The design of an ammonia synthesis

fixed bed reactor

TMC Ncube

CJJ 421

2022-10-29
The design of an ammonia synthesis fixed
bed reactor

TMC Ncube
18171525

Department of Chemical Engineering

University of Pretoria

CJJ 421

2022-10-29
 The design of an ammonia synthesis fixed
bed reactor

Executive summary

This report presents the design of the fixed bed reactor for the synthesis of ammonia
throught the haber-bosch process where nitrogen and hydrogen react. The nitrogen is
from an air separation unit and the hydrogen is formed through the oxy-steam reforming
process at a process plant formed by group 6 where LNG is the raw material.

In the design, the kinetic model is defined using information from literature, the physical
model is also formed taking into consideration the effects of external and internal mass
control. The kinetic model solution is then solved followed by the mechanical design of
the reactor. A summary of the design is as shown in Figure 1 below

Property Value
Flowrate (kg h) 169014
mass H2 15
mass NH2 85
Temperature (K) 723
Pressure (MPa) 30
Catalyst particles
Particle diameter (mm) 8
Bulk density (kg h−1
Porosity 0.46
Catalyst weight (kg h−1 15808.12
Reactor
Thickness (mm) 415
Length (m ) 4.63
Tubes 81
Reactor diameter (m) 2
Shell diameter (m) 2.83
Reactor volume (m) 11
Tube length 1.8

Table 1: Design specification

Figure 1 below shows the reactor dimensions and size

i
 Figure 1: The reactor dimensions

The process flow diagrams of the process plant are shown below.

ii
 Process flow diagram (PFD)

Air separation unit

Waste N2

23 Oxygen

24 Nitrogen

11
High
pressure

DC-101

46

Air 1 GC-101 GC-102

GC-103 GE-101
2 3 10
4 5 6
1335.74 kW 1253.80 kW 1418.72 kW 8 12
13
7 -167.29 kW
9
HX-101 HX-102 HX-103 14
-1174 kW -1375 kW HX-104
-10988 kW -693 kW 20

GE-102 Argon
rectification
iii

-71.61 kW DC-103 21
18
Low 16
121
pressure

DC-102 HX-105
2311 kW
15 17 22
70

19

ST-101

Bottling

Stream description Units Air 1 2 3 4 5 6 7 8 9 10 11 12 Compressors Turbines Columns Heat Exchangers Heat Exchangers Tanks
Flowrate kg/h 59871 59871 59871 59871 59871 59871 59871 59871 8981 50890 50890 20000 30890 GC-101 GE-101 DC-101 HX-101 HX-103 Argon storage
Temperature K 303 303 383 313 388 306 390 299 299 299 95 95 99 ΔP = 97 kPa W = -167.29 kW 5.45m ID x 46.23m A = 279.99 m2 A = 669.88 m2 7.85m ID x 11.78m
Pressure kPa 101 101 198 198 366 346 655 635 635 635 570 560 560 W = 1335.74 kW ΔP = -440 kPa P=560 kPa Duty = -1174 kW Duty = -1525 kW P = 100 kPa
Argon %mole 0.0093 0.0093 0.0093 0.0093 0.0093 0.0093 0.0093 0.0093 0.0093 0.0093 0.0093 0 0.0157 Material =C.S Material =C.S Stages = 46 ΔT=-70 K ΔT=-91 K T = 87 K
Nitrogen %mole 0.7812 0.7812 0.7812 0.7812 0.7812 0.7812 0.7812 0.7812 0.7812 0.7812 0.7812 1 0.6315 Material =C.S Material =C.S Material =C.S Material =C.S
Oxygen %mole 0.2095 0.2095 0.2095 0.2095 0.2095 0.2095 0.2095 0.2095 0.2095 0.2095 0.2095 0 0.3529 GC-102 GE-102 DC-102 HX-102
ΔP = 168 kPa W = -71.61 kW 21.94m ID x 70.35m A = 459.02 m2 HX-105
Stream description Units 13 14 15 16 17 18 19 20 21 22 23 24 Waste N2 W = 1253.80 kW ΔP = -460 kPa P = 120 kPa Duty = -1375 kW A = 564.67 m2
Flowrate kg/h 20000 8981 8981 12800 11684 20022 9025 29708 1116 1116 9025 29708 20022 Material =C.S Material =C.S Stages = 70 ΔT=-88 K Duty = 2311 kW
Temperature K 79 110 84 92 92 80 92 99 92 87 298 298 298 Material =C.S Material =C.S ΔT=218 K
Pressure bar 120 590 130 120 120 120 120 560 120 100 120 120 120 GC-103 DC-103 HX-104 Material =C.S
Argon %mole 0 0.0093 0.0092 1.07E-06 5.31E-07 0.0279 0 3.24E-07 0.99999 0.999993 1.11E-08 4.58E-08 2.79E-02 ΔP = 309 kPa 5.93m ID x 121.61m Heat exchange
Nitrogen %mole 1 0.7812 0.7856 0 0 0.8037 0 1 0 0 0 1 0.8037 W = 1418.72 kW P=120 kPa network
Oxygen %mole 0 0.2095 0.2052 0.999999 1 0.1684 1 4.58E-08 6.63E-06 6.63E-06 1 0 0.1684 Material =C.S Stages = 121 Net duty= -693 kW
Material =C.S
 Hydrogen production and ammonia synthesis

