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AmmoniA operAtions

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.

T
he ammonia industry has seen sig- affect the catalysts performance and can temperatures up to 1010C. The aver-
nificant change in recent decades as lead to costly equipment failure. age heat flux may be as high as 94,000-
high turnover, leaner organisational 110,000 W/m2.
structures, and new operations have shifted Primary reformer reactions Firing is usually controlled such that
the demographics of the operations and The main reactions in the primary reformer tube wall temperatures are maintained at
technical personnel staff. These changes are: values that will give a reasonable tube life.
have resulted in a loss of long-term opera- By design and industry practice, maximum
Steam reforming of hydrocarbons
tional knowledge and can lead to incidents allowable tube wall temperatures give an
of equipment and catalyst damage during CnH2n+2 + n H2O n CO + (2n+1) H2 in-service life of about 100,000 hours.
operation and upset conditions. H > 0
As catalyst technology continues to Steam reforming of methane Carbon formation reactions
improve, the products high performance CH4 + H2O CO + 3 H2 With no steam present and at normal
are best enabled when accompanied by a H = 88700 Btu/lb-mole reformer operating temperatures, all hydro-
thorough understanding of the chemical and (206 kJ/mol) carbons will decompose into carbon and
physical principles of catalytic reactions1. Water-gas shift hydrogen via the following reaction:
CO + H2O CO2 + H2 Thermal cracking
Carbon formation in H = -17,600 Btu/lb-mole CH4 C + 2 H2
primary reformers (-41 kJ/mol)
Cracking reactions are favoured thermody-
An important step in the ammonia manu- Overall, the process is endothermic. A lower namically at high temperature. In the pres-
facturing process is steam reforming; the CH4 leakage is favoured by higher exit tem- ence of steam, gasification reactions also
conversion of hydrocarbons into hydrogen. perature, higher steam-to-carbon ratio, and occur over the primary reformer catalyst as:
The primary reformer is the main piece of lower exit pressure. Gasification
equipment for this and represents the larg- The standard primary reformer system C + H2O CO + H2
est expenditure in terms of capital and on- is comprised of a tubular furnace where
going energy costs. Optimum performance the feed stream passes over a catalyst Operating the reformer at conditions that
of the reformer and the installed reforming packed in multiple banks of externally drive this reaction can prevent the accumu-
catalyst is critical to ensuring high plant heated tubes. With improvements in tube lation of carbon deposits. When conditions
productivity and efficiency. Poisoning, foul- metallurgy, primary reformers operate at exist that favour hydrocarbon cracking,
ing or incorrect operation can adversely pressures up to 6,000 kPa and tube wall the heavier hydrocarbons in the feed will

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AmmoniA operAtions

crack first. As this occurs, the active sites temperatures will have a drastic impact on
Fig 1: Comparative average TWT
of the catalyst become masked, resulting the tube life. A TWT increase of as little as
surveys of two charges of
in less reforming reaction and higher gas 10oC may result in up to a 30% shortened
catalyst at a 1200 STPD
temperatures, which further increases the life-time of the reformer tubes.
ammonia plant
tendency for cracking and coke deposition. The use of a high activity/shape opti-
Common causes of carbon formation mised reforming catalyst results in lower
and deposition are low steam/gas ratio 1750 Benchmark tube wall temperatures and a significant
operation, heavy hydrocarbons in the feed, Clariant cost and efficiency advantage to an opera-
1700
sulphur poisoning, and temperature excur- tor. As an example, a 1,200 short t/d plant

