Soda Ash ( Sodium carbonate)

Manufacturing Process

Dr. Md Shahinoor Islam

Soda ash industry status

 In the eighteenth century soda ash was produced by LeBlanc
process based on roasting salt cake with carbon and limestone.

 The synthetic process for the manufacture of soda ash by

ammonia soda process was developed by Ernest Solvay in 1861.

 Natural deposits of soda containing sodium carbonate (known as

Trona) mostly occur in America, East Africa, Mexico and China.

 About 30% of world soda ash production (90% of this is in U.S.

alone) is from natural deposits and the rest 70% from synthetic
process.
There is no soda ash industry in Bangladesh
 Properties

Mol. Wt. 106

M.P. 851deg.C.
B.P. Decomposes
Soluble in water 8.9 gm/100gm at 20 deg.cel.

Grade s: 99% sodium carbonate washing soda ( Na2CO3 .10

H2 O)
 Methods of production
Sodium carbonate is manufactured by following
process.
1. Le Blanc Process (synthetic soda ash)
2. Solvay Process (synthetic soda ash)
3. DUAL and NA Processes (synthetic soda ash)
4. Monohydrate Process
5. Sesqui-carbonate Process
6. Carbonation Process
7. Alkali Extraction Process

Leblanc process
The process has only historical importance,
because is now been replaced completely by
Solvay process or modified by Solvay process.

Raw materials Basis:

 1000kg Sodium carbonate (98% yield)
 Common salt = 1126kg
 Sulfuric acid = 945kg
 Lime stone = 963kg
 Coke = 463kg
 Leblanc process

LeBlanc process
 Common salt is first mixed with the conc. H2SO4 in equivalent
quantities and heated in a cast iron salt cake furnace by flue
gases from adjacent coal of fire.
 NaHSO4 along with HCl gas is formed and heated in a furnace
to produce Na2SO4 cake.
 The salt cake is broken or pulverized, mixed with coke and
limestone and charged into black ash rotary furnace
consisting of refractory lined steel shells.
 The mass is heated by hot combustion gases entering at one
end and leaving at the others. The molten porous gray mass
thus formed known as black ash is separated from the calcium
sludge by leaching with water .
 Leblanc Process
The extract containing Na2CO3, NaOH, and other
impurities is sprayed from the top of a tower in
counter current to flow of hot gases from the black
ash furnace.
 The sodium carbonate thus obtained is concentrated
in open pans and then cooled to get sodium
carbonate.
The product is calcined to get soda ash which is re-
crystallized to Na2CO3.10H2O. The sludge containing
mostly CaS is left behind as alkali waste.

Reactions
Solvay or ammonia soda process
Overall Reaction: 2 NaCl + CaCO3 → Na2CO3 + CaCl2

Raw material : Salt, coal and limestone

Quantitative requirements for 1 to of Na2CO3

Salt : 1.55 tons
Limestone 1.2 tons
Coke 0.09tons
High pressure steam: 1.35 tons
Low pressure steam: 1.60 tons
Ammonia losses: 1.5 kg
Cooling water : 40-60 tons
Electric power: 210 KWH
Plant Capacity: 200-2000 tons/day

Process Description

In 1869 Solvay discovered that NH3 dissolved in an NaCl

solution and then reacted with CO2 .

Ammonia is dissolved in a salt solution and ammoniate brine

solution is allowed to react with CO2 which is obtained by
calcining lime stone with coke.

A precipitate of NaHCO3, thus obtain is then calcined to

produce high purity Na2CO3.

2 NaCl + CaCO3 → Na2CO3 + CaCl2

 Block Diagram

Steps
The following steps are involved in solvay process and in this
process some amount of ammonia recycled back as
feedstock to start new round of solvay process.

