Level 3 - Plant Assessment Optimization - Ammonia - Electronic Handout

Topsoe Academy™ Plant Assessment/Optimization
Ammonia Level 3
Plant
Assessment/Optimization
The foundation of optimal performance
Topsoe Academy™
Identify and solve issues standing in the

way of optimal performance
2
1
Ammonia Level 3
Agenda
Primary reformer and convection section
• Convection section assessment

• Duty
• Temperature readings
• Oxygen surplus and false air
• Primary reforming catalyst assessment

• Reforming reactions and catalyst
• Operating parameters
• Approach to equilibrium
• Operational challenges

Zoom in
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Ammonia Level 3
The heart of the plant
Optimized plant
Optimized reformer
Convection section assessment

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3
Ammonia Level 3
Duty
Affects the operation of the rest of the plant
• The duty available in the convection section can be adjusted by changing the bridge wall
temperature and/or by changing the flue gas flow
• How can the flue gas temperature and flow be adjusted?
Duty Firing on top row burners Combustion air
Duty
The distribution of duty down through the convection section
• Combustion air increase

• Higher flue gas flow – Lower flue gas temperature
• Lower ΔT at the upper coils
• The duty will shift to the lower coils
• Combustion air decrease

• Higher flue gas temperature
• Higher ΔT at the upper coils
• Less duty left to the lower coils
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Ammonia Level 3
Duty
The distribution of duty down through the convection section
• Increased firing on top row burners

• Higher flue gas temperature
• Higher ΔT at the upper coils
• Limited effect on lower coils
• Little effect on process gas temperature at the outlet of the
reformer tubes
Temperature readings
Flue gas temperatures
• Unreliable:
• Flue gas temperature readings close to upper coils
• Reliable:
• Bridge wall temperature
• Below the lowest superheater coils
• Stack temperature
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5
Ammonia Level 3
Temperature readings
Stack temperature
• The biggest contributor to the energy loss of the plant

• The stack temperature should be as low as possible
• What determines the lower limit of the stack temperature?

• Enough duty to all coils in the convection section must be ensured
• The metal temperature of the last coil must be above the dew points for:
Sulfuric acid Carbonic acid

• Condensation of sulfuric acid or carbonic acid will cause corrosion of the coil
11
Oxygen surplus in the flue gas

Safety and optimal performance
• No post combustion criteria:

• Oxygen > 2 dry vol % or air > 10%
• Local conditions may lead to post combustion

• Local explosions pose a safety risk
• Local overheating of tubes decreases the tube lifetime
• Fluctuating pressure in the furnace
• Soot formation in the burners

• Flame impingement
• Local overheating of tubes and burner tip
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6
Ammonia Level 3
False air
• Air ingress through coil penetration through

the convection section wall
• Cooling of the coil
• Higher oxygen content at the stack than at

the bridge wall
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Reasons for low inlet temperature to the feed purification section

Brainstorm
• Silent brainstorm – Write down all reasons you can think of – 2 min
• Plenum discussion
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7
Ammonia Level 3
Reasons for low inlet temperature to the feed purification section

Brainstorm
• Flue gas temperature/flow
• Feed stock composition
• Bypass valve leaking
• Thermal cracking in feed gas coil
• Fouling on the outside of the coil
• Too much preheating of process air

15
Convection section assessment

The biggest contributor to energy loss in the plant
• The coil duties can be adjusted by adjusting

the combustion air and the top row firing
• Flue gas temperature readings close to the

upper coils are usually not reliable Coil duties
Stack
• The stack temperature should be kept as temperature
low as possible
Post
combustion
• No post combustion criteria:
• Oxygen > 2 dry vol % or air > 10%
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8
Ammonia Level 3
Primary reforming catalyst assessment

17
Reforming reactions and catalyst
Reaction
Reforming (general) CnHm + n H2O + Q → n CO + (n + ½m) H2
Reforming (methane) CH4 + H2O + Q ↔ CO + 3 H2
Shift CO + H2O ↔ CO2 + H2
• Ni based catalyst
• 7-hole shape to optimize pressure drop and

strength
• Can be promoted with alkali to increase carbon

resistance
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9
Ammonia Level 3
Operating parameters
Clickers
How will an increase in the outlet pressure

affect the methane concentration?
Reaction
Reforming CH4 + H2O + Q ↔ CO + 3 H2
1. The concentration will decrease

2. The outlet pressure does not affect the
concentration
3. The concentration will increase
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Clickers
How will an increase in the outlet temperature

affect the methane concentration?
Reaction

2. The outlet temperature does not affect the
concentration
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Ammonia Level 3
Clickers
How will an increase in the S/C ratio affect the

methane concentration?
Reaction

2. The S/C does not affect the concentration
21
Approach to equilibrium
Theoretical maximum conversion
• Equilibrium: The highest theoretical conversion at given operating parameters

(gas composition, temperature, pressure)
CH4 concentration
Approach to
equilibrium
Outlet conditions
Equilibrium curve
22
Tequilibrium Tactual
Temperature
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Ammonia Level 3
• Reforming ATE ATE = Tactual – Tequilibrium
• How can the calculated ATE be negative?

