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ENERGY LOST IS LOST FOR EVER

Chlorine is used in a vast range of processes to create thousands of


indispensable products. Chlorine is everywhere. If you drink a glass of water,
take medicine, clean your teeth or drive to work you are benefiting from
chlorine compounds. Even your bodies own digestive system depends upon a
chlorine compound (hydrochloric acid) to break down foodstuffs.

The prospects for the establishment of the chloro-alkali industry is assessed by


the demands for caustic soda, chlorine and related products, the raw material
base for electrolysis of brine as well as available process technologies.

As a result of import constraints, the sector is characterized by low capacity


utilization with only 17% of firms operating between 69-79% installed capacity
and 33% firms operating under 20% installed capacity. The sector is hard-hit by
the recent trade liberalization, having to compete with imported products both in
quality and price.

In the industrialized countries, it is largely the demand for chlorine for the
synthesis of various organo-chloro compounds which has stimulated growth and
expansion of the chloro-alkali industry. For every tonne of chlorine made, 1.1
tonnes of caustic soda (100%) and 0.03 tonnes of hydrogen are produced.

Chlorine can also be prepared from hydrochloric acid by oxidation of the


hydrogen chloride (Deacon's process) and from bleaching powder.

Production of chlorine is extremely energy intensive. Energy consumption per


unit weight of product is not far below that for iron and steel manufacture and
greater than for the production of glass or cement. Since electricity is an
indispensable raw material for the production of chlorine, the energy
consumption corresponding to the electrochemical reaction cannot be reduced.
Energy savings arise primarily through applying more efficient technologies and
reducing ancillary energy use.

Most investment proposals encounter the problem of choice of process


technology for the electrolysis. Three different process technologies are applied
in the electrolytic production of caustic soda and chlorine. The technologies are
characterized by the type of electrolytic cell used, namely, the diaphragm cell,
mercury cell and the membrane cell. In all the processes, saturated brine 300-
315 g/L is fed into the electrolytic cells.

In the diaphragm cell process, the anolyte is separated from the catholoyte by
asbestos diaphragm to prevent contact between chlorine produced at the anode
and the caustic soda and hydrogen at the cathode. In the membrane cell process,
cat-ion exchange membranes are used to separate the anode and cathode
compartment of the electrolytic cell. At the anode, chlorine ions discharge with
evolution of chlorine gas. At the cathode, hydrogen is evolved and caustic soda
is formed. The cat-ion exchange is impermeable to the chloride ions and
therefore the caustic soda produced contains only trace levels of sodium
chloride. In mercury cell process, the liquid mercury cathode forms amalgam
with sodium. The amalgam is removed from the cell and reacted with water in
denuders to give caustic soda and hydrogen. Chlorine is liberated at the anode.

Factors which were considered in the choice of process technology include


flexibility of scaling capacity utilization and environmental impact. Other
factors considered were cell materials, power consumption and current effi-
ciency.

Choice of process technology: The membrane cell process, compared with


diaphragm and the mercury cell processes, has superior economic characteris-
tics. The membrane cell process operates in modules. It therefore provides for
easy reduction or expansion of capacity to the demand for caustic soda and
chlorine. It has low power consumption as a result of low voltage drops at the
electrodes and membranes, closer electrode spacing, lower chlorine and
hydrogen over voltages. The membrane cell process produces high purity
caustic soda. The cell design does not use hazardous materials such as mercury
or asbestos. Operating in modules and combining superior economic
characteristics, the membrane cell process is considered most appropriate choice
for the electrolysis of brine.

Each of these processes utilizes NaCl salt as the primary raw material. The salt
is electrolytically split using direct current (DC) electricity, resulting in Chlorine
and an available sodium ion (Na+) that is reacted with water in the cell to make
Caustic Soda and by-product Hydrogen. The hydrogen by-product produced is
used as a fuel source, sold to hydrogen customers, or to produce high purity
(burner grade) Hydrochloric Acid.

A fourth technology that produces commercially available quantities of Caustic


Soda solutions is a chemical conversion of trona ore.

Five major energy saving areas having maximum potential:

1. Compressed air is a major energy source. But how efficiency this is

produced, is often takes a back seat. Preparation of corrosion free


compressed air will not only increase energy efficiency but also will have
cascading effect downstream in terms of maintenance.

a. A simple pH test on a condensate sample can indicate the presence


of corrosive gases in the airstream. A pH of 7 is neutral. If the pH is
less than 7, the condensate is acidic and it will attack copper and
steel. If the pH is greater than 7, the condensate is basic and it will
attack metals such as aluminum. This test will simply indicate the
presence of a corrosive compound that will dissolve in water to
form an acid or a base. Compounds that do not form acids or bases
when mixed with water will not change the pH of the condensate.

b. Another way is to hang a metal strip in the air stream, usually in

the particulate filter housing, for a period of time. The strip then is
sent to a laboratory for analysis. As corrosive gases react with the
base metal of an air compressor component, a chemical product in
the form of a film will build up on the surface of the base metal.
Specially prepared copper and silver strips are usually exposed for
a time period varying from 30 to 90 days. Analysis of the test strip
will reveal the average film thickness built up during the test
period.

c. One way to measure mass gain in a compact package is to provide


an exciting force to the test sample, causing it to vibrate, such as
quartz crystal microbalance. The first natural frequency is
dependent upon the mass of the sample. As mass increases, the
frequency will decrease. If the frequency can be measured, then the
change in frequency can be correlated to the change in mass, and
then to the change in film thickness and the incremental corrosion
rate.

