Master On Hydrogen Processes

Green Hydrogen Production for Fuel Cell Applications and Consumption in SAIAMC
Research Facility
Stanford Chidziva
A thesis submitted in fulfilment of the requirements for the degree of Doctor Philosophiae, in
the Department of Chemistry, University of the Western Cape.
Supervisor: Dr Mykhaylo Lototskyy
Co-Supervisors: Prof Sivakumar Pasupathi,
Prof Bernard J Bladergroen
18 May 2020
FINAL COPY
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http://etd.uwc.ac.za/
ABSTRACT
Research Facility
S. Chidziva
PhD Thesis, Department of Chemistry, University of the Western Cape
Today fossil fuels such as oil, coal and natural gas are providing for our ever growing energy
needs. As the world’s fossil fuel reserves fast become depleted, it is vital that alternative and
cleaner fuels are found. Renewable energy sources are the way of the future energy needs. A
solution to the looming energy crisis can be found in the energy carrier hydrogen. Hydrogen
can be produced by a number of production technologies. One hydrogen production method
explored in this study is electrolysis of water.
The proposed study aims to investigate the integration of a hydrogen production, compression
and dispensing system. Hydrogen will be produced using a solid polymer electrolyte (SPE)
electrolyser powered by both photovoltaic and grid power. The produced hydrogen will be
compressed using a metal hydride compressor and stored in the SAIAMC gas storage facility.
A dispensing system will be developed to fuel various FC prototypes, amongst others the golf
cart, forklift, fuel cell bicycle and fuel cell chargers. It is expected that this study will contribute
in promoting use of clean fuel, hydrogen derived from renewable energy sources that will
facilitate the transition to the hydrogen economy. A crucial aspect of the proposal is the
establishment of design and operation protocols around hydrogen safety.
18 May 2020
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KEY WORDS
Metal hydride
Electrolyser
Hydrogen economy
Renewable energy
Hydrogen compression
Hydrogen safety
Efficiency
Electrode
Stack
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DECLARATION
I declare that Green hydrogen production for fuel cell applications and consumption in
SAIAMC research facility is my own work, that it has not been submitted for any degree or
examination in any other university, and that all the sources I have used or quoted have been
indicated and acknowledged by complete references.
Stanford Chidziva. 18 May 2020
Signed.........................................
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DEDICATION
I dedicate this thesis to my wife Patience Chidziva, son Emmanuel Chidziva, daughter
Elizabeth Chidziva
&
My mother Cornelia Chidziva and late father Richard Garikayi Chidziva
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ACKNOWLEDGEMENTS
Firstly, I would like to express my sincere gratitude to my supervisor Dr Mykhaylo Lototskyy

for the continuous support of my Ph.D. study and related research, for his patience,
motivation, and immense knowledge. His guidance helped me in all the time of research and
writing of this thesis. I could not have imagined having a better advisor and mentor for my
Ph.D. study.
Besides my supervisor, I would like to thank my core supervisors Professor Bernard

Bladergroen & Professor Sivakumar Pasupathi, for their insightful comments and
encouragement, but also for the hard questions, which incensed me to widen my research
from various perspectives.
My sincere thanks also goes to Dr Cordelia Sita who started this PhD study with me before
migrating to the USA, Dr Marek Malinowski your systems integration expertize made the
PhD journey easier, and Dr Piotr Bujlo, who supported me tremendously during my research.
Without their precious support, it would not be possible to conduct this research.
Last but not the least; I would like to thank my wife Patience, my son Emmanuel and my
daughter Elizabeth for supporting me spiritually and physically throughout writing this thesis
and my life at large.
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TABLE OF CONTENTS
Research Facility ............................................................................................................................ i
ABSTRACT............................................................................................................................................ ii
KEY WORDS ........................................................................................................................................ iii
DECLARATION ................................................................................................................................... iv
DEDICATION ........................................................................................................................................ v
ACKNOWLEDGEMENTS ................................................................................................................... vi
LIST OF FIGURES ............................................................................................................................. xiii
LIST OF TABLES ................................................................................................................................xvi
ACADEMIC OUTPUT REPORTED IN THIS RESEACH ................................................................xvii
PUBLISHED PAPERS ....................................................................................................................xvii

DRAFTED PAPERS .......................................................................................................................xvii
PROTOTYPE ..................................................................................................................................xvii
POSTER PRESENTATION ........................................................................................................... xviii
NOMENCLATURE .............................................................................................................................xix
CHAPTER 1 – GENERAL INTRODUCTION ...................................................................................... 1
1.1 INTRODUCTION .................................................................................................................. 1

1.2 BACKGROUND .................................................................................................................... 1
1.3 PROBLEM STATEMENT ..................................................................................................... 4
1.4 MOTIVATION OF STUDY ................................................................................................... 5
1.5 HYPOTHESIS OF THE STUDY ........................................................................................... 5
1.6 NOVELTY OF THE STUDY................................................................................................. 5
1.7 AIMS AND OBJECTIVES .................................................................................................... 6
1.8 RESEARCH QUESTIONS..................................................................................................... 6
1.9 RESEARCH FRAMEWORK ................................................................................................. 7
1.10 SCOPE AND DELIMITATION OF THE STUDY................................................................ 8
1.11 THESIS STRUCTURE ........................................................................................................... 8
CHAPTER 2 - LITERATURE REVIEW ............................................................................................... 9
2.1WHAT IS HYDROGEN? .................................................................................................................. 9
a) HYDROGEN AS FUEL ........................................................................................................... 10

b) ADVANTAGES OF USING HYDROGEN AS A FUEL ........................................................ 11
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2.2 HYDROGEN PRODUCTION METHODS ................................................................................... 13
i. ELECTROLYSIS ..................................................................................................................... 16
ii. PLASMA ARC-DECOMPOSITION ............................................................................... 16
iii. H2O THERMOLYSIS ....................................................................................................... 17
iv. THERMO-CHEMICAL H2O SPLITTING ...................................................................... 17
v. PV ELECTROLYSIS, PHOTO CATALYSIS, AND PHOTO ELECTROCHEMICAL
METHOD ..................................................................................................................................... 19
vi. DARK FERMENTATION ............................................................................................... 21
vii. HIGH TEMPERATURE ELECTROLYSIS..................................................................... 23
viii. HYBRID THERMOCHEMICAL CYCLES .................................................................... 23
ix. COAL GASIFICATION ................................................................................................... 24
x. FOSSIL FUEL REFORMING .......................................................................................... 25
xi. BIO PHOTOLYSIS AND PHOTO FERMENTATION .................................................. 26
xii. ARTIFICIAL PHOTOSYNTHESIS ................................................................................. 26
xiii. PHOTO ELECTROLYSIS ............................................................................................... 27
2.3 FINANCIAL COMPARISON OF HYDROGEN PRODUCTION METHODS ..................... 31
a. ENERGY AND EXERGY EFFICIENCIES COMPARISON OF HYDROGEN

PRODUCTION METHODS ............................................................................................................ 32
b. OVERALL COMPARISON OF HYDROGEN PRODUCTION METHODS ........................ 33
2.4 MOST EFFICIENT HYDROGEN PRODUCTION METHOD: ELECTROLYSIS ............... 34
a. ELECTROLYSIS ..................................................................................................................... 35
b. ELECTRODE POTENTIALS .................................................................................................. 36
d. ELECTROLYSIS COMPARTMENT. ..................................................................................... 43
e. ELECTROLYSIS THROUGH ELECTROLYTIC CELLS ..................................................... 44
2.5 ELECTROLYSERS .................................................................................................................. 46
a) PEM ELECTROLYSERS......................................................................................................... 47
b) ALKALINE ELECTROLYSERS............................................................................................. 47
c) ELECTROLYSIS AND SAFETY CONSIDERATIONS ........................................................ 48
2.6 HYDROGEN STORAGE ......................................................................................................... 50
2.6.1 GASEOUS HYDROGEN STORAGE ............................................................................. 50

SAFETY ISSUES OF GASEOUS STORAGE ............................................................................ 51
a. LOSS OF CONTAINMENT ............................................................................................ 51
b. MATERIALS – BLISTERING ........................................................................................ 51
c. FILLING ORIENTATION ............................................................................................... 52
d. PRESSURE RELIEF DEVICES ...................................................................................... 53
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e. HEATING EFFECTS DURING FILLING ...................................................................... 53
2.6.2 LIQUID HYDROGEN STORAGE..................................................................................... 54
SOME SAFETY ISSUES LIQUID HYDROGEN STORAGE .................................................... 55
a. LOSS OF CONTAINMENT ............................................................................................ 55
b. BOIL OFF ......................................................................................................................... 55
c. ICE FORMATION ........................................................................................................... 56
2.6.3 SOLID STATE HYDROGEN STORAGE ....................................................................... 57
SOME POTENTIAL SAFETY ISSUES OF METAL HYDRIDES ............................................ 58
a. PYROPHORIC MATERIALS ......................................................................................... 58
b. RISK OF EXPLOSION .................................................................................................... 59
c. HEAT MANAGEMENT .................................................................................................. 59
d. TOXICITY ........................................................................................................................ 59
2.7 METAL HYDRIDE HYDROGEN COMPRESSORS ............................................................. 59
2.7.1 METAL-HYDROGEN SYSTEM .................................................................................... 60

2.7.2 GENERAL LAYOUT OF A METAL HYDRIDE SYSTEM .......................................... 60
2.7.3 APPLICATION OF METAL HYDRIDE H2 COMPRESSORS ...................................... 63
a. ISOTOPE HANDLING .................................................................................................... 63
b. CRYOGENICS/SPACE.................................................................................................... 63
c. UTILISATION OF LOW-GRADE HEAT ....................................................................... 63
d. THERMALLY DRIVEN ACTUATORS ......................................................................... 64
e. HYDROGEN REFUELLING STATIONS ...................................................................... 64
2.8 PHOTOVOLTAIC ELECTROLYSIS ...................................................................................... 65
2.9 HYDROGEN SAFETY ............................................................................................................ 65
2.9.1 PHYSICAL AND CHEMICAL PROPERTIES OF HYDROGEN .................................. 67

a. BUOYANCY AS SAFETY ASSET................................................................................. 67
b. DIFFUSIVITY AND VISCOSITY .................................................................................. 68
c. INTERACTION WITH METALS ................................................................................... 68
d. COMBUSTION PROPERTIES ........................................................................................ 68
e. STOICHIOMETRIC MIXTURE, EQUIVALENCE RATIO AND MIXTURE
FRACTION................................................................................................................................... 69
f. HEAT OF COMBUSTION .............................................................................................. 69
g. FLAMMABILITY LIMITS .............................................................................................. 69
h. QUENCHING ................................................................................................................... 69
2.9.2 HYDROGEN HEALTH HAZARDS ............................................................................... 70
2.9.3 DETECTION AND HYDROGEN SENSORS ................................................................. 71
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CHAPTER 3 RESEARCH DESIGN AND METHODOLOGY .......................................................... 72
INTRODUCTION ................................................................................................................................ 72
3.1 PROJECT DESIGN & SPECIFICATIONS ............................................................................. 72
a. STACK SPECIFICATIONS ..................................................................................................... 74

