New ATR Based Ammonia Process

Until now, large-scale ammonia production in single line configuration has suffered from a lack of
demonstrated plant concepts with proven feasibility and competitiveness and traditionally, the
industry has perceived 3,500 MTPD as the limit in single line capacity. However, the
commercialization of the catalyst, SK-501 FlexTM, has enabled that the benefits of low S/C
autothermal reforming technology (ATR) is now available to the ammonia industry. Consequently,
ammonia plants with single line capacities above 6,000 MTPD solely based on industrially proven
equipment sizes and catalysts could become plant owners’ preferred choice due to resulting benefits
from economy of scale.

Per Juul Dahl, Christian Speth, Annette E. Krøll Jensen,

Marcus Symreng, Merethe Kjul Hoffmann, Pat A. Han, Svend Erik Nielsen
Haldor Topsøe A/S

H2/CO industry closely followed by the gas-to-

liquids (GTL) industry. The technology break-
Introduction through came in the early stages of the develop-

T his paper presents Haldor Topsoe’s new ing GTL industry, which suffered from the lack
ammonia process based on advanced au- of a cost effective solution that could meet the
tothermal reforming. H2/CO ratio needed for the Fischer-Tropsch
process and produce syngas in large single line
Ammonia plant owners will benefit from an in- capacity at the same time.
novative and very competitive technology ap-
plication defying existing single line plant ca- The ATR technology became a real game
pacity limits while staying within referenced changer removing the limitations that other
applications of technology elements. The pro- technologies had in reaching the optimal syngas
cess is equally suitable for stand-alone ammonia composition. The advanced ATR technology
plants and for integrated urea complexes. It is provides plant owners with a huge leap towards
also an inherently safer process than the conven- economy of scale in combination with signifi-
tional. cant operational expenditure (OPEX) improve-
ments through lower specific net energy con-
Haldor Topsoe pioneered advanced autothermal sumption (SNEC), high reliability and uptime,
reforming throughout the 1990ies and commer- lower requirements for operators and reduced
cialized the low steam-to-carbon (S/C) ATR maintenance. Today, the combined industrial
technology in 2002. The first industry to take operation exceeds 70 years and both industries
advantage of this unique technology was the regard the ATR technology as highly successful.
The technology is continuously developed and

2017 161 AMMONIA TECHNICAL MANUAL

 improvements are made in very close collabora- Today’s large-scale ammonia plant technologies
tion with customers. all use some degree of tubular steam reforming.
This is a very mature technology, which has
Large-scale GTL plants producing syngas significant drawbacks. When scaling the capaci-
equivalent to more than 6,000 MTPD (6,613 ty, the scaling exponent is very close to one re-
STPD) of ammonia have already been in opera- sulting in an almost linear function. Additional-
tion for 10 years. A few years back, the ATR ly, although it is technically possible to build
technology was introduced to the methanol in- large tubular steam reformers, they become in-
dustry and consequently, Topsoe’s first 5,000 creasingly difficult to operate in terms of con-
MTPD (5,511 STPD) ATR based methanol trol, safety and maintenance regardless of the
plant is under construction with expected start- specific type of tubular reformer. According to
up in 2018. market feedback, the upper practical capacity
limit for this technology is around 3,500 MTPD
It has been Haldor Topsoe’s focus to also make (3,858 STPD) of ammonia, and the way forward
the benefits of the ATR technology available to for the tubular reforming technology should be a
the ammonia industry and to utilize its operation division into more trains. However, that would
at low S/C ratio to enable much larger single jeopardize the benefit from economy of scale in
train ammonia plants. Topsoe has enabled this this very important plant section, which typical-
through the development and commercialization ly corresponds to ~25% of total plant cost. Fur-
of its high temperature shift catalyst, SK-501 thermore, some of the synthesis loops currently
FlexTM, which has been in successful industrial proposed and in operation increase complexity
operation for more than 3 years. and overall capex cost due to multiple pressure
levels and reactors.
Consequently, large-scale ATR based ammonia
plant technology solely based on industrially Front end CAPEX cost
proven equipment sizes and catalysts is now
available to the market. SMR based
Beyond reference
Capacity
SMR based
Cost

