Blue Ammonia

Synthesis Process
GROUP 4, SEMESTER 2 2023
NEVE ANNETT, SHAY O’SULLIVAN, KHANH VAN DIEP
1.Block Flow Diagram – Blue Ammonia Process
2.Opera onal Condi ons of the Major Equipment

2.1 Steam Methane Reformer (SMR)

Opera onal Condi ons:

Nickel - containing reforming catalyst used to create a par al conversion, roughly 65% of the
methane. Outlet temperature is lowered to around 1273.15K and has a methane content of 0.5%
from the original feed into the products [1].

Reac ons:
206𝑘𝐽
𝐶𝐻 + 𝐻 𝑂 ⇌ 𝐶𝑂 + 3𝐻 Δ𝐻 =+
𝑚𝑜𝑙
165𝑘𝐽
𝐶𝐻 + 2𝐻 𝑂 ⇌ 𝐶𝑂 + 4𝐻 Δ𝐻 =+
𝑚𝑜𝑙

2.2 Water Gas Shi Reac on (WGS)

Opera onal Condi ons:

At high temperature, from 1105K at a pressure of 2,000 to 4,000 kPa, with an iron-based catalyst,
Fe2O3 prevents the sintering of iron oxide crystallites. Roughly a 67% conversion in reac on [2].

Reac ons:
206𝑘𝐽
𝐶𝑂 + 3𝐻 ⇌ 𝐶𝐻 + 𝐻 𝑂 Δ𝐻 =−
𝑚𝑜𝑙
165𝑘𝐽
𝐶𝑂 + 4𝐻 ⇌ 𝐶𝐻 + 2𝐻 𝑂 Δ𝐻 =−
𝑚𝑜𝑙

2.3 Haber-Bosch Reactor

Opera onal Condi ons:

Temperature of 623.15 to 723.15 K at a high pressure of 15,000 to 30,000 kPa. The most common
catalyst is usually iron oxide based [2]

Reac on:
92.44𝑘𝐽
𝑁 + 3𝐻 ⇌ 2𝑁𝐻 Δ𝐻 =−
𝑚𝑜𝑙

2.4 Compressors

Opera onal Condi ons:

As the reactor process in Haber-Bosch is exothermic the process requires staged cooling and catalyst
beds to limit temperature rise and allow for maximized conversion opportuni es. This is under high
pressure and moderate temperature as per above. However, energy requirement for compression is
roughly 8.3-9.7kWh/kg NH3 [3].
2.5 Tube-cooling converter

Opera onal Condi ons:

The main gas will be heated to 473.15K with a heat exchanger. Then, the gas enters the cooling tubes
interac ng with the catalyst beds and absorbs the heat ll 673.15K [2]. Based on the temperature
difference between the reac ng gas and the cooling tubes increasing, the heat is efficiently removed
when the tubes absorb. Due to the high ammonia concentra on, the pace of reac on starts to slow
down when the reac ng gas approaches the bo om of the catalyst bed, which causes cooling to
prevail and causes the reac ng gas' temperature to drop.

2.6 Storage - Pressure Storage

Opera onal Condi ons:

For this method, the cylindrical pressure vessels used in this procedure are built to withstand
pressures of roughly 2.5 MPa. To avoid having walls thicker than 30 mm, larger spherical containers
are only made to withstand pressures of roughly 1.6 MPa.

To prevent solar radiant hea ng, the tank may be painted with reflec ve paint or, more frequently in
hot areas, covered with an external insula ng covering. In theory, inert gas will be carried by liquid
ammonia as it is introduced into storage from the synthesis loop. Pressure control for the tank is
given by the controlled release of inert gas through a pressure relief valve in addi on to the
regulated safety pressure relief valves.

2.7 Refrigera on

Opera onal Condi ons:

Once the vapours have been split the ammonia is then condensed and cooled to a temperature of
~277.65K. The requirement for NH3 to be fed to storage requires however a temperature of 239.15K
so a cold duty of 1.7 x 106kcal/hr must be generated [4].

