SMR for fuel cell grade hydrogen

Affordable and sustainable production of blue hydrogen is key to the successful use of
fuel cells in transportation

KALPANA GUPTA, ISHITA AGGARWAL and MARUTHI ETHAKOTA

Technip India

W
orldwide, the transport
sector is one of the sig-
nificant contributors to Grey Hydrogen Blue Hydrogen Green Hydrogen
greenhouse gas emissions. In 2018, Energy Fossil fuels Fossil fuels Biomass Renewable
energy
global CO2 emissions increased by Themo-
CO2
2% worldwide and this has focused chemical
conversion
capture Water
Biomass
attention on decreasing these emis- processes Electrolysis
Coal Coal
sions by the transport sector. Production
gasification/SMR gasification/SMR Gasification
Still, there is a negligible contri-
bution of renewable sources to fuel Hydrogen
Hydrogen
the transport sector. Among alterna-
tive fuels, hydrogen is emerging as
a promising solution to decarbonise
Solid hydrogen Liquid hydrogen Gaseous hydrogen
transport, while in the power sector (chemical storage) at -253˚C
Transport
renewable energy has already taken & storage
a good share, but hydrogen’s share H2
is negligible. Transportation (Pipeline, Truck/rail, Ship)

Complete cycle of hydrogen

The complete chain of hydrogen As chemical As fuel
production, transport, storage, and Use

use is shown in Figure 1. Hydrogen

is produced mainly via three plat-
Ammonia/ Refinery Iron/ Power/ Heating for Transport
fertiliser steel/mining energy storage/ buildings (heavy motor
forms: thermal processes, elec- power
integration
and industry vehicles,
ships, planes)
trolysis, and biological processes.
Traditionally, hydrogen is produced
from fossil fuel by coal gasification Figure 1 Complete life cycle of hydrogen
and steam reforming. Globally, 48%
of hydrogen is produced by natural the fertiliser (30%), refinery (50%), Hydrogen production by SMR
gas steam reforming and 30% by oil metal processing and food, electri- The most reliable and efficient pro-
reforming. Of the remainder, 18% is cal and aerospace industries. The cess for hydrogen production is
generated by coal gasification, and next highest is the mobility sector. steam reforming of fossil fuels. SMR
only 1% of hydrogen is produced by Predicted demand for hydrogen as can be generally divided into the
green processes. a fuel is 4 million t/y by 2030. following steps: feed pretreatment,
Produced hydrogen is stored in Serious attention is given to pro- steam reforming, shift process, syn-
gaseous/liquid or metal hydride ducing low-carbon hydrogen. thesis gas cooling, and purification
form. Hydrogen need not be stored Indeed, green hydrogen with a zero (see Figure 2). The primary reaction
and transported in the case of carbon footprint is the future. With of reforming is strongly endother-
on-site generation and consump- technologies available for  CO2 cap- mic. The heat needed to drive the
tion, as in a refinery or fertiliser ture and storage, well-developed reaction forward is usually supplied
plant. At the same time, storage methods of hydrogen production by burning natural gas and thus pro-
and transportation is an integral such as steam methane reforming ducing CO2. Carbon monoxide (CO)
part of the use of hydrogen as fuel. (SMR) can be relied on for near- in the output stream from the pri-
Currently, hydrogen is utilised term developments. The reforming mary reaction is usually converted to
mostly as a chemical in various process, combined with CO2 capture CO2 via the water gas shift reaction
industries and refineries. Today, and storage, has emerged as a sus- to increase hydrogen production:
70  million t/y of produced hydro- tainable solution and is described in
gen is mainly used as a chemical in detail in this article. CH4 + H2O + heat ⇌ CO + 3H2 [1]

www.digitalrefining.com/article/1002563 PTQ Q4 2020 89

Steam
Steam CO2

Steam drum
CO2 capture

BFW

Steam

Desulphuriser Solvent
Reformer

Steam HT DMW
shift Preheat Hydrogen
Purification gas
Boiler unit
BFW
Preheat Cooler
Purge gas
Natural gas Separator to burners