HX-117
155484 kW
66 GC-109 65 69 Purge
HX-112 HX-113 HX-114 HX-115
-1147 kW -1158 kW -1205 kw -66766.9 kW 67 138 kW
RX-103
64
53 55 57 59
60
56 62 63 68
54
Nitrogen 52 58 61 HX-116
GC-105 GC-106 GC-107 GC-108 -185506 kW
ST102
9745 kW 14652 kW 22218 kW 24926 kW
51

MSC-101 AC-101
Ammonia
48
47
49

Oxygen
46
50
36 HX-111
GC-104 25
44
-5489.8 kW
ST-101
979 kW HX-106 RX-101 RX-102 SC-101 45
-5.1 kw 29

31 32 33
F-101
30 GE-103 34 FD-101
LN G 37
26 HX-107 HX-108
-33468 kW -17022 kW -11243 kW 38
P-101 HX-109
123 kW 1369 kW HX-110
iv

28 35 5084 kW
43 39
40

Water 42
27 B-101 70
41
P-102 P-103
425 kW 2 kW

Stream description Units LNG Water Oxygen 25 26 27 28 29 30 31 32 33 34 Compressors Pumps Columns Heat Exchangers Heat Exchangers Tanks Reactors Turbines Furnace
Flowrate kg/h 26422 54046 9024 9024(oxygen) 26422(LNG) 54046(water) 26422(Methane) 9024(oxygen) 89492 89492 89492 89492 89492 GC-104 P-101 FD-101 HX-106 HX-112 ST-103 RX-101 GE-103 F-101
Temperature K 111 298 298 520 112 298 520 520 1173 719 473 473 313 ΔP = 1300 kPa ⴄ =78.239 1 m ID x 4m A =0.085 m2 A = 75.48 m2 LNG storage ATR P = 1300 kPa P = 1400 kPa
Pressure kPa 100 100 100 1500 1400 1400 1400 1400 1400 100 100 100 200 W = 979 kW NPSH = 0.4 m P= 200 kPa Duty = -5.1 kW Duty = -1147 kW 31.1m ID x 46.6m Combust W = -33468 kW T = 520 K
Water %mass - 1 - - - 1 - - 0,36 0,36 0,36 0,05 0,05 Material =C.S Duty = 123 kW Duty = -261 kW ΔT=-2 K ΔT=-20 K P = 100 kPa 1.21m ID x 6.03 m Material =C.S heating LNG=15119 kW
Hydrogen %mass - - - - - - - - 0,1 0,1 0,1 0,13 0,13 Material =C.S Material =C.S T = 111 K Duty=-31363 kW Material =C.S
Carbon monoxide %mass - - - - - - - - 0,47 0,47 0,47 - - GC-105 AC-101 HX-107 HX-113 Material =C.S Reform
Carbon dioxide %mass - - - - - - - - 0,07 0,07 0,07 0,86 0,86 ΔP = 304 kPa P-102 1.36m ID x 24.52m A = 340.75 m2 A = 710.33 m2 0.38m ID x 1.88 m Boiler
Stream description Units 35 36 37 38 39 40 41 42 43 44 45 46 47 W = 9745 kW ⴄ =85.4847 P = 100 kPa Duty = -17022 kW Duty = -1158 kW ST-102 Duty=127353 kW B-101
Flowrate kg/h 363 89129 29624 29624 - Water for boiling Cold water 12217 12217 12217 17407 29,97 117377 Material =C.S NPSH = 10 m Stages = 16 ΔT=-246 K ΔT=20 K Ammonia storage Material =C.S Duty = 50009 kW
Temperature K 313 313 310 373 373 - - 417 417 313 409 313 Duty = 425 kW Material =C.S 185.35m ID x 92.68m P=1400 kPa