 Brine purification
 Slake lime preparation
 Ammoniation of brine
 Reactions in Solvay tower/carbonating tower
 Reactions in klin / Separation of solid sodium hydrocarbonate
 Formation of sodium carbonate
 Ammonia Recovery
Chemistry of Solvay process

Area and operation

 Preparation brine
• Saturated solution of NaCl is used.
• Impurities such as calcium and magnesium have to
be removed from brine.
• Magnesium ions, Mg2+, are precipitated as insoluble
magnesium hydroxide, Mg(OH)2, by the addition of
an alkaline reagent. The most commonly used
reagent is milk of lime as this is already produced in
large quantity for ammonia recovery; another
possibility consists of using sodium hydroxide
(NaOH).

Preparation brine
• Calcium ions, Ca2+ are precipitated as insoluble
calcium carbonate, CaCO3, by reaction with sodium
carbonate.
• The precipitated carbonates and hydroxide are
removed by filtration.
• Sometimes sulfate are removed with BaCl2 or the
hot brine is treated with OH¯ and CO3-2 ions.
 Ammoniation of brine
 The purified brine is allowed to percolate down the ammonia
tower in which ammonia gas is passed through the bottom in
a counter current fashion.
 The brine solution thus takes up the necessary amount of
ammonia and liberates heat.
 Some carbon dioxide is also absorbed by ammonia, as a result
of which some insoluble carbonate is also precipitated.
 The ammoniated brine is allowed to settle, coded to about
30°C and pumped to the carbonating tower.

Carbon dioxide formation

 Limestone is calcined at 950 - 1100 °C to get CO2 in a lime kiln
filled with coke.
 The calcium carbonate (CaCO3) in the limestone is partially
converted to quicklime (calcium oxide (CaO) and carbon
dioxide:

 CaCO3 → CO2 + CaO

 CaO obtained from the lime kiln is converted into slaked lime
and pumped to the ammonia recovery tower
 Carbonation of ammonium brine
CO2 from the lime kiln is compressed and passed
through the bottom of carbonating tower down
which ammoniated brine percolates.
Carbonating towers operated in series with several
precipitation towers are constructed of cast iron
having 22-25 meter height, 1.6-2.5 meter in
diameter.
During the precipitation cycle, the temperature is
maintained about 20-25°C at the both ends and 45-
55°C at the middle by making use of cooling coils,
provided at about 20 ft above the bottom.

Carbonation of ammonium brine

The ammonium carbonate first reacts with CO2 to
form ammonium bicarbonate and the latter reacting
with salt, forms sodium bicarbonate.
The heat of exothermic reaction is removed by
cooling coils.
 Filtration
 NaHCO3 slurry is then filtered on a rotary vacuum
filter which helps in drying of bicarbonate and in
recovering ammonia.
The filter cake after removal of salt and NH4Cl by
washing with water, sent to a centrifugal filter to
remove the moisture or calcined directly.
During washing, about 10% NaHCO3 also passes into
filtrate.
The filtrate containing NaCl, NH4Cl, NaHCO3 and
NH4HCO3 is treated with lime obtained from lime
kiln to recover NH3 and CO2.

Vacuum Filter
 Calcination
• NaHCO3 from the drum filter is calcined at
about 200°C in a horizontal calciner, which is
either fired at feed end by gas or steam
heated unit.
• The heating being through the shell parallel
to the product, which prevent the formation
of bicarbonate lumps.
• The hot soda ash form the calciner is passed
through a rotary cooler and packed in bags.

Calcination
• The exit gases (CO2, NH3, steam etc.) are cooled and
condensed to get liquid ammonia; the rich CO2 gas is
cooled and returned to the carbonating tower.
• The product from the calciner is light soda ash.

• 2 NaHCO3 → Na2CO3 + H2O + CO2

• To produce dense soda ash, sufficient water is milled
with it to form more mono hydrate Na2CO3.H2O and
the mixture is recycled.
 Recovery of ammonia
 The ammonia is recovered in a strong ammonia liquor
 The filtrate obtained from washing of NaHCO3 from the rotary
filter is fed into the heater, where free ammonia and carbon
dioxide are driven off by distillation.
 Dry lime or milk of lime (slaked lime) obtained from lime kiln
is fed through the lime inlet and mixed with the liquor from
the heater.
 As the liquor flows down the column, calcium chloride and
calcium sulfate are formed and NH3 gas is released.

