Increased steam

methane reformer
throughput
 Increased steam
methane reformer
throughput
Marie Basin and Daniel Gary, Air Liquide
William Whittenberger and Jumal Shah, Johnson Matthey

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© 2018 Johnson Matthey group

2 Johnson Matthey
Reprinted from Petroleum Technology Quarterly, Catalysis 2017
Switching to a foil based catalyst technology raised
throughput substantially for a hydrogen producer

Air Liquide delivers hydrogen and carbon monoxide to a Roussillon SMR unit
wide range of companies in the refining and chemicals
indus­try by operating more than 50 steam methane The Air Liquide SMR plant in Roussillon was started up
reformer (SMR) units worldwide. Each unit is designed to in 2010 (see Figure 1). It includes the following units: a
respond to demand which can vary over time. Amongst its hydrodesul­phurisation unit, a reformer that comprises 12
fleet, Air Liquide has a 12-tube SMR in Roussillon, France. reformer tubes with a diameter of 5in and one burner,
The plant’s nominal hydro­gen capacity was reached with a CO shift reactor, and a PSA unit for final product
conventional reform­ing catalyst and could not be increased purification. The plant operates with a natural gas feed and
any further due to the limitation of the reformer flue gas has a nominal capacity of 2450 Nm3/h of hydrogen with
temperature. However, in 2015 the customer foresaw conventional catalyst.
an increase in its hydro­gen consumption. Accordingly,
Air Liquide was required to investigate solutions to The production rate was constrained by a high flue gas
debottleneck the plant. exit temperature which was close to its maximum value
of 1000°C. This high flue gas temperature prevented
Air Liquide approached Johnson Matthey which has been increasing the process gas exit temperature.
involved in the development of steam reforming catalysts
for many decades. Johnson Matthey identified its recently Figure 1. Air Liquide
com­mercialised CATACELTM SSRTM as a possible solution. steam methane
This next generation reforming catalyst is a coated, foil reformer unit in
based alternative to metal impreg­nated ceramic pellets. Roussillon, France
Simulations suggested the enhanced heat transfer, activity
and pres­sure drop properties would allow the reformer
throughput to be increased by the desired rate. In August
2015, the conventional pelleted cat­alyst was entirely
replaced by CATACEL SSR, with the objective of increasing
the production rate by 5%.

Johnson Matthey 3
Reprinted from Petroleum Technology Quarterly, Catalysis 2017
 CATACEL SSR The stacked fans deliver supe­rior heat transfer by
impinging gas on the internal surface of the reforming
For many years, catalyst impregnated ceramic pellet tube rather than rely­ing on convective heat transfer
media has driven steam methane reform­ing reactions mechanisms. During operation, gas flows down the tube
in hydrogen, methanol, and ammo­nia plants. Steam and encounters the first fan struc­ture. It cannot move
reforming catalyst design is a balance between many through the fan and therefore it is forced out of the
competing require­ments and catalyst features such triangular ducts. The process gas thus jets directly onto
as strength, heat transfer, activity, pressure drop and the internal surface of the reformer tube, where it gathers
avoidance of unwanted side reactions such as carbon heat. Having nowhere else to go, the gas flows around
formation. By adopting a foil based structure, CATACEL the edges of the fan and back into the triangular duct on
SSR breaks away from many of the lim­itations imposed the under­side of the fan (see Figure 3). The washers that
by the use of ceramic pellets. It is a catalyst system that separate the fans from one another facilitate this flow back
exhibits a higher activ­ity, improved heat transfer, lower into the fan. Once inside the fan, the gas is free to move to
pressure drop and improved resistance to carbon formation the next fan in the stack and repeat the process.
all at the same time. Performance of this technology has
been proven in the hydrogen market since May 2012.1 The features of CATACEL SSR result in approximately 20-
30% more heat transfer for the same (or lower) pres­sure
CATACEL SSR uses a special high temperature alloy as a drop when compared to traditional catalyst pellets. In
substrate material. Alloy strip is formed into engineered addition, the fans offer 1.5 to 2.0 times more geometric
foil structures called fans (see Figure 2). The fans are surface area than conventional pellets. Thus it provides
coated with a nickel based steam reforming catalyst a step change in the achievable performance from
using a proprietary process that ensures the catalyst conventional pel­leted steam reforming catalyst. Figure
remains attached to the surface of the foil during the 4 shows a comparison of the different generations of
catalyst lifetime. The fans are stacked one upon another pelleted ceramic catalyst against CATACEL SSR.
in the reforming tube, separated by thin metal washers.
The outer edges of the fans are located close to, but not
touching, the internal surface of the tube.

