1

Executive summary

This investigation reports comparisons of different ammonia processes in order to select the
most viable process for a new ammonia plant. The main considerations were energy
efficiency and scale-up flexibility. Other factors such as costing and environmental analyses
were not included because of insufficient information.
In light of these criteria, the Uhde process was chosen as the most suitable process.
However, the Selectoxo CO shift unit was chosen instead of conventional shift conversion in
the Uhde process. The process operates at high pressure (140-210 bar) resulting in high
converter conversions and low refrigeration costs. It has the least net energy consumption
(28 GJ/tNH
3
) among the options that were evaluated.
Most of the CO
2
produced can be sold to steel manufacturers. The ammonia produced is
pure (<1ppm H
2
O, >99.99mol% ammonia).
The following assumptions were made:
The reformer feed was CH
4

The reformer plant uses a primary and secondary reformer, thus pressure swing
absorption and intermediate temperature shift were not applicable


2

Introduction

Ammonia synthesis is essentially the process of reacting nitrogen with hydrogen to form
ammonia. The purpose of this report is to compare process design options for the
construction of a new 300,000 ton/yr ammonia plant with provision for future expansion to
450,000 ton/yr. The new plant is to be located on a green-field site 5km east of the town of
Sasolburg and the process feed is syngas from an adjacent reformer plant.
Construction was approved with the following conditions:
Atmospheric emissions will comply with current South African law, and will be subject
to carbon tax
There will be zero liquid effluents, by use of lined evaporation ponds.



















3

Evaluation of process options

Since the feed is syngas from a reformer; processes that do not use reforming and syngas
were not considered. The overall process is highlighted in Figure1 (Appl 1999).


Figure 1 Process options for ammonia synthesis (Appl 1999)

The process will be assessed in the sequence highlighted in Figure 1.




4

Shift conversion

Conventional high temperature/low temperature shift (HTS/LTS) is used by most plants to
convert CO from the reformer plant to CO
2
and H
2
via steam addition. Selectoxo however,
has developed a better process.
HTS/LTS gives a CO slip of 0.1-0.3vol% whereas Selectoxo achieves 0.03vol%. A small slip
is necessary for low methanation costs and lower risk of a runaway methanation reaction
(Agarwal n.d.). HTS/LTS requires excess steam to supress side reactions (this increases the
load on downstream purifiers) and the H/N ratio depends on the reformer. Selectoxo on the
other hand does not require excess steam and it regulates the H/N ratio for optimal
converter performance. The Selectoxo process however, is new and is not as well
researched as HTS/LTS.
The Selectoxo process was chosen for this design because it offers good efficiency and it
reduces the operating costs on downstream units.

CO
2
removal

CO
2
and residual CO have to be removed from the reactor feed because they are catalyst
poisons (Appl 2006). Various chemical and physical absorption systems are available for
CO
2
removal e.g. aMDEA, Benfield, Amine Guard and Selexol. Table 1 compares physical
and chemical processes (Uhde n.d.).
Table 1 Comparison of physical and chemical solvents
Physical Solvent Chemical Solvent
CO
2
dissolves without forming chemical
compounds, and can thus be flashed
CO
2
is fixed as chemical compound requiring
heat for separation
High loading capacity at high CO
2
partial
pressure (>10 bar)
Solubility approaches saturation value at high
CO
2
partial pressure (>10 bar)
Low absorption at low CO
2
partial pressure
(<10 bar)
Good absorption at low CO
2
partial pressure
(<10 bar)



5

To achieve low oxide concentrations at low costs (in order to reduce final purification costs),
better solvents that have properties of both types of solvents have been developed. These
are compared in Table 2.
Table 2 Energy Consumption of CO2 removal technologies (Appl 1999).
Process Heat requirement (kJ/mol CO
2
)
MEA (without Amine Guard) 209
MEA (with Amine guard iii) 116
Benfield hot potash (1stage) 88
BASF aMDEA process (1stage) 73
Benfield LoHeat 28- 35
BASF aMDEA process (2 stage) 28- 30


From an energy requirement perspective, the BASF aMDEA two-stage process is the best
process. The aMDEA process offers the following additional properties (Uhde n.d.):
>96% CO
2
recovery rate and >99vol% CO
2
this can be sold to steel manufactures
(for welding processes) such as Clotan Steel which is less than 25km away from the
plant
No corrosion inhibitors required
Minimal solution losses- does not degrade during operation thus no solution
reclaiming required
No toxic solvents
No crystallisation problems
Flexible for scale-up/scale-down
Therefore the BASF aMDEA process (2 stage) was selected for this design.