temperature, F
sions resulting from poor firing control. 1650 in North America was able to realise such
Higher catalyst activity can reduce carbon an advantage by installing the high activity
1600
formation potential by lowering gas temper- ReforMax reforming catalyst from Clariant.
ature when methane concentration is high 1550 The Kellogg-designed primary reformer of
enough for cracking, thereby reducing the 1500 this plant was initially designed to produce
carbon formation potential. 0 5 10 15 600 short t/d of ammonia. After several
The overall effect of carbon formation on months on stream expansions, the reformer now operates at
the primary reformer is reduced conversion, a high heat flux of around 110,000 W/m2.
increased pressure drop and increased tube Figure 1 shows that the mean TWT is 55C
wall temperatures which, if severe, can be Fig 2: IR thermographic image of a cooler with catalyst from Clariant than with
seen as hot bands on the tubes. Not only row of reformer tubes the previous competitor charge.
does the carbon deposit block active sites, Additionally, the maximum tube wall
its formation within the pores of the catalyst temperature was also lowered and the
can cause catalyst breakage. number of tubes with TWTs exceeding the
temperature limit of 927C was cut from
Monitoring program five to zero, significantly reducing the risk
During routine operation of a primary of potential tube failure.
reformer, a monitoring program assists in Effective monitoring of the TWTs and
optimising the catalysts performance as balancing of the firing of the reformer fur-
well as providing early detection of issues nace can extend the life of the tubes and
that can lead to catalyst or tube failure. optimise the performance of the catalyst
Three performance parameters are typically (Figures 2 and 3).
trended during operation; calculated CH4
approach to equilibrium (ATE), tube wall tem- Fig 3: Plotted TWT surveys showing Pressure drop
peratures (TWT), and relative pressure drop. the heat distribution across the The impact of increasing primary reformer
reformer pressure drop is reduced plant efficiency,
Approach to equilibrium caused by the lowering of the suction pres-
Reformer catalyst activity is commonly temperature F sure at the synthesis gas compressor, and
top level: surface profile 1625-1650
expressed as CH4 ATE, which is the differ- North 1600-1625 the resulting higher horsepower require-
1575-1600
ence between the measured catalyst outlet 1550-1575 ments to maintain the desired loop pres-
1525-1550
temperature and the calculated equilibrium 1500-1525 sure. Depending on pressure relief valve
temperature for the observed methane set-points, a higher reformer P may also
leakage. An increased ATE or methane slip 1650 require reduction of plant operating rates if
1625
from the front-end results in a higher purge 1600
1575
1550
near those limits.
1525
rate from the synthesis loop and increased 1500
EW
Using Clariants proprietary Cat-Trends
EE
energy consumption for the plant. While DW
DE program, calculated ATE and relative
CW
operating the primary reformer at higher CE
BW
BE
pressure drop can be trended over time.
exit temperature can mitigate this effect, top level: top profile
AW
AE Carbon deposition on the catalyst will
the cost of increased fuel requirements temperature F
1625-1650
manifest itself as increasing ATE, increas-
and the impact of hotter tube wall tempera- North 1600-1625
1575-1600
ing relative pressure drop and increasing
tures must be considered when choosing 1550-1575
1525-1550 TWTs. In severe cases, visual hot bands
to operate in that non-optimal mode. 1500-1525
on the tubes will also become evident.

Tube wall temperatures Operational control factors for


Tube costs are a significant item in the minimising carbon formation
EW
overall economics of a reforming plant. EE To prevent carbon formation, a minimum
DW
The goal is to operate the reformer under DE steam-to-carbon (S/C) ratio must be main-
CW
conditions that result in the lowest possi- CE tained at all times. This value is contingent
BW
ble tube wall temperatures (TWTs) consist- BE on the composition of the feed gas, firing
ent with satisfactory reformed gas quality. AW
AE rates, operating pressure and incoming
Even a slight increase in the tube wall feed temperature. Most carbon formation

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AmmoniA operAtions

incidents occur, however, during transient feed-gas in an upstream desulphurisation


Fig 4: The impact of sulphur
conditions such as start-up, operating trips step to levels less than 0.1 ppmv. Sulphur
concentration in feed gas on
or shutdowns. Modern operating plants is not a permanent poison for short-term
the tube wall temperature
typically have a low S/C trip interlock exposures and when removed from the
in the reformer
that cuts out the feed-gas to protect the feed, the catalyst can regain the original
reformer during upset conditions. Addition- activity. However, sulphur poisoning can
ally, a properly installed minimum stop on 70 deactivate the catalyst to the extent that