One of the biggest trends in the chemical indus- Development

try for years has been a pull for plants with larg- of ATR based
ATR based
er single line capacity The availability of this
2017
well-proven technology to ammonia producers
is a breakthrough in the industry as it accommo- Capacity
dates such a need. The trend has been driven by
wishes to take advantage of economy of scale Figure 1. Comparison between steam methane
and to reduce operating cost in a quest to reduce reformer (SMR) vs. ATR
total product cost, similar to what has been the
case in the H2/CO and GTL industries. The In comparison, the ATR technology scales with
market for large scale ammonia plants with ca- a lower exponent. Figure 1 illustrates the differ-
pacities above 3,500 MTPD (3,858 STPD) has ence in scaling between tubular steam reforming
not really picked up speed, to a certain extent and ATR. The ATR based plant is referenced
due to lack of demonstrated plant concepts with within the full capacity range to above 6,000
proven feasibility and competitiveness above MTPD (6,613 STPD). Based on its new applica-
this capacity, which is traditionally perceived as tion continuous developments and improve-
the limit in single line capacity. ments to technology as well as the catalysts

AMMONIA TECHNICAL MANUAL 162 2017

 could reduce cost even further. The dotted line When scaling up plant capacity, size matters.
indicates where the SMR technology is beyond The ATR has a small physical footprint provid-
reference, which is above 3,500 MTPD (3,858 ing extremely high reforming intensity. Picture
STPD) ammonia. With SMR being a very ma- 1 shows how small the reactor is, even though
ture technology further cost reduction is not to its capacity corresponds to 6,000 MTPD (6,613
be expected. STPD) of ammonia. Picture 2 shows the large
footprint of a tubular reformer and a secondary
From a capital expenditure (CAPEX) perspec- reformer with a capacity of 1,500 MTPD (1,653
tive, both plant types can be considered for low- STPD).
er capacities. The ATR technology is competi-
tive from well inside the conventional SMR In comparison, the plot sizes of the ATR and the
capacities and clearly, it becomes the preferred secondary reformer are almost similar and cor-
choice at large capacities because of its refer- responds to less than 5% of the plot size of the
enced single line capacity above 3,500 MTPD SMR.
(3,858 STPD) and the resulting benefits from
economy of scale to lower the CAPEX. Where
oxygen is available over the fence, the ATR
technology is even more attractive from a
CAPEX point of view.

Detailed studies show the following additional

advantages of Topsoe’s ATR based reforming
units:
1. 3% lower SNEC, which is a very significant
OPEX benefit.
2. Up to 50% make-up water savings, which is
especially important in areas where water is a
scare resource.
3. An average availability above 99% of the Picture 2. SMR based reforming section with
ATR reforming unit. secondary reformer, 1,500 MTPD (1,653 STPD)
ammonia plant

It is critically important to stay within the com-

mercially available standard sizes for equipment
and piping. Exceeding these can be expensive
because this will limit the number of possible
vendors and increase cost with a scaling factor
exceeding one. Picture 3 illustrates how large
the piping sizes can be.

Haldor Topsoe’s ATR based plant offers unique

benefits which make the plant live up to such
prerequisites. The most significant differences
between a traditional SMR based plant and an
ATR based plant is the S/C ratios, where the
Picture 1. ATR with an equivalent capacity of traditional SMR based plants operate at S/C ra-
more than 6,000 MTPD (6,613 STPD) of am-
monia