b. COOLING SYSTEM ................................................................................................................ 78
c. WATER SUPPLY SYSTEM .................................................................................................... 79
d. BALANCE OF PLANT ............................................................................................................ 81
e. HYSA SYSTEMS PEMWE PROTOTYPE P&ID ................................................................... 82
f. HYSA SYSTEMS PEMWE PROTOYPE ASSEMBLY LIST AS PER P&ID ............... 83
g. ELECTROLYSER ELECTRICAL CONNECTIONS LAYOUT ............................................ 86
i. STACK ELECTRICAL CONNECTIONS ....................................................................... 87
ii. ANODE WATER SUPPLY PUMPS ELECTRICAL CONNECTIONS ......................... 90
iii. PLC + DISPLAY & GENERAL POWER SUPPLY ........................................................ 91
iv. SOLENOID & PRESSURE TRANSDUCER ELECTRICAL CONNECTIONS ............ 92
v. FANS AND RELAYS ELECTRICAL CONNECTIONS ................................................ 93
3.2 INTEGRATION PHASE 1 ................................................................................................... 94
a. PROTOTYPE SYSTEM PLC OPERATION ........................................................................... 99
b. PLC CONTROLLER WITH DEDICATED ALGORITHM ............................................ 99
3.3 PROTOTYPE TESTING AND COMMISSIONING ......................................................... 101
PROTOTYPE PEMWE OPERATING MANUAL ........................................................................ 101
3.3.1 GENERAL INFORMATION ......................................................................................... 101
a) SAFETY ......................................................................................................................... 102
b) HYDROGEN GENERATION ....................................................................................... 103
c) OXYGEN GENERATION ............................................................................................. 103
d) WATER SPECIFICATIONS .......................................................................................... 104
e) PROCESS WATER UTILISATION .............................................................................. 104
f) PROCESS WATER TEMPERATURE DIFFERENTIAL ............................................. 105
g) PROTON WATER PRODUCTION ............................................................................... 105
h) PROTON WATER RECIRCULATION ........................................................................ 106
i) SPECIFICATION PROCESS WATER FLOW RATE .................................................. 106
j) DC POWER SUPPLY .................................................................................................... 107
k) PRESSURE SENSORS .................................................................................................. 107
l) TEMPERATURE SENSORS ......................................................................................... 107
m) THERMAL MANAGEMENT SUBASSEMBLY ......................................................... 107
3.4 HYSA SYSTEMS GREEN HYDROGEN SYSTEM HAZOP .......................................... 108
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a) HYSA SYSTEMS PROTOTYPE PEMWE HAZOP ............................................................. 108
b) HYSA SYSTEMS PEM WATER ELECTROLYSE HAZOP STUDY ......................... 109
c) PROTOTYPE PEM ELECTROLYSER SYSTEM SAFETY ................................................ 114
3.5 HYDROGEN COMPRESSION AND STORAGE ........................................................................ 115
SAFETY PRECAUTIONS FOR MH COMPRESSOR ............................................................. 119
3.6 HYDROGEN SUPPLY, COMPRESSION AND DISTRIBUTION ...................................................... 121
CHAPTER 4 – RESULTS .................................................................................................................. 123
INTRODUCTION .............................................................................................................................. 123
PROTOTYPE PEM WATER ELECTROLYSIS SYSTEM SPECIFICATION ................................ 123
I. HYDROGEN PRODUCTION ............................................................................................... 124

II. ELECTROLYSIS SYSTEM EVALUATION AND PERFORMANCE ................................ 127
III. EFFICIENCY ..................................................................................................................... 132
IV. POLARISATION CURVES ........................................................................................... 138
V. PEM COST ANALYSIS ........................................................................................................ 139
VI. HYDROGEN COMPRESSION AND SUPPLY ................................................................ 143
VII. PEM STACK FAILURE .................................................................................................... 147
a) ANALYSIS OF DEFECTIVE STACKS ........................................................................ 149
I. STACK HYDROSTATIC TEST, ........................................................................................... 149
II. STACK DISASSEMBLY AND INSPECTION OF COMPONENTS ........................... 150
b) PLAN FOR REFURBISHMENT ................................................................................... 151
VIII. QUANTITATIVE RISK ASSESSMENT .............................................................................. 151
IX. HYDROGEN PRODUCTION, COMPRESSION AND SUPPLY TO SAIAMC FACILITY &

FUEL CELL PROTOTYPE REFUELLING ...................................................................................... 152
CHAPTER 5 – CONCLUSIONS AND RECOMMENDATIONS .................................................... 154
INTRODUCTION .......................................................................................................................... 154

GENERAL CONCLUSIONS ......................................................................................................... 154
GAPS FROM THE LITERATURE RELATED TO THE CURRENT STUDY............................ 155
FINDINGS OF THIS STUDY........................................................................................................ 158
RECOMMENDATIONS .................................................................................................................... 164
CHAPTER 6 – REFERNCES AND APPENDIX .............................................................................. 165
1. REFERENCES ............................................................................................................................ 165
2. APPENDIX 1 .......................................................................................................................... 173
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PEM ELECTROLYSER OPERATION MANUAL ........................................................................... 173
SYSTEM OPERATION ....................................................................................................................... 173

I. PRE-START UP PROCEDURE .................................................................................... 173
II. STARTUP CHECK LIST ....................................................................................................... 173
III. ELECTROLYSIS SYSTEM START UP SEQUENCE AND OPERATION ................ 174
IV. SYSTEM SHUT DOWN ................................................................................................ 178
V. CHECKLIST AFTER OPERATION ............................................................................. 179
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LIST OF FIGURES
Figure 1: Current main hydrogen production routes (Molkov V. , 2012). ................................ 1
Figure 2: Global energy systems transition in the period from 1850 to 2150 (Dunn, 2002,
Volume 27) (Jordan, 2006) ........................................................................................................ 3
Figure 3: Research Framework .................................................................................................. 7
Figure 4: Hydrogen Content Factor (HCF), Greenization Factor (GF) and Environmental
Impart Factor (EIF) of hydrogen and other fossil fuels. (Yilanci, Dincer, & Ozturk, 2009)... 12
Figure 5: Selected hydrogen production methods (Dincer, 2012). .......................................... 13
Figure 6: Production cost of selected hydrogen production methods (per kg of hydrogen)
(Acar & Dincer, 2014). ............................................................................................................ 32
Figure 7: Energy and exergy efficiencies of selected hydrogen production methods (Acar &
Dincer, 2014). .......................................................................................................................... 33
Figure 8: Electrode Standard Potentials (Chaplin, 2017) ........................................................ 43
Figure 9: Electrolysis System (Santosa, Eckerta, & Eduardo De Rossia, 2017) ..................... 45
Figure 10: Operating System of Alkaline and PEM Electrolysers (Santosa, Eckerta, &
Eduardo De Rossia, 2017) ....................................................................................................... 46
Figure 11: Types of risks related to H2 production, storage and use (Dubois, et al., 2013) ... 50
Figure 12: Hydrogen storage gravimetric capacity versus temperature for different materials
investigated within DOE programme in 2007-2009 (Energy, 2009). ...................................... 58
Figure 13: General layouts of MH Compressors: (a) Periodically operated, (b) One-stage
continuously operated, (c) Two stage continuously operated .................................................. 62
Figure 14: Project concept Overview ...................................................................................... 73
Figure 15: PEMWE System Block diagram ............................................................................ 74
Figure 16: Process connections of the EL100 cell stack Sticker nearest to fitting designates
the process connection ............................................................................................................. 76
Figure 17: EL 100 Stack .......................................................................................................... 77
Figure 18: Type plate and electrical leads of the EL100 stack ................................................ 77
Figure 19: Stack cooling System ............................................................................................. 78
Figure 20: Ultra-pure water supply system .............................................................................. 80
Figure 21: Process and instrumentation diagram (P&ID) PEMWE ........................................ 82
Figure 22: Equipment list......................................................................................................... 85
Figure 23: Stack Electrical Connections .................................................................................. 87
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Figure 24: Electrical leads of EL100 stack positive and negative polarity designated by
sticker. Electrical grounding of stack facilitated by M6 bores of stainless steel compression
plates ........................................................................................................................................ 88
Figure 25: Cell Voltage Monitoring & thermocouples; the bores can feature voltage probes,
temperature sensors .................................................................................................................. 89
Figure 26: Anode water supply pumps Electrical connections ................................................ 90
Figure 27: PLC + Display & General Power supply ............................................................... 91
Figure 28: Solenoid valves & Pressure Transducer Electrical Connections............................ 92
Figure 29: Fans and Relays Electrical Connections ................................................................ 93
Figure 30: HySA systems PEM Water Electrolyser Overview ............................................... 94
Figure 31: HySA systems PEMWE PLC home screen ........................................................... 95
Figure 32: HySA systems PEMWE PLC- Measurement Data screen ..................................... 95
Figure 33: HySA systems PEMWE PLC- Cell Voltage screen ............................................... 96
Figure 34: HySA systems PEMWE PLC- Electrical parameters screen ................................. 96
Figure 35: HySA Systems Prototype PEMWE Overview ....................................................... 97
Figure 36: HySA Systems PEM Water Electrolyser prototype PLC windows ....................... 98
Figure 37 Flowchart of control algorithm, PLC managed, manual or automatic operation .. 100
Figure 38: Electrolyse cell operating principle ...................................................................... 102
Figure 39: MH compressor (MHC) installed at SAIAMC hydrogen supply facilities; the
insets show main system components. SG – steam generator; CT – cooling tower; CP –
cylinder pack .......................................................................................................................... 116
Figure 40: MH Heating and Cooling circuit .......................................................................... 117
Figure 41: Summary MH Compressor operation chart.......................................................... 120
Figure 42: Schematic for complete H2 supply, compression and supply .............................. 121
Figure 43: PEMWE operation mode...................................................................................... 124
Figure 44: Mass of hydrogen produced ................................................................................. 126
Figure 45 Electrical characterization of the 1.0 Nm3/hr PEMWE stack; lower heating value of
hydrogen taken for calculation of efficiency ......................................................................... 129
Figure 46: Electrolysis system performance, including Balance of Plant and two stacks under
operation ................................................................................................................................ 130
Figure 47: Performance of the system in terms of capability to produce chemical energy of
hydrogen, Calculated based on the higher heating value of this fuel (39.49 kWh/kg) .......... 131
Figure 48: System Stack power and Efficiency ..................................................................... 134
Figure 49: Hydrogen production versus System Efficiency .................................................. 136
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hydrogen, calculated based on the higher heating value of this fuel (39.49 kWh/kg) ........... 137
Figure 51: Voltage-current characteristics (Polarisation Curve) ........................................... 138
Figure 52: Breakdown of the incurred cost for the integration and commissioning of
Prototype PEM water Electrolyser (Cost in South African Rand 2016-2019) ...................... 143
Figure 53: Pressure – composition isotherms for H absorption at TL=298 K (a) and H
desorption at TH=403 K (d) for MH H2 compression alloys: LaNi4.9Sn0.1 (1), La0.8Ce0.2Ni5 (2)
and C14-Ti0.65Zr0.35 (Mn, Cr, Fe, Ni) 2+x (3). ......................................................................... 145
Figure 54: Typical operation of MH compressor at SAIAMC; heating / cooling time 25
minutes, average productivity 1.2 Nm3/h. Left Y-axis: T1, T2 – temperatures in the first and
the second compression modules, respectively; P(in) – H2 suction pressure; P(out) – H2
discharge pressure; P(1-2) – H2 pressure between stages 1 and 2; P(2-3) – H2 pressure
between stages 2 and 3. Right Y-axis: H2 flow in the suction line of the compressor. ......... 147
Figure 55: PEMWE readings indicating failure of the stacks................................................ 148
Figure 56: Stack Current/ Voltage when failure occurred ..................................................... 149
Figure 57: Damaged MEAs ................................................................................................... 150
Figure 58: Damaged Flow Fields ........................................................................................... 150
Figure 59: PEMWE System H2 release scenarios.................................................................. 152
Figure 60: Summary of Prototype PEM Electrolyser operation chart ................................... 180
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LIST OF TABLES
Table 1: Higher (HHV) and Lower (LHV) heating values of Hydrogen and common fuels at
25 degrees and 1 atm (Dincer, 2012) ....................................................................................... 11
Table 2: Hydrogen production methods from primary energy and material sources (Acar &
Dincer, 2015) ........................................................................................................................... 16
Table 3: Comparison: dark and bio-photolysis Photo fermentation (P.C Hallenbeck, 2012) . 22
Table 4: Fossil fuel reforming technologies comparison (Parthasarathy & Narayanan, 2014).
.................................................................................................................................................. 25
Table 5: Benefits and challenges for H2 production mechanisms (Acar & Dincer, 2014) ...... 30
Table 6: Standard specifications for alkaline, PEM and SOE Electrolysers (Santosa, Eckerta,
& Eduardo De Rossia, 2017) ................................................................................................... 35
Table 7: Standard Reduction Potentials at 25oC (Frank., 1967) .............................................. 37
Table 8: Current and Voltage (Chen, Dong, Wang, Wang, & Xia, 2016) ............................... 41
Table 9: Alkaline and PEM Electrolysers main characteristics (Holladay, Hu, King, & Wang,
2009) ........................................................................................................................................ 48
Table 10 Stack Specifications .................................................................................................. 75
Table 11: Mass balance of EL100 electrolysis process ......................................................... 105
Table 12: Technical; parameters of 2.0 Nm3/h hydrogen production system........................ 123
Table 13: The comparison of parameters recorded and calculated at different cell’s voltage
for single electrolysis stack and whole electrolysis system consisting of 2 stacks ................ 128
Table 14: System Capital, Installation and Maintenance Costs ............................................ 139
Table 15: System Operation Costs ......................................................................................... 140
Table 16: System units and standards .................................................................................... 141
Table 17: Total Cost of H2 per Kg ........................................................................................ 142
Table 18: The comparison of parameters recorded and calculated at different cell’s voltage
for single electrolysis stack and whole electrolysis system consisting of 2 stacks ................ 159
xvi
ACADEMIC OUTPUT REPORTED IN THIS RESEACH
PUBLISHED PAPERS
1. Mykhaylo Lototskyy, Yevgeniy Klochko, Moegamat Wafeeq Davids, Lydia
Pickering, Dana Swanepoel, Gerhard Louw, Burt van der Westhuizen, Stanford
Chidziva, Cordelia Sita, Bernard Bladergroen, Vladimir Linkov, Industrial-scale
metal hydride hydrogen compressors developed at the South African Institute for
Advanced Materials Chemistry; Materials Today: Proceedings 5 (2018) 10514-10523;
2. Mykhaylo Lototskyy, Moegamat Wafeeq Davids, Dana Swanepoel, Gerhard Louw,

