Solvay Process

Jonathan Bauer
Keith Sager
Uche Onyewuenyi
Lam Nguyen
Background

 Developed by Ernest Solvay in the 1860s

 Worldwide production in 2005 was 42 billion kilograms
 Equivalent to 13 lbs per person per year
 Raw materials are salt brine and limestone from mines
 In 1884 the Solvay Brothers (Ernest and Alfred) created a joint venture to in
the United States called the Solvay Process Company
 There are no more solvay processing plants in North America
 Natural deposits of trona (Na3(CO3)(HCO3)·2H2O) are cheaper
Applications of Soda Ash

 Glass making
 Soda-lime glass
 Cheaper, can be re-softened and re-melted
 Good for recycling
 Soap and Detergent
 Cheaper alternative to lye (NaOH)
 Common alkali in many chemical factories
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Kiln

 𝐶𝑎𝐶𝑂3 → 𝐶𝑂2 + 𝐶𝑎𝑂

CaCO3  Temperature = 950 – 1100°C

CO2
CaO
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Ammonia Absorber

Brine
 No reaction takes place
 Ammonia mixes with brine
 Mushroom shape baffles
 Controls flow of brine for proper
mixing and saturation

Ammonia
and Brine
NH3
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Solvay Tower

 𝑁𝑎𝐶𝑙 + 𝐶𝑂2 + 𝑁𝐻3 + 𝐻2 𝑂 →

𝑁𝑎𝐻𝐶𝑂3 + 𝑁𝐻4 𝐶𝑙
 Temperature is 0°C
 Mushroom baffle plates
 Breaks up CO2
 Controls flow through tower
 Lower part of tower is cooled
because reaction is exothermic
 Vacuum filter at tower bottom
NH4Cl
NaHCO3
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Water Bed

 𝐶𝑎𝑂 + 𝐻2 𝑂 → 𝐶𝑎 𝑂𝐻 2

 Calcium oxide comes from kiln

 Calcium hydroxide is sent to
ammonia recovery tower
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Ammonia Recovery Tower

NH3 NH4Cl  2𝑁𝐻4 𝐶𝑙 + 𝐶𝑎𝑂 → 2𝑁𝐻3 + 𝐶𝑎𝐶𝑙2 +

𝐻2 𝑂
 Overall reaction for water bed and
recovery tower
 CaCl2 and H2O fall out bottom of
tower
 Temperature is 100°C

Ca(OH)2
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Heater (Calcifier)

 2𝑁𝑎𝐻𝐶𝑂3 → 𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂 + 𝐶𝑂2

CO2  Rotary heater at 300°C
 Carbon dioxide is recirculated with
kiln product and sent to solvay
tower
NaHCO3  Final product is recovered as a
solid
Na2CO3
 CaCO3

BRINE
AMMONIA BRINE

KILN

AMMONIA
ABSORBER SOLVAY CO2
NH3

TOWER

CaO
NH4Cl
WATER BED

NaHCO3

Ca(OH)2
AMMONIA
RECOVERY HEATER
TOWER

Na2CO3
Chemical Reactions Summary

1. 𝑁𝑎𝐶𝑙 + 𝐶𝑂2 + 𝑁𝐻3 + 𝐻2 𝑂 → 𝑁𝑎𝐻𝐶𝑂3 + 𝑁𝐻4 𝐶𝑙

2. 𝐶𝑎𝐶𝑂3 → 𝐶𝑂2 + 𝐶𝑎𝑂
3. 2𝑁𝐻4 𝐶𝑙 + 𝐶𝑎𝑂 → 2𝑁𝐻3 + 𝐶𝑎𝐶𝑙2 + 𝐻2 𝑂
4. 2𝑁𝑎𝐻𝐶𝑂3 → 𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂 + 𝐶𝑂2

5. 𝟐𝑵𝒂𝑪𝒍 + 𝑪𝒂𝑪𝑶𝟑 → 𝑵𝒂𝟐 𝑪𝑶𝟑 + 𝑪𝒂𝑪𝒍𝟐

Thermodynamics

 Overall Process
𝒌𝑱
 −𝟏𝟏𝟑𝟎. 𝟕𝟕 + (−𝟖𝟕𝟕. 𝟑) − 𝟐 −𝟒𝟎𝟕. 𝟐𝟕 − 𝟏𝟐𝟎𝟔. 𝟗 = 𝟏𝟑. 𝟑𝟕
𝒎𝒐𝒍

 Reaction 1
𝑘𝐽
 −948 + −315 − −407 + −393.5 + −45.9 + −242 = −176
𝑚𝑜𝑙

 Reaction 2
𝑘𝐽
 (−393.5) + (−635.1) − −1206.9 = 178.3
𝑚𝑜𝑙

 Reaction 3
𝑘𝐽
 2 −45.9 + −877.3 + −242 − −315 + −635.1 = −261
𝑚𝑜𝑙

 Reaction 4
𝑘𝐽
 −1130.77 + −242 + −393.5 − 2 −948 = 129.8
𝑚𝑜𝑙
Questions?
References

 http://en.wikipedia.org/wiki/Solvay_process
 http://en.wikipedia.org/wiki/Soda_lime_glass
 http://en.wikipedia.org/wiki/Trona
 http://www.citycollegiate.com/sblock2.htm
 http://scifun.chem.wisc.edu/chemweek/PDF/Sodium_Bicarbonate_&_Sodium
_Carbonate.pdf