Figure 2 SMR process with CO2 capture flow scheme

CO + H2O ⇌ CO2 + H2 + heat [2] SMR also has a small footprint per to DNV-GL1, “We will ultimately
tonne of hydrogen produced. move to a green hydrogen econ-
The reformed gas is cooled and omy. But we are convinced that you
routed to a shift reactor to max- Classification of hydrogen can make the step towards green
imise the hydrogen content. The Depending on the production hydrogen via blue hydrogen first.”
produced syngas is further cooled method and feed source, hydro- Hence blue hydrogen can be a sup-
and process condensate is sepa- gen is classified as blue, grey, or ply step between grey hydrogen
rated out. The reformed gas has an green hydrogen. Hydrogen from and green hydrogen. Production of
approximate composition of H2 74 coal, oil, and natural gas is grey blue hydrogen offers several advan-
mol%, CH4 7 mol%, CO 1 mol%, hydrogen. All of these non-renew- tages in the near to medium term as
and CO2 18 mol%, the exact propor- able sources and production meth- it utilises conventional, large-scale
tions depending on feed composi- ods, when integrated with a CO2 commercial hydrogen production
tion, operating conditions, and the capture unit, then produce blue pathways and infrastructure, with
selected process scheme. The gases hydrogen. Hydrogen produced 75% of global hydrogen production
are purified in the PSA section to from biomass, wind, solar, and relying on natural gas.
remove CO, CO2, and CH4 impuri- hydro-powered electrolysis is green Hydrogen as fuel is used in the
ties and produce grey hydrogen. hydrogen. Green hydrogen is typ- transportation sector in two ways:
To produce low-carbon ‘blue ically produced via electrolysis of as an internal combustion engine
hydrogen’, a carbon capture process water in which water is split into (ICE), or as a fuel cell electric vehi-
is integrated into the base scheme. hydrogen and oxygen. Dedicated cle (FCEV). The ICE has a disad-
A solvent based CO2 capture pro- ‘green’ hydrogen production elec- vantage in terms of nitrogen oxides
cess is illustrated in Figure 2. The trolysis remains a niche component or NOx formation, inefficiency,
captured CO2 can be used in a vari- of global hydrogen production. But higher maintenance, and unsafe
ety of industries. with renewable energy sourced operation.
SMR is an efficient, widely electricity costs on a downwards
used, and economical process. trajectory (from solar photovoltaics, Fuel cells
The efficiency of SMR and its spe- onshore, and offshore wind), focus A fuel cell is a device that generates
cific energy consumption are best and interest are growing. There electricity through an electrochem-
among current commercially avail- are three distinct types of electro- ical reaction, not combustion. In a
able hydrogen production methods. lyser: alkaline electrolysis, proton fuel cell, hydrogen and oxygen are
SMR is the most reliable technol- exchange membrane electrolysis combined to create electricity, heat,
ogy and has the highest availabil- (PEM), and solid oxide electrolysis and water. The fuel cell can produce
ity among all hydrogen production cells (SOECs). direct current (DC) power to run
methods. The process can be eas- an electric vehicle. There are many
ily integrated with CO2 capture Blue and green hydrogen types of fuel cell, including the pro-
options, has very low NOx emis- Blue and green hydrogen are the ton exchange membrane fuel cell
sions, and there is no liquid dis- solution to decarbonised hydro- (PEM), solid oxide fuel cell (SOFC),
charge from the processing unit. gen fuel production. According alkaline cell, and so on. The PEM

90 PTQ Q4 2020 www.digitalrefining.com/article/1002563

device is the only fuel cell found to
be suitable for automobiles. It has
an overall efficiency of 40-60% and,
when running on pure hydrogen, Heat Heat
the only emission is water vapour -e -e
(see Figure 3).
Figure 4 shows applications of fuel
cells in stationary plant, transporta-
tion, and materials handling. Their Hydrogen in Oxygen in

application to road transportation

Membrane
is discussed in this article. The fuel
cell has several benefits including Water out
low to zero emissions, high effi- anode cathode
ciency, reliability, fuel flammability,
energy security, durability, scalabil- Fuel cell
ity, and quiet operation.