• Tmeasured = 790°C
• Tequilibrium = 800°C
• ATE = 790°C – 800°C = -10°C
• Heat loss = 20°C

• Tactual = 810°C
• ATE = 810°C – 800°C = 10°C
Equilibrium curve
• Heat loss dependents on furnace type
• Can also be explained by inconsistent data
23
Topsoe Web-Calculations™
• Through Topsoe Web-Calculations™ you can

get access to our ATE calculation tools
• Following data is required

• Pressure
• Temperature
• Gas compositions
• S/C ratio
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Ammonia Level 3
Monitor the development of the methane slip
• At stable operating conditions the methane slip should be stable
25
Operational challenges
Carbon formation
• Whisker carbon • Pyrolytic carbon

• Catalytic cracking • Thermal cracking
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Ammonia Level 3
Catalytic cracking – Whisker carbon
• On Ni crystals
• Physical damage of catalyst
• Risk when catalyst is exposed to dry

hydrocarbons and high temperatures
• During start-up due to lack of steam
• During start-up due to hydrocarbons in N 2
27
Thermal cracking – Pyrolytic carbon
• Formed on hot catalyst surface
• No physical damage of the catalyst pellets
• Risk at high temperatures with low catalyst

activity
• Due to sulfur poisoning
• During operation
• Can lead to formation of hot spots → Hot

bands
28
14
Ammonia Level 3
Pyrolytic carbon caused by sulfur poisoning
CnHm CnHm
500°C
850°C
Highly active Sulfur poisoned
29 catalyst catalyst
Pyrolytic carbon caused by sulfur poisoning
• Hot bands caused by pyrolytic

carbon on the catalyst
• No physical damage of the

catalyst pellets
• Caused by sulfur poisoning

which deactivates the catalyst
• Cleaning required after unloading
• Can be possible to regenerate

the catalyst
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15
Ammonia Level 3
Pressure drop development
• Whisker carbon
Jump in • Many start-ups/shutdowns (planned vs. trip)
pressure
• Reduced number of tubes in operation
drop
• Change of feed stock, load, S/C
Gradual
increase in • Pyrolytic carbon
pressure • Change of feed stock, load, S/C
drop
31
Visual inspection of the tubes

Tube wall temperatures
• Regular visual inspection of the reformer

tubes → Potential issues will be spotted
• Tube wall temperature measurements to

confirm that the design temperature is not
exceeded
• Helps facilitate long tube lifetimes
• A large subject and not part of the scope

• In-depth training in the Topsoe Academy™
course “Steam Reformer
Assessment/Optimization”
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16
Ammonia Level 3
Primary reforming catalyst assessment

The heart of the plant
• The methane equilibrium is determined by:

• Outlet pressure
• Outlet temperature
• S/C
Methane slip
• The development of the pressure drop and Pressure

the methane slip should be monitored drop
Carbon
• Two types of carbon formation: formation
• Whisker carbon can be formed when
operating with no/very little steam
• Sulfur poisoning can lead to formation of
pyrolytic carbon
33

Zoom out
34
17
Ammonia Level 3
Methane slip
→ Ammonia
production
Steam Effect on
production reforming
Lowering
stack
temperature
Too low
Effect on oxygen
HDS content in
furnace
35
Agenda
Secondary reformer
• Secondary reformer reactor assessment

• Surface temperature
• Reactor internals
• Secondary reforming catalyst assessment

• Secondary reforming reactions and catalyst
36
18
Ammonia Level 3
Secondary reformer
Zoom in
37
Ensuring optimal production
Increased
Low Reduce
hydrogen
methane slip inerts in loop
production
Optimal
production
Ensuring
optimum
H2/N2 ratio
38
19
Ammonia Level 3
Secondary reformer reactor assessment

39
Surface temperature
Frequent visual inspection is required
• Thermo indicative paint

• Used to quickly verify that the surface
temperature is not too high
• Change in color is irreversible
• Surface temperature is typically ~150°C Up to 180°C

At 180 - 220°C
At 310 - 350°C
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Ammonia Level 3
Reactor internals
Can only be inspected at T/A
Refractory Burner
Outlet system Tiles
41
Reactor internals
Can only be inspected at T/A
• Problems with the burner can lead to

an uneven flame
• Can cause hot spots
• Can cause pressure drop issues
• Partial evaporation of target tiles and refractory

• Can cause hot spots
• Can cause pressure drop issues
• Issues with inert material

• Fouling of downstream equipment such as the
waste heat boiler
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21
Ammonia Level 3
Secondary reformer reactor assessment

• The temperature of the pressure shell

should be checked frequently
Visual
• The reactor internals should be checked at inspection
T/A
Check
internals
• Problems with internals can cause
operation/performance issues Thermo
indicative
paint
43
Secondary reforming catalyst assessment

