Hydrogen Liquefaction Chain: Co-Product Hydrogen and Upstream Study

DEGREE PROJECT IN CHEMICAL ENGINEERING
SECOND CYCLE, 30 CREDITS

STOCKHOLM, SWEDEN 2020
Hydrogen liquefaction chain:

Co-product hydrogen and
upstream study
Salomé Lusson
Supervisor: Florian Jalia (ENGIE)
Examiner: Dr. Shareq Mohd Nazir (KTH)
Company: ENGIE, Lab CRIGEN (Stains, France)
Swedish title: Vätskekvävningskedja: Samproduktväte och uppströmsstudie
Course code: KE200X Degree Project in Chemical Engineering
Trita number: TRITA-CBH-GRU-2021:008
KTH ROYAL INSTITUTE OF TECHNOLOGY

SCHOOL OF ENGINEERING SCIENCES IN CHEMISTRY, BIOTECHNOLOGY AND HEALTH
1
Acknowledgements
This thesis has been conducted at the Lab CRIGEN at ENGIE under the scope of the Division of
Energy Processes and Department of Chemical Engineering at Stockholm KTH Royal Institute of
Technology.
Firstly, I would like to thank my supervisor at ENGIE, Florian Jalia for his great support and
management during this project as well as the provided knowledge. Furthermore, I would like to give
thanks to ENGIE for giving me the opportunity to work on this subject.
Thanks to Frédéric Legrand and Gabrielle Menard for welcoming me in the Liquefaction lab. And
thanks to Rémi, Audrey, Hamza, Yassine, Sanae, Assia and Laurent for their time and help when I
needed it during this project, for sharing their knowledge with me and for welcoming me and being
great colleagues. I have felt welcome at Lab CRIGEN.
Finally, I would like to express my thankfulness towards my examiner Shareq Mohd Nazir for
supporting me during this project and sharing his experience with me.
2
Abstract
The European Green Deal declared that Europe must decarbonize to become carbon-neutral within
2050. To do so, the European Parliament emphasized hydrogen as a major tool for energy transition.
In regard of current environmental challenges, liquid hydrogen has raised interest as energy carrier
for energy storage and transport. Due to growing use of renewable energy sources such as solar and
wind energy, intermittent sources will increase. Hydrogen production methods will become mostly
intermittent with renewable energies. However, due to historical hydrogen production by steam
methane reforming, liquefaction was developed at steady nominal charge. In order to feed current
liquefaction processes with renewable hydrogen, a buffer system will become required. This thesis
studies the effect of buffer and liquefaction combination on performances and cost.
In order to carry out this liquefaction from intermittent source, the study is performed based on
industrial data from a variable co-product hydrogen profile. This profile acts as a simplified case. The
scope of the study is drawn by considering compressed hydrogen as temporary storage for the buffer
while liquefaction unit is modelled around Linde Leuna cycle. The technical-economical study covers
sensitivity analysis on both buffer and liquefaction unit. For the buffer unit, storage capacity, storage
pressure, liquefaction flexibility and recuperation rate impacts are examined. Liquefaction sensitivity
analysis includes pressure drop, electricity cost and capacity study.
It is highlighted that 100% gaseous hydrogen recovery is not profitable due to high costs increase for
recuperation higher than 95%. Storage pressure and capacity as well as liquefaction flexibility drive
buffer cost and recuperation rate of the co-product hydrogen. Considering liquefaction study, results
highlight that pressure drops cause first order deviations in energy consumption as well as on cost.
Results show that the specific buffer cost is evaluated between 71% and 59% of liquefaction cost.
Hence the thesis raises attention on future work on heat exchangers design, pressure drop
optimization and liquefaction unit flexibility to allow an optimized renewable liquid hydrogen
production.
3
Content
Acknowledgements ................................................................................................................................... 2
Abstract ...................................................................................................................................................... 3
Content ...................................................................................................................................................... 4
List of tables............................................................................................................................................... 5
List of figures ............................................................................................................................................. 6
Nomenclature .............................................................................................................................................7
Abbreviations .............................................................................................................................................7
1. Introduction ...................................................................................................................................... 8
1.1. Physical and thermal properties of hydrogen .......................................................................8
1.2. Production ............................................................................................................................9
1.2.1. Hydrogen as main product ...........................................................................................9
1.2.2. By-product hydrogen ....................................................................................................9
1.3. Storage .............................................................................................................................. 10
1.4. Liquid hydrogen challenges .............................................................................................. 11
1.4.1. Joule-Thomson coefficient ........................................................................................ 11
1.4.2. Hydrogen isomers ..................................................................................................... 12
1.5. Hydrogen liquefaction impact on value chain.................................................................... 12
1.6. Liquefaction ....................................................................................................................... 13
1.6.1. Liquefaction process ................................................................................................. 13
1.6.2. Liquefaction plants and industrial cycles ................................................................... 13
1.6.3. Precooling strategies ................................................................................................. 16
2. Research questions .......................................................................................................................... 17
3. Process/technology description ......................................................................................................18
3.1. Gaseous hydrogen production profile ............................................................................... 18
3.2. Liquefaction process ......................................................................................................... 19
3.2.1. Linde Leuna with open nitrogen precooling cycle ..................................................... 19
3.2.2. Alternative precooling: closed nitrogen cycle ............................................................ 20
4. Methodology..................................................................................................................................... 21
4.1. Buffering study .................................................................................................................. 21
4.1.1. Buffering configurations............................................................................................. 21
4.1.2. Performances features .............................................................................................. 23
4.2. Liquefaction ....................................................................................................................... 24
4.2.1. Simulation procedure ................................................................................................ 24
4.2.2. Pressure drops .......................................................................................................... 25
4.2.3. Economic calculations ............................................................................................... 27
4.2.4. Electricity cost ........................................................................................................... 29
4.2.5. Storage pressure ....................................................................................................... 29
4
4.2.6. Procedure for results expression .............................................................................. 29
5. Results and discussion.................................................................................................................... 30
5.1. Buffering ............................................................................................................................ 30
5.1.1. Configurations results ................................................................................................ 30
5.1.2. Economics ................................................................................................................. 32
5.2. Liquefaction ....................................................................................................................... 34
5.2.1. Performances ............................................................................................................ 34
5.2.2. Pressure drops .......................................................................................................... 35
5.3. Final analysis: buffer and liquefaction combination .......................................................... 38
6. Sensitivity analysis .......................................................................................................................... 39
6.1. Electricity cost ................................................................................................................... 39
6.2. Storage pressure ............................................................................................................... 40
6.3. Liquefaction flexibility ........................................................................................................ 41
6.4. Time basis ......................................................................................................................... 41
7. Conclusions and future work ......................................................................................................... 42
References................................................................................................................................................ 43
Appendix 1: Buffering – Economic tables.............................................................................................. 47
List of tables
Table 1: Physical and thermal properties of hydrogen ............................................................................ 8
Table 2: Hydrogen comparison with other fuels from [4] ...................................................................... 8
Table 3: World hydrogen production by source in 2014 (Million metric tons) from Brown, 2014[19]
...................................................................................................................................................................10
Table 4: Performances table for industrial (black) and conceptual (blue) plants ............................. 16
Table 5: Main statistical features of the production profile ................................................................... 19
Table 6: Properties of n-H2, p-H2 and o-H2 from HYSYS databank (from Aspen HYSYS V8.6 and
Aspen Plus V10 in bold) .......................................................................................................................... 24
Table 7: Correlation to calculate p-H2 equilibrium content depending on temperature (McCarthy,
Hord, & Roder, Selected Properties of Hydrogen (Engineering Design Data), 1981) ......................... 25
Table 8: Pressure drops in HEX based on Putselyk work [48] ............................................................ 26
Table 9: Parameters for pressure drops calculations ( 1: assumed as constant in HEX and equal to inlet
value)........................................................................................................................................................ 27
Table 10: Density and technological cost for several CGH2 systems at 293K (20°C).......................... 29
Table 11: Performances for the +/-20% flexibility configuration .......................................................... 31
Table 12: Performances of +/-20% flexibility and gauges control 30-70% .......................................... 31
Table 13: Performances of +/-20% flexibility and gauges control 90-99% .......................................... 31
Table 14: Performances of +/-20% flexibility and additional H2O electrolysis at 2TPD .................... 31
Table 15: Performances of +/-20% flexibility and additional H2O electrolysis at 1.5TPD .................. 31
Table 16: Performances of +/-20% flexibility and additional H2O electrolysis at 1TPD ..................... 31
Table 17: Relative energetic results for basis LN2 simulations ............................................................. 34
Table 18: Energetic results for basis SN2 simulations, in relation to LN2 results ............................... 35
Table 19:Relative key parameters for 0.1 bar (LP) and 0.01 bar (HP) pressure drops ....................... 36
Table 20: Electricity prices for industries in Europe (data from 2019) ............................................... 39
Table 21: Comparison of buffer performances between hourly and daily basis .................................. 42
5
List of figures
Figure 1: Hydrogen production methods [7] ........................................................................................... 9
Figure 2: Allocation of hydrogen storage methods based on energy density and H2 weight content [23]
...................................................................................................................................................................10
Figure 3: J-T inversion curves of common cryogenic fluids a) Methane; b) Air; c) Neon; d) Hydrogen;
e) Helium, Windmeier et al. [28] ............................................................................................................ 11
Figure 4:Ortho and para-hydrogen distribution depending on temperature....................................... 12
Figure 5: Liquefaction process recap ...................................................................................................... 13
Figure 6: Praxair process flow diagram [38] .......................................................................................... 14
Figure 7:Air Products process flow diagram [39]................................................................................... 14
Figure 8: Process flow diagram of Linde Leuna from [41] .................................................................... 15
Figure 9: Process flow diagram of nitrogen open-loop pre-cooling cycle in Linde .............................. 16
Figure 10: Upstream process flowsheet ..................................................................................................18
Figure 11:GH2 variable production over the year (data from ENGIE) .................................................18
Figure 12: : GH2 production distribution from Figure 12 ...................................................................... 19
Figure 13: Linde Leuna process and open precooling ........................................................................... 20
Figure 14: Closed nitrogen cycle flowsheet ............................................................................................ 20
Figure 15: Scenario with unique liquefaction charge ............................................................................. 21
Figure 16: Liquefaction flexibility at +/- 20% of nominal charge ........................................................ 22
Figure 17: Liquefaction flexibility and gauges control for liquefaction charge rating ......................... 22
Figure 18: Liquefaction flexibility supported by additional electrolysis .............................................. 23
Figure 19: Buffer size (blue) and recuperation rate (orange) as function of nominal liquefaction charge
.................................................................................................................................................................. 30
Figure 20: Buffer profile for a 1.5TPD water electrolysis and 15 tons storage..................................... 32
Figure 21: Buffer profile for a 2TPD water electrolysis and 15 tons storage ........................................ 32
Figure 22: Key parameters and specific utility cost of buffer configurations (except WE) ................ 32
Figure 23: Key parameters and specific utility cost of WE buffer configurations ............................... 33
Figure 24: Recuperation rate and SUC for flexibility and gauges systems .......................................... 33
Figure 25: Hot (red) and cold (blue) composite curves of the LN2 system .......................................... 34
Figure 26: Hot and cold composite curves of the SN2 system .............................................................. 35
Figure 27: ΔSLC evolution with pressure drops at 5TPD ..................................................................... 36
Figure 28: ΔSEC evolution with pressure drops at 5TPD .................................................................... 36
Figure 29: Pressure drops in HEX based on packed bed catalysis model ........................................... 37
Figure 30: Liquefaction scale-up and buffer combination, SN2 system with 0.1-0.01 bar pressure
drops ........................................................................................................................................................ 38
Figure 31: Sensitivity analysis of electricity cost on SLC at 5TPD ........................................................ 39
Figure 32: ΔSLC as function of buffer storage pressure ...................................................................... 40
Figure 33: ΔCAPEX as function of buffer storage pressure ................................................................. 40
Figure 34: Liquefaction flexibility impact on major parameters for a 7.5 GH2 tons buffer capacity .. 41
6
Nomenclature
T Temperature 𝜇 Joules-Thompson coefficient
P Pressure µ Viscosity
𝑚̇ Mass flow rate 𝑟 Recuperation rate
H Enthalpy %𝑝 Inlet para-hydrogen percentage
S Entropy %𝑝 Equilibrium para-hydrogen percentage
ρ Density 𝐷 Catalyst particle diameter
𝜀 Bed void fraction 𝐴 Bed cross section
𝑢 Fluid flowrate 𝐿 Conversion reactor length
ΔSEC Relative SEC 𝑓 Friction coefficient
ΔSLC Relative SLC Wi Work of component i
ΔSUC Relative SUC Ex Exergy
ΔCAPEX Relative CAPEX
Abbreviations
CAPEX Capital Expenditures
CGH2 Compressed Gaseous Hydrogen
J-T Joule-Thompson
GH2 Gaseous hydrogen
HEX Heat Exchangers
HP High Pressure
LH2 Liquid hydrogen
LNG Liquefied Natural Gas
LN2 Open Nitrogen precooling cycle
LP Low Pressure
NLC Nominal Liquefaction Charge
NPV Net Present Value
n-H2 Normal hydrogen
o-H2 Ortho-hydrogen
OPEX Open expenditures
p-H2 Para-hydrogen
PtG Power to Gas
SEC Specific Energy Cost
SLC Specific Liquefaction Cost
SN2 Closed Nitrogen precooling cycle
SUC Specific Utility Cost
TPD Tons per day
WE Water Electrolysis
7
1. Introduction
1.1. Physical and thermal properties of hydrogen

1.1.1. General information
Hydrogen is the lightest element in the periodic table with a standard atomic weight of 1.008. Under
its monoatomic form H, this element is the most abundant chemical compound that gathers almost
75% of all baryonic mass. Physical and thermal properties of hydrogen are listed in the following
Table 1.
Table 1: Physical and thermal properties of hydrogen
Density 0.08988g/L (0°C, 101.325kPa)
Melting point 14.01K, -259.14°C (1atm)
Boiling point 20.28K, -252.87°C (1atm)
Triple point 13.8033K, -259°C, 7.042kPa
Critical point 32.97K, 1.293MPa
Heat of vaporization 0.904kJ/mol (1atm)
Specific heat 14.304J/kg-K (1atm)
Conductivity 187mW/m-K (1atm)
Today hydrogen is mainly used for ammonia production and refinery processes [1]. However, use of
hydrogen for broad mobility is still under development today and its industrial activity in mobility are
limited to space applications1. Despite its utility in order to reduce greenhouse gases emissions and
its great potential as energy carrier, there are challenges with hydrogen value chain such as safety
issues, production cost and transportation.
1.1.2. Hydrogen vs fossil fuels

