Clean Hydrogen Production from SMR

Trapti Chaubey*1, Paul Terrien1, Solene Valentin2, Dennis Vauk3, Jean-Pierre Tranier2
and Uttam Shanbhag1
1
Air Liquide Delaware Research & Technology Center, Newark, DE, USA
2
Air Liquide Claude Delorme Research Center, Jouy en Josas, France
3
Air Liquide Energy Market, Houston, TX, USA
*T: +1-302-286-5450, F: +1-302-286-5583, E: Trapti.Chaubey@airliquide.com
ABSTRACT
Steam Methane Reformer (SMR) is commonly used to produce hydrogen, carbon
monoxide and syngas from fossil fuels. The production of hydrogen is associated
with carbon dioxide (CO2) emission into the atmosphere. Hydrogen plants represent
one of the largest single sources of CO2 emissions in a typical refinery. For this
reason, improving their design and operation has become critical for energy
producers, even more so under a possible future CO 2 cap and trade environment.
With the integration of Lurgi, Air Liquide group has acquired vital expertise in the
design and engineering of syngas and hydrogen plants. Together, Air Liquide and
Lurgi have developed innovative technologies to reduce CO 2 emissions and to
improve the reliability, availability, efficiency and capital costs of hydrogen plants.
Carbon dioxide emission from hydrogen plants can be reduced using several
different separation techniques to extract CO 2 from the flue gas, syngas or PSA offgas. The captured CO2 can be further compressed, transported and sequestered for
under-ground storage, used for enhanced oil recovery or for industrial and consumer
applications. Air Liquide is using its extensive experience in gas separation and
purification processes such as cryogenic, absorption and membrane to develop low
cost CO2 capture technique. The selection of capture technology will depend on the
composition of feed gas, electricity cost, steam cost and the carbon tax for the
hydrogen plants.
INTRODUCTION
Hydrogen is widely used in a refining and petrochemical industry for several different
processes like hydro-cracking, hydro-treating, numerous hydrogenation reactions
etc. It is commonly produced in a steam methane reformer as shown in Figure 1. The
hydrocarbon feed stock undergoes pre-treatment to remove sulphur in order to avoid
catalyst poisoning. The highly endothermic reforming reaction occurs at a high
temperature of 800-950C and pressure of 290-500 psi. The heat for the reforming

reaction is provided by the combustion of fuel gas (natural gas and PSA off-gas) with
air in the combustion zone producing flue gas laden with CO 2. The reformation of
natural gas and steam results in product termed as synthesis gas (syngas) that
comprises H2, CO, CO2 along with un-reacted methane and steam. The heat
available from the high temperature syngas and flue gas is used to heat boiler feed
water to produce steam required for the reaction along with some surplus quantity of
steam for export. The syngas from the steam methane reformer is further sent to the
water gas shift (WGS) reactor to produce additional hydrogen from the oxidation of
CO to CO2. During this process, carbon dioxide content increases in the syngas
downstream of the WGS reactor. The product gas from the WGS reactor is treated in
a Pressure Swing Adsorption (PSA) unit to recover nearly pure H 2 product. The CO2
in the syngas is discharged as part of the PSA off-gas. This PSA off-gas is typically
sent to SMR as fuel since it contains un-reacted methane, CO and some hydrogen.

Figure 1. Schematic of Hydrogen plant based on SMR

CO2 CAPTURE TECHNOLOGIES
Air Liquide offers various different separation and purification technologies for
industrial gas applications. The choice of capture technologies depends on several
factors including cost of capture, recovery rate of CO 2, utility consumption, utility cost
etc. Air Liquide/Lurgi is evaluating several capture solutions from hydrogen plants to
reduce CO2 emissions. Table 1 shows the CO 2 content and total pressure of different
gas streams from the hydrogen plant.
Table 1. CO2 content and Total Pressure for different gas streams in SMR plant
Gas Stream
Typical CO2 content
Total Pressure
Syngas after SMR
5-10%
290 500 psi
Syngas after WGS
15-20%
290 500 psi
PSA Off-gas
45-50%
<30 psi
Flue Gas
20-25%
<30 psir