Figure 2. CATACEL SSR fan (left)

and stack (right)

Figure 3. Gas forced out of duct

and back into the underside vents

4 Johnson Matthey
Reprinted from Petroleum Technology Quarterly, Catalysis 2017
 Increasing hydrogen throughput by increasing reforming temperature
Activity Conventional catalyst CATACEL SSR
Relative performance indicator Heat transfer
Flue gas temperature, °C 1000.1 997.5
Pressure drop
Reformer exit temperature, °C 816 828.5
S/C 3.24 3.1
Pressure drop, bar 0.68 0.51
Dry syngas flow rate, Nm3/h 4043 4178
Methane slip, mol% 6.7 6.2
Hydrogen production before PSA, Nm3/h 2965 3078
Hydrogen throughput, Nm3/h 2450 2490
Performances in capacity increase
Increase in syngas flow rate, % - 3.3
Increase in hydrogen before PSA, % - 3.8
Rings 4-hole Quadralobe CATACEL SSR
Tflue gas - Tsyngas , °C 184 169

Figure 4. Relative performances of various Table 1.

steam reforming catalysts

Installation at Roussillon Increasing hydrogen throughput by increasing

reforming temperature
CATACEL SSR is
supplied as preassebled The enhanced heat transfer provided by CATACEL SSR
stacks up to a metre allows additional burner firing to take place before the
long. The fans are maximum flue gas exit temperature is reached. Thus it is
mounted on a support possible to achieve a higher reformer exit temperature for
structure that sits within the same flue gas temperature. Consequently, following
the central space of the the instal­lation at Roussillon the methane conversion is
fans. This aids in the higher and the hydrogen production from the reformer
speed and accuracy of is improved. Table 1 compares the conventional catalyst
the catalyst installation. performances with that of CATACEL SSR for the maximum
flue gas tempera­ture allowed.
As previously described,
the outer edges of The increased capacities in syngas and hydro­gen
each fan must be production before purification (by pres­sure swing
located close to but adsorption, PSA) are 3.3% and 3.8%, respectively,
not touching the inside compared to former operation. The increase in dry syngas
tube surface and each flow rate is in line with predictions. Besides, this capacity
stack must rest directly over the stack below without any enhancement is achieved at a lower reformer pressure
gaps that could create hot spots. However, the internal drop than with conventional catalyst: 0.51 bar instead of
surfaces of reformer tubes can be quite irregular, especially 0.68 bar.
on plants that have been in service for some time. Hence
the installation of CATACEL SSR is managed using patent The heat transfer enhancement by CATACEL SSR is also
protected deployment technology that forms part of the highlighted by the lower difference between syngas and
support structure along with patent protected installation flue gas temperatures com­pared to conventional catalyst:
tools and methodologies. initially 184°C, reduced to 169°C.

During the installation at Roussillon, each stack of fans

was inserted in a compressed con­figuration and engaged
with the stack (or sup­port) below. Using compressed air, it
was then expanded to bring the fan edges into the correct
position versus the tube wall. Deposition was observed
on the wall of some tubes but it was scraped off and did
not inhibit the loading. The installation was completed
according to schedule. Outage and pressure drop
measurements during and on completion of the loading
confirmed each stack had successfully interlocked with the
stack below.

Johnson Matthey 5
Reprinted from Petroleum Technology Quarterly, Catalysis 2017
 Increasing hydrogen throughput by increasing Performance over a year in operation
plant load
A year of operation with CATACEL SSR was achieved
The previous case clearly indicates that addi­tional burner without any incident. Data was collected from September
firing is possible thanks to CATACEL SSR. The increased 2015 until September 2016 to compare with the
hydrogen production is achieved through a higher performance of pellets over the year 2014. Plant loads
reformer exit tem­perature and thus a higher methane for both time periods are shown in Table 3. As can be
conver­sion. However, the hydrogen production of the unit seen, the plant was operated at more than 100% load
can be increased more substantially by also increasing (with respect to dry syngas production) with the cat­alyst
the plant load in addition to increas­ing burner firing. for an extended period of time. Obviously, the plant load
Table 2 summarises the per­formances of CATACEL SSR is dependent on the operator’s demand but the results
in this operating mode and compares it to operation with clearly show that a maximum increase of hydrogen
previous con­ventional catalyst under the limitation of the throughput by over 5% was successfully sustained.
maximum flue gas temperature.
Such an increase in produc­tion was possible because
In this operating mode, the syngas flow rate is increased the flue gas temperature at the reformer exit remained
by 6.3%. The hydro­gen throughput from the reformer is below the threshold of 1000°C, even at 106% load. Figure
5.7% higher. This capacity increase is achieved at a lower 5 shows the decrease of flue gas temperature when the
reformer pressure drop than with pellets: 0.57 bar instead plant is operated with CATACEL SSR compared to oper­
ation with conventional pellets. For a load range between
of 0.68 bar.
91% and 100%, the flue gas tempera­ture is decreased by
up to 7°C, giving a margin to increase the plant hydrogen
throughput.
Increasing hydrogen throughput by increasing plant load

