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1 
PROJECT TOPIC 
MANUFACTURE OF CHLORINE– 
CAUSTIC 
SODA USING ELECTROLYSIS 
PROCESS 
BHARATI VIDYAPEETH 
COLLEGE OF ENGINEERING 
CHEMICAL DEPARTMENT 
Prof. R.K.Kulkarni 
Presented by 
Ankush Gupta 
Aviral Kandpal 
Sushant Mali
Introduction to Caustic soda / Chlor 
2 
Alkali Industry 
• The Chlor-Alkali industry in India forms an important component of 
basic chemicals industry ,comprising around 74% of the basic 
chemicals production in India. 
• The Chlor-Alkali Industry in the country produces mainly Caustic 
Soda, Chlorine and Soda Ash. 
• The geographic distribution of Chlor-alkali processes world-wide 
differs appreciably (production capacity of chlorine): 
-western Europe, predominance of mercury cell process (June 
2000): 55% 
-United States, predominance of diaphragm cell process: 75% 
-Japan, predominance of membrane cell process: >90%
3
PROPERTIES OF CHLORINE-CAUSTIC 
4 
SODA-HYROGEN 
CAUSTIC SODA 
Physical State Solid. 
Appearance White pellets. 
Odor Odorless. 
Vapor Pressure 1 mm Hg @ 739 CO 
Boiling Point 1390 CO @ 760 mm Hg 
Freezing/Melting Point 318 CO 
Solubility Soluble. 
Specific Gravity/Density 2.13 g/cm3. 
Molecular Formula NaOH. 
Molecular Weight 40.00 
PH 14 (5% aq soln).
5 
CHLORINE
6 
HYDROGEN 
APPEARANCE AND STATE Colorless gas at normal temperature and 
pressure 
ODOR Odorless 
MOLECULAR WEIGHT 2.016 
BOILING POINT (1 atm) 423.0 _F (-252.8 _C) 
SPECIFIC GRAVITY (Air =1) 0.06960 
FREEZING POINT/MELTING POINT -434.5 °F (-259.2 _C) 
GAS DENSITY (At 70 F (21.1 C) and 1 atm): 0.00521 lb/ft3(0.08342 kg/m3) 
SOLUBILITY IN WATER (Vol/Vol at 60 F (15.6 
0.019 
C) 
SPECIFIC VOLUME (At 70 F (21.1 C) and 1 atm 192 ft3/lb (11.99m3/kg)
7 
LITERATURE SURVEY
8 
SERIA 
L NO 
NAME OF AUTHOR YEAR OF 
RESEARCH 
RESEARCH TOPIC DESCRIPTION 
1 S.koter.A.warszaws 
ki 
2008 Electromembrane 
process in environmental 
protection 
Use of bipolar membrane is 
emphasized.recovery of 
valuable chemicals from 
effluents& waste gases 
Application of ion exchange 
membrane “green” power 
source is also discussed 
2 yohannes kiros 
&martin bursell. 
2008 Low energy consumption 
in chlor alkali cells using 
oxygen reduction 
electrodes 
Gas diffusion electrode for 
use as a cathode to 
replace the traditional 
hydrogen evolving 
electrode in chlor-alkali 
electrolysisProblems 
associated with ‘flooding’ 
or‘wetting’ are minimised 
by attempt to stablize 
cathode
9 
SERIAL 
NO 
NAME OF 
AUTHOR 
YEAR OF 
RESEARCH 
RESEARCH TOPIC DESCRIPTION 
3 Babatope 
A.olufemi,willia 
ms o.ozoute & 
ololane 
o.komolafe 
2011 Studies on production 
of caustic soda using 
solar powered 
diaphragm cells. 
The research served as an 
encouraging inquistive foundation 
into possibility of producing 
caustic soda directly from solar 
powered electrolytic diaphragm 
cells in comparison with present 
conventional modes of 
electrochemical production . 
4 K.juttner,u 
galla,h 
schmieder 
2008 Electrochemical 
approaches to 
environmental 
protection in process 
industry 
•. Protection of environment 
through implementation of 
effluent treatment productio 
integrated process for 
minimization of waste and 
toxic 
•Anode destruction of organic 
pollutants and new 
electrochemical abatement 
techniques for purification of 
the gaseS
10 
SERIAL 
NO 
NAME OF 
AUTHOR 
YEAR OF 
RESEARCH 
RESEARCH TOPIC DESCRIPTION 
5 Subrata Basu, 
Swapan Kumar 
Mukhopadhyay, 
Amitava 
Gangopadhyay 
and Sujata G. 