2 NH4Cl + CaO → 2 NH3 + CaCl2 + H2O

Kinetics and thermodynamics

• The overall reaction shows that salt and calcium
carbonate are the only raw materials and need to
supply the plant continuously that produce sodium
carbonate and calcium chloride.
CaCO3 + 2NaCl→ Na2CO3 + CaCl2
• Overall reaction of ammoniation of brine and then
treatment of carbon dioxide to ammoniated brine.
2NaCl + 2H2O +2NH3 + 2CO2 → 2NaHCO3 + 2NH4Cl
 Kinetics and thermodynamics
• The above reaction shows the role of ammonia and
carbon dioxide in the process, and also determines
the yield of the final product.
• The reaction is divided in to two steps.
2NH3 + 2CO2 +2H2O→ 2NH4HCO3 ---- (a)
2NaCl + 2NH4HCO3 → 2NaHCO3 + 2NH4Cl ---- (b)

Kinetics and thermodynamics

• Reaction (a) is undoubtedly favored by low
temperature because it requires the dissolution of
gas in water, is displaced to right by virtue of the fact
that reaction (b), which utilizes the product by
subtracting it from (a) is displaced in the same
direction.
• The precipitation of NaHCO3 according to (b) which
is the driving force behind the entire method.
 Kinetics and thermodynamics
• The most physicochemical conditions for the forward step of
reaction (b) which causes precipitation of NaHCO3 are as
under :
 To maintain lowest possible temperature in order to lower
the solubility off sodium bicarbonate
 To maintain the greatest possible concentration of one or
both the salts appearing on the product side of reaction (b)
with the aim of lowering still further solubility of sodium
bicarbonate.

Kinetics and thermodynamics

• These conditions serve to bring about appreciable increase in
the yields of NaHCO3 and permit the most effective use of
most costly reagent NH4HCO3 in reaction (b).
• If precipitation temperature is always kept low, the sodium
bicarbonate separates in a microcrystalline form which is
difficult to filter and it is soluble during subsequent washing
on the filter which increase requirement of NaCl.
 Kinetics and thermodynamics
• Experimentally, the conditions which are most effectively
reconcile the physicochemical aspect of precipitation of
sodium bicarbonate economically are as under :
 284gm/liter (≈4.9mole/liter) of NaCl reacting with 7 6gm/liter
(≈4.5mole/liter) of NH3 instead of equimolecular solution of
two reagents
 Relatively high temperature (60-650C) at the start so as to
allow the formation of well-developed NaHCO3 crystallization
seeds and increasing the volume of these seeds to decrease
the solubility of salt with gradual cooling.

Major engineering problems

(a) Development of suitable calcining equipment:

Moist NaHCO3 will cake on sides of klin, preventing effective

heat transfer through the shell.

The klin 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

calciners in newer installations.
 Major engineering problems

(b) Economic balance on tower design:

the tower height, pressure and temperature are optimized,
giving approximately 75% yield of NaHCO3 from NaCl.

(c) Ammonia recovery: NH3 inventory costs 4-5 times that of

Na2 CO3 inventory so losses must be kept low.
(d) plant modernization
(e) waste disposal.
 Uses

Advantages of Solvay process

 Can use low-grade brine
 Less electric power and less corrosion problems
 With current fertilizer shortage, all of the ammonium chloride
will be used as a mixed chemical fertilizer ingredient, so co-
product disposal no problem.
 The recovered carbon dioxide is reused.
 When properly designed and operated, a Solvay plant can
reclaim almost all its ammonia, and consumes only small
amounts of additional ammonia to make up for losses.
 The only major inputs to the Solvay process are salt,
limestone and thermal energy, and its only major byproduct is
calcium chloride, which is sold as road salt.
 Does not require ammonia plant investment
 Disadvantages of Solvay process
Higher salt consumption
Higher investment in ammonia recovery unit verses
crystallization units for ammonium chloride
Waste disposal of calcium chloride brine stream
More steam consumption
Higher capacity plant for economic break-even
operation