Hydrogen is not an energy source but an energy carrier [2]. Its use is at heart of current zero-carbon
goals in Europe since the European Parliament emphasized hydrogen as an important tool for energy
transition. The European Green Deal declared that Europe must decarbonize its economy and become
carbon-neutral within 2050 [3]. Therefore, European goal is to invest in research for green energy
and storage development, including hydrogen technologies.
When compared with other fuels such as reported in Table 2, hydrogen reaches higher energy content
than any other fuel. Its energy -to-weight ratio is three times higher than gasoline diesel or kerosene.
However, hydrogen’s flammability is higher and care has to be taken in order to secure its use. Its
ignition temperature is 858K while gasoline’s is 501K and hydrogen ignites easily on a wide range of
composition when mixed with O2 or air [4].
Table 2: Hydrogen comparison with other fuels from [4]
Flammability Explosive
Gravimetric energy density Volumetric energy density
Fuel limits limits
MJ/kg kWh/kg MJ/L kWh/L vol% vol%
200bar H2 120 33.3 2.1 0.58 - -
Liquid H2 120 33.3 8.4 2.33 4-75 18.3-59.0
Methanol 19.7 5.36 15.7 4.36 6-36.5 6-36
Petrol 42 11.36 31.5 8.75 1-7.6 1.1-3.3
Diesel 45.3 12.08 35.5 9.86 - 0.6-7.5
Kerosene 43.5 12.08 31.0 8.6 - 0.7-5
8
1.2. Production
1.2.1. Hydrogen as main product
Even if there are many raw materials from which hydrogen can be produced such as biomass or algae,
it is currently produced mainly from fossil fuels. It represents 96% of the world’s hydrogen production
[5]. Production by steam methane reforming (SMR) is the major route that thermo-chemically
converts natural gas into hydrogen. The remaining 4% of total hydrogen production account for
hydrogen generation from water electrolysis (see Figure 1) [6,7]. Despite its very low share of
hydrogen production, attraction for this technology has been growing because it is more environment
friendly and because of its increasing level of maturity complimented with decreasing technology
costs.
Electrolysis
4%
Oil/Napht
a (SR) Natural
30% gas (SR)
48%
Coal (SR)
18%
Figure 1: Hydrogen production methods [7]
A study on current patents published by M.Dehghanimadvar et al. [8], in order to evaluate technology
attractiveness based on the calculation of the ratio of granted patent to published one. This study
shows that a lot of focus is on electrolysis as a production path for hydrogen. According to previous
figure there are new emerging technologies such as photobiology, thermochemical water splitting or
Kvaerner process. Photobiology is based on biohydrogen production from microorganisms like algae
or bacteria. It is a simple and efficient method that may achieve economic feasibility within the
following years [9]. Water splitting uses solar heat to split H2O molecules into H2 and O2. This path is
still under development because of high temperatures and materials demands [10].
The high interest for electrolysis highlighted by M.Dehghanimadvar et al.[8] can be justified by
Power-to-Gas (PtG) solution development. Several publications have reported interest in energy
storage by hydrogen production especially for variable renewable energy sources (VRES) such as wind
turbines or solar panels. VRES are likely to see their share in overall electricity demand increase and
hydrogen has many advantages including that it has multi-purposes: electricity conversion with fuel
cells, transportation fuel or natural gas injection [11]. PtG is based on H2 production by electrolysis
when VRES produce surplus electricity. Today 99% of electricity is stored by pumped-hydro energy
storage however higher volumetric energy densities are reached H2 [6].
1.2.2. By-product hydrogen
Production routes presented in Figure 1 are those that aim at producing H2 where H2 is the main
product. However, it does not consider low grade H2 produced by industrial processes. H2 is a by-
product in industries such as caustic soda, chlorine, propane production and the sodium methoxide
production [12,13]. In caustic soda plants H2 is produced along with NaOH but is often wasted or used
on-site for heat production [14]. Chlore-alkali processes – that mainly aim at producing chlorine and
sodium hydroxide – have an estimated production capacity of hydrogen in the U.S. of 0.4 million
tonne per year [15]. By-product H2, simultaneously produced with other main products from
industrial processes, is sometimes vented to the atmosphere. However, because this H2 is already
9
produced at scale, it is a low cost H2 source (~1$/kgH2) and could require no additional capital
investment because of its high purity [16,17].
According to Maisonnier, 2007 [18], the hydrogen market includes three main categories of hydrogen:
captive H2, merchant H2 and by-product. Captive hydrogen means H2 on-purpose H2 production for
direct use. Merchant H2 is bought from by-product and captive industries and sold to other
companies. While by-product is the resulting H2 that can be used for on-site purposes (process or
energy) or sold or wasted. In 2014 world by-product hydrogen production was estimated to reach
40% of the total hydrogen production [19].
Table 3: World hydrogen production by source in 2014 (Million metric tons) from Brown, 2014[19]
Source Production (MMT) %
Captive 55.39 54
By-product 40.93 40
Merchant 6.16 6
Total 102.48 100
Maisonnier highlighted that surplus hydrogen from industrial processes could feed H2 processes for
mobility or transport case [18]. Industrial surplus is defined as production excess, wasted by-product
H2 and by-product H2 that is currently used for on-site heat/energy application but that could be
recover after energy source substitution. Surplus H2 in Europe was estimated to value between 2 and
10bn Nm3 corresponding to 1-6 million vehicles. Hence, there is a high potential to use this by-product
H2 as energy carrier source. However, as specified in the report, these number can vary based on real
production data, processes, production schedule on site-by-site basis.
In the present work, the goal will be to analyse by-product H2 valorisation from a variable gaseous
hydrogen (GH2) source. Even if H2 recovery for transport applications is attractive due to the reported
high energy density, publications also reveal chosen storage path to be an issue and a potential source
of exergy losses [20]. This project is undertaking a case study on variable hydrogen sourcing feasibility
for production of liquid hydrogen.
1.3. Storage
State-of-art systems for hydrogen storage are compressed gaseous hydrogen (CGH2), liquid hydrogen,
line packing and salt caverns. CGH2 is the most common way to reach high storage densities. The
pressure of the storage depends on the application. Or stationary tubes H2 is generally compressed to
200-350 bar while for automotive applications on-board systems achieves storage pressures up to
700 bar [21,22].
Figure 2: Allocation of hydrogen storage methods based on energy density and H2 weight content [23]
One inconvenient of CGH2 is the compression cost. In contrast, chemical hybrids or metal hybrids are
rely on reversible absorption of hydrogen at low pressure and low temperature [24]. These methods
also have the advantage to be less land intensive, and to have both higher energy density and H2
10
content (see Figure 2). However, the cost of these technologies is still too high to be considered in this
study.
According to Figure 2, liquid hydrogen (LH2) has a high H2 content and a good energy density, higher
than CGH2. The production of 1kg of LH2 requires theoretically between 4 and 10 kWh [25]. This
amount of energy represents 30% of the combustion energy stored in hydrogen and in practice this
value increases due to real efficiencies. Technical issues such as boil-of production and heat influx in
storage vessels reduces LH2 efficiency [26,27]. Due to these energy issues LH2 has been preferred for
industries which are more concerned with performance rather than cost such as space industry.
However recent attention for LH2 as energy carrier for heavy mobility has brought the challenge to
develop better energy efficient processes.
1.4. Liquid hydrogen challenges
1.4.1. Joule-Thomson coefficient
H2 liquefaction is usually performed by flashing GH2 into a Joules-Thomson (J-T) valve. This
transformation is an isenthalpic expansion based on the Joule-Thomson effect. Joule-Thomson effect
is used particularly in cooling cycles to bring refrigerant temperature below the ambient and also for
gas liquefaction.
This effect results from non-ideal behaviour of a fluid. It reflects the existence of intermolecular
repulsion and attractions forces as explained by Hirschfelder, Ewell and Roebuck in 1938. In order to
measure this effect, the adiabatic Joule-Thomson coefficient is defined. It evaluates the change of
temperature under isenthalpic expansion per pressure drop variation.
𝜕𝑇
𝜇 = = 𝜇 (𝑃, 𝑇) (1.1)
𝜕𝑃
𝐻 = 𝑈 + 𝑃𝑉 (1.2)
If gas is ideal its enthalpy is only a function of temperature and is independent of pressure. Therefore,
if transformation is isenthalpic, a pressure variation cannot cause a change in temperature. As we are
not working with ideal gases we can therefore use this effect. J-T coefficient can have a positive or
negative value depending on the temperature. It reflects a heating or cooling transition. Changes in
coefficient’s value happens at the inversion temperature. Positive or negative regions can be witnessed
in inversion diagram. In positive regions, expansion produces temperature drop. Above inversion
temperature J-T coefficient is negative. As the inversion temperature is different for every gases,
liquefaction or cooling processes will be different.
Figure 3: J-T inversion curves of common cryogenic fluids a) Methane; b) Air; c) Neon; d) Hydrogen; e)
Helium, Windmeier et al. [28]
11
According to the previous Figure 3, H2 and helium have very low inversion temperature values. They
can be cooled down or liquefied by J-T expansion only at extremely low temperatures (<170K and
<50K respectively).
1.4.2. Hydrogen isomers
Hydrogen exists in two main forms depending on the spin configuration: ortho-hydrogen (o-H2) and
para-hydrogen (p-H2). The conversion between these forms is slow especially at low temperatures
unless catalysis is performed. Most of the physic-chemical properties of p-H2 and o-H2 are only
slightly different. The melting and boiling points differ only by 0.1-0.2K at all pressures. However,
there are considerable differences in heat capacity and related properties, such as thermal
conductivity [29].
100
90
80
70
60 %para
%mass
50
% ortho
40
30
20
10
0
0 100 200 T (K) 300 400 500
Figure 4:Ortho and para-hydrogen distribution depending on temperature
Conversion from o-H2 to p-H2 is an exothermic reaction. If this conversion is not performed before
storage because conversion heat is higher than H2 heat of vaporization, so it leads to LH2 loss, boil-
off production and efficiency decrease. In order to avoid this phenomenon conversion is usually
carried out along with liquefaction steps [29]. In commercial liquefaction plants the outgoing LH2
reaches at least 95% p-H2. Theoretical specific energy consumption (SEC) of n-H2 at 300K to LH2 at
~20K and 1 bar is 3.94kWh/kgLH2. However industrial liquefaction plants achieve higher SEC values
like 12-15 kWh/kgLH2 because ideal Carnot cycle cannot be performed adding to irreversibility [28].
Conversion is technically performed by heat exchangers filled with catalyst material however for
simulation purposes and studies converters are modelled with separated conversion reactors [30,31].
There are different types of conversion reactors. When using adiabatic converters, the heat generated
by the exothermic conversion reaction is not removed [30]. The working stream is cooled, converted
by catalyst and thus partially reheated. It is further cooled in a step-shape route along the equilibrium
curve. While in continuous converters, the heat generated is continuously removed and the fluid
further cooled in order to follow the equilibrium curve.
1.5. Hydrogen liquefaction impact on value chain