Dastidar 
2013 Characteristic Change 
of Effluent from a Chlor-alkali 
Industry of 
India due to Process 
Modification 
The main focus of this paper 
is on the evaluation of waste 
minimization at source due to 
process modification. The 
possible 
improvement of the treatment 
of effluent is also duly 
considered. 
6 A. Rezaee, J. 
Derayat, ,S.B. 
Mortazavi, Y. 
Yamini and M.T. 
Jafarzadeh 
2005 Removal of Mercury 
from chlor-alkali 
Industry Wastewater 
using 
Acetobacter xylinum 
Cellulose 
•The removal of mercury ions 
by cellulose of Acetobacter 
xylinum was 
investigated in the synthetic 
and chlor-alkali wastewater. 
•Efficiency of 
mercury ion removal from 
chlor-alkali industry 
wastewater by aluminum 
sulfate and ferric 
chloride was also determined.
Competitive Manufacturing 
11 
Process 
• There are 3 types of electrolytic 
processes used in the production of 
chlorine: 
(1) The diaphragm cell process 
(2) The mercury cell process 
(3) The membrane cell process 
• A salt solution is electrolyzed by 
the action of direct electric 
current that converts chloride ions 
to elemental chlorine. The overall 
process reaction is: 
In all 3 methods, the chlorine is 
produced at the positive electrode 
(anode) and the caustic soda and 
hydrogen are produced, directly or 
indirectly, at the negative electrode 
(cathode).
The Diaphragm cell process 
12
13 
FEATURES 
DIAPHRAGM CELL 
• In the diaphragm cell process, there are two 
compartments separated by a permeable diaphragm. 
• Brine is introduced into the anode compartment and 
flows into the cathode compartment. 
• Similarly to the Membrane Cell, chloride ions am 
oxidized at the anode to produce chlorine, and at the 
cathode, water is split into caustic soda and hydrogen. 
• The diaphragm prevents the reaction of the caustic soda 
with the chlorine. 
• A diluted caustic brine leaves the cell. 
• The caustic soda must usually be concentrated to 50% 
and the salt removed. This is done using an evaporative 
process.
The Mercury cell process 
14
15 
FEATURES 
MERCURY CELL 
• Electric current flowing through the cell decomposes the brine passing 
through the narrow space between the electrodes, liberating chlorine 
gas at the anode and metallic sodium at the cathode 
• The chlorine gas is accumulated above the anode assembly and 
discharged to the purification process. 
• As it is liberated at the surface of the mercury cathode and the sodium 
immediately forms an amalgam (a 'mixture' of two metals) 
• The liquid amalgam flows from the electrolytic cell to a separate 
reactor, called the decomposer, where it reacts with water in the 
presence of a graphite catalyst to form caustic soda (sodium hydroxide) 
and hydrogen gas. 
• The sodium-free mercury is fed back into the electrolyser and reused.
The membrane cell process 
16
17 
FEATURES 
MEMBRANE CELL 
• This technology uses water-impermeable ion-conducting membrane. 
• The membrane is made of a special resin which permits cations 
(positive ions) to pass through. 
• The anode chamber of a membrane electrolytic cell is filled with 
brine, and the cathode chamber with water. 
• These ions migrate when a current is applied: the positively charged 
sodium ions pass through the membrane to the cathode chamber, 
while the negatively charged chloride ions are discharged on the 
anode surface to form chlorine gas . 
• Water in the cathode chamber partly dissociates into hydrogen and 
hydroxide ions. 
• The hydrogen ions capture electrons on the cathode surface to form 
hydrogen gas. 
• The hydroxide ions are attracted to the anode, but blocked by the 
membrane, and react with the sodium ions from the anode chamber 
to form caustic soda (sodium hydroxide, NaOH)
SELECTION OF THE PROCESS 
18 
MEMBRANE CELL PROCESS 
• The membrane cell process has inherent 
ecological advantages over the two older 
processes, as it does not use mercury or 
asbestos. 
• It is the most energy efficient process. 