2.8 Shipping - Trucks and Rail Cars

Opera onal Condi ons:

The most popular techniques include using pressure vessels for anhydrous ammonia (maximum
permissible opera ng pressure is roughly 2.5 MPa), and vessels for 25% aqueous ammonia at
ambient pressure. On the other hand, vessels created for high-concentra on aqueous ammonia at
higher pressure (maximum permi ed opera ng pressure according to ammonia content up to 1.6
MPa).
3. Material Balances

3.1 Natural Gas Requirement

𝑁 + 3𝐻 ↔ 2𝑁𝐻
10 𝑘𝑔
1𝑀𝑇𝑃𝐴 (𝑁𝐻 ) = 1 ×
𝑦𝑟
17.03𝑔
𝑀𝑊 (𝑁𝐻 ) =
𝑚𝑜𝑙
1 × 10
𝑛(𝑁𝐻 ) = = 5.87 × 10
0.01703
Ra o from equa on:

1 : 3 : 2

Therefore,

𝑛(𝑁 ) = 29. 4 × 10

𝑛(𝐻 ) = 88.1 × 10

𝐶𝐻 + 𝐻 𝑂 → 𝐶𝑂 + 3𝐻
16.05𝑔
𝑀𝑊(𝐶𝐻 ) =
𝑚𝑜𝑙
Ra o for CH4 and NH3:

1 : 2

29.4 × 10 𝑚𝑜𝑙
𝑛(𝐶𝐻 ) =
𝑦𝑟
4083.3𝑚𝑜𝑙
𝑛(𝐶𝐻 ) =
ℎ𝑟
𝑛𝑅𝑇
𝑉=
𝑃
Assump on of normal condi ons [5]:

Pressure = 101.325kPa

Temperature = 273.15K

R Gas Constant = 8.314 J/mol.K

𝑁𝑚
𝑉 = 9.15 × 10
ℎ𝑟
3.2 SMR Reac on

𝐶𝐻 + 𝐻 𝑂 → 𝐶𝑂 + 3𝐻
From Previous CH4 = 4083.3𝑚𝑜𝑙/ℎ𝑟

Ra o from equa on for CH4 and H2O

1 : 1

Therefore,

𝑛(𝐻 𝑂) = 4083𝑚𝑜𝑙/ℎ𝑟
𝐶𝐻 × 𝜉 = 𝑚𝑜𝑙(𝐶𝑂) 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
= 1429𝑚𝑜𝑙
2𝑚𝑜𝑙 𝐶𝑂 = 𝑚𝑜𝑙(𝐶𝑂 ) 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝑚𝑜𝑙
= 500.15
ℎ𝑟
𝐻 , = 𝜉 × (𝐶𝐻 )

= 12249𝑚𝑜𝑙/ℎ𝑟
𝐻 , = 500.15𝑚𝑜𝑙/ℎ𝑟

CH4 remaining:

𝐶𝐻 , − 𝐶𝐻 , = 2654 𝑚𝑜𝑙/ℎ𝑟

H2O consistent with CH4 calcula ons with stoichiometric coefficients.

500.15 𝑚𝑜𝑙
𝐶𝑂 , =
ℎ𝑟

3.2 WGS

𝐶𝑂 + 𝐻 𝑂 → 𝐶𝑂 + 𝐻
As per previous:
1429 𝑚𝑜𝑙
𝑛(𝐶𝑂) =
ℎ𝑟
Ra o from equa on:

CO : H2O : H2

1 : 1 : 1

With CO/H2O remaining will be 0

Total H2

𝐻 = 500.15 + 12249
𝑚𝑜𝑙
= 12749.15
ℎ𝑟
3.3 Harber-Bosch Reactor

Assuming N2 supply to the process is 40% excess, H2 is the limi ng reactant.

Feed of H2 taken from the WGS, as above.

𝐻 = 500.15 + 12249
𝑚𝑜𝑙
= 12749.15
ℎ𝑟
The ra o from equa on:

N2 : H2 : NH3

1 : 3 : 2

A single-pass conversion of ~10-15%, fsp=15%

−𝜉𝑣
𝑓 =
𝑛
−𝜉 × −3
= = 15%
12749.15
𝑚𝑜𝑙
𝜉 = 637 (𝑚𝑜𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔)
ℎ𝑟
The overall conversion is 98% including recycle stream, fOA=98%

𝑓 𝑛
=
𝑓 𝑛 +𝑛
15% 12749.15
=
98% 12749.15 + 𝑛(𝑅𝑒𝑐𝑦𝑐𝑙𝑒)
𝑚𝑜𝑙
𝑛(𝑅𝑒𝑐𝑦𝑐𝑙𝑒) = 70545
ℎ𝑟
Recycle stream flow rate = 70545 mol/hr
4. CO2 Emission