Despite the previous discussed challenges, hydrogen liquefaction is important in value chain. LH2 has
great potential for transportation purposes. As mentioned in section 1.3, LH2 has higher energy
density than common CGH2. Kramer et al. have studied hydrogen supply chain for automotive use
and they concluded that liquefaction of hydrogen is competitive [32]. When liquefaction is integrated
in hydrogen value chain, both energy consumption and cost are gathered in the liquefaction unit [33].
Even though liquefaction is energy intensive, the real positive impact happens in the downstream part
because hydrogen stored as LH2 enables to reduce truck-transportation by 6-10 times in comparison
with CGH2 [34-36].
12
Advantages of LH2 use were demonstrated by Ishimoto et al.[37] by comparing LH2 and ammonia
(NH3). NH3 is a liquid organic hydrogen carrier (LOHC). This method is also used as hydrogen storage
path (see Figure 2). Ishimoto et al.[37] calculated under optimistic assumptions that the levelized cost
of LH2 chain could be close to meeting the Japan H2 cost target of 2.5€/kgH2 (~3$/kgH2).
1.6. Liquefaction
1.6.1. Liquefaction process
Liquefaction process is a combination of three boxes as depicted in the following Figure 5. The first
compression box increases the pressure of the returning refrigerants before going into pre-cooling
and cooling boxes. The precooling fluid runs in the precooling box in order to cool the feed H2 down
to around 80K. Feed H2 is cooled afterwards to around 21K before being expanded in a J-T valve and
liquefied. GH2 input and LH2 output characteristics ranges around (290K, 20 bar) and (21K, 2 bar)
respectively.
Figure 5: Liquefaction process recap
Liquefaction processes can be differentiated by their cooling cycles. In hydrogen liquefaction there
are two main cooling cycles: Claude and Brayton. Brayton processes work with cooling power
provided by isentropic expansion while Claude process is a mixed cycle. It is based on cooling energy
provide by isenthalpic expansion (J-T valve) and partial isentropic expansion.
1.6.2. Liquefaction plants and industrial cycles
1.6.2.1. Praxair
Today Praxair has five hydrogen liquefaction plants in the United-States which can handle hydrogen
liquefaction capacities from 6 to 35TPD [38]. According to the process flowsheet represented in the
following Figure 6, the Praxair liquefier follows a Claude pre-cooling configuration assembled with
external LN2 refrigeration.
13
Figure 6: Praxair process flow diagram [38]
Liquefaction is proceeded through a unique system with 3 heat exchangers (HEX) and H2 to be
liquefied is fed at 21 bar and 298K. The first HEX takes its cooling capacity from GN2 while the second
takes it as well from LN2 as partially from the H2 feed and finally the third exchanger is cooled by a
hydrogen refrigeration cycle based on hydrogen expansion through turbines and Joule-Thomson (J-
T) valve [39].
The outgoing LH2 is leaving at 21bar and 20K with a 95%p-H2composition. Typical energy
consumption values for this cycle is between 12.5 to 15kWh/kgLH2 and the exergy efficiency is around
19-24%. As specified before, the conversion of o-H2 to p-H2 is carried out by a 2-steps conversion
system in continuous mode.
1.6.2.2. Air Products process
Air Products is the biggest liquid hydrogen producer with liquefaction plants mainly located in the
Gulf coast region. The produced LH2 is used in refinery or chemical applications. These plants can
reach production capacities that range from 20 to 30TPD and they were built between 1985 and 1995.
The process depicted in the Figure 7 is designed to produce 36TPD of LH2. It consists of 4 HEX
including 2 HEX filled with catalyst’s material. Therefore, conversion from n-H2 to 97%p-H2
composition can be performed during the liquefaction. The feed H2 is inserted in the process at 18
bar, 305K, and is leaving at 3.6 bar and 25K with a 95%p-H2 [40].
Figure 7:Air Products process flow diagram [39]
14
The feed H2 is cooled until 83K by the first two HEX through an open LN2 pre-cooling cycle combined
with a compressed neon (Ne) loop. Ne is used here because of its ability to be compressed to the
targeted compression ratio only by a reasonable number of stages. Ne is thereafter expanded in two
turbo expanders to provide cooling power.
1.6.2.3. Linde processes
Linde has two installed hydrogen liquefaction plants in Germany: a first one in Ingolstadt that was
built in 1991 and secondly a more recent built in 2008 in Leuna. According to Figure 8, liquefaction
system consists a Claude-Brayton cycle which LH2 production can go up to 1 to 100 TPD with eight
HEX that can be divided in 2 boxes: a pre-cooling box and a cold box. In the pre-cooling box the feed
H2 is cooled from 298K to 80K through 2 HEX which cooling comes from H2 refrigerant loop and an
open LN2 pre-cooling cycle. Then feed H2 enters the cold box where it is cooled until 20K and
expanded in a J-T valve to 1.3bar. The o-p conversion is ensured within seven of the eight HEX filled
with catalyst material. After that the final composition of LH2 reaches 95%p-H2.
Figure 8: Process flow diagram of Linde Leuna from [41]
1.6.2.4. Industrial and conceptual plant summary
There are industrial liquefaction plants in operation today which require between 11 and 15
kWh/kgLH2. According to following Table 4 conceptual plants such as Quack or Krasae-in have lower
energy consumption. These data will be used as references and simulated cycles performances will be
compared to them.
15
Table 4: Performances table for industrial (black) and conceptual (blue) plants
Flow Exergy
Stream properties SEC
Process rate Refrigeration efficiency
in/out (bar/K) (kWh/kgLH2)
(TPD) (%)
Praxair 35 N2 precooling to 80K In: 21/298 12.5-15 19-24
[39] + H2 Claude cycle Out: 1/20
Air Products 30-35 Open LN2 precooling + In: 18.2/302 12-15 19-22
[39,40] H2 Claude cycle Out: 3.6/25
Linde N2 precooling to
4.4 In: 20/<305 13-15 21
Ingolstadt 80K and H2 Claude
Out: 1.3/21
[33] cycle
Linde Leuna 5 N2 precooling to 80K In: 24/310 11.9 23.6
[33] and H2 Claude cycle Out: 1.3/20
Matsuda and 300 LN2 precooling + H2 In: 50/300 8.5 47
Nagamei [42] Claude Out: 1/20.4
MR Kleemenko
Krasae-in 100 In: 21/298 5.91 49
precooling + Joule-
[43] Out: 1.9/19.45
Brayton cascade cycle
Quack Propane precooling to
170 In: 80/300 7-8 -
[44] 220K + He/Ne JB
Out: 1/20.15
cooling to 25K
IDEALHY MR Kleemenko
50 In: 20/293 ~6.3 -
[45] precooling to 130K +
Out: 2/22.8
JB cooling
LN2 precooling to 80K
Kuzmenko + He cooling JB In: 16/300
5.4 12.7 34.6
et al. [46] integrated with the N2 Out: 1.5/19.9
Claude
1.6.3. Precooling strategies
The current process uses nitrogen in an open-loop to pre-cool the hydrogen feed to 80K (-193°C). As
illustrated in Figure 9, liquid nitrogen is supplied in a scrubber to separate vaporized gas from
condensed nitrogen. The liquid nitrogen flows in the second heat exchanger (HX2) and cools the
hydrogen to 80K (-193°C). Catalytic conversion is proceeded in this heat exchanger consuming LN2
cold power. The gaseous nitrogen, from the nitrogen separator, is mixed to the one coming from HX2.
The mixture provides cold power in the first heat exchanger to cool hydrogen and refrigerant from
ambient temperature to approximatively 100K (-173°C). Eventually, nitrogen at ambient temperature
is rejected in the atmosphere.
Figure 9: Process flow diagram of nitrogen open-loop pre-cooling cycle in Linde
16
The optimized design with closed N2-Brayton Pre-cooling system introduces a more complexed
system. It reduces the refrigeration power needed to cool down nitrogen before its partial liquefaction.
Nitrogen is however still cooled in an external heat exchanger. According to internal research at
ENGIE for high capacity liquefaction, precooling SEC was calculated and it represented 47% of the
total process SEC. Additionally, CAPEX which were not estimated would be naturally increased.
2. Research questions
Given the previous state-of-the-art of hydrogen liquefaction, several sources name liquid hydrogen
(LH2) as a promising energy carrier and storage solution. Based on market data gaseous hydrogen
(GH2) is mainly produced by SMR while electrolysis is gaining priority due to zero carbon goal in
energy fields. As reported previously electrolysis can be performed from several sources and
production can be steady or more intermittent depending on raw material. Due to the recent and
future development of renewable energies such as solar or wind energy, there is a growing need in
energy storage system. Hydrogen has been identified by governments and executives in Europe as an
interesting storage solution. LH2 has advantages in terms of storage and therefore transport solutions.
Even if literature clearly underlines the possibility of hydrogen liquefaction and the PtG development
for intermittent energy source, there are not clearly studying technical feasibility of H2 liquefaction
from intermittent source.
As a result, this thesis aims at studying liquefaction of hydrogen from varying source. The study is
focused on the upstream liquefaction chain that includes intermediate GH2 storage and liquefaction
unit. Further units such as refueling station or LH2 storage are not undertaken as they are not specific
to variable co-generated hydrogen. Before starting any simulations or economic evaluation it is clear
that a trade-off between GH2 and liquefaction capacity will need to be considered. The goals of the
thesis is to answer the following research questions:
- To what extent should by-product H2 be recovered in this intermittent sourcing case?

- What are the critical points of liquefaction from variable GH2 production?
The overall goal of this thesis is to study the impact of H2 intermittence on liquefaction. It is a first
step into H2 liquefaction from intermittent renewable source. In the case of intermittent renewable
source, GH2 variations are stronger than in this case. Therefore, this thesis is a first simplified case
study. The impact of this study is to get into liquefaction flexibility study and heat exchanger design
for pressure drop optimization.
17
3. Process/technology description
As specified in the previous research goal part, the process under study is composed of two main
units: buffering and liquefaction. Gaseous hydrogen (GH2) production and purification are out of the
scope of this project because purification depends on the production path so GH2 is assumed to be
almost pure H2 without the need of purification. Furthermore, liquid hydrogen (LH2) storage and
terminal unit are also not considered because once LH2 is produced, the process for these units is
similar whatever the production method or GH2 source is. Therefore, the upstream system consists
in a buffer system with compressors, temporary storage tank, expander and heater, and a liquefaction
unit (see Figure 10).
² Liquefaction
Figure 10: Upstream process flowsheet
3.1. Gaseous hydrogen production profile

GH2 is produced from a variable source referring to the following Figure 11. Statistical analysis are
performed on this profile. Main results are listed in Table 5 and the production distribution is
represented in Figure 12.
12
Mean H2 daily production [TPD]
10
0
0 50 100 150 200 250 300 350
Days
Figure 11:GH2 variable production over the year (data from ENGIE)
18
Figure 12: : GH2 production distribution from Figure 12
Referring to statistical information in Table 5, production values are mainly gathered between 6.4
and 9.6TPD. However, values can still reach very low or very high values such as approximately 3.17
and 10TPD respectively. Therefore, the buffering system must withstand these high fluctuations, and
this might have an impact on the storage capacities’.
Table 5: Main statistical features of the production profile
Mean [TPD] 8.20
Variance 1.63
Standard deviation 1.27
Minimum [TPD] 3.17
Maximum [TPD] 10.5
Temporary storage for liquefaction is designed for two different reasons. First one is to compensate
production below the mean value in order to avoid liquefaction’s shutdown. It is a process issue. On
the other hand, temporary storage helps to recover high production values and avoid wasting them.
In this case it is an economic issue. In the light of the previous figures it is clear that a temporary
storage is needed at least to compensate very low production values. Study’s goal is to find buffer
design that combines the smallest cost and a good LH2 capacity because pressurized storage price is
high and land use limitation is important.
In order to answer this issue a first scenario is designed and described in the following part 4.1. To
design the optimal buffering system, several scenarios are studied and the system is gradually made
more complex. The recuperation rate is calculated in each configuration (see Eq. 4.3) and GH2 storage
is firstly assumed to value 300 bar to limit land use but limit potential cost.
3.2. Liquefaction process
3.2.1. Linde Leuna with open nitrogen precooling cycle
According to the previous literature review, the pre-cooling strategies will be integrated to the Linde
Leuna configuration. The first configuration is following the actual pre-cooling system of the Linde
Leuna with a liquid N2 open-loop. The process flow diagram (PFD) is shown in the Figure 13 below.
There are three principal stream lines: the feed H2, the H2 refrigerant and the N2 pre-cooling.
19
HP MP
Compression
box
LP
Precooling Cooling
box box
Figure 13: Linde Leuna process and open precooling
The H2 feed is supplied at 290K, 21bar. It enters the pre-cooling box in which in it is cooled to 78K by
means of two HEX. Only the second HEX is filled with catalyst while in the first the composition
remains at the n-H2 value. Then the stream enters the cooling box in which it will be fed into five
successive HEX all filled with catalyst material. The H2 feed is continuously cooled until 24K thanks
to H2 refrigerant cooling power. Finally, the H2 feed is cooled to 22.5K by final HEX, supplied with
cooling duty from the H2 refrigerant expansion by a J-T valve, and further expand to 1.3bar by a J-T
valve.
Along the liquefaction process, the cooling power is supplied from two sources: the precooling and
the refrigerant. The N2 pre-cooling stream is simulated with a liquid N2 input at 78K and 1.1bar. The
entirety of this input flows into the second HEX and further in the first HEX to cool it until around
103K. Eventually the gaseous N2 is released in the atmosphere. As for the H2 refrigerant, its cooling
capacity is optimized by dividing it into three pressure levels: a high pressure (HP), medium pressure
(MP) and low pressure (LP). The HP and MP are coming from the same fraction of the initial
refrigerant stream while the LP stream comes from the other fraction. They are further gathered in
the compression box to be compressed back to their initial pressure of 34bar.
3.2.2. Alternative precooling: closed nitrogen cycle
As explained previously the current study is undertaking pre-cooling comparison for the Linde Leuna
process. Therefore, the previous flowsheet is modified: compression and cooling boxes designs are
kept identical however the pre-cooling box is changed.Figure 14 presents the process diagram of the
Linde Leuna modified with the single pressure nitrogen cycle. It is composed of 4 HEX and the last
one is filled with catalyst material.
Figure 14: Closed nitrogen cycle flowsheet
20
Focusing on the pre-cooling stream, N2 at 285K and 50bar is cooled in the first HEX to 241K.Then
nitrogen is divided in 2 fractions. One of these fractions is sent to the second HEX to be cooled to
approximately 100K and expanded to 1.1bar producing cooling power fueling the HEX. After leaving
the first HEX, this N2 fraction is mixed with the second fraction which was also expanded to 1.1bar
previously. These gathered fractions are further compressed in stages to 50bar.
4. Methodology
All assumptions and strategies for the system under study are reported in this section. Firstly, chosen
buffering configurations are described with reference to their monitoring process. Liquefaction
simulations and economic model are explained thereafter.
4.1. Buffering study
4.1.1. Buffering configurations
4.1.1.1. Simple liquefaction
In this first simple scenario only the nominal liquefaction charge is accepted by the liquefaction unit.
Figure 15 explains the construction process of the buffer with 𝑏(𝑡) the quantity stored in the buffer at
the time t. The liquefaction unit works at a fixed nominal charge 𝑚̇ . If the production flow coming
from the electrolysis 𝑚̇ is higher than this value then excess is stored in the buffer whereas if 𝑚̇ is
lower the deficit is taken from the buffer.
𝑚̇ = 𝑚̇ ?
No Yes
𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) + (𝑚̇ − 𝑚̇ ) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)
Figure 15: Scenario with unique liquefaction charge
4.1.1.2. Flexible liquefaction
This second scenario depicted in Figure 16 is made more complex by adding liquefaction’s flexibility.
Moreover, referring to the previous conclusion a size limitation 𝐵 is implemented. Different values
are tested from 5 to 15 tons.
Based on internal data, realistic flexibility of ±20% is considered. For a fixed nominal liquefaction
charge 𝑚̇ , the liquefaction unit is designed as being able to accept gaseous inflows from 80% of
𝑚̇ to 120% of 𝑚̇ . In case of inflow deficiency or excess, the buffer will supply or store necessary
quantities. This system should decrease buffer’s size – and so the cost – because it increases the range
of liquefaction charge.
21
0.80 ∗ 𝑚̇ < 𝑚̇ < 1.20 ∗ 𝑚̇ ?
No Yes
𝐼𝑓 0.80 ∗ 𝑚̇ > 𝑚̇ 𝐼𝑓 1.20 ∗ 𝑚̇ < 𝑚̇ 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)
𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

+ (𝑚̇ − 0.80 ∗ 𝑚̇ ) + (𝑚̇ − 1.20 ∗ 𝑚̇ )
𝑏(𝑡) < 𝐵
OK 𝑏(𝑡) = 𝐵
Figure 16: Liquefaction flexibility at +/- 20% of nominal charge
4.1.1.3. Liquefaction flexibility and gauges control
Another buffering configuration is considered in this study. The process is described in Figure 17. This
system includes flexible liquefaction and gauges control. Gauges are set depending on buffering tank
filling. Between 30% and 70% filling, the GH2 flows sent to the liquefaction unit must value between
80% of 𝑚̇ and 120% of 𝑚̇ like in the second scenario. If buffering tank filling is lower than 30%
the liquefaction unit is set to function at a fixed 80%𝑚̇ . Likewise, if buffering tank filling is higher
than 70% the liquefaction unit is set to function at a fixed 120%𝑚̇ . This configuration is designed to
see if a more complex buffering system would help enhance performances.
30% < 𝑏(𝑡) < 70%?