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22
Ammonia Level 3
Secondary reforming reactions and catalyst
Reaction
Combustion (hydrogen) 2 H2 + O2 → H2O + Q
Combustion (methane) CH4 + 1½ O2 → CO +2 H2O
Shift CO + H2O ↔ CO2 + H2
• Ni based catalyst
• 7-hole shape to optimize pressure drop and strength
• Possible top layer of ring shape to minimize pressure

drop increase rate
• Higher void shape
45
Outlet temperature
• The methane slip and the outlet

temperature are connected, which in turn is
a result of the operating conditions
• The development in the methane slip

should be followed
• Stable slip at stable operating conditions
• The outlet temperature is therefore an

important parameter to be able to measure
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23
Ammonia Level 3
Outlet temperature
Air
Monitor drifting
Feed
Ensure ideal thermocouple

type for temperature range
Outlet
temperature
High Ensure correct installation
temperature and calibration
Purge on the thermocouples
“Two out of three”-trip

setting
47
Air flow
• The air flow determines the H2/N2 ratio for

the ammonia synthesis
• The air flow influences the outlet

temperature heavily
• The inlet temperature of the air will also

affect the outlet temperature
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Ammonia Level 3
Example – Air flow
49
Example – Air inlet temperature
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Ammonia Level 3
Example – S/C
51
Example – S/C
S/C at PR Outlet CH4 slip, dry mol

inlet temperature, °C %
3.11 980 0.39

3.46 990 0.27
3.81 998 0.19
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Ammonia Level 3
• Increasing pressure drop rate can be caused by

• Ruby deposition
• Refractory dust
• Low steam purity or impurities from upstream units
• Change of feed stock, load, S/C
• The pressure drop may determine the catalyst

lifetime
• Should be monitored frequently
• Catalyst skimming or complete catalyst replacement
53
Ruby deposition
Reaction
Ruby deposition Al2O3 + 3 H2O (g) ↔ 2 Al(OH)3 (g)
• Formation depends on
• Surface/gas temperature in combustion chamber
• Refractory hot face material
• Top-layer material
• Color is determined by impurities
• Can be removed at T/A by catalyst skimming or by full

catalyst replacement
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Ammonia Level 3
Ruby deposition
• Good flow through the reactor is important Outer

refractory
• Ruby obstructs the gas flow through the Inner

catalyst → Pressure drop increase refractory
• Hot spots on pressure shell
Deposit
55
Issue: A hot spot on the surface of the secondary reformer

3C
• Uneven flow distribution caused by ruby

Cause deposition
• Problems with reactor internals
Pressure drop increase

Consequence •
• Potential reactor damage
• Follow the development of the hot spot closely

Corrective • Cool the reactor with air/steam
action • Inspect reactor internals and catalyst at next T/A
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Ammonia Level 3
Secondary reforming catalyst assessment

• The methane slip is determined by:

• Outlet from primary reformer
• Outlet temperature
• Air flow Pressure
drop
• Air inlet temperature
• S/C
• Feed composition Methane slip
Monitor
• The development in the methane slip and trends
the pressure drop should be monitored
• Ruby deposition may cause pressure

drop to increase
57
Secondary reforming
Zoom out
58
29
Ammonia Level 3
Secondary reformer
Zoom out
Air flow →
H2/N2 ratio in
NH3 loop
Methane slip
→ Ammonia
production
59
Agenda
Shift reactors
• Shift assessment and optimization

• Shift reaction and catalysts
• Temperature profile
• Optimizing shift operation
• Ammonia gain
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Ammonia Level 3
Shift reactors
Zoom in
61
Boost performance by utilizing more of your catalyst’s potential
Low CO
slip
Hydrogen
gain
Increase
ammonia
production
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Ammonia Level 3
Shift assessment and optimization

63
Shift reaction and catalysts
Reaction • Exothermic reaction

Shift CO + H2O ↔ CO2 + H2 + Q
• High temperature shift (HTS)
• Fe/Cr based, Cu promoted
• Low temperature shift (LTS)

• Cu, Zn and Al based
• Possibility of protective top layer
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Ammonia Level 3
• Equilibrium: The highest theoretical conversion at given operating parameters

(gas composition, temperature, pressure)
Equilibrium curve
Inlet conditions
CO concentration
Approach to
equilibrium
Outlet conditions
65
Tactual Tequilibrium
Temperature
• Shift ATE ATE = Tequilibrium – Tactual

Equilibrium curve
• How can the calculated ATE be negative?

• Can be explained by inconsistent data
• Optimum ATE is 5-10°C
• Topsoe Web-Calculations™
• Development in the CO slip should be

followed
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Ammonia Level 3
Optimizing shift operation
Too cold Optimal Too hot

Inlet CO
Equilibrium curve
CO concentration
Operational curve
Optimal ATE
5-10°C
67
Temperature
Temperature profile
Thermocouple 1
Thermocouple 2
Thermocouple 3
Thermocouple 4
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Ammonia Level 3
Temperature profile
Clickers
Which temperature profile has the largest exotherm?
1. A
2. B
3. C
69
Temperature profile
Clickers
What ATE does temperature profile A represent?
1. ATE = 0°C
2. ATE = 5-10°C
3. ATE = 20°C
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Ammonia Level 3
Temperature profile
Clickers
What ATE does temperature profile B represent?
1. ATE = 5-10°C
2. ATE = 20°C
3. ATE = 0°C
71
Temperature profile
Clickers
What ATE does temperature profile C represent?
1. ATE = 0°C
2. ATE = 20°C
3. ATE = 5-10°C
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Ammonia Level 3