increase in tubewall temp, F


the steam valve ensures that steam con- 60 less reforming is done and elevated gas
tinues to flow through the reformer in an 50 temperatures cause high tube wall tem-
emergency trip to sweep all feed-gas out 40 peratures. Even small amounts of sulphur
of the reformer. Complete isolation of the 30 in the feed can significantly influence the
feed-gas valve during a trip or shut-down is 20 tube wall temperatures as shown in Fig. 4.
necessary before steam cut-out. 10 If the temperature rises to the point
Controlled start-up and shutdown pro- 0
where carbon formation occurs, pressure
cedures and emergency interlocks are 0.0 1.0 2.0 3.0 drop will increase and catalyst perform-
designed to avoid carbon formation. The sulphur in feed, ppmv ance will be further compromised.
objectives are to: In a 600 short t/d design ammonia plant,
l Prevent over-firing and thus tempera- the desulphurisation unit was bypassed due
ture excursions during rate changes. that all tubes have similar operating to vessel design concerns. During this time,
This typically considers the following conditions i.e. even flow and even heat the high performance ReforMax primary
operating parameters: fuel flow, fuel through all tubes. reformer catalyst was exposed to inlet sul-
pressure, flue-gas temperature, proc- l Ensure sufficient steam flow exists for phur levels of up to 3 ppmv for nine months.
ess gas pressure, steam flow, feed-gas adequate mixing of steam and feed-gas As expected, catalyst poisoning occurred
flow, combustion air flow, exit process well before the tube inlet manifold. which resulted in activity loss in the 30-40%
gas temperature and the number and top inlet tube location.
location of burners lit. Often a manual Visual monitoring of the tubes and burners The plant was subsequently brought
start-up rate guide is used and in some is critical to detect any issues during the down and a successful steam-air regenera-
cases an algorithm with interlocks start-up process. tion procedure was done with the assistance
guides the operator during the start-up. of Clariant technical support. On re-start, the
l Maintain a high S/C ratio during rate
Sulphur poisoning as root cause for reformer experienced full recovery to pre-inci-
changes. This is typically achieved by carbon formation dent performance levels and tube wall tem-
increasing the steam flow before the feed- Sulphur has an adverse impact on reform- peratures; visual success of the decoking
gas on start-up and reducing the feed-gas ing catalyst activity as it reacts with the procedure is reflected in Fig. 5.
before the steam on shutdowns. reforming catalysts active nickel compo- The ReforMax catalyst withstood the
l Ensure sufficient and even flow distri- nent and forms an equilibrium condition intense conditions during this high sulphur
bution throughout the entire reformer. over the active sites of the catalyst: exposure time-frame and continued to pro-
Before feed gas is introduced to the vide the full expected design life-time.
Ni + H2S NiS + H2
reformer during start-up, the steam Given the impact of sulphur poisoning
flow should be sufficient to ensure The sulphur must be removed from the on the performance of the reformer, the

Fig 5: The reformer tube appearance before and after a decoking procedure

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AmmoniA operAtions

Table 1: Impact of changes in performance of selected front-end catalysts on Fig 6: Secondary reformer exit
energy costs and lost production in a 1,500 short t/d ammonia plant methane slip over time
with membrane purge gas recovery
0.7
Change in performance Change in energy Lost production 0.6
cost ($/annum) ($/annum)

CH4 leakage, %
0.5
Primary 5.6C increase in ATE 15,000 170,000 0.4
reformer
0.3
Secondary 5.6C increase in ATE 30,000 370,000
0.2
reformer
0.1
HTS 1% increase in CO leakage 56,000 590,000
0
1 10 14 17 19 25 34
LTS 0.1% increase in CO leakage 160,000 2,000,000 time on-stream, months

