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The document discusses the chlor-alkali industry and production of soda ash, caustic soda, and chlorine. It describes the Solvay process used to produce soda ash from salt, coal, limestone and ammonia. The dual process is also discussed as a modified version of the Solvay process. For caustic soda production, it describes the membrane cell electrochemical process as the preferred modern method over mercury cell and diaphragm cell processes due to lower energy usage and environmental impact.

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Chlor-Alkali Industries

Soda ash by using Solvay process and dual process

Caustic soda and Cl2 by using membrane separation
The chlor-alkali industry represents production of three major industrial chemicals
• Soda ash (Sodium carbonate-Na2CO3)
• Caustic soda (Sodium Hydroxide-NaOH)
• Chlorine ( Cl2)
• Hydrogen
Chlor Alkali is considered to be one of the oldest industrial sectors, which plays a key role in
supplying chemicals to other manufacturing sectors such as textiles, pulp & paper, alumina,
soaps & detergents, pharma, etc.
As on 2012, India constituted to 4% of global chlor alkali capacity, with installed capacity and
production of 3.1 Million MTPA and 2.6 Million MTPA respectively.

Chlor_Alkali_Sector_Report_2018.pdf
Soda Ash (Sodium Carbonate-Na2CO3 )
Physical
• M.wt = 106
• Mp. 851 °C
• Density @ 20 °C = 2.53 g/cm3;
Chemical
• Thermal Decomposition at 1000 °C/200 Pa
Na2CO3  Na2O + CO2
Manufacturing process
• Le Blanc Process ( 1773)
• Solvay or ammonia-soda Process
• Dual Process ( Na 2CO3 + NH4Cl)
• Soda ash from deposits
Le Blanc Process ( 1773)
Salt cake ( sodium sulfate) reacts with limestone to give soda ash and a troublesome side
product gypsum (calcium sulfate)
2 NaCl + H2SO4  Na2SO4 + 2 HCl
Na2SO4 + 2C  Na2S + 2 CO2

Na2S + CaCO3  Na2CO3 + CaS

Poor economics and excessive pollution caused by the hydrochloric acid and calcium sulfide by-product led to the
eventual demise of the Leblanc process.

The process is no longer used

Solvay Process (1864)
In 1864, a Belgian chemist, Ernest Solvay, developed a
process to produce soda ash from calcium carbonate
(limestone) and sodium chloride (salt).

CaCO3(s) + 2 NaCl(aq) Na2CO3 + CaCl2

Raw materials required

• Salt
• Coal Ernest Solvay
• Limestone
• Ammonia

http://pubs.acs.org/subscribe/journals/tcaw/11/i02/html/02chemchron.html
• Carbonation Tower
• 2 NH3 + CO2 + H2O  (NH4)2CO3 (exothermic)
• (NH4)2CO3 + CO2 + H2O  2 NH4HCO3
• NH4HCO3 + NaCl  NaHCO3 + NH4Cl2
Middle of Carbonator
• Ammoniation Tower
• NH3 + H2O  NH4+ OH-
• CO2 + H2O  HCO3 -
• Lime Kiln
• CaCO3  CaO + CO2
• C + O2  CO2
• Slaker
• CaO + H2O  Ca(OH)2
• Calciner
• 2 NaHCO3  Na2CO3 + CO2 + H2O
• Ammonia Recovery
• 2 NH4Cl + Ca(OH)2  CaCl2 + 2 NH3 + 2 H2O
Preparation and purification of brine:

Saturated sodium chloride brine is first purified to prevent scaling of downstream

process equipment and to prevent contamination of the final product and is pumped
to the ammonium absorber tower

Ammoniation of brine:
NH3 (aq) + H2O(l)  NH4+ OH- (aq) + 34900 kJ
CO2 + H2O  HCO3 -
The ammoniated partially carbonated brine is cooled to 30OC and pumped to the
carbonating tower.
Carbonation tower: (Precipitation of Bicarbonate)