Temperature profile
Rule of thumb: Conversion of 1 mol % CO gives an exotherm of ~7°C
A Too hot
B Optimal
Temperature
ΔT
C Too cold
0 Bed depth, % 100
73

The control room
Adjust the inlet
temperature 2-3°C
If the CO slip ↓
Wait for the bed
and ΔT ↑, proceed.
temperatures to
Otherwise retract
stabilize
the last step
Measure the CO
Calculate the ΔT
slip at the reactor
across the reactor
outlet
Check if the ΔT is
greater than
before the
adjustment
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Ammonia Level 3
Optimizing shift operation Adjust the inlet

The control room – Example temperature 2-3°C
Wait for the bed

temperatures to
stabilize
Calculate the ΔT
across the reactor
Temperature
ΔT ΔT Check if the ΔT is
greater than
before the
adjustment
Measure the CO
slip at the reactor
outlet
Bed depth, %
If the CO slip ↓
CO slip: 0.29 0.26 Otherwise retract
the last step
75
Optimizing shift operation Adjust the inlet

The control room – Example temperature 2-3°C
Wait for the bed

temperatures to
stabilize
Calculate the ΔT
across the reactor
Temperature
ΔT ΔT Check if the ΔT is
greater than
before the
adjustment
Measure the CO
slip at the reactor
outlet
Bed depth, %
If the CO slip ↓
CO slip: 0.26 0.27 Otherwise retract
the last step
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38
Ammonia Level 3
Catalyst deactivation
• HTS Reaction
Iron carbide formation 5 Fe3O4 + 32 CO ↔ 3 Fe5C2 + 26 CO2
Fischer-Tropsch n CO + (n+m) H2 ↔ CnHm + n H2O
Temperature
77
Bed depth, %
• HTS
• LTS
• Condensation → Physical damage of catalyst
• P 100 ≈ Dewpoint
• Catalyst poisoning
Temperature
78
Bed depth, %
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Ammonia Level 3
• During operation both HTS and LTS

catalysts will sinter
• Operating at too high temperatures will speed
up this process
• This means that even with no poisoning

temperature optimization will be required
• Increasing the inlet temperature → Increased
reaction speed → Lowering the ATE
79
80
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Ammonia Level 3
• Increasing pressure drop is often a sign of

issues
• Can be caused by a number of things:

• Boiler leakages
• Catalyst milling
• Carry-over of boiler solids and dust from
upstream equipment
• We recommend monitoring the

development of the pressure drop
81
Temperature profiles
• Heat loss at outlet?

• ATE appears to be 0°C but is
actually 5-10°C
82
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Ammonia Level 3

actually 5-10°C
• Which temperatures should be

trusted?
• Confirm exotherm with CO
conversion
83

actually 5-10°C

trusted?
conversion

trusted?
conversion
84
42
Ammonia Level 3
Issue: Unexpected shift temperature profile

3C
- Right side thermocouples

- Left side thermocouples • Channelling in the reactor – More flow in one side
Cause due to improper loading (not uniform)
Temperature
Consequence • Not possible to achieve optimal conversion
Corrective • Optimize the temperature based on hottest side

action • Ensure proper loading at next change-out
Bed depth, %
85
Ammonia gain
A low CO slip is important
Assuming that the amount of CO outlet the shift section is reduced by 1 mol
• H2 generated in shift converters
• CO + H2O → CO2 + H2
• 1 mol gained
• H2 not consumed in methanator
• CO + 3 H2 → CH4 + H2O
• 3 mol gained
• The extra N2 added to the secondary reformer, to produce NH3 from the gained H2, means
extra O2 from the air
• N2 + 3 H2 ↔ 2 NH3
• O2 + 2 H2 → 2 H2O
.
• x= (4 − x) .
2, x = 0.6
• Overall H2 gain = 1+3 – 0.6 = 3.4 mol (per mol CO reduced)

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43
Ammonia Level 3
Ammonia gain
Calculation
• Neglect hydrogen gain from purge loss What is the daily ammonia gain (MTPD)?
• Assume CO has been lowered with 0.05 mol % • Total mol flow
50,000 Nm3/h
• Assume an LTS outlet flow of 50,000 Nm3/h = 2,232 kmol/h
22.4 Nm3/kmol
• Molar volume of ideal gas = 22.4 Nm3/kmol • Hydrogen gain
0.05
• MWNH3 = 17.0 g/mol 2,232 kmol/h · 3.4 · = 3.79 kmol/h
100
• Ammonia synthesis • Ammonia synthesis
3.79 kmol/h · 2/3 = 2.53 kmol/h
N2 + 3 H2 ↔ 2 NH3
• NH3 mol flow
2.53 ·103 mol/h · 17.0 g/mol
• Assuming an ammonia price of 450 USD/MT = 0.043 t/h
the gain corresponds to around 148,500 USD • Daily ammonia gain
per year 0.043 t/h · 24 = 1.0 MTPD
87
Shift assessment and optimization