The CO2 capture technologies using amines, cryogenics and membranes have been
developed to produce clean hydrogen product. Syngas as produced from the SMR
was not considered as a potential capture location because of low CO 2 partial
pressure and offers no potential advantage over treating syngas after the WGS
reactor. Figure 2 shows the CO2 capture technologies favorable for different CO2 inlet
composition and product purity. Amine based absorption solution can be used for low
CO2 content in the inlet stream either upstream of the SMR Pressure Swing
Adsorption unit or on Flue gas from the SMR unit. The cryogenic capture solution
can capture CO2 from the PSA off-gas because of higher CO2 content. Membranes
are typically used on a high pressure stream because of higher separation efficiency.
The flux across the membrane can be increased by increasing the differential
pressure across the membrane. Membranes can be used as an add-on module to
the non-condensable stream from the cryogenic unit to increase hydrogen
production.

Figure 2. CO2 capture technologies

Amine based Absorption Solution

Figure 3. Amine solution for CO2 Capture from syngas or flue gas
Amines like Mono ethanol amine (MEA) or activated Methyl Di-ethanol amine
(aMDEA) are commonly used to chemically absorb CO2 from flue gas or syngas.

More than 50% of Air Liquides HYCO (H2 and CO co-production) plants are
operating with amine units to remove CO 2 from syngas. Figure 3 shows the amine
based absorption solution to capture CO 2 from syngas or flue gas. Amine solvents
absorb CO2 in a packed bed absorption column with CO 2 lean gas exiting the top of
the bed. CO2 rich amine solvent is regenerated in the stripping column at high
temperature to release CO2 and recycle the lean solvent back into the absorption
column. Amines have been evaluated on syngas for partial CO 2 capture and on flue
gas for complete CO2 capture. Amines were not evaluated on PSA off-gas, since the
amount of CO2 present in syngas after WGS reactor is same as the PSA off-gas but
is available at higher pressure prior to the PSA.
Cryogenic Solution
A Cryogenic CO2 capture system has been developed by Air Liquide and is being
offered as a CO2 Compression and Purification Unit (CO 2 CPU) as shown in Figure
4. Air Liquides first demonstration unit is under construction to capture CO 2 from a
power plant in Australia. CO2 CPU requires higher CO2 content in the feed gas and
the PSA off-gas was evaluated as a potential location for the CO 2 capture using
CPU. The CO2-CPU consists of a series of unit operations, the first being
compression of the gas to a high pressure using several stages of centrifugal
compressor. The final outlet pressure may range from 450 psi to 1500 psi. The high
pressure gas is partially condensed to separate non-condensable gases from liquid
CO2. The CO2 rich stream is further purified in a distillation column. Furthermore, the
non-condensable gas stream is sent to SMR as fuel.

Figure 4. CPU solution for CO2 capture from PSA off-gas

Cryogenics and membrane Solution

Figure 5. CPU & Membrane solution for CO2 capture from PSA off-gas
Air Liquide MEDALTM offers commercial gas separation membranes. Figure 5 shows
the schematic for capturing CO2 from PSA off-gas using CPU in combination with a
membrane. The non-condensable gas from the CO2-CPU is rich in hydrogen. A
membrane unit may be used to treat the non-condensable gas to separate H 2/CO2
from CO/CH4. The H2/CO2 stream may be sent to the H 2 PSA to boost hydrogen
production while the CO/CH4 stream may be recycled back to SMR as fuel. Another
advantage of this scheme is that it can be used for retrofit to increase the hydrogen
production of an existing plant while capturing CO2.
NEXT GENERATION SMR
Air Liquide/Lurgi together is optimizing its SMR plants to reduce overall CO 2
emissions while simultaneously increasing plant reliability and efficiency. The design
of the pre-reformer, the reformer furnace and the shift section has been optimized to
reduce CO2 emissions prior to capture while increasing the rate of capture. With
continuous improvements, the average energy consumption of Air Liquides HYCO
plants has decreased over 5% between 2003 and 2008 causing reduced CO 2
emissions (1) Lurgis Top fired Reformers has an advantage of high temperature
applications up to 950C and a range of small to large world-scale capacities. The
strength of their design is a high plant efficiency and reliability, optimized turn around
cycles, broad product and feedstock ranges, low utility consumption and low
investment and maintenance cost (1). The next generation of Lurgi Reformers
designed with CO2 capture will be able to capture from 63% to 92% of the produced
CO2.
RESULTS
CO2 Recovery
The recovery of CO2 separation and purification units is shown in Table 2. All capture
solutions have high recoveries typically >90% from the treated gas stream. The
overall recovery of the CO2 unit depends on the percent of total CO2 available in the
gas stream for capture. It is interesting to note that the overall CO 2 recovery was
slightly lower for the CPU with membrane solution albeit with a higher hydrogen
production.
Table 2. CO2 recovery using different separation techniques