d. Once the air has been identified as corrosive, something must be

done to protect the internal mechanisms of the compressed air


system. The most common method of removing chemicals from
the air is gas-phase filtration or dry scrubbing the air. This
compressor protection system removes gaseous contaminants from
the air stream by way of adsorption, absorption, and
chemisorptions. An adsorbent media, such as granular activated
carbon, will attract other substances and hold them on the surface
of the adsorbent particle. Absorption is a similar process in which
the attracted chemical penetrates into the internal structure of the
filtration media. The major problem with these two types of media
is that they will sometimes release the captured gases. Carbon
based media such as coconut shell carbon will release lower
molecular weight gases in favor of high molecular weight gases. A
chemisorbing media, such as potassium permanganate-impregnated
alumina, will chemically react with some contaminant gases,
oxidizing them and removing the possibility that they could be
released. A filtration system supplier can recommend the
appropriate chemical media type.

e. Existing compressors handling more capacity can be increased by

trimming internal parts of unit, and reduced the power


consumption. Use of 90 deg. longer radius bends in suction and
delivery lines is always energy efficient.

2. Variety of pumping system exists in this industry handling variety of


chemical. We do focus on the mature of the materials to be handled by
pumps, but seldom look for energy efficient routes.

a. The positive displacement action of the pump lifts the raw sewage

from the sump into the cutting chamber of the macerator. The
sewage and any textile and fibrous matter is macerated and then
pumped away to the main gravity sewer. When the pumping cycle
ends, un-macerated material falls back into the sump, clearing the
suction pipe for the next duty run. Low suction velocities ensure
foreign object damage is eliminated, unlike pumping stations with
submersible pumps. Any large objects remain in the sump for
periodic removal, avoiding any pump damage.

b. A chlorine manufacturing plant is achieving significant cost

savings from the installation of a Compact Mutrator. The pump


previously used on sewage was unable to cope with the increased
demand from the site development and generated a Rs.250, 000
annual repair bill. With the installation of complete sewage
pumping station, the system works unattended and has been
entirely trouble-free since installation. Pumping the sewage at
4m3/h, the packaged system uses 15% less electricity and is driven
by a 4kW motor, compared with the two 5.5kW motors used
previously. The benefit offered by progressing cavity pumps is that
head is independent of speed and therefore, they can be operated at
a far lower speed than before - 400rpm compared with 960rpm,
thereby reducing wear, while maintaining high head capability.

3. Typical electrolysis of brine solution requires low voltage DC power.

Low voltage drives are energy efficient methods and needs no


introduction. Market growth can also be attributed to the increasing
awareness of its energy saving and enhanced process performance
benefits among end users. Adopting drives to reduce energy costs. This is
propelling the low-voltage drives market forward.

4. SPECIFIC POWER CONSUMPTION DETAILS need monitoring and

control and make the same subject to audit and statutory compliances.
UNITS 2002-03 2003-04 2004-05
Annual Production MT 65842 77274 80209
Total Energy per Annum KWH (lakhs) 1815.87 2111.78 2214.18
Total Thermal Energy Million K cal 55901.82 56842.29 44474.07
Total Annual sales turnover Cost Rs. Lakhs 5578.7 6769.2 17688
Total Energy Cost Rs. Lakhs 5631.45 6699.62 7070.58
Energy Cost as % of Production Cost % 55.4 55.4 64
DC Electrolysis Power Consumption KWH/MT 2639 2346 2402
AC Rectification Power Consumption KWH/MT 2340 2406 2464
AC Power Consumption with Aux. KWH/MT 2726 2682 2725
Auxiliary Power Consumption KWH/MT 296 275 261
Steam Consumption Mkcal/MT 0.85 0.73 0.55

5. Coal-fired power plants can add PVC scrap to their coal and make
byproduct hydrochloric acid. The result would be elimination of mercury
both from coal-fired stacks as well as from the obsolesced chlorine
manufacturing facilities. There would also be greenhouse gas benefits
and elimination of the environmental problems associated with disposing
of millions of tons of waste PVC.

The Energy Policy in our industry is always part of our ESOH policy for ISO
14000 and OHSAS 18000 standards and it is shown as under.
Suggestions for effective implementation of EC Act in Chloro Alkali sector.
Apart from the conventional practice of involving people as a participation
systems, which is always mandatory and to be encouraged, technological
improvements are essential in making continuous improvements. And for
this mediocrity needs sharpening and encouragements to technical inputs is
paramount.
• Encourage and provide incentive to adopt membrane technology in
next 5 years. Stop manufacturing by other harmful processes using
asbestos or mercury after following first step.
• EC Act to be made a part of Pollution Control Board’s area of control.
Consents must encompass Energy standards also.
• Pursue EC Act among municipalities. This will create awareness
among masses. In a market driven economy, this industry must have
ways to efficiently manufacture a lower capacities also. Else
discourage to operate and will ensure better capacity utilization in
efficient processes.
• Chlorine is never used independently. It is mostly a feed stock for
other processes. Decentralization of Chlorine manufacturing at the
point of use will reduce many handling and storage systems of
Chlorine gas. This is being practiced but need to be speeded up.
• Renewable sources of energy are on the look out across the globe.
How about renewable sources of Chlorine? This organo-chloro
chemistry needs further research and promotion.

Under the current technological scenario, electrolysis of brine solution with


membrane separator is the most efficient and friendly. However, addition of
PVC along with coal in a coal fired power plants will produce HCl as by-
product and allow us to take a fresh look at the entire Chloro-Alkali industry.