• It is extremely safe to operate it and it produces 
a consistently high quality of caustic soda.
19
20
21 
Thermodynamic Feasibility 
• The standard free energy, ΔGº tells us the thermodynamic 
feasibility of a reaction. Since the standard electrode 
potential of a reaction, E° and ΔG° are intimately linked; 
one can use the standard electrode potentials of a reaction 
to calculate the thermodynamic feasibility of a reaction. 
ΔGo= -nFEo 
n= no of electrons transferred 
F= Faraday constant = 96630 J/V.mol 
Eo = Cell voltage 
So, ΔGo = -1*96630*6  -579780 J/mol 
ΔGO << 0 
SO THIS REACTION IS FEASIBLE
PROCESS FLOW DIAGRAM 
22
23 
Pressure & Temperature 
Combinations for condensing gas 
•High pressure (7-10 atms), water cooling 
•Medium pressure (2-3 atms), Refrigeration at 
- 20oC 
•Low pressure (5-10 cm H2O), Refrigeration at 
-400C
24 
Quantitative Requirements 
• Basis of Product : 1 ton of Cl2 ; 1.15 tons of NaOH(98%) . 
• Plant capacities : 100-1000 tons/day of Cl2 in a series of electrolysis 
units each producing 0.5 – 2 tons Cl2 per day 
Sulphric Acid (98%) 5-6 kg 
Sodium hydroxide 10-15 kg 
Steam 11 tons 
Electricity 2900 KWH
25 
• DIAPHRAGM CELL TYPE 
• Anode : Cl - - e  ½ Cl2 
• Cathode: Na+ H2O + e  Na+ + OH- + ½ H2 
• Overall: NaCl + H2O  NaOH + ½ H2 + ½ Cl2 
• MERCURY CELL PROCESS 
• Anode: Cl- - e  ½ Cl2 
• Cathode: Na+ + e  Na 
: Na + Hg  NaHg(amalgam) 
• Denuding: NaHg + H2O  NaOH + ½ H2 + Hg 
• Overall: NaCl + H2O  NaOH + ½ H2 +Cl2 
• 2NaCl + 2H2O  2NaOH + H2 +Cl2
2NaCl + 2H2O  2NaOH + H2 +Cl2 (58.5) (18) 
26 
(40) (2) (70) 
( 28.75) (28.75) (28.75) (14.375) (14.375) Kmoles 
(1681.8) (517.5) (1150) (28.75) (1006) Kg 
• Sample calculation 
Moles = weight / molecular weight 
For NaCl 
Moles = 1150/40  28.75 Kmol 
NaCl formed (Kg) = 28.75 * 58.5  1681.8 kg (1700 Kg).
27 
Factors affecting Plant location 
• Adequate Supply of Raw materials. 
• Proximity to the market — Minimum supply time. Relative cost low 
(one third of caustic plants are attached to paper and rayon mills). 
• Transport Facilities — Good capacity and speedy transportation. 
• Supply of Labor — Cheap Labor Supply. 
• Power— Regular Power Supply for operation machinery at full 
capacity. 
• Supply of Capital — Required for Initial promotion and Expansion. 
• Natural Factors — Land, Water, Climate(Agriculture based 
Industries). 
• Political Factors — Favorable Development Policies. 
• Government Subsidies — Exemptions, Rebates and Subsidies. 
• Historical and religious factors. 
Need careful analysis of such factors as cheap power and salt sources 
coupled with risisng cost of transportation.
28 
Locations of caustic soda plants 
NAME PROCESS USED 
Durgapur Chemicals Ltd 
Mercury cell 
(Durgapur W.B) 
J.K Chemicals Ltd ,thane 
(Maharastra) 
Mercury cell 
Sirpur Paper mills ,sirpur 
khaghaz nagar(A.P) 
Diaphragm cell 
Chemfab Alkalies ltd 
(pondicherry) 
Membrane cell 
Rohtas Industries ltd ( bihar) Mercury cell
REFERENCES 
1 ) Subrata Basu , Swapan Kumar Mukhopadhyay , Amitava 
Gangopadhyay and Sujata G. Dastidar “International Research 
Journal of Environment Sciences Characteristic Change of Effluent 
from a Chlor-alkali Industry of India due to Process Modification” 
2013. 