Pressure kPa 200 200 100 100 50 - - 50 100 100 100 100 100 GC-106 Material =C.S SC-101 HX-108 HX-114 P = 29891 kPa RX-102 T=525 K
Water %mass 1 0,05 0,05 0,05 - - - - - - 8,00E-02 - 9,00E-02 ΔP = 1013 kPa 1.97m ID x 35.54m A=214.27 A = 51.84 m2 T = 313 K Shift-gas reactor Material =C.S
Hydrogen %mass - 0,14 - - - - - - - - - - - W = 14652 kW P-103 P=50 kPa Duty = -11243 kW Duty = -1205 kW Material =C.S 2.70m ID x 13.50m
MEA %mass - - 0,95 0,95 - - - 1,00E+00 1,00E+00 1,00E+00 0,91 - 0,91 Material =C.S ⴄ =64.0504 Stages = 16 ΔT=-160 K ΔT=-20 K Duty=-16731 kW
Carbon dioxide %mass - 0,81 0,001 0,001 - - - - - - 0,02 1 - NPSH = 10.2 m Material =C.S Material =C.S
Stream description Units 48 49 50 51 52 53 54 55 56 57 58 59 60 GC-107 Duty = 2 kW HX-109 HX-115
Flowrate kg/h 30541,9 15058 2911 12144 41724,8 41724,8 41724,8 41724,8 41724,8 41724,8 41724,8 41724,8 41724,8 ΔP = 3749 kPa Material =C.S MSC-101 A = 421.77 m2 A = 19.44 m2 RX-103
Temperature K 313 318 318 318 298 469 449 703 683 1060 1040 1801 723 W = 22218 kW 1.13m ID x 4.52m Duty = 1369 kW Duty = -66766.9 kW Haber process reactor
Pressure kPa 100 100 100 100 101 380 365 1369 1354 5076 5060 30000 30000 Material =C.S ΔP = 1 kPa ΔT=63 K ΔT=-1078 K 0.92m ID x 4.61m
Water %mass - 0,19 1 - - - - - - - - - - Material=CS Duty=-16731 kW
Hydrogen %mass - 0,81 - 1 0,85 0,85 0,85 0,85 0,85 0,85 0,85 0,85 0,85 GC-108 HX-110 (reboiler HX-116(condenser) Material =C.S
MEA %mass 1 - - - - - - - - - - - - ΔP = 24926 kPa A = 932.46 m2 A = 10.33 m2
Nitrogen %mass - - - - 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 W = 48049 kW Duty = 5084 kW Duty = -185506 kW
Stream description Units 61 62 63 64 65 66 67 68 69 70 Ammonia Purge Material =C.S ΔT=44 K ΔT=-410 K
Flowrate kg/h 169014 169014 169014 135380 127257 127257 127257 33635 8123 54046 33635 8123 Material =C.S
Temperature K 723 723 313 313 313 314 723 313 313 520 313 313 GC-109 HX-111(condenser)
Pressure kPa 30000 30000 29891 29891 29891 30000 30000 29891 29891 1400 29891 29891 ΔP = 101 kPa A = 185.97 m2 HX-117
Water %mass - - - - - - - - - 1 - - W = 138 kW Duty = -5489.8 kW A = 502.17 m2
Nitrogen %mass 0,85 0,004 0,0028 0,0002 0,004 0,004 0,004 - 0,004 - - 0,004 Material =C.S ΔT=-96 K Duty = 155484 kW
ammonia %mass - 0,45 0,997 0,997 0,309 0,309 0,309 9,80E-01 3,09E-01 - 9,80E-01 3,09E-01 ΔT=408 K
hydrogen %mass 0.15 0,55 0.0002 0,0028 0,69 0,69 0,69 0,02 0,69 - 0.02 0.69 All Material =C.S
Contents