No Yes
𝐼𝑓 𝑏(𝑡) < 30% 𝐼𝑓 𝑏(𝑡) > 70% 0.80 ∗ 𝑚̇ < 𝑚̇ < 1.20 ∗ 𝑚̇ ?
No Yes
𝑚̇ = 1.20 ∗ 𝑚̇ ?
No Yes
𝑚̇ = 0.80 ∗ 𝑚̇ ? 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)
𝐼𝑓 0.80 ∗ 𝑚̇ > 𝑚̇ 𝐼𝑓 1.20 ∗ 𝑚̇ < 𝑚̇
No Yes 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)
+(𝑚̇ − 𝑚̇ )
𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)
𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) + (𝑚̇ − 0.80 ∗ 𝑚̇ ) + (𝑚̇ − 1.20 ∗ 𝑚̇ )
+(𝑚̇ − 𝑚̇ )
Figure 17: Liquefaction flexibility and gauges control for liquefaction charge rating
The red stars identify actions that depend on storage size limitation. Other gauges setting will be
tested afterwards: 90-99%. Through this, the impact of gauges setting can be examined.
22
4.1.1.4. Liquefaction flexibility and water electrolysis
Based on the second configuration, liquefaction’s flexibility is considered again however the quantity
of GH2 taken from buffer is lowered with the water electrolysis unit in case of deficiency.
This additional water electrolysis unit has a small production capacity (CAP). Its capacity is supposed
to be 100% flexible so the GH2 production range from water electrolysis is between 0 and CAP.
Referring to the previous scenario, the excess or deficiency in incoming H2 were compensated by the
buffer as long as its size limit enabled it. In this case, when incoming flows are lower than 80% of the
nominal charge, the additional water electrolysis intervenes and furnishes as much as possible GH2
to reach 0.80𝑚̇ . The following Figure 18 represents this system with water electrolysis support.
0.80 ∗ 𝑚̇ − 𝐶𝐴𝑃 < 𝑚̇ < 1.20 ∗ 𝑚̇ ?

No Yes
𝐼𝑓 0.80 ∗ 𝑚̇ > 𝑚̇ 𝐼𝑓 1.20 ∗ 𝑚̇ < 𝑚̇ 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)
Addition of water 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

electrolysis unit at a + (𝑚̇ − 1.20 ∗ 𝑚̇ )
CAP
𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) +

(𝑚̇ − 0.80 ∗ 𝑚̇ − 𝐶𝐴𝑃)
Figure 18: Liquefaction flexibility supported by additional electrolysis
4.1.2. Performances features
In this part performances are evaluated by means of specific utility cost (SUC), CAPEX and
recuperation rate. These features are defined in the formula below.
𝑆𝑈𝐶 = [𝑘𝑊ℎ/𝑘𝑔 ] (4.1)
𝐶𝐴𝑃𝐸𝑋 = 𝐶𝐴𝑃𝐸𝑋 + 𝐶𝐴𝑃𝐸𝑋 + 𝐶𝐴𝑃𝐸𝑋 [𝑀$] (4.2)

𝐺𝐻 𝑠𝑒𝑛𝑡 𝑡𝑜 𝑙𝑖𝑞𝑢𝑒𝑓𝑎𝑐𝑡𝑖𝑜𝑛
𝑟= [%] (4.3)
𝑇𝑜𝑡𝑎𝑙 𝐺𝐻 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝐶𝐴𝑃𝐸𝑋 calculations refer to installed CAPEX. The economic model is based on internal
references. 𝐶𝐴𝑃𝐸𝑋 is estimated from the maximal flowrate to be compressed and the
pressure storage. 𝐶𝐴𝑃𝐸𝑋 is the CAPEX of the additional water electrolysis unit. Its value is also
obtained from internal basis and is a function of the CAP.
The recuperation rate (Eq 4.3) is relevant to evaluate the cost of the recuperation. Due to the variable
production profile depicted in Figure 11 (page 18), high production days causes high needs in storage
if these GH2 quantities want to be recovered. However, the higher the storage the more expensive it
gets. Therefore, there is a trade-off between recuperation and cost.
SUC and CAPEX values will be respectively expressed in relation to specific cost of the liquefaction
unit with open nitrogen precooling at 5TPD and its related CAPEX.
23
4.2. Liquefaction
4.2.1. Simulation procedure
Gaseous hydrogen (GH2) is fed to the liquefaction unit at around 20 bar and 25°C (298K) with H2 at
normal hydrogen (n-H2) composition: 25% p-H2 and 75% p-H2. This H2 feed is converted starting
from the cooling box along with cooling and liquefaction to around 20K and 1.3 bar. The p-H2 content
is higher than 95% at the outlet.
In this study all liquefaction processes are simulated with Aspen Hysys® software. H2 conversion is
simulated with an adiabatic reactor that is going to be further explain in the following subpart 4.2.1.2.
 H2 is fed at 21 bar and around 290K. LH2 is supplied at the end at 21K and 1.3 bar.
 Isomer composition of refrigerant hydrogen is assumed to always be the n-H2 composition.
 Stream properties are constant.
 Compressors isentropic efficiency is set at 80%. Electrical-to-mechanical efficiency of the
compressors equals 95%.
 Expanders isentropic efficiency is 85%. It is assumed that all this energy can be recovered
and can help compensate compressors work consumption.
 Pressure drops in the pipes are neglected.
 The lowest value of the minimum approach of heat exchangers (HEX) is 2K.
Minimum approach of HEX is established at least 2K except for the last HEX due to the easier heat
exchange. Firstly, pressure drops are neglected in order to draw up base simulations. They will be
considered afterwards.
4.2.1.1. Hydrogen model
In both open and close-N2 precooling processes there are two types of H2 streams: the H2 refrigerant
and the H2 feed to be liquefied. While the first is assumed to have a fixed composition of n-H2, the
second will see its composition change with the conversion taking place in cooling HEX. Peng-
Robinson thermodynamic model is chosen for H2 refrigerant and N2 because it is the most enhanced
model available in Aspen Hysys® that applies on a large range of temperature and pressure (T>2K,
P<1000bar) [30,47]. Soave-Redlich-Kwong model is used in Krasae-in thesis in PRO/II, but the
author specifies that Peng-Robinson equation of state gives quite similar results [48]. However, this
model does not include ortho and para specifications and the behaviour of the mixture o-H2 + p-H2
does not fit the one described in publications.
N-H2 is equivalent to a mixture of 75% o-H2 and 25% p-H2. However, when using Peng-Robinson
model, enthalpy and heat capacity are different at 30 bar and 300K for n-H2 and o-H2+p-H2 mixture.
These irregularities strongly influence heat transfer and temperature variations along the liquefaction
cycle. Therefore, MBWR model is used as advised by Aspen Hysys® support. With this model, n-H2
and p-H2+o-H2 mixture have similar properties with less than 0.05% difference.
HYSYS databank provides information on the different allotropes of hydrogen which are itemized in
the following Table 6.
Table 6: Properties of n-H2, p-H2 and o-H2 from HYSYS databank (from Aspen HYSYS V8.6 and Aspen Plus
V10 in bold)
Properties p-H2 o-H2 n-H2
Molecular weight (g/mol) 2.016 2.016 2.016
Normal boiling point (K) 20.27 20.43 20.39
Ideal Liq density (kg/m3) 70.84 70.55 70.57
TC (K) 32.98 33.26 33.19
PC (bar) 12.93 13.20 13.13
VC (m3/kmol) 0.06414 0.0641 00641
Acentricty -0.2208 -0.2144 -0.2160
Viscosity coefficient a/b -0.00296/0.2833 0.00701/0.2926 -0.36739/0.13233
24
Heat of formation @25°C (kJ/kmol) 58 - -
Heat of combustion @25°C (kJ/kmol) -2.419e5 -2.418e5 -2.419e5
Enthalpy basis offset (kJ/kmol) -9325 0 -8288
-49.68312/
0/1.67668e1/ 0/1.0796e1/
13.83761/
Mass vapor enthalpy (ideal gas at 0K) -5.35667e-3 1.98671e-2/
2.999806e-4/
= a+bT+cT2+dT3+eT4+fT5 (kJ/kg) /5.74841e-6/ 3.82053e-5/
3.45893e-7/
(heat of vaporization) -2.76062e-9 3.13544e-8/
-9.712927e-11/
/5.49333e-13 -8.86155e-12
7.731201e-15
According to H2 critical point, over 13 bar and 33K H2 is in supercritical state. Instead of indicating
supercritical state, Aspen Hysys ® identifies H2 as vapor phase but it appears that there are no issues
during fluid properties calculations.
4.2.1.2. Conversion
Based on previous literature and internal work it has been decided to simulate H2 ortho-to-para
conversion in adiabatic reactors [47]. In Aspen HYSYS, conversion reactors only consider polynomial
conversion as follows: 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 (%) = 𝐶 + 𝐶 𝑇 + 𝐶 𝑇 .
For each temperature the equilibrium composition of feed H2 can be calculated from the following
correlation.
Table 7: Correlation to calculate p-H2 equilibrium content depending on temperature (McCarthy, Hord, &
Roder, Selected Properties of Hydrogen (Engineering Design Data), 1981)
10K<T<50K T>50K
.
25 ∗ 9.7016 ∗ 10 ∗ 𝑇 + 100
% p-H2 −0.0169 ∗ 𝑇 + 0.4747 ∗ 𝑇 + 97.209
9.7016 ∗ 10 ∗ 𝑇 . +1
On the basis of the correlation in Table 7, p-H2 content is calculated for each outgoing temperature in
HEX. It is assumed that equilibrium is reached in each HEX so that (%𝑝 − 𝐻 ) = (%𝑝 − 𝐻 ) .
Conversion is simulated with a conversion reactor. %pi is the inlet p-H2 fraction in percentage and
%peq the outlet p-H2 fraction in percentage.
With a spreadsheet we calculate the equilibrium composition with the correlation in Table 7 and the
percentage of conversion of o-H2 into p-H2 that will lead to this equilibrium composition by using the
formula.
By passing through the reactor Aspen Hysys® automatically calculates the corresponding heat
transfer and the stream leaves the reactor with an equilibrium composition and a higher temperature.
Finally, the stream passes for the second time through the heat exchanger to be cooled to the same
temperature as the stream entering the reactor.
Calculations are performed by the software so at the end the energy removed from the feed stream
will only depend on the final state (and not on an external correlation). The difference with the real
conversion will come from the repartition of this energy during the cooling, thus the composite curve.
4.2.2. Pressure drops

4.2.2.1. Heat exchangers
Based on the process description in section 3.2 page 19 and methodology, a first basic simulation is
designed with no pressure drops. The goal is to consider these pressure drops so a sensitivity analysis
will be performed to see the impact on key parameters and economic features. Firstly three pressure
drop values are considered: 0.01 ,0.1 and 0.2 bar. These values are set on every stream and are equal
in every HEX. For each simulation CAPEX, SEC and SLC are estimated and at the end compared.
25
There are different ways to consider pressure drops in the literature. While some consider them to be
equal in all heat exchangers other give specified values. For instance, in Chang et al. work [49],
pressure drops for Brayton cycle were assumed to value 0.1 bar in all HEX. On the other hand Putselyk
specified different values [49]. These values are reported in the following Table 8.
Table 8: Pressure drops in HEX based on Putselyk work [48]
HEX TYPE HP/LP HP/MP HP/GN2 HP/LN2
MINIMAL UA [W/K] 4.39E+05 4.39E+05 1.30E+04 7.88E+04
HP 2.55 3.55 1.5 8.65
∆PF [MBAR]
LP 81.5 27.5 3.85 -
According to the previous Table 8 there are differences in pressure drops depending on flow
pressures. It appears that an average value of 0.01 bar for HP streams and 0.1 for LP streams. Hysys®
does not give size calculations indication. However, pressure drops are a function of design
parameters (see Eq. 5.1). In order to get more information and in an attempt to predict pressure drops,
a further study has been undertaken to get more pressure drop estimations.
𝑢 𝐿
∆𝑃 = 4𝑓𝜌 (4.4)
2𝐷
(𝑓 is the friction coefficient, 𝜌 fluid density, 𝑢 is the fluid flowrate in m/s and 𝐷 the hydraulic
diameter in m)
Based on internal studies Aspen Exchangers Design & RatingTM. module is used with each HEX
divided into groups of binary HEX: 1 cold stream + 1 hot stream. Thus, size is calculated for each
binary HEX and the maximal size is assigned to each group of binary HEX. At the end a simplified
estimation of possible pressure drops can be obtained.
4.2.2.2. Catalysis for ortho-to-para conversion
Not only heat exchangers have pressure losses, catalysis for ortho-to-para conversion causes pressure
drops as well. Several correlations are available in the literature. Wayne Lawrence Staats, Jr.’s thesis
presents a pressure drop calculation for catalyst bed needed for an hydrogen liquefaction pilot plant
[51]. These calculations are based on a previous work of Hutchinson on hydrous ferric oxide that
assumed the conversion to be limited by diffusion of hydrogen from the stream to the catalyst material
[52]. This assumption was validated in the thesis so it is used in the present work.
According to this diffusion-limited model, the 1-D mass transfer in a packed bed is expressed in the
following equation [53]:
𝑥 −𝑥 (4.5)
=𝑒 ̇
𝑥 −𝑥
Where the term on the left stands for the approach, 𝑥 is the p-H2 mass fraction, 𝑚̇ the mass flowrate
of H2 through the packed bed, 𝑔 the total mass transfer conductance and 𝑃 the transfer perimeter.
The latest is defined as:
6(1 − 𝜀 )𝐴 (4.6)
𝑃=
𝐷
where 𝐷 is the catalyst particle diameter, 𝜀 is the designed void fraction in the packed bed and 𝐴 the
bed cross section. Equations 5.2 and 5.3 can therefore be combined in Eq.4.7:
𝑥 −𝑥 6(1 − 𝜀 )𝐴 𝐿 (4.7)
− ln =𝑔
𝑥 −𝑥 𝐷 𝑚̇
26
And the bed cross section area can be extracted for a fixed length packed bed and void fraction. Once
these design calculations are performed, the results can be applied for pressure drops calculations.
Base pressure drops expression is the Ergun correlation (Eq.4.8) that is valid for Reynolds number
between 1<Re<104 [51].
. (4.8)
= +
with:
𝐿 =𝐷 (4.9)
𝑚̇ (4.10)
𝑣 =
𝜌𝜀 𝐴
The combination of these equations enables to estimate pressure drops during the conversion by
assuming that the results can be kept identical from conversion reactors to filled HEX. The following
table considers parameter values taken from technical information on the catalyst IONEX® and
Wayne Lawrence Staats, Jr.’s thesis [51,54].
Table 9: Parameters for pressure drops calculations ( 1: assumed as constant in HEX and equal to inlet value)
𝑔 1.34*10-2kg/(m2.s) 𝜌1 Extracted from Hysys® at each HEX
𝐷 5*10-4m 𝜇1 Extracted from Hysys® at each HEX
𝜀 0.3 𝑚̇ 5.79*10-2kg/s
4.2.3. Economic calculations

