xxxii
5. CASE STUDIES ................................................................................................xxxiii
5.1 RE-COATING OF ANODE AND CATHODE WITH MEMBRANE CHANGE xxxiii
5.2 fully automatic control of brine feed temperature .................................. xxxiii
5.3 PREHEATING OF FEED BRINE USING CHLORINE IN RECUPERATOR .......... xxxiv
5.4 CONVERSION OF CAUSTIC CONCENTRATION PLANT FROM DOUBLE
EFFECT TO TRIPLE EFFECT ...................................................................................... xxxv
5.5 REPLACING RECIPROCATING COMPRESSOR WITH FREON SCREW
COMPRESSOR FOR CHLORINE LIQUEFACTION .............................................. xxxv
5.6 CONVERSION OF HOT WATER FIRED SINGLE EFEECT VAM MACHINE
WITH DOUBLE EFFECT VAM MACHINE ............................................................. xxxvi
5.7 IMPROVEMENT OF POWER FACTOR BY ADDING CAPACITOR ................ xxxvi
5.8 REPLACEMENT OF OLD LOW EFFICIENCY TRANSFORMER WITH NEW
ENERGY EFFICICENT TRANSFORMER ...............................................................xxxvii
5.9 REPLACEMENT OF CONVENTIONAL MAGNETIC CHOKES WITH
ELECTRONIC CHOKES ....................................................................................... xxxviii
6. INTERNET OF THINGS (IOT) .......................................................................... xxxix

6.3 Apps for Productivity Assessment and Improvement .................................. xli
ABBREVIATIONS .................................................................................................... xliv
BIBLIOGRAPHY ....................................................................................................... xlv
ACKNOWLEDGEMENT
Mr. Ramkumar Shankar Ex-President

Alkali Manufacturers Association of
India (AMAI), New Delhi
Mr. K Srinivasan, Secretary General
Thyssenkrupp Industrial Solutions

(India) Ltd., Mumbai
Dr. Ranga Rao, GM- Chlor Alkali Division
Mr. Kalyana Sundaram, Asst. Vice President
Tamil Nadu Petro Products Ltd (TPL), Mr. Muthu Kumarasamy, Head Operations
Chennai
Mr. N. Surya Kumar, Sr. Engineer
Mr. Jayapalan, AGM

Travancore Chemicals Cochin, Cochin
Mr. Ajith, Manager
Mr. R Jeyakumar, Executive Vice President

DCW-Sahupuram
Mr. Subhash Tandon, Executive Vice President
Andhra Sugars, Kovvur

Mr. G Venkat Rao, Chief Elect. Engineer
Sree Rayalaseema Alkalies and Allied

Chemicals Ltd., Kurnool Mr. Elluri Ramaiah, Vice President (Mech.),
1
PREFACE
It is now widely accepted that we have to limit the temperature rise to 2oC to mitigate effects
of climate change. This requires changing the portfolio of energy basket from fossils to non-
renewables, reduce energy use through energy efficiency and conservation and reduce GHG
emissions.
The broad intent and its goals can only be achieved by coordinated actions at various level by
society, business, industry and government. As part of its endeavour the Government of India
is formulating policies, action plans to support and guide industry and entrusted National
Productivity Council to prepare of Best Practices Manual for Reducing GHG Emissions in
various sectors namely, Thermal Power Plant, Chlor Alkali, Cement, Pulp and Paper and
Iron and Steel.
This manual is expected to serve as reference manual for

• Identifying sources of GHG emissions
• Assess and quantify emissions.
• Evaluate and assess potential to improve energy efficiency and reduce GHG emissions.
• Propose a menu of options which industry can consider for assessment and
implementation.
The scope of this manual covers GHG emissions in the plant boundary and does not include
transportation of raw materials, products and wastes to secured landfills, emissions from
domestic waste treatment and emissions from sales and other offices.
It is hoped the manual will be handy reference and guide for all levels of engineers and
managers working in the sector.
2
STUDY TEAM
Project Coordinator Mr. R Virendra, Dy. Director General,

National Productivity Council
Team Coordinator Mr. D Sreenivasulu, Dy. Director

Mr. R Idhayachander, Dy. Director

Team Members
Mrs. Preethi Dineshkumar, Asst. Director
Mrs. V G Sandhya, Asst. Director

Mr. N.K. Kuttiappan, President

LVK Enviro Consultants, Chennai
Advisors Mr. J. Nagesh Kumar, Director

Centre for Energy Environment and Productivity, Chennai
Mr. K Pattabi, Ex General Manager

Tamil Nadu Petro Products Ltd, Chennai
3
1. INTRODUCTION
1.1 BACKGROUND
Energy is a major driver of economy and the per capita consumption of energy is a lead
indicator of its development. The fossil fuels, constituting 72.4% of the energy basket as of
2013 1, is the major contributor of GHG emissions and consequently global warming. The
wider consensus that the temperature rise is to be limited to 2oC requires reducing GHG
emissions by changing the portfolio of energy mix from fossil fuels to non-renewable
sources, and reducing energy use through energy efficiency and conservation.
India is a net energy importing country and its GDP growth is one of the highest in the world.
To maintain its growth rate as well as to ensure energy security and meet its committed GHG
emission target reduction (30-35%) by 2030 from 2005 levels, India has been taking
measures to shift its energy consumption towards renewable energy, besides adopting energy
conservation and management measures. Studies indicate potential to reduce GHG emissions
as shown in Figure 1.1.
Figure 0.1 Indian GHG Emission Scenario (Past, Current & Projected)
Source: Pathways to lowcarbon_economy_Version2
1
http://data.worldbank.org/indicator/EG.USE.COMM.FO.ZS
4
As can be seen, industrial sector’s GHG reduction potential is about 680 million tonnes CO 2 e
per year. In line with these projections provided by various studies, Government of India has
evolved policies, action plans and mission oriented programs to address the following
objectives and issues.
• Energy security – to meet present and future needs

• Environmental impact-to address local emissions & global climate change
• Economic development – to create a sustainable development
• Ease of implementation
1.2 ABOUT THE PROJECT
To ensure effective translation of policy and implementation of action plans, Department of

Industrial Policy & Promotion (DIPP), under Ministry of Commerce & Industry, Government
of India has entrusted National Productivity Council of India (NPC) with the project titled
“Preparation of Good Practices Manuals for Green House Gas Emission Reduction in Five
Energy Intensive Industry Sectors in India” under the 12th Plan period (2012-2017).
The scope of the project is to conduct field and questionnaire survey in five selected energy
intensive sectors (Thermal Power Plant, Chlor Alkali, Cement, Pulp and Paper and Iron and
Steel) of Indian economy, and bringing out manuals on Good Practices for GHG Emission
reduction in the selected energy intensive sectors. Out of these five energy intensive sectors,
this manual highlights the best practices involved for reducing Green House Gases Emission
Reduction in the chlor-alkali sector.
This manual brings out sources and trends driving India’s greenhouse gas emissions in the
chlor-alkali sector, outlining present situation and technologies that offer potential for
significant emission reductions through enhanced energy efficiency that will put India on a
sustained low-carbon path without sacrificing economic growth. It also highlights the
Government of India policies and interventions that spur energy efficiency and GHG
reduction activities in the sector eventually leading to improving energy security.
1.3 METHODOLOGY
For preparing this manual, the following methodology was adopted:
• Sector reports were prepared with inputs from questionnaire survey, detailed field
visits and audits, workshops and guidance from steering committee.
5
• The synopses of the reports were extracted to prepare this manual for comprehensive
presentation of information and provide guidelines for implementation of GHG
emission reduction options.
• Feedback on the manual contents and the material was sought and received from
industries, Alkali Manufacture’s Association, and other stakeholders and the same
was incorporated in the final manual
1.4 GREENHOUSE GASES AND ITS IMPACT
Over the last 100 years, it has been found out that the earth is getting warmer and warmer,
unlike previous 8000 years when temperatures have been relatively constant. The present
temperature is 0.3−0.6 °C warmer than it was 100 years ago. The key greenhouse gas (GHG)
causing global warming through human enhanced GHG effect is carbon dioxide.
The natural greenhouse effect is the process by which radiation from the earth's atmosphere
warms its surface to a temperature above what it would be without its greenhouse gases
naturally present in the atmosphere. The greenhouse gases naturally present in the
atmosphere include carbon dioxide, water vapor, methane, nitrous oxide, and ozone.
Certain human activities add to the levels of most of the naturally occurring gases. For
example, carbon dioxide is released to the atmosphere when fossil fuels such as oil, natural
gas, coal, wood etc are burned. The enhanced greenhouse gas effect is the further rise in
average earth’s temperature due to increase in the amount of carbon dioxide and other
greenhouse gases in the earth's atmosphere due to human activities. Both these effects are
depicted in Figure 1.2.
Figure 1.2 Natural and Human Enhanced Greenhouse Effect
Green House Gases (GHG) is of two types namely direct and indirect. Direct GHG contribute
directly to the greenhouse effect in the atmosphere by trapping the infrared radiation near the
6
earth’s surface. The major GHG gases identified by Intergovernmental Panel on Climatic
Change (IPCC) are carbon dioxide, methane, nitrous oxide, hydrogen fluorocarbons, per
fluorocarbons, sulphur hexafluoride.
Indirect GHG control the oxidising capacity of the troposphere by reducing the hydroxyl
radical distribution thereby increasing the residence time of direct greenhouse gases, such as
methane and ozone. Although there are a number of ways of measuring the strength of
different greenhouse gases in the atmosphere, the Global Warming Potential (GWP) is the
most used indicator.
GWP depends upon the greenhouse gas ability to absorb heat in the atmosphere. HFCs and
PFCs are the most heat-absorbent. Methane traps over 21 times more heat per molecule than
carbon dioxide, and nitrous oxide absorbs 270 times more heat per molecule than carbon
dioxide. The GWPs for different GHGs are presented in Table 1.1.
Table 1.1 Direct and Indirect Green House Gases and its GWP
GHG Name Common Sources Atmospheric Global
Lifetime Warming
(years)* Potential
CO 2 Carbon Dioxide Fossil fuel combustion, forest 50-200 1
clearing, cement production etc.
CH 4 Methane Landfills, production and 12 21

distribution of natural gas and
petroleum, fermentation from the
digestive system of livestock, rice
cultivation, fossil fuel
combustion, etc.
N2O Nitrous Oxide Fossil fuel combustion, fertilizers, 150 310
nylon production, manure, etc.
HFC's Hydro Refrigeration gases, aluminum 264 Up to

fluorocarbons smelting, semiconductor 11,700
manufacturing, etc.
PFC's Per fluorocarbons Aluminum production, 10,000 Up to 9200
semiconductor industry, etc.
H2 Hydrogen Chlor alkali production etc 100 5.8
The Figure 1.3 shows comparison of per capita CO 2 emission for the top five GHG emitting
countries of the world and EU. India—owing to higher population—per capita CO 2 emission
is the least. However, in terms of absolute emissions India is the third largest CO 2 emitting
7
country, behind the US and China (2015) and contributing about 6 % (2.3 Gt CO 2 ) of global
emissions (WEO 2015).
Figure 1.3 Per capita CO 2 Emissions
Impacts of Global Warming
Rise in Global Temperature

Observations show that global temperatures have risen by about 0.6 °C over the 20th century.
There is strong evidence now that most of the observed warming over the last 50 years is
caused by human activities. The various climate models predict that the global temperature
will rise by about 6 °C by the year 2100.
Rise in Sea Level

In general, the faster the climatic change, the greater will be the risk of damage. The mean
sea level is expected to rise 9−88 cm by the year 2100, causing flooding of low lying areas
and other damages.
Food Shortages and Hunger

Water resources will be affected as precipitation and evaporation patterns change around the
world. This will affect agricultural output. Food security is likely to be threatened and some
regions are likely to experience severe food shortages and hunger.
Models also predict an average increase in temperature in India of 2.3−4.8oC for the
benchmark doubling of carbon dioxide scenario. It is estimated that 7 million people would
be displaced, 5700 km2 of land and 4200 km of road would be lost, and wheat yields could
decrease significantly.
8
Due to rising energy demand, India’s CO 2 emissions are expected to grow at the rate of 7%
and surpass the present EU-28 emissions by 2020. As a part of mitigation effort, India is
committed to increase its share of non-fossil energy sources from current 19% to 40% by
2030. However, combustion of fossil fuel will continue to be the single major contributor to
the global warming in the coming years and hence the focus is on efforts to opt for renewable
energy and enhance energy efficiency.
1.5 OUTLINE OF ENERGY SCENARIO IN INDIA
The energy mix of India for 2013 presented in the pie chart (Figure 1.4) indicates fossil fuel
is the main stay of India’s energy mix.
Figure 2.4 Primary Energy Demand in India for 775 MTOE

(Source : IEA, 2015)
Industrial energy demand has almost doubled over the 2000-2013 period, with strong growth
from coal and electricity. Large expansion in the energy-intensive sectors is anticipated in the
future. The present energy consumption in these energy intensive sectors in the country is
high compared to the developed world. The major energy consuming sectors in the country
are Iron & Steel, Chemicals, Textiles, Aluminium, Fertilizers, Cement & Paper. These sectors
account for about 60% of the total energy consumption in industry. The energy consumption
in manufacturing is relatively high in India which is reflected in the Specific Energy
Consumption (SEC). This, therefore, provides an opportunity to reduce energy consumption
and thereby GHG emissions. The typical SECs in different manufacturing sectors is
presented in Table 1.2.
9
Table 1.2 Specific Energy consumption in Energy Intensive Industries
Sl. Industrial Sector Specific Energy Consumption (SEC)
No.
India World
1 Iron and Steel 6.5–7.0 GCal/Ton 4.5–5.5 GCal/Ton
2 Cement 80 kWh/T 110 kWh/T
3 Aluminium 4300 kWh/T (Refinery) 3850 kWh/T (Refinery)
16500 kWh/T (Smelter) 15250 kWh/T (Smelter)
4 Fertilizer 7.7 GCal/T of Urea 6.5 GCal/T of Urea
5 Paper and Pulp 8.4 Steam consumption/Ton 4.5 Steam

consumption/Ton
6 Textile 7.1 GCal/Ton 3.1 GCal/Ton
7 Chlor Alkali 3.1 GCal/T (Soda ash) 2.6 GCal/T (Soda ash)
2.1 GCal/T (Caustic Soda) 1.8 GCal/T (Caustic Soda)
Energy Conservation and GHG Emission Reduction Initiatives by Government
The major policies that are currently promulgated and being implemented to meet the energy
and climate challenge are summarized in Table 1.3.
Table 1.3: Government Policies and Initiatives for Energy Conservation