Executive summary i

1 Introduction 1

2 Kinetic model 2

2.1 Catalyst choice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2.2 Reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2.3 Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3 Physical model 7

3.1 External mass transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.1.1 Mears’criterion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2 Energy balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.3 Mass balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.3.1 Specific heat capacity . . . . . . . . . . . . . . . . . . . . . . . . . 9

3.3.2 Heat of reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4 Model solution and Design 10

4.1 Reactor choice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4.2 Preliminary design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4.2.1 Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

4.2.2 Temperature profile . . . . . . . . . . . . . . . . . . . . . . . . . . 11

4.3 Amount of catalyst in the reactor . . . . . . . . . . . . . . . . . . . . . . 12

4.4 Pressure drop across the reactor . . . . . . . . . . . . . . . . . . . . . . . 12

iii
 4.5 Reactor construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

4.5.1 Catalyst tubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

4.5.2 Shell diameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.5.3 Catalyst volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.5.4 Reactor length . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

4.5.5 Bed diameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4.5.6 Reactor volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4.5.7 Material of construction . . . . . . . . . . . . . . . . . . . . . . . 14

4.5.8 Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4.6 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

A Appendix A.1

iv
1 Introduction

A plant that uses LNG as feed and has three independent units—the air separation,
hydrogen production, and ammonia production—was designed to produce 36 000 kg of
ammonia per hour. The air separation unit separates nitrogen, oxygen, and argon into
their most pure forms. In the Haber-Bosch process, the pure nitrogen will react with the
hydrogen to produce ammonia. The created ammonia is packaged and sold along with
the argon.

In this report the reactor in which the haber-bosch ammonia synthesis reaction takes
place is designed. Reaction kinetics discovered in the literature was used to develop
the reactor. The assumptions made in the preliminary stage if the design were checked
through calculations to ensure that the design was sound. The reactor feed conditions
are as shown in Table 2 below

Property Value
Flowrate (kg h) 169014
% mass H2 15
% mass NH2 85
Temperature (K) 723
Pressure (MPa) 30

Table 2: The reactor feed inlet conditions

1
2 Kinetic model

The ammonia production reaction is represented by Equation 1 below

N2(g) + 3 H2(g) −
↽−
−⇀
− 2 NH3(g) ∆Hf◦ = −92.44 kJ/mole (1)

which is an exorthemic reaction (Hicks, 2008). Le Chatelier’s Principle states that reac-
tions carried out under greater pressure will favor the forward reaction, which produces
more ammonia (Puspitasari & Yahya, 2011).