6

Final purification

The recommended oxide concentration in the reactor is <5ppm (Appl 2006). For residual
oxide removal, methanation; methanolation, cryogenic methods and nitrogen washing are
mainly used. Table 3 shows the advantages and disadvantages of each.
Table 3 Comparison of oxide removal technologies
Process Advantages Disadvantages
Methanation Simplest process- low-
maintenance
Cheapest
Oxides <5ppm
No temperature and pressure
reduction required
H
2
consumption
Requires control of LTS effluent
concentrations
Highly exothermic- hazardous

Methanolation Reduces H
2
consumption
Produces valuable methanol
Requires clean-up methanation
Additional plant required
Braun purifier Maintains required H/N ratio
Oxides <5ppm
High pressure loss
Low temperatures (-180
o
C)
Expensive to maintain and operate
Difficulty scaling up/down
Liquid nitrogen Maintains required H/N ratio
Oxides <5ppm
Liquid nitrogen expensive in large
quantities
-190
o
C operating temperature
Expensive process

Methanation was chosen because its low cost and efficiency outweigh the H
2
consumption
(Appl 2006). This process will be followed by molecular sieve drying as this saves energy in
the synthesis loop (Appl 1999).






7

Synthesis Loop

For industrial scale ammonia production from syngas; almost all the available technologies
use the Haber process. Some of the leading processes are compared in Table 4.
Table 4 Energy consumption of ammonia processes (Apple 2006)
Process Net energy consumption (GJ/tNH
3
)
Kellog Low-energy 27.9 (unconfirmed)
Haldor Topsoe 29.2 (actual plant)
Uhde 28 (actual plant)
LEAD process 29.3 (unconfirmed)

There are a number of factors to consider when choosing a synthesis loop e.g. installation
costs; catalyst lifespan and cost; maintenance requirements and production rate. Due to
limitations in knowledge and resources; most of these factors have not been considered.
The Uhde synthesis loop was chosen for this design because apart from its energy
efficiency, it requires no change in equipment sizes for scale-up (Uhde n.d.) i.e. the plant can
be designed to produce 300,000 ton/yr and only minor changes in operating conditions and
catalyst volume will be required for 450,000 ton/yr. The Uhde process works best with the
BASF aMDEA CO
2
removal process- which was chosen for CO
2
removal. It can also
incorporate the Selectoxo process instead of shift conversion. Furthermore, the following
benefits can be realised with Uhde:
High conversion synthesis loop, thus smaller heat exchangers and reduced power
usage since recycle is reduced
Low refrigeration cost because most ammonia condenses without refrigeration
Reliable catalysts used- no precious metal which may be too expensive in future
Produces 1.1-1.5t/tNH
3
of steam at 112bar, 520
o
C for utilities and for sale to adjacent
plants
H/N ratio is 2.95 thus H
2
consumption by methanation is compensated for
(Uhde n.d.)



8

Process Description

Syngas comes from an adjacent existing reformer plant (at 33 bara; 370C) with the
following composition:
Table 5 Syngas composition






The syngas then enters the Selectoxo unit which operates at 330-370
o
C, 32 bar where the
CO is converted to CO
2
via the water-gas-shift reaction:
CO+H
2
OCO
2
+H
2
H = 41.2 kJ/mol
The H/N ratio in the effluent is 3.05 and CO is 0.03%vol- this gas goes to the CO
2
removal
stage where CO
2
is reduced to less than 50ppm.
After CO
2
removal, the gas enters the methanation unit operating at 25 35 bar and 250
350
o
C with the following reactions:
CO+3 H
2
CH
4
+H
2
O H = 206 kJ/mol
and
CO
2
+4H
2
CH
4
+2H
2
O H = 165 kJ/mol
This unit reduces oxide concentration to <10ppm. The last purification stage is molecular-
sieve drying which reduces the inerts and water concentration in the make-up gas. This is
followed by compression to 140-210bar. Thereafter, the compressed gas is converted to
ammonia via:
N
2
+3H
2
2NH
3
H = 92.44 kJ/mol
The ammonia is then stored as liquid for transporting.
Component Composition
H
2
0.376
N
2
0.156
H
2
O 0.319
CO 0.1
CO
2
0.047
Ar 0.002