Energy Requirement for CO2 capture

CO2 capture solutions like amine and CPU need electricity for compression and
steam for regeneration. Figure 6 shows the relative stream and electricity
requirement for the different applications outlined in Table 2. The steam requirement
for amines solution is high because of the high regeneration energy. The low partial
pressure of CO2 in flue gas results in a higher steam requirement for amine
regeneration. The steam and electricity requirement for both CPU cases (with and
without membrane) is the same. The electricity requirement for the amine treatment
of syngas and flue gas is the same since it is employed to compress CO 2 to the final
product pressure for sequestration (typically 2175 2540 psi). The electricity
requirement for CPU is relatively higher because of the additional energy required to
compress feed stream with non-condensable prior to purification.

Figure 6. Specific steam and electricity requirement for different separation

techniques
CO2 Capture Cost

Figure 7. CO2 capture cost

The overall CO2 capture cost plays an important role in the selection process of the
capture technology. Figure 7 shows the CO2 capture cost per short ton of CO2
produced versus the rate of CO2 captured. This cost will include capture,
compression and drying. It does not include transportation or sequestration as these
costs will vary from project to project. CPU on PSA off-gas or Amine on Syngas have

lower capture rate at lower cost compared to Amines on Flue gas that provide a
higher capture rate at a correspondingly higher cost. As the CO 2 capture on syngas
or PSA off-gas is more cost effective, the Next Generation SMR was optimized to
shift more CO2 production from combustion to syngas. This way the cost of CO 2
capture is reduced and overall capture rate can be increased for capture solutions on
syngas or PSA off-gas. Typical CO2 cost for capturing 63% to 73% CO2 produced by
such a large SMR would cost between $30 to $40/short ton.
SUMMARY
Air Liquide/Lurgi offers a wide portfolio of CO2 capture technologies including
absorption, cryogenic and membrane. The selection of capture technology depends
on several factors including the feed stream conditions (CO 2 content, pressure,
temperature), CO2 recovery of capture unit, electricity and steam requirement, cost of
electricity and steam and overall capture cost. Air Liquide/Lurgi have used their
experience to optimize the next generation of steam methane reformers specifically
designed to reduce CO2 capture cost and increase CO2 capture rate.
REFERENCES
1. Vauk, D., Kuttner, H., Impact of Greenhouse Gas Legislation on Hydrogen
Plant Design and Operation, NPRA 2010 Annual Meeting AM10-143
2. Nazim Z. Muradov, T. Nejat Veziroglu; Green path from fossil-based to
hydrogen economy: An overview of carbon-neutral technologies, International
Journal of Hydrogen Energy 33 (2008) 6804-6839
3. Vauk, D., Kuttner, H., Hydrogen Management in a CO2 Constrained
Environment, ERTC 14th Annual Meeting, Berlin, November 2009
4. Chaubey, T., Terrien, P., Valentin, S., Tranier, J-P., Shanbhag, U., Comparison
of CO2 capture technologies on hydrogen plants, Ninth Annual Conference on
Carbon Capture and Sequestration, May 2010
KEYWORDS
Hydrogen, Steam Methane Reformer, CO2 Capture, Amine, Cryogenic, Membrane,
CPU, HYCO, Syngas, Carbon tax