Policy /Initiative Statement Key Features of the Policy
Energy Policies
1. National Electricity Policy • Access to Electricity - Available for all households in next
five years
2. National Rural • Availability of Power - Demand to be fully met by 2012.
Electrification Policy Energy and peaking shortages to be overcome and adequate
spinning reserve to be available.
• Supply of Reliable and Quality Power of specified standards
in an efficient manner and at reasonable rates.
• Per capita availability of electricity to be increased to over
1000 units.
10
3. National Tariff Policy • Minimum lifeline consumption of 1 unit/household/day.
2006 • Financial turnaround and commercial viability of electricity
Sector.
• Protection of consumers’ interests.
Industrial Energy Efficiency Programs
1. National Mission for • Market-based approaches to unlock energy efficiency
Enhanced Energy opportunities, estimated to be about Rs. 74,000 crores (2014-
Efficiency (NMEEE) 15)
(a) Market Transformation • Annual fuel savings in excess of 23 million toe
for Energy Efficiency • Cumulative avoided electricity capacity addition of 19,000
(MTEE) MW
(b) Energy Efficiency • CO 2 emission mitigation of 98 million tons per year
Financing Platform
(EEFP)
(c) Perform, Achieve, and
Trade (PAT) Mechanism
for Energy Efficiency
2. National Mission on Works on Municipal Solid Wastes, urban storm water & water
Sustainable Habitat mgmt. & energy efficiency
(NMSH)
3. Energy efficiency • BIS: formulations and implementations of national
Standards and Labelling standards/production, quality and EMS certifications
Program BEE : key thrust of EC Act, 2001
1. Capacity Building for • Build capacity at the State and Central level, and develop a
Industrial Pollution framework to address these issues in a comprehensive and
Management systemic manner under an area-wide management approach.
• The proposed project is aligned with the endeavour of the
GoI to establish a National Program for Rehabilitation of
Polluted Sites (NPRPS) as a framework for scaling up clean-
up and rehabilitation of polluted sites and facilitate the
reduction of environmental and health risks associated with
legacy polluted sites.
Capping, Trading and Taxing
1. Tax on Coal to Fund All means to instil price signals to spur energy efficiency and
Clean Energy using cleaner fuels
11
2. Renewable portfolio • States can choose to apply the RPS requirement to all its
standards/obligation utilities or only the investor owned utilities.
• Renewable Purchase • States can also define what technologies are eligible to count
Obligation (RPO) under towards the RPS requirements.
the Electricity Act 2003
is mandated at the state
level (discussed below
in “National Policies
Implemented at the State
Level”)
3. RECS (Renewable •Aimed at addressing the mismatch between availability of RE
Energy certificate resources in state and the requirement of the obligated
System) entities to meet the renewable purchase obligation (RPO)
• Cost of electricity generation from renewable energy sources
is classified as cost of electricity generation equivalent to
conventional energy sources and the cost for environmental
attributes.
• Two categories of certificates, viz., solar certificates issued to
eligible entities for generation of electricity based on solar as
renewable Cost of Electricity Generation by Renewable
Sources Cost Equivalent to Conventional Source Cost for
Environmental Attributes energy source, and non-solar
certificates issued to eligible entities for generation of
electricity based on renewable energy sources other than
solar
Subsidies for Energy Conservation
1. Financial incentives • Creating capacity in the area of solar, wind, bio-mass and
through the Jawaharlal other forms of renewal energy generation
Nehru National Solar • Supports financially as well as technically to promote solar
Mission heater other solar applications widely in the country and
2. Financial incentives by particularly in the areas where conventional energy is not
the Ministry of New and possible to supply
Renewable Energy • Long term energy security
through the Indian • Ecologically sustainable growth
Renewable Energy • Set target-20,000MW
Development Agency
Energy Conservation in Buildings and Municipalities

Energy Conservation • Provide technical support to BEE to implement the ECBC in
Building Code a rigorous manner
• Develop reference material and documentation to support the
Code
12
• Develop ECBC Training material for workshops and training
programs
• Develop a road map for ECBC implementation
1. Municipal Demand-Side Municipal Demand Side Management (MuDSM) is devised to
Management take care of the most common and other issues which are seen as a
hurdle by the Municipality to shift itself towards the energy
2. State Energy efficient zone from the existing situation of high amount of energy
Conservation Fund consumption.
Energy Conservation in Agriculture and Forestry Activities
Agriculture, forestry, and • Consists of those activities, methodologies, awareness, policy
other land use policies and technologies that influence consumer (farmers)
behaviour and changes their (farmers) consumption patterns.
1. Agricultural Demand -
Side Management • The objective of the AgDSM programme is to reduce peak
(AgDSM) demand, shift the time during which electricity is consumed
2. National Mission for to off-peak hours and to reduce the total quantum of
Sustainable Agriculture consumption.
3. National Mission for a
Green India
1.6 GHG EMISSION FACTORS
The emission factors considered for calculations in this manual are tabulated in Table 1.4
(CEA, 2014).
Table 1.4 Typical GHG Emission Factors

No. Parameter Units Factor
1 Grid Electricity Kg CO 2 /kWh 0.82
2 CPP Electricity
a) Coal Fired Kg CO 2 /kWh 1.03
b) Diesel Fired kg CO 2 /kWh 0.62
c) Gas Fired kg CO 2 /kWh 0.49
3 Coal (Sub-bituminous) kg CO 2 /kg 1.1
4 Diesel/Furnace oil kg CO 2 /kg 3.12
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2. CHLOR ALKALI SECTOR PROFILE
2.1 INTRODUCTION
The chlor-alkali industry in India is around 60 years old. There are around 37 caustic soda
units spread across India with total installed capacity of 3.20 MMT per annum with the top
10 chlor-alkali plants producing about 60% as shown in Table 1.1. Most of the units have a
capacity under 100,000 MTPA with capacity utilisation in the range 79-85%. The Table 2.1
shows the number of plants in India along with their total capacity.
Table 2.1 Distribution of Chlor Alkali Plants in India

Region No of Capacity range Total Installed Capacity Installed Capacity
plants TPD TPD Distribution (%)
East 8 40-365 1147 13
West 16 40-800 4615 52
North 4 235-335 1171 13
South 9 110-375 1943 22
As can be seen from Figure 2.3 more chlor-alkali industries are located in western Zone
(54%) followed by South with 21%. This can be attributed to two factors namely, availability
of salt, the main raw material for the industry and location of user industry in the area.
2.2 CAPACITY UTILIZATION
The average capacity utilization in the Indian industries is around 67.5 %.(2009-14) with
installed capacity remaining stagnant since 2011-12 owing to economic downturn world over
and reduced off-take from industries like aluminium. The Figure 2.1 shows production vs.
capacity utilization for the period 2009-2014.
14
3.5
2.5
Thousand MT
1.5 Installed Capacity

Production
1
0.5
0
2009-10 2010-11 2011-12 2012-13 2013-14
Source:Annual Report-Chlor-Alkali industries
Figure 2.1 Installed Production vs. Capacity (2009−2014)
Segregation of chlor-alkali plants is done based on scale of production is shown in Table 2.2.
Since membrane process is the only used technology in India currently, classification is made
based on this basis.
Table 2.2 Capacity Based Segregation (2013-14)
Process <100 TPD 100-500 TPD1 >500 TPD1

Nos of units 5 21 6
Installed Capacities(TPY) 85675 19,05,610 12,33,500
Annual Energy Consumption <12000 15000-90000 35000-1,12,000
range (TOE)
Specific Energy Consumption NA 0.335-0.310 0.227-0.310
(TOE/T)
Annual GHG emission range, <0.129 0.162-1.047 0.408-1.302
(Million Tons ofCO 2 )
NA= Not Available; 1= D
15
2.3 USES OF CAUSTIC AND CHLORINE
Sodium Hydroxide or caustic soda is an important chemical which is used in various sectors
namely pulp & paper, alumina, soaps & detergents, inorganic chemicals, etc. About 25% of
the production used for captive consumption while the rest is used for merchant trade.
The use of caustic sector-wise is shown in Table 2.3. The level of integration for chlorine in
India is very low as compared to West Europe and North America, which have an integration
level of about 86% and 52%, respectively. While plants outside India are Chlorine centric,
plants in India are Caustic centric. These plants co-produce chlorine in the ratio of 1:0.89.
All plants are running on state of the art energy efficient membrane cell technology.
Table 2.3 Breakup of Caustic Consumption in Different Industrial Sectors

Alumina 14% Textiles 21%
Pulp and Paper 15% Dyes & Inks 3%
Organics 12% Water treatment 3%
Inorganics 8% Pesticide 1%
Soap and Detergents 7% Others 16%
Textile industry followed by pulp and paper and aluminum industries account for the largest
share of caustic soda consumption. The different uses caustic soda and chlorine are given in
Table 2.4.
Table 2.4 Uses of Caustic and Chlorine for Various Products/Applications
USE/INDUSTRY PRODUCTS OR APPLICATIONS OF USE
Production of metals Alumina, propylene oxide, polycarbonate resin, epoxies, synthetic

and resource fibers, soaps, detergents, rayon and cellophane.
Caustic soda is used for pulping wood chips. Chlorine and its
Pulp and paper industry
compounds are used to bleach wood pulp in the paper production.
Petroleum and natural gas Caustic soda is used as a drilling fluid.
Manufacture of Chlorine is used for making ethylene dichloride, glycerin,

organic chemicals glycols, chlorinated solvents and chlorinated methane.
Used for making plastics, most notably polyvinyl chloride (PVC),
Plastic industry which is being used extensively in building and construction,
16
Pesticides 96 per cent of all pesticides are produced using chlorine
A variety of chlorinated compounds are used as industrial

Industrial solvents
solvents, including the main ingredient used in dry cleaning.
Water treatment Chlorine is used in 98 per cent of the water treatment plants in the
world.
Pharmaceuticals 85 per cent of all pharmaceuticals use chlorine.
Domestic bleaches, flame-retardants, food additives,

Other relevant applications
refrigerants, insulation, computer chip manufacturing and
hospital disinfectants.
Chlor-alkali sector provides direct & indirect employment to about 1.5 lakh people. Nearly
50,000 people including contract labour work in the units manufacturing caustic soda and
soda ash plants. In the XIIth Five Year Plan, the industry envisages employment increase to
the extent of 5%.
2.4 EXPORTS AND IMPORTS
The Figure 2.2 shows the export and import trend over the period 2009-2014.
400
300
200 IMPORTS(1000MT)
100 EXPORTS(1000MT)
0
2009-10 2010-11 2011-12 2012-13 2013-14
Figure 2.2 Indian Imports & Exports of Caustic Soda
2.5 PERFORMANCE AND PRODUCTIVITY INDICATORS
Labour Productivity
Labour productivity trend indicates production of 56-65 MT/quarter per employee as per
DGFT reports shown in Table 2.5 which translates to 0.85-1 T NaOH/ employee. Some units
during survey have indicated the labour productivity is 0.35 T NaOH/ employee. The labour
productivity of European plants reported in BREF is 0.65 T NaOH/ employee.
17
Table 2.5 Labour Productivity
Productivity (Production/employee) MT per Quarter
Quarter 2006-07 2007-08 2008-09 2009-10
Q1 56.03 59.67 65.16 63.30
Q2 57.46 62.54 66.77 65.14
Q3 60.25 63.15 59.97 -
Q4 62.11 65.17 62.28 -
From the above table, the labour productivity is showing increasing trend over the years. The
variations in labour productivity may also be due to restriction in production due to difference
in chlorine and caustic prices at global level.
Energy Consumption of Chlor-alkali Industry
The raw material involved in the production of caustic soda is salt and water. Electric energy
is used in conversion of salt into caustic soda lye, chlorine and hydrogen gas. Thermal energy
is used in brine preparation and preparing flakes from lye. In most units hydrogen generated
is used as fuel to concentrate lye and produce caustic flakes. This is an energy intensive
process where energy costs accounts for 50-60% of total production cost based on cost of
power.
The electrolysis phase is the most energy intensive phase. This process involves conversion
of AC power to DC power through a rectifier and involves electric conversion losses.
Amongst the chlor alkali processes the membrane cell process produces30-35% NaOH
concentration and thus the thermal energy required to concentrate the lye to the saleable
product concentration is much less in membrane process compared to diaphragm process.
Specific Energy Consumption
Grid power cost in India ranges from Rs. 3.85 to Rs. 6.0 as compared to Rs. 0.8 in Middle
East, Rs. 2.25 in USA and Rs. 1.98 in Europe making energy conservation and energy
efficiency attractive in Indian chlor-alkali industries.
The specific energy consumption range for chlor-alkali process in relation to the scale of
production is shown in Figure 2.3.
18
SEC vs PRODUCT OUTPUT
0.36
CONSUMPTION,TOE/T
0.34
SPECIFIC ENERGY
0.32
0.3
0.28
0.26
0.24
0.22 y = -1E-07x + 0.3229
0.2 R² = 0.1275
0 50,000 100,000 150,000 200,000 250,000 300,000
PRODUCT OUTPUT,T
Figure 2.3 Specific Energy Consumption vs. Production
As can be seen the correlation of SEC with respect to scale of production is not strong. It is
seen that an average of 5-11% savings in specific energy consumption can be achieved in
80% of the production units. The considered bandwidth comprises of the specific energy
consumption variations between efficient and inefficient technologies.
The variations in specific energy consumption can be attributed to economies of scale,

different cell generation technologies, improved rectifiers, adopting zero gap technology and
ODC technology each of which represent options to conserve energy by units having higher
specific energy consumption.
As per BEE PAT reports, specific energy consumption varies between 0.262 and 0.997
TOE/T of NaOH. Energy saving target of 0.054 MTOE/yr. which is 5% less than it was in
2008-09 was given by BEE under PAT scheme. This constitutes 0.81% of total national
energy saving targets assessed under PAT. The section-wise breakup of energy consumed in
chlor-alkali sector is shown in Table 2.6.
Table 2.6 Typical Section-wise Break-up of Energy Consumption