4.2.3.1. Key parameters
The Specific Energy Consumption, referred as SEC in this paper, is the energy required to
produce a kilogram of liquid hydrogen and characterizes a process. The liquefaction of hydrogen is
energy-consuming thus SEC is a key parameter to evaluate the performance of a cycle. As SEC is
relative to the product outlet flowrate it is independent of the capacity of the plant and both small-
size and big-size plants can reach low energy consumption.
The way SEC is calculated can vary depending of the inlet and outlet conditions and the technology
used. For instance, if inlet hydrogen is considered as already compressed, compression isn’t included
in the SEC, or if the precooling is made with LNG it can be considered as energy free as whether it is
used in the process or not LNG will be evaporated. It is recommended to be careful when comparing
SEC with other studies.
In this paper all SEC values will be calculated for an inlet H2 feed stream at 21 bar and 290K and a
supplied LH2 at 1.3 bar using Eq. 4.13. The power requirements are the sum of compressors and
expanders powers. SEC can be divided in precooling SEC and cooling SEC. The precooling SEC is
calculated with the power requirements of the precooling cycle, in case of an open precooling cycle.
𝑘𝑊ℎ ∑ 𝑃𝑜𝑤𝑒𝑟 (𝑘𝑊) ∗ 24 (ℎ)

𝑆𝐸𝐶 = (4.11)
𝑘𝑔 1000 ∗ 𝐿𝐻2 𝑝𝑟𝑜𝑑 𝑓𝑙𝑜𝑤 (𝑇𝑃𝐷)
𝑃𝑟𝑒𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑟𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑛𝑡 𝑐𝑜𝑠𝑡 ($/𝑡) 𝑃𝑟𝑒𝑐𝑜𝑜𝑙𝑖𝑛𝑔 𝑟𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑛𝑡 𝑓𝑙𝑜𝑤 (𝑇𝑃𝐷)
𝑆𝐸𝐶 = ∗ (4.12)
𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 𝑐𝑜𝑠𝑡 ($/𝑀𝑊ℎ) 𝐿𝐻2 𝑝𝑟𝑜𝑑 𝑓𝑙𝑜𝑤 (𝑇𝑃𝐷)
Exergy (J) is the maximum useful work possible during a process that brings the system into
equilibrium. It is the energy that is available to be used. After the system and surroundings reach
equilibrium, the exergy is equal to zero. Exergy is always destroyed when a process is irreversible, for
27
example loss of heat to the environment. This destruction is proportional to the entropy increase of
the system together with its surroundings.
Exergy is defined as:
𝐸𝑥 = 𝐻 − 𝑇 𝑆 (4.13)
Where H (J) and S (J/K) are the enthalpy and entropy, Ex (J) the exergy and T0 (K) the reference
environmental temperature.
The exergy efficiency is the ratio between the minimum net power needed, without irreversibility (or
destroyed exergy) and the actual work needed. It can be calculated for a system or a process. This
study is important to determine exergy losses (true thermodynamic losses) in processes and systems.
In this study, the exergy balance is made on the whole liquefier process:
̇
𝑊 + 𝑊 + 𝑒𝑥 𝑚 = 𝑊 + 𝑒𝑥 𝑚̇ + 𝐸𝑥 (4.14)
Where 𝑊 is the work of the component i (J), 𝑚 the mass of the component i (kg), 𝑒𝑥 the exergy of a
component i (J/kg) and 𝐸𝑥 the exergy destroyed (J).The net power is then minimal when no
exergy is destroyed, and then equal to Exproduct – Exfeed.
Thus,
𝑊 𝐸𝑥 − 𝐸𝑥 𝑆𝐸𝐶
𝜂 = = = (4.15)
𝑊 ∑𝑊 𝑆𝐸𝐶
The final formula is the one used to estimate the exergy efficiency of each process, with 𝑆𝐸𝐶 =
3.94 𝑘𝑊ℎ/𝑘𝑔 . This value includes hydrogen liquefaction and ortho-para conversion.
4.2.3.2. Economic model
The aim of this study is to estimate liquid hydrogen production cost. The steps and equipment costs
calculation details are presented below.
This study has been validated in the restricted context of empirical relationships based on internal
confidential data related to previous studies conducted on LNG at CRIGEN and on an economic
analysis of hydrogen liquefaction systems published by the International Association for Hydrogen
Energy (SYED, SHERIF, VEZIROGLUS, & SHEFFIELD, 1998). To evaluate liquid hydrogen price, it
will first be necessary to evaluate the equipment costs, that will determine the plant’s CAPEX and
OPEX. Finally, liquid hydrogen price will be estimated by an NPV calculation (Net Present Value).
Final CAPEX, meaning the cost of the installed liquefaction plant depend on numerous costs. It can
be expressed as:
𝐶𝐴𝑃𝐸𝑋 = 𝑓 ∗𝑓 ∗𝑓 ∗ 𝑆𝑈𝑀 (4.16)
Where 𝑆𝑈𝑀 is the sum of the major equipment costs (compressors, turbine and cryogenic exchanges
lines), 𝑓 is the cost factor of collateral equipment (chillers, valves, pumps and piping), 𝑓 the
equipment installation cost factor including engineering costs, construction, insurances and
unexpected events, and 𝑓 the complete plant installation cost factor (liquefaction process,
pretreatment, liquid hydrogen storage and utilities). These factors are confidential and based
on internal economic models.
28
OPEX includes:
 Fixed OPEX, representing maintenance and labor costs.
 Variable OPEX, representing especially utilities.
The liquid hydrogen price will be the one for which the NPV is equal to 0. NPV is the addition of the
plant cash-flows along its life, containing all the investments cost, depreciation and aging. Thus, NPV
is related to the plant CAPEX and OPEX and to the following financial assumptions:
 Plant lifetime: 20 years.

 Use/availability rate: 85%/year.
 Actualization rate: 10%.
 Imposition rate: 35%.
 Inflation rate: 1% Sensitivity analysis.
Several parameters can impact economic or energy evaluation of the buffering unit and the
liquefaction system. For the buffering, the pressure storage and the electricity cost both impact these
evaluations as they affect the compression and expansion work as well as economic evaluation.
Liquefaction system electricity cost affects SLC evaluation. Moreover, pressure drops cause a decrease
in pressure as streams pass through HEX. Therefore, local pressure increases or inlet pressure
increase are needed. This can strongly impact key parameters and economic evaluation.
4.2.4. Electricity cost
According to the economic model described in section 4.2.3.2, the electricity cost impacts strongly the
SLC evaluation. As electricity cost depends on the market location or the electricity source and as it
can vary from one year to another, a sensitivity study on electricity cost will be performed. This change
in electricity cost is consider for the liquefaction unit as well as in the buffering study because
compression before temporary storage tank requires electrical input.
4.2.5. Storage pressure
As the CGH2 pressure increases, H2 volumetric density increases as summarized in Table 10. However
technological cost increases as well because material must resist to higher pressure and insulation
must be ensured. In addition to technological issues for the storage tank, there is also a higher
compression work if the storage pressure is increased.
Table 10: Density and technological cost for several CGH2 systems at 293K (20°C)
Storage pressure (bar) Density (kg/m3)
100 7.80
200 14.71
300 20.87
500 33.34
4.2.6. Procedure for results expression
All key parameters and economic results will be expressed in relation to chosen reference values. This
reference case is Linde Leuna (LN2) system at 5TPD with 95% compressors efficiency and without
pressure drops. Therefore SEC, SLC, SUC and CAPEX will be given in relation to LN2 SEC, SLC and
CAPEX values. Therefore, relative parameters are introduced as:
𝑆𝐸𝐶
∆𝑆𝐸𝐶 = [∅] (4.17)
𝑆𝐸𝐶(𝐿𝑁 )
29
𝑆𝐿𝐶
∆𝑆𝐿𝐶 = [∅] (4.18)
𝑆𝐿𝐶(𝐿𝑁 )
𝑆𝑈𝐶
∆𝑆𝑈𝐶 = [∅] (4.19)
𝑆𝐿𝐶(𝐿𝑁 )
𝐶𝐴𝑃𝐸𝑋
∆𝐶𝐴𝑃𝐸𝑋 = [∅] (4.20)
𝐶𝐴𝑃𝐸𝑋(𝐿𝑁 )
5. Results and discussion
5.1. Buffering
As seen in section 4.1.1 there are 4 configurations understudied based buffer and liquefaction
properties:
(1) Steady liquefaction with unique liquefaction charge

(2) Flexible liquefaction with ±20% nominal liquefaction charge
(3) ±20% flexible liquefaction and gauges control
(4) ±20% flexible liquefaction and water electrolysis support
As a reminder, liquefaction charge refers to the mass flow of GH2 sent to the liquefaction unit and
results consider that compressors and water electrolysis unit.
5.1.1. Configurations results
As stated in part 4.1.1 (page 21) the first buffering configuration to be considered is a simple one based
on the assumption that the liquefaction unit can only liquefy at a constant flowrate. After Excel®
calculations, the required storage tank size depending on the fixed nominal liquefaction charge (NLC)
is represented in the following Figure 19. The recuperation rate can value more than 1 due to the
necessary addition of initial GH2. Minimum buffer size is obtained for an 8.1TPD liquefaction charge.
However, the related buffer size is 90 tons. It is not an acceptable size due to technical and economic
reasons. After discussions with the project team at ENGIE and available data, the buffer size is set at
20 tons.
450 1.2
400
1
350
Recuperation rate
Buffer's size (t)
300 0.8
250
0.6
200
150 0.4
100
0.2
50
0 0
6.5 7 7.5 8 8.5 9
Nominal liquefaction charge (TPD)
Figure 19: Buffer size (blue) and recuperation rate (orange) as function of nominal liquefaction charge
All the following buffering configurations previously detailed are performed by using Excel®.
According to previous methodology, maximum NLC is calculated as well as the respective
recuperation rate (Eq. 4.3). All configuration results are summarized in the following tables. In order
to calculate CAPEXcompression, the maximal GH2 flowrate to be compressed to 300 bar is listed in each
case.
30
Table 11: Performances for the +/-20% flexibility configuration
Size (tons) 20 15 10 8.5 7.5 5
Max. NLC (TPD) 7.8 7.6 7.4 7 6.8 6
Recup. Rate (%) 99.9 99.3 98.1 95.2 93.6 85.8
Max. GH2 to compression (TPD) 1.18 1.23 1.09 1.05 1.29 1.06
According to Table 11, the second configuration considering liquefaction flexibility enables to reach
7.8TPD with a storage capacity 78% lower than the simplest configuration. Therefore, liquefaction
flexibility is a significant optimization and design parameter. Data displayed in Table 11 highlights
that the bigger the storage, the higher the recuperation rate. This is a consequence of the increasing
waste of GH2 when buffer size limit is decreased.
The third configuration in this study includes liquefaction flexibility like the previous ones but this
time the liquefaction functioning is controlled by gauges. These gauges are set depending on the buffer
filling as depicted in Figure 17 page 22.
Table 12: Performances of +/-20% flexibility and gauges control 30-70%
Size (tons) 15 10 8.5 7.5 5
Max. NLC (TPD) 8.2 7.4 6.3 5.9 5.2
Recup. Rate (%) 99.19 97.2 89.6 85.2 75.6
Max. GH2 to compression (TPD) 2.59 3.23 2.02 2.34 2.90
Table 13: Performances of +/-20% flexibility and gauges control 90-99%

Size (tons) 15 10 8.5 7.5 5
Max. NLC (TPD) 8.2 7.4 7.0 6.6 6
Recup. Rate (%) 99.19 97.2 94.58 91.19 85.18
Performances are higher than the second configuration, which is based only on liquefaction flexibility,
only for the 15 tons case. Afterwards, performances are lower.
When the nominal liquefaction charge increases, the range values of possible GH2 flowrate to be sent
directly to liquefaction increase. Therefore, it becomes harder to compensate the very low GH2
production days. Therefore, an additional water electrolysis (WE) unit is introduced in the last
configuration. It supplies external GH2 to reduce buffer compensation and increase the maximum
nominal liquefaction charge for each size limitation.
Table 14: Performances of +/-20% flexibility and additional H2O electrolysis at 2TPD
Size (tons) 15 10 8.5 7.5 5
Max. NLC (TPD) 8.4 8.4 8.4 8.4 8.4
Recup. Rate (%) 100 100 100 100 100
Table 15: Performances of +/-20% flexibility and additional H2O electrolysis at 1.5TPD
Size (tons) 15 10 8.5 7.5 5
Max. NLC (TPD) 8.2 8.2 8.2 8.2 7.9
Recup. Rate (%) 99.9 99.9 99.9 99.9 99.5
Table 16: Performances of +/-20% flexibility and additional H2O electrolysis at 1TPD
Size (tons) 15 10 8.5 7.5 5
Max. NLC (TPD) 8.1 8.1 7.8 7.7 7.3
Recup. Rate (%) 99.9 99.9 99.5 99.3 97.1
31
According to the data presented in Table 14, Table 15 and Table 16, addition of the water electrolysis
unit achieves higher nominal liquefaction charges. The higher the additional capacity, the higher the
nominal liquefaction charge. Besides liquefaction charge increase, another effect of this addition is
the drop of performances variations. The maximum NLC is more stable and depends less on the buffer
size. The liquefaction flexibility and the additional capacity widen the possible GH2 flowrate and high
buffer size are not fully filled (see Figure 20 and Figure 21).
5 9
H2 mass in the buffer (tons)