9

Mass balance assumptions

The operating conditions and typical parameters for each unit were taken from Appl (1999).
The key assumptions were:
CO concentration leaving the Selectoxo unit is 0.03vol%
96% CO
2
recovery from CO
2
removal
<5ppm oxides in synthesis make-up
>99.99% of H
2
in the make-up stream is converted
Mass is conserved










10

Selexol CO
removal
process
Methanation/
Purification
CO
2

Removal
Ammonia
Synthesis
Syngas
CO2
Off-gas
Ammonia
Purge gas
1 2
5
3
6
11
Compression
7
10
Molecular
sieve
drying
9
12
8 Off-gas
Purge gas 4
Ammonia Synthesis Plant
Unique number: 74
Date: 2013/07/25

Figure 2 Ammonia synthesis block flow diagram

11

Table 6 Stream table preliminary mass balance


Stream 1 2 3 4 5 6 7 8 9 10 11 12
Temperature
o
C 370 350 35 35 350 330 330 300 300 450 30 50
Pressure bar 33 32 1 2 30 32 32 30 30 200 20 20
Phase Gas Gas Gas Gas Gas Gas Gas Gas Gas Gas Liquid Gas
Total Flow kg/hr 113000 113000 44700 25700 43100 3610 39500 1070 38400 38400 37900 523
Mass flow kg/hr
Hydrogen 5400 6830 0 6.83 6830 0 6630 22.4 6610 6610 0 0
Nitrogen 31400 31400 0 3.14 31400 0 31400 0 31400 31400 0 0
Water 41200 28300 184 25500 2650 2700 229 228 0.229 0.229 0 0.229
Carbon monoxide 20100 6.03 0 0 6.03 123 123 110 12.3 12.3 0 12.3
Cabon dioxide 14800 46400 44600 186 1670 385 385 381 3.85 3.85 0 3.85
Argon 574 574 0 0 574 362 710 284 426 426 0 426
Methane 0 0 0 0 0 40 41.9 41.9 0.0419 0.0419 0 0.0419
Ammonia 0 0 0 0 0 0 0 0 0 0 37900 80.1
Molar fraction
Hydrogen 0.376 0.476 0 0.0024 0.721 0 0.74 0.242 0.745 0.745 0 0
Nitrogen 0.156 0.156 0 0.0000787 0.237 0 0.25 0 0.253 0.253 0 0
Water 0.319 0.219 0.01 0.995 0.0311 0.859 0.00283 0.274 2.86E-06 2.86E-06 0 0.00113
Carbon monoxide 0.1 0.00003 0 0 0.0000455 0.0251 0.000979 0.0854 0.0000989 0.0000989 0 0.0392
Cabon dioxide 0.047 0.147 0.99 0.00297 0.00803 0.0502 0.00195 0.188 0.0000197 0.0000197 0 0.00782
Argon 0.002 0.002 0 0 0.00303 0.0518 0.00396 0.154 0.0024 0.0024 0 0.952
Methane 0 0 0 0 0 0.0143 0.000585 0.0567 5.91E-07 5.91E-07 0 0.000234
Ammonia 0 0 0 0 0 0 0 0 0 0 1 0


12

References

Agarwal, P. n.d,. Ammonia: The Next Step. Available at:
http://www.out.ac.tz/avu/images/Chemistry/10_Industrial%20Chemistry/industrial_readings/a
mmonia%20%20next%20step.pdf. Last accessed 25th Jul 2013
Appl, M, 1999. Ammonia processes and industrial practice. 1st ed. Weinheim New York :
WILEY-VCH.
Appl, M 2006, 'Ammonia', Ullmann's Encyclopedia of Industrial Chemistry, WILEY-VCH,
Weinheim, vol 2. pp. 44-100.
Uhde n.d ., Ammonia. Available at: http://www.thyssenkrupp-
uhde.de/fileadmin/documents/brochures/uhde_brochures_pdf_en_5.pdf. [Accessed 25 July
2013]



13