Section Energy kWh/T NaOH %
Primary & Secondary Brine plant 22.84 0.75
Membrane Cell plant 2784.47 90.91
Chlorine Treatment plant 84.52 2.76
Caustic Concentration unit 8.69 0.28
Caustic Evaporation unit 6.24 0.20
Waste water Treatment plant 5.01 0.16
19
Sodium Hypo plant 3.22 0.11
Utility plants 147.72 4.82
Total 3062.72 100
Energy Consumption Trend in Various Generations of Membrane Cells
The membrane cell has developed continuously since its broad scale implementation in the
1980s. The initial developments focused on anode and cathode coatings, membrane types,
reduction of the cathode-membrane gap, electrolyte circulation in the cells, and gas release
from electrodes and membranes.
In the 1990s, the electric resistance in the cell structure was decreased by gradually switching
from monopolar to bipolar electrolyser configurations. Due to these developments, there was
also an increase in the maximum current density which could be applied. The impact of these
developments on the specific electricity consumption is shown in Figure 2.4.
2200
POWER CONSUMPTION
2130
(kWh/t NaOH
2070
2100
2055
2035
2000
4 5 5 PLUS 6
GENERATION
Figure 2.4 Power Consumption (kWh/t NaOH) Trend
2.6 BENCHMARKS FOR CHLOR-ALKALI INDUSTRY
Water conservation and benchmarking to world standards improves not only water
productivity but also energy productivity due to lesser pumping and treatment costs. The best
benchmarks cited are tabulated in Table 2.7.
20
Table 2.7 Best Benchmarks for Chlor-Alkali Industry
Section/ Process Comparable Benchmarks
Labour productivity3 0.65-1.0 T NaOH per employee
#Total Water requirement 5.9 m3/T NaOH (48% lye )
• Process water 2-2.25 m3/T NaOH
• Cooling Water6 2.5-2.9 m3/T NaOH
• Domestic Water9 0.045 m3/T NaOH (45 lpcd)
Total Energy Requirement8 3040kWh/T NaOH(0.262 TOE/T NaOH)
(Low end of BEE target)
Water treatment 1.3 kWh/T NaOH
Brine purification 2.5 kWh/T NaOH
Cell house (design stage) kWh/T NaOH @ CD of 6.0 KA/m2
• Mono-polar membrane 2550 (@CD of 4KA/m2)
• Mono-polar – zero gap 2470 (@CD of 4KA/m2)
• Bipolar 4th Gen zero gap 2130
• Bipolar 5 Gen zero gap
th 2070
• Bipolar 6th Gen zero gap 2020 - 2035
• ODC 1550
Caustic concentrator – Steam Economy 3 effect: 0.5-0.4
(Steam to vapour ratio) 4 effect:0.29
5 effect: 0.23
i
Energy required for flaking 95 kWh/ T NaOH ( Best benchmark reported)
Chlorine liquefaction – Energy requirement 120-200 kWh/ T NaOH
for 98% liquefaction.
Boiler efficiency 80%
Pump efficiency 65%
#Total water requirement assessment is based on the following
1 T lye (48%) produced,
97.5% Cl 2 generated is liquefied
2% of un-liquefied Cl 2 is converted to 33% HCl
0.5% of un-liquefied Cl 2 coming through vents is converted to 18% NaOCl
3-Stage
21
3. CHLOR-ALKALI MANUFACTURING PROCESS
3.1 OVERVIEW OF CHLOR-ALKALI PRODUCTION
The schematic of chlor-alkali manufacturing process is shown in Figure 3.1. The main raw
material for chlor-alkali production is brine. The brine (NaCl) is sent to electrolytic cell
where it is electrolysed to form caustic soda (NaOH). Additionally chlorine and hydrogen
gases are evolved. Chlorine is directly sold as a by-product after liquefaction. Hydrogen is
partly used as fuel in the boiler and partly converted to HCl. Excess hydrogen is vented.
Figure 3.1 Schematic of Chlor-alkali Manufacturing Process
22
3.2 BRINE PREPARATION
Raw salt is mixed with treated water to prepare saturated brine solution (300-330 gpl) which
is then purified to reduce the concentration of impurities (Ca, Mg, Ba, Sr, and metals) to the
desired levels required for the electrolytic process.
The treatment is done in two steps, primary and secondary. In the primary treatment, Mg, Ca,
Sr, SO 4 are removed and in the secondary treatment trace levels of the above impurities are
removed to meet the purified brine quality requirements. The brine preparation and
purification is shown in Figure 3.1.
Maintaining the efficacy of each treatment will reduce load on downstream treatment but also
reduces energy requirements due to lesser brine depletion requirements and increased brine
treatment requirements.
Figure 0.1 Brine Preparation and Purification
23
3.3 CELL HOUSE
The purified brine at 65-70ºC is fed into the electrolyser or cell house. The brine is
decomposed mainly into caustic, chlorine and hydrogen. The side reactions cause release
oxygen, chlorate, etc. The reactions involved are as follows:
Anode Cl 2(g) + 2 e- 2Cl- (aq)

Cathode Cl 2(g) + 2 e- 2Cl- (aq)
Overall reaction 2 NaCl (aq) + 2 H 2 O (l)  2 NaOH (aq) + Cl 2(g) + H 2 (g)
Energy supplied in AC form is transformed into DC form in rectiformer for decomposition of

brine. Electrical energy losses and inefficiencies occur due to the following reasons.
• Rectiformer energy losses during conversion from AC to DC.

• Increasing energy consumption over time due to aging of membranes and electrodes.
• Energy losses due to undesirable side reactions.
The power consumption is reported as DC/AC kWh/ton of caustic in Indian Chlor-alkali

plants whereas in European countries it is reported in DC/AC kWh/ton of chlorine.
The theoretical voltage requirement for decomposition of brine is 2.2V. In practice, the
decomposition voltage requirement varies from 3.5V - 2.9V. The theoretical DC energy
requirement is 1474 kWh/ton of caustic (100%) or 1663 kWh/ton of Cl 2 (100%).
The consumption of electricity is also influenced by current density, brine feed temperature,
coating of electrode.
Relationship between Cell Voltage and Current density 2
The operating cell voltage is a function of current density. At current densities above 1
KA/m2, the operating cell voltage varies almost linearly with the current density. It can be
expressed by the following relationship:
U cell = U o + k * i volts
U o denotes the cell decomposition voltage whereas i denotes the current density. The values
of U o and k depend on the different cell parameters and electrolysis conditions. The typical
values for a bi-polar cell process are as follows:
U o = 2.42 volts, k = 0.217 volts x m2 /KA
2
Source: AMAI, Delhi
24
The effect of current density on cell voltage can be determined by the empirical equation as
given by the following relation:
E= 2.41 + 0.329 i + 0.24 log i
𝟔𝟔𝟔𝟔𝟔𝟔 ∗ 𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪 𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗𝒗

𝑨𝑨𝑨𝑨𝑨𝑨𝑨𝑨𝑨𝑨𝑨𝑨 𝑫𝑫𝑫𝑫 𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷 𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪 =
𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪 𝐄𝐄𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇
Where,
E = Cell voltage (V)
I = Current density (kA/m2)
Relationship between Life of Electrode and Power Consumption
The effect of coating of electrodes life on power consumption is given by the following
relation:
𝑃𝑃𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪 (𝒌𝒌𝒌𝒌𝒌𝒌/𝑻𝑻 𝑵𝑵𝑵𝑵𝑵𝑵𝑵𝑵)
= 𝑭𝑭𝑭𝑭𝑭𝑭𝑭𝑭𝑭𝑭 𝒚𝒚𝒚𝒚𝒚𝒚𝒚𝒚 𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑 𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄 (𝒌𝒌𝒌𝒌𝒌𝒌/𝑻𝑻 𝑵𝑵𝑵𝑵𝑵𝑵𝑵𝑵) + 𝟑𝟑𝟑𝟑3
Where, n= life of the membrane in years
Relationship between Brine Temperature and Power Consumption
Reduction in feed brine temperature will increase the specific energy consumption. The effect
of brine feed temperature on power consumption is given by the following relation:
𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷 𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪𝑪 (𝒌𝒌𝒌𝒌𝒌𝒌/𝑻𝑻 𝑵𝑵𝑵𝑵𝑵𝑵𝑵𝑵) = 𝟏𝟏. 𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝐓𝐓 𝟐𝟐 − 𝟐𝟐𝟐𝟐𝟐𝟐. 𝟖𝟖𝟖𝟖𝟖𝟖 + 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏
Where, T = Temperature of Brine feed in ℃
3
The equation is based on best yearly cumulative value of power rise due to ageing of membranes. However, on an average
the power rise is reported by AMAI is in the range of 40 – 60 kW/T/year
25
Power consumption kWh/T NaOH
3000
Power Consumption 2800
2600
2400
2200
2000
60
62
64
66
68
70
72
74
76
78
80
82
84
86
88
90
92
94
96
98
100
Temperatuce ºC
Figure 3.2 Graph on Brine Temperature v/s Power Consumption
Back migration of NaOH to Cathode causes formation of O 2 , OCl-, and ClO 3 . The back
migration and side reactions cause 3-7% loss of current efficiency with respect to caustic
production. The reaction governing side reactions are given as follows:
HOCl  OCl- + H+
2HOCl + OCl-  ClO 3 + 2H+ + 2Cl-
2H 2 O  O 2 + 4H+ + 4e-
Assessing Cell House Performance
Assessing the current efficiency of the cell house is important to operate the cell house
efficiently and to determine the power consumption. The assessment can be made by direct or
indirect method.
The direct method is the simplest method to calculate the current efficiency and it is based on
the mass of product produced per unit of electrical input. However, the NaOH (100%)
production of a cell house cannot be measured with sufficient accuracy to give meaningful
results.
Direct Method
𝐾𝐾𝐾𝐾 𝑜𝑜𝑜𝑜 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 (%) = 𝑥𝑥100
𝐾𝐾𝐾𝐾 𝑜𝑜𝑜𝑜 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑡𝑡ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
To resolve this problem, the chlor-alkali industry uses indirect method which is an anodic
balance approach, i.e., the compositions of the anode gas and the anolyte. The formulae used
for efficiency assessment and the model calculation are given below.
26
Indirect Method
𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶 ℎ𝑜𝑜𝑜𝑜𝑜𝑜 (%) = 100 − 𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶 − 𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶3 − 𝜂𝜂𝑂𝑂2 − 𝜂𝜂𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
Where,
𝐾𝐾𝐾𝐾 𝑜𝑜𝑜𝑜 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁

𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶 = 𝑥𝑥100
1.492 𝑥𝑥 𝑄𝑄 𝑥𝑥 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 𝑜𝑜𝑜𝑜 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
1.042 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶 = 𝑥𝑥100
𝑄𝑄 𝑥𝑥 2 𝑥𝑥 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 𝑜𝑜𝑜𝑜 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
1.97[�𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶3 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑥𝑥 𝑉𝑉𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 � − �𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶3 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑥𝑥 𝑉𝑉𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 �]

𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶3 = 𝑥𝑥100
𝑄𝑄 𝑥𝑥 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 𝑜𝑜𝑜𝑜 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
2𝑉𝑉𝑂𝑂2 (100 − 𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶 − 𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶3 )

𝜂𝜂𝑂𝑂2 = 𝑥𝑥100
(𝑉𝑉𝐶𝐶𝑙𝑙2 + 2𝑉𝑉𝑂𝑂2 )
[𝐶𝐶𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 + 0.7548 𝐶𝐶𝑁𝑁𝑁𝑁2𝐶𝐶𝐶𝐶3 + 0.4762 𝐶𝐶𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 3 ]𝑥𝑥𝑉𝑉𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑥𝑥 100

𝜂𝜂𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑥𝑥100
1.4923 𝑥𝑥 𝑄𝑄 𝑥𝑥 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 𝑜𝑜𝑜𝑜 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Where,
𝜂𝜂𝐶𝐶𝐶𝐶𝐶𝐶3,𝑂𝑂2,𝐶𝐶𝐶𝐶𝐶𝐶 Current efficiency loss due to chlorate, oxygen, ClO formation
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶3,𝐶𝐶𝐶𝐶𝐶𝐶 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ,𝐶𝐶𝐶𝐶𝐶𝐶3 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 Concentration of ClO 3 , ClO in the anolyte, feed brine (grams/ liter)
𝑉𝑉𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 ,𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 Volumetric flow rate of the anolyte, feed brine (m3/hr)
𝑉𝑉𝑂𝑂2, 𝐶𝐶𝐶𝐶2 Volume of O 2 , Cl 2 in the anode gas composition (%)
𝜂𝜂𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 Current efficiency due to alkali (NaOH, NaHCO 3 and Na 2 CO 3 )
𝐶𝐶𝑁𝑁𝑁𝑁2𝐶𝐶𝐶𝐶3,𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 3,𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 Concentration of NaCO 3 , NaHCO 3 , NaOH in the feed brine
(grams/litre)
Sample Calculation
Analysis Data Field Data

𝐶𝐶𝑁𝑁𝑁𝑁2𝐶𝐶𝐶𝐶3 0.212 gpl 𝑉𝑉 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 3 m3/hr
𝐶𝐶 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 0.0005 gpl 𝑉𝑉𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 2.36 m3/hr.
𝐶𝐶𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 3 5 gpl Q 61.5 kA
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶3 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 10.604 gpl Number of cells 3
𝐶𝐶 𝐶𝐶𝐶𝐶𝐶𝐶3 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 7.6 gpl Cell voltage 2.7 V
670 ∗ 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣

𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐷𝐷𝐷𝐷 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 =
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐷𝐷𝐷𝐷 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶

𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝐴𝐴𝐴𝐴 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 =
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑦𝑦
Cell Current efficiencies are seen to range from 92% to 96% mainly variant with type of
coatings deployed, condition and frequency/periodicity of recoating.
27
3.4 CAUSTIC CONCENTRATION
Electrolysis of brine yields 32% caustic. This is concentrated to 48% using 3 to 5 stage
multiple effect evaporators or concentrated to 98% by further concentrating the 48% lye. In
Indian chlor-alkali plants, 3-stage falling film evaporators are generally being used for
evaporating the 32% caustic solution to 48% concentration as they have better heat transfer
coeeficient and less fouling tendency. Low pressure steam is used for concentration in the
evaporators.
This 48% lye is sold out or it is fed to the flaking unit to produce flakes using thermic fluid
heaters. The concentrated high temperature anhydrous caustic soda is cooled in rotary flaker
by cooling water and converted into caustic soda solid flakes at their fusing point
temperature. The process flow diagram for concentrating 32% lye to 48% is shown in Figure
3.3 and the process of caustic fusion is shown in Figure 3.4.
28
32% Caustic 36% Caustic 42% Caustic
13.9TPH, 95°C 11.9TPH, 144°C
15.6TPH, 78°C
75°C 1
32°C
117°C
CW in Surface condenser 168°C
Evaporator -1
Evaporator -3
Evaporator -2
CW out
33°C
680mmHg 680mmHg 680mmHg
Sep-3
Sep-2
Sep-1
60°C
Steam
47°C
2.6 TPH, 198°C
10.42TPH, 85°C 10.42TPH, 170°C
Solution Heater-
Solution heater-2
Product cooler
Flash
Process 2 steam
condensate 13.9TPH, 11.9TPH,
72°C 120°C
10.42TPH,
170°C
1
CW in
34°C
CW out 0.47 TPH Steam

39°C 100°C condensate
Figure 3.3 Process Flow Diagram for Caustic Concentration
29
Sugar@5%
Vapour
Pre-concentrator
@300°C
48% to 57%
48%
Lye
Tank
Furnace oil/Hydrogen
Chimney
Condensate
@90°C
Final Concentrator
90°C
57% to 98%
Hot Air 400°C
Air pre- Salt