Boost performance by utilizing more of your catalyst’s potential
• Operating with the optimal ATE of 5-10°C

will ensure maximum conversion and thus
a low CO slip
Optimal ATE
is 5-10°C
• The development in the CO slip, the
pressure drop and the deactivation should Hydrogen
be followed gain
Monitor the
• If the CO slip is reduced by 1 mol the overall deactivation
H2 gain will be 3.4 mol
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44
Ammonia Level 3
Shift section
Zoom out
89
Shift section
Zoom out
Steam
Adjustment
production
of BFW flow
in WHBs
Changing the Adjusting

inlet other BFW
temperature preheaters
Adjustment
of BFW
preheater
90
45
Ammonia Level 3
Agenda
Feed purification section
• Feed purification section assessment

• Feed purification catalyst and absorbent
• ZnO lifetime assessment
• Chemisorption
• Case story
91

Zoom in
92
46
Ammonia Level 3
Consequences of a malfunctioning feed purification section

Avoid poisoning of downstream catalysts
Steam reformer Shift reactor
93
Feed purification section assessment

94
47
Ammonia Level 3
Feed purification catalyst and absorbent
• Hydrogenation catalyst • Sulfur absorbent

• CoMo or NiMo on Al • ZnO absorbent
• Lifetime determined by maximum level of • Lifetime determined by average level of total
organic sulfur sulfur
• Converts organic sulfur to H2S • Traps H2S inside porous system of absorbent
Reaction Reaction
Hydrogenation RSH + H2 → H2S + RH Sulfur absorption H2S + ZnO ↔ H2O + ZnS
95
Minimum sulfur level and poisons
• For the hydrogenator there is such a thing

as a minimum required level of sulfur
• Active form is CoMo-Sx/NiMo-Sx phase
• Prolonged run with low/no sulfur will strip

off the sulfur → Lower activity
• Mainly an issue with peaks of organic sulfur
• Can be solved by dosing with sulfur
• Catalyst/absorbent poisons:
• Heavy metals – Deactivates the CoMo/NiMo
• Chlorine – Deactivates the ZnO
• High CO2/H2O content – Can physically weaken
the ZnO pellets
96
48
Ammonia Level 3
Operating temperature
• Recommended range: 350-380°C
• Avoid risk of hydrocracking and carbon laydown
97
Hydrocracking and carbon laydown
Name Reaction Name Reaction

Hydrocracking C2H6 + H2 → 2 CH4 + Q Carbon laydown CH4 → C + 2 H2
• Exothermic so temperature will increase • At high temperatures and low hydrogen
• Consumes hydrogen which increases

affinity for carbon laydown
98
49
Ammonia Level 3
Recycle hydrogen
• Reduce risk of carbon laydown
• Ensure full conversion of organic sulfur
• Recommended hydrogen content in the gas

• NG: 2-5 vol %
• LPG: minimum 0.05 Nm3 H2/kg hydrocarbon
• Naphtha: minimum 0.1 Nm3 H2/kg hydrocarbon
99
ZnO lifetime assessment

Keep track of the sulfur
100
50
Ammonia Level 3

Keep track of the sulfur
• These predictions give an indication about

when to change out the absorbent
• The prediction is only as good as the

supplied data
• Drastic changes in the sulfur level or feed

flow will require a revised extrapolation
• More data → Better prediction
101

Calculation
• Sulfur uptake calculated by Topsoe is 300 kg • What is the expected maximum lifetime?
• Flow of sulfur
• Assume average flow of 5,000 Nm3/h
2 · 10-6 · 5,000 Nm3/h = 0.01 Nm3/h
• Assume average S level of 2 ppmv
• Mass flow of sulfur
• MWsulfur = 32.1 g/mol
0.01 Nm3/h
• Molar volume of ideal gas = 22.4 Nm3/kmol = 446·10-6 kmol/h
22.4 Nm3/kmol
446·10-6 kmol/h · 32.1 kg/kmol
• When nearing the end of the calculated = 143·10-4 kg/h
sulfur uptake extra precaution should be • Calculated maximum lifetime
taken 300 kg
= 20935 h ≈ 2.5 years
143·10−4 kg/h
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Ammonia Level 3
Chemisorption
Reaction
Reverse shift CO2 + H2 + Q ↔ CO + H2O
Sulfur absorption H2O + ZnS ↔ H2S + ZnO
• The equilibrium will be affected by CO2 and

H2O in the feed as well as the operating
temperature
• Equilibrium H2S will be chemisorbed further

down in the reactor
• Absorption lifetime vs. chemisorption lifetime

103
Chemisorption
104
52
Ammonia Level 3
Feed purification section assessment

Avoid poisoning of downstream catalysts
• Sulfur slip can often be identified on

downstream catalysts
• The operating temperature and hydrogen level

are important to ensure optimal performance
Poison down
stream
• The sulfur absorbent lifetime can be assessed
by frequently and accurately measuring the Operating
sulfur levels temperature
• Chemisorption can cause a slip of equilibrium Lifetime

sulfur
105
Case story
106
53
Ammonia Level 3
Case story
Optimization of feed purification operation due to slip of equilibrium sulfur
• Observations
• High inlet temperature (~425°C)
• High level of hydrogen (~4 dry mol %)
• Very lean gas, but high CO2 content (~8 dry mol %)
• All three parameters influence the equilibrium and result in an early and high slip of
equilibrium sulfur
Reaction
Reverse shift CO2 + H2 + Q ↔ CO + H2O
Sulfur absorption H2O + ZnS ↔ H2S + ZnO
107
Case story
100
425°C
90
80
H2S slip, ppbV
70
60
400°C
50
40
30 375°C
20
350°C
10
0
0 1 2 3 4 5
H2 concentration inlet ZnO, mol %

