Solvay Process
The Solvay process is also known as the ammonia soda process. The Solvay process was
developed by the Belgian Ernest Solvay (1838 – 1932) in 1861. The Solvay process is the most
accepted technology for producing synthetic soda ash because the investment and maintenance
costs are low compared to other processes. The basic raw materials that are used in this process
include salt, limestone and coke or natural gas and also ammonia as a cyclic reagent.
The Solvay process can be summarized by the following theoretical global chemical
reaction, which involves two main components which are sodium chloride and calcium
carbonate.
2NaCl + CaCO3 Na2CO3 + CaCl2
The above reaction cannot be applied directly in practice, the Solvay process needs the use of
other substances and also many different process steps before getting to the final product
which is soda ash.
The Solvay process includes the following stages:
1. Production of a saturated salt solution
NaCl + H2O
2. Burning of limestone and the CO2 recovered which is used in stage 4 while CaO is used in
stage 7.
CaCO3 CaO + CO2
3. Saturation of the salt solution with ammonia
NaCl + H2O + NH3 + CO2
4. Precipitation of bicarbonate by adding carbon dioxide (from stage 2 and 6)
NaCl + H2O + NH3 + CO2 NH4Cl + NaHCO3
5. Filtration and washing of sodium bicarbonate
6. Thermal decomposition of sodium bicarbonate to sodium carbonate (the carbon dioxide
that is given off is recycled to stage 4)
2NaHCO3 Na2CO3 + H2O + CO2
7. Production of milk of lime
CaO + H2O Ca(OH)2
8. Recovery of ammonia by distillation of the mother liquor from stage 4 with milk of
lime ( the ammonia that is released is recycled to stage 3)
2NH4Cl + Ca(OH)2 2NH3 + CaCl2 + 2H2O
Because the Solvay process recycled its ammonia, it consumed only brine and limestone, and
had calcium chloride as its only waste product. This made it substantially economical.
Process description
1. Brine purification: The first step is brine purification, this step is done in order to get a pure
sodium chloride solution. Sodium chloride used as a raw material in glass is available naturally,
it is frequently obtained by solution mining of salt deposits. Brine always contains
inorganic impurities such as magnesium and calcium salts and some brines also contain sulfates.
If the impurities are not removed they cause production problems: they react with alkali
and carbon dioxide to produce insoluble salts, and also affect the quality of the finally
produced soda ash. The purification of the brine is carried out by the lime - soda treatment or
lime– soda process. In the lime– soda process, magnesium ions are precipitated as hydroxide
with milk of lime (Ca(OH)2 concentration: 170 – 185 kg/m3) and calcium ions are precipitated
as carbonate with soda ash (Na 2CO3 concentration: 65 – 80 kg/m 3). The lime– soda process is
given by the chemical reactions:
Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+
Ca2+ + Na2CO3 CaCO3 + 2Na+
The brine is transferred to the ammonia absorbers after the separation form the precipitated
impurities.
2. Limestone burning and lime slaking: The acceptable limestone must be of very high purity
(SiO2: < 3% ; Fe2O3 – Al2O3 : < 1.5%) or contain low concentration of impurities. The limestone
must be hard and strong with the same coarse size. The limestone is frequently mixed with about
7 % of metallurgical– grade coke or coal and burned in vertical shaft kilns. The limestone is
calcinated with coke to produce carbon dioxide which is used in the carbonation stage and it also
produces calcium oxide which is used for the distillative recovery of ammonia. The
burning of the limestone (CaCO3) is carried out at a temperature between 950℃ and 1100℃.