Heater 98% molten caustic @ 350°C
Heater
Flue
Gas
Distributor
Salt Tank
Hot water
@43°C Flaker Solid Caustic
Cooling
water@
Caustic Flakes, 33°C
98%
65°C
Figure 3.4 Process Flow Diagram of Caustic Fusion
30
Energy Consumption for Caustic Lye Concentration
Both steam and electricity is used for concentrating lye. The energy consumption in
concentrating lye is given in the following Tables:
Table 3.1 Basis and Assumptions for Assessment of Electrical Energy Consumption
For Caustic lye Concentration
Water to be
Basis TPD TPH
evaporated
Production 48% lye 250
32% 375 41.67
36% 333.33 47.62
42% 285.71 35.71
Total water evaporated 125
Steam Requirement (assuming 3
stage MEE and Steam economy
of 0.5) 62.5 2.6
Flash steam (assuming 18%) 11.25 0.47
Process and steam condensate
recovery (assumed) % 0.95
Process+ Flash steam condensate
Recovery 176.25 7.34
Process condensate loss 8.81
Process condensate loss /T NaOH 0.04
Formulae /Thumb-rule/
Constants
𝑄𝑄(𝑚𝑚3/𝑠𝑠)𝑥𝑥 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 ℎ𝑒𝑒𝑒𝑒𝑒𝑒 (ℎ𝑑𝑑 − ℎ𝑠𝑠, 𝑚𝑚)𝑥𝑥 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 (𝑘𝑘𝑘𝑘/𝑚𝑚3)𝑥𝑥 𝑔𝑔 (𝑚𝑚/𝑠𝑠2)

𝑃𝑃 (𝑘𝑘𝑘𝑘ℎ𝑟𝑟) =
1000 𝑥𝑥 𝜂𝜂𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑥𝑥 𝜂𝜂𝑀𝑀𝑀𝑀𝑀𝑀
𝐾𝐾𝐾𝐾 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑓𝑓𝑓𝑓𝑓𝑓 ℎ𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 (𝐾𝐾𝐾𝐾 )

Quantity of fuel required for salt heating� ℎ𝑟𝑟 � = 𝐾𝐾𝐾𝐾
𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 � �∗𝜂𝜂 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓
𝐾𝐾𝐾𝐾
g 9.81 m/s2
9700 kcal/Kg
LDO calorific value 40740 kJ/Kg
Cp (NaOH) 3.4 kJ/Kg. K
Cp (H 2 O) 4.2 kJ/Kg. K
Assumptions:
Pump efficiency factor 0.65
31
Motor efficiency factor 0.95 IE4
Vacuum pump efficiency 0.72
Boiler Efficiency factor 0.8
3-Stage MEE 0.5
4-Stage MEE 0.3
5-stage MEE 0.25 Kg steam/ Kg water evaporated/
Thermic Fluid heater (Furnace)
Efficiency 0.78
Cp/Cv 1.4
Mass rate of water vapour 186.86 Kg/hr
Table 3.2 Electrical Energy Requirement Assessment in Caustic Lye Concentration
Head Energy
Flow, Q Density (ρ)
Details (hd-hs) Consumption, P
m3/d m kg/m3 kW
32% Feed Pump-1 286.26 30.00 1310 49.65
Process Condensate Pump-1 176.25 30.00 1000 23.33
Vacuum Pump-1 16.59
Condensate Steam Pump-1 11.25 30.00 1000 1.49
Separator Pump-36% 245.64 30.00 1357 44.13
36% Feed Pump 238.10 30.00 1400 44.13
Vacuum Pump-2 16.59
42% Feed Pump 195.69 30.00 1460 37.83
Separator Pump-42% 195.69 30.00 1460 37.83
Vacuum Pump-3 16.59
48% Lye Pump 166.00 30.00 1506 33.10
Total energy consumption, kWh/day 321.24
SEC for 250 TPD of NaOH 1.28
GHG emission in kg of CO 2e (1 kWh = 0.91 kg CO 2 ) 1.17
Table 3.3 Thermal Energy Requirement Assessment in Caustic Concentration (lye )
Steam required T/250T NaOH T/T NaOH

MEE 62.5 0.25
VAM 0.5 0.002
OTHERS 0
Steam 63 0.252
Fuel used for steam generation LDO
Steam/Fuel 13
Fuel used for steam generation 4.85 0.02
Fuel used for salt heating 18.27 0.07
32
Table 3.4 Electrical Energy Requirement Assessment in Caustic Concentration (flakes)
Production (TPD) Water to be evaporated (TPH)

48% Caustic Lye 250
57% Caustic Lye 210.53 8.77
98% Caustic 122.45 5.10
Salt used for heating 57% lye 345.8 14.41
Formulae /Thumb-rule/ Constants

𝑘𝑘𝑘𝑘 𝐾𝐾𝐾𝐾
𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶, 𝑞𝑞(𝐾𝐾𝐾𝐾) = 𝑚𝑚 � � ∗ 𝐶𝐶𝐶𝐶 � � ∗ Δ𝑇𝑇(𝐾𝐾)
ℎ𝑟𝑟 𝐾𝐾𝐾𝐾. 𝐾𝐾
𝑄𝑄(𝑐𝑐𝑐𝑐𝑐𝑐 )𝑥𝑥𝑥𝑥𝑥𝑥 (𝑖𝑖𝑖𝑖𝑖𝑖 ℎ )

Blower Power, 𝑃𝑃(𝐻𝐻𝐻𝐻) =
6365𝑥𝑥 𝜇𝜇
g 9.81 m/s2
Cp (HT Salt) 0.32 kJ/kg K
Cp (HT Salt) 1.34 Kcal/kg ºC
Assumptions
Pump efficiency 0.65
Motor efficiency 0.95 IE4
Flow Head Density Energy
Details Q (hd-hs) (ρ) Consumption
m3/d m Kg/m3 kW
48% feed pump 166.00 30 1506 33.10
57% feed pump 135.82 30 1550 27.87
Salt pump 192.53 30 1796 45.78
Flaker blower 2.20
Flaker cutter motor 1.50
Total energy consumption, KWh/day 110.45
SEC for 250 TPD of NaOH 0.44
Table 3.1 Thermal Energy Requirement Assessment in Caustic Concentration (flakes)

Fuel for salt heating:
Mass of 57% caustic, TPH 8.77
Temperature of heated salt To, °C 350.00
Temperature of caustic flakes Ti, °C 90.00
Difference in temperature, °C 260.00
Heat energy consumed in final concentrator 7754385.96
Fuel for salt heating (kg/hr) 244.02
Fuel for salt heating (T/250T NaOH) 5.86
33
Table 3.6 Heat Transfer Salt Requirement
Mass of Diff in temp Diff in temp

Cp of NaOH Mass of HT salt Cp of HT salt
NaOH (NaOH) (HT salt)
Kg/hr. KJ/Kg K ºC Kg/hr. KJ/Kg K ºC
8750 3.4 =(350-90) 14408 1.34 =(400-30)
3.5 CHLORINE
Chlorine generated in cell house is partially dissolved in return brine solution and the
remaining is released as gas. Saturated chlorine is released from cell house at 80-90°C. It
contains brine mist, impurities like N 2 , H 2 , O 2 , CO 2 and traces of chlorinated hydrocarbons.
Chlorine is cooled to 18°C using chiller and dried using 96-98% H 2 SO 4 to avoid downstream
corrosion and minimise Cl 2 .nH 2 O formation. Six−stage H 2 SO 4 counter-current contact
towers are used to reduce water content to 20 mg/m3.
The dried Cl 2 is passed through demisters to remove H 2 SO 4 droplets. The dried Cl 2 is

compressed using centrifugal compressors by maintaining chlorine temperatures <120°C as
dry chlorine at high temperature react uncontrollably with iron. The compressed gas is cooled
to -13°C at 1 bar using any of the following liquefaction system (refer Table 3.7).
Table 3.7 Chlorine Gas Liquefaction

Liquefaction system Refrigerant Costs1
High pressure (7–16 bar) and High Water Low energy costs
temperatures (~40°C)
Medium pressure (2–6 bar)and Water, Moderate energy
medium temperatures (between - HCFC/HFC or costs
10°C and -20ºC) ammonia
Normal pressure (~1 bar) and low Mainly High energy costs
temperatures (below -40ºC) HCFC/HFC or
ammonia
Along with chlorine gas, ingress air constituting non-condensable gases is also present. After
liquefaction the non-condensable gases containing chlorine traces are scrubbed before
venting out to meet the emission standards for chlorine. These gases termed as tail gases are
absorbed in caustic solution to produce hypo or synthesized to produce other products like
HCl, bleach and FeCl 3 .
The process of chlorine liquefaction and scrubbing of tail gases is illustrated in Figure 3.5.
34
Depleted brine with chlorine Anolyte Extracted chlorine Cl2 from cell house
Vacuum
chamber
tank
DECHLORINATION Sodium bi sulphite

Lean brine Brine saturator
Sodium hydroxide
Chlorine primary
Chlorine cooling with cooling
compressor water
CHLORINE LIQUEFACTION
Recirculated Refrigerant
Liquid Liquefier Chlorine secondary
chlorine Compressor CW cooling with chilled
Unliquefied chlorine
Hydrogen 98%
Padding air
from cell H2SO4Tank
compressor Combustion chamber Chlorine to
house drying tower
98%
Bottlin CW in 78% H2SO4
Tank
Absorber-cooler CW out
HCl PRODUCTION Cl2 free
HCl storage tank
Chiller NP2
Tail gas NaOH 18% Scrubber
storage With NP3
NP1 NaOH
NaOCl
Figure 3.5 Process Flow Diagram for Chlorine Liquefaction
35
3.6 HYDROGEN GAS MANAGEMENT
During the caustic production in cell house, hydrogen is released along with chlorine. The
produced hydrogen is used in the following ways:
• Steam generation (15%)

• HCl production (64%),
• Bottled (7%), based on the market requirement and balance hydrogen is vented out
to atmosphere.
The percentage of vented hydrogen varies from plant to plant and averages about 14%.
3.7 UTILITIES
Water Treatment
Water is required mainly for brine operation. The number of water treatment steps
depends on water treatment method selected. In chlor-alkali plants, the treatment is
primarily focused to control calcium and magnesium. A typical water treatment system in
a chlor-alkali plant is as follows:
Clarifier  MG-Filter  Strong Acid Cation unit  Degasser  Strong base Anion unit
Alternatively, water can be treated using RO with 75% throughput followed by mixed bed
resin to reduce the chemical consumption. Considering the environmental effects of using
chemicals and life cycle analysis of entire water treatment system, this choice is better
despite higher energy consumption in RO treatment.
Since, most plants use ion exchange process for demineralisation, this manual covers
aspects pertaining to this process only. The process flow diagram given in Figure 3.6
depicts a typical treatment system, commonly used in chlor-alkali industries along with
energy usage areas in terms of pumping and mixing.
vii
Figure 3.6 Water Treatment System Process Flow
Water Consumption
In chlor-alkali plants, water uses can be summarized as follows:
• Process water for brine preparation

• Preparation of reagents used for the brine purification
• Production of caustic in the cell house
• Dilution of the produced caustic in the caustic circuit
• Water for steam generation
• Cooling water for cooling tower water makeup, and
• Domestic use.
Reported specific water consumption for a chlor-alkali plant varies from 4-12 m3/Ton of
NaOH. The wide variation in water consumption could be due to the following:
• Raw water quality

• Caustic form (48% caustic lye vs. 98% caustic flakes)
• Amount of HCl and Hypo produced.
• Steam and process condensate recovery
• Reuse of alkaline waste brine generated during ion exchange column regeneration
An understanding of water uses and consumption will help conserve water and reduce
energy consumed in treating and pumping water across the production chain.
viii
Assessment of Water Consumption in Chlor-alkali Plant
Water required is the summation of:
• Water required for NaCl reaction.
• Water that goes with lye
• Steam and blow down losses
• Vapour losses during caustic concentration
• Water lost with water treatment and brine sludge cake
• Water lost through evaporation and blow-down in cooling towers
• Water used for preparing chemicals for tail gas scrubbing and others
Water balance for chlor-alkali plant considering brine preparation, steam, HCl production
and tail gas treatment is shown in Table 3.8.
Table 3.8 Water Balance
A - PROCESS
A1- For Brine preparation
2NaCl+ 2H 2 O 2NaOH + Cl 2 + H 2
117 + 36  80 + 71 + 2
NaCl concentration 320 g/l
Water required for brine preparation as per NaCl
concentration 3.2 m3/T NaCl
1T NaCl 0.684 T NaOH
NaCl required 1.463 T/T NaOH
Water required for brine preparation 4.680 m3/T NaOH
Water required based on stoichiometry 0.450 T/T NaOH
3
Water required for 48% lye 1.083 m /T NaOH Lye
Brine Treatment
Assume, 0.2% impurities in NaCl 0.020 T/T NaCl
0.029 T/T NaOH Lye
Moisture in cake assuming 30% solids content 0.068 T/T NaOH Lye
Water required for make-up brine preparation 1.639 T/T NaOH Lye
A-2: Steam
Steam economy @ 2.19 T water evaporation/ T Steam 0.457 T Steam/T water
Water to be evaporated for Concentrating lye from 32-
48% 0.500 T water/ T lye
Steam required for Concentrating lye from 32-48% 0.600 4 T Steam/T Lye
Blow-down losses (2% of steam generated) 0.009 T/T NaOH Lye
Condensate recovery loss (95% recovery assumed) 0.023 T/T NaOH Lye
ix
Steam loss 0.032 T/T NaOH Lye
Process condensate loss (Assumed 5%) 0.031 m3/T NaOH Lye
Steam and process condensate makeup water required 0.063
A-3 HCl production* (It is assumed 2% of Cl 2 generated that is not liquefied is only
converted to HCl. For additional HCl production adjustment according to calculations
below needs to be made)
H 2 + Cl 2 2 HCl
2 + 71  73
Water required for diluting 1 T HCl to 33% 3.030 m3/ T 100% HCl
HCl Production (2% liquefied Cl 2 ) 0.018 T 100% HCl/T NaOH
Water required for 33% HCl production 0.103 T/T NaOH Lye
HCl Production (33%) 0.086 T 33% HCl/ T NaOH
A-4 Tail Gas Treatment (It is assumed 0.5% of Cl2 generated comes out as tail gas that is
converted to NaOCl. For additional NaOCl production adjustment according to
calculations below needs to be made)
Cl 2 + 2 NaOH2 NaOCl+ H 2
71 + 80 149 + 2
Cl 2 in tail gas 0.0088 T/T NaOH Lye
NaOCl produced 0.0186 T/T NaOH Lye
NaOCl (18% produced) 0.1031
Water required for 18% NaOCl (tail gas scrubbing) 0.0845
FOR PROCESS [ A-1 +A-2+ A-3+ A-4] 1.92 m3/T NaOH Lye
B - Cooling
Water required for cooling tower losses (Assumed) 2.9 m3/T NaOH Lye
C- Domestic
Labour productivity (0.3-1 is reported. Assumed 0.8 0.8
for Calculation)
Domestic water requirement ( 45 Lit/ Person as per 0.036
factories act) m3/T NaOH Lye
Total Primary and Secondary treated water 4.69

required m3/T NaOH Lye
Assuming 5% water losses along with water

treatment sludge
Total Raw water required 4.9 m3/T NaOH Lye
Energy Consumption for Water Treatment