H2 mass in the buffer (tons)
8
4 7
6
3
5
2 4
3
1 2
1
0 0
0 100 200 300 400 0 100 200 300 400
Day Day
Figure 21: Buffer profile for a 2TPD water Figure 20: Buffer profile for a 1.5TPD water
electrolysis and 15 tons storage electrolysis and 15 tons storage
According to the statistics performed on production data (Table 5), the average GH2 flowrate is
8.20TPD. In the fourth configuration with WE, maximal NLC are closer to 8.20TPD even higher than
it but the costs might be very high due to WE addition. Therefore, even if the other configurations
give NLC lower than 8.20TPD, they might be preferred for economic reasons.
5.1.2. Economics
Based on the previous performances, CAPEX and SUC are calculated for a CGH2 storage at 300 bar.
Results are given in relation to 200 bar storage of 20 tons of CGH2 with a 1.06TPD maximum flowrate.
Details of CAPEX and SUC calculations are summarized in Appendix 1: Buffering – Economic tables
page 47 while final values are reported in the following Figure 22 and Figure 23.
1.20 9
8
1.00
7
0.80 6
NLC (TPD)
5
ΔSUC
0.60
4
0.40 3
2
0.20
1
0.00 0
15 10 8.5 7.5 5
Buffer size limit (GH2 tons)
+/-20%: SUC +/-20%+gauges 30-70: SUC
+/-20%+gauges 90-99: SUC +/-20%+gauges90-99: NLC
+/-20%: NLC +/-20%+gauges30-70: NLC
Figure 22: Key parameters and specific utility cost of buffer configurations (except WE)
32
300 8.6
8.4
250
8.2
8
200
NLC (TPD)
7.8
150 7.6
ΔSUC
7.4
100
7.2
7
50
6.8
0 6.6
15 10 8.5 7.5 5
+/-20%+WE2.0: SUC +/-20%+WE1.5: SUC
+/-20%+WE1.0: SUC +/-20%+WE2.0: NLC
+/-20%+WE1.5: NLC +/-20%+WE1.0: NLC
Figure 23: Key parameters and specific utility cost of WE buffer configurations
In Figure 22 it is showed that ΔSUC values are increasing in each configuration when buffer limit is
increased. Low buffer limit brings low ΔSUC but also low NLC value and therefore a final lower LH2
capacity over the whole value chain. For instance, for the configuration with +/-20% flexibility and
the configuration with 30-70% gauges control, reducing the buffer limit from 15 tons to 5 tons lowers
ΔSUC to 0.56 and 0.40 respectively.
Concerning Figure 23 the addition of water electrolysis (WE) unit strongly raise ΔSUC due to high
WE CAPEX. Focusing on the 2TPD WE case in this figure (red data), ΔSUC is constant because
CAPEX for a 2TPD WE unit is strongly higher than CAPEX variations due to buffer size decrease. In
the case of 1TPD WE, the reduction of buffer size does not cause a ΔSUC reduction like in Figure 23.
This is due to the small difference in CAPEX value and the fact that the NLC decreases so the specific
cost increases even if the buffer size is reduced.
1.40
1.20
1.00
0.80
ΔSUC
0.60
0.40
0.20
0.00
60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0 105.0
Recuperation rate (%)
Flexibility Gauges 30-70% Gauges 90-99%
Figure 24: Recuperation rate and SUC for flexibility and gauges systems
Due to the high cost of WE addition these buffer configurations are no longer considered. In order to
discuss the cost of recuperation increase, data from the remaining 3 configurations are depicted in
Figure 24 above. Several conclusions can be drawn from it. First, gauges system at 90-99% have
higher ΔSUC values under 90% recuperation. On the other hand the gauges configuration at 30-70%
gives lower costs and data are closed to the flexibility system. Referring to data highlighted in red, 30-
70% gauges give lower recuperation for higher ΔSUC values. For every system, the higher the
33
recuperation the higher the ΔSUC. Above 97%, ΔSUC increases are similar for all configurations. To
increase the recuperation from 97% to around 99% would raise ΔSUC from around 0.70 to 0.96.
A 0.26 ΔSUC increase for only 2% more in GH2 recuperation is considered too much therefore
working on buffer size with recuperation lower than 90% seems to be a good compromise between
recuperation and cost. The combination with the liquefaction unit will be further discussed after
liquefaction unit study.
5.2. Liquefaction
5.2.1. Performances
Liquefaction processes are simulated on Hysys® based on the PFD in Figure 13 and Figure 14.
350
300
Temperature (K)
250
200
150
100
50
0
0.0E+005.0E+05 1.0E+06 1.5E+06 2.0E+06 2.5E+06 3.0E+06 3.5E+06 4.0E+06
Heat flow (kJ/h)
Figure 25: Hot (red) and cold (blue) composite curves of the LN2 system
Composite curves are extracted from the performances of each HEX to be summarized in Figure 25
reports that this base process has good thermodynamic performances. The cold composite curve
follows the hot composite curve. The effect of the liquid nitrogen precooling is witnessed by the
plateau at 78K. This Linde Leuna process is set as the basis result in this project and all economic or
energy results will be expressed in relation to it.
Table 17: Relative energetic results for basis LN2 simulations
Energy
ΔSEC (Ø) 1
ΔSECPRECOOLING 0.44
ΔSECCOOLING 0.56
Relative exergy efficiency 1
ΔSLC (Ø) 1
The relative specific energy consumption (ΔSEC) is therefore set at 1 as stipulated in Table 17. In the
simulation, nitrogen is assumed to be supplied at liquid state and the energy from the transportation
or the source is not considered. Therefore, it could add additional energy consumption to the value
calculated above. Despite that fact, LN2 energy consumption is still lower than industrial liquefaction
plants whose energy consumption ranges between 11 and 15 kWh/kgLH2.
34
350
300
250
Temperature (K)
200
150
100
50
0
0.0E+00 1.0E+06 2.0E+06 3.0E+06 4.0E+06 5.0E+06 6.0E+06
Heat flow (kJ/h)
Figure 26: Hot and cold composite curves of the SN2 system
In comparison with the previous liquefaction process using open nitrogen precooling, the SEC is lower
by 13% (see Table 18). Therefore the exergy efficiency is higher in this SN2 system. Compared to
literature data listed in Table 4 the obtained SEC ranges below industrial plants energy consumption
and close to conceptual plants values.
Table 18: Energetic results for basis SN2 simulations, in relation to LN2 results
Energy
ΔSEC (Ø) 0.87
ΔSECPRECOOLING 0.31
ΔSECCOOLING 0.56
Relative exergy efficiency
1.15
(compared to k)
ΔSLC (Ø) 0.86
Focusing on SLC comparison, SN2 configuration enables to reduce ΔSLC value by 14%. Furthermore,
LN2 system requires constant supply in LN2 while SN2 uses a closed loop. By taking into consideration
all the previous comments, SN2 configuration will be only studied in the rest of the project.
5.2.2. Pressure drops

5.2.2.1. Heat exchangers
According to initial simulations, pressure drops were neglected however the literature has showed
that pressure drop impact must be considered. The sensitivity analysis is performed for at 5TPD
capacity like initial performances and the results from these analysis will be adapted for the economic
analysis. As specified in the beginning of this section assuming pressure drops in HEX is a more
realistic scenario. It is primarily assumed that the pressure drops are equals in all heat exchangers
and three different values are evaluated: 0.01bar, 0.1bar and 0.2 bar.
35
1.05
0.99
1.00
0.96
0.95
ΔSLC
0.90
0.87
0.86
0.85
0.80
0.75
0 0.01 0.1 0.2
Pressure drop (bar)
Figure 27: ΔSLC evolution with pressure drops at 5TPD
According to Figure 27 and Figure 28 the addition of pressure drops increases both energy
consumption and liquefaction cost. Due to the gradual loss of pressure in returning refrigerant
streams, final pressures entering the compression box are below 1 bar. Therefore, initial returning
pressures from refrigerant expansion should be increased. It affects the cooling power and
intermediate temperatures and refrigerant flowrate must be optimized.
As revealed by Figure 28 below, the precooling cycle is less impacted than cooling system. Energy
performances are not increased much after 0.01 bar pressure drops addition. However, if 0.1 bar and
0.2 bar pressure drops are added, ΔSEC rises by 17% and 29% respectively. These increases are
making SEC values closer to SEC values from industrial liquefaction plants (see Table 4).
1.20
1.00
0.35
0.80 0.33
0.31 0.31
ΔSEC
0.60
0.40
0.66 0.72
0.56 0.57
0.20
0.00
0 0.01 0.1 0.2
Cooling Precooling
Pressure drop (bar)
Figure 28: ΔSEC evolution with pressure drops at 5TPD
As specified in part 4.2.2.1 page 25 pressure drops estimations are performed with Aspen Exchangers
Design & RatingTM. This study also revealed variations in pressure drops depending on streams
pressure like Putselyk study [50]. Therefore pressure drops distribution is adapted and 0.1 bar is
allocated to LP streams while 0.01 is allocated to HP streams. The performance and economics results
based on these assumptions is shown in Table 19.
Table 19:Relative key parameters for 0.1 bar (LP) and 0.01 bar (HP) pressure drops
ΔSEC ΔSLC ΔCAPEX
0.96 0.96 1.30
Both ΔSEC and ΔSLC of these pressure drops assumptions have values close to the 0.1 bar case in
Figure 27 and Figure 28. It means that the pressure drops on HP streams have less impact on SEC
36
and SLC than those on LP streams. This is due to the compensation for pressure drops that is needed
for returning LP streams.
At the same time, some heat exchanger suppliers were contacted in order to get pressure drops
estimations. Discussion with them confirmed that pressure drop depends on heat exchanger
geometry and heat exchanger type. The supplier has been working to design the appropriate heat
exchanger configuration by setting a 0.2-0.4 pressure drops limit. However these hight pressure
drops might be due to the fact that the supplier was not working with multi-streams heat exchangers.
In another literature report from Nazir et al. [55] the authors are studying hydrogen production from
gas switching reforming. They assumed that pressure drops are 2% of the inlet pressure at gas side
and 0.4 bar in liquid side. However in the present study, gas and liquid side have not been treated
differently. After discussion with the project team at ENGIE 2% pressure drop has been considered
to be too high, it would result to a total 2.8 bar pressure drop in the feed H2 line (see Figure 14).
However, pressure drops in the liquid side are close to the pressure drop limits from the supplier.
It is assumed that heat exchangers can be optimized at best so that pressure drops value 0.1 bar.
Pressure drops mainly depend on heat exchangers design and optimization. Therefore, optimistic
assumptions are made and the last configuration tested (see Table 19) is kept as
reference for heat exchangers pressure drops for the final evaluation.
5.2.2.2. Catalysis
The results from the study of catalysis pressure drops is given in Figure 29. For the chosen parameters
pressure drops value in all HEX are represented as a function of the approach (see Eq.4.5). At very
low approach (0.01%) pressure drops equal between 0.03 and 0.24 bar. It is clear that pressure drops
depends on the approach and therefore on conversion space size. However, in this study there are no
heat exchanger sizing so pressure drops cannot be allocated based on dimensions.
3.0
2.5
Pressure drop (bar)
HEX3
2.0
HEX4
1.5 HEX5
1.0 HEX6
HEX7
0.5
HEX8
0.0
0 10 20 30 40 50 60
Approach (%)
Figure 29: Pressure drops in HEX based on packed bed catalysis model
Furthermore, a quick sensitivity analysis on the effect of the bed void fraction in HEX3 shows that for
0.01% approach, the pressure drops can decrease from 0.87 bar to 0.03 bar if the bed void fraction is
increased from 0.3 to 0.6.
According to Donaubauer et al.’s kinetics for ortho-para hydrogen conversion during liquefaction, the
higher the inlet pressure of the HEX the better the conversion [55]. Therefore, the possible pressure
drops occurring during conversion could impact the following conversions. In the present study the
conversion is assumed to reach around 100% however real conversions will be less than 100%. Thus,
final isomer composition of LH2 would be changed so performances would differ as boil-off gas could
be produced. However, this project does not examine HEX design and as catalysis pressure drops are
strongly depend on it, they will be neglected in the following sections.
37
Finally pressure drops are considered equal to 0.1 bar for LP streams and 0.01 bar for
HP streams while pressure drops from conversion are set to 0.1 bar. Therefore, feed H2 streams
loose 0.11 bar at each conversion-HEX. This final simulation gives ΔSEC and ΔSLC of 0.96 and 0.96.
In comparison with state-of-art Linde Leuna SEC, the obtained SEC is still lower than the 11-12
kWh/kgLH2.
5.3. Final analysis: buffer and liquefaction combination

According to previous discussion in section 5.1.2 (page 32), the second buffer configuration with
±20% flexibility appears to be a better choice as it enables higher nominal liquefaction charge (NLC)
at lower buffer size. Results highlighted that increasing the NLC requires to increase buffer size hence
the specific utility cost increases at high NLC. However, this increase might be compensated with
liquefaction unit scale-up. Therefore, this final discussion aims at studying the combination of the
two units and their cost combinations.
With regard to liquefaction unit, pressure drops must be considered because they can affect energy
consumption and liquefaction cost drastically. With final pressure drops consideration (0.1+0.01
bar), it gives a 18% SEC increase in comparison with SN2 simulation without pressure drops. The final
pressure drops assumptions for a 5TPD capacity gave respective ΔSEC and ΔSLC values of 1.65 and
0.96. However, these costs might be affected by scale-up requirement due to NLC values from buffer
unit.
2.00 105
1.80
100
1.60
Recuperation rate (%)

