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AmmoniA operAtions

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 Süd-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.


he ammonia industry has seen significant change in recent decades as
high turnover, leaner organisational
structures, and new operations have shifted
the demographics of the operations and
technical personnel staff. These changes
have resulted in a loss of long-term operational knowledge and can lead to incidents
of equipment and catalyst damage during
operation and upset conditions.
As catalyst technology continues to
improve, the products’ high performance
are best enabled when accompanied by a
thorough understanding of the chemical and
physical principles of catalytic reactions1.

affect the catalyst’s performance and can
lead to costly equipment failure.

Primary reformer reactions
The main reactions in the primary reformer
Steam reforming of hydrocarbons
CnH2n+2 + n H2O

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

Overall, the process is endothermic. A lower
CH4 leakage is favoured by higher exit temperature, higher steam-to-carbon ratio, and
lower exit pressure.
The standard primary reformer system
is comprised of a tubular furnace where
the feed stream passes over a catalyst
packed in multiple banks of externally
heated tubes. With improvements in tube
metallurgy, primary reformers operate at
pressures up to 6,000 kPa and tube wall

Nitrogen+Syngas 321 | January - February 2013 

temperatures up to 1010°C. 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.

Carbon formation reactions
With no steam present and at normal
reformer operating temperatures, all hydrocarbons will decompose into carbon and
hydrogen via the following reaction:
Thermal cracking

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:
C + H2O

CO + H2

Operating the reformer at conditions that
drive this reaction can prevent the accumulation of carbon deposits. When conditions
exist that favour hydrocarbon cracking,
the heavier hydrocarbons in the feed will


caused by the lowering of the suction pressure at the synthesis gas compressor. and temperature excursions resulting from poor firing control. firing rates. the maximum tube wall temperature was also lowered and the number of tubes with TWTs exceeding the temperature limit of 927°C was cut from five to zero. visual hot bands on the tubes will also become evident.200 short t/d plant in North America was able to realise such an advantage by installing the high activity ® ReforMax reforming catalyst from Clariant. and the resulting higher horsepower requirements to maintain the desired loop pressure. the reformer now operates at a high heat flux of around 110. This value is contingent on the composition of the feed gas. In severe cases. Most carbon formation Nitrogen+Syngas 321 | January . While operating the primary reformer at higher exit temperature can mitigate this effect. its formation within the pores of the catalyst can cause catalyst breakage. a minimum steam-to-carbon (S/C) ratio must be maintained at all times. Three performance parameters are typically trended during operation. Common causes of carbon formation and deposition are low steam/gas ratio operation. increased pressure drop and increased tube wall temperatures which. tube wall temperatures (TWT).AmmoniA operAtions Fig 1: Comparative average TWT surveys of two charges of catalyst at a 1200 STPD ammonia plant 1750 Benchmark Clariant 1700 temperature. After several expansions. 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. a higher reformer ∆P may also require reduction of plant operating rates if near those limits. 1650 1600 1550 1500 0 5 10 15 months on stream Fig 2: IR thermographic image of a row of reformer tubes Monitoring program During routine operation of a primary reformer. Effective monitoring of the TWTs and balancing of the firing of the reformer furnace can extend the life of the tubes and optimise the performance of the catalyst (Figures 2 and 3). if severe. Higher catalyst activity can reduce carbon formation potential by lowering gas temperature when methane concentration is high enough for cracking. calculated ATE and relative pressure drop can be trended over time. °F crack first. Not only does the carbon deposit block active sites. The overall effect of carbon formation on the primary reformer is reduced conversion. ® Using Clariant’s proprietary Cat-Trends program. can be seen as ‘hot bands’ on the tubes. thereby reducing the carbon formation potential. sulphur poisoning. Even a slight increase in the tube wall temperature °F 1625-1650 1600-1625 1575-1600 1550-1575 1525-1550 1500-1525 temperatures will have a drastic impact on the tube life. Carbon deposition on the catalyst will manifest itself as increasing ATE. resulting in less reforming reaction and higher gas temperatures. the active sites of the catalyst become masked. Approach to equilibrium Reformer catalyst activity is commonly expressed as CH4 ATE. which further increases the tendency for cracking and coke deposition. As an example. heavy hydrocarbons in the feed. Additionally. EW EE DW DE CW CE BW BE AW AE To prevent carbon formation. Figure 1 shows that the mean TWT is 55°C cooler with catalyst from Clariant than with the previous competitor charge. Fig 3: Plotted TWT surveys showing the heat distribution across the reformer top level: surface profile North 1650 1625 1600 1575 1550 1525 1500 EW EE DW DE CW CE BW BE top level: top profile 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.February 2013 . a monitoring program assists in optimising the catalyst’s performance as well as providing early detection of issues that can lead to catalyst or tube failure. The goal is to operate the reformer under conditions that result in the lowest possible tube wall temperatures (TWTs) consistent with satisfactory reformed gas quality. 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. significantly reducing the risk of potential tube failure. a 1. increasing relative pressure drop and increasing TWTs. The Kellogg-designed primary reformer of this plant was initially designed to produce 600 short t/d of ammonia. The use of a high activity/shape optimised reforming catalyst results in lower tube wall temperatures and a significant cost and efficiency advantage to an operator.000 W/m2. which is the difference between the measured catalyst outlet temperature and the calculated equilibrium temperature for the observed methane leakage. Depending on pressure relief valve set-points. A TWT increase of as little as 10oC may result in up to a 30% shortened life-time of the reformer tubes. operating pressure and incoming feed temperature. Operational control factors for minimising carbon formation Tube wall temperatures Tube costs are a significant item in the overall economics of a reforming plant. calculated CH4 approach to equilibrium (ATE). and relative pressure drop. As this occurs.