Yevgeniy Klochko, Fahmida Smith, Fatema Haji, Ivan Tolj, Stanford Chidziva,
Sivakumar Pasupathi, Vladimir Linkov, Hydrogen refuelling station with integrated
metal hydride compressor: layout features and experience of three-year operation;
International Journal of Hydrogen Energy 45 (2020) 5415-5429
3. Mykhaylo Lototskyy, Moegamat Wafeeq Davids, Ivan Tolj, Yevgeniy Klochko,

Bhogilla Satya Sekhar, Stanford Chidziva, Fahmida Smith, Dana Swanepoel, Bruno
G. Pollet. Metal hydride systems for hydrogen storage and supply for stationary and
automotive low temperature PEM fuel cell power modules; International Journal of
Hydrogen Energy: 40 (2015) 11491-11497
DRAFTED PAPERS
1. Stanford Chidziva, Marek Malinowski, Bernard Bladergroen, Sivakumar Pasupathi,
Mykhaylo Lototskyy; PEM water electrolysis system performance and system safety
integration; Przeglad Elektrotechniczny registration: PE5891
2. Boris Tarasov; Pavel V. Fursikov; Alexey A Volodin; Mikhail S Bocharnikov;
Yustinas Y Shimkus; Aleksey M Kashin; Volodymyr A Yartys; Stanford Chidziva;
Sivakumar Pasupathi; Mykhaylo V Lototskyy. Metal hydride hydrogen storage and
compression systems for energy storage technologies; International Journal of
Hydrogen Energy; Manuscript HE-D-20-01322
PROTOTYPE
 HySA 2 Nm3/h PEM Water Electrolyser system
xvii
POSTER PRESENTATION
1. Industrial-Scale Metal Hydride Hydrogen Compressors Developed At South African
Institute For Advanced Materials Chemistry on the 15th International Symposium on
Metal-Hydrogen Systems August 2016, Interlaken – Switzerland
xviii
NOMENCLATURE
PEM – Proton Exchange Membrane

FC – Fuel cell
SAIAMC – South Africa Institute of Advanced material Chemistry
PLC – Programmable Logic controller
HHV – Higher Heating Value
LHV – Lower Heating Value
MH – Metal Hydride
PEMEC – Proton Exchange Membrane Electrolysis Cell
UPW – Ultra-Pure Water
PV- Photovoltaic
DC – Direct Current
HAZOP – Hazard Operability Study
BOP – Balance of plant
BOP – Balance of Plant
HCF - Hydrogen content factor
GF - Greenization Factor
EIF - Environmental Impact factor
SPE - Solid Polymer Electrolyte
P&ID - Process & Instrumentation Diagram
xix
CHAPTER 1 – GENERAL INTRODUCTION
1.1INTRODUCTION
This chapter introduces the study and brings out the overview of the study. During
this chapter the research objectives, the hypothesis of the study are highlighted, as
well as the design and methodology approach for the study. The research outline,
framework of the study and delimitations are included in this chapter.
1.2 BACKGROUND
The world has a looming energy crisis; the traditional non-renewable energy in form of
fossil fuels is facing extinction. The reality of fossil fuel depletion, environmental
pollution leading to global warming, climate changes, and a need for alternative energy
supply with low carbon footprint has opened research for alternative energy sources.
The energy crisis has given birth to the Hydrogen economy. Hydrogen is an alternative
energy source to the current energy crisis. A wide range of technologies can generate
hydrogen such as: reforming of natural gas, liquefied petroleum gas, gasoline. etc.;
gasification of coal and biomass; electrolysis of water using nuclear, fossil or renewable
energy sources; photo electrochemical/photo catalytic splitting of water; thermolysis
and thermo-chemical cycles (Conte, Lacobazzi, Ronchetti, & Vellone, 2001), (Badwal,
Giddey, & Phair, 2006)
Figure 1: Current main hydrogen production routes (Molkov V. , 2012).
1
It is clear from Figure 1 that the majority of hydrogen used today is produced from
fossil fuels. About 95% of the total global hydrogen production is captive meaning it is
used at the site where it is produced. Renewable hydrogen does not yet make up a
significant part of the market, hopefully more renewable hydrogen will become
available as customers demand renewable fuel and the cost of renewable power
becomes more competitive (Molkov V. , 2012).
Fossil fuels are non-renewable energy source that currently account for about 90
percent of world energy consumption (including manufacturing, heating, cooking,
electricity and fuel for cars). Petroleum leads with a share of about 40% of total world
energy consumption, followed by coal (24%) and natural gas (22%) (enviroliteracy.org,
2007)
The problem with humanity’s heavy reliance on these sources of energy is that reserves
are finite, and are rapidly running out. There are also health and environmental concerns
surrounding the use of fossil fuels e.g. greenhouse gas emissions leading to global
warming and climate changes. An estimated 4.6 million people die each year due to air
pollution (enviroliteracy.org, 2007) and global warming is widely regarded as one of
the most critical issues facing the planet. Additionally, given the market volatility of
the oil price and the tenuous political climate surrounding oil production and delivery,
researching cleaner, renewable energy alternatives to fossil fuels will contribute to a
sustainable, stable energy future for South Africa and the world.
A solution to world energy crisis can be found in the energy carrier hydrogen. Hydrogen
is the most abundant element in the universe; it possesses a high energy density and it
can be produced from water using almost any primary energy source. Many scientists
believe that hydrogen is the best way to store renewable energy, especially solar and
wind power (Awad & Veziroglu, 1984).
From the global energy systems transition as shown in Figure 2 below hydrogen is
emerging as the alternative energy source that will meet the ever increasingly
sustainable economic growth beyond 2050. The most important consequence of a
hydrogen economy is the replacement of the 20th century 'hydrocarbon society' by a
sustainable one based on hydrogen (Dincer & Zamfirescu, 2012).
2
This replacement occurs at a time when 90 percent of the energy worldwide is being
delivered primarily by fossil fuels, and most experts now agree that sometime during
the early to middle decades of the twenty-second century, and perhaps much earlier,
sustainable sources transformed into hydrogen and electric currencies will dominate
civilisation's energy system (Sperling & Cannon, 2004)
Figure 2: Global energy systems transition in the period from 1850 to 2150 (Dunn, 2002,
Volume 27) (Jordan, 2006)
Hydrogen production from renewable energy sources is an environmental friendly

initiative that leads to a climate of clean future industry. High-quality hydrogen
(approximately 99.999% purity) can be produced by the electrochemical conversion of
water to hydrogen and oxygen through a process known as water electrolysis (Carmo,
Fritz, & Mergel, 2013). In this hydrogen generation process, electricity is applied to the
electrode assembly and water is split at the anode into oxygen and protons. The protons
diffuse through the conducting membrane to the cathode to form hydrogen (Khan, et
al., 2006).
Anode: H2O (L) → 1/2O2 (g) + 2H+ + 2e- (1)
Cathode: 2H+ + 2e- → H2 (g) (2)
Full reaction H2O (L) → H2 (g) + 1/2O2 (g) (3)
3
When the electricity is provided by a renewable source of energy (e.g. wind or solar),
then a truly zero emission hydrogen supply is achieved. Solid Polymer Electrolysers
(SPE) can be coupled to distributed, intermittent renewable electricity sources (e.g.
wind generators or solar panels), in order to store energy generated from excess
electricity as hydrogen in gas cylinders or in metal hydrides (Khan, et al., 2006) . The
stored hydrogen can later be used in hydrogen fuel cells to generate electricity at one’s
convenience (like a battery). Advantages of a Proton Electrolyte Membrane (PEM)
electrolyser are that they produce much higher current densities; smaller mass – volume
characteristics; high degree of gas purity; increased level of safety (no circulation of
caustic electrolyte); possibility of combining fuel cell and Electrolyser modes (Khan,
et al., 2006). The low gas crossover rate of the polymer electrolyte membrane (yielding
hydrogen with high purity), allows the PEM Electrolyser to work under a wide range
of power input (economical aspect). This is because the proton transport across the
membrane responds quickly to the power input, not delayed by inertia as in liquid
electrolytes.
1.3PROBLEM STATEMENT
Heavy dependence on fossil fuels and the environmental effects caused by the
consumption of fossil fuels has resulted in global warming. The depletion of fossil fuels
has resulted in increased research and development of alternative energy to replace
fossil fuels. A substantial amount of funding has been released by governments and
private sector to try and find a solution to a possible energy crisis looming in the near
future. Hydrogen has been identified as an alternative energy source due to its high
energy density and easy of production. Hydrogen is a renewable clean energy that is
environmentally friendly as it promotes reduction of global warming. South Africa’s
economy has a drive to reduce carbon footprint through initiatives like the White Paper
on Renewable Energy of 2003 released by the Department of Energy which is one of
the policy documents that laid foundation for the promotion of renewable energy
technologies in the country.
4
1.4 MOTIVATION OF STUDY
Global energy systems transition in the period from 1850 to 2150 (Dunn, 2002, Volume
27) (Jordan, 2006), see Figure 2, clearly shows a serious depletion of fossil fuels and a
need of alternative energy to meet the increasing global sustainable economic growth.
There is a market niche for systems that produce renewable energy in the form of
hydrogen in the world at large. The systems must supply clean hydrogen to the growing
hydrogen economy. Competitive safe technology for hydrogen production technology
is a key to the growth of hydrogen economy. The cost of complete and certified systems
is relatively high, and it creates sufficient room for the development of a low cost
integrated system. Hydrogen is a highly flammable gas, the integration of a system that
produces hydrogen does have several safety challenges which must be mitigated and at
the same time create a positive public awareness that will result in acceptance of such
systems as safe to operate.
1.5 HYPOTHESIS OF THE STUDY

Safe operation of integrated complex hydrogen production, compression and storage,
technical viability under certain constrains.
1.6 NOVELTY OF THE STUDY

