The Solvay and Haber-Bosch

Khanh B. Vu, Ph. D.

Department of Chemical Engineering
International University
Vietnam National University
Manufacturing sodium carbonate by the Solvay
process
Industrially, sodium carbonate = 'soda ash'

Soda
ash

Light Heavy
ash ash

Fine powder Bigger particle size

Denser
The uses of sodium carbonate
Sodium Carbonate Market

Compound Annual Growth Rate (CAGR)

Compound Annual Growth Rate (CAGR)
Imagine you invested $10,000 in a portfolio with the returns outlined below:

From Jan. 1, 2018, to Jan. 1, 2019, your portfolio grew to $13,000 (or 30% in year one).
On Jan. 1, 2020, the portfolio was $14,000 (or 7.69% from January 2019 to January 2020).
On Jan. 1, 2021, the portfolio ended with $19,000 (or 35.71% from January 2020 to January
2021). We can see that on an annual basis, the year-to-year growth rates of the investment
portfolio were quite different as shown in the parentheses.

On the other hand, the compound annual growth rate smooths the investment’s performance
and ignores the fact that 2018 and 2020 were vastly different from 2019. The CAGR over that
period was 23.86% and can be calculated as follows:
 1 Rate at which an investment would have
𝐸𝑉 7
grown if it had grown at the same rate every
2= − 1 × 100
18.1 year and the profits were reinvested at the
end of each year.
EV = ?

Compound Annual Growth Rate (CAGR)

Sodium Carbonate Market
Sodium Carbonate Market
Global production capacity
1%

24%

48%

27%

Solvay Hou Trona Others

Key Players
• Solvay
• FMC
• Haihua Group
• GHCL
• Tata Chemicals
• Nirma
• Huachang Chemical • Sichuan Hebang Corporation Limited
• Hubei Shuanghuan • BOTASH SA
• Jilantai Salt Chemical • Lianyungang Soda Ash
• Şişecam Group • Sanyou Chemical
•Yuanxing Energy • Qingdao Soda Ash
• Ciech
• Shandong Haihua Group Co. Ltd.
• Tronox Limited
• Genesis Energy
• OCI Chemical
• DCW Limited
Solvay Process

The obvious way to prepare sodium carbonate from sodium chloride

and calcium carbonate

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

What is problem with the above chemical reaction?

kJ
∆G0 = −1051.6 − 816.0 − −2x393.1 − 1129 = 47.6
mol
2NaCl(s) + CaCO3(s) Na2CO3(s) + CaCl2(s)

∆G0 = −1047.6 − 748.1 − −2x384.0 − 1128.0 = 100.3 kJ/mol

∆H0 = −1131 − 795.8 − −2x411.2 − 1207 = 102.6 kJ/mol
∆S0 = 135 + 104.6 − 2x72.13 + 92.9 = 2.44 J/mol
∆G0 = 102.6 − T × 2.44 × 10−3 < 0, T > 42,000K
Solvay Process

An indirect route must be found

NaCl(aq)+ NH3(aq)+ H2O(I) + CO2(g) ⇌ NH4Cl(aq) + NaHC03(s)

kJ
∆G0 =−210.5 − 851.0 − −393.1 − 26.5 − 237.1 − 393.4 = −11.4
mol
0
kJ
∆H = −299.6 − 950.8 − −407.3 − 80.29 − 285.8 − 393.5 = −83.5
mol
Energy is provided by burning coke, heat generated is used to
decompose the calcium carbonate to provide carbon dioxide

CaCO3(s) ⇌ CaO(s) + CO2(g)

DH0 = 177.8 kJ/mol At 25 oC, DG0 = 130.0 kJ/mol

DS0 = 160.5 J/K·mol DG0 = 0 at 835 oC
dùng nhiệt độ cao để delta G bé hơn 0
DG0 = DH0 – TDS0 Temp. = 950 -1100 oC
Solvay Process

NaCl(aq)+ NH3(aq)+ H2O(I) + CO2(g) ⇌ NH4Cl(aq) + NaHC03(s)

Solubility of four salts

Temp, 0C NaCl NH4HCO3 NH4Cl NaHCO3
0 357 120 298 69
20 358.5 217 374 95.4
30 359 269 467 109

