DUAL (Modified Solvay process)

DUAL process is also known as modified Solvay process because the producers made
several modifications to the original Solvay process. DUAL process was developed and
operated in Japan. The modified Solvay process came in commercial use in 1980 . This
synthetic process combines the production of soda ash with the production of
ammonium chloride. The ammonium chloride produced is crystallized by cooling and
through the addition of solid sodium chloride unlike in the Solvay process. The
importance of the DUAL process in Japan is due to the high cost of imported rock salt
and the use of the ammonium chloride as a fertilizer especially in rice cultivation
[Örg03]. There are several plants that are using the DUAL process in other parts of the
world, most of the plants are situated in China.

DUAL process uses mainly salt (sodium chloride), carbon dioxide and ammonia as raw
materials. This process does not require limestone, an important raw material that is
used in the Solvay process. The ammonium chloride is formed through the following
chemical reaction:

NaCl + NH3 + CO2 + H2O NaHCO3 + NH4Cl

Ammonia is recovered in the Solvay process. In the modified Solvay process

ammonium chloride is retained and crystallized out and separated by adding sodium
chloride.

Raw materials

Basis: 1000 kg of Sodium carbonate

Crystalline Salt = 1260 kg

Ammonia = 325 kg
High pressure steam = 1350kg
Low pressure steam = 100kg
Cooling water = 50000 - 80000kg
Electric power = 450KWH
Co-product (NH4Cl) = 620kg

Sources of raw material

Common salt can be obtained from sea water, salt lake and sub – soil water

Ammonia can be synthesized by Haber – Bosch

The liquor from carbonation tower, containing ammonium chloride, unreacted NaCl and
traces of sodium carbonate is ammoniated in ammonia absorber. The ammoniated
liquor is sent to a bed of washed salt in salt dissolver. The resulting liquor is gradually
cooled to 00C in refrigerating tank unit, resulting into crystallize out ammonium chloride.
The slurry containing ammonium chloride is thickened and NH4Cl is centrifuged and
dried. In this process ammonium chloride is obtained as co-product. These is the
principal modification of dual process in which ammonium chloride is recovered as co-
product rather than liberation of the contained ammonia for recycle as in the Solvay
process.

The liquor obtained after separation of NH4Cl is charged to series of carbonation towers
in which CO2 is passed from bottom in the counter current flow of liquor. The resulting
sodium bicarbonate is thickened into thickener and centrifuged. It is then calcined into
sodium carbonate.

Major engineering problem

Salt purification

Solid salt which is used to obtain better crystallization yields of NH4Cl cannot be purified
as with brine feeds in Solvay process. Only purification method is mechanical washing
and dewatering.

Corrosion

Ammonium chloride solution is quite corrosive to equipment involved in crystallization

and solids recovery. So, corrosion resistant material or rubber-lined units are preferred.

Refrigeration Cost

Actual refrigeration cost is variable but to maintain the temperature around 00C, the
electric requirements are still double than Solvay's operation.

Choice of process

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

Disadvantage of Solvay process

Higher salt consumption
Waste disposal of CaCl2-brine stream
Higher investment in ammonia recovery units than crystallization unit of NH 4Cl
More steam consumption
Higher capacity plant set up require for economic break even operation (100 v/s 55tons/day)
NH4Cl will be used as mixed fertilizer ingredient which minimizes the disposal problem of Duel
process.

Plant location

One ton of soda ash production requires 8 tons of brine. As the salt sources are the key
factor and they are less widely distributed than limestone or coal. There so plant should
be located nearby the salt sources.

Sodium bicarbonate is not manufactured by refining the crude NaHCO3 obtained

from Solvay's process in the vacuum drum filters due to following reasons

 It is very difficult to dry completely

 Loss of ammonia during the process
 NaHCO3 is not as pure as obtained during Solvay's process
 Small traces of ammonia in the products makes it unfit for many applications

SODIUM BICARBONATE

MANUFACTURE

Sodium bicarbonate is manufactured in the carbonation tower, same as used in

Solvay‘s Process.

Raw material
Basis : 1000 kg of Sodium bicarbonate (98% yield)
Sodium carbonate = 643.74kg
Carbon dioxide = 267.28kg
Water = 109.40kg

Sources of raw material

Sodium carbonate to be obtained by dual process (Modified Solvay process).
Pure CO2 shall be obtained from by recovery from flue gas

Reaction
Na2CO3 + CO2 + H2O 2NaHCO3
Saturated solution of soda ash is passed from the top of a carbonating tower.
Compressed CO2 gas is admitted in counter currently from the bottom of the tower. The
temperature of the tower is maintained at 40°C by the cooling coils, provided above the
bottom of the tower. The suspension of bicarbonate formed is removed from the bottom
of the tower, filtered and washed on a vacuum rotary drum filter. After centrifugation, the
product is dried on continuous belt conveyor at 70°C to get 99.9% pure sodium
bicarbonate.

BAKING POWDERS

Sodium bicarbonate is primarily used in cooking (baking), as a leavening agent for

producing aeration and lightness in breads and cakes. NaHCO3 often impetrated an
unpleasant taste or even a yellowish colour due to alkalinity of the sodium carbonate
formed, the search for better reagents continued.

PROPERTIES
Molecular formula : NaHCO 3
Molecular weight : 84.01gm/mole
Appearance : White crystal
Odour : Odourless
Boiling point : 8510C
Melting point : 3000C
Density : 2.20gm/mL (liquid)
Solubility : Soluble in water