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Keylessonsto
optimiseammonia
plantperformance
Understanding the basic principles of catalytic reactor operation in an ammonia plant can
help to avoid costly performance and operating problems. M. Anderson, and S. Osborne
of Clariant Corporation (formerly Sd-Chemie) focus on three particular topics that have
a significant impact on production performance: 1) chemistry, consequences and avoidance
of carbon formation in the steam reformer; 2) proper flow distribution in catalytic reactors,
and 3) the impact of improper plant operation on catalyst and equipment.
n CO + (2n+1) H2
H > 0
Steam reforming of methane
CO + 3 H2
CH4 + H2O
H = 88700 Btu/lb-mole
(206 kJ/mol)
Water-gas shift
CO2 + H2
CO + H2O
H = -17,600 Btu/lb-mole
(-41 kJ/mol)
Carbon formation in
primary reformers
An important step in the ammonia manufacturing process is steam reforming; the
conversion of hydrocarbons into hydrogen.
The primary reformer is the main piece of
equipment for this and represents the largest expenditure in terms of capital and ongoing energy costs. Optimum performance
of the reformer and the installed reforming
catalyst is critical to ensuring high plant
productivity and efficiency. Poisoning, fouling or incorrect operation can adversely
temperatures up to 1010C. The average heat flux may be as high as 94,000110,000 W/m2.
Firing is usually controlled such that
tube wall temperatures are maintained at
values that will give a reasonable tube life.
By design and industry practice, maximum
allowable tube wall temperatures give an
in-service life of about 100,000 hours.
C + 2 H2
Cracking reactions are favoured thermodynamically at high temperature. In the presence of steam, gasification reactions also
occur over the primary reformer catalyst as:
Gasification
C + H2O
CO + H2
AmmoniA operAtions
Benchmark
Clariant
1700
temperature, F
1650
1600
1550
1500
10
15
months on stream
Monitoring program
During routine operation of a primary
reformer, a monitoring program assists in
optimising the catalysts performance as
well as providing early detection of issues
that can lead to catalyst or tube failure.
Three performance parameters are typically
trended during operation; calculated CH4
approach to equilibrium (ATE), tube wall temperatures (TWT), and relative pressure drop.
Approach to equilibrium
Reformer catalyst activity is commonly
expressed as CH4 ATE, which is the difference between the measured catalyst outlet
temperature and the calculated equilibrium
temperature for the observed methane
leakage. An increased ATE or methane slip
from the front-end results in a higher purge
rate from the synthesis loop and increased
energy consumption for the plant. While
operating the primary reformer at higher
exit temperature can mitigate this effect,
the cost of increased fuel requirements
and the impact of hotter tube wall temperatures must be considered when choosing
to operate in that non-optimal mode.
North
1650
1625
1600
1575
1550
1525
1500
EW
EE
DW
DE
CW
CE
BW
BE
AW
2
AE
North
temperature F
1625-1650
1600-1625
1575-1600
1550-1575
1525-1550
1500-1525
Pressure drop
The impact of increasing primary reformer
pressure drop is reduced plant efficiency,
caused by the lowering of the suction pressure at the synthesis gas compressor, and
the resulting higher horsepower requirements to maintain the desired loop pressure. Depending on pressure relief valve
set-points, a higher reformer P may also
require reduction of plant operating rates if
near those limits.
temperature F
1625-1650
1600-1625
1575-1600
1550-1575
1525-1550
1500-1525
EW
EE
DW
DE
CW
CE
BW
BE
AW
AE
AmmoniA operAtions
70
60
50
40
30
20
10
0
0.0
1.0
2.0
sulphur in feed, ppmv
3.0
NiS + H2
Fig 5: The reformer tube appearance before and after a decoking procedure
AmmoniA operAtions
0.7
Change in energy
cost ($/annum)
Lost production
($/annum)
Primary
reformer
15,000
170,000
Secondary
reformer
30,000
370,000
HTS
1% increase in CO leakage
56,000
590,000
LTS
160,000
2,000,000
4
0.5
0.4
0.3
0.2
0.1
0
Fig 7: Photo of the surface of the secondary reformer showing mixing of catalyst
and inert balls and bed disruption
0.6
CH4 leakage, %
Change in performance
10 14 17 19 25 34
time on-stream, months
AmmoniA operAtions
a plants life. Clariants HTS ShiftMax catalyst was able to survive major boiler leaks
at the 1,600 short t/d Terra plant4. In this
case, the HTS was flooded with water from
a major boiler failure and a dry out procedure was successfully implemented under
the direction of Clariant. Besides the effect
of wetting the catalyst, accumulated boiler
solids from boiler leaks can also increase
the catalysts pressure drop and create poor
gas distribution issues. The impact of water
and boiler solid carryover can be minimised
by using a high voidage inert top layer.
During operational upsets, temperature
controller swings can lower the inlet temperature of the shift converters below the
dew point and wet the catalyst. Operating
the LTS at an inlet temperature 17-22C
above dew point can reduce this potential.
Boiler feed water quenches are normally
installed upstream of shift converters in
order to control inlet temperature as well
as lower the CO equilibrium. Atomisation
is critical to prevent wetting the catalyst
AmmoniA operAtions
6
Conclusion
In summary, understanding the basic principles of catalytic reactor operation in an
ammonia plant can help to avoid costly performance and operating problems. Operations and technical crews should routinely
review and analyse process monitoring
systems and procedures to ensure that the
consequences of mal-operation are understood and best available procedures and
technology are in place. Understanding the
impact on catalyst and process equipment
from a safety perspective and an operational cost standpoint is important so that
potential adverse situations are avoided
or minimised in magnitude. With this complete knowledge and understanding, high
performance catalysts can achieve their full
utilisation and maximise the efficiency and
n
productivity of the plant.
References
1. Gebert S., Cai Y,. and Kniep B.: Continuous
improvement in ammonia catalysts Nitrogen + Syngas (Jan-Feb 2012).
2. Rice D.: The value of catalyst performance
in ammonia plants AIChE 2002.
3. Rice D.: Loading of primary reformer catalyst tubes AIChE 1993.
4. Borzik K., Howerton R. and Archer T.: Successful recoveries from major WHB failures
experience AIChE 2007.
5. Richardson J., Wagner J., Drucker R., Rajesh
H.: Understanding hydrocarbon reactions
during LTS catalyst reductions AIChE 1996.