The ammoniated brine is then sent to the carbonating columns where sodium
bicarbonate is precipitated by contacting the brine with carbon dioxide

2 NH3 + CO2 + H2O  (NH4)2CO3 (exothermic)

(NH4)2CO3 + CO2 + H2O  2 NH4HCO3
NH4HCO3 + NaCl  NaHCO3 + NH4Cl2
Middle of Carbonator
NaHCO3 is less soluble and precipitates on the internals of the carbonating column.
• At the end of the make cycle, the slurry is drained and the solid NaHCO 3 is filtered.
However, considerable amounts of NaHCO 3 remain in the column after the slurry is
drained.
• A series of five or more columns with appropriate piping interconnections are used for
continuous operation.
• The carbonation is favored by higher pressures and low temperature.
Filtration of bicarbonate

• The slurry from the carbonating columns is fed to continuous vacuum filters or centrifuges
where NaHCO3 crystals are recovered.
• The filter cake is carefully washed to control residual chloride while maintaining acceptable
yield.
• Yield losses on washing are on the order of 10%.

Calcining the bicarbonate to Soda Ash

• The filtrate is then calcined at 175–2250C to produce sodium carbonate, carbon dioxide and
water vapor:
• 2 NaHCO3  Na2CO3 + CO2 + H2O
CO2 is recovered, compressed and recycled back to the carbonating columns as needed.
Recovery of Ammonia :

The traditional Solvay process recovers ammonia by reacting the ammonium chloride in the
filtrate liquor with milk of lime
2 NH4Cl + Ca(OH)2  CaCl2 + 2 NH3 + 2 H2O

Production of milk of lime:

The milk of lime and much of the carbon dioxide needed in the Solvay process are produced
from limestone.
The reaction is carried out in a kiln at 950–11000C
CaCO3  CaO + CO2
C + O2  CO2
CO2 is recovered from the exhaust by filtration to remove entrained dust, compressed and
sent to the carbonization columns.
The lime is cooled and slaked with water.
CaO + H2O  Ca(OH)2
Major Engineering problems:
(a)Development of suitable calcining equipment
• Moist NaHCO3 will cake on sides of kiln, preventing effective heat transfer through shell.
• Kiln must be equipped with heavy scraper chain inside and wet filter cake must be mixed with
dry product to avoid caking.
• These problems can be avoided by using fluidized bed calciner.

(b)Ammonia recovery
• NH3 recovery costs 4-5 times more than that of Na2CO3 so losses must be kept low.
• By proper choice of equipment design and maintenance, losses can be as low as 0.2% of
recycle load.

(c ) Waste disposal
• Large quantities of CaCl2 -NaCl liquor is generated during the process which is Either used
elsewhere or disposed as waste.

(d) Economic balance on tower design and Plant Modernization

The tower height, pressure and temperature are optimized.
Advantage of Solvay process
• Less electric power
• Less corrosion problem
• Use of low grade brine
• Not a problem of disposal of co-product
• Does not require ammonia plant

Disadvantage of Solvay process

• Higher salt consumption
• Waste disposal of CaCl2 -brine stream
• Higher investment in ammonia recovery units than crystallization unit of NH4Cl
• Higher capacity plant set up require for economic break even operation
Dual Process ( Modified Solvay)
The principal modification of the dual process is the recovery of NH4Cl
a coproduct rather than liberation of the contained ammonia for
recycle as in the solvay process.
The liquor from the bicarbonate filters is mixed with washed salt feed
to aid in precipitation of the NH4Cl which is crystallized in a
refrigerated tank-continuous unit at 0oC.
The slurry is centrifuged and the NH4Cl Crystals are dried in a rotary
drum hot air dryer.
Then packaged in bags for shipping
Major Engineering Problems:
Caustic soda
• The primary product of the chlor alkali industry is caustic soda, with
chlorine and hydrogen generated as byproducts in the ratio of
1.00:0.89:0.025.