1.40
95
1.20
Δcost
1.00 90
0.80
85
0.60
0.40
80
0.20
0.00 75
6 6.8 7 7.4 7.6
NLC (TPD)
Rel. SLC Rel. SUC Recup. rate
Figure 30: Liquefaction scale-up and buffer combination, SN2 system with 0.1-0.01 bar pressure drops
According to Figure 10 (page 18), outgoing streams from the buffer need to be expanded from 300
bar to 21 bar in order to be liquefied. GH2 is stored at round 290K in the buffer tank. However, this
storage temperature is higher than H2 inversion temperature therefore if H2 pressure is decreased
temperature will decrease. After expansion and heater simulation with Aspen Hysys®, H2
temperature is calculated to drop by 127K and 21.3kW/TPDH2 are required to heat up stream. It adds
a relative cost of 0.01 to cost calculated in Figure 27.
According to Figure 30, when NLC is increased ΔSLC is decreased. Scale-ups to 6, 6.8, 7, 7.4, 7.6TPD
causes respectively 3, 4, 5 and 6% ΔSLC decrease. The studied NLC values are linked to NLC values
calculated in Table 11 (page 31) for the second buffer configuration with ±20% flexibility. According
to previous economical calculations on buffer system, if buffer limit is increased from 7.5 tons to 10
tons then ΔSUC increases from 0.59 to 0.71. However, this increase cannot be compensated by
liquefaction scale-up given that ΔSLC is only reduced by 0.02.
38
Furthermore, at 6TPD the liquefaction unit gathers 66% of the total upstream cost whereas at 7.6TPD
it equals 45%. The increase of buffer size makes buffer section the major cost intensive
unit.
6. Sensitivity analysis
6.1. Electricity cost

During the previous economic analysis an electricity cost of 75$/MWh was considered. However,
this cost can vary depending on the electricity source or liquefaction plant location. For instance, in
Europe, the following Table 20 lists electricity prices (excluding taxes) among several European
countries [55]. Prices are expressed in dollar based on conversion data on the 11/01/2021 [58].
Table 20: Electricity prices for industries in Europe (data from 2019)
Country Price (€/MWh) Price ($/MWh)
Germany 90.4 109.8
Italy 116.6 141.7
France 71.7 87.1
Spain 86.4 105.0
Estonia 75.7 92.0
Finland 56.7 69.0
Sweden 52.7 64.0
United Kingdom 132.4 160.9
Therefore, a sensitivity analysis is carried out for electricity prices from 50$/MWh to 100$/MWh
with step change of 10$/MWh. This sensitivity analysis is performed for both buffering and
liquefaction unit. For the SLC, the sensitivity analysis is conducted on the final model from part 5.2.2
page 35.
1.20
1.00
0.80
ΔSLC
0.60
0.40
0.20
0.00
50 60 70 80 90 100
Electricity cost ($/MWh)
Figure 31: Sensitivity analysis of electricity cost on SLC at 5TPD
Figure 31 reveals that SLC variations are linearly dependent on electricity cost. An increase of
10$/MWh in electricity cost causes a 3% rise in ΔSLC. Reference electricity cost was 75$MWh. In the
pressure drops study, Figure 27 showed that the assumption with 0.1bar pressure drop in all HEX
could increase ΔSLC by 12%.
However, it is important to understand that sensitivity analysis results are strongly dependent on the
economic model. Different industrial clients or research groups might differ on what to include as
well as coefficient value for estimations.
With the economic model used in the present study, we can conclude that electricity cost affects the
overall cost but less than pressure drops consideration.
39
6.2. Storage pressure
In the previous buffer study, the storage pressure was considered equal to 300 bar. However, Table
10 page 29 highlighted that the higher the pressure, the higher the hydrogen – so the energy – density.
High pressures apparently require less volumes. But this increase in pressure storage comes with
more complex technologies for storage tank. Therefore, CAPEX increases and safety issues are higher.
Nevertheless, it is necessary to review how this pressure might affect the overall cost of the chain
value.
The effect of storage pressure is studied for the second configuration with ±20% flexibility. Specific
utility cost (SUC) values are expressed with reference to the initial results for 300 bar of pressure
storage.
1.80
1.60
1.40
1.20
100 bar
1.00
ΔSUC
200 bar
0.80
0.60 300 bar
0.40 500 bar

0.20
0.00
0 5 10 15 20 25
Figure 32: ΔSLC as function of buffer storage pressure
6.00
5.00
4.00
100 bar
ΔCAPEX
3.00 200 bar
2.00 300 bar

500 bar
1.00
0.00
0 5 10 15 20 25
Figure 33: ΔCAPEX as function of buffer storage pressure
Figure 32 and Figure 33 shows that ΔSLC and ΔCAPEX variations are alike for all storage pressure
values. There is an average 23% and 12% decrease in ΔSUC values for a respective 100 bar and 200
bar storage pressure in comparison with 300 bar. As for increasing storage pressure up to 500 bar, it
increases ΔSUC by 29%.
Decreasing the pressure storage has economic advantages however it would increase land use.
According to density values in Table 10 (page 8), 10 tons of GH2 at 300 bar take up 479m3 whereas at
200 bar and 100 bar they take up 680m3 and 1282m3 respectively.
40
ΔSUC variations due to storage pressure choice are equal or higher than ΔSLC variations with
pressure drops that equals between 3% and 12% increase. Therefore, storage pressure must be
thought through.
6.3. Liquefaction flexibility

In section 5.1 page 30, buffer configuration considered liquefaction flexibility with a ±20% variation
of the nominal liquefaction charge (NLC). This assumption of liquefaction flexibility is based on
discussion with the project team at ENGIE. However, other literature reports that -40% of NLC can
be considered as a technical liquefaction flexibility today [59].
Liquefaction flexibility depends on technological limitations and equipment. It seems interesting to

see the possible impact of liquefaction flexibility improvements on buffer performances and therefore
liquefaction and buffer combination. This sensitivity study appears to be justified due to the future
increase of intermittent renewable energies and the development of hydrogen liquefaction. New NLC
and ΔSUC are calculated and are reported in the following Figure 34.
0.8 1.7
0.7
1.6
0.6
0.5 1.5
ΔCAPEX
ΔSUC
0.4
0.3 1.4
0.2
1.3 Relative
0.1 SUC
Relative
0 1.2 CAPEX
±20% -35% -40% -45%
Liquefaction flexibility
Figure 34: Liquefaction flexibility impact on major parameters for a 7.5 GH2 tons buffer capacity
According to Figure 34 above, to change the flexibility from ±20% from -35% enables to decrease
ΔSUC by 19%. It is the major ΔSUC reduction because changing liquefaction flexibility from -35% to
-45% only reduces ΔSUC by 9%. In this project ±20% flexibility was considered based on internal
data, however to consider -40% as reported in literature would decrease ΔSUC by 26%. Hence the
total upstream cost would be reduced.
In section 5.3 page 38, liquefaction flexibility was highlighted to be the most economically interesting
buffer configuration. As a partial conclusion, this sensitivity analysis completes these previous buffer
discussions by revealing that liquefaction flexibility optimisation can lead to upstream cost reduction
and is therefore a critical parameter in hydrogen liquefaction from variable GH2 source. It would
enable to offset the upstream cost increase described in Figure 30.
6.4. Time basis

Data presented in Figure 11 are based on daily average. All calculations that have been performed
therefore assume that GH2 inflow are strictly equal to the average value the entire day. However, the
available data can be studied under more focused scale.
After calculating standard deviation for each daily average value, standard deviations vary between
0.001TPD and 2.76TPD. According to standard deviation definition the lower the standard deviation
value the more homogeneous daily GH2 production. The mean value of standard deviation is
0.544TPD. Therefore, GH2 production data can be considered to be quite homogeneous.
41
In order to see if these deviations impact the second configuration (±20% flexibility), calculations are
made based on hourly production data and not the daily average as before. Maximal nominal
liquefaction charge (NLC) and recuperation rate are evaluated for the same buffer capacity as
previous analysis. These results are summed up in following Table 21.
Table 21: Comparison of buffer performances between hourly and daily basis
Size (tons) 15 10 8.5 7.5 5
Max. NLC (TPD) 7.4 7.4 7.4 7.3 6.6
Hourly basis
Recup. Rate (%) 98.04 98.04 98.04 97.22 90.90
Max. NLC (TPD) 7.6 7.4 7 6.8 6
Daily basis
Recup. Rate (%) 99.3 98.1 95.2 93.6 85.8
In comparison with initial results from Table 11 NLC values are higher or equal for 15 and 10 tons
limits. However, for lower limits, the new NLC values are 6%, 9% and 23% higher. These differences
are the consequences of hourly production deviations from the average value used before. To further
evaluate the time basis effect, liquefaction ramp up and down rates should also be considered.
7. Conclusions and future work