2017 163 AMMONIA TECHNICAL MANUAL

 tio around 3 and an ATR based plant operates at synthesis section, the new ATR layout uses a
S/C ratio around 0.6. single S-300 ammonia converter in a standard,
Consequently, steam throughput decreases by well-proven Haldor Topsoe ammonia synthesis
80%. The ATR based plant also benefits from loop with single pressure level. More important-
an inert free ammonia synthesis with the re- ly, today the required converter size is already
quired nitrogen admitted just upstream of the well referenced with ammonia converters hav-
ammonia synthesis section, whereas the conven- ing a catalyst volume above 150 m3 (5,300 ft3).
tional plant introduces the nitrogen in the re- For information, an inert free 4,000 MTPD
forming section. (4,409 STPD) ammonia synthesis loop in an
ATR based plant will require only 105 m3
These features enable significantly reduced pipe (3,700 ft3) of catalyst.
and equipment sizes not only in the frontend (re-
forming, shift and CO2 removal sections), but
also in the backend (ammonia synthesis section) Technology
including a smaller synthesis gas compres- Haldor Topsoe’s ATR technology operating at
sor/recirculator, ammonia converter and high- S/C ratio of 0.6, has already been described in
pressure heat exchangers. A further advantage details, please refer to “References”, during the
of the inert free synthesis gas is that a purge gas last 15 years. Without any further changes, this
ammonia wash and hydrogen recovery unit is technology can be used as a synthesis gas gen-
not required. erator in an ammonia plant. In fact, the ATR
technology is very well suited as a synthesis gas
hub supplying synthesis gas to ammonia, meth-
anol, GTL, CO and other synthesis gas consum-
ing processes. The ATR reactor design consists
of a burner, a combustion chamber, target tiles,
a fixed catalyst bed, a catalyst bed support, a re-
fractory lining, and a reactor pressure shell as
illustrated in Figure 2.

Picture 3. Large sizes of piping and valves can

make a considerable impact on CAPEX.

The design of the inert free ammonia synthesis

Figure 2. Topsoe’s ATR reformer
loop provides another huge advantage. Where
other large-scale designs require multiple pres-
sure levels and multiple reactors in the ammonia

AMMONIA TECHNICAL MANUAL 164 2017

 Figure 3. Simplified process sheet of Topsoe’s ATR based ammonia plant

The ATR based ammonia technology is not only Shift section - by-product formation close to
about a change in reforming technology. Reduc- zero
ing the reforming S/C ratio from 3 to 0.6 has a
huge impact on the entire process scheme. This The conventional plant based on tubular reform-
calls for innovative re-design of various plant ing has a shift section containing a high temper-
sections, the main challenge being a workable ature shift step followed by a low temperature
shift section. shift step. A standard high temperature shift us-
es
With the ATR based ammonia technology the a Fe/Cr based catalyst that cannot operate at S/C
use of two high temperature shift reactors in se- ratio below 2.6. To overcome this limitation,
ries, a nitrogen wash to remove the CO, and re- Haldor Topsoe installed the first charge of SK-
cycling of shift by-products has resulted in nu- 501 FlexTM in an industrial plant in 2014.
merous benefits such as by-product formation The temperature profiles from the HTS reactor
being reduced close to zero. Several conven- at the industrial reference (Figure 4) show that
tional process steps such as methanation, purge SK-501 Flex™ is successfully resistant to poi-
gas recovery, ammonia absorption and hydrogen sons, at start-of-run and after 28 months of op-
recovery become obsolete, thus resulting in less eration.
need of compressor/recycle power and signifi-
cantly reduced sizes of high-pressure equipment
and piping.

Figure 3 shows the main process steps for the

new ATR based ammonia plant, and Table 1
provides a comparison of the main differences
between a conventional ammonia plant and the
ATR based ammonia plant. Figure 4. HTS reactor: Temperature profiles

2017 165 AMMONIA TECHNICAL MANUAL

 The SK-501 FlexTM in itself is a game changer loop where it acts as an inert and it builds up if
based on promoted zinc aluminum spinel, which not purged out. A high content of inert requires a
can operate at very low S/C ratios at typical high rate of purge gas. When ammonia has been
high temperature shift conditions, but without washed out, the purge gas is used as fuel in the
risk of mechanical integrity or by-products as- tubular reformer. Hydrogen is partly recovered
sociated with a Fe/Cr catalyst. This catalyst en- and recycled to the synthesis loop.
ables a shift section that perfectly matches the
S/C ratio of 0.6 in the ATR based design. In the ATR based process, a nitrogen wash re-
places the conventional steps for methanation,
In conventional plants, the iron based high tem- ammonia wash and hydrogen recovery. The ni-
perature shift catalyst sets the minimum allowa- trogen wash removes both the slip of CO from
ble S/C ratio for the shift section. When the S/C the shift section and the CH4 slip from the re-
ratio is lowered to 0.6, three factors limit the forming section. The off gas from the nitrogen
shift section, i.e. the required water content to wash can be used as fuel without any further
perform the shift reaction, the acceptable CO treatment. This design generates an inert free
slip, and the formation of by-products. synthesis gas, which provides benefits in terms
of less need of compressor/recycle power and
An efficient solution to these limitations is the significantly reduced sizes of high-pressure
introduction of a second shift operated at medi- equipment and piping.
um to high temperature in combination with re-
circulation of steam from the process conden- The well-known issue of undesired shift by-
sate stripper. Depending on the specific product formation links closely to S/C ratio and
requirement, the catalyst in this second shift can temperature. The amount of by-products in-
either be SK-501 FlexTM or a Cu based catalyst. creases at low S/C operation, and especially the
formation of the main by-product, methanol in-
In conventional plant designs, the slip of CO is creases at low temperature.
converted to methane in a downstream methana-
tor. This methane goes to the ammonia synthesis