10 𝑘𝑔
1𝑀𝑇𝑃𝐴 (𝑁𝐻 ) = 1 ×
𝑦𝑟
300 𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑑𝑎𝑦𝑠 = 7200 ℎ𝑜𝑢𝑟𝑠
𝑘𝑔
= 138.89
ℎ𝑟
𝑚𝑜𝑙
𝐶𝑂 = 500.15
ℎ𝑟
𝑚𝑜𝑙
𝐶𝑂 , = 1429.15
ℎ𝑟
𝑚𝑜𝑙
𝑇𝑜𝑡𝑎𝑙 = 1929.3
ℎ𝑟
84.908𝑘𝑔
𝑚(𝐶𝑂 ) = 1929.3 × 44.0095 =
ℎ𝑟
𝑚(𝐶𝑂 )
𝐹𝑜𝑜𝑡𝑝𝑟𝑖𝑛𝑡 𝑉𝑎𝑙𝑢𝑒 =
𝑚(𝑁𝐻 )
𝑘𝑔 𝐶𝑂
= 0.61
𝑘𝑔 𝑁𝐻
CO2 is also produced by u li es such as hea ng units and compressors. Hea ng units are predicted
to emit 0.4kg of CO2 per kg of NH3, while compressors emit around 0.2kg.

The addi on of these variables brings the CO2 emissions to 1.21 kg per kg of NH3, which is rela vely
like the given footprint value of 1.5 kg per kg of NH3.
5. Energy Consump on

As per literature and in the project brief the es ma on of energy consump on during the blue
ammonia process is ~10-20kWh/kg of NH3. To confirm this es mate we separated the highest
por ons of the process into three substan al processes which require large amounts of energy. The
addi on of the reac ons, refrigera on and compression/heat exchangers all contribute to this.

The reac ons in the process are within the SMR, WGS and HB process and reactors.
206𝑘𝐽
𝐶𝐻 + 𝐻 𝑂 ⇌ 𝐶𝑂 + 3𝐻 Δ𝐻 =+
𝑚𝑜𝑙
165𝑘𝐽
𝐶𝐻 + 2𝐻 𝑂 ⇌ 𝐶𝑂 + 4𝐻 Δ𝐻 =+
𝑚𝑜𝑙
41𝑘𝐽
𝐶𝑂 + 𝐻 𝑂 ⇌ 𝐶𝑂 + 𝐻 Δ𝐻 =−
𝑚𝑜𝑙
92.44𝑘𝐽
𝑁 + 3𝐻 ⇌ 2𝑁𝐻 Δ𝐻 =−
𝑚𝑜𝑙
𝑘𝐽
𝑇𝑜𝑡𝑎𝑙 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝐸𝑛𝑒𝑟𝑔𝑦 = 237.5
𝑚𝑜𝑙
𝑛(𝑁𝐻 )
𝑇𝑜𝑡𝑎𝑙 𝐴𝑚𝑚𝑜𝑛𝑖𝑎 = 58.7199𝑚𝑜𝑙
𝑘𝑔
13945.97𝑘𝐽
𝑘𝐽 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑖𝑛 𝑠𝑦𝑠𝑡𝑒𝑚 𝑓𝑜𝑟 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠 =
ℎ𝑟
Refrigera on as stated in Task 2:
1.7𝑘𝑐𝑎𝑙
𝑇𝑜𝑡𝑎𝑙 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝐸𝑛𝑒𝑟𝑔𝑦 =
ℎ𝑟
13628𝑘𝐽
=
ℎ𝑟
Compressors and Heat Exchangers as well taken from Task 2 data and informa on, based off
literature:
𝑘𝑊ℎ
𝑇𝑜𝑡𝑎𝑙 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝐸𝑛𝑒𝑟𝑔𝑦 ≈ 8.3 − 9.78
𝑘𝑔
Therefore,

15.96𝑘𝑊ℎ
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 =
𝑘𝑔 (𝑁𝐻 )
This verifies the statement in the project brief.
References

[1] Hydrogen produc on: Steam Methane Reforming (SMR) [Internet]. Découvrez la Greentech.
Available from: h ps://www.discoverthegreentech.com/en/hydrogen/produc on/steam-methane-
reforming/

[2] Appl M. Ammonia. 1999 Mar 11; Available from:

h ps://onlinelibrary.wiley.com/doi/book/10.1002/9783527613885

[3] Allen J, Panquet S, Bas ani A. Electrochemical Ammonia: Power to Ammonia Ra o and Balance of
Plant Requirements for Two Different Electrolysis Approaches. Fron ers in Chemical Engineering.
2021 Nov 30;3:765457.

[4] AMMONIA Concept and applica on MAGED ELKOMI [Internet]. Available from:
h ps://ureaknowhow.com/wp-content/uploads/2021/06/2021-Elkomi-Ammonia-process-
descrip on-NH3-
refrigera on.pdf#:~:text=However%2C%20the%20requirement%20is%20that%20the%20ammonia%
20fed

[5] Daham A. Basic Principles and Calcula ons in Chemical Engineering First Year [Internet]. Available
from: h ps://ceng.tu.edu.iq/ched/images/lectures/chem-lec/st1/c3/basic-1.pdf