Several hydrogen production methods are available on the market (Dincer, Green
methods for Hydrogen productions, 2012). During this study one hydrogen production
method, namely electrolysis is used. Electrolysis using a Polymer Electrolyte
Membrane (PEM) electrolyser is investigated in this study. The novelty of this study
emanates from the integration of a prototype PEM electrolyser coupled to a metal
hydride compressor and the application of hydrogen safety on the integration of
hydrogen production and compression systems. The success of this project creates job
opportunities through production and sales of such locally produced systems that can
also ultimately result in growth of the economy of our country, South Africa.
5
1.7AIMS AND OBJECTIVES
This project aims at feasibility study of the integration of fuel cell and hydrogen storage
technologies, demonstrating South African competencies in the renewable hydrogen
space, by the development and preliminary tests of a prototype green hydrogen
production, compression and dispensing system for fuel cell applications including
general hydrogen consumption at SAIAMC research facility. Special attention is paid
to the operation safety of the prototype system.
The main objectives of the study include:
 The design of an 8.4kW Polymer Electrolyte Membrane Water Electrolyser
(PEMWE) with a hydrogen production rate of 2 Nm3/hr and hydrogen discharge
pressure of 20 bars.
 Construction and commissioning of a 8.4kW PEMWE prototype system
 A HAZOP study on the integration of PEM Water Electrolyser prototype
system with the balance of plant.
 Integration of PEM water electrolyser prototype system with a locally
developed 5 Nm3/h MH compressor.
 Integration of PEM water electrolyser prototype system to a locally produced
4.2kW Photovoltaic supply.
1.8 RESEARCH QUESTIONS

To achieve the above aims and objectives during this study the following research
questions are going to be answered:
i. What are the optimum technical parameters at which the integrated system can
operate safely with high productivity?
ii. What is the system optimum operation point when efficiency is at maximum?
iii. What design or operational measures in integrated system is required to
mitigate hazards at high productivity?
iv. What recommendations could be suggested for further development of
integrated system?
6
1.9 RESEARCH FRAMEWORK
To answer the above research questions extensive literature review has been carried out
and explained in the Chapter 2, literature review. However, a structure needs to be
formulated in order to meet all the specified objectives of the study. The following
framework is used in accordance with the objectives of the study, it’s outlined as
follows:
Figure 3: Research Framework
7
1.10 SCOPE AND DELIMITATION OF THE STUDY
Due to time and funding challenges, some modifications to our prototype system have
been recommended for further development if funding is secured.
1.11 THESIS STRUCTURE

The thesis is comprised of six chapters including this introduction chapter, which gives
an overview of the study. The chapters unfold in a chronological sequence from chapter
one to six.
8
CHAPTER 2 - LITERATURE REVIEW
Renewable energy is the future energy source of the world. Considerable resources and
expertise is being harnessed worldwide to address the future energy crisis. Governments and
the private sector have all agreed in funding research of renewable energy as the alternative
future energy source. In this study, we are going to look into the literature of one of the
renewable energy source hydrogen. The literature is going to address two key areas namely
hydrogen production and storage.
2.1WHAT IS HYDROGEN?
As a unique gas, Henry Cavendish discovered hydrogen in 1766. It was given the name
‘’water forming’’ by Antoine Lavoisier seven years later, who proved that water was
composed of hydrogen and oxygen. The word ‘’hydrogen’’ originates from the Greek word
hydor (water) and gignomai (forming). However, it has to be mentioned that hydrogen was
observed and collected by Robert Boyle in 1671, who dissolved iron in diluted hydrochloric
acid, i.e. long before it was recognised as a unique gas by Henry Cavendish (Molkov V. ,
2012).
Hydrogen is one of the main components of water and of all organic matter and it’s widely
spread not only in the Earth but also in the entire Universe. It is the most abundant element in
the universe representing 75% by mass or 90% by volume of all matter. Hydrogen forms
0.15% of the Earth crust (Molkov V. , 2012).
Atomic number of hydrogen (symbol H) in the periodic table is one and atomic mass is 1.008
g/mol. The hydrogen atom is formed by a nucleus with one unit of positive charge (proton)
and one electron. In normal conditions hydrogen is a gas formed by diatomic molecules, H2
(molecular mass 2.016) in which two hydrogen atoms have formed a covalent bond (Molkov
V. , 2012).
9
Standard properties of Hydrogen (Molkov V. , 2012)
 Colourless
 Odourless
 Nontoxic
 Non-metallic
 Tasteless
 Highly combustible diatomic gas with molecular formula H2.
There are three hydrogen isotopes namely Protium (found in more than 99.985% of the
natural element; only a proton in the nucleus), Deuterium (found in nature in 0.015%
approximately; a proton and a neutron in the nucleus) and Tritium (appears in small
quantities in nature, but can be artificially produced by various nuclear reactions; a proton
and two neutrons in the nucleus) with atomic mass 1, 2 and 3 respectively (Molkov V. ,
2012).
a) HYDROGEN AS FUEL
Hydrogen is a promising fuel, can be obtained from different sources of raw materials,
including water. This is a renewable and sustainable source, which can obtain a high
hydrogen purity via electrolysis. Among the processes for obtaining hydrogen from the water,
the electrolytic conversion is the best known, in which two electrodes are responsible for
conducting electricity and production of this gas. However, to promote this segregation, some
technological challenges must be overcome, as the efficiency of electrolysers, efficiency and
durability of the main fuel cells and the integration of the electrolysis systems for supply and
energy, aiming to reduce production costs (Santosa, Eckerta, & Eduardo De Rossia, 2017).
The production of H2 is an environmentally attractive process and can occur via routes
considered sustainable, as the electrolysis of water, charcoal and biomass gasification, photo-
electrolysis, biological processes and reforming (Kasai, 2014). This fuel can be obtained from
a variety of methods, the main are characterized by production from fossil and renewable
sources by steam reforming, dry reforming, thermal decomposition and cracking natural gas,
petroleum hydrocarbon oxidation and coal gasification. These methods require the use of
high energy load to which the process occurs (Kelly, 2014).
Reducing the dependence on fossil fuels and minimizing environmentally harmful emissions
can be achieved by sustainable energy sources. With near-zero or zero end-use emissions and
10
continually replenished resources, hydrogen can be an ideal sustainable energy carrier. Some
of the advantages of hydrogen can be listed as (Acar & Dincer, 2014):
b) ADVANTAGES OF USING HYDROGEN AS A FUEL

1. High energy conversion efficiencies.
2. It can be produced from water with no emissions
3. It is abundant
4. Hydrogen can be stored in different forms like gas, liquid, or in combination with
metal hydrides)
5. Hydrogen can be transported over long distances
6. Hydrogen can be easily converted to other forms of energy
7. Hydrogen has both a higher HHV and LHV compared to conventional fossil fuels.
See Table 1 below.
On the other hand, a number of hydrogen production methods are still under development,
this results in high production costs and low system efficiencies (Acar & Dincer, 2014).
Fuel HHV (kJ/g) LHV (kJ/g)

Hydrogen 141.9 119.9
Methane 55.5 50.0
Gasoline 47.5 44.5
Diesel 44.8 42.5
Methanol 20 18.1
Table 1: Higher (HHV) and Lower (LHV) heating values of Hydrogen and common fuels at
25 degrees and 1 atm (Dincer, 2012)
Here, we go further to compare hydrogen with other conventional fuels in terms of

Environmental Impact Factor (EIF), Greenization Factor (GF) and Hydrogen Content Factor
(HCF) to emphasize the importance of hydrogen as a unique option, through the following
equations:
(4)
(5)
11
(6)
Where EIFmax is the maximum value of EIF among the evaluated options. In this specific case
with 3.6, coal is selected as the EIFmax. As can be seen from Figure 4 below, with increasing
hydrogen content (HCF), the energy sources become greener (increasing GF) and the
environmental impact (EIF) decreases. This is a clear advantage of hydrogen in terms of
reducing carbon-related emissions. In order to take full advantage of the hydrogen economy,
it needs to be produced from renewable or vast sources at low costs (Dincer & Acar, Review
and evaluation of hydrogen production methods for better sustainability, 2015)
Among the possible hydrogen production methods studied in the literature, natural gas steam
reforming is the most commonly used process, resulting in heavy GHG emissions. Around
50% of the global hydrogen demand is met by natural gas steam reforming, 30% comes from
oil reforming, 18% from coal gasification, 3.9% from water electrolysis, and 0.1% from other
sources (Muradov & Veziroglu, 2005).
In order to remove the adverse effects of fossil fuel utilization on the environment, human
health, and the climate, hydrogen should be produced from clean and abundant sources with
environmentally benign methods (Levin & Chahine, 2010) and (Awad & Veziroglu, 1984).
This concept is called as “green hydrogen production”.
Figure 4: Hydrogen Content Factor (HCF), Greenization Factor (GF) and Environmental
Impart Factor (EIF) of hydrogen and other fossil fuels. (Yilanci, Dincer, & Ozturk, 2009)
12
Green hydrogen technologies are not quickly accessible with sensible effectiveness and
expense. For instance, studies on effectiveness and cost of PV electrolysis for large and small
scale hydrogen production show that PV electrolysis is currently expensive (>$5/kg for H2)
and it cannot reach high conversion efficiencies (with energy and exergy efficiencies less
than 5%) (Yilanci, Dincer, & Ozturk, 2009).
A total of 19 hydrogen production methods are compared based on energy and exergy
efficiencies, production cost, global warming potential (GWP), acidification potential (AP),
and social cost of carbon. (Acar & Dincer, 2015)
2.2 HYDROGEN PRODUCTION METHODS
Hydrogen can be produced by a number of technologies using renewable and non-renewable

sources.
Figure 5: Selected hydrogen production methods (Dincer, 2012).
Figure 5 summarises the current methods used to produce hydrogen. Hydrogen is an

abundant element found in many substances in nature like fresh and sea water, biomass,
hydrogen sulphide, and fossil fuels.
13
With the aim of producing hydrogen with zero or low environmental impact, green hydrogen,
all carbon dioxide and other pollutants must be removed when hydrogen is extracted from
fossil fuels. Some other sources to generate hydrogen are thermal, electrical, photonic, and
biochemical energy.
In Table 2 below, the overview and brief description for hydrogen production process from
primary energy and material origins. The electrical and thermal energy can be harnessed from
fossil fuels (should be processed to be regarded as “clean”), renewable energies such as
solar, wind, hydro, wave, ocean, and thermal, biomass, nuclear, or recycled energy (Acar &
Dincer, 2015).
The photonic energy comes from solar irradiation, while biochemical energy is recovered
from organic matter. In addition to four major primary sources listed in Table 2 (electrical,
thermal, biochemical, and photonic), there are also hybrid forms of energy such as electrical-
thermal, photonic-biochemical, and electrical-photonic. Water, biomass, and fossil fuels are
the material sources evaluated. In cases where fossil fuel is utilized, hydrogen production
process includes CO2 separation and sequestration (Acar & Dincer, 2015).
A total of 19 hydrogen production methods are compared based on energy and exergy
efficiencies, production cost, global warming potential (GWP), acidification potential (AP),
and social cost of carbon.
Method Source Brief Description
Primary energy Material
Direct current is used to split water

into O2 and H2 (electrochemical
M1 Electrolysis Electrical Water reaction)
Cleaned natural gas is passed through

Plasma arc plasma arc to generate H2 and carbon
M2 decomposition Fossil Fuel soot
Thermal decomposition of water

M3 Thermolysis Thermal Water (steam) at temperatures over 2500 K
14
Thermochemical
process: Water Cyclical chemical reactions (net
M4 Splitting Water reaction: water splitting into H2)
Thermochemical
M5 process: Biomass Biomass Thermo-catalytic conversion
Thermochemical
process:
M6 Gasification Conversion of biomass into syngas
Conversion of liquid biomass

M7 Biomass Reforming (biofuels) into H2
PV panels are used to generate

M8 PV Electrolysis Photonic Water electricity
Water is split into H2 by using the

electron-hole pair generated by the
M9 Photo catalysis photo catalyst
Photo- A hybrid cell simultaneously

electrochemical produces current and voltage upon
M10 method absorption of light
Biological systems are used to