Energy is consumed for
• Pumping water from one treatment stage to other.
• Supplying air in the degasser
x
• Mixing the chemicals
Energy consumption for a typical 250 TPD caustic plant (48% lye) consuming 1225
m3/day (Specific Water consumption = 4.9 m3/T NaOH) water will contribute only about
1.8 kg of CO 2 /T of NaOH.
Energy Consumption for Brine Purification
Energy is primarily consumed for mixing and dosing chemicals and pumping brine from
one purification stage to another. Energy consumption and methodology of assessing
GHG emissions in a typical brine purification plant considering a typical 250 TPD caustic
plant consuming 410 m3/day water is presented in Table 3.10.
Table 0.10 Assessment of Energy Requirement in Brine Purification
Production 250 TPD lye

Q(m /s)x Total head (hd-hs, m)x density (kg/m )𝑥𝑥 𝑔𝑔 (𝑚𝑚/𝑠𝑠2)
3 3
g 9.81 m/s2
Mixing power 10 W/m3
Assumptions:
Motor efficiency 0.95 IE4
Equipment Flow, Head Density Energy

Details
Number Q (hd-hs) (ρ) Consumption
m3/d m Kg/m3 kW
B-PE-1 Brine saturator pump 481 30 1200 76.40
B-PE-6 Brine precipitator pump 481 30 1200 76.40
B-PE-7 Clarifier pump 481 30 1200 76.40
B-PE-9 Anthracite filter pump 481 30 1200 76.40
Anthracite filter pump 481 30 1200 76.40
B-PE-10 Polishing filter pump 481 30 1200 76.40
B-PE-11 Ion-exchange pump 481 30 1200 76.40
B-PE-2 NaOH Pump 0.0020 10 1350 0.000119
B-PE-3 Na 2 CO 3 pump 0.0013 10 1100 6.47E-05
B-PE-4 Ba 2 CO 3 Pump 0.0013 10 1100 6.47E-05
xi
B-PE-5 Flocculant pump 0.0013 10 1100 6.47E-05
B-PE-8 Precoat pump 0.0013 10 1100 6.47E-05
Mixers
B-ME-1 Brine Saturator Mixer 481 4.81
B-ME-7 Brine Precipitator Mixer 481 4.81
B-ME-8 Clarifier Mixer 481 4.81
B-ME-2 NaOH Mixer 481 4.81
B-ME-3 Na 2 CO 3 mixer 481 4.81
B-ME-4 Ba 2 CO 3 mixer 481 4.81
B-ME-5 Flocculant mixer 481 4.81
B-ME-6 Precoat solution mixer 481 4.81
Total 726.05
SEC kW/T NaOH lye 2.90
GHG emission in kg of CO 2e (1 kW = 0.91 kg CO 2 ) 2.64
Steam Generation and Distribution
Steam is the primary source of thermal energy in a chlor-alkali plant constituting 6 % of

total energy consumed. In chlor-alkali industry steam is primarily used for the following:
• Concentrating caustic lye from 30-32% to 48% in a triple effect back feed falling
film evaporator. The heat carried by vapours generated by exchanging steam heat
is used to concentrate caustic from 32-36-42-48% in succession.
• Used as mechanical energy in steam ejectors for creating vacuum,
• In Vapour-absorption refrigeration systems for liquefying chlorine in place of
ammonia chillers.
The areas where steam is used and the quality of steam used is summarized in Table 3.11.
Table 3.11 Steam Consumption in Chlor-alkali Unit
Pressure
Application Remarks
Level(s)
Thermal Application
Brine Processing Brine to cell house is required at 65-
Heating L, M 70ºC and hence needs to be heated
Anthracite regeneration L,M using LP steam.
Chlorine Processing Vaporising liquid chlorine for
Vaporization L downstream use. Tail gas chlorine
Tail gas stripping L recovery using a vapour-absorption
Condensate stripping L refrigeration chilling plant.
Caustic processing
Heating L, M
Evaporation M, H
Purification M, H
xii
Pressure
Application Remarks
Level(s)
Plant-wide Used for tracing leakages, purging of
Tracing L equipment during maintenance,
General utility L, M cleaning, brine conditioning, etc.
Purging (equipment and lines) L
Mechanical Application
Ejectors M, H
*Legend (Steam Pressure): L =low (<900kPa), M= medium (900 kPa to 1800 kPa), H = High pressure
(>1800 kPa)
Furnace oil or hydrogen generated in process is used to generate steam. The generation
and distribution of steam on an average constitutes energy losses to the tune of 20-30%.
The steam condensate after recovering flash for use in 2nd effect evaporator is used as
boiler feed. The process condensate along with flash steam condensate is used to makeup
brine water.
Specific steam requirements in cell house vary from about 0.5−0.7 tons per ton of NaOH.
This variation is due to varying multiple effects for concentration of caustic from 32% to
48% as shown in Table 3.12.
Table 3.12 Specific steam Consumption (Tons/Ton of NaOH)
3-Stage MEE 0.5

4-Stage MEE 0.3
5-stage MEE 0.25
For VAM chillers, steam consumption in terms of kg steam/TR for multiple stages is
given in Table 3.13.
Table 3.13 Steam Economy of VAM(Kg Steam/TR)

1-Stage VAM 8 kg @2 bar
2-Stage VAM 4 kg @8 bar
3Stage VAM 3.5 kg @10 bar
The other steam efficiency measures include the following:
• Recovering heat from products (Cl 2 gas used to heat feed brine)
• Recovery of steam condensate
• Using MVR or TVR.
xiii
For a 250 TPD plant, major requirement is in caustic concentration which is about 80-90%
of the total steam requirement. Hence, the steam requirement based on number of
evaporator effects and their steam economy along with requirements in other sections can
be calculated as follows:
For a 250 TPD caustic plant @ 0.7 tons steam/Ton NaOH @ 178°C and 10 bar
Steam required =175 TPD
= 7.3 TPH
Assuming boiler efficiency of 80%, boiler capacity = 9.11 TPH
Boiler capacity required = 10 TPH
Based on steam requirement it can be considered a boiler of around 10 TPH is suitable for
a 250 TPD caustic plant. The steam generated is used for evaporation in a closed cycle.
Compressors
In chlor-alkali plants, compressorsreciprocating/rotary and centrifugal compressors for

various applications such as,
• Supplying instrumentation air.

• Chlorine displacement by padding compressor.
• For compressing dry chlorine before liquefaction.
Benchmarks considered for energy consumption for generating compressed air are:
Compressor type Benchmarks (kWh/Nm3/min)

Centrifugal 0.07
Reciprocating 0.11
Screw 0.09
Benchmarks considered for chlorine liquefaction are:
Chiller Compressor Benchmarks

using Freon /NH 3 (kWh/TR)
Centrifugal 0.6
Reciprocating 0.9
Screw 0.75
VAM chillers are increasingly used for reducing/ or optimising energy usage.
xiv
Energy Consumption for Cl 2 Liquefaction
Assuming centrifugal compressors being used for compression of chlorine,

For a 250 TPD caustic plant @ 222 TPD of Cl 2 , produced,
1T NaOH = 0.8875 T Cl 2
887.5 kg Cl 2 = 280.175 m3 Cl 2 @ STP
= 341 m3 Cl 2 @ 60°C and 1 atm.
For 250 TPD = 222 T of Cl 2 is produced
= 75,700 m3 Cl 2 /day
= 52.57 m3Cl 2 /min (@60ºC)
= 47 Nm3 Cl 2 /min
Energy required for compressing Cl 2 using centrifugal compressor @ 0.07 kwh./Nm3/min.
Total energy = 0.07* 47

= 3.29 KWh/ min
Amount of Cl 2 produced = 222/ (24*60)
= 0.15
Energy required /T Cl 2 = 3.29/0.15

= 21.93 kW/T NaOH
Energy Consumption for Instrumentation
Assumed that no. of instruments requiring air in the chlor alkali plant is 20.
Compressed air @ 5 Nm3/instrument/ min = 20 x 5 x 24
= 2400 Nm3/hr.
Power required for reciprocating compressor = 0.11 x 144000

= 15840 kWh/ 250 T NaOH
= 63.36 kWh/T NaOH
Transformers and Rectifiers
Two types of transformers namely power transformer and distribution transformer are
used. Power transformers are high voltage step-down transformer used in the range of 132
KV/11KV, 33KV/11KV to bring the power to the plant. Distribution transformer used are
in the range 125 kVA to distributed the power to the utilities.
Transformer efficiency varies in the range of 93% old- 97% energy efficient. Rectiformers
used in the plant is the combination of step-down transformer and rectifier which converts
AC to DC. The different types of rectiformers used in chlor-alkali plants are
xv
• Oil forced water forced(OFWF) cooling
• Oil natural air natural(ONAN) cooling
• Oil forced water flow(OFW) cooling
Rectiformer efficiency various from 91% (old –diode based) to 98% new-thyristor based.
Energy Losses in Transformer and Rectiformer

AC power consumption required for the production of caustic efficiency of the
transformer is assessed by direct and indirect method. Direct method is simple output by
input of the transformer. Indirect method various heat losses occurred in the transformer is
considered and efficiency is computed.
Performance Assessment of Transformer
Direct Method:
𝑇𝑇𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂
𝜂𝜂𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 (%) = 𝑥𝑥100
𝑇𝑇𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
Indirect Method:
𝑇𝑇𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
𝜂𝜂𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 (%) = 𝑥𝑥100
𝑇𝑇𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
Formula Used:
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝑘𝑘𝑘𝑘𝑘𝑘 2
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 = � � 𝑥𝑥 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝐾𝐾𝐾𝐾𝐾𝐾
Where,
𝑇𝑇𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 Input to the transformer (kW)

𝑇𝑇𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 Output from the transformer (kW)
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 Copper Losses at operational load (kW)
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 Iron Losses or No load losses (kW)
𝜂𝜂 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 Efficiency of Transformer (%)
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑁𝑁𝑁𝑁 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 No load losses in the transformer
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 Full load losses in the transformer
xvi
Performance Assessment of Rectiformer
Direct Method
𝑅𝑅𝑅𝑅𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂
𝜂𝜂𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 (%) = × 100
𝑅𝑅𝑅𝑅𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
Indirect Method
𝜂𝜂𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 (%) = 𝜂𝜂𝑅𝑅𝑅𝑅_𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 (%) 𝑥𝑥 𝜂𝜂𝑅𝑅𝑅𝑅_𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 (%)
Formulae Used:
𝑅𝑅𝑅𝑅𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶

𝜂𝜂𝑅𝑅𝑅𝑅_𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 (%) =
𝑅𝑅𝑅𝑅𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 − 𝑚𝑚𝑡𝑡𝑡𝑡 𝐶𝐶𝑡𝑡𝑡𝑡 (𝑇𝑇𝑡𝑡𝑡𝑡 _𝑖𝑖𝑖𝑖 − 𝑇𝑇𝑡𝑡𝑡𝑡 _𝑜𝑜𝑜𝑜𝑜𝑜 )

𝜂𝜂𝑅𝑅𝐹𝐹𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 (%) =
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝑘𝑘𝑘𝑘𝑘𝑘 2
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 =� � 𝑥𝑥 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝐾𝐾𝐾𝐾𝐾𝐾
{𝑅𝑅𝑅𝑅𝐼𝐼𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 }– 𝑚𝑚𝑡𝑡 𝐶𝐶𝑝𝑝 (𝑇𝑇𝑖𝑖𝑖𝑖 − 𝑇𝑇𝑜𝑜𝑜𝑜𝑜𝑜 )
𝜂𝜂𝑅𝑅𝑅𝑅_𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 (%) =
𝑅𝑅𝑅𝑅𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 −𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
�𝑅𝑅𝑅𝑅𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 − 𝑚𝑚𝑡𝑡𝑡𝑡 𝐶𝐶𝑡𝑡𝑡𝑡 (𝑇𝑇𝑡𝑡𝑡𝑡 _𝑖𝑖𝑖𝑖 − 𝑇𝑇𝑡𝑡𝑡𝑡 _𝑜𝑜𝑜𝑜𝑜𝑜 )�– 𝑚𝑚𝑟𝑟𝑟𝑟 𝐶𝐶𝑟𝑟𝑟𝑟 (𝑇𝑇𝑟𝑟𝑟𝑟 _𝑖𝑖𝑖𝑖 − 𝑇𝑇𝑟𝑟𝑟𝑟 _𝑜𝑜𝑜𝑜𝑜𝑜 )
𝜂𝜂𝑅𝑅𝐹𝐹𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 (%) = .
𝑅𝑅𝐹𝐹𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 −𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖 − 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶
Where,
𝑅𝑅𝑅𝑅𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 Input to the Rectiformer (kW)

𝑅𝑅𝑅𝑅𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂 Output from the Rectiformer (kW)
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 Transformer Copper Losses at operational load (kW)
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 Transformer Iron Losses or No load losses (kW)
η RF_transformer Efficiency of Transformer of Rectiformer (%)
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 No load losses in the transformer of rectiformer
𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 Full load losses in the transformer of rectiformer
𝑚𝑚𝑟𝑟𝑟𝑟 Mass flow rate of rectifier coolant (kg)
𝐶𝐶𝑟𝑟𝑟𝑟 Specific heat of rectifier coolant
𝑇𝑇𝑟𝑟𝑟𝑟 _𝑖𝑖𝑖𝑖 Input Temperature of rectifier coolant (℃)
𝑇𝑇𝑟𝑟𝑟𝑟 _𝑜𝑜𝑜𝑜𝑜𝑜 Output Temperature of rectifier coolant (℃)
𝑚𝑚𝑡𝑡𝑡𝑡 Mass flow rate of transformer coolant (kg)
𝐶𝐶𝑡𝑡𝑡𝑡 Specific heat of transformer coolant
𝑇𝑇𝑡𝑡𝑡𝑡 _𝑖𝑖𝑖𝑖 Input Temperature of transformer coolant (℃)
𝑇𝑇𝑡𝑡𝑡𝑡 _𝑜𝑜𝑜𝑜𝑜𝑜 Output Temperature of transformer coolant (℃)
xvii
The Table 3.14 shows methodology of calculation of energy loss in Transformer and its
cooling water requirement.
Table 3.14 Energy Loss in Transformers
BASIS 250 TPD 48% lye

Assumed 5th Gen Bi-
Energy consumption in DC kW/T of NaOH 2390 polar
DC power required 597500 kW/day
AC to DC conversion Efficiency 97.5 %
Energy loss 15320 kW/day
Energy loss per hr. 638 KWh.
Energy loss 548985 kcal
Assumed rectiformer type: Oil Forced Water Forced Cooling type
Consider,
Cp oil 0.85 kcal/kg ºC
Temp difference of oil 3 ºC
Mass of oil 215288.3 kg/hr.
Cooling water required 26229.58 kg/hr.
CT water flow rate required 26.23 m3/hr.
For a typical set of cooling towers in a chlor- alkali industry, the parameters measured are
given in table 3.15.
Table 3.15 Assessment of Energy Requirements for Cooling Needs
Production: 250 TPD lye