Fig 7: Photo of the surface of the secondary reformer showing mixing of catalyst catalyst bed include gas distributor issues,
and inert balls and bed disruption vessel design issues, movement of catalyst
during operational upsets and initial loading
techniques.
Movement of catalyst at the top of a bed
caused by poor feed distributor designs,
burner issues in a secondary reformer or
plant upsets can create flow or channeling
issues, and result in changes in perform-
ance. Such an event was experienced
recently in a 1,750 short t/d ammonia plant.
During operation, the secondary reformer
experienced an increase in methane leak-
age from around 0.3% to over 0.5% (Fig. 6).
On shutdown it was found that there was
mixing of the catalyst and inert balls which
were pushed up toward the walls of the ves-
sel (Fig. 7). The root cause was traced back
to an operational upset that caused high
gas velocities and bed movement creating
unevenness/flow distribution issues in the
bed which subsequently compromised the
choice of high activity desulphurisation Using the results of a study carried overall performance.
catalyst should not be under-estimated. out to examine the impact of such opera- The purpose of any initial loading of cat-
Proper monitoring of the total sulphur slip tion, the cost impacts can be converted alyst and support media is to achieve a uni-
from the pre-treatment section ensures to dollar values to demonstrate the large form density throughout the bed to ensure
that the reforming catalyst is protected. impact they can have on overall plant prof- proper flow distribution. In fixed beds cross-
itability. This study was based on a 1,500 sectional uniformity is also desired.
Flow distribution in reactors short t/d ammonia plant with membrane The primary reformer is one of the most
purge gas recovery2. Assuming a produc- intensive and time-consuming reactors to
The design of a catalytic reactor considers tion rate of 1,500 short t/d, $2.70 per load and carries severe penalties if tubes
effective flow and distribution of the feed- MMBtu natural gas and $450/t ammonia, are loaded improperly. With no physical
gas through the catalyst bed volume. Poor the table above shows the results in terms means for balancing the feed gas flow
distribution of gas flow can lead to bypass- of potential costs. through tubes, catalyst with non-uniform
ing/channeling within the catalyst bed and As shown in Table 1, the increase in loaded density results in non-uniform flow
ineffective utilisation of the loaded cata- costs associated with lost production and rates which in turn cause some tubes
lyst volume. This manifests itself in higher if the lower production can be compensated to operate hotter than the average tube
calculated ATE in primary and secondary by a higher energy input in energy costs temperatures. Additionally, catalyst bridg-
reformers, higher CO leakage in HTS and can be significant for these different sce- ing can occur when particles interlock to
LTS reactors, higher COx from methana- narios. It is clear that proper initial design, form a bridge across the tube cross-
tors and reduced conversion from ammonia procedures and operation is imperative to section. These voids within the catalyst
converters. The impact of these non-opti- ensure stable and optimal catalyst perform- layer result in localised overheating of the
mal conversions is less efficient and more ance from start of run (SOR) to end of run tube. Hot tubes fail prematurely and can
costly operation of the NH3 plant. (EOR). The potential causes of poor flow in a be very costly. It has been estimated that

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AmmoniA operAtions

Fig 8: Photo of reduced particle size of HTS catalyst after Fig 9: Photo of fused inert ball, floating screen and catalyst
exposure to extreme temperatures caused by air removed from the HTS following exposure to air and
introduction to the HTS reactor extreme temperatures

a 2.5% lower than average tube flow rate Complete isolation of the air flow to the during start-up of the primary reformer can
can result in an 4-6C hotter tube wall tem- secondary reformer is required in a sec- lead to instantaneous flashing at the hot
perature3. Further experience has shown ondary reformer trip to protect downstream catalyst releasing enough energy to rupture
that tube wall temperatures in the area of catalysts. In one incident at a 1,700 short reformer tubes. Water entrainment can
a catalyst void are about 16-28C hotter t/d ammonia plant in North America, the occur when low point drains are plugged
than the surrounding area of the tube. HTS catalyst performance was greatly or not used during shutdown and start-up.
affected following an upset during start-up HTS and LTS are particularly at risk due to
The impact of plant operations on catalyst of the secondary reformer. A high pres- their location downstream of the HP boiler,
Many catalyst failures are the result of sure air flow condition resulted in air to quenches and temperature controls. When
poor operation or operational upsets. To the HTS for a short duration. The event water comes in contact with catalyst, cata-
illustrate the significant potential negative occurred relatively fast and other events lyst breakage and increased pressure drop
impacts, a number of different examples were occurring so it was not even noticed results from water vaporising out of the cata-
for various catalytic services are discussed by the operations team. lyst pores at a faster rate than the porosity
below. Shortly after stabilising plant rates, of the catalyst will allow. The HTS catalyst is
however, the performance of the charge in very susceptible to leaks from the upstream
Reduced/pyrophoric catalyst terms of CO leakage, while acceptable to HP boiler which are almost inevitable during