2.1 Catalyst choice

According to Hicks, 2008, activating molecular hydrogen and molecular nitrogen are
the two tasks that the inorganic catalyst must complete.The catalyst must also prevent
atomic hydrogen or atomic nitrogen from chemically reacting with the catalyst to form
stable hydrides or nitrides. Similar to high chemisorption of the Lewis base ammonia on a
Lewis acid catalyst surface, this would self-poison the catalyst. Therefore, a system that
offers free electrons to activate the chemical components is necessary for the selection of
the catalyst. It must be a mild enough activation by electron transfer to produce reactive
atomic species. Chemically, the best catalysts are iron and ruthenium, while strongly
Lewis acidic systems like Ti or Mo and strongly basic systems like Ni and Pt are not
suitable options (Hicks, 2008). Therefore, a comparison was done between the iron and
ruthenium catalysts to pick a suitable one for the design of the reactor.

The best metal for ammonia production and breakdown at low temperatures and low
pressures is well-known to be ruthenium however, one of the biggest issues that slows
ammonia synthesis under favorable conditions for Ru is hydrogen toxicity (Fang et al,
2022). This is due to the catalyst’s surface hydrogen adsorption, which inhibits nitrogen
dissociation, reducing the Ru-based catalyst’s activity, especially at low reaction temper-
atures (Doyle, 2018). According to Fang et al, 2022, the annual production of ruthenium,
which is a relatively rare metal, is thought to be 30 tonnes. Although Ru-based catalysts
may recover more than 95% of Ru, their price makes them unsuitable for application
in industrial ammonia production. The also have a carbon base and ammonia synthesis
processes methanize carbon, which is quite disadvantageous (catalyst, 2022).

Considering that Ru is scarce and expensive, and the catalysts are susceptible to hydro-
gen poisoning, iron based catalysts were used. There are different types of iron-based

2
catalysts namely; cobalt, magnetite and wustite-containing catalysts, with wustite hav-
ing the highest activity (catalyst, 2022). The catalyst used in the design is the iron-oxide
catalyst, Fe2 O3 -FeO. Magnetite is fused throughout the manufacturing process using
potassium, calcium, and other elements as well as alumina oxides as promoters. The fol-
lowing action is internal reduction Oxygen is eliminated, and consequently, the catalyst
structure changes to porous iron. The interphases are flanked by promoters between pore
walls and crystal (Jassim, 2021).

2.2 Reaction mechanism

Coker, 2001 states that studies on the production of ammonia on iron catalysts indicate
that surface imine radicals are responsible for the reaction. The intermediate elementary
steps are represented by Equations 2 to 7 as follows;

N2(g) −−→ 2 N2(ads) (2)

H2(g) −−→ 2 H(ads) (3)

N(ads) + H(ads) −−→ NH(ads) (4)

NH(ads) + H(ads) −−→ NH2(ads) (5)

NH2(ads) + H(ads) −−→ NH3(ads) (6)

NH3(ads) −−→ NH3(g) (7)

The net equation is however the focal point of the design.

2.3 Kinetics

The kinetic model used in this design is based on the method employed by (Suhan et al,
2020) and will be discussed in this section. The rate equation using nitrogen adsorption
as the slow step is given by the Temkin–Pyzhev equation

α  1−α 
aH 2 3 aN H3 2
 
2
rN H3 = 2k ka aN2 − (8)
aN H32 aH2 3

in the units kmol m−3 h −1 , where k is the reaction’s rate constant, ka is the equilibrium
constant, ai is the activity of the component and α is a constant ranging from 0.5 to 0.75.

3
A value of 0.5 is used for the design.

The reaction rate relations are as follows

1 1
− rN2 = − rH2 = rN H3 (9)
3 2

The activity is calculated from the fugacities as follows

fi
αi = (10)
fi 0

where fi 0 is the reference fugacity and it is taken as 1 atm giving

αi = yi γi P (11)

in which ϕi is the fugacity coefficient, yi is the mole fraction of the component and P is
the pressure of the gas mixture.