Evaporation Loss (m /hr.)= 0.00085 ∗ 1.8 ∗ 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟(m3/hr) ∗ (𝑇𝑇1 -T2 )

3
𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿
Blow down=
𝐶𝐶𝐶𝐶𝐶𝐶−1
CT Losses, (𝑚𝑚3/ℎ𝑟𝑟) = Evaporation Loss + drift loss + Blowdown loss+COC
Total cooling water required,(m3/hr)=Quantity of cooling water required (m3/hr)+CT
Losses(m3/hr)
g 9.81 m/s2
Pump Efficiency 0.65
Motor Efficiency 0.95
Cp Cl 2 0.48 kJ/kg K
Cp NaOH 3.4 kJ/kg K
Cp HCl 33% 4.18 kJ/kg K
Cp H 2 O 4.18 kJ/kg K
xviii
Cp H 2 SO 4 1.38 kJ/kg K
Energy released due to NaOCl formation 1463 kJ/Kg of Cl 2 gas
Latent heat of vaporization of water 2319 kJ/kg
Heat of fusion of NaOH 209.2 kJ/kg
Assumption
Head 10 m
Density 1000 kg/m3
Density Freon 3660 kg/m3
Motor efficiency 0.95
Drift Loss 2%
COC 4
Energy requirement for pumps used for cooling is given in Table 3.16.
Table 3.16 Energy Requirement Assessment for Pumps Used for Cooling Needs
Q P SEC
kWh/ T
Process unit kWh/da kWh/da
m3/hr. m3/s NaOH
y y
lye
Caustic Concentration
Process Condensate 1480.36 0.41 1567.9 1567.9
13.13
Product Cooling 69.73 0.019 73.85 73.85
Caustic Flaking
Process Condensate 5.71 0.002 6.05 6.05
0.27
Flaking Drum 26.53 0.007 28.10 28.10
Chlorine Liquefaction
Chlorine Cooling 4.35 0.001 4.61 4.61
HCl Cooling 54.70 0.015 57.94 57.94
Transformers 27.02 0.008 28.62 28.62 4.35
Freon chiller 298.8
Miscellaneous 32.78 0.009 34.72 34.72
VAM 90.57
Total 108.32
xix
4. BEST PRACTICES
This section includes area-wise best practices including energy efficiency and
conservation measures in the chlor alkali plant.
4.1 CELL HOUSE
The energy losses in the cell house can be broadly classified as follows:
• Energy losses due to side reactions in the cell

• Energy losses due to voltage drop across different sections of the cell
Reducing Energy Losses due to Side Reactions
The Table 4.1 shows energy efficiency potential by controlling side reactions in cell.
Table 0.1 Energy Efficiency Potential by Controlling Side Reactions in Cell

Side Reaction Typical Parameters for Improvement
Reduction in
Efficiency (%)
HOClOCl- + H+ 1.3 • The partial pressure of chlorine.
• The concentration of Cl- ions, i.e. the
2HOCl +OCl ClO 3 +
-
2.3
concentration of salt in anolyte.
2H+ + 2Cl-
+ -
• O 2 and ClO 3 - can be depressed by selecting
2H 2 O O 2 + 4H + 4e 4.1
anode coating with suitable characteristics
and/or by decreasing the pH in anode
compartment. Acidifying brine to pH<6
before feeding to membranes to increase life
of anode coating, reduce formation of O 2 ,
OCl-, ClO 3 .
Frequency of Analysis
The frequency of analysis of various streams entering and leaving the cell room is given in
Table 4.2.
xx
Table 4.2 Recommended Analysis Frequencies
Stream Analysis Frequency
Cell room feed and exit brine gpl NaCl 2 hr.
Cell room feed brine ppm Ca, Mg 4 hr.
Electrolyser feed and exit brine pH 2 hr.
Cell room exit caustic % NaOH 2 hr.
Electrolyser exit caustic % NaOH 2 hr
Cell room chlorine gas % O2, H2 8 hr.
Electrolyser chlorine gas % O2, H2 Daily
Source: AMAI, Delhi
Reducing Voltage Drop in Cells
The Table 4.3 shows various components of cell voltage and possible solutions.
Table 4.3 Energy Losses in Cell House and Possible Solutions

Components Factors for Design Operation & Maintenance
of Cell Improvement Consideration Measures
Voltage
Membrane IR Mechanical High performance Regular replacement of membrane at
drop strength and membrane like the recommended period (3-5 years)
resistance improved to maintain the designed voltage
mechanical drop. Every year due to membrane
strength, reduced aging effect power consumption
resistance etc. increases by 35 kWh/MT of caustic
production
Cathode and Cathodic and Research on Recoating of anode and cathode at
anode over anodic coating, different alloys of the recommended period (8 years) to
potential feed water quality, coating, catalytic maintain the designed voltage drop.
brine purity cathode
Electrolyte IR Brine purity, gap Reducing the gap Maintaining low impurities level in
drop between anode between anode the brine system. Stringent brine
and cathode, brine and cathode quality check, Automatic control the
feed temperature feed brine temperature
xxi
Reducing Energy Consumption by Operating at Lower Current Density through
Addition of Cell Elements
The energy consumption in electrolysis varies linearly with the cell operating current
density. The energy consumption can be reduced by operating the cells at lower current
density. This can be achieved by increasing the number of cell elements and operating the
cell elements at lower current density without sacrificing the level of production. The cost
incurred on adding the cell elements can be recovered by way of decrease in energy
consumption while maintaining the same level of production. The payback period varies
from 3 to 4 years.
Reducing Membrane Voltage Drop

The energy consumption on account of voltage drop across the membranes can be
controlled by regularly monitoring the condition of membranes for energy performance
and replacing them when limit prescribed by the supplier is exceeded.
Apart from the replacement of membranes, the anode and cathode pans are required to
recoated and repaired as and when their condition deteriorates. This will keep cell voltage
within the prescribed level and prevent damage and premature failure of the membranes.
The purity of aqueous sodium chloride fed into the cell elements for electrolysis should be
maintained by removing calcium and magnesium impurities before being fed into the cell.
The presence of calcium and magnesium impurities reduces the current efficiency of the
membranes and causes accelerated ageing. The recommended limit for calcium and
magnesium impurities is 20 ppb.
Structural and Contact Voltage Drop

The records of structural and contract voltage drops at the commissioning stage of the
plant should be maintained as a benchmark for periodic monitoring and control.
Electrolyte Concentration
The cell voltage varies with electrolyte concentration.increase is approximately of 20
mV per percent increase in NaOH concentration.
Electrolyte Temperature
The electrolysis should be carried out at optimum temperature to minimize energy
consumption. The cell voltage varies with electrolyte temperature. Cell voltage decreases
by 5 to 10 mV per degree increase in electrolyte temperature.
xxii
Energy Savings with Improved Membrane Technology
Over the years, there have been continuous improvements in membrane technology in
terms of energy performance and GHG emission reduction in Tons of CO2 equivalent per
T of NaOH Production. The Table 4,4 summarizes the development and
commercialization of different technologies to reduce the energy consumption through
voltage drop reduction in different areas.
Table 4.4 GHG Emission Reduction for Various Combinations

of Technology Conversions
Mono- 6th Oxygen

2nd 3rd 4th 5th
polar generation Depletion
Technologies generation generation generation generation
zero Bi-polar Cathode
Bi-polar Bi-polar Bi-polar Bi-polar
gap zero gap (ODC)
Mono-polar 0.07 0.14 0.35 0.39 0.45 0.49 0.93
Mono-polar
X 0.06 0.28 0.32 0.37 0.42 0.85
zero gap
2nd generation
X X 0.21 0.25 0.31 0.35 0.79
Bi-polar
3rd generation
X X X 0.04 0.09 0.14 0.58
Bi-polar
4th generation
X X X X 0.06 0.10 0.54
Bi-polar
5th generation
X X X X X 0.05 0.48
Bi-polar
6th generation
Bi-polar zero X X X X X X 0.44
gap
Rectifiers
The rectifiers convert AC to DC and supply DC for the process of electrolysis. Therefore,
they occupy a significant role as regards continuity, reliability and energy efficiency of the
operation.
The efficiency of rectifiers may be defined as the ratio of DC power output at rectifier
terminals to the AC power input at rectifier transformer terminals. The efficiency of
rectifiers may vary from a low 94% to a high 97% or more. Since the volume of power
handled by the rectifiers in chlor-alkali plants is large, even 1% change in efficiency
results in significant energy losses/savings.
xxiii
The rectifier efficiency depends upon the designed DC output voltage. The present trend is
to deploy rectifier units with higher DC output voltage. The operating efficiency of the
rectifier units also depends upon their loading. The low loading of the rectifiers reduces
poor power factor and increases harmonic distortion. The I2R losses increases which lead
to poor energy efficiency.
The present trend is to replace conventional rectifiers with high DC output voltage diode
based rectifiers or thyristor based rectifiers.
Installation of Harmonic Filter Banks/Power Factor improvement Capacitors

The rectifier loads constitutes more than 80% of the total plant load. Being non-linear
load, they are major source of harmonics generation. The power factor of rectifier can be
low as 0.85 depending upon the loading of rectifier transformers. The reduced power
factor results in higher line distribution losses, poor voltage regulation and increased KVA
loading of transformers and generators.
However, the losses generated due to harmonics can be reduced by carrying out the study
of harmonics present in an electrical system and installing suitably designed harmonic
filter banks. The harmonic filter banks apart from mitigating the harmful effects of
harmonics are also used for power factor improvement. The benefits of installing the
harmonic filter banks/power factor improvement capacitors are as follows:
• The line/distribution losses (I2R losses) are reduced.

• The harmful effects arising from harmonics in the system are reduced.
• The voltage regulation at the load end is improved.
• The KVA loadings of the transformers, generators and cables etc are reduced,
creating scope for further useful loading (KW loading) of the transformers,
generators and cables.
Some electric supply companies offer monetary incentives to consumers for improvement
in power factor. The payback period on installation of capacitors for power factor
improvement can be as low as 6 months.
They also mandate Total Harmonic Distortion (THD) to be maintained below a specified
limit and levy penalties in case of THD value exceeding the limit.
xxiv
4.2 CHLORINE LIQUEFACTION AND TAIL GAS TREATMENT
Chillers/Liquefaction Units
• Efficiency of refrigeration increases as temperatures of the liquid before flashing

becomes lower. The process is carried out by sub-cooling using the plant cooling
water. If sub-cooling is inadequate with the available cooling water, use of
economizers will help to evaporate and cool the remaining liquid.
• Multi staging provides marginal energy savings as well as improves safety as
compressed gas temperature is reduced.
• The refrigerants with higher boiling points are recommended. The lower boiling
refrigerants require more energy for refrigerationthey require higher
compression pressures for condensation by cooling water.
• Operation of steam−based vapour absorption machine (VAM) in place of vapor
compression chillers for energy savings if feasible.
• Application of VFDs in refrigeration compressors operating on variable loads.
Scrubber (Tail Gas Handling)
The various factors influencing scrubber performance are as follows:
• Inlet Cl 2 concentration
• Inlet air flow rate
• Recirculation rate
• Packing height
• Capacity of the scrubbing liquor for absorption of chlorine
About 1-8% of Cl 2 produced ends up as tail gas. The chlorine absorption unit is sized
based on the gas flow and not on chlorine production capacity of the plant. The gas flow is
based on the flow of inert gas injected to keep the hydrogen concentration below the
explosivity limits. The majority of the plants work with gas flows in the range 2000–8000
m3/h.
The commonly used scrubber is spray type scrubber which is simple in design and cost-
effective. Pressure drop is low and consequently power consumption is only 0.5-2
HP/1000 CFM. The operating efficiency is about 90% for a particle size of +8µm.
xxv
4.3 HYDROGEN GAS MANAGEMENT
Thermal Energy Conservation by using Hydrogen as Fuel in Boiler
The existing oil-fired burner can be modified to handle hydrogen as a fuel. In most plants
about 15% of hydrogen is used as fuel along with furnace oil. Combustion of one kg of
hydrogen releases 28922 kcal/kg of heat.
Table 4.4 GHG Emission Reduction with Hydrogen as Fuel in Boiler

No. Parameters Units Value Basis
1 Hydrogen generation factor Kg H 2 /Ton NaOH = 25
2 Average H 2 used as fuel for % = 15
process heating of total H 2
generated
3 Average H 2 used as fuel of total H 2 kg H 2 /Ton of = 3.75
generated NaOH
4 Combustion Calorific value of H 2 Kcal/ kg of H 2 = 28922
6 Annual H 2 production for 250 TPD H 2 kg /yr. = 20x 105 25x250x320
(considering 320 working days)
7 Hydrogen used as fuel kg H 2 /yr. = 225000 20 x 105 x 0.15 x
0.75
8 Heat availability (assuming 80% kCal/yr. = 52059 x (225000 x 231377
combustion efficiency) 106 x.08)
9 Annual FO usage if H 2 is not used Kl /yr. 859 (1.65x 52059 x
(considering 10,000 kcal/l and 106 ) /(10000x1000)
combustion efficiency of 65%
10 Annual GHG reduction for a T CO 2 /yr. 2783 (859 x 3.24)
typical 250 TPD plant (1 kl
furnace oil = 3.24 t CO 2 )
Electrical Energy Conservation by Using Hydrogen as Fuel in Fuel Cells
Average reported flaring of H 2 which is a waste of energyis about 14%. This energy
can be potentially recovered by deploying fuel cells. Based on this equivalent power
generation and reduction in GHG emissions by recovering energy from vented hydrogen
for a typical 250 TPD plant is assessed and presented in Table 4.5.
xxvi
Table 4.5 Captive PEM Fuel cell based Power Generation
S. Parameters Units Value Rationale
No
1 Hydrogen generation factor Kg H 2 /Ton = 25
NaOH
2 Average H 2 vented of total H 2 % = 14
generated
3 Average H 2 vented of total H 2 kg H 2 vented = 3.5 0.14 x 25
generated /Ton of NaOH
4 Specific hydrogen consumption in Kg H 2 /kWh = 0.06 At 50%
PEM fuel cell conversion
efficiency in
Proton Exchange
Membrane fuel
cell.
5 Specific energy generation from kWh/Kg H 2 = 16.67 1/0.06
PEM fuel cell using hydrogen
6 Annual H 2 production for 250 TPD H 2 kg /year = 20x 105 25x250x320
(considering 320 working days)
8 Hydrogen available for Fuel Cells kg H 2 /year = 210000 20 x 105 x 0.14 x
(75% of 14% vented ) 0.75
9 Potential captive electricity kWh/yr. = 3.5 x (16.67 x 210000)
generation using Hydrogen PEM 106
fuel cells.
10 Annual GHG reduction for a typical T CO 2 /yr. 3185.6 3.5 x 106 x 0.91
250 TPD plant (1 kWh = 0.91 kg
CO 2 )
11 Savings from energy generated H 2 Crore Rs/yr. = 1.75 (120.82 x 106 x
(@Rs 5/kWh) 6.5)/107
4.3.1 CAUSTIC CONCENTRATION
Energy efficiency techniques include the following:
• Flashing of condensate to produce steam for use in later effect operating at low
pressure
• Increasing number of effects in evaporatormultiple effect evaporator to reduce
steam consumption.
• Reducing losses in process and steam condensate.
For a multiple effect evaporator steam consumption varies from 0.5-0.25 kg steam/ kg
water evaporated depending on the number of effects. The measured steam consumption
xxvii
less than design indicate scope for improvement. The following factors affect evaporator
performance:
• Scaling
• Improper vacuum supply
• Required steam pressure
• condensate evacuation issues
• Tube corrosion leading to puncture
• Performance of heat exchanger before evaporator (If applicable)
These issues can be addressed by choosing the right type of evaporator and adopting best
operation and maintenance practices as follows:
Selecting an Evaporator
Whenever the evaporation rate is above 1,350 kg/h, multi-effect evaporation should be
considered. In a double effect evaporator, evaporation is approximately 2 kg of water from
the product for each kg of steam supply. In chlor-alkali industries, 3-stage falling film
evaporator is preferred.
Using retrofits life TVR and MVR
Thermo Vapour Recompression (TVR)