M11 Dark fermentation Biochemical Biomass generate H2 in the absence of light
Electrical and thermal energy are

High temperature Electrical used together to drive water splitting
M12 electrolysis +Thermal Water at high temperatures
Hybrid Electrical and thermal energy are

thermochemical used together to drive cyclical
M13 cycles chemical reactions
M14 Coal gasification Conversion of coal into syngas
15
Fossil fuel Fossil fuels are converted to H2 and
M15 reforming CO2
Photonic + Biomass+ Biological systems (microbes,

M16 Bio photolysis Biochemical water bacteria, etc.) are used to generate H2
Fermentation process activated by

M17 Photo fermentation exposure to light
Artificial Chemically engineered systems

M18 Photosynthesis mimic photosynthesis to generate H2
Photo electrodes and external

Electrical + electricity are used to drive water
M19 Photo electrolysis Photonic Water electrolysis
Table 2: Hydrogen production methods from primary energy and material sources (Acar &
Dincer, 2015)
The following is a summary overview of the current hydrogen production methods:
i. ELECTROLYSIS
Currently the most basic industrial process for almost pure hydrogen production is
water electrolysis, and its significance is expected to increase in the future. Water
electrolysis is based on the movement of electrons which are supported by an external
circuit. Alkaline, polymer membrane, and solid oxide electrolyser are the key
electrochemical hydrogen production technologies (Santosa, Eckerta, & Eduardo De
Rossia, 2017).
ii. PLASMA ARC-DECOMPOSITION

Plasma is an ionized state of matter which contains electrons in an excited state and
atomic species. Plasma has a potential to be used as medium for high voltage electric
current release due to the presence of electrically charged particles. Natural gas
(mostly methane) dissociates to hydrogen and carbon black (soot) as a result of
thermal plasma activity. Carbon black is in solid phase which remains at the bottom
while hydrogen is collected in gas phase. The decomposition reaction of methane to
hydrogen and carbon is written as (Fulcheri, et al., 2002):
16
(7)
Reaction (7) is studied by Fulcheri et al (Fulcheri, et al., 2002); their thermal plasma
reactor has 3 electrodes connected to a 3 phase voltage. Plasma gas is introduced to 2
of the 3 electrodes and methane is inserted from the top of the reactor. Their results
show a 100% pure hydrogen production with zero CO2 emissions (solid state carbon
black remains at the bottom of the reactor). Plasma arc decomposition can be
classified as “high temperature pyrolysis”. (Gaudernack & Lynum, 1998) State that
plasma cracking has a potential to reduce hydrogen production cost by at least 5%,
compared to large scale steam methane reforming with carbon dioxide sequestration.
iii. H2O THERMOLYSIS

Water thermolysis, also known as single step thermal dissociation of water, reaction
can be written as:
(8)
In order to accomplish a reasonable degree of dissociation, the reaction requires a heat

source which could provide temperatures above 2500 K. For instance, at 3000 K and
1 bar, the degree of dissociation is 64%. One of the challenges of this production
method is the separation of H2 and O2. Therefore, the mixture needs to be cooled
down before being sent to the separation process. The experimental solar thermolysis
of water study conducted by Baykara (Baykara, 2004) achieves 90% of the
equilibrium at a residence time of 1 ms and temperature of 2500 K. The results also
show that if the product gases are rapidly cooled to 1500–2000 K (in few
milliseconds); recombination of H2 and O2 can be avoided by effective hydrogen
separation with the use of palladium membranes.
iv. THERMO-CHEMICAL H2O SPLITTING

Thermochemical water splitting cycles have a major advantage of not requiring
catalysis to drive the individual chemical reactions. Except water, which is the
material source of hydrogen production, all chemicals used in the thermochemical
cycle can be recycled. Other advantages of thermochemical water splitting cycles can
be listed as (Dincer, 2012):
17
a. No need for O2–H2 separation membranes,
b. Reasonable temperature requirement range of 600–1200 K, and
c. Zero or low electrical energy requirement.
Balta et al (Balta, Dincer, & Hepbasli, 2009) summarized the review articles on
thermochemical water splitting available in the literature. Being fully developed and
demonstrated in Japan and the US, the S–I cycle are considered as technically viable.
On the other hand, the commercial viability of these cycles needs to be proven. The
first reaction of S–I cycles is thermally driven and it can be written as.
(9)
The product gases (H2O and SO3) are separated and heated up to 800–900 °C. Then
SO3 gas is decomposed thermally according to:
(10)
After separation from O2, SO2 undergoes an exothermic reaction with iodine and
water which occurs at low temperatures spontaneously:
SO2 (g) + I2 (g) + 2H2O (l) → 2HI (g) + H2SO4 (aq) (11)
Lastly, HI thermally decomposes into H2 at temperatures around 425–450 °C:
(12)
Since there are no side reactions happening during S–I cycle, it is reasonably
straightforward to separate and reuse the chemicals used in (9), (10), (11) and (12)
Because of the relatively high reaction temperature requirements of S–I cycles, there
are not many sustainable thermal energy sources available to drive the individual
reactions in the cycle. Nuclear, concentrated solar, and biomass combustion heat can
be listed as possible sustainable thermal energy sources to drive the S–I cycle
reactions. In the hybrid version of S–I cycles, hydrogen generating reaction is
supported electrochemically (Balta, Dincer, & Hepbasli, 2009).
Thermochemical conversion of biomass, gasification, and biofuel reforming
18
When using biomass to extract hydrogen, the moisture content should be kept below a
certain level by drying or supercritical steam gasification. Some of the examples of
biomass are wood sawdust and sugar cane. The general biomass conversion is:
(13)
Where ClHmOn is the general chemical symbol of the biomass. Tar is the undesired
product of this reaction since it has adverse effect on the process (i.e. slugging and
fouling). There are numerous catalysts used to control, minimize, and prevent the
formation of tar as a result of reaction 13.
In order to produce hydrogen, solid biomass undergoes the following gasification

reaction:
(14)
In this regard, fixed bed, moveable bed and fluidized bed are treated as the common
types of gasifiers used in the gasification process. Based on the amount of provided
heat, the process is called either auto thermal or thermal. In auto thermal gasification,
the required heat is provided by the partial oxidation in the gasifiers. Hydrogen
production from liquid biofuels (i.e. ethanol and methanol) occurs via thermochemical
processes (Dincer, 2012).
v. PV ELECTROLYSIS, PHOTO CATALYSIS, AND PHOTO

ELECTROCHEMICAL METHOD
PV based electrolysis process includes photovoltaic (PV) panels, DC bus bar, AC
grid, accumulator battery set, Electrolyser and hydrogen storage canisters. PV based
electrolysis is one of the most expensive hydrogen production methods; with current
technology, the cost of hydrogen from PV electrolysis is about 25 times higher than
that of fossil fuel alternatives. However, the cost of this process has been continuously
decreasing and this factor is estimated to go down to six (Rand & Dell, 2009).
The photo catalysis converts photonic energy (comes from solar irradiation) to
chemical energy (hydrogen). The energy carried by the photon is proportional to the
frequency of the radiation and given by hν where h is the Planck constant and ν is the
frequency. When a photon hits the photo catalyst, an electron-hole pair is generated
and the obtained electrical charge is utilized to dissociate water. In order for a photo
19
catalyst to split water and generate hydrogen, it should have an appropriate band gap
and properly located conduction and valance bands for oxidation/reduction reactions
(Dincer, 2012).
Furthermore, rapid generation and separation of electron-hole pairs is essential when

picking an appropriate photo catalyst. In the literature, semiconductors (i.e. TiO2) and
metal oxides (i.e. Fe2O3) are heavily studied as photo catalysts. Also, chemically
modified and engineered complex supramolecular devices are utilized to perform
photocatalytic reactions. Acar et al. (Acar, Dincer, & Zamfirescu, 2014) reviewed and
assessed various simple and complex photo catalysts based on their H2 production
yield, efficiency, and impact on human health and the environment. The photo-
reduction and photo oxidation reactions can be written as.
(15)
(16)
Here, photo-electrochemical cells (PEC) convert solar energy to an energy carrier via
light stimulated electrochemical processes. In a PEC, solar light is absorbed by one or
both of the photo-electrodes and at least one of them is a semiconductor. PECs can
produce either chemical or electrical energy. They are also used to treat hazardous
aqueous wastes (Quan, Yang, Ruan, & Zhao, 2005). The working principle of the
semiconductor in a PEC is similar to a PV cell.
In both cases, photons with higher energy than the band gap generate electron-hole
pairs and this electric field is used to oxidize/reduce water. PEC systems combine
solar energy absorption and water electrolysis into a single unit. This is a clear
advantage of PEC because they do not require a separate power generator such as a
PV cell and therefore they are more compact (Dincer, 2012).
There are many kinds of photosensitive semiconductors investigated in the literature.

The most promising option so far is agreed to be TiO2. In addition to TiO2, several
other semiconductors have been studied, such as, ZnO, Fe2O3, BiVO4, and WO3
(Dincer, 2012).
20
vi. DARK FERMENTATION
Biochemical energy, which is stored in organic matter, can be used by living creatures
to extract hydrogen in the absence or presence of light. Dark fermentation is the
conversion of biochemical energy stored in organic matter to other forms of energy in
the absence of light (this case might happen when there is reduced supply of light)
(Dincer, 2012).
The bioreactors used for dark fermentation are simpler and cheaper compared to
photo fermentation since the process does not require solar input processing.
Hydrogen production by dark fermentation has several other advantages such as the
ability to produce hydrogen from organic waste and therefore control and stabilize
biological waste which has a potential danger of contamination (Dincer, 2012).
For instance, dark fermentation can be integrated into wastewater treatment systems
to produce H2 from wastewater. Producing hydrogen from organic waste has a
potential to reduce hydrogen production costs since organic waste (including
wastewater) is cheap and easily available. Hydrogen production from water diluted
olive oil by study by Koutrouli et al. (Koutrouli, et al., 2009) Shows a maximum 640
g of H2 per tonne of olive pulp. A hydrogen production yield of around 77 g H2 per kg
of glucose is reported by Das and Veziroglu (Das & Veziroglu, 2008).
Low production capacity per unit of (production facility) capital investment is one of
the major challenges of anaerobic digestion. Some of the advantages and
disadvantages of dark fermentation compared to bio photolysis and photo
fermentation as well as the future prospects of these methods are listed in Table 3
below:
21
Process Advantages Disadvantages Future prospects
Near term
incremental
Abundant Separation of H2 improvement
Bio photolysis supply(water) and O2 possible
Immobilisation might
Carbon independent Low conversion bring some
pathway efficiencies improvement
Only products are H2 Large surface area Material science

and O2 requirement breakthrough
Metabolic
Readily available waste Low volumetric engineering is
streams as supply production rate required
Near term
incremental
Photo Nearly complete Low conversion improvement
fermentation substrate conversion efficiencies possible
Can use variety of Large surface area Material science

streams requirement breakthrough
Metabolic
Large amounts of engineering is
by products required
Two stage systems

Simple reactor Reactor to reactor can extract additional
Dark fermentation technology variation energy,
Low COD
High production rates removal Decrease COD
Table 3: Comparison: dark and bio-photolysis Photo fermentation (Hallenbeck, Abo-