108
54
Ammonia Level 3
Case story
4.5 100
Hydrogen recycle
H2 recycle
4 90
Equilibrium sulfur, ppb

Equilibrium
Eq. sulphursulfur
Hydrogen recycle, %
3.5 80
70
3
60
2.5
50
2
40
1.5
30
1 20
0.5 10
0 0
109

Zoom out
110
55
Ammonia Level 3

Zoom out
H2 recycle
flow → Purge
gas flow
Change inlet
temperature
→ Waste
heat section
duty
H2 recycle
flow → H2
recovery unit
capacity
111
Agenda
Heat exchangers
• Case story
• Heat exchanger assessment

• Signs of problems
112
56
Ammonia Level 3
Heat exchangers
Zoom in
113
Ensure efficient heat transfer
High energy
efficiency
Good and
sound heat
exchangers
Optimal
Long lasting
plant
catalysts
performance
114
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Ammonia Level 3
Case story
115
Case story
BFW heat exchanger leak caused water in LTS reactor
• Inlet temperature to LTS reactor decreased

and dropped below the dew point before
the operators shut down the plant
• Water could be drained from the bottom of
the reactor. Special catalyst drying
procedure was initiated
• Leak in upstream BFW heat exchanger was
discovered and repaired
• Due to fast and proper actions the plant
was able to save the catalyst charge and
continue operation for 3 years
116
58
Ammonia Level 3
Heat exchanger assessment

117
Signs of problems
The temperature approach is higher than anticipated
Counter current flow

• Check whether temperature measurements
might be erroneous
• Flow on both sides should be checked

Approach
• Fouling is a probable reason

• Inspect and clean when possible Co-current flow
• Root cause investigation
Approach
118
59
Ammonia Level 3
Fouling
Refractory dust
119
Fouling
Heat exchanger – Duty
After chemical
cleaning in T/A-15
After online
cleaning
After chemical
cleaning in T/A-14
120
60
Ammonia Level 3
Fouling
Heat exchanger – Cooling water side velocity
After chemical
cleaning in T/A-15
After online
cleaning
After chemical
cleaning in T/A-14
121
Issue: The inlet temperature to the LTS is too high

3C
Cause • Fouling of the BFW preheater
Decreased lifetime of the catalyst

Consequence •
• Higher CO slip
Bonus info: The bypass • Check the BFW quality

valve around the BFW Corrective • Increase the flow of the BFW
preheater has been closed action • Inspect and clean the BFW preheater at next T/A
more and more over time
122
61
Ammonia Level 3
Signs of problems – Continued

The temperature approach is lower than anticipated
Counter current flow

• Check whether temperature measurements
might be erroneous
• Flow on both sides should be checked

Approach
• Are there signs of leakage in the heat

exchanger?
Co-current flow
• Chemical analysis
• Evaluation of consequences
• Shut down for repairs
• Root cause investigation
Approach
123
Issue: The pH in the steam drum has increased over time

3C
• Leakage in either loop WHB or in loop BFW

Cause preheater
• Normal operation: Synthesis gas leaking into

the steam system
Consequence • Start-up/shutdown: Steam or water may leak
into the ammonia loop
Bonus info: There is a smell • Shut down carefully, keeping the loop pressure
of ammonia in the steam
Corrective higher than the steam pressure at all times
drum blow down
action • Inspect and repair the heat exchanger
124
62
Ammonia Level 3
• Mal-operation
• Wrong process design
• Wrong mechanical design
Causes • Bad quality of manufacture of
exchanger and upstream equipment
• Fouling
• Leakage
• External, visible, noise, smell
Operational
challenges • Internal, requires analysis
• Affects stream temperatures

• Affects overall plant performance
Suboptimal • Unexpected shutdown
performance
125
Heat exchanger assessment

Ensure efficient heat transfer
• High approach in a heat exchanger can

be a sign of fouling. Low approach in a
heat exchanger can be a sign of leakage
Leakage
• Always check the temperature readings
and flows on both sides
Root cause
analysis
• Evaluate the consequences of the

problem and take necessary action Fouling
• Investigate the root cause
126
63
Ammonia Level 3
Heat exchangers
Zoom out
127
Heat exchangers
Zoom out
Steam Performance
production of turbines
Inlet
Steam
temperature
quality
to reactors
Effects of Effects of
heat heat
exchanger exchanger
fouling leakages
Duty shifting
to/from Catalyst
other heat poisoning
exchangers
128
64
Ammonia Level 3
Agenda
Ammonia loop and converter
• Ammonia converter assessment and optimization

• Ammonia synthesis and catalyst
• Optimizing ammonia catalyst operation
• Case story
• Ammonia loop assessment