When steam is available at pressures in excess of 3 bar(g) and preferably over 7 bar(g),
thermo vapour recompression can be adopted. In this operation, a portion of the steam
evaporated from the product is recompressed by a steam jet venturi and returned to the
steam chest of the evaporator. Steam efficiency depends on the steam pressure and the
number of effects over which TVR is applied. TVR can be used along with multi-effect to
provide even larger steam efficiencies.
Mechanical Vapour Recompression (MVR)
This process takes the vapour that has been evaporated from the product, compresses the
vapour mechanically and then uses the higher pressure vapour in the steam chest. The
energy supplied to the compressor is drawn from an electrical motor/ steam turbine/gas
turbine/internal combustion engine.
xxviii
4.4 STEAM GENERATION AND DISTRIBUTION
Typical losses reported in steam generation and distribution is presented in Table 4.9.
Table 4.9 Losses in Steam Generation and Distribution

Heat Loss Areas %
Steam Generation Losses
Heat Loss in flue gas 15
Radiation and Convection Heat Loss 3
Boiler Blow-down 2
Steam Distribution losses
Insulation (Steam and condensate) 6.4
Steam trap station failure 3.6
Condensate losses 3.8
Total 38.8
The various energy efficiency opportunities are as follows:
Recovery of Seam and Process Condensate

As against potential condensate recovery of about 90%, average recovery observed in
industries is in the range 70-80% indicating saving potential of 0.6% of thermal energy.
Reducing Boiler Blowdown

By managing and treating boiler feed and condensate water to desired quality, blow-down
losses can be maintained at 2%.
Effective Insulation of Boiler and Steam Distribution System

Through effective insulation, radiation and convection losses can be minimised to 3% in
boiler and 6.4% in steam distribution.
Selection, Periodic Monitoring and Repair of Steam Traps

Suitable steam traps shall be selected and maintained for removal of condensate.
By adopting the best practices summarized above, the losses in steam generation and
distribution can be brought down to 39% to 30%. Considering steam generation and
distribution constitutes 6% of total energy used in the sector, a 10% reduction in thermal
energy consumption amounts to 0.6% of total energy saved.
Other Energy Efficiency Opportunities include the following
• Avoiding steam leaks

• Utilising steam at the lowest acceptable pressure
xxix
• Increasing number of effects in multiple effect evaporator (95%)
• Using thermo-compressor to reuse low pressure steam
4.5 ENERGY EFFICIENCY IN PUMPING SYSTEM
Typical energy efficiency measures in pumping system include avoiding throttling for
flow control, adopting multiple pump arrangement, and applying variable frequency
drives for variable flows, replacing pump or motor or both and periodic preventive
maintenance.
Avoiding Throttling Operation
This is the common method of controlling the flow from a pump. Throttle valves control
flow by
• By increasing the upstream backpressure
• By increasing the backpressure on a pump
Multiple-pump arrangement
Multiple pumps operation comprises several smaller pumps in combination (series or

parallel). It is adopted when a single pump is unable to operate close to its best efficiency
because of wide variation in flow requirements.
The advantages in using combinations of smaller pumps rather than a single large pump
are:
• Operating flexibility
• Redundancy in case of a pump failure
• Lower maintenance requirements due to pumps operating near their BEP
• Higher efficiency.
Variable frequency drives (VFD)
They are the preferred option when pumps operate for at least 2000 hours per year and
process flow rate requirements vary by 30% or more over time. VFD eliminates the need
for throttling valves and motor starters. VFD saves energy by varying the pump rotational
speed as power is proportional to the cube of motor speed.
xxx
Motor Replacement
Right motor ratings, efficiency and motor loading influence energy consumption.
Oversized as well as undersized motors, result with increased energy losses. Ideally
motors should operate at 75-100% load. When motors are operated under lightly loaded
conditions, power factor is reduced.
Some commonly encountered problems and measures to improve energy efficiency that
can be used to address them are summarised in Table 4.10.
Table 4.10 Common Problems in Pump and Measures to Improve Energy Efficiency
S. No Common Problem Potential Measures to Improve Efficiency
1 Unnecessary water demand Reduce water demand on system through flow
on pumping system and water balance studies
2 Pump throttling Adopt variable speed drive
3 Oversized pump • Select pump that operates near to Best
Efficiency Point (BEP)
• Change impeller
• Trim impeller
4 Inefficient piping Reconfigure during maintenance.
configuration
5 Oversized/ inefficient motor Adopt energy efficient motor
Potential savings with energy efficiency measures are given in Table 4.11.
Table 4.11 Potential Savings with Energy Efficiency Measures

S. No Energy Savings opportunities Potential Savings
1 Replace throttling valve with speed control 10%
2 Install parallel pumping system for highly 10%
variable loads
3 Replace motor with energy-efficient motor 1–3%
4 Replace old pump with a more efficient pump 10–20%
xxxi
4.6 ENERGY EFFICIENCY IN TRANSFORMERS AND RECTIFIERS
Following are the best practices followed in the plant to conserve energy in transformer
and rectiformer.
Optimization of Loading of Transformer
• By locating transformer close to the load center, considering other features like
centralized control, operational flexibility etc, will bring down the distribution loss
in cables.
• Under fluctuating loads, transformers should be used in parallel so that load is
shared and transformers operate close to the maximum efficiency range.
Replacing existing Transformer with Energy Efficient Transformers
• By using energy efficient transformers, efficiency improves from 95−97%.

• By using amorphous transformers efficiency improves to 97−98.5%.
Energy Conservation Measures in Rectiformer
Energy loss in AC to DC conversion ranges from 5- 10%. Design rectifier efficiencies

range from 91-94% (old diode type) to 97-98% (thyristor type), while the operational
efficiencies are typically 0.5 to 1.0 % less than design. The options are:
• Apart from clean contacts, cooling, ventilation, actual loading on the rectifier system
influences efficiency.
• Replacement of older thyristor controlled rectifiers with more efficient diode
rectiformers increases the rectiformer efficiency to about 4-6% and saves about 5% of
the total connected load. For a 250 TPD plant annual energy reduction is 930400 kWh
and GHG reduction of 8466 Tons of CO 2 equivalent.
4.7 ENERGY EFFICIENCY IN LIGHTING SYSTEM
The various energy efficiency options in lighting system include the following:
• Use separate transformer for lighting to have better control over voltage.
• Replace HPMV & MH lights with LED lights
• Adopt lighting controls to eliminate unnecessary lighting
• Install lighting occupancy sensors
• Use day lighting.
xxxii
5. CASE STUDIES
5.1 RE-COATING OF ANODE AND CATHODE WITH MEMBRANE CHANGE
Case Study-1: Re-coating of anode and cathode with membrane change

Description Value Remarks
Energy saving due to recoating of anode and 20 Cell voltage increases by
cathode (kWh/T of caustic) 31 mv per year =20 kW/T
NaOH i.e; (31/1000 x 670)
Energy Saving due to membrane change (kWh/T 35 Increase in power
of caustic) consumption by 35 kWh/T
Cost saving (Rs/T of caustic)(5 x (20+35)) 275 @ Rs 5 /kWh
Cost saving/ annum for 250 TPD plant operating 1,92,50,000
for 280 days
Investment required for recoating for 250 TPD 12,50,00,000
caustic plant
Simple Pay-back period in Years 6.5
(12,50,00,000/1,92,50,000)
GHG reduction by recoating and membrane 50 GHG factor of 0.91Kg
change (kg CO 2e / T of caustic)(20+35)*0.91 CO 2 /kWh
Annual GHG saving (kg CO 2e ) 35,00,000 280 days basis @ 250 TPD
caustic
Courtesy: The Andhra Sugars Ltd
5.2 FULLY AUTOMATIC CONTROL OF BRINE FEED TEMPERATURE
Case Study-2: Replacement of semi-automatic control of brine feed temperature with fully
automatic system
Energy saving due to control of brine feed 14.5 1.3595T 2 − 227.86𝑇𝑇 + 11670
temperature within the range of 1 degree
Centigrade (90 – 89)(kWh/T of caustic)
(𝟏𝟏. 𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑 ∗ 𝟗𝟗𝟗𝟗𝟐𝟐 − 𝟐𝟐𝟐𝟐𝟐𝟐. 𝟖𝟖𝟖𝟖 ∗ 𝟗𝟗𝟗𝟗 + 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏) – (𝟏𝟏. 𝟑𝟑𝟑𝟑𝟑𝟑𝟑𝟑 ∗ 𝟖𝟖𝟖𝟖𝟐𝟐 − 𝟐𝟐𝟐𝟐𝟐𝟐. 𝟖𝟖𝟖𝟖 ∗ 𝟖𝟖𝟖𝟖 + 𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏𝟏) = 14.5
Cost saving (Rs/T of caustic) (5 x (14.5)) 72.5 @ Rs 5 /kWh
Cost saving/annum for 250 TPD plant operating 5075000
for 280 days
Investment 1000000 Rs 1 crore investment for 250
TPD plant
Simple Pay-back period in Years 1.97 years
10000000/5075000
xxxiii
GHG reduction by recoating and membrane 13.2 GHG factor of 0.91Kg
change (kg CO 2e / T of caustic)(14.5)*0.91 CO 2 /kWh
Annual GHG saving (kg CO 2e ) 924000 280 days basis @ 250 TPD
caustic
Courtesy: The Andhra Sugars Ltd
5.3 PREHEATING OF FEED BRINE USING CHLORINE IN RECUPERATOR
Case Study-3: Pre heating of feed brine from 60oC to 68oC using chlorine gas coming out of
electrolyser at 80oC in recuperator

Steam required to heat brine from 60-90oC 397 36300 MT of steam
(kg of steam / T of caustic) requirement for brine heating
from 60-90oC for 250 TPD
Steam required to heat brine from 68-90oC 145 23100 MT of steam
(kg of steam / T of caustic) requirement for brine heating
from 68-90oC for 250 TPD
Cost of steam saving by pre heating of feed 184.2 @ Rs 2002 / MT of Steam
brine from 60oC to 68oC using chlorine gas
coming out of electrolyser at 80oC using
recuperator saving (Rs./T of caustic)
(397-145)/1000 * 2002
Savings in Rs./yr operating 280 days/yr 1,28,94,000
Investment Rs. 1,20,00,000
(Rs. 1.29 cr /Rs. 1.2 cr)
GHG reduction by preheating brine (kg CO 2e / 176.6 GHG factor of 0.91 Kg
T of caustic) CO 2 /kWh,
(397-145)*(660/860)*0.91 Steam caloric value 660kcal/kg
Annual GHG saving (kg CO 2e ) 12362000 280 days basis @ 250 TPD
caustic
Courtesy: The Travancore – Cochin Chemicals (TCC) Ltd
xxxiv
5.4 CONVERSION OF CAUSTIC CONCENTRATION PLANT FROM DOUBLE
EFFECT TO TRIPLE EFFECT
Case Study-4: Conversion of caustic concentration plant from double effect to triple effect.

Steam requirement in MT for double effect 1 1MT of steam / MT of
evaporator for 1MT of caustic concentrated caustic concentrated
Steam requirement in MT for triple effect 0.55
evaporator for 1 MT of caustic concentrated
Annual cost saving of steam (Rs./T of caustic) 97200 @ Rs 600 / MT of Steam
(1-0.55) * 600*360
Savings in Rs./yr operating 360 days/yr
Cost saving/ annum for 250 TPD plant operating 243 lakhs
(97200*250)
Investment required for 250 TPD caustic plant 300 lakhs
(300/243)
GHG reduction (kg CO 2 e/ T of caustic) 314 GHG factor of 0.91 Kg
(1-0.55)*1000*(660/860)*0.91 CO 2 /kWh,
Steam calorific value
660kcal/kg
Annual GHG saving (kg CO 2e ) (0.314*250*360) 282.8 lakhs
for 250 TPD caustic
Courtesy: M/s. Sree Rayalaseema Alkalies and Allied Chemicals Ltd.
5.5 REPLACING RECIPROCATING COMPRESSOR WITH FREON SCREW

COMPRESSOR FOR CHLORINE LIQUEFACTION
Case Study-5: Conversion of reciprocating compressor with Freon screw compressors for
chlorine liquefaction
The power reduction for the conversion of 12 kWh / MT
reciprocating compressor with Freon Screw of chlorine
For 250 TPD caustic production the expected 222 MT
chlorine
The Annual power reduction for the conversion of 7.45 lakhs
reciprocating compressor with Freon Screw for
250 TPD Caustic (222x12x280 days)
Annual cost saving in lakhs (7.45 lakhs x 5) 37.25 @ Rs 5 /kWh
Investment on Freon compressor 120 lakhs
xxxv
(120/37.25)
Annual GHG saving (kg CO 2e ) (7.45 lakhs*0.91) 6.8 lakhs GHG factor of 0.91 Kg
for 250 TPD caustic CO 2 /kWh,
5.6 CONVERSION OF HOT WATER FIRED SINGLE EFEECT VAM MACHINE WITH
DOUBLE EFFECT VAM MACHINE
Case Study-6: Conversion of hot water fired single effect vapour absorption machine (VAM)
machine with double effect VAM
The steam consumption for single effect VAM 8.16 kg/TR
The steam consumption for double effect VAM 3.88 kg/TR
Annual cost saving of steam (Rs./TR ) 5319 @ Rs 600 / MT of Steam
(8.16-3.88) * 280*600/1000
Savings in Rs./yr operating 280 days/yr
For a 250 TPD caustic plant TR required 345
Cost saving/ annum for 250 TPD plant 18.35 lakhs
operating (5319* 345)
Investment required for 345 TR 52 lakhs
(52/18.35)
GHG reduction (kg CO2e/ T of caustic) 4.13 GHG factor of 0.91 Kg
(8.16-3.88)*(660/860)*0.91 *(345/250) CO 2 /kWh,
Steam caloric value 660kcal/kg
Annual GHG saving (kg CO 2e ) (4.13*250*280) 2.9 lakhs
for 250 TPD caustic
5.7 IMPROVEMENT OF POWER FACTOR BY ADDING CAPACITOR
Case Study-7: Improvement of power factor from 0.96 to 0.99 by adding capacitor in the
existing capacitor banks. The average loading of transformer is 16000 kVA
Present kW load (KVA*PF) = 16000 *0. 96 =15360
kVAr required = kW [tan φ1 – tan φ2] =15360{(tan (cos-1PF 1 ) – tan (cos-1PF 2 ) }
= 15360{(tan (cos-10.96) – tan (cos-10.99) }
=15360*0.108
=1658.8 kVAr
New kVA = (old PF/New PF)*old kVA = (0.96/0.99) * 16000
=15515.2
xxxvi
Annual cost savings in Rs due to reduction = (16000– 15515.2)*12*150 = 8.72 lakhs
in kVA (@ Rs. 150 per kVA)= (old kVA –
New kVA) * 12 * 150
Cost of capacitor in Rs. taking Rs.1200/ =1658.8 * 1200
kVAr for 1658.8 kVAr =19.9 lakhs
Payback period in yrs (19.7/8.72) 2.26
5.8 REPLACEMENT OF OLD LOW EFFICIENCY TRANSFORMER WITH NEW