Catalysts are often in the reduced metal allow operation, was higher than expected. a plants life. Clariants HTS ShiftMax cata-
state during operation in HDS, HTS, LTS, After approximately a year on-stream, the lyst was able to survive major boiler leaks
methanator and ammonia synthesis reac- decision was made to unload the catalyst at the 1,600 short t/d Terra plant4. In this
tors. Exposure to air can result in spontane- during a shut-down. Inspection of the reac- case, the HTS was flooded with water from
ous ignition with extremely high localised tor showed that the overall outage from the a major boiler failure and a dry out proce-
temperatures causing catalyst failure, manway had increased by over 0.9 m and dure was successfully implemented under
fusing and equipment damage. For turna- that in a particular area of the bed the cat- the direction of Clariant. Besides the effect
rounds and longer shut-down periods, alyst particle size was reduced from 6x6 of wetting the catalyst, accumulated boiler
ensuring a continuous positive pressure mm to roughly 3x3 mm. The support balls solids from boiler leaks can also increase
inert blanket is one routine monitoring item. were also found fused to melted screen the catalysts pressure drop and create poor
Discharging of pyrophoric catalyst without pieces which in turn were fused to cata- gas distribution issues. The impact of water
first oxidising it must be done under nitro- lyst. For this level of shrinkage and fusion and boiler solid carryover can be minimised
gen with precautions taken to avoid ingress to occur it is estimated that temperatures by using a high voidage inert top layer.
of air to the vessel by a chimney effect. In must have exceeded 870C. It is important During operational upsets, temperature
cases where repair work is required around to note that despite this significant temper- controller swings can lower the inlet tem-
vessels without adequate isolation, the risk ature exposure, the Clariant catalyst was perature of the shift converters below the
is particularly high and continuous nitrogen still able to achieve an acceptable level of dew point and wet the catalyst. Operating
purge is necessary. It should be noted that performance with no pressure drop issues. the LTS at an inlet temperature 17-22C
without flow through the catalyst bed, tem- (Figs 8 and 9) above dew point can reduce this potential.
perature measurements do not accurately Boiler feed water quenches are normally
represent the bed temperatures nor do Impact of water on catalyst installed upstream of shift converters in
they detect localised peak temperatures. Water can affect the integrity of all cata- order to control inlet temperature as well
They can, however, give some indication or lysts and in some cases can lead to cata- as lower the CO equilibrium. Atomisation
warning of an issue. strophic incidents. Water entrainment is critical to prevent wetting the catalyst