the high performance ReforMax primary reformer catalyst was exposed to inlet sulphur levels of up to 3 ppmv for nine months. Modern operating plants typically have a low S/C trip interlock that cuts out the feed-gas to protect the reformer during upset conditions. process gas pressure. Additionally. In a 600 short t/d design ammonia plant. On re-start. Before feed gas is introduced to the reformer during start-up. pressure drop will increase and catalyst performance will be further compromised. The ReforMax catalyst withstood the intense conditions during this high sulphur exposure time-frame and continued to provide the full expected design life-time.0 2. feed-gas flow.AmmoniA operAtions Fig 4: The impact of sulphur concentration in feed gas on the tube wall temperature in the reformer increase in tubewall temp. l Ensure sufficient steam flow exists for adequate mixing of steam and feed-gas well before the tube inlet manifold. Even small amounts of sulphur in the feed can significantly influence the tube wall temperatures as shown in Fig. Given the impact of sulphur poisoning on the performance of the reformer. the reformer experienced full recovery to pre-incident performance levels and tube wall temperatures.February 2013  3 . Sulphur poisoning as root cause for carbon formation Sulphur has an adverse impact on reforming catalyst activity as it reacts with the reforming catalysts active nickel component and forms an equilibrium condition over the active sites of the catalyst: Ni + H2S NiS + H2 The sulphur must be removed from the feed-gas in an upstream desulphurisation step to levels less than 0. If the temperature rises to the point where carbon formation occurs. the desulphurisation unit was bypassed due to vessel design concerns. However.0 sulphur in feed. sulphur poisoning can deactivate the catalyst to the extent that less reforming is done and elevated gas temperatures cause high tube wall temperatures. Visual monitoring of the tubes and burners is critical to detect any issues during the start-up process. ppmv 3. This typically considers the following operating parameters: fuel flow. visual success of the decoking procedure is reflected in Fig. catalyst poisoning occurred which resulted in activity loss in the 30-40% top inlet tube location. Sulphur is not a permanent poison for short-term exposures and when removed from the feed. During this time. l Maintain a high S/C ratio during rate changes. the Fig 5: The reformer tube appearance before and after a decoking procedure Nitrogen+Syngas 321 | January .0 1.0 that all tubes have similar operating conditions i. The objectives are to: l Prevent over-firing and thus temperature excursions during rate changes. operating trips or shutdowns. 4. Often a manual start-up rate guide is used and in some cases an algorithm with interlocks guides the operator during the start-up. As expected. °F incidents occur. the steam flow should be sufficient to ensure 70 60 50 40 30 20 10 0 0. Complete isolation of the feed-gas valve during a trip or shut-down is necessary before steam cut-out. during transient conditions such as start-up. l Ensure sufficient and even flow distribution throughout the entire reformer. fuel pressure. the catalyst can regain the original activity. exit process gas temperature and the number and location of burners lit. even flow and even heat through all tubes. 5. however. Controlled start-up and shutdown procedures and emergency interlocks are designed to avoid carbon formation. flue-gas temperature. steam flow.e. The plant was subsequently brought down and a successful steam-air regeneration procedure was done with the assistance of Clariant technical support.1 ppmv. a properly installed minimum stop on the steam valve ensures that steam continues to flow through the reformer in an emergency trip to sweep all feed-gas out of the reformer. combustion air flow. This is typically achieved by increasing the steam flow before the feedgas on start-up and reducing the feed-gas before the steam on shutdowns.