ENERGY EFFICICENT TRANSFORMER
Case Study-8: Replacement of old low efficiency transformer with new energy efficient
transformer for 250 TPD plant
Basis 250 TPD Caustic

SEC 2500 kWh/ T NaOH lye
Annual working days 320
DC Energy consumption/ 200000000 kWh/ year
year
Rectiformer efficiency 97 %
AC 206185567 kWh
Power 26847.07904 kWh
KVA @0.9 PF 29830.08782
MVA assuming 10% 32.8130966 Say 35 MVA
factor of safety
Unit Old transformer Energy efficient
transformer
Loading 75% 75%
Efficiency 97 99
Transformer rating MVA 20 20
Rated no-load loss kW 18 15
Rated load loss kW 107 100
Total loss kW 78.1875 71.25
Annual Operation Hrs. 8000 8000
Annual Energy Loss kWh 625500 570000
Annual Energy Saving kWh 55500
Total annual saving in Rs Lakhs 3
@ Rs 5/kwh
CO 2 emission @ 0.91 ton/annum 51
kg/kWh
Purchase price difference lakhs 10
xxxvii
Payback period Yrs. 3.6
GHG emission reduction Ton/annum 89.30
for 250 TPD of 35 MVA
transformer (51/20)*35
5.9 REPLACEMENT OF CONVENTIONAL MAGNETIC CHOKES WITH

ELECTRONIC CHOKES
Case Study-9: Replacement of conventional magnetic chokes with energy saving electronic
chokes (1500 nos.) for electrical energy savings and reduction of failure of
tube rods.
Electrical energy saved in kWh by replacing with =1500 * 56.5 = 0.85 lakhs
electronic choke (saving is 56.5 kWh/choke/year @
4200 burning hours)
GHG emission reduction (0.85 *0.91) in Tons of 77.350
CO 2 eq./annum
Electrical energy saved @ Rs. 5 / kWh =0.85 * 5 = Rs 4.25 lakhs
Investment @ Rs. 200/electronic choke =200*1500=3 lakhs
Pay back period in Yrs. (3/4.25) 0.7
xxxviii
6. INTERNET OF THINGS (IOT)
6.1 OVERVIEW
As the world’s expendable energy resources deplete and the industrial sector is being
asked to deliver more to a growing population, energy efficiency has taken center stage to
ensure the longevity of these energy resources, and the Internet of Things can play a
crucial role. The emergence of the Internet of Things (IoT) almost certainly is the most
important single development in the long evolution of energy management. The insight
derived from data collected from new Internet-connected devices can be used to develop
new services, enhance productivity and efficiency, improve real-time decision making,
solve critical problems, and create new and innovative experiences.
Traditionally, many plants do not have the technology in place to track and measure
energy use. On top of that, information on a plant’s energy production and consumption is
not consolidated into a single place. Energy production and consumption data is often not
visible in real time and is not presented at a level granular enough to reflect how changes
in behaviour affect energy use. With limited information at their disposal, energy
managers can have a difficult time finding the places where energy use could improve. To
develop a clear energy-saving strategy and drive energy-saving behaviour, managers need
to boost monitoring capabilities and this data needs to be coordinated into a single system.
The Internet of Things (IoT) captures information seamlessly from the sensors and
machines that monitor all aspects of the manufacturing process. The information it returns
offer greater visibility into actionable data that can result in significant energy savings.
Network sensors track energy performance, monitor for leaks and flag any subpar
operating situations. Adding Internet of Things sensor technology to a plant allows for
real-time alerts that notify energy managers about wasteful situations. Energy managers
can then take timely action before their operation loses large amounts of money. Further,
the Internet of Things gets the right information to the right expert– whether that person is
an onsite manager, an off-site facility specialist, or a third party expert—when they need
it, so they can make the best decisions to improve energy performance.
6.2 APPLICATIONS OF IOT IN CHLOR-ALKALI PLANTS
Few applications of IOT are presented as follows:
xxxix
Chlorine Electro-Chemical Process Optimization
A process optimizer balances the current efficiency across cells to optimize performance
and to identify and diagnose faults. The software can be operated with any DCS platform.
Data is interpreted and performance variability in oxygen, hydrogen and chlorine is
determined. It improves cell performance, product quality, membrane life and production.
Rectifier Control
Application specific control features include:
• Constant current control

• Power factor regulation
• Ampere-hours regulation
• Active compensation of DC current over swing due to tap changing
• Trending
PVC Reaction Process Optimisation
PVC is one of the product manufactured using chlorine generated from cell house.
Operating and controlling PVC reactors is a key area for better product quality,
productivity and cost reduction.
Off-line tool has model calibrated with historical data and enables “what if” scenarios to
be carried out for maximizing output, minimizing cost and improving product quality.
On-line tool can be used to support batch optimization and characterization. The model
supports on-line real-time parameterization to predict, control and optimize such items as
initiator charge and reactor temperature profile. As a result, reaction times are optimized;
plant throughput increases and coarse out-of-specification batches are detected earlier.
Predictive Asset Management
Predictive asset management tool determine the operating conditions of manufacturing

assets without the use of dedicated asset monitoring equipment. Using existing sensor data
and known fault conditions, predictive asset management tools determine the operating
conditions of manufacturing assets without the use of dedicated asset monitoring
equipment. This approach is particularly beneficial in areas of the plant where operating
conditions make it difficult to take specific measurements. It will reduce planned and
unplanned maintenance costs.
xl
6.3 APPS FOR PRODUCTIVITY ASSESSMENT AND IMPROVEMENT
This section lists various Apps available free of cost online which can be installed in smart
phones and used on daily basis for
1. Process improvement
2. Resource optimisation
3. Troubleshooting
Few apps are listed below for reference.

S. No. App Logo Description
1 Plutocalc is problem solver suite for water
treatemnt, wastewater, hydraulics, environmental
chemistry and unit conversions.
2 The Association of Water Technologies (AWT)

calculations app allows water treaters to do basic
water treatment calculations on their mobile
device. The app allows you to determine your
boiler system conditions, conduct a cooling tower
survey, calculate dealkalizer capacity and
determine energy savings.
3 The Heat Exchanger calculator is based on
Effectiveness – NTU method.
4 User can calculate heat loss and outside surface

temperature of an insulated pipe and a bare pipe
to surroundings.
5 Helps user to calculate some basic technical

values about air compressors.
6 It is for persons who need to install a compressor.

Includes calculations for:
• Buffer capacity
• Pipe diameter
• Pressure drop
xli
• Cooling air required
• Unit conversion
• Leakage calculations
• Condesate formed
7 It helps to calculate gas compressor requirements
such as actual flow, head and power. Produces
output reports.
8 It is ideal steam application tool. Calculations

involved from steam generation to condensate
loop. Equipped with steam tables and unit
conversions.
9 Gives access to steam table and saturated steam

pipe sizing tool without internet.
10 Allows check efficiency of pumps and other

rotating equipment.
11 Can be used for design and selection of

centrifugal pumps, positive displacement pumps,
electric motors, machinery components.
12 App provides calculation for volume, surface

area, flash steam calculation, pump shaft power,
pipe flow calculation, cooling tower process
calculation, etc.
13 User can get lighting design for commercial and

industrial lighting. User can create own lighting
solutions through app.
14 This app is intended for use as a quick reference

guide for identifying types of workplace
respiratory protection that may be appropriate for
use when handling certain types of chemicals.
xlii
15 This Indian Red Cross Society First Aid
application provides you first aid guidelines to
handle day-to-day emergencies.
The information included is updated using the

latest international guidelines for first aid (2015-
2016).
xliii
ABBREVIATIONS
AMAI Alkali manufacturer association of India

BAT Best available technology
BCM Billion cubic meters
CD Current density
CE Current efficiency
CFL Compact fluorescence light
CIL Coal India Ltd
EPDM Ethylene propylene dinene monomer
ETP Effluent treatment plant
FEB Fluorinated ethylene propylene
GHE Greenhouse emissions
gpl Gram per litre
HCL Hydro chloric acid
LED Light emitting diode
lpm Liters per minute
Mn Million
MT Metric Ton
MTOE Million tons of oil equivalent
MW Mega watts
NaClO Sodium hypochlorite
NaClO 3 Sodium chlorate
PEM Polymer electrolyte membrane
PPb Parts per billion
ppm Parts per million
PTFE Poly tetra fluro ethylene
RO Reverse osmosis
SCCL Singareni collieries company Ltd
T Tons
TPD Tons per day
VFD Variable frequency drive
xliv
BIBLIOGRAPHY
1. Industry Reports of Alkali Manufacturers Association of India

2. Chlorine Safety - World Chlorine Council
3. XIIth five year plan – Report on Indian chemical industry
4. Handbook of Chlor-Alkali Technology – Thomas F. O’ Brien, Tilak V.
Bommaraju and Fumio Hine
5. Degremont -Water Treatment Handbook
6. GE Water Treatment Handbook
7. Energy Audit data gathered from Andhra Sugars Ltd., Travancore Chemicals,
TPL, DCW Sahupuram and other industries.
8. Water manual by CII, 2011
9. Best Available Techniques (BAT) Reference Document for the Production of
Chlor-alkali by European Commission, Industrial Emissions Directive
2010/75/EU, 2014
11. Handbook of Public Water Systems, Second edition, 2001, HDR Engineering Inc.
13. Best Available Techniques (BAT) Reference Document for the Production of
Chlor-alkali by European Commission, Industrial Emissions Directive
2010/75/EU, 2014
16. Thyseen Krup Tech forum article Issue 1, 2013, published by ThyssenKrupp AG,
Germany
17. Sustainable engineering & technology developments for energy conservation:
Chlor- alkali Industry by S. K. Dodiya and Dr. R. L. Yadav, Chemical Industry
Digest. June 2015.
18. Report on Setting up standards and Norms for Energy Usage in Chlor-alkali Sector
prepared by National Productivity Council, Chennai
19. Perry’s Handbook on Chemical Engineering, 8th Edition.
20. Guide book for National Certificate exam for energy managers and Energy
auditors by Bureau of Energy Efficiency
21. www.swagelokenergy.com
22. Best Practice Guide: Steam, Hot Water & Process Heating: Obrieni
23. Guide book for National Certificate exam for energy managers and Energy
auditors by Bureau of Energy Efficiency
xlv

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Copyright 2017 National Productivity Council

2. CHLOR ALKALI SECTOR PROFILE ..................................................................... 14

3. CHLOR-ALKALI MANUFACTURING PROCESS .................................................. 22

4. BEST PRACTICES ................................................................................................ xx

6. INTERNET OF THINGS (IOT) .......................................................................... xxxix

Mr. Ramkumar Shankar Ex-President

Thyssenkrupp Industrial Solutions

Mr. Kalyana Sundaram, Asst. Vice President

Mr. Jayapalan, AGM

Mr. R Jeyakumar, Executive Vice President

Andhra Sugars, Kovvur

Sree Rayalaseema Alkalies and Allied

This manual is expected to serve as reference manual for

Project Coordinator Mr. R Virendra, Dy. Director General,

Team Coordinator Mr. D Sreenivasulu, Dy. Director

Mr. R Idhayachander, Dy. Director

Mrs. V G Sandhya, Asst. Director

Mr. N.K. Kuttiappan, President

Advisors Mr. J. Nagesh Kumar, Director

Mr. K Pattabi, Ex General Manager

• Energy security – to meet present and future needs

1.2 ABOUT THE PROJECT

To ensure effective translation of policy and implementation of action plans, Department of

For preparing this manual, the following methodology was adopted:

1.4 GREENHOUSE GASES AND ITS IMPACT

Figure 1.2 Natural and Human Enhanced Greenhouse Effect

CH 4 Methane Landfills, production and 12 21

HFC's Hydro Refrigeration gases, aluminum 264 Up to

Figure 1.3 Per capita CO 2 Emissions

Impacts of Global Warming

Rise in Global Temperature

Rise in Sea Level

Food Shortages and Hunger

1.5 OUTLINE OF ENERGY SCENARIO IN INDIA

Figure 2.4 Primary Energy Demand in India for 775 MTOE

1 Iron and Steel 6.5–7.0 GCal/Ton 4.5–5.5 GCal/Ton

2 Cement 80 kWh/T 110 kWh/T

3 Aluminium 4300 kWh/T (Refinery) 3850 kWh/T (Refinery)

16500 kWh/T (Smelter) 15250 kWh/T (Smelter)

4 Fertilizer 7.7 GCal/T of Urea 6.5 GCal/T of Urea

5 Paper and Pulp 8.4 Steam consumption/Ton 4.5 Steam

6 Textile 7.1 GCal/Ton 3.1 GCal/Ton

2.1 GCal/T (Caustic Soda) 1.8 GCal/T (Caustic Soda)

Energy Conservation and GHG Emission Reduction Initiatives by Government

Table 1.3: Government Policies and Initiatives for Energy Conservation

Energy Conservation in Buildings and Municipalities

1.6 GHG EMISSION FACTORS

Table 1.4 Typical GHG Emission Factors

Table 2.1 Distribution of Chlor Alkali Plants in India

2.2 CAPACITY UTILIZATION

1.5 Installed Capacity

Source:Annual Report-Chlor-Alkali industries

Figure 2.1 Installed Production vs. Capacity (2009−2014)

Table 2.2 Capacity Based Segregation (2013-14)

Process <100 TPD 100-500 TPD1 >500 TPD1

Table 2.3 Breakup of Caustic Consumption in Different Industrial Sectors

Pulp and Paper 15% Dyes & Inks 3%

Organics 12% Water treatment 3%

Soap and Detergents 7% Others 16%