Nitrogen+Syngas 321 | January - February 2013  5


AmmoniA operAtions

and proper design and maintenance of perature run-away are both considered. extent that the resultant exotherm elevates
the quench valve/nozzles is imperative. Studies have been done to understand the methanator temperature to equipment
Quench valves also require complete iso- what happens at elevated temperatures design limits, process gas should be imme-
lation during a shutdown to prevent water that cause run-away. In the case of a natu- diately shut off or vented upstream.
buildup in low point piping areas that can ral gas carrier, CuO reacts with methane at The operation and control of the CO2
be entrained onto the catalyst on restart. 246C via the following reaction5: removal system is critical to maintaining
the inlet levels to the methanator. Plants
CH4 + 4CuO 4Cu0 + CO2 + 2H2O
Water treatment that have been revamped or are running at
The steam quality in an ammonia plant is This is also exothermic creating even higher than design throughputs can push
typically monitored to ensure protection of higher bed temperatures. At temperatures the CO2 removal system to maximum load.
rotating equipment. However it is also an near 370oC, hydrogen can be produced by At these conditions, small fluctuations can
important consideration for reforming cata- hydrocarbon cracking, which can lead to lead to gross carryover of solution and CO2
lyst. Carry-over and deposition of silica and temperature run-away. Under such circum- breakthrough. Some solutions can poison
sodium on reforming catalyst can act like a stances vessel design temperatures can and permanently deactivate the methana-
permanent poison by physically covering the be exceeded. tor catalyst, or leave deposits on the top
active sites of the catalyst. This can cause of the bed which reduces catalyst activity
poor reformer performance, increased pres- Methanator operation by blocking active sites and also leads to
sure drop and increased TWTs at the top Methanator operations are seldom given increased pressure drop. Severe liquid
of the tubes. These contaminants can also much attention and COx concentrations are carryover of all solutions can also cause
be introduced to the process via boiler feed typically not measured. However upstream physical damage of the catalyst further
water quenches upstream of the reformer. conditions affect its performance and can increasing the pressure drop. A skim of the
A well controlled and monitored water treat- have an adverse effect on plant efficiency, catalyst is can sometimes be performed to
ment program is necessary for effective production and even equipment. correct the situation.
catalyst performance. During start-up, the front end of the
plant is brought up and the synthesis gas Conclusion
LTS reduction is introduced into the synthesis loop. The
LTS reduction is a procedure required to inlet temperature of the methanator is typi- In summary, understanding the basic prin-
activate the catalyst and is typically per- cally controlled by available steam and the ciples of catalytic reactor operation in an
formed every 3 to 4 years. It is a process feed/effluent exchanger. The introduction ammonia plant can help to avoid costly per-
that can have catastrophic consequences of low temperature make-up gas to the loop formance and operating problems. Opera-
if not done carefully. The infrequency of can introduce higher levels of COx. These tions and technical crews should routinely
the procedure requires a thorough review higher concentrations increase the poten- review and analyse process monitoring
before performing the procedure. tial for ammonium carbamate formation systems and procedures to ensure that the
The CuO in the LTS catalyst is reduced within the loop that fouls equipment and consequences of mal-operation are under-
to copper metal by an exothermic reac- increases the loop pressure drop, which stood and best available procedures and
tion. To effect the reduction, hydrogen is in turn increases the energy requirements technology are in place. Understanding the
carefully and precisely added to a carrier of the plant. In addition to ammonium car- impact on catalyst and process equipment
gas (natural gas or nitrogen) and the bed bamate formation, ammonia synthesis from a safety perspective and an opera-
temperatures are closely monitored. Meas- catalyst is temporarily poisoned by oxygen- tional cost standpoint is important so that
ures taken to achieve adequate control of ates and this will adversely impact plant potential adverse situations are avoided
hydrogen include: production and loop performance. Once or minimised in magnitude. With this com-
l complete isolation/blinding of any the COx levels are returned to normal, plete knowledge and understanding, high
potential sources of hydrogen other production rates can take quite some time performance catalysts can achieve their full
than reduction gas especially when at before recovering. If ammonia synthesis utilisation and maximise the efficiency and
higher pressure than the carrier gas; catalyst is exposed to high COx levels for productivity of the plant. n
l gas composition analysis of the reduc- long periods of time, the poisoning affects
tion and carrier gases (Note: natural can be permanent. References
gas carrier gas should be free of hydro- In addition to operating conditions at
1. Gebert S., Cai Y,. and Kniep B.: Continuous
gen recycle); the methanator, upsets at the upstream improvement in ammonia catalysts Nitro-
l reliable supply of reduction and carrier LTS reactor that cause increased inlet CO gen + Syngas (Jan-Feb 2012).
gas flows, including reduction gas flow to the methanator can overload the avail- 2. Rice D.: The value of catalyst performance
meter calibration at constant conditions able capacity of the catalyst and lead to in ammonia plants AIChE 2002.
of carrier gas flow and back pressure; higher COx leakage. 3. Rice D.: Loading of primary reformer cata-
l Gas testing schedule of inlet and outlet Upsets at the CO2 removal unit tend to lyst tubes AIChE 1993.
hydrogen concentrations. be more frequent and can have a greater 4. Borzik K., Howerton R. and Archer T.: Suc-
impact on the methanator. Also CO2 is cessful recoveries from major WHB failures
Caution statements in a procedure describe more difficult to methanate than CO, so experience AIChE 2007.
reducing or removing reduction gas at cer- higher levels can overwhelm the methana- 5. Richardson J., Wagner J., Drucker R., Rajesh
tain peak temperatures. Achieving optimum tor and result in premature COx leakage. In H.: Understanding hydrocarbon reactions
catalyst performance and preventing tem- cases where the CO2 increases to such an during LTS catalyst reductions AIChE 1996.

6 Nitrogen+Syngas 321 | January - February 2013

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