2) S.Koter.A.Warszawski “Polish Journal of Environmental Studies 
Electro- membrane Processes in Environment Protection” (2000) 
3) Yohannes Kiros and Martin Bursell “International Journal 
Electrochemistry Science Low Energy Consumption in Chlor-alkali 
Cells Using Oxygen Reduction Electrodes (2008)” 
4) Rezaee, J. Derayat, S.B. Mortazavi,Y. Yamini and M.T. Jafarzadeh 
“American Journal of Environmental Sciences Removal of Mercury 
from Chlor-alkali Industry Wastewater using Acetobacter xylinum 
Cellulose(2005)” 
29 
5) Dryden’s outlines of chemical technology (2012)

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Manufacture of caustic soda and chlorine using electrolysis process ........... CONTD . http://www.slideshare.net/AnkushGupta40/phase23

  • 1. 1 PROJECT TOPIC MANUFACTURE OF CHLORINE– CAUSTIC SODA USING ELECTROLYSIS PROCESS BHARATI VIDYAPEETH COLLEGE OF ENGINEERING CHEMICAL DEPARTMENT Prof. R.K.Kulkarni Presented by Ankush Gupta Aviral Kandpal Sushant Mali
  • 2. Introduction to Caustic soda / Chlor 2 Alkali Industry • The Chlor-Alkali industry in India forms an important component of basic chemicals industry ,comprising around 74% of the basic chemicals production in India. • The Chlor-Alkali Industry in the country produces mainly Caustic Soda, Chlorine and Soda Ash. • The geographic distribution of Chlor-alkali processes world-wide differs appreciably (production capacity of chlorine): -western Europe, predominance of mercury cell process (June 2000): 55% -United States, predominance of diaphragm cell process: 75% -Japan, predominance of membrane cell process: >90%
  • 3. 3
  • 4. PROPERTIES OF CHLORINE-CAUSTIC 4 SODA-HYROGEN CAUSTIC SODA Physical State Solid. Appearance White pellets. Odor Odorless. Vapor Pressure 1 mm Hg @ 739 CO Boiling Point 1390 CO @ 760 mm Hg Freezing/Melting Point 318 CO Solubility Soluble. Specific Gravity/Density 2.13 g/cm3. Molecular Formula NaOH. Molecular Weight 40.00 PH 14 (5% aq soln).
  • 6. 6 HYDROGEN APPEARANCE AND STATE Colorless gas at normal temperature and pressure ODOR Odorless MOLECULAR WEIGHT 2.016 BOILING POINT (1 atm) 423.0 _F (-252.8 _C) SPECIFIC GRAVITY (Air =1) 0.06960 FREEZING POINT/MELTING POINT -434.5 °F (-259.2 _C) GAS DENSITY (At 70 F (21.1 C) and 1 atm): 0.00521 lb/ft3(0.08342 kg/m3) SOLUBILITY IN WATER (Vol/Vol at 60 F (15.6 0.019 C) SPECIFIC VOLUME (At 70 F (21.1 C) and 1 atm 192 ft3/lb (11.99m3/kg)
  • 8. 8 SERIA L NO NAME OF AUTHOR YEAR OF RESEARCH RESEARCH TOPIC DESCRIPTION 1 S.koter.A.warszaws ki 2008 Electromembrane process in environmental protection Use of bipolar membrane is emphasized.recovery of valuable chemicals from effluents& waste gases Application of ion exchange membrane “green” power source is also discussed 2 yohannes kiros &martin bursell. 2008 Low energy consumption in chlor alkali cells using oxygen reduction electrodes Gas diffusion electrode for use as a cathode to replace the traditional hydrogen evolving electrode in chlor-alkali electrolysisProblems associated with ‘flooding’ or‘wetting’ are minimised by attempt to stablize cathode
  • 9. 9 SERIAL NO NAME OF AUTHOR YEAR OF RESEARCH RESEARCH TOPIC DESCRIPTION 3 Babatope A.olufemi,willia ms o.ozoute & ololane o.komolafe 2011 Studies on production of caustic soda using solar powered diaphragm cells. The research served as an encouraging inquistive foundation into possibility of producing caustic soda directly from solar powered electrolytic diaphragm cells in comparison with present conventional modes of electrochemical production . 4 K.juttner,u galla,h schmieder 2008 Electrochemical approaches to environmental protection in process industry •. Protection of environment through implementation of effluent treatment productio integrated process for minimization of waste and toxic •Anode destruction of organic pollutants and new electrochemical abatement techniques for purification of the gaseS
  • 10. 10 SERIAL NO NAME OF AUTHOR YEAR OF RESEARCH RESEARCH TOPIC DESCRIPTION 5 Subrata Basu, Swapan Kumar Mukhopadhyay, Amitava Gangopadhyay and Sujata G. Dastidar 2013 Characteristic Change of Effluent from a Chlor-alkali Industry of India due to Process Modification The main focus of this paper is on the evaluation of waste minimization at source due to process modification. The possible improvement of the treatment of effluent is also duly considered. 6 A. Rezaee, J. Derayat, ,S.B. Mortazavi, Y. Yamini and M.T. Jafarzadeh 2005 Removal of Mercury from chlor-alkali Industry Wastewater using Acetobacter xylinum Cellulose •The removal of mercury ions by cellulose of Acetobacter xylinum was investigated in the synthetic and chlor-alkali wastewater. •Efficiency of mercury ion removal from chlor-alkali industry wastewater by aluminum sulfate and ferric chloride was also determined.