Quality of hydrogen
The quality of hydrogen required
for a fuel cell is different to that of
hydrogen used in a typical refin-
ery (see Table 1).2 SOFCs can accept Figure 3 Operation of a fuel cell
refinery quality hydrogen, but most
PEM fuel cells need higher purity,
according to ISO-14687-2. Primary power
The small number of impurities Stationary
present in hydrogen fuel affects the Back-up power

performance of the PEM cell. To Bus/truck/rail

meet the required quality of hydro- Fuel cell

gen, various schemes have been
Transportation Aerial/underwater vehicle
application

explored, for instance pressure Marine

swing adsorption (PSA), membrane
Material handling Fork-lift
separation, catalytic conversion,
either alone or in combination. The
PSA system is designed to remove Figure 4 Major fuel cell applications
many contaminants to even lower
levels, with a compromise in hydro- Quality of hydrogen for a refinery and a fuel cell
gen recovery.
Inert compounds included in
Components Refinery Fuel cell
the ISO and SAE standard specifi- Hydrogen (H2), vol% 99.9 99.97
cations are helium (He), nitrogen Methane (CH4), ppmv Balance <2
(N2), argon (Ar), methane (CH4) and Nitrogen (N2), ppmv 50 100
other saturated hydrocarbons (par- Carbon monoxide (CO), ppmv 20 <0.2
Carbon dioxide (CO2), ppmv 20 <2
affins), and carbon dioxide (CO2). Water (H2O), ppmv 50 5
These compounds are considered Chlorides & chlorines, ppmv 1 <0.05
inert because they do not affect the Sulphur, ppmv Negligible <0.004
electrochemical reactivity of the
PEM fuel cell but are included in Table 1
the specification because they can
dilute the hydrogen fuel stream of components such as seals, gas- gen, but this is negligible for the
and affect system operation. It is kets, and valve seats and cause fuel overall cost model.
important to note that the ISO and leaks and other problems.
SAE standards limit total non-hy- CO2 and water can be removed CO2 capture
drogen gases in the fuel to 300 easily, while CO and N2 are the The second biggest challenge on
ppm. However, the oxygen content most challenging contaminants to the path to a hydrogen economy is
required is less than 5 ppm. remove. In SMR, sulphur is mostly CO2 capture and storage. All fos-
The presence of particulate matter removed in the feed (natural gas ) sil fuel routes produce CO2 as a
(PM) in the hydrogen fuel stream pretreatment section as it is poi- byproduct. Biomass gasification, a
should not directly affect a PEM sonous to the reformer catalyst. non-fossil route, also generates CO2.
fuel cell’s performance and durabil- The extra purity required for fuel The electrolysis route also produces
ity. Still, PM can affect the integrity slightly increases the cost of hydro- CO2 if the electricity consumed is

www.digitalrefining.com/article/1002563 PTQ Q4 2020 91

fuel cell grade hydrogen are sum-
103 marised in Table 2. The cost of nat-
N2
ural gas used for this case study is
100 ppm $9-10/MMBtu, and hydrogen deliv-
102
ery pressure is 350 barg. The key
CO parameters vary as per size of the
101 unit, quality of hydrogen, hydrogen
>0.2 ppm delivery pressure, and geographical
100
location.
Blue hydrogen’s capital cost is
Concentration, ppm

0.2 ppm
15- 20% higher than that of grey
10 hydrogen. The cost of production is
-1

CO limits recovery slightly more for blue hydrogen. At

10-2 the same time, there is a significant
reduction in CO2 emissions with
CH4 blue hydrogen.
<<10 ppm