000 Flow distribution in reactors The design of a catalytic reactor considers effective flow and distribution of the feedgas through the catalyst bed volume.5% (Fig.500 short t/d ammonia plant with membrane purge gas recovery 0.3 0.000 Secondary reformer 5. higher CO leakage in HTS and LTS reactors.7 Change in energy cost ($/annum) Lost production ($/annum) Primary reformer 5. the increase in costs associated with lost production and – if the lower production can be compensated by a higher energy input – in energy costs can be significant for these different scenarios.750 short t/d ammonia plant. Proper monitoring of the total sulphur slip from the pre-treatment section ensures that the reforming catalyst is protected. 7). Assuming a production rate of 1. 6).6°C increase in ATE 15.4 0.2 0. movement of catalyst during operational upsets and initial loading techniques. catalyst bridging can occur when particles interlock to form a “bridge” across the tube crosssection. the table above shows the results in terms of potential costs. Additionally. % Change in performance Using the results of a study carried out to examine the impact of such operation.AmmoniA operAtions Fig 6: Secondary reformer exit methane slip over time Table 1: Impact of changes in performance of selected front-end catalysts on energy costs and lost production in a 1.000 HTS 1% increase in CO leakage 56.500 short t/d.6 CH4 leakage.3% to over 0.1% increase in CO leakage 160. The purpose of any initial loading of catalyst and support media is to achieve a uniform density throughout the bed to ensure proper flow distribution.000 370.000 LTS 0. Such an event was experienced recently in a 1. 0. With no physical means for balancing the feed gas flow through tubes. On shutdown it was found that there was mixing of the catalyst and inert balls which were pushed up toward the walls of the vessel (Fig.000 590. The primary reformer is one of the most intensive and time-consuming reactors to load and carries severe penalties if tubes are loaded improperly. It has been estimated that Nitrogen+Syngas 321 | January .6°C increase in ATE 30. The impact of these non-optimal conversions is less efficient and more costly operation of the NH3 plant. The potential causes of poor flow in a 1 10 14 17 19 25 34 time on-stream.5 0. catalyst with non-uniform loaded density results in non-uniform flow rates which in turn cause some tubes to operate hotter than the average tube temperatures. procedures and operation is imperative to ensure stable and optimal catalyst performance from start of run (SOR) to end of run (EOR). 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 overall performance. $2. This study was based on a 1. the secondary reformer experienced an increase in methane leakage from around 0. During operation.000 2.000 170. As shown in Table 1. higher COx from methanators and reduced conversion from ammonia converters.70 per MMBtu natural gas and $450/t ammonia. These voids within the catalyst layer result in localised overheating of the tube. the cost impacts can be converted to dollar values to demonstrate the large impact they can have on overall plant profitability.500 short t/d ammonia plant with membrane purge gas recovery2. This manifests itself in higher calculated ATE in primary and secondary reformers.February 2013 . Poor distribution of gas flow can lead to bypassing/channeling within the catalyst bed and ineffective utilisation of the loaded catalyst volume. It is clear that proper initial design. months catalyst bed include gas distributor issues. Movement of catalyst at the top of a bed caused by poor feed distributor designs. Hot tubes fail prematurely and can be very costly. and result in changes in performance. 4 0.1 0 Fig 7: Photo of the surface of the secondary reformer showing mixing of catalyst and inert balls and bed disruption choice of high activity desulphurisation catalyst should not be under-estimated. In fixed beds crosssectional uniformity is also desired.000. burner issues in a secondary reformer or plant upsets can create flow or channeling issues. vessel design issues.