At low temperatures, NaHCO3is much less soluble than NH4Cl

and crystallises out. This moves the equilibrium in the Solvay tower
reaction to the right. The sodium hydrogencarbonate is filtered out and
heated to form sodium carbonate.
160 – 230 0C
2NaHC03(s) Na2C03(s) + CO2(g) + H2O(g)
Solvay Process

NaCl(aq)+ NH3(aq)+ H2O(I) + CO2(g) ⇌ NH4Cl(aq) + NaHC03(s)

The calcium oxide from the decomposition of the limestone is slaked

with water to form calcium hydroxide
CaO(s)+ H2O(I) Ca(OH)2(s)
The calcium hydroxide is used to regenerate the ammonia

Ca(OH)2(s) + 2NH4Cl(aq) CaCl2(aq) + 2NH3(aq) + 2H2O(I)

Solvay Process
Solvay Process
Solvay Process

lò nung

Ca(OH)2 + NH4Cl

NH4Cl
dd sau khi lọc

A simplified flow diagram for the Solvay process showing the ammonia
and carbon dioxide cycles
Solvay Process

top reason tăng thời gian tiếp xúc của chất khí với chất lỏng (chết fluid)
-> độ chuyển hóa (converrsion) cao
gas
Bot

Describe in words or in chemical equations the processes that are

occurring in the areas labelled A, B and C? What substances are
represented by the arrows labelled a, b, c and d?
Solvay Process

The main by-product is calcium chloride. A little of this can be sold for use in refrigeration,
curing concrete and as a suspension in oil drilling.
Solvay Process

The temperature profile of a Solvay tower

Solvay Process
Solvay Process
Haber-Bosch Process

NaCl(aq)+ NH3(aq) + H2O(I) + CO2(g) ⇌ NH4Cl(aq) +

NaHC03(s)

Haber-Bosch Process

N2(g) + H2(g) ⇌ NH3(g)

Haber-Bosch Process

Top ammonia-producing countries, 2016

85%

https://marketpublishers.com/lists/23570/news.html
Haber-Bosch Process
Haber-Bosch Process: Thermodynamics

N2 (g) + 3H2 (g) 2NH3 (g)

Enthalpy: ∆H0 = -92 kJ

Entropy: ∆S0 = -199 kJ

Free energy: ∆G0 = ∆H0 −𝑇∆S0 = -33 kJ

Overall reaction is product favored at 25°C, but….activation energy

is high (breaking triple bond of N2)
Haber-Bosch Process: Thermodynamics

Low temperature shifts the equilibrium to the right, but means

a slow reaction rate. Fe catalyst improves this.

A high pressure favours also shifts the equilibrium to the

right because this is the side with fewer gas molecules.

Temperatures around 500 oC and pressures of over

150 atmospheres give a yield of ammonia of about 15%.

Product removal: In practice, equilibrium is not reached

as unreacted gases are recycled and the ammonia gas is
removed as a liquid.
Haber-Bosch Process: Current process

Ammonia is manufactured from N2 and H2. The nitrogen is available

from the raw material, air. (something which is available naturally).
The other feedstock for the manufacture of NH3 is hydrogen which is
usually produced from methane.
Haber-Bosch Process: Ammonia synthesis

T = 400 – 500 °C
P = 150–250 bar
Cat.: Fe3O4 mixed with KOH, Al2O3, and SiO2
Haber-Bosch Process

Each metric ton of ammonia packs about

5 MW h of energy. “The best, most
efficient Haber-Bosch plants work at
around 10 MW h per metric ton of
ammonia,”. “So we’re approximately only
50% efficient. It’s wasting a lot of energy
for what you get.”

https://cen.acs.org/environment/green-chemistry/Industrial-ammonia-production-emits-CO2/97/i24
Haber-Bosch Process

enzyme : expensive, mass - production (scale-up)

, ko bền, complex

Nitrogenase is the only enzyme known to reduce N2 to NH3 at ambient

temperature and pressure. The enzyme breaks down the energy-rich
adenosine triphosphate (ATP) to adenosine diphosphate (ADP) and uses
that energy to power the transfer of electrons from an iron-sulfur cluster
(cyan/yellow) through a phosphorus cluster (pink/yellow) to the iron-
molybdenum catalytic cofactor (orange), where N2 gets reduced.