Capital cost
-4

The capital cost of a hydrogen unit

CO2 includes contributions from equip-
ment, bulk materials, erection,
H2S=O engineering, and taxes. Among the
73 74 75 76 77 78 equipment, the reformer package
H2 recovery, % contributes around 35-40% and the
compressor 15-20%.
Figure 5 Typical PSA recovery and concentration of impurities7
Operating cost
Comparison of grey and blue hydrogen The main contributor to the operat-
ing cost of a hydrogen plant is the
natural gas feed (55-75%), while the
Parameter Grey hydrogen Blue hydrogen balance is due to utilities and other
Capital cost, M$/TPA H2 0.009-0 .013 0.01-0.016
Cost of production, $/kg 2.8 2.94
plant overhead, hence the operating
System efficiency, % 62-65 58-60 cost of hydrogen depends greatly
Specific energy, Gcal/1000 Nm3 H2 4.1 4.2 on natural gas prices (see Figure
CO2 emission, kg CO2/kg H2 8-12 0.2-4 6). Hydrogen production costs
*The value presented in the table is typical and depends on various factors like geographical location, therefore depend on geographical
size of the unit, feedstock, and utility price. location and availability of natu-
ral gas. Another associated cost is
Table 2 that of hydrogen compression from
20-30 barg to 350-700 barg, which
produced from a non-renewable The method of CO2 removal can leads to an increase in the price by
source. Thus, for an actual hydro- be solvent based or adsorption $0.27-$0.54/kg.
gen economy, effective CO2 capture based, though the former method is
and disposal is required. mostly used in the SMR process. Disposal of CO2₂
A fossil fuel based hydrogen unit Of the other emerging technol- SMR, along with CO2 capture, can
typically produces 8-12 kg CO2/kg ogies, biomass gasification pro- be used to produce cost-effective
H2. The integration of a CO2 recov- cess produces 17-19 kg CO2/kg H2. hydrogen for fuel cells, but it is
ery option with the basic scheme Though biomass is carbon neutral crucial to dispose of the captured
can reduce emissions by 0.2-4 feed thus overall carbon dioxide CO2 to close the loop. There are
kg CO2/kg H2. There can be two emissions for the process is not con- various methods for CO2 disposal.
locations to recover CO2 from the sidered. Electrolysis emits 50 kg CO2 based enhanced oil recovery
hydrogen producing unit: pre-com- CO2/kg H2 if the power source is (EOR) is a significant application
bustion CO2 removal, which is CO2 non-renewable, but can be as low of recovered CO2. CO2 based EOR
recovery from synthesis gas; and as 0.3 kg CO2/kg H2 if the power involves pumping compressed
post-combustion CO2 removal, source is renewable. CO2 through injection wells to
which is CO2 recovery from flue an oil-bearing formation. This
gas. The first option is cost-effective Case study restores pressure in the forma-
and removes up to 0.2-4 kg CO2/ SMR is extensively used for hydro- tion and forces the remaining oil
kg H2. The second method is cost- gen production around the world. toward production wells. It also
intensive but can reduce CO2 emis- The key parameters for small capac- mixes with the oil, expanding its
sions by only 0.1-1 CO2/kg H2. ity production of grey and blue volume and reducing its viscos-

94 PTQ Q4 2020 www.digitalrefining.com/article/1002563

ity. This enables it to flow more
quickly through the porous rock of
the oil reservoir. Injection of CO2 15.00
into mature oil fields is increas-
NG, $/MMBtu
ingly considered the most effective
10.00
method available to revive output.
Algae based carbon dioxide (CO2)
sequestration has gained more 5.00
interest due to its ability to utilise H2, $/kg
produced CO2 as a carbon source,
its high capacity for CO2 fixation, 0.00
and a faster growth rate than con-
ventional crop plants. The biomass
produced can be used as a feedstock Figure 6 Hydrogen price compared with natural gas price
for other value-added products
such as biofuels and chemicals.
A hydrogen unit integrated with
12.0
a fertiliser unit using recovered CO2 10.8
for urea production is another pos- 10.0