The fugacity of hydrogen is calculated from Equation 12

γH2 = exp exp[−3.8402T 0.125 + 0.541] × P − exp[−0.1263T 0.5 − 15.98] × P 2

+ 300 × exp[−0.011901T − 5.941] × exp[−P/300] (12)

meanwhile the fugacities of nitrogen and ammonia are calculated from Equation 13 as

γi = A + BT + CP + DT 2 + EP 2 (13)

using the constants in Table 3 as shown below

4
 Component N2 NH3
Constants A 0.93431737 0.1438966
B 0.2028538 x 10−3 0.2028538 x 10−2
C 0.295896 x 10−3 -0.4487672 x 10−3
D -0.270727x 10−6 -0.1142945 x 10−5
E 0.4775207 x 10−6 0.2761216 x 10−6

Table 3: The constants for calculating the fugacities of N2 and NH3

The temperature is in K and the pressure in kPa. The mole fractions of the components
are determined as using the Equations 14 to 16

YN2 (1 − X)
yN 2 = (14)
1 − 2XYN2

YH2 − 3XYN2
yH2 = (15)
1 − 2XYN2

YN H3 + 2XYN2
yN H3 = (16)
1 − 2XYN2

where Yi represents the mole fractions of the components before the occurrence of the
reaction and X is the fractional conversion of N2 , which is the limiting reagent. X is
determined from a mole balance over the reactor.

The arrhenius equation in employed to calculated the rate constant

E
k = k0 e− RT (17)

where k0 =8.849 × 1014 is the pre-exponetial factor, E = 170560 kJ kmol−1 is the activation
energy determined at average temperature values, T is the design temperature and R =
8.314 kJ kmol−1 K−1 is the universal gas constant (Suhan et al, 2020).

The equilibrium constant is calculated using the Equation 18, which covers a wide range
of temperatures and pressures.

2001.6
log10 ka = −2.691122logT − 5.519265 × 10−5 T + 1.848863 × 10−6 T 2 + + 2.689 (18)
T
5
The kinetic model is as shown in Table 4 with the parameters in Table 5

Equation
  α 
aH2 3 aN H3 2 1−α
h i
2
Reaction rate rN H3 = 2k ka aN2 aN H 2
− aH2 3
3
E
Reaction rate constant k = k0 e− RT
Equilibrium constant log10 ka = −2.691122logT − 5.519265 × 10−5 T
+1.848863 × 10−7 T 2 + 2001.6
T
+ 2.689

Table 4: The kinetic model

Parameter Value
alpha 0.5
k0 8.849x1014
−1
E (kJ kmol ) 170560

Table 5: The parameter used in the kinetic model

6
3 Physical model

3.1 External mass transfer

Property Value
Particle size (mm) 8.00
Particle density (kg m3) 4.90
Void fraction 0.46
Bulk density (kg L) 2.65

Table 6: The properties of the iron-oxide catalyst used in the design, adapted from (Jassim,
2021)

The void fraction is as given by Dyson & Simon, 1968 and the particle size was taken as
the average of the range 6-10 mm.

The effectiveness factor is calculated using the Equation 19 from Dyson & Simon, 1968

η = b0 + b1 T + b2 X + b3 T 2 + b4 X 2 + b5 T 3 + b6 X 3 (19)

with the constants at 30 MPa given as follows;

• b0 = -4.6757259

• b1 = 0.02354872

• b2 = 4.687353

• b3 = -3.463308 × 10−5

• b4 = -11.28031

• b5 = 1.540881 × 10−8

• b6 = 10.46627

3.1.1 Mears’criterion

The mears’criterion states that if the condition in Equation 20 is satisfied then effects of
external mass transfer can be disregarded (Foggler, 1999).