The HTS catalyst is very susceptible to leaks from the upstream HP boiler which are almost inevitable during ® a plant’s life.February 2013  during start-up of the primary reformer can lead to instantaneous flashing at the hot catalyst releasing enough energy to rupture reformer tubes. Further experience has shown that tube wall temperatures in the area of a catalyst void are about 16-28°C hotter than the surrounding area of the tube. temperature measurements do not accurately represent the bed temperatures nor do they detect localised peak temperatures. the HTS catalyst performance was greatly affected following an upset during start-up of the secondary reformer. For turnarounds and longer shut-down periods. For this level of shrinkage and fusion to occur it is estimated that temperatures must have exceeded 870°C. Atomisation is critical to prevent wetting the catalyst 5 . ensuring a continuous positive pressure inert blanket is one routine monitoring item. It is important to note that despite this significant temperature exposure. Water entrainment can occur when low point drains are plugged or not used during shutdown and start-up. The event occurred relatively fast and other events were occurring so it was not even noticed by the operations team.9 m and that in a particular area of the bed the catalyst particle size was reduced from 6x6 mm to roughly 3x3 mm. A high pressure air flow condition resulted in air to the HTS for a short duration. fusing and equipment damage. In cases where repair work is required around vessels without adequate isolation. however. Shortly after stabilising plant rates.AmmoniA operAtions Fig 8: Photo of reduced particle size of HTS catalyst after exposure to extreme temperatures caused by air introduction to the HTS reactor a 2. Water entrainment Nitrogen+Syngas 321 | January . In this case.600 short t/d Terra plant4. give some indication or warning of an issue.5% lower than average tube flow rate can result in an 4-6°C hotter tube wall temperature3.700 short t/d ammonia plant in North America. however. Operating the LTS at an inlet temperature 17-22°C above dew point can reduce this potential. the performance of the charge in terms of CO leakage. In one incident at a 1. HTS. Besides the effect of wetting the catalyst. quenches and temperature controls. Discharging of pyrophoric catalyst without first oxidising it must be done under nitrogen with precautions taken to avoid ingress of air to the vessel by a chimney effect. catalyst breakage and increased pressure drop results from water vaporising out of the catalyst pores at a faster rate than the porosity of the catalyst will allow. LTS. a number of different examples for various catalytic services are discussed below. It should be noted that without flow through the catalyst bed. The impact of plant operations on catalyst Many catalyst failures are the result of poor operation or operational upsets. When water comes in contact with catalyst. To illustrate the significant potential negative impacts. while acceptable to allow operation. the HTS was flooded with water from a major boiler failure and a dry out procedure was successfully implemented under the direction of Clariant. HTS and LTS are particularly at risk due to their location downstream of the HP boiler. After approximately a year on-stream. (Figs 8 and 9) Impact of water on catalyst Water can affect the integrity of all catalysts and in some cases can lead to catastrophic incidents. was higher than expected. They can. the Clariant catalyst was still able to achieve an acceptable level of performance with no pressure drop issues. Boiler feed water quenches are normally installed upstream of shift converters in order to control inlet temperature as well as lower the CO equilibrium. During operational upsets. methanator and ammonia synthesis reactors. Fig 9: Photo of fused inert ball. temperature controller swings can lower the inlet temperature of the shift converters below the dew point and wet the catalyst. the decision was made to unload the catalyst during a shut-down. floating screen and catalyst removed from the HTS following exposure to air and extreme temperatures Complete isolation of the air flow to the secondary reformer is required in a secondary reformer trip to protect downstream catalysts. The impact of water and boiler solid carryover can be minimised by using a high voidage inert top layer. The support balls were also found fused to melted screen pieces which in turn were fused to catalyst. Clariant’s HTS ShiftMax catalyst was able to survive major boiler leaks at the 1. Inspection of the reactor showed that the overall outage from the manway had increased by over 0. accumulated boiler solids from boiler leaks can also increase the catalyst’s pressure drop and create poor gas distribution issues. Reduced/pyrophoric catalyst Catalysts are often in the reduced metal state during operation in HDS. Exposure to air can result in spontaneous ignition with extremely high localised temperatures causing catalyst failure. the risk is particularly high and continuous nitrogen purge is necessary.