sible solution, while conversion to 8.0

Cost, $/kg

valuable chemicals is an emerging 6.0

5.8
solution for disposal.
4.0 2.9 3.4
2.0
Decentralised production of 2.0
hydrogen 0
The normal capacity of a hydrogen SMR Coal Biomass Electrolysis Biomass-
plant in a refinery is 10 000-350 000 gasification gasification microbial
Nm3/h. In the case of fuel hydrogen,
a small capacity plant can be looked Figure 7 Cost comparison for hydrogen production technologies
upon to fulfill local requirements. A
small, modular hydrogen unit with Fuel cell grade hydrogen ulate matter are significantly lower
a capacity range of 100-1000 Nm3/h The hydrogen produced by steam in the case of a fuel cell vehicle.
avoids challenges related to hydro- reforming fossil fuels requires fur- Although FCEVs are currently
gen transport and distribution. ther purification to achieve fuel more expensive to operate than bat-
cell grade. The primary process is tery electric and internal combus-
SMR compared with other emerging followed by compression (to 350 tion commercial vehicles, they are
technologies barg/750 barg) to fill cylinders for set to become much lower in cost as
Hydrogen from biomass gasifi- storage, followed by transportation manufacturing technology matures,
cation or biogas reforming are to fuel cell-powered vehicles. economies of scale improve, hydro-
promising as applications of car- A comparison of a hydrogen-pow- gen fuel costs decline, and infra-
bon-neutral feedstock, but not ered fuel cell vehicle and a conven- structure develops.
proven at the commercial scale yet. tion internal combustion engine is
On the other hand, hydrogen from summarised in Table 3. A typical FCEV & battery electric vehicle (BEV)
electrolysis is only promising if hydrogen filling station of 1200- BEVs and FCEVs both have zero
the electricity is generated from a 1500 kg/day can serve 50 city buses exhaust emissions and the ability to
renewable source and excess elec- or 250 passenger cars or 18 trucks. be fuelled using renewable and sus-
tricity is available. Electrolysis is an Heavy-duty vehicles represent a tainable energy sources through the
inefficient process at 55-60 kWh/ lower percentage of the total vehi- use of electric motors.
kg H2; the hydrogen price depends cle fleet but contribute more in the In the case of FCEVs, the major
on the electricity price. Power con- total percentage of emissions from concerns are hydrogen production,
sumption for the electrolysis pro- all vehicles, which makes them an delivery and storage to the vehicle
cess is expected to come down area of focus for fuel cell applica- hydrogen tank and consumption
in the future through extensive tions. Fuel cell buses can replace of hydrogen by the fuel cell vehi-
research. In a nutshell, SMR with conventional buses in range, power, cle during operation. In the case of
carbon capture (blue hydrogen) is and passenger capacity. The fuel battery electric vehicles, the main
the most suitable option in the near cell operating cost is at par with a concerns are electricity generation,
term while biomass gasification fossil fuelled vehicle. CO2 emissions transmission in the grid, charging
and electrolysis are mid-term solu- are 60-80% lower when using blue the battery, and use during vehicle
tions. Other pathways like dark fer- hydrogen, compared to fossil fuelled operation.
mentation and solar-hydrolysis are vehicles. Other emissions like NOx, BEVs have the advantage in vehi-
projected as long term solutions. unburned hydrocarbons and partic- cle cost and operating cost (see