*) An equivalent production of 4,000 MTPD

Table 1. Comparison of main differences between a conventional and an SMR based ammonia plant

AMMONIA TECHNICAL MANUAL 166 2017

 The ATR operates at low S/C ratio, but a high are cost efficient and the process technology
temperature is accepted as long as the CO slip is well proven.
kept at an acceptable level. This is part of the
reason for selecting only high temperature CO2 removal and nitrogen wash – inert free
shifts. synthesis gas
Topsoe has successfully designed the new pro-
cess to reduce by-product formation to practical- The CO2 removal unit in an ATR based ammo-
ly zero. An innovative and simple solution that nia plant can be a standard commercial solution.
recycles the by-products achieves this. However, it is an advantage to remove CO2 to a
lower level than in a conventional plant, as re-
After the shift section, by-products will be part- maining CO2 will have to be removed by a
ly condensed out together with the process con- downstream drier unit. The CO2 absorber is
densate. Further amounts of by-products can be relatively smaller than for conventional design
washed out of the synthesis gas to the level re- because no nitrogen is added to the synthesis
quired. The solution also eliminates the well- gas.
known problem of especially methanol entering
the CO2 removal section in conventional process After the CO2 removal section, the synthesis gas
layouts. The process condensate and washing contains mainly H2 with CH4, Ar, CO, CO2 and
water, which contains the by-products from the H2O. At first, CO2 and H2O is removed in a syn-
shift, flows to a process condensate stripper, thesis gas drier unit and then CH4, Ar and CO
where practically all shift by-products are are removed in a nitrogen wash, in which N2 is
stripped off. admitted to the synthesis gas to adjust the hy-
The resulting stripper steam, which now con- drogen to nitrogen ratio to the level required by
tains the by-products from the shift, is recycled the ammonia synthesis. This results in an inert
to the synthesis gas inlet at the high temperature free ammonia synthesis gas, and that makes a
shift section. This has several advantages: purge gas ammonia wash and hydrogen recov-
• The main by-product formation is by equi- ery unit obsolete.
librium reactions. Adding an equilibrium by-
product component to the feed of an equilib- Plant reliability and availability – excellent
rium byproduct generator, such as a shift re- track record demonstrated
actor, will stop further formation of that To meet very competitive industrial require-
component. The main shift by-product, ments in large-scale plants, where each added
methanol, is formed by an equilibrium reac- day of operation can be worth more than one
tion. million euros, plant reliability and availability
• Dissolved synthesis gas in the process con- are of utmost importance. Topsoe’s ATR based
densate returns to the process. reforming units have demonstrated availability
• The stripper steam will increase the S/C in factors greater than 99% as an average over op-
the shift section. Even if this is not strictly erating periods exceeding 5 years.
necessary, it reduces the CO slip, making
the net effect of the recycling positive. Environmental impact – potential CO2
The process concept based on two high tem- reductions
perature shift reactors in series, a nitrogen wash The environmental impact of a process is an in-
to remove the CO, and recycling of shift by- direct safety element. Release of greenhouse
products has solved all the challenges in design- gases and other contaminants has an impact on
ing a workable shift section of a low S/C ATR people’s health and safety. The overall energy
based ammonia plant. The involved solutions consumption figures for an ATR based design is

2017 167 AMMONIA TECHNICAL MANUAL

 up to 3% lower than for the conventional design • The ASU is within referenced size up to a
and a considerable part of the energy does not capacity above 6,000 MTPD (6,613 STPD).
need to come from fossil fuels. The power for
the air separation unit can come from sustaina- A review of the above list shows that the pro-
ble resources, thus reducing the CO2 re- cess equipment of the ATR based ammonia
lease/MTPD of product considerably. See table plant is referenced up to an equivalent capacity
2. of 4,000 MTPD (4,409 STPD) and that a capaci-
ty above 6,000 MTPD (6,613 STPD) is possible
by accepting proven references from other in-
dustrial processes.