Hashesh, & Ghosh, 2012)
22
vii. HIGH TEMPERATURE ELECTROLYSIS
High temperature electrolysis is a method of electrolysis where steam is dissociated to
H2 and O2 at temperatures between 700 and 1000 °C. This method is generally
considered as more efficient than conventional room temperature electrolysis
(efficiency increases with increasing temperature). In high temperature electrolysis,
water is converted to steam by using thermal energy (Dincer, 2012).
The system components are either heated directly by the steam supply or indirectly by
heat transfer. Thus the electrical energy need of this type of electrolysis is lower than
that of conventional electrolysis methods. Another advantage of this method is the
possibility of achieving zero greenhouse gas emissions when a clean heat source (i.e.
solar, geothermal, and/or nuclear) is used as external heat source (Dincer, 2012).
However, due to high operating temperatures, the system components have to meet
specific requirements for an efficient hydrogen generation. Current challenges of high
temperature electrolysis can be listed as (Dincer, 2012):
a. Chemically stable electrolyte development with high ionic and low electronic
conductivity,
b. Porous, chemically stable electrode research in highly reducing/oxidizing
environments with good electronic conductivity and coefficient of thermal
expansion similar to the electrolyte.
c. Engineering chemically stable materials at high temperatures and highly
reducing/oxidizing environments.
viii. HYBRID THERMOCHEMICAL CYCLES

Hybrid thermochemical cycles operate at lower temperatures compared to thermally
driven water splitting cycles mentioned in thermochemical Water Splitting. External
energy needs of the individual electrochemical reactions are met by thermal and
electrical energies. Since hybrid cycles operate at lower temperatures, other
sustainable thermal sources apart from solar, high temperature nuclear and biomass
combustion (such as recovered waste heat from nuclear and geothermal facilities) can
be used to drive the involved processes (Acar & Dincer, 2014).
23
Cu–Cl cycle is proposed as an outstanding hybrid cycle as investigated in the
literature. The operating temperature of this cycle does not exceed 550 °C. Among
different types of Cu–Cl cycles, “five-step” version is the most studied one. This
version is composed of three thermally driven chemical reactions, one
electrochemical reaction, and one physical drying step. In Cu–Cl cycles, the thermal
energy source is used partially to drive the cycle directly and partially to generate the
required electricity. The major advantage of Cu–Cl cycles is hydrogen generation
from low grade temperature sources, especially those which can be considered as
sustainable thermal energy. Nuclear heat, industrial heat, waste heat recovered from
power plants, concentrated solar heat, heat resulting from municipal waste
incineration, and geothermal heat can be listed as sustainable thermal energy sources
(Acar & Dincer, 2014).
ix. COAL GASIFICATION

With current state of technology and worldwide coal reserves, coal is an economical
and technically practical option to produce hydrogen in large scale plants. Compared
to the existing methods (i.e. electrolysis), gasification is more suitable for converting
coal to hydrogen. In gasification, coal is partially oxidized with steam and O2 in a
high-temperature and high-pressure reactor and the products are mainly H2, CO,
mixed with steam and CO2 (syngas). This syngas goes through a shift reaction in
order to increase the hydrogen yield (Acar & Dincer, 2014).
The gas product can be processed and cleaned in cases where there is a need to
recover elemental sulphur or sulphuric acid. Some of the syngas can further be
processed and used in gas turbines to generate electricity. Despite some advantages of
coal gasification, due to high carbon content of coal, this method causes higher CO2
emissions compared to other available hydrogen production technologies. Carbon
capture and storage technologies are currently developed in order to address this issue
At present, hydrogen production cost of coal gasification is slightly higher than that of
natural gas steam reforming. However, coal gasification techniques are less well-
defined than those used in the steam reforming of natural gas. In terms of economics,
making hydrogen from coal differs from other fossil fuels: the unit raw material costs
24
are lower while the unit capital costs are higher for the coal gasification plants (Acar
& Dincer, 2014).
x. FOSSIL FUEL REFORMING

Steam reforming, partial oxidation, and auto-thermal reforming are three main fossil
fuel reforming technologies to produce hydrogen. The advantages and challenges of
each of these processes are listed in Table 4 below.
Technology Advantages Disadvantages

Steam Reforming Most developed industrial process Highest air emissions
No oxygen requirement
Lowest operating temperature
Best H2/CO ratio
Auto thermal Lower process temperature than partial Limited commercial experience
Reforming oxidation
Low methane slip Air/oxygen requirement
Partial Oxidation Reduced desulfurization requirement Low H2/CO ratio
No catalyst requirement High operating temperatures
Low methane slip Complex handling process
Table 4: Fossil fuel reforming technologies comparison (Parthasarathy & Narayanan,

2014).
In addition to H2, CO and CO2 are emitted in the end of a reforming process. Steam
reforming generally requires an external heat source but it does not demand oxygen to
drive the process. It has a lower operating temperature and higher H2/CO ratio than
partial oxidation and auto thermal reforming.
In partial oxidation, hydrocarbons are partially oxidized with oxygen to produce

hydrogen. The source of heat to drive this process is derived from the partial
oxidation (combustion) reaction. There is no catalyst requirement in partial oxidation
and it is more sulphur tolerant compared to steam and auto thermal reforming. The
pressure requirement of auto thermal reforming is lower than partial oxidation
(Parthasarathy & Narayanan, 2014).
25
Auto thermal reforming and partial oxidation do not need an external heat source.
However, both of these processes require pure oxygen feed which increases
complexity and cost with the addition of oxygen separation units. Compared to other
fossil fuel reforming technologies, steam reforming (particularly steam methane
reforming) is the least expensive and most common method to produce hydrogen
(Holladay, Hu, King, & Wang, 2009).
xi. BIO PHOTOLYSIS AND PHOTO FERMENTATION

Bio photolysis and photo fermentation are photonic-driven biochemical hydrogen
production processes from water. Kotay and Das (Kotay & Das, 2008) categorize
hydrogen production via bio photolysis into direct, indirect, and photo fermentation.
In bio photolysis, some light-sensitive microorganisms are used as biological

converters in a specially designed photo-bioreactor. Among possible microorganisms,
the most suitable ones are microalgae since they can be cultured and have a potential
to generate hydrogen in closed systems which permits hydrogen capture. Cultured
micro-algal strains show high hydrogen yields (Kotay & Das, 2008).
The major advantage of bio photolysis is the ability to produce hydrogen from water
in an aqueous environment at ambient temperature and pressure. However, it was only
demonstrated at laboratory scale and not yet fully developed for commercial use.
The general hydrogen generation reactions with the help of photo-activated enzymes
are (Dincer, Green methods for Hydrogen productions, 2012):
(17)
(18)
xii. ARTIFICIAL PHOTOSYNTHESIS

Artificial photosynthesis is a bio-mimetic process mimicking the natural
photosynthesis process to accomplish the following (Dincer, Green methods for
Hydrogen productions, 2012):
 PV-based electricity generation: to support the grid system.

 Dry agriculture: with this method, carbohydrates (food), liquid fuels, chemical
feed stocks, and polymers for fibre manufacture can be produced with near or
absolute chemical minimum water usage. This amount is thousands of times
26
lower than the conventional agriculture water usage. The system has an
enzyme bed reactor system which fixes CO2 from the air (or other convenient
sources) and it is powered by hydrogen and bioelectric transducers.
 Hydrogen production: electrolytic decomposition of water into H2 and O2 can
be achieved by mimicking photosynthesis.
Although the technology is not mature enough to be applied to large scale

manufacturing, artificial photosynthesis has a significant potential to lower global
water usage and support clean energy systems by generating electricity and hydrogen
from photonic energy (Kotay & Das, 2008).
xiii. PHOTO ELECTROLYSIS

The process where heterogeneous photo catalysts is applied on one or both of the
electrodes is called photo electrolysis. In addition to solar irradiation exposure, the
electrolysis cell should be supported by electrical energy to conduct photo
electrolysis. Therefore, in photo electrolysis, both photonic and electrical energies are
converted to chemical energy (hydrogen) (Acar & Dincer, 2014).
The photo electrolytic hydrogen production mechanism includes the following steps:
a. Generation of an electron-hole pair with the help of a photon that has

sufficiently high energy (higher than the band gap of the p–n junction),
b. Flow of electrons from the anode to the cathode generating electricity current,
c. Decomposition of water into hydrogen ions and gaseous oxygen,
d. Reduction of hydrogen ions at the cathode to form hydrogen in gas form,
e. Separation of the product gases, processing, and storage.
The performance of a photo electrolytic system depends on the type of photon

absorbing material, their crystal structure, surface properties, corrosion resistance, and
reactivity. There usually is a trade–off between photo electrode stability and photon
energy–to hydrogen conversion efficiency: the high efficiency photo electrodes
generally have poor stability in electrolytes while the chemically stable photo
electrodes show poor water splitting efficiencies (Acar & Dincer, 2015)
In the end, in order to be able to move to a sustainable and clean energy supply,
hydrogen should be produced from clean energy sources instead of fossil fuels.
27
Production quantity, efficiency, cost, system reliability and environmental impact are
some of the major concerns of hydrogen energy research.
It is now widely accepted that carbon-free society is not possible without hydrogen
economy. This study reviews and assesses current efforts to produce hydrogen with
minimum cost, environmental and social impact as well as maximum efficiency.
These efforts are to help address adverse effects of excessive fossil fuel utilization and
any energy crisis that might happen in the near future with green solutions (Acar &
Dincer, 2015).
The key benefits and critical challenges of the selected hydrogen production method
are summarised in Table 5 below.
28
Photo
Fossil Fuel Biofuel Coal and biomass Thermochemical Water electrochemical
Reforming Reforming gasification method electrolysis method Biological method
Critical
Challenges
Effective Efficient
High capital Low system photocatalytic microorganisms for
High capital costs costs High reactor costs Cost effective reactor efficiency material sustainable production
High operation
and
maintenance High capital Low system Optimal microorganism
Design costs System efficiency Long term technology costs efficiency functionality
High operation Design Feedstock impurities System Cost effective Reactor material
and maintenance feedstock Carbon capture and Effective and durable integration reactor Long-term selection Long term
costs quality storage material Design issues technology technology
Major R&D
Needs
Hydrogen Durable and
Efficiency and yield and Low cost and efficient Robust, low cost Durable and efficient photo Microorganism
cost efficiency purification materials cheap materials catalyst functionality
29
Low cost and Low Corrosive-
efficient temperature Ease of manufacture resistant
purification production Co-fed gasifiers and application membranes Low cost materials New organisms
Low cost and Durable, active Active, stable and
Feedstock pre- efficient Carbon capture and and cheap cheap supporting
treatment production storage System optimization catalyst materials Inexpensive methods
High volume, low cost, Large scale High volume Low cost and durable
Optimization Optimization Hydrogen quality flexible system design applications production material
Automated Regional best Cost of feedstock Storage and
process control feedstock preparation Efficient heat transfer production rate System control System optimization
Feedstock pre- High capacity and low
Reliability treatment Tolerance of impurities Reliability Reliability Power loses costs system
Key Benefits
No pollution
Most viable Low cost syngas with renewable Low operation
approach Viability production Clean and sustainable energy sources temperature Clean and sustainable
Lowest current Existing Abundant and cheap Existing Clean and Tolerant of diverse
cost infrastructure feedstock Recycled chemicals infrastructure sustainable water conditions
Existing Integration with
infrastructure fuel cells Self-sustaining
Table 5: Benefits and challenges for H2 production mechanisms (Acar & Dincer, 2014)
30
2.3 FINANCIAL COMPARISON OF HYDROGEN PRODUCTION
METHODS
When it comes to calculating the cost of hydrogen production, there are several uncertainties
since the cost is strongly affected by the production technology's advancement level,
availability of existing infrastructure, and the feedstock prices (Acar & Dincer, 2014).
The literature survey results of average hydrogen production costs (per kg of hydrogen) are
presented in Figure 3 below for the nineteen hydrogen production methods identified. Among
the selected methods, hydrogen production cost of water electrolysis, thermochemical water
splitting, biomass gasification, photo catalysis, coal gasification, and fossil fuel reforming are
taken from Parthasarathy and Narayanan (Parthasarathy & Narayanan, 2014). Plasma arc
decomposition, thermochemical biomass conversion and reforming, dark fermentation, bio
photolysis, photo fermentation, artificial photosynthesis, and photo electrolysis cost data is
compiled from Uddina et al (Uddina, Dauda, & Abbas, 2013).
Thermolysis, PV electrolysis, high temperature electrolysis, and hybrid thermochemical

cycles’ hydrogen production cost data are obtained from Ngoha and Njomo (Ngoha &
Njomo, 2012). And the hydrogen production cost of photo electrochemical method is attained
from Trainham et al (Trainham, Newman, Hoertz, & Akunuri, 2012).
According to Figure 6 below, the most financially advantageous methods for hydrogen
production are steam methane reforming, coal and biomass gasification, and plasma arc
decomposition. Thermochemical cycles and biomass conversion, as well as hybrid
thermochemical cycles also seem to be competitive to fossil fuel and biomass prices. It
should be noted that in this study the average of production costs are taken from the literature
(Dincer, 2012).
Photo electrochemical systems give the highest production cost per kg of hydrogen.
However, this method is in early R&D phase and one of the major advantages of this method
is its local applications. Therefore, the production costs related to PEC operation are expected
to decrease in the future as PEC systems technology gets more advanced (Trainham,
Newman, Hoertz, & Akunuri, 2012).
31
Figure 6: Production cost of selected hydrogen production methods (per kg of hydrogen)
a. ENERGY AND EXERGY EFFICIENCIES COMPARISON OF