7
 −rA ρb nR
< 0.15 (20)
kc CAb

where n is the order of the recation, R is the catalyst particle radius in m, CAb is the
solid catalyst density in kg m−3 , kc is the mass transfer coefficient in m s−1 and the bulk
density of the catalyst bed, ρb in kg m−3 is calculated as

ρb = (1 − ϕ)ρc (21)

where ρc is the bulk density of the bed in kg m−3 and ϕ is the porosity, also referred to
as the void fraction.

According to ammonia-nitrogen-fertilizer, DN H3 the effective diffusion coefficient of

ammonia is calculated from:

   " #
ϕ T 1 1 − yN H3s
DN H3 = yH2s y (22)
τ 273 P D N H −H
− DN HN2s−N
3 2 3 2

where τ = 2.2 is the catalyst tortuosity factor, T is the temperature in K, P is the pressure
in atm, yis is the mole fraction of the component at the catalyst surface, DN H3 −H2 = 0.257
m2 h−1 and DN H3 −N2 = 0.0799 m2 h−1 are the binary ammonia-hydrogen and ammonia-
nitrogen diffusion constants respectively.

3.2 Energy balance

The energy balance can be calculated as follows

dT η(−∆HR )rN H3
= (23)
dL FT Cpmix

3.3 Mass balance

The conversion over the reactor is calculated from Equation ?? as

C0 − C1
X= (24)
C0

8
where the subscripts 0 and 1 indicate the initial and final concentrations respectively.

The mass balance over the reactor is determined from

dX ηrN H3 A
= (25)
dL 2FN2

where the flowrate of nitrogen, FN2 in kmol h−1 , can be determined form:

FN2 = uCA (26)

in which A is the area of the reactor in m2 , C is the concentration on the reactant in

kmol m−3 and u is the velocity of flow in m h−1 .

3.3.1 Specific heat capacity

The specific heat capacity of the mixture is calculated using Equation 27 as shown below

X
Cpmix = yi Cpi (27)

where Cpi is the specific heat capacity of the component. The correlations for the heat
capacities were found in (Green & Perry, 2008) as given by Equations 28 to 30

CpH2 = 6.62 + 0.00081T (28)

CpN2 = 6.50 + 0.00100T (29)

CpN H3 = 6.70 + 0.00630T (30)

The correlations are applicable for ranges 273-2500 K, 300-3000 K and 300-800 K for
hydrogen, nitrogen and ammonia respectively.

9
3.3.2 Heat of reaction

The heat of reaction is calculated using the equation below

∆hr = FN2 X∆H (31)

where FN2 is the intial flowrate of nitrogen and ∆H is the heat of formation as given in
Equation 1.

4 Model solution and Design

4.1 Reactor choice

The reactor chosen for the design is the packed bed reactor because the reaction is
catalytic and the volume of ammonia produced in the plant is large scale. The advantages
and disadvantages of the reactor are as follows;

• Advantages
Low operating costs, ongoing operation, and high conversion per catalyst mass

• Disdvantages
There could be an unwanted thermal gradient and insufficient temperature regula-
tion.

Considering that the plant should be profitable and a higher yield of the ammonia is
desired, the PBR is a good choice.

4.2 Preliminary design

For the preliminary design, the conversion of the limiting reagent, nitrogen in this case is
taken as 29.5 % per single pass through the reactor is specified as taken from literature,
together with the temperature and pressure from the group project.

10
4.2.1 Assumptions

The assumptions applied in the design of the reactor for simplification and trial-and-error
prposes, which are tested in the subsequent sections are as listed below;

• Steady state operation.

• The reactor is autothermal.

• There is negligible pressure drop in the reactor.

• There is no mechanical or shaft work.

• The reactor is modelled as adiabatic and the exothermic reaction supplies enough
heat.

• Kinetic and potential energies are neglected.

• No phase change occurs in the reactor.