  • 11. Competitive Manufacturing 11 Process • There are 3 types of electrolytic processes used in the production of chlorine: (1) The diaphragm cell process (2) The mercury cell process (3) The membrane cell process • A salt solution is electrolyzed by the action of direct electric current that converts chloride ions to elemental chlorine. The overall process reaction is: In all 3 methods, the chlorine is produced at the positive electrode (anode) and the caustic soda and hydrogen are produced, directly or indirectly, at the negative electrode (cathode).
  • 12. The Diaphragm cell process 12
  • 13. 13 FEATURES DIAPHRAGM CELL • In the diaphragm cell process, there are two compartments separated by a permeable diaphragm. • Brine is introduced into the anode compartment and flows into the cathode compartment. • Similarly to the Membrane Cell, chloride ions am oxidized at the anode to produce chlorine, and at the cathode, water is split into caustic soda and hydrogen. • The diaphragm prevents the reaction of the caustic soda with the chlorine. • A diluted caustic brine leaves the cell. • The caustic soda must usually be concentrated to 50% and the salt removed. This is done using an evaporative process.
  • 14. The Mercury cell process 14
  • 15. 15 FEATURES MERCURY CELL • Electric current flowing through the cell decomposes the brine passing through the narrow space between the electrodes, liberating chlorine gas at the anode and metallic sodium at the cathode • The chlorine gas is accumulated above the anode assembly and discharged to the purification process. • As it is liberated at the surface of the mercury cathode and the sodium immediately forms an amalgam (a 'mixture' of two metals) • The liquid amalgam flows from the electrolytic cell to a separate reactor, called the decomposer, where it reacts with water in the presence of a graphite catalyst to form caustic soda (sodium hydroxide) and hydrogen gas. • The sodium-free mercury is fed back into the electrolyser and reused.
  • 16. The membrane cell process 16
  • 17. 17 FEATURES MEMBRANE CELL • This technology uses water-impermeable ion-conducting membrane. • The membrane is made of a special resin which permits cations (positive ions) to pass through. • The anode chamber of a membrane electrolytic cell is filled with brine, and the cathode chamber with water. • These ions migrate when a current is applied: the positively charged sodium ions pass through the membrane to the cathode chamber, while the negatively charged chloride ions are discharged on the anode surface to form chlorine gas . • Water in the cathode chamber partly dissociates into hydrogen and hydroxide ions. • The hydrogen ions capture electrons on the cathode surface to form hydrogen gas. • The hydroxide ions are attracted to the anode, but blocked by the membrane, and react with the sodium ions from the anode chamber to form caustic soda (sodium hydroxide, NaOH)
  • 18. SELECTION OF THE PROCESS 18 MEMBRANE CELL PROCESS • The membrane cell process has inherent ecological advantages over the two older processes, as it does not use mercury or asbestos. • It is the most energy efficient process. • It is extremely safe to operate it and it produces a consistently high quality of caustic soda.