Chlor_Alkali_Sector_Report_2018.pdf
Caustic soda can be produced using either of the three electrochemical
cell technologies:
(1) Diaphragm cell
(2) Mercury cell
(3) Membrane cell.
Mercury cell method produces chlorine free sodium hydroxide but the
use of several tonnes of mercury leads to extremely serious
environmental problems and The chlorine and sodium hydroxide
contaminated with trace amounts of mercury.
The membrane and diaphragm method use no mercury, but the
sodium hydroxide contains chlorine which has to be removed.
The manufacturing process of caustic soda is considered an energy
intensive process and the recent years has witnessed the sector upgrade
the technology from mercury cell technology, which consumes around 3200
kWh/ MT of caustic soda, to membrane cell technology, thereby reducing
the energy demands by at least 20%.
Membrane cell process
Brine solution is fed into the anode half of the system, and
chlorine is separated from the brine, wherein the electric
current passed through the anode helps to produce chlorine
gas.
The caustic solution is dispersed along the cathode through
the permeable membrane, and 30-35% caustic soda and
hydrogen is exited from the cathode shell.
The power consumption of utilizing membrane cell technology
is significantly lesser, i.e., 2400 – 2500 kWh/MT caustic soda,
thereby implicating the increase in production for the amount
of power consumed by mercury cell technology
The main disadvantage of this technology is the need to
replace membranes at regular intervals, unless otherwise
could increase the overall specific energy consumption of the
production.

Use semipermeable membrane to separate anode and cathode compartments. Separate compartments by
porous chemically active plastic sheets; that allows sodium ions to pass but reject hydroxyl ions.
Membrane cell process
Saturated brine is passed into the first chamber of the cell where the
chloride ions are oxidized at the anode to chlorine:
2Cl– → Cl2 + 2e-
At the cathode, hydrogen in the water is reduced to hydrogen gas,
releasing hydroxide ions into the solution:
2H2O + 2e– → H2 + 2OH–
The non-permeable ion exchange membrane at the center of the cell
allows the sodium ions (Na+) to pass to the second chamber where they
react with the hydroxide ions to produce caustic soda (NaOH). The overall
reaction for the electrolysis of brine is thus:
2NaCl + 2H2O → Cl2 + H2 + 2NaOH
A membrane cell is used to prevent the reaction between the chlorine and hydroxide
ions. If this reaction were to occur the chlorine would be disproportionate to form
chloride and hypochlorite ions:
Cl2 + 2OH– → Cl– + ClO– + H2O
At higher temperatures, 333K, Chlorate can be formed:
3Cl2 + 6OH– → 5Cl– + ClO3– + 3H2O
Because of the corrosive nature of the chlorine produced, the anode has to be made
from a non-reactive metal such as titanium, whereas the cathode can be made from
steel.
In the membrane cell, the anode and cathode are separated by an ion-permeable
membrane. Saturated brine is fed to the compartment with the anode (the anolyte).
A DC current is passed through the cell and the NaCl splits into its constituent
components. The membrane passes Na+ ions to the cathode compartment
(catholyte), where it forms sodium hydroxide in solution. The chloride ions are
oxidized to chlorine gas at the anode, which is collected, purified and stored.
Hydrogen gas and Hydroxide ions are formed at the cathode.
Unit Operation and Unit Process Concepts
( Ref. Dryden Pg.no 15-31)
A formula for successful chemical industries production can be expressed
as the equation:

Commercial Production = f ( Chemical Changes + Physical Changes)

In chemical engineering and related fields, a unit operation is a basic step in a

process. Unit operations involve bringing a physical change such as
separation, crystallization, evaporation, filtration etc. For example, in milk
processing, homogenization, pasteurization, chilling, and packaging are each
unit operations which are connected to create the overall process. A process
may have many unit operations to obtain the desired product. Unit process
involves bringing a chemical change such as Alkylation, combustion,
esterification etc.,
Unit Operations
Unit Process
Chemical Technology

Introduction
CHEMICAL PROCESS INDUSTRIES
INTRODUCTION
CHEMICAL PROCESS INDUSTRIES
INTRODUCTION