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. Severe liquid carryover of all solutions can also cause physical damage of the catalyst further increasing the pressure drop. the front end of the plant is brought up and the synthesis gas is introduced into the synthesis loop. During start-up. production and even equipment. high performance catalysts can achieve their full utilisation and maximise the efficiency and n productivity of the plant. Wagner J. hydrogen can be produced by hydrocarbon cracking. ammonia synthesis catalyst is temporarily poisoned by oxygenates and this will adversely impact plant production and loop performance.. and Archer T. the poisoning affects can be permanent. increased pressure drop and increased TWTs at the top of the tubes. Upsets at the CO2 removal unit tend to be more frequent and can have a greater impact on the methanator. Once the COx levels are returned to normal. In the case of a natural gas carrier. Conclusion In summary. Under such circumstances vessel design temperatures can be exceeded. Water treatment The steam quality in an ammonia plant is typically monitored to ensure protection of rotating equipment. In addition to operating conditions at the methanator. Methanator operation Methanator operations are seldom given much attention and COx concentrations are typically not measured.: “Successful recoveries from major WHB failures experience” AIChE 2007. 5. which in turn increases the energy requirements of the plant. Gebert S.: “Understanding hydrocarbon reactions during LTS catalyst reductions” AIChE 1996. These contaminants can also be introduced to the process via boiler feed water quenches upstream of the reformer. The infrequency of the procedure requires a thorough review before performing the procedure. 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. Borzik K. At temperatures near 370oC. It is a process that can have catastrophic consequences if not done carefully. process gas should be immediately shut off or vented upstream.AmmoniA operAtions and proper design and maintenance of the quench valve/nozzles is imperative. A skim of the catalyst is can sometimes be performed to correct the situation. These higher concentrations increase the potential for ammonium carbamate formation within the loop that fouls equipment and increases the loop pressure drop. understanding the basic principles of catalytic reactor operation in an ammonia plant can help to avoid costly performance and operating problems. Howerton R. References 1.February 2013 . However it is also an important consideration for reforming catalyst. l Gas testing schedule of inlet and outlet hydrogen concentrations. production rates can take quite some time before recovering.. 4. small fluctuations can lead to gross carryover of solution and CO2 breakthrough. LTS reduction LTS reduction is a procedure required to activate the catalyst and is typically performed every 3 to 4 years. hydrogen is carefully and precisely added to a carrier gas (natural gas or nitrogen) and the bed temperatures are closely monitored. 3. If ammonia synthesis catalyst is exposed to high COx levels for long periods of time. Carry-over and deposition of silica and sodium on reforming catalyst can act like a permanent poison by physically covering the active sites of the catalyst. Rice D.. l reliable supply of reduction and carrier gas flows. Quench valves also require complete isolation during a shutdown to prevent water buildup in low point piping areas that can be entrained onto the catalyst on restart.: “Loading of primary reformer catalyst tubes” AIChE 1993. To effect the reduction. The CuO in the LTS catalyst is reduced to copper metal by an exothermic reaction. In addition to ammonium carbamate formation. With this complete knowledge and understanding. However upstream conditions affect its performance and can have an adverse effect on plant efficiency. 2.: “The value of catalyst performance in ammonia plants” AIChE 2002. or leave deposits on the top of the bed which reduces catalyst activity by blocking active sites and also leads to increased pressure drop. Studies have been done to understand what happens at elevated temperatures that cause run-away. Caution statements in a procedure describe reducing or removing reduction gas at certain peak temperatures. l gas composition analysis of the reduction and carrier gases (Note: natural gas carrier gas should be free of hydrogen recycle). Drucker R. Some solutions can poison and permanently deactivate the methanator catalyst. Achieving optimum catalyst performance and preventing tem- 6 perature run-away are both considered. CuO reacts with methane at 246°C via the following reaction5: CH4 + 4CuO → 4Cu0 + CO2 + 2H2O This is also exothermic creating even higher bed temperatures. Cai Y. so higher levels can overwhelm the methanator and result in premature COx leakage. Richardson J. A well controlled and monitored water treatment program is necessary for effective catalyst performance. At these conditions. Rice D. Rajesh H.. which can lead to temperature run-away. Measures taken to achieve adequate control of hydrogen include: l complete isolation/blinding of any potential sources of hydrogen other than reduction gas especially when at higher pressure than the carrier gas.: “Continuous improvement in ammonia catalysts” Nitrogen + Syngas (Jan-Feb 2012). Nitrogen+Syngas 321 | January . and Kniep B.. The inlet temperature of the methanator is typically controlled by available steam and the feed/effluent exchanger. Plants that have been revamped or are running at higher than design throughputs can push the CO2 removal system to maximum load. In cases where the CO2 increases to such an extent that the resultant exotherm elevates the methanator temperature to equipment design limits. Also CO2 is more difficult to methanate than CO. The operation and control of the CO2 removal system is critical to maintaining the inlet levels to the methanator.. The introduction of low temperature make-up gas to the loop can introduce higher levels of COx. This can cause poor reformer performance. upsets at the upstream LTS reactor that cause increased inlet CO to the methanator can overload the available capacity of the catalyst and lead to higher COx leakage. including reduction gas flow meter calibration at constant conditions of carrier gas flow and back pressure.