  • 19. 19
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  • 21. 21 Thermodynamic Feasibility • The standard free energy, ΔGº tells us the thermodynamic feasibility of a reaction. Since the standard electrode potential of a reaction, E° and ΔG° are intimately linked; one can use the standard electrode potentials of a reaction to calculate the thermodynamic feasibility of a reaction. ΔGo= -nFEo n= no of electrons transferred F= Faraday constant = 96630 J/V.mol Eo = Cell voltage So, ΔGo = -1*96630*6  -579780 J/mol ΔGO << 0 SO THIS REACTION IS FEASIBLE
  • 23. 23 Pressure & Temperature Combinations for condensing gas •High pressure (7-10 atms), water cooling •Medium pressure (2-3 atms), Refrigeration at - 20oC •Low pressure (5-10 cm H2O), Refrigeration at -400C
  • 24. 24 Quantitative Requirements • Basis of Product : 1 ton of Cl2 ; 1.15 tons of NaOH(98%) . • Plant capacities : 100-1000 tons/day of Cl2 in a series of electrolysis units each producing 0.5 – 2 tons Cl2 per day Sulphric Acid (98%) 5-6 kg Sodium hydroxide 10-15 kg Steam 11 tons Electricity 2900 KWH
  • 25. 25 • DIAPHRAGM CELL TYPE • Anode : Cl - - e  ½ Cl2 • Cathode: Na+ H2O + e  Na+ + OH- + ½ H2 • Overall: NaCl + H2O  NaOH + ½ H2 + ½ Cl2 • MERCURY CELL PROCESS • Anode: Cl- - e  ½ Cl2 • Cathode: Na+ + e  Na : Na + Hg  NaHg(amalgam) • Denuding: NaHg + H2O  NaOH + ½ H2 + Hg • Overall: NaCl + H2O  NaOH + ½ H2 +Cl2 • 2NaCl + 2H2O  2NaOH + H2 +Cl2
  • 26. 2NaCl + 2H2O  2NaOH + H2 +Cl2 (58.5) (18) 26 (40) (2) (70) ( 28.75) (28.75) (28.75) (14.375) (14.375) Kmoles (1681.8) (517.5) (1150) (28.75) (1006) Kg • Sample calculation Moles = weight / molecular weight For NaCl Moles = 1150/40  28.75 Kmol NaCl formed (Kg) = 28.75 * 58.5  1681.8 kg (1700 Kg).
  • 27. 27 Factors affecting Plant location • Adequate Supply of Raw materials. • Proximity to the market — Minimum supply time. Relative cost low (one third of caustic plants are attached to paper and rayon mills). • Transport Facilities — Good capacity and speedy transportation. • Supply of Labor — Cheap Labor Supply. • Power— Regular Power Supply for operation machinery at full capacity. • Supply of Capital — Required for Initial promotion and Expansion. • Natural Factors — Land, Water, Climate(Agriculture based Industries). • Political Factors — Favorable Development Policies. • Government Subsidies — Exemptions, Rebates and Subsidies. • Historical and religious factors. Need careful analysis of such factors as cheap power and salt sources coupled with risisng cost of transportation.
  • 28. 28 Locations of caustic soda plants NAME PROCESS USED Durgapur Chemicals Ltd Mercury cell (Durgapur W.B) J.K Chemicals Ltd ,thane (Maharastra) Mercury cell Sirpur Paper mills ,sirpur khaghaz nagar(A.P) Diaphragm cell Chemfab Alkalies ltd (pondicherry) Membrane cell Rohtas Industries ltd ( bihar) Mercury cell
  • 29. REFERENCES 1 ) Subrata Basu , Swapan Kumar Mukhopadhyay , Amitava Gangopadhyay and Sujata G. Dastidar “International Research Journal of Environment Sciences Characteristic Change of Effluent from a Chlor-alkali Industry of India due to Process Modification” 2013. 2) S.Koter.A.Warszawski “Polish Journal of Environmental Studies Electro- membrane Processes in Environment Protection” (2000) 3) Yohannes Kiros and Martin Bursell “International Journal Electrochemistry Science Low Energy Consumption in Chlor-alkali Cells Using Oxygen Reduction Electrodes (2008)” 4) Rezaee, J. Derayat, S.B. Mortazavi,Y. Yamini and M.T. Jafarzadeh “American Journal of Environmental Sciences Removal of Mercury from Chlor-alkali Industry Wastewater using Acetobacter xylinum Cellulose(2005)” 29 5) Dryden’s outlines of chemical technology (2012)