129

Zoom in
130
65
Ammonia Level 3
Maximum ammonia production at lowest energy consumption
• The ammonia production is the plant

money-maker
• Optimizing the front-end catalyst

performance ensures the best possible
conditions for the ammonia production
• But optimizing the performance of the

ammonia synthesis catalyst is equally
important
131
Ammonia converter assessment and

optimization
132
66
Ammonia Level 3
Ammonia synthesis and catalyst
Reaction • Exothermic reaction

Ammonia synthesis N2 + 3 H2 ↔ 2 NH3 + Q
• Reaction facilitated by high pressure
(4 molecules ↔ 2 molecules)
• Iron based catalyst (magnetite)

• Electronic promoter: K2O
• Structural promoters: AlO3, CaO, MgO, SiO2
133

KM 111
• Topsoe’s latest development within ammonia

synthesis catalysts is KM 111
• First reference started up December 2015

• S-200 with a capacity of 690 MTPD
• > 15 bar pressure reduction compared to EOR
• 20 hours saved in reduction time
• Currently 24 references, out of which 8 have

been started up
• Development of a new catalyst requires trials in

pilot and production scale
134
67
Ammonia Level 3

KM 111
• The features of the new catalyst have

been tested in R&D using an
accelerated aging plot
• The plot indicates that there is a

significant activity gain with KM 111
• Furthermore, KM 111 has the same

long-term stability as KM1
135

Comparison of KM1R and KMR 111 performance
Catalyst change
800 Production KM1 KM111 250

Operating pressure, Kg/cm2
600 220
Production, MTPD
400 190
Pressure
200 160
0 130
1995
0 2000
5 2005
10 2010
15 2015
20 2020
25
Time
136
68
Ammonia Level 3
H2/N2 ratio
• Keep H2/N2 in the range 2.8-3.1

• Adjust process air flow to the secondary reformer
• In case of deviation
• Increase purge gas flow
• Adjust make up gas flow
• At H2 recovery upset
• Adjust process air
137
S-300 converter
Equilibrium curve Equilibrium curve
Max. conversion
Operating curve
138
69
Ammonia Level 3
S-300 converter
Rule of thumb: production of 1 mol %

Equilibrium curve ammonia gives an exotherm of ~15°C
Max. conversion
Operating curve
Optimal ATE is 10-20°C

139
Optimizing ammonia catalyst operation

Practical example – S-300 converter
620
570
520
470
420
370
320
ATE: 10-20 °C
270
140
70
Ammonia Level 3

Practical example – S-300 converter
ATE > 10-20 °C
141

The control room
Adjust the inlet
temperature 3-5°C
If the NH3
production ↑ and Wait for the bed
ΔT ↑, proceed. temperatures to
Otherwise retract stabilize
the last step
Calculate the ΔT
Measure the NH3
across the
production
bed/reactor
Check if the ΔT is
greater than
before the
142
adjustment
71
Ammonia Level 3

Cascading changes (S-300 revamped)
TIC
Bed 1
• Changing the temperatures – More difficult than in the
Cold bypass
shift section valve
• To get the full picture we must look at what goes on inside
the converter
Bed 2
• Example: Increase bed 1 inlet temperature

• Slightly closing the cold bypass →
Main inlet
• Increased inlet temperature to bed 1 → valve
Bed 3
• Bed outlet temperature increases and the change cascade
through the converter → TIC
• Inlet temperature to bed 1 increases further until an
“equlibrium” is reached
• If the inlet temperature to bed 2/3 now needs adjustment
the overall conditions will again be affected Boiler BFW Rest of
Preheater the loop
143
• Both the exotherm and the loop pressure

can be used as guidelines during the
Bed ΔT
optimization
• Inverse connection 340 345 350 355 360 365 370 375
Inlet temperature, °C
• Highest exotherm →
Loop pressure
• Highest conversion →
• Fewest reactants in the loop →
• Lowest loop pressure
340 345 350 355 360 365 370 375
Inlet temperature, °C
144
72
Ammonia Level 3
Catalyst poisoning
• Temporary poisons • Permanent poisons

• Occupy active sites • Occupy active sites
• In equilibrium with the gas phase • Irreversible
• Oxygen compounds • Sulfur, phosphorus, chlorine, arsenic
H H
N N O
Fe surface
145
Ammonia converter assessment and optimization

• The H2/N2 ratio should be in the range 2.8-3.1
• The ammonia synthesis is facilitated by a high

loop pressure Catalyst
poisons
• The optimal ATE is 10-20°C Optimal ATE

is 10-20°C
• There are two types of catalyst poisons:

• Oxygen compounds are a temporary poisons
• Sulfur, chlorine etc. are permanent poisons
H2/N2 ratio
146
73
Ammonia Level 3
Case story
147
Case story
Full recovery of catalyst activity after catalyst poisoning
• Observations
• Sudden increase in loop pressure
• Significant decreased catalyst activity 1
Catalyst activity
• Solution 0.5
• Recommendation to investigate make-up gas

Poisoning period
purification section (methanation section in 0

newer plants)
• Make-up gas purification replaced
-0.5
• Outcome
• Fully regained catalyst activity in 3 months -1
0 20 40 60 80 100
• The catalyst charge was in operation for more
than 10 years Catalyst age, months
148
74
Ammonia Level 3
Ammonia loop assessment