4.2.2 Temperature profile

The reactor is assumed to be autothermal and the adiabatic temperature increase due to
the exothermic reaction is represented by

∆T = Tout − Tin (32)

To get the preliminary temperature, when the length of the bed is not yet known, the
mass and energy balances are combine to form Equation 33

(∆hr)(FAo /a)
∆T = − X (33)
FT 0 Cpmix

where FA0 and FT 0 are the feed flowrate of nitrogen and the total feed flowrates respec-
tively. a is the stoicheometric coefficient of nitrogen.

11
4.3 Amount of catalyst in the reactor

The mass of catalyst in the reactor is calculated using Equation below

FN2 XN2
mcat = (34)
RN H 3

4.4 Pressure drop across the reactor

The pressure drop across the reactor is calculated from the Ergun Equation 35

∆P 150µ(1 − ϵ)2 1.5vs 2 ρ(1 − ϵ)

= v s + (35)
L Dp2 ϵ2 Dp ϵ3

where Dp is the particle diameter, L is the length of the reactor µ is the viscosity, ρ is
the particle density and vs is the superficial velocity determined from

Q
us = (36)
A

in which Q is the flowrate and A is the cross sectional area of the bed in m2 .

4.5 Reactor construction

In this section the catalyst size and specifications are used in calculating the dimensions
required for the reactor considering the mass and energy balances.

4.5.1 Catalyst tubes

The equation for determining the number of catalyst tubes is used is

πdtube 2 Ltube
ntubes = ρcat (37)
4

12
4.5.2 Shell diameter

The shell diameter of the reactor is calculated from the number of tubes, the diameter of
the tubes and the perforation factor determined from Equation 39

r
ntubes
Ds = Dtube (38)
ω

where Dtube is the diameter of the catalyst particles and

π
ω= √ (39)
2a2 3

where the value of a is chosen to be 1.5.

4.5.3 Catalyst volume

The volume of the catalyst is determined from the catalyst mass and density using Equa-
tion 40

mcat
Vcat = (40)
ρcat

where the catalyst density is given by:

ρcat = ρb (1 − ϕ) (41)

in which ρb is the bulk density of the catalyst particles.

4.5.4 Reactor length

The length of the current tubes added to the shell diameter is thought to represent a
reasonable approximation of the reactor. The length of the reactor as a whole, including
the shell, head section, and catalyst tubes, is its total length. The following equation was
used to compute the length of the reactor:

Lreactor = Ltube + Ds (42)

13
4.5.5 Bed diameter

The diameter of the bed is determined from the volume of the catalyst and the length of
the bed.

r
4Vcat
Dbed = (43)
πLbed
where the length of the bed, Lbed , is 0.8 of the length of the reactor, Lreactor .

4.5.6 Reactor volume

Both the catalyst tubes and the pressure vessel assume a cylindrical shape. A cylinder
also includes the shell that surrounds the tubes. Thus, the basis of the reactor volume is
the cylinder volume,

πDs 2 Ltube 4π( D2s )2

Vreactor = + (44)
4 3

4.5.7 Material of construction

The elements and compounds involved in the reaction are corrosive and the reaction tem-
peratures are high and this can make the reactor susceptible to corrosion. To maximise
the durability of the reactor material, stainless steel 304 is used for construction of the
reactor parts.

4.5.8 Diagram

4.6 Discussion

A calculation of the pressure drop was completed in python and a plot of how it varies
with length was made as shown in Figure 2 below

The pressure drop was found to be 257.44 Pa, which confirms that the drop in pressure
is negligible relative to the reaction pressure of 30 MPa.

The final design was therefore the one disregarding pressure drop. The temperature and
conversion profiles did not supply much information as can be seen from the plots in the

14
 Figure 2: The pressure drop across the reactor

Appendix. It is recommended that there be a recycle and a bypass stream to increase

the conversion of nitrogen so that the plant can be profitable.

15
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16
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A Appendix

A.1
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