Conventional catalyst CATACEL SSR The overall efficiency of the reformer and water gas shift
Flue gas temperature, °C 1000 1000 section can be assessed by con­sidering the total natural gas
Reformer exit temperature, °C 816 819 flow rate required to produce syngas. Figure 6 presents this
S/C 3.2 3.1
data for different plant loads. The savings on natural gas
Pressure drop, bar 0.68 0.57
Dry syngas flow rate, Nm3/h 4043 4299 with CATACEL SSR are high thanks to better conversion in
Methane slip, mol% 6.7 7.0 the reformer due to higher reforming temperatures, and
Hydrogen production before PSA, Nm3/h 2965 3135 lower fuel consumption due to increased heat transfer in
Hydrogen throughput, Nm3/h 2450 2553
the reformer. Savings are in the range of 3-4% for loads
Performances in capacity increase
Increase in syngas flow rate, % 6.3
between 80% and 105%, even reaching 5% at a load of
Increase in hydrogen before PSA, % 5.7 106%.
Tflue gas - Tsyngas , °C 184 181

Table 2.
CATACEL SSR Conventional catalyst
1000
Flue gas exit temperature, ºC

990
Plant load
980
Plant load range Pellets CATACEL SSR
(dry syngas production) (% of operating time) (% of operating time)
970
Below 50% 4.2 2.0
51-70% 6.3 2.3 960
71-80% 13.4 38.2
950
81-90% 19.0 18.1
91-100% 57.1 14.9
940
101-105% 0.0 19.8 81-90 91-100 101-105 106+
>105% 0.0 4.7 Plant load, %
-
Figure 5. Comparison of flue gas exit temperature for
various plant loads
Table 3.

6 Johnson Matthey
Reprinted from Petroleum Technology Quarterly, Catalysis 2017
Conclusions Collaboration between Air Liquide and Johnson Matthey
facilitated an understanding of the end user requirements,
Hydrogen is used in oil refin­eries, chemical plants and in identifying the existing bot­tlenecks and possible solutions.
clean transportation solu­tions. Due to changing market Although the SMR at Air Liquide’s Roussillon plant is
conditions there is a greater need to be able to operate tailored for conventional pelleted reforming catalyst, the
flexibly, robustly and efficiently to meet the user’s needs. benefits of the coated foil based structure to overcome the
As a world leader in gases, technology and services previously observed limit on flue gas exit temperature were
for industry and health, Air Liquide is always striving demonstrated. CATACEL SSR catalyst has and continues
to explore process improvements and thereby exceed to demonstrate that it is mechanically and chemically
customer expectations. robust over a range of operating conditions. Assessing the
reduction in total natural gas usage at different plant rates,
Steam reforming remains the dominant pro­cess for Air Liquide has been also able to val­idate the increased
the production of hydrogen. Despite being a mature plant efficiency and highlight the long term value. By
process there is still an opportu­nity to employ innovative employing the novel cat­alyst, the required 5% increase
technologies to drive improvement. Structured CATACEL in throughput was achieved successfully and without
SSR technol­ogy represents the next generation of steam incurring any capital cost to modify the plant equipment
reforming catalysts offered by Johnson Matthey, delivering as oth­erwise may have been necessary.
a significant improvement in perfor­mance compared to
traditional pelleted catalysts. Adoption of the catalyst has References
shown the bene­fits of cooler tubes with lower methane
slip and lower pressure drop. Whilst greater benefits may 1. Farnell P, Whittenberger W, Foil supported catalysts
be achieved with a reformer designed around the catalyst,2 deliver high performance in steam reformers, Nitrogen +
even for existing plants it can improve performance that Syngas 2015 International Conference, Istanbul, Feb 2015.
can then allow the unit limits to be overcome.
2. Whittenberger W, CATACEL SSR novel structured
CATACEL SSR Conventional catalyst
catalysts for high performance in steam reformers, PTQ
108 Catalysis, 31-33, 2015.
106
Marie Basin is a Research Engineer with Air Liquide
104
Research and Development. She is a chemical engineer
Plant efficiency

102 and graduated from École Nationale Supérieure des

100 Industries Chimiques (ENSIC Nancy, France) and Imperial
98 College London.
96
94
Daniel Gary is Senior International Expert in gas
production and gas purification with Air Liquide. He
92
81-90 91-100 101-105 106+ graduated from University Paul Sabatier Toulouse in
Plant load, % chemical engineering.
Figure 6. Plant efficiency (syngas flow/total natural gas
Jumal Shah is a Hydrogen Technologist with Johnson
flow) at various loads
Matthey in Billingham, UK. He holds a MEng in chemical
engineering from the University of Bradford.

William A Whittenberger is Site and Technology Director

with Johnson Matthey, which acquired the assets of Catacel
Corp in 2014. He co-founded Catacel in 2001. He holds a
bachelor’s degree in mechanical engineering from Ohio
State University, and a MBA from Pepperdine University.

Johnson Matthey 7
Reprinted from Petroleum Technology Quarterly, Catalysis 2017
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© 2018 Johnson Matthey group

1706JM/0718/0/ENR