www.digitalrefining.com/article/1002563 PTQ Q4 2020 95

Comparison of a city bus, car and truck References and further reading
1 Heading for hydrogen – The oil and gas
City bus Car Truck outlook for hydrogen, from ambition to reality,
Hydrogen, Km/MJ 0.08 0.84 0.09 DNV-GL.
CNG/gasoline/diesel, Km/MJ 0.06 0.58 0.14 2 Hydrogen fuel quality specifications for
Travel/day, Km/day 250 500 800 polymer electrolyte fuel cells in road vehicles,
FCEV op. cost, $/km 0.26 0.03 0.23 US Department of Energy, 2 Nov 2016; ISO-
CNG/gasoline/diesel op. cost, $/km 0.2 0.05 0.21
14687-2.
CO2 emissions-grey hydrogen-WTW, kg CO2/km 1.26 0.13 1.12
CO2 emissions-blue hydrogen- WTW, kg CO2/km 0 .2 0.02 0.18 3 Hydrogen Economy, 8 May 2017, https://doi.
CO2 emissions-CNG/gasoline/diesel, kg CO2/km 1.1 0.11 0.68 org/10.1016/B978-0-12-811132-1.00014-6.
4 Global Energy Review 2020, IEA, Paris www.
iea.org/reports/global-energy-review-2020.
Table 3 * typical data collected from open literature and estimated for Indian sub-continental
5 Hydrogen production and storage: R&D
priorities and gaps, IEA: N. p., 2006. Web.
FCEV vs BEV 6 Hydrogen at scale for fuel cell electric bus,
Ballard, Sept 2019.
FCEV BEV 7 Papadias D D, Ahmed S, Kumar R, Joseck
Vehicle cost, 1000$ 40-50 18-25 F, Hydrogen quality for fuel cell vehicles – A
Weight*, kg 1280 2270 modelling study of the sensitivity of impurity
Storage vol*, It 100-310 560 content in hydrogen to the process variables in
Refuelling time*, min 3-5 60-240 the SMR-PSA pathway, 2009.
Pickup time (0-100), sec 10 5.5
Operating cost, $/km 0.15 0.03-0.06 Kalpana Gupta is Deputy Chief Engineer with
CO2 emissions, kg CO2/km 0.15 0.4-0.6 Technip India. She has 19 years’ experience
Overall efficiency, % 40-60 70-80 in the oil and gas industry and is involved in
*Values given for vehicles with a 300-mile range projects related to decarbonisation, sustainable
chemistry, and the hydrogen economy. She
Table 4 * typical data collected from open literature and estimated for Indian sub-continental holds a BTech in chemical engineering from
MNIT Jaipur, MTech from IIT Delhi, and a
Table 4). The major drawback of grade hydrogen at 350 barg pressure diploma in renewable energy from TERI
University Delhi.
BEVs is that they usually have a at a cost of <$2.8/kg with an invest-
Email: [email protected]
limited range due to the size and ment of $ 9000-15 000/t/y H2.
Ishita Aggarwal is a Process Engineer with
the cost of batteries needed for vehi- At the next stage, SMR integrated Technip India. She has worked in sustainable
cle power. The refuelling of battery with a CO2 recovery option is avail- energy projects including bioethanol,
systems requires several hours, able with a slight increase in invest- biomass gasification, and waste plastic to
rather than a few minutes with an ment to reduce CO2 generation energy. She holds a bachelor’s degree in
FCEV, and CO2 emissions are much substantially. chemical engineering from Panjab University,
lower in the case of FCEVs. Emerging technologies like bio- Chandigarh.
mass gasification producing green Maruthi Ethakota heads the Process &
Conclusion hydrogen are promising, but the Technology department of TechnipFMC India.
Hydrogen is a decarbonising fuel technology is at the development He has 25 years’ experience, has executed
several hydrogen and syngas projects
with high potential for transporta- stage. The oldest technology,
worldwide, and previously worked as Product
tion and power generation. But it widely studied, is water electroly-
Development Manager with Technip Benelux,
has to overcome many challenges sis. However, the efficiency of the involved in developing new technologies for
before establishing itself as the process from electricity to hydrogen hydrogen and syngas production. He holds a
cleanest available fuel. Production is low and the process is the most master’s degree in chemical engineering from
of low-carbon, cost-effective hydro- environmentally friendly only if the IIT Kanpur.
gen is the foremost challenge. source of power is renewable.
SMR, typically producing refin- A small hydrogen unit of 100-500
ery grade hydrogen, is on hand to Nm3/h can fuel 10-50 city buses or
produce fuel cell grade hydrogen 50-250 passenger cars. A fuel cell
for transportation and power gen- powered bus has an operating cost
eration at an affordable cost and in of $0.2-0.3/km and reduces CO2
a sustainable way. The SMR process emissions compared with fossil
used in refineries and other appli- fuelling by 60-80%. Blue hydrogen
cations requires modification in its should help to create the infrastruc-
purification section to produce fuel ture required for the use of fuel cells LINKS
cell grade hydrogen. The purification in the transportation sector.
step has a solution based on PSA More articles from the following
with or without a catalytic process Acknowledgment categories:
for producing fuel cell grade hydro- Our thanks to Koos Overwater, Vice President Hydrogen Technologies
gen. A small, modular SMR base New Technologies, Technip Benelux for his
support and guidance.
hydrogen unit can produce fuel cell

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