Carbon dioxide is produced by decomposition of limestone and also by combustion of
carbon in the fuel: CaCO3 CaO + CO2 (burning of limestone in lime kilns)
The kiln gases are diluted with nitrogen from the combustion air. The gas contains 37– 42%
CO2, stone dust, ash particles and other gaseous impurities. The hot gas is cooled and cleaned by
direct contact with water. The gas is then transferred to the Carbon dioxide compressors and then
passed through to the carbonating columns. The lime from the kiln is cooled by the air which is
entering the lower parts of the shaft kiln. After the cooling, the lime is discharged from the
kiln and reacted with used cooling water (50 – 65℃) to produce a thick suspension of calcium
hydroxide (Ca(OH)2 ) in water (concentrated milk of lime at temperature range of 90 –
100℃):
CaO + H2O Ca(OH)2 (Lime slaking)
The calcium oxide (CaO) content of the milk of lime can get to 5.5 mol/L in favorable
conditions. The milk of lime is added to the distillation step in the recovery of ammonia. Before
milk of lime is added to the distillation step, coarse sand and unburnt limestone are
removed by sieves, mixed with new limestone and recycled to the kiln.
3. Ammonia absorption: The gas from the distillation step contains ammonia (NH3) and
carbon dioxide (CO2) and is saturated with water vapor in an absorption tower. At this stage of
ammonia absorption, the gas is absorbed by purified brine. The obtained ammoniac brine
consists of 85– 90 kg/m3 ammonia and 40 – 50 kg/m3 carbon dioxide. The sodium chloride
content is decreased from 300 g/L to 260 g/L because of the increase in the specific volume
of the liquor caused by the addition of ammonia and by dilution with water. The reactions
occurring in the absorption stage are strongly exothermic and given by the chemical equations:
NH3 + H2O NH4OH + amount of heat = -34 900kJ
2NH4OH + CO2 (NH4)2CO3 + H2O + amount of heat = - 90850 kJ
The reaction requires cooling of the liquid. The brine needs cooling (394 kcal/kg) of the product
soda ash during ammonization. This process is done at slightly less than atmospheric pressure.
The temperature of inlet brine is about 30℃ and that of exit is about 36℃ to 42℃.
4. Precipitation of bicarbonate: The precipitation of sodium carbonate is an exothermic
process.
NaCl + NH4HCO3 NaHCO3+ NH4Cl + energy
This reaction involves the reaction of ammoniated brine and carbon dioxide. The ammoniated
brine comes from the absorption stage whereas carbon dioxide comes from the lime kiln
or from the calcination stage. The ammoniated brine is pumped to the top of one of the
columns that is used to precipitate bicarbonate (NaHCO3). This column which has been
fouled or partially plugged with sodium bicarbonate after several days of crystallization is
referred to as a “cleaning” column. Lime kiln gas is compressed to about 414 kPa, enters the
bottom of the column and bubbles up through the solution and also absorbs a large amount of
carbon dioxide. The concentration of carbon dioxide that is in the liquid leaving the column is
kept below the bicarbonate precipitation level. However, if precipitation occurs, then it gets
dissolved by the fresh ammoniated brine which is assisted by gas agitation. Relatively little
cooling is required in this tower. The liquor leaving this column is fed to the top of the remaining
columns of the block. Carbon dioxide from lime kiln also injected from the bottom of these
columns. These columns are known as ‘Making Column’ as the precipitation of Sodium
Bicarbonate is allowed here. This precipitation process is accompanied by the evolution of
considerable heat which must be removed to improve yield. Crystals formed during the
carbonation step gradually foul the heat – exchange surfaces and so these crystallizing columns
must have the capability to be acted like the “cleaning” column.
The liquid is then placed in parallel to the top of the other columns. The temperature in the
columns is 50 – 60℃. The precipitation of sodium bicarbonate happens after making the
columns to receive the mixture of kiln gas and bicarbonate calciner gas that bubbles up
through the solution. The suspension of bicarbonate in mother liquor leaves the carbonation
stage at a temperature of 30℃. Nitrogen gas and some carbon dioxide and ammonia are
vented from the crystallizing tower columns and collected before they are recycled to the
absorption stage.
5. Filtration of Bicarbonate: Bicarbonate crystals are normally separated from the mother
liquor by the use of vacuum filters, band filters and centrifuges. The slurry, collected from the
crystallizing towers, is fed to continuous vacuum filters or centrifuges which separate the
crystals from the “filter liquor.” When filters are used vacuum pumps pull the air through the
cake and after that, the gas that is carrying ammonia and some carbon dioxide gas is
cleaned and released to the atmosphere.