HYDROGEN PRODUCTION METHODS
Efficiency is defined as useful output by consumed input. Energy efficiency of a hydrogen

production method can be calculated as.
(19)
Where the mass flow rate of produced hydrogen, LHV is the lower heating value of
hydrogen (121 MJ/kg) and is the rate of energy input to the process. The following
equation is used for exergy efficiency:
(20)
Here, is the chemical exergy of hydrogen and is the rate of exergy input into the
process. The efficiency data used in this study are taken from (Holladay, Hu, King, & Wang,
2009), (Ismail & Bahnemannc, 2014), (Singh & Wahid, 2015), (Karunadasa, Chang, &
Long, 2010), (Ibrahim, Kamarudina, & Minggua, 2014), and (Dincer & Zamfirescu, 2012).
32
Figure 7 presents the energy and exergy efficiency data of selected hydrogen production
methods from which it can be seen that fossil fuel reforming, plasma arc decomposition, and
coal and biomass gasification are advantageous over other methods. On the other hand,
photonic energy based hydrogen production methods show the poorest performance among
the selected production methods (Acar & Dincer, 2014).
Figure 7: Energy and exergy efficiencies of selected hydrogen production methods (Acar &
Dincer, 2014).
b. OVERALL COMPARISON OF HYDROGEN PRODUCTION

METHODS
In this section, the environmental, social, financial, and technical assessment results are
normalized in order to compare each method effectively. GWP, AP, SCC and production
costs are normalized based on the following equation (Acar & Dincer, 2014):
(21)
The ranking is between 0 and 10, where 0 means poor performance and 10 indicates the ideal
case (zero-cost and zero-emissions). Lower costs and emissions are given higher rankings.
“0” is assigned to the highest cost and emissions in selected categories. For example, in terms
33
of GWP, coal gasification method gives the highest emissions; therefore, the GWP ranking of
coal gasification is assigned to be “0”. Efficiencies are normalized based on the following
equation:
(22)
The ranking range is again between 0 and 10, 0 means poor performance and 10 indicate the
ideal case (100% efficiency). Higher rankings mean higher efficiencies. The normalized
emissions, cost, and efficiency rankings are presented in table 7.
The hypothetical ideal case refers to zero-cost and emissions, which also means zero SCC.
The energy and exergy efficiency of this ideal case is 100%. In terms of energy and exergy
efficiency, closest performance to the ideal case is reached by fossil fuel reforming and
biomass gasification. However, biomass gasification gives considerably high AP (low AP
ranking) compared to other selected methods. SCC rankings of biomass gasification are also
low (Acar & Dincer, 2014).
2.4 MOST EFFICIENT HYDROGEN PRODUCTION METHOD:

ELECTROLYSIS
From the literature the most energy efficient hydrogen production method has emerged to be
electrolysis. The most common technology of electrolysis include:
 Alkaline electrolyser
 Proton exchange membrane (PEM) electrolyser
 Solid oxide electrolysis cells (SOEC)
Table 6 summarizes the typical specifications of alkaline, polymer membrane (PEM), and
solid oxide electrolysers (SOE). Of the parameters listed in Table 6, efficiency and the
current density are the most important parameters. Efficiency of an electrolysis cell is
calculated based on the ideal and actual energies needed to drive the reaction.
34
Specification Alkaline PEM SOE
Technology maturity state of the art Demonstration R&D
Cell temperature, oC 60 - 80 50 - 80 900 - 1000
Cell pressure, bar <30 <30 <30
Current density, A/cm2 0,2 - 0,4 0,6 - 2,0 0,3 - 1,0
Cell voltage, V 1,8 - 2,4 1,8 - 2,2 0,95 - 1,3
Power Density, W/cm2 Up to 1,0 Up to 4,4 -
Voltage efficiency, % 62 - 82 67 - 82 81 - 86
Specific system energy
consumption, kWh/Nm3 4,5 - 7,0 4,5 - 7,5 2,5 - 3,5
Hydrogen production, Nm3/hr <760 <30 -
Table 6: Standard specifications for alkaline, PEM and SOE Electrolysers (Santosa, Eckerta,
& Eduardo De Rossia, 2017)
Catalysts are used in order to increase current density and rate of electrolysis reactions.
Platinum is one of the most commonly used heterogeneous catalysts – applied to the surface
of the electrodes. Homogeneous catalysts can also be used during electrolysis. Due to their
high turnover rates, homogeneous catalysts are less expensive than the heterogeneous ones
(Karunadasa, Chang, & Long, 2010)
a. ELECTROLYSIS
Electrolysis is the production of a chemical reaction by means of an electric current (Jones &
Atkins, 2002) Electrolysis is a method used for quantitative separations. The electrolytic
method can be applied to the quantitative removal and determination of one or more different
metallic ions from solution or maybe used, with carefully controlled conditions, to effect a
separation of ions of one metal from those of several metals (Frank., 1967).
They are fundamental laws related to electrolysis:
The Coulomb is the quantity of electricity that will cause the deposition or removal of
0.001118g of silver at an electrode. An Ampere, the unit of current is 1 coulomb per second.
The Ohm is the unit of resistance. The Volt or unit of electromotive force (emf) causes a
35
current of 1 Ampere to flow through a resistance of 1 Ohm. The Volt-Coulomb or Joule is the
unit of electrical energy and the Volt-Ampere or Watt is the unit of electrical power (Frank.,
1967).
Ohm’s law gives the relation between current, resistance and electromotive force.
(23)
Where I is in Amperes, electromotive force in Volts V, and resistance R in Ohms.
The Faraday, 96 493 coulombs, is the amount of electricity equivalent to Avogadro’s number
of electrons transferred in either an oxidation or a reduction process. Because this quantity of
electrons must be removed to oxidise a gram equivalent of any substance and the same
number of electrons must be taken to reduce a gram equivalent, a Faraday is that quantity of
electricity used in transforming a gram equivalent of any substance at an electrode (Frank.,
1967).
The two laws of electrolysis, usually referred to as a Faraday’s law, can be stated as follows
(Frank., 1967):
2.1 The quantity of a given substance that is liberated at an electrode is proportional to the
quantity of electricity that is passed through the system.
2.2 The amounts of different substances that are deposited by the same quantity of
electricity are proportional to the chemical equivalent weights of these substances.
These laws are only applicable if the current efficiency does not vary and is 100% for the
substance being measured.
b. ELECTRODE POTENTIALS
If any chemical element that is a conductor of electricity is placed in contact with a solution
containing its ions, a potential difference develops at the interface between the electrode and
solution. The magnitude and sign or direction of this potential depend upon the relative
tendency of the atoms of the element to give off or accept electrons to form ions of the
element. Depending on the nature of the element and the concentration of its ions in solution,
the potential of the electrode may be positive, zero or negative relative to the solution (Frank.,
1967).There are two major factors that determine the electrode potential relative to another
electrode. First is the activity of the electrolytic solution pressure of the element which is the
36
tendency of the element to furnish ions. Ata a given temperature and pressure this is a
characteristic constant for a stable form of an element but varies if the electrode is strained
mechanically or if a metastable crystalline form of the metal is present (Frank., 1967).
Second is the activity of the dissolved ions of the element, which in turn varies with the
concentration at constant temperature. A table of standard potentials at a 25 oC that apply to
the condition unit activity ( approximately 1 molar) of the ions and one atmosphere pressure
for gases given in Table 7.
Reduction Half-Reaction Standard Reduction Potential (V)
F2(g)+2e- → 2F-(aq) +2.87
S2O82-(aq)+2e- → 2SO42-(aq) +2.01
O2(g)+4H+(aq)+4e- → 2H2O(l) +1.23
Br2(l)+2e- → 2Br-(aq) +1.09
Fe3+(aq)+e- → Fe2+(aq) +0.77
I2(l)+2e- → 2I+(aq) +0.54
Cu2+(aq)+2e- → Cu(s) +0.34
Sn4+(aq)+2e- → Sn2+(aq) +0.15
S(s)+2H+(aq)+2e- → H2S(g) +0.14
2H+(aq)+2e- → H2(g) 0.00
Sn2+(aq)+2e- → Sn(g) -0.14
V3+(aq)+e- → V2+(aq) -0.26
Fe2+(aq)+2e- → Fe(s) -0.44
Cr3+(aq)+3e- → Cr(s) -0.74
Zn2+(aq)+2e- → Zn(s) -0.76
Mn2+(aq)+2e- → Mn(s) -1.18
Na+(aq)+e- → Na(s) -2.71
Li+(aq)+e- → Li(s) -3.04

Table 7: Standard Reduction Potentials at 25oC (Frank., 1967)
37
The potentials shown above are standard reduction potentials and all reactions are written as
reductions. For oxidations, which is the same as considering the reactions in table 1 written in
the opposite direction, the magnitude of the potential will remain the same but the sign will
be opposite (Frank., 1967).
Creating an electric potential through water causes positive ions, including the inherent
hydrogen ions H3O+, to move towards the negative electrode (cathode) and negative ions,
including the inherent hydroxide ions OH-, to move towards the positive electrode (anode).
At sufficient potential difference, this may cause electrolysis with oxygen gas being produced
at the anode and hydrogen gas produced at the cathode (Marini, et al., 2012). The electrolysis
of water usually involves dilute, or moderately concentrated, salt solutions in order to reduce
the power loss driving the current through the solution, but the presence of salt is not a
requirement for electrolysis.
Thus (Chaplin, 2017),
Anode +ve 6H2O(l) O2(g) + 4H3O+(aq) + 4e-(to anode) E° = +1.229 V, pH 0 E°' = +0.815 V
Cathode -ve 4e-(from cathode) + 4H2O(l) 2H2(g) + 4OH-(aq) E° = -0.828 V, pH 14 E°' = -0.414 V
Where (l), (g) and (aq) show the states of the material as being liquid, gas or aqueous
solution, and with the electrical circuit passing the electrons back from the anode to the
cathode. The reactions are heterogeneous, taking place at the boundary between the electrode
and the electrolyte with the aqueous boundary layer subject to concentration and electrical
potential gradients with the presence of the generated gaseous Nano bubbles and
microbubbles (Chaplin, 2017).
Generally the water next to the electrodes (Pedroza, Poissier, & Fernández-Serra, 2015)will
change pH due to the ions produced or consumed. If the electrode compartments are
separated by a suitable porous membrane then the concentration of H3O+ in the anolyte and
OH- in the catholyte (and hence the increase in the respective conductivities) are both
expected to increase more than if there is free mixing between the electrodes, when most of
these ions will neutralize each other. Small but expected differences in the solutions’ pHs
next to the anode (anolyte) and cathode (catholyte) cause only a slight change to the overall
38
potential difference required (1.229 V). Increasing the acid content next to the anode due to
the H3O+ produced will increase its electrode potential (for example: pH 4 E = +0.992 V) and
increasing the alkaline content next to the cathode due to the OH- produced will make its
electrode potential more negative (for example: pH 10 E = -0.592 V). If the anode reaction is
forced to run at pH 14 and the cathode reaction is run at pH 0 then the electrode potentials are
+0.401 V and 0 V respectively as shown on Potential vs pH table below (Chaplin, 2017).
Potential vs pH table (Chaplin, 2017)
a) Anode pH 0 2 H2O O2 + 4H+ + 4e- E°= +1.229 V