149
Optimal production at given feed rate
• Keep circulating rate high

• Keep recirculater bypass closed
• Keep inert level low
• Keep level by purging
• Higher level retards production
• Higher purge → Loss of N2 and H2
• Keep ammonia in recycle gas low
• Keep final chiller temperature low
• Low chiller temperature → High load on
ammonia compressor
• Keep converter inlet at optimum
temperature
• Adjust bypass around BFW preheater
150
75
Ammonia Level 3
Loop pressure
• The loop pressure cannot be controlled
• Changes in loop pressure is a symptom of

other changes in the synthesis loop
• A high loop pressure is a symptom of

suboptimal performance of the synthesis
loop
151
Ammonia loop
Questions
Decrease in… Loop pressure
Circulation rate Increasing
Make-up gas quantity Decreasing
Inert level Decreasing
Purge gas flow Increasing
Ammonia content at inlet of converter Decreasing
H2/N2 ratios below 2.8 Increasing
Catalyst activity Increasing

152
76
Ammonia Level 3
Protection against suboptimal performance and unforeseen shutdowns
• Unplanned shutdowns and poor

performance is very costly in the long run
• Mechanical issues
• Heat exchanger (HotEx) bypass
• Pressure tapping leakage
• Wrong temperature indication in converter
153
Heat exchanger (HotEx) bypass
• Missing/damaged gland packing will result

in high loop pressure and poor catalyst
performance
• Can be verified by checking the ammonia

concentration u/s and d/s HotEx
154
77
Ammonia Level 3
Pressure tapping leakage
155
Wrong temperature indication in converter
• Uneven temperature readings outlet 1st bed
156
78
Ammonia Level 3
Ammonia loop assessment

• Parameters that affect the synthesis loop

efficiency:
• Purge flow
• Recycle ratio Inert level
• Ammonia separation temperature
• Inert level in MU gas
Purge flow
• The loop pressure is a symptom of changes

in above parameters
Loop
pressure
157

Zoom out
158
79
Ammonia Level 3

Zoom out
Inert level –
Affected by
frontend and
Lower chiller CO2 removal
Duty shifting
T → Efficient
to/from
loop but ↑
other heat
energy
exchangers
consumption High purge
↓ energy
consumption
but loss of H2
in HRU
H2/N2 ratio
controlled by
secondary
reformer
159
Summary
Primary reformer & Secondary reformer Shift reactors

convection section
• Methane slip • H2/N2 ratio • CO slip
• Oxygen surplus • Hot spots • Pressure drop
• Stack temperature • Pressure drop • Inlet temperature
160
80
Ammonia Level 3
Summary
Feed purification Heat exchangers Ammonia loop and

section converter
• Operating conditions • Fouling • Loop pressure
• Lifetime assessment • Leakage • Temperature difference
• Chemisorption • Evaluate consequences over converter
161
Topsoe Academy™
Thank you for your attention
February 10, 2016
81

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Topsoe Academy™ Plant Assessment/Optimization

Identify and solve issues standing in the

• Convection section assessment

• Primary reforming catalyst assessment

Primary reformer and convection section

The heart of the plant

Convection section assessment

• How can the flue gas temperature and flow be adjusted?

Duty Firing on top row burners Combustion air

• Combustion air increase

• Combustion air decrease

• Increased firing on top row burners

• The biggest contributor to the energy loss of the plant

• What determines the lower limit of the stack temperature?

Sulfuric acid Carbonic acid

Oxygen surplus in the flue gas

• No post combustion criteria:

• Local conditions may lead to post combustion

• Soot formation in the burners

• Air ingress through coil penetration through

• Cooling of the coil

• Higher oxygen content at the stack than at

Reasons for low inlet temperature to the feed purification section

Reasons for low inlet temperature to the feed purification section

• Flue gas temperature/flow

• Feed stock composition

• Bypass valve leaking

• Thermal cracking in feed gas coil

• Fouling on the outside of the coil

• Too much preheating of process air

Convection section assessment

• The coil duties can be adjusted by adjusting

• Flue gas temperature readings close to the

Primary reforming catalyst assessment

Reforming reactions and catalyst

• 7-hole shape to optimize pressure drop and

• Can be promoted with alkali to increase carbon

How will an increase in the outlet pressure

1. The concentration will decrease

How will an increase in the outlet temperature

1. The concentration will decrease

How will an increase in the S/C ratio affect the

1. The concentration will decrease

• Equilibrium: The highest theoretical conversion at given operating parameters

• Reforming ATE ATE = Tactual – Tequilibrium

• How can the calculated ATE be negative?

• Heat loss = 20°C

• Through Topsoe Web-Calculations™ you can

• Following data is required

• At stable operating conditions the methane slip should be stable

• Whisker carbon • Pyrolytic carbon

• Physical damage of catalyst

• Risk when catalyst is exposed to dry

• Formed on hot catalyst surface

• No physical damage of the catalyst pellets

• Risk at high temperatures with low catalyst

• Can lead to formation of hot spots → Hot

• Hot bands caused by pyrolytic

• No physical damage of the

• Caused by sulfur poisoning

• Can be possible to regenerate

Visual inspection of the tubes

• Regular visual inspection of the reformer