The filter cake is washed carefully with water and the remaining mother liquor chloride is
eliminated. The mother liquor chloride is sent to a calcination stage and the mother liquor in
liquid phase is sent to the distillation stage for the recovery of ammonia.
6. Calcination of Bicarbonate to soda ash: Calcination of bicarbonate is usually performed in
rotary calciners. The rotary calciners are heated externally with coal, oil or gas or internally with
steam. Thermal decomposition of crude bicarbonate to carbonate gives out carbon dioxide,
ammonia and water vapor. The carbonate product is technical-grade soda ash that contains
sodium chloride. The main reaction is
2NaHCO3 CO2 + H2O + Na2CO3
and other reactions are NH4HCO3 NH3 + CO2 + H2O
NaHCO3 + NH4Cl NH3+ CO2 + H2O + NaCl
Heat is required for the calcinations of bicarbonate. The amount of heat that is needed is 0.92
GJ/t of soda ash but the stated value does not include the amount of heat required for
drying the product. The total heat required for calcinations of bicarbonate in rotary calciners is
3.7 GJ/t of soda ash. The heat is provided at a temperature of 180℃. The temperature for the
decomposition of sodium bicarbonate (NaHCO3) is 87.7℃.
Gases removed from the rotary calciners contain carbon dioxide, ammonia, water, some
leakage air and large amounts of sodium carbonate and bicarbonate dust. The gas is cooled
and also washed with brine and water to remove ammonia to condense water before it is used
in the carbonation stage. The condensates that are formed are sent to the distillation stage for the
recovery of ammonia.
7. Recovery of Ammonia: The permeate liquor contains unreacted sodium chloride and
substantially all the ammonia with which the brine was originally saturated. The “fixed”
ammonia or ammonium chloride corresponds stoichiometrically to the sodium bicarbonate
that had been precipitated. “Free” ammonia includes ammonium hydroxide, bicarbonate,
carbamate and the several possible carbon compounds of ammonia that decompose at moderate
temperatures. Before preheating, sulfide solution may be added for corrosion protection. The
sulfide is distilled for eventual absorption by the brine in the absorber. The permeate liquor is
preheated by indirect contact with the gases leaving the distiller. The warmed feed liquor then
enters the main coke or bubble cap filled sections of the distiller where heat decomposes
free ammonium compounds and steam strips almost all of the free ammonia and carbon
dioxide. The carbon dioxide free solution then treated with milk of lime. Here the ammonium
chloride reacts with the milk of lime and evolved ammonia gas which is vented back to the
distiller. The resulting hot calcium chloride solution, containing residual ammonia in the form
of ammonium hydroxide, flows back to the lower section of the distiller. Low pressure
steam sweeps all of the ammonia out of the limed solution.
The final solution, known as “distiller waste”, contains calcium chloride, unreacted
sodium chloride and the excess lime which is diluted by the condensed steam. Distiller
waste also contains the inert of this solution. The waste liquors are pumped to settling basins
where the suspended solids are deposited. The clear over flow contains dissolved salts which are
objectionable contaminants and needed to be treated. The hot (56℃) mixture of wet ammonia
and carbon dioxide leaving the top of the distiller is cooled to remove water vapor before being
sent to the absorber.
By-Products
Calcium Chloride: Relatively few synthetic soda ash plants recover calcium chloride. To
produce calcium chloride, the distiller waste liquor is settled and then evaporated in multiple
effect evaporators and thus most of the sodium chloride get separated. The remaining solution is
further concentrated to yield CaCl2.2H2O. This solution is then cooled to form flakes which are
finally dried in a rotary dryer, giving a product of 77-80% pure calcium chloride.
Simultaneously, a small amount is processed to form anhydrous salt.
Ammonium Chloride: In one process for manufacturing ammonium chloride as a by-product,
more ammonia is firstly added to the permeate liquor and is chilled to 10℃. Solid sodium
chloride is then dissolved and so ammonium chloride precipitates which is separated for sale.
The mother liquor is recycled to the carbonation operation.