Safety
Table 2. Potential reduction in CO2 emission
The most important parameter when designing
and operating an ammonia plant is safety, both
Proven design in terms of personal safety, environmental im-
pact and process reliability. All new design
A main criterion for the development of the work needs to address these key issues.
ATR based process has been to utilize known
and industrially proven process steps and The ATR based plant significantly improves all
equipment. three parameters. It offers several benefits that
• The low S/C ATR reforming concept has make it inherently safer than conventional plants
been in industrial operation since 2002 and and it has the potential to bring down the num-
it is referenced up to an equivalent ammonia ber of days with lost production significantly.
capacity above 6,000 MTPD (6,613 STPD).
• The high temperature shift reactors are with- Personal safety and fieldwork
in referenced size at a capacity of 4,000
MTPD. The main difference between the conventional
• Topsoe’s SK-501 FlexTM catalyst has been and the ATR based process design is the reform-
in industrial operation since 2014. ing section. It is well known that tubular reform-
• The CO2 removal section is within refer- ing involves a great deal of manual operation in
enced size at an equivalent ammonia capaci- the field, and that it can be difficult to imple-
ty above 6,000 MTPD (6,613 STPD). ment and maintain a comprehensive Safety In-
tegrated System (SIS) for this technology for the
• The synthesis gas drier and wash section is
same reason. Scaling up the conventional tubu-
industrially proven and available from a
lar reforming capacity does not change this situ-
number of suppliers.
ation. The amount of work in the field will in-
• The synthesis gas compressor/turbine is
crease and more field operators will be required.
within referenced size at an ammonia capac-
ity of 4,000 MTPD (4,409 STPD). Larger
compressors/turbines are in industrial opera-
tion in other industries.
• The ammonia converter is within referenced
size up to a capacity above 4,000 MTPD
(4,409 STPD).
• The refrigeration compressor is within refer-
enced size up to a capacity above 4,000
MTPD

AMMONIA TECHNICAL MANUAL 168 2017

 tional requirements to be satisfied before start of
an activity in order to safeguard the plant.
The ATR itself requires no fieldwork during op-
eration. Typically, in every work shift only a
plant walk-through is necessary to perform sur-
face monitoring and alternatively, camera sur-
veillance can replace the human surface moni-
toring of the ATR shell.

An ATR based plant still requires some field-

work, but much less than a conventional plant
with tubular reforming and more importantly, it
Picture 4. Manual inspection of tube tempera- does not increase in a similar way when scaling
ture in a tubular reformer up capacity. The difference in fieldwork be-
A large part of the manual fieldwork relating to tween large scale tubular reforming and ATR
tubular reforming, regardless of its type, is re- could be as much as 2 to 3 persons in favor of
quired to avoid unplanned shutdowns, tube rup- ATR.
tures and to secure continuous performance. An ATR based plant therefore reduces the num-
ber of Lost Time Incidents, simply because less
The replacement of a tubular reformer with an people are prone to accidents. Fieldwork can
ATR reactor has many additional installation turn into control room work with more time
and operating advantages: spent proactively to optimize performance. See
Picture 5.
- Tube ruptures no longer exist, and the risk of
unplanned shutdowns decreases.
- The required amount of fieldwork significantly
decreases, since field measurements are no
longer required.
- Human interaction with the reformer no long-
er exists.
- The required skill sets will be different and the
dependence on the procedures, tools and fre-
quency for tube measurements is no longer pre-
sent.
- The needed amount of surveillance data is
much less for one reactor, and data quality im-
proves significantly due to a simpler automated Picture 5. Safer working environment with time
process. to optimize performance
The ATR based design incorporates a complete Process reliability
integrated SIS, which is in place during startup,
normal operation and shut down. The control A higher degree of automation has a hugely pos-
system will guide plant operators, thus ensuring itive impact on safety and reliability. It reduces
safe operation in all operating modes, and a the risk of human error considerably simply be-
permissive system ensures that no mistakes are cause of the reduced number of needed operator
made. The permissive system has a set of condi- interactions, and when interactions are required
by setting up strict permissives. This is a win-