This thesis focused on an industrial by-product H2. Considering that renewable energy use will
increase in the future, intermittent GH2 source might increase. Hydrogen liquefaction is an
advantageous storage and transport solution for hydrogen. Due to the recent attention drawn towards
liquid hydrogen in Europe combined with the increasing intermittent production of hydrogen, it is
important to study liquefaction and intermittency in combination. Intermittent energy have large
variation from one season to another, especially for solar and wind energy. In this thesis, we focused
on an industrial intermittent by-product source which varied less than renewable sources. This thesis
is a simplified case leading towards future projects at ENGIE such as liquefaction flexibility and heat
exchanger design for pressure drop optimization.
In order to answer the research questions, the upstream study was firstly divided into two: buffer and
liquefaction. In the buffer section, different configurations were studied as well as their impact on
gaseous H2 recuperation rate and costs. Secondly, the liquefaction unit was studied and it showed that
closed-nitrogen precooling and H2 Claude cooling resulted in improved performance. Hence this
system was considered for pressure drop study and in combination with buffer unit by performing
capacity scale-up studies.
Results indicate that 100% recuperation rate is not ideal due to the increase in specific costs.
Therefore, trade-off between recuperation rate and cost is required. With regards to liquefaction cost,
a 0.1 bar pressure drop showed a 10% cost increase. The study with buffer-liquefaction combination
concluded that reduction in liquefaction cost with capacity increase is lower than buffer costs
increase. Therefore, by-product GH2 recovery up to 90% with 59%-71% of the liquefaction cost is
preferred. Furthermore, storage pressure and liquefaction flexibility are critical for liquefaction from
variable source. Results show 30% of ΔSUC increase for storage pressure increases of 200 bar and a
19% ΔSUC drop by ensuring -35% liquefaction flexibility.
These conclusions are drawn by assuming no cost increase in liquefaction and compressors between
initial simulations and flexibility scenario as well as assuming that compressors and electrolyser
tolerate variability. Technical adaptation to variability would increase costs. Specific buffer cost was
calculated using CAPEX cost from data provided at ENGIE. Electricity costs in OPEX can affect the
results. Future work is recommended in this topic. Effect of pressure drop due to the presence of
catalysts should also be evaluated. Finally, the thesis also presents that changing the time scope for
the buffer shows different performance of the buffer system.
42
References
[1] Zohuri, B. The Chemical Element Hydrogen. In: Hydrogen Energy. 2019. p.1-35.
[2] Gamon, C. Rapport sur une approche européenne globale de stockage de l'énergie.
2020. Commission de l'Industrie, de la Recherche et de l'Energie. European
Parliament.
[3] European Commission. (11.12.2019). The European Green Deal. Brussels.
[4] Godula-Jopek, A. Hydrogen Production: by Electrolysis. 2015. Wiley-CVH Verlag
GmbH & Co.
[5] S. Banerjee, M.N. Musa, A.B. Jaafar. Economic assessment and prospect of hydrogen
generated by OTEC as future fuel. International Journal of Hydrogen Energy
2017; 42 (1):26-37.
[6] A. Cornell. Hydrogen production by electrolysis. 1st international conference on
electrolysis. Copenhagen, Denmark. June 2017: 12-15.
[7] Isao A (Anon). Statistics of hydrogen production and consumption, Energy Careers and
Convers Syst. vol.1. (UNESCO-EOLSS Sample chapters) [Dec. 4, 2016].
[8] Mohammad Dehghanimadvar, Reza Shirmohammadi, Milad Sadeghzadeh, Alireza
Aslani, Roghaye Ghasempour. Hydrogen production technologies: Attractiveness and
future perspective. International Journal of Energy Research 2020;vol.44, issue 11.
[9] R.S. Poudyal, I. Tiwari, A.R. Koirala, H. Masukawa, K. Inoue, T. Tomo, M.M.
Najafpour, S.I. Allakhverdiev, T.N. Veziroglu. Hydrogen production using
photobiological methods. In: Compendium of Hydrogen Energy.
[10] M. Roeb, C. Agrafiotis and C. Sattler. Hydrogen production via thermochemical water
splitting. In: Compendium of Hydrogen Energy. p.319-347.
[11] Domenico Ferrero, Martina Gamba, Andrea Lanzini, Massimo Santarelli. Power-to-
Gas Hydrogen: Techno-economic Assessment of Processes towards a Multi-purpose
Energy Carrier. Energy Procedia 2016;101:50-57.
[12] Evonik. Evonik Annouces Capacity Increase of Sodium Methylate in Mobile. 2016,
Alabama.
[13] K. Hou, R. Hughes. A comparative simulation analysis of propane dehydrogenation in
composite and microporous membrane reactors. Journal of Chemical Technology &
Biotechnology 2003; 78 (1): 35-41.
[14] Takahide Haneda, Atsushi Akisawa. Technological assessment of PEFC power
generation system using by-product hydrogen produced from a caustic soda plant.
International Journal of Hydrogen Energy 2017; 42 (5): 3240-3249.
[15] EIA (Energy Information Administration). The impact of increased use of hydrogen on
petroleum consumption and carbon dioxide emissions. SR/OIAF-CNEAF/2008- 04;
September 2008.
[16] Elgowainy A. Resourcing by-product hydrogen from industrial operations. Argonne
National Laboratory. Presentation at H2@Scale Workshop May 24 2017. University of
Houston.
[17] Dong-Yeon Lee, Amgad Elgowainy, Qiang Da. Life cycle greenhouse gas emissions of
hydrogen fuel production from chlor-alkali processes in the United States. Applied
Energy 2018;217:467-479.
[18] Guy Maisonnier, Jérôme Perrin, Dr. Robert Steinberger-Wilckens. European
Hydrogen Infrastructure Atlas. Part II: Industrial surplus hydrogen and markets and
production. 7 March 2007. Roads2HyCom.
43
[19] Daryl Brown. US and World Hydrogen Production – 2014. CryoGas International
2016;March: 32-33.
[20] M. Ludwig,C. Haberstroh,U. Hesse. Exergy and Cost Analyses of Hydrogen-Based
Energy Storage Pathways for Residual Load Management. International Journal of
Hydrogen Energy 2015; vol 40 (35):11348-11355.
[21] Klell M. Storage of hydrogen in the pure form. In: Handbook of hydrogen storage.
Wiley-VCH Velrag GmbH & Co. KGaA. 2010. p.1-37.
[22] Edwards R et al. Well-to-Tank Report Version 4.A. In: Godwin S et al., editors. JEC
Well-to-Wheels Analysis, Joint Research Center; 2014, p.148.
[23] Reuß, Markus & Grube, Thomas & Robinius, Martin & Preuster, Patrick &
Wasserscheid, Peter & Stolten, Detlef. Seasonal storage and alternative carriers: A
flexible hydrogen supply chain model. Applied Energy 2017;200:290–302.
[24] Zhou T, Francois B. Modeling and control design of hydrogen production process for
an active hydrogen/wind hybrid power system. Internation Journal of Hydrogen
Energy 2009;34(1):21–30.
[25] Sørensen B. Hydrogen and fuel cells: emerging technologies and applications.
Academic Press; 2018.
[26] Zohuri B. Cryogenics and liquid hydrogen storage. In: Hydrogen Energy. 2019. p. 121-
39.
[27] Zhang F, Zhao P, Niu M, Maddy J. The survey of key technologies in hydrogen energy
storage. International Journal of Hydrogen Energy 2016;41(33):14535-14552.
[28] Windmeier, Christoph & Barron, Randall. (2013). Ullmann's Encyclopedia of
Industrial Chemistry: Cryogenic Technology.
[29] Detlef Stolten, B. E. (2016). Hydrogen Science and Engineering: Materials, Processes,
Systems, and Technology. Wiley-VCH.
[30] U.Cardella. Large-scale Hydrogen Liquefaction under the Aspect of Economic
Viability. Dissertation for Fakultät für Maschinenwesen 2018. Technische Universität
München.
http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:91-diss-20181130-1442078-
1-3
[31] Majid Asadnia, M. M. A novel hydrogen liquefaction process configuration with
combined mixed refrigerant systems. International Journal of Hydrogen Energy
2017:15564-15585.
[32] Kramer GJ, Huijsmans JPP, Austgen DM. Clean and green hydrogen. In: 16th World
hydrogen energy conference; 2006.
[33] David O. Berstad, Jacob H. Stang, Petter Neckså. Large-Scale Hydrogen Liquefier
Utilising Mixed-Refrigerant Pre-Cooling. International Journal of Hydrogen Energy
2010;35:4512-4523.
[34] Wolf J. LH2 makes you mobile. Linde Rep Sci Technol 2003;1: 30–5
[35] Ahluwalia RK, Hua TQ, Peng J-K. Fuel cycle efficiencies of different automotive on-
board hydrogen storage options. Int J Hydrogen Energy 2007;32(15):3592–602.
[36] Markert F, Nielsen SK, Paulsen JL, Andersen V. Safety aspects of future infrastructure
scenarios with hydrogen refuelling stations. Int J Hydrogen Energy 2007;32(13):2227–
34.
[37] Yuki Ishimoto, Mari Voldsund, Petter Neksa, Simon Roussanaly, David Berstad,
Stefania Osk Gardarsdottir. Large-scale Production and Transport of Hydrogen From
Norway to Europe and Japan: Value Chain Analysis and Comparison of Liquid
Hydrogen and Ammonia as Energy Carriers. International Journal of Hydrogen Energy
2020.
44
[38] Krasae-in, S., Stang, J. H., & Neksa, P. Development of large-scale hydrogen
liquefaction processes from 1898 to 2009. International Journal of Hydrogen Energy
2010;35:4524-4533.
[39] Drnevich, R. Hydrogen Delivery Liquefaction and Compression. May 7, 2003.
Available at:
https://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/liquefaction_comp_pres_
praxair.pdf
[40] Air Products. USA Brevet n° US4765813, 1988.
[41] Stolzengurg, & Mubbala. (2013). Integrated Design for demonstration of Efficient
Liquefaction of Hydrogen (IDEALHY)
[42] Matsuda, H., & Nagami, M. (1998). Study of large hydrogen liquefaction process.
Kanagawa, Japan: Nippon Sanso Corp. WE-NET:summary of annual reports
[43] Songwut Krasae-in. Optimal Operation of a Large-scale Liquid Hydrogen Utilizing
Mixed Fluid Refrigeration System. International Journal of Hydrogen Energy 2014;
Vol.39(13):7015-7029.
[44] Berstad, D., Stang, J., & Neksa, P. (2009). Comparison criteria for large-scale hydrogen
liquefaction processes. Int. J. Hydrogen Energy, 34, 1560-1568.
[45] K. Stolzenburg, D. Berstad, L. Decker, A. Elliott, Ch. Haberstroh, C. Hatto, M. Klaus,
N.D. Mortimer, R. Mubbala, O. Mwabonje, P. Nekså, H. Quack, J.H.R. Rix, I. Seemann,
H.T. Walnum. Efficient Liquefaction of Hydrogen: Results of the IDEALHY Project.
XXth energie – symposium, Stralsund/Germany, 7 – 9 November 2013.
[46] Kuzmenko, I. F., Morkovkin, I. M., & Gurov, E. I. Concept of Building Medium-
Capacity Hydrogen Liquefiers With Helium Refrigeration Cycle. Chemical and
Petroleum Engineering 2004; 40.
[47] Aspen Technologies, Inc. (2013). Aspen Physical Property System, Physical Property
Methods. Version Number V8.4.
[48] Krasae-in, S. (2013). Efficient Hydrogen Liquefaction Processes. Doctoral theses,
Norwegian University of Science and Technology, Department of Energy and Process
Engineering, Trondheim.
[49] Ho-Myung Chang, Bo Hyun Kim, Byungil Choi. Hydrogen Liquefaction Process with
Brayton Refrigeration Cycle to Utilize the Cold Energy of LNG. Cryogenics 108
2020:103093.
[50] S. Putselyk . Novel concept of 60-120kW at 4K refrigerator. IOP Conference Series:
Materials Science and Engineering 278 2017:012096.
[51] Wayne Lawrence Staats, Jr. Analysis of a supercritical hydrogen liquefaction cycle.
M.S. Thesis, Massachusetts Institute of Technology, June 2008.
[52] H.L.Hutchinson. A Kinetics Study of the Para-ortho Shift of Hydrogen. M.S. Thesis,
University of Colorado, 1964.
[53] A. F. Mills. Heat and Mass Transfer. Boston: Irwin, 1995.
[54] Molecular Products Inc. Ionex® - Type O-P Catalyst, Technical Datasheet. Available
at: https://www.molecularproducts.com/products/ionex-type-op-catalyst Reviewed
on 13/01/2021
[55] S. M. Nazir, J. H. Cloete, S. Cloete, S. Amini. Efficient Hydrogen Production With CO2
Capture Using Gas Switching Reforming. Energy 2019; 185:372-385.
[56] Philipp J. Donaubauer, Umberto Cardella, Lutz Decker, Harald Klein. Kinetics and
Heat Exchanger Design for Catalytic Ortho-Para Hydrogen Conversion during
Liquefaction. Chemical Engineering Technology 2019;42(N°3):669-679.
45
[57] Electricity price for industries in the European Union in 2019. Statista. Available at:
https://www.statista.com/statistics/1046605/industry-electricity-prices-european-
union-country/ Reviewed on 11/01/2021.
[58] Boursorama. Available at :
https://www.boursorama.com/bourse/devises/convertisseur-devises/dollar-euro
Reviewed on 11/01/2021.
[59] David Berstad, Jacob Stang, Petter Nekså. A Future Energy Chain Based on Liquefied
Hydrogen. 1st Trondheim Gas Technology Conference. SINTEF Energy Pesearch,
2009.
46
Appendix 1: Buffering – Economic tables
LIQUEFACTION ±20% FLEXIBILITY
Limitation (tons) 20 15 10 8.5 7.5 5
Nominal charge (TPD) 8 7.6 7.4 7 6.8 6
Recuperation rate(%) 85.8 99.3 98.1 95.2 93.6 85.8
Storage 3.93 2.94 1.96 1.67 1.47 0.98

ΔCAPEX (Ø)
Compression 0.11 0.11 0.10 0.10 0.11 0.10
ΔSUC (Ø) 1.31 1.02 0.71 0.64 0.59 0.46
LIQUEFACTION ±20% FLEXIBILITY + WATER ELECTROLYSIS
CAP/ Limitation (tons) 15 10 8 .5 7.5 5
Nominal charge (TPD) 8.1 8.1 7.8 7.7 7.3
1 TPD ΔCAPEX (Ø) 526.0 525.0 524.8 524.6 524.1
ΔSUC (Ø) 220 165 171 173 183
1.5 TPD ΔCAPEX (Ø) 702.0 701.0 700.7 700.5 700
ΔSUC (Ø) 264 218 217 217 225
2 TPD ΔCAPEX (Ø) 851.7 850.7 850.4 850.2 849.7
ΔSUC (Ø) 220 165 171 173 183
LIQUEFACTION ±20% FLEXIBILITY +GAUGES
Limitation (tons) 15 10 8.5 7.5 5
Recuperation rate(%) 99.19 97.2 89.6 85.2 75.6
Storage 2.94 1.96 1.67 1.47 0.98

ΔCAPEX (Ø)
Compression 0.16 0.18 0.14 0.15 0.17
ΔSUC (Ø) 0.96 0.74 0.68 0.63 0.48
47

Hydrogen Liquefaction Chain: Co-Product Hydrogen and Upstream Study

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hydrogen Liquefaction Chain: Co-Product Hydrogen and Upstream Study

Uploaded by

Copyright:

Available Formats

DEGREE PROJECT IN CHEMICAL ENGINEERING

SECOND CYCLE, 30 CREDITS

Hydrogen liquefaction chain:

Supervisor: Florian Jalia (ENGIE)

Examiner: Dr. Shareq Mohd Nazir (KTH)

Company: ENGIE, Lab CRIGEN (Stains, France)

Swedish title: Vätskekvävningskedja: Samproduktväte och uppströmsstudie

Course code: KE200X Degree Project in Chemical Engineering

Trita number: TRITA-CBH-GRU-2021:008

KTH ROYAL INSTITUTE OF TECHNOLOGY

1.1. Physical and thermal properties of hydrogen

1.1.2. Hydrogen vs fossil fuels

1.2.1. Hydrogen as main product

Figure 1: Hydrogen production methods [7]

1.2.2. By-product hydrogen

1.4. Liquid hydrogen challenges

1.4.1. Joule-Thomson coefficient

1.4.2. Hydrogen isomers

Figure 4:Ortho and para-hydrogen distribution depending on temperature

1.5. Hydrogen liquefaction impact on value chain

1.6.1. Liquefaction process

Figure 5: Liquefaction process recap

1.6.2. Liquefaction plants and industrial cycles

1.6.2.2. Air Products process

Figure 7:Air Products process flow diagram [39]

1.6.2.3. Linde processes

Figure 8: Process flow diagram of Linde Leuna from [41]

1.6.2.4. Industrial and conceptual plant summary

1.6.3. Precooling strategies

Figure 9: Process flow diagram of nitrogen open-loop pre-cooling cycle in Linde

- To what extent should by-product H2 be recovered in this intermittent sourcing case?

Figure 10: Upstream process flowsheet

3.1. Gaseous hydrogen production profile

3.2. Liquefaction process

3.2.1. Linde Leuna with open nitrogen precooling cycle

3.2.2. Alternative precooling: closed nitrogen cycle

Figure 14: Closed nitrogen cycle flowsheet

4.1. Buffering study

4.1.1. Buffering configurations

4.1.1.1. Simple liquefaction

𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) + (𝑚̇ − 𝑚̇ ) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

Figure 15: Scenario with unique liquefaction charge

4.1.1.2. Flexible liquefaction

𝐼𝑓 0.80 ∗ 𝑚̇ > 𝑚̇ 𝐼𝑓 1.20 ∗ 𝑚̇ < 𝑚̇ 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

4.1.1.3. Liquefaction flexibility and gauges control

30% < 𝑏(𝑡) < 70%?

0.80 ∗ 𝑚̇ − 𝐶𝐴𝑃 < 𝑚̇ < 1.20 ∗ 𝑚̇ ?

𝐼𝑓 0.80 ∗ 𝑚̇ > 𝑚̇ 𝐼𝑓 1.20 ∗ 𝑚̇ < 𝑚̇ 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

Addition of water 𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡)

𝑏(𝑡) = 𝑏(𝑡 − 𝑑𝑡) +

Figure 18: Liquefaction flexibility supported by additional electrolysis

4.1.2. Performances features

𝑆𝑈𝐶 = [𝑘𝑊ℎ/𝑘𝑔 ] (4.1)

𝐶𝐴𝑃𝐸𝑋 = 𝐶𝐴𝑃𝐸𝑋 + 𝐶𝐴𝑃𝐸𝑋 + 𝐶𝐴𝑃𝐸𝑋 [𝑀$] (4.2)

4.2.1. Simulation procedure

4.2.1.1. Hydrogen model

4.2.2. Pressure drops

4.2.2.2. Catalysis for ortho-to-para conversion

4.2.3. Economic calculations

𝑘𝑊ℎ ∑ 𝑃𝑜𝑤𝑒𝑟 (𝑘𝑊) ∗ 24 (ℎ)

Exergy is defined as:

4.2.3.2. Economic model