2017 169 AMMONIA TECHNICAL MANUAL

 win situation since a reduced amount of human en equipment sizes and catalysts. Its process
errors result in less lost time accidents, increases steps are referenced to this capacity when ac-
the availability of the plant and thereby reduces cepting references from other similar industrial
the environmental impact by reducing flaring processes.
caused by erroneous upset situations.
The key benefits for plant owners utilizing the
Automation of the ATR plant operation also ATR based ammonia process include a huge
provides the possibility to establish remote op- leap towards economy of scale in combination
eration which can provide the benefit of less er- with significant OPEX improvements through
rors and more efficient operation. The net result lower specific net energy consumption, high re-
is a higher general safety level and a better bot- liability and uptime, lower requirements for op-
tom line. erators and reduced maintenance.
Because of the resulting benefits from economy
Environmental impact of scale to lower the CAPEX, the ATR based
ammonia process clearly becomes the preferred
The SK-501 FlexTM catalyst provides the plant choice at large capacities. Adding to this, de-
with other benefits due to its complete absence tailed studies show 3% lower specific net ener-
of chromium, most notably the highly toxic gy consumption, a very significant OPEX bene-
hexavalent chromium found in iron-based HTS fit.
catalysts in the market. With SK-501 Flex™, A demonstrated average availability above 99%
plants avoid the potential risk that hexavalent of Topsoe’s ATR based reforming units sup-
chromium poses to personnel safety and to the ports its competitiveness.
environment during product handling and dur-
ing operation. By avoiding this risk, plants also The process is an inherently safer process than
reduce the possibility of unplanned and costly the conventional. Using Haldor Topsoe’s ATR
downtimes as well as long-term liability issues. technology requires much less fieldwork than a
conventional plant with tubular reforming and
Conclusion more importantly, it does not increase in a simi-
lar way when scaling up capacity. It is a more
The introduction of the ATR based ammonia automated process safeguarded by the control
process will allow plant owners to benefit from and safety system, reducing the number of pos-
an innovative and very competitive technology sible human errors.
application defying existing single line plant ca-
pacity limits. Combined with less environmental impact, the
above is an answer to required improvements on
Conventional ammonia process technology still general safety issues and the reason for the ATR
has a merit for many years to come. It is a fully based ammonia process technology becoming
optimized and refined technology, but it loses plant owners’ preferred choice in future plants.
competitiveness for large-scale capacities due to
its scaling exponent and at the same time be-
comes increasingly difficult to operate in terms
of control, safety and maintenance regardless of References;
the specific type of tubular reformer [1] T.S. Christensen, I. I. Primdahl, Hydcar
Proc., 73 (1994) 39
The ATR based process enables ammonia plants [2] W.S. Ernst, S.C. Venables, P.S. Christensen,
with single line capacities above 6,000 MTPD A.C. Berthelsen, Hydcar Proc. 79(3), 2000,
(6,613 STPD) solely based on industrially prov- 100C.

AMMONIA TECHNICAL MANUAL 170 2017

 [3] K. Aasberg-Petersen, T.S. Christensen, I.
Dybkjaer, J. Sehested, M. Østberg, R.M.
Coertzen, M.J. Keyser and A.P. Steynberg. .
“Synthesis gas production for FT synthesis”,
Stud. Surf. Sci.Cat. 152, (2004), 258
[4] P.J.Dahl, T.S. Christensen, S. Winter-
Madsen, S.M. King, “Proven autothermal
reforming technology for modern large-scale
methanol plants“, Proc. Nitrogen+Syngas
2014 conference, Paris, February 2014.
[5] “Process burners for syngas production”, Ni-
trogen+Syngas, 305, May-June 2010, 37
[6] T.S. Christensen, J.R. Larsen, L.J.Shah, M.
Stenseng, “Market-leading developments for
oxygen-blown secondary and autothermal
reformers”, Proc. Nitrogen+Syngas 2017
conference, London, March 2017
[7] ATR movie: www.topsoe.com

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