b) Anode pH 14 4 OH- O2 +H2O + 4e- E°= +0.401 V
c) Cathode pH 0 4 H+ + 4e- 2H2 E°= 0.0 V
d) Cathode pH 14 4 H2O + 4e- 2H2 +4OH- E°= -0.828 V
This does not mean that because the electrolysis can be achieved with a (minimum) voltage
of +0.403 V (c and b, above right) (Chen, Dong, Wang, Wang, & Xia, 2016), it breaks the
thermodynamic requirement of 1.229 V as there is a further input of energy required in
keeping the electrode compartments at the required pHs and solute concentration.
The current flowing indicates the rate of electrolysis. The amount of product formed can be
calculated directly from the duration and current flowing, as 96,485 Coulombs (i.e. one
Faraday) delivers one mole of electrons; with one Faraday ideally producing 0.5 moles of H2
plus 0.25 moles of O2. Thus, one Ampere flowing for one second (one Coulomb) produces
39
5.18 µmol H2 (10.455 µg, 0.1177 mL at STP) and 2.59 µmol O2 (82.888 µg, 0.0588 mL at
STD; 4.9 kW h/m3 H2 at 60% efficiency), if there are no side reactions at the electrodes
(Chaplin, 2017); that is:
 Number of moles = Coulombs/ (unsigned numeric charge on the ion ˣ Faraday)

 Number of moles = (Current in Amperes ˣ time in seconds)/ (unsigned numeric charge
on the ion ˣ Faraday)
The gases produced at the electrodes may dissolve, with their equilibrium solubility
proportional to their partial pressure as gases in the atmosphere above the electrolytic surface.
Oxygen gas is poorly soluble (~44 mg kg-1, ~1.4 mM at 0.1 MPa and 20 °C, but only ~0.29
mM against its normal atmospheric partial pressure). Hydrogen gas is less soluble (~1.6 mg
kg-1, ~0.80 mM at 0.1 MPa and 20 °C but only ~0.44 nM against its very low normal
atmospheric partial pressure). It may take considerable time for the solubility to drop from
their initially-super-saturated state to their equilibrium values after the electrolysis has ended
(Chen, Dong, Wang, Wang, & Xia, 2016).
Although theoretically as described above, the current passing should determine the amounts
of hydrogen and oxygen formed, several factors ensure that somewhat lower amounts of gas
are actually found. Some electrons (and product) are used up in side reactions, some of the
products are catalytically reconverted to water at the electrodes particularly if there is no
membrane dividing the electrolysis compartments, some hydrogen may absorb into the
cathode (particularly if palladium is used) and some oxygen oxidizes the anode. Finally some
gas remains held up in the Nano-bubbles for a considerable time and some gas may escape
measurement (Chaplin, 2017).
The above description hides much important science and grossly over-simplifies the system.
The actual potential required at any position within the electrolytic cell is determined by the
localized concentration of the reactants and products including the local pH of the solution,
instantaneous gas partial pressure and effective electrode surface area loss due to attached gas
bubbles. In addition, a greater potential difference (called over potential) is required at both
electrodes to overcome activation energy barriers and deliver a significant reaction rate
(Chaplin, 2017).
Typically at good electrodes, such as those made of platinum, that may total an addition of
about half a volt to the potential difference between the electrodes. In addition a further
potential difference is required to drive the current through the electrical resistance of
40
electrolytic cell and circuit; for a (typical) one Ohm cell circuit resistance, each Ampere
current flow would require a further one Volt and waste one Watt of power. This power (and
consequent energy) loss (~20 %,) (Carmo, Fritz, & Mergel, A comprehensive review on PEM
water electrolysis, 2013)causes the electrolyte to warm up during electrolysis.
Table 8: Current and Voltage (Chen, Dong, Wang, Wang, & Xia, 2016)
To clarify:
 The minimum necessary cell voltage to start water electrolysis is the potential 1.229V.
 The potential necessary to start water electrolysis without withdrawing heat from the
surroundings is -ΔH°'/nF = 1.481 V.
This results in at least a 21% unavoidable loss of efficiency. Normally further heat is
generated, and efficiency lost, from the over potentials applied (Chaplin, 2017).
The efficiency of electrolysis (Mazloomi, S.K, & Sulaiman, 2012)increases with the
temperature as the hydrogen bonding reduces. If the pressure over the electrolysis is
increased, then more current passes for the same applied voltage. However the output of gas
per Coulomb and the heating effect are both decreased.
This is due to the increased solubility of the gases and smaller bubbles both reducing the cell
resistance and increasing recombination reactions. Although reducing the distance between
electrodes reduces the resistance of the electrolysis medium, the process may suffer if the
closeness allows a build-up of gas between these electrodes (Mazloomi, S.K, & Sulaiman,
2012).
41
Low to higher pulsed potential increases the reaction (current) and accelerates both the
movement of bubbles from the electrode surface and the mass transfer rate in the electrolyte,
which lowers the electrochemical polarization in the diffusion layer and further increases
hydrogen production efficiency (Hourng, Lin, & L.-W., 2014). The rate of change of the
current density (and hence efficiency) can be increased using a magnetic field (Hourng, Lin,
& L.-W., 2014).
Pure water conducts an electric current very poorly and, for this reason, is difficult (slow) to
electrolyse. However, usually some salts will be added or present in tap and ground waters
which will be sufficient to allow electrolysis to proceed at a significant rate.
However such salts, and particularly chloride ions, may then undergo redox reactions at an
electrode. These side reactions both reduce the efficiency of the electrolysis reactions (above)
and produce new solutes. Other electrolytic reactions may occur at the electrodes so
producing further solutes and gases (Chaplin, 2017).
In addition, these solutes may react together to produce other materials. Together the side
reactions are complex and this complexity increases somewhat when the voltage applied to
the cell is greater than that required by the above reactions and processes. The likely reactions
within the electrode compartments are described below. Some of these may only occur to a
very small extent and other reactions may also be occurring that are not included. Standard
electrode potentials are shown below (Chaplin, 2017):
42
Figure 8: Electrode Standard Potentials (Chaplin, 2017)
d. ELECTROLYSIS COMPARTMENT.
Cathode and anode reactions in the electrolytic cell with some of their constituent molecules,
ions and radicals are given below. Other materials may be present and some of the materials
given may be at very low concentrations and/or have short half-lives.
The amount of O3 produced (relative to molecular oxygen) depends on the over potential, pH,
radicals present and anode material. O2 evolution is greater than that for O3 due to the lower
potential required. At low over potentials, very little O3 may be produced but at high current
densities and over potentials, up to a sixth of the oxidized molecules may be O3 in total. As
O3 is more much more soluble than O2, there may twice the dissolved O3 than O2 but the
bubble gas will contain about 20 times the O2 than O3 (Naya & Okada, 2012).
Tin oxide anodes have proved useful for the production of O3, particularly if doped with Sb
and Ni, as they bind both oxygen molecules and hydroxyl radicals to facilitate the O3
production (Chen, Wang, & Q.-Y., 2013). Decomposition of ozone gives rise to several
43
strong oxidants including hydroxyl radicals (·OH); an extremely strong oxidizer capable of
killing viruses, amoebae, algae and dangerous bacteria, such as MRSA and Legionella.
Although charged ions are attracted into the compartments by virtue of the applied potential,
oppositely charged ions are created in both compartments due to the electrolytic reactions.
Thus for example, Na+ ions enter the catholyte from the anode compartment but excess OH-
is produced at the same time at the cathode.
The concentration of the OH- ions will be generally expected to be greater than the increase
in cations in the catholyte and the concentration of the H3O+ ions will be generally expected
to be greater than any increase in anions in the anolyte. Often a conductive but semi-
permeable membrane (nafion, a strongly hydrated sulfonated tetrafluoroethylene based
copolymer (Ito, Maeda, Nakano, & Takenaka, 2011), for example) is used to separate the two
compartments and reduce the movement of the products between the electrode
compartments; a process that improves the yield by reducing back and side reactions (Carmo
M. , Fritz, Mergel, & Stolten, 2013). Due to the easier electrolysis of water containing 1H
rather than 2H (D) or 3H (T), electrolysis can be used for producing water with reduced or
enriched isotopic composition.
When electrolysis uses short voltage pulses of alternating polarity at above 100 kHz the
Nano-bubbles produced contain both H2 and O2 gases that can spontaneously react (combust)
to form water whilst producing pressure jumps (Postnikov, Uvarov, Lokhanin, & Svetovoy,
2017).
e. ELECTROLYSIS THROUGH ELECTROLYTIC CELLS
Electrolysis of water is regarded as a promising technology because of its simplicity, low

maintenance requirement and handling in the renewable energy space. Electrolysis involves
the oxidation and reduction reactions producing hydrogen gas separated from the oxygen gas
in a controlled environment.
44
However, even if sustainable usually is used only to obtain hydrogen with high purity (Wang,
Wang, & Gong, 2014). The generation of energy as a supplement, not an alternative to fossil
fuel sources, and hydrogen may have various destinations as the production of ammonia,
methanol, pharmaceuticals, etc. Hydrogen energy carrier has low gas emissions that
drastically reduce global warming.
Electrolysis occurs with power supply (Figure 9), being necessary to dissolve an ionic
substance, but which in turn does not participate in the reactions involved. This
decomposition of water occurs due to the electric potential which makes the chemically
feasible reaction.
Figure 9: Electrolysis System (Santosa, Eckerta, & Eduardo De Rossia, 2017)
According Stefanelli (Stefanelli, 2015), the electrolytic cells consist of two electrodes, and
these are determined according to the electrolyte present in each. The electrolysers are
classified into unipolar (type tank) and bipolar (filter press). One way to improve efficiency
of the electrolysis process is the increase in electrode surface area and changes in its
composition (Lim RJ, 2014). Between the electrodes there is a membrane acting as an
45
electrolyte that blocks electrons (Stefanelli, 2015). These electrolytes are responsible for the
dissociation of oxygen.
2.5 ELECTROLYSERS
The most widespread electrolysis system are based on alkaline and PEM electrolysers. The
alkaline electrolysis is one of the most developed technologies, and is considered a simple
method where the electrolytes have basic character (Santosa, Eckerta, & Eduardo De Rossia,
2017). The electrolysis may alternatively be performed with a so-called polymer electrolyte
membrane (PEM), one of the most promising technologies for decomposing water, providing
greater efficiency and purity of the gas. However, it is little explored (Carmo, Frit, Mergel, &
Stolten, 2013). Figure 10 shows the systems of alkaline Electrolyser and PEM, respectively.
Figure 10: Operating System of Alkaline and PEM Electrolysers (Santosa, Eckerta, &
Eduardo De Rossia, 2017)
46
a) PEM ELECTROLYSERS
Proton Exchange Membrane (PEM) electrolysis, based on a solid polymer electrolyte (i.e.,
usually Nafion). PEM electrolysis is attractive for small-size plants, mainly because it has an
easier plant management and it does not require the use of hazardous chemicals. Moreover,
PEM cells are more compact (usually, one third of volume compared to alkaline), have a
faster response time and better dynamic behaviour characterized by high partial-load
performance compared to the alkaline ones, thus they are more suitable for the integration
with fluctuating renewable energy sources such as wind and solar (Ferrero & Santarelli,
2017).
Among the various technological applications of electrolysis, the production of hydrogen at

high pressure is attracting more and more interest, especially when considering the necessary
storage requirements. In fact, high pressure electrolysis – both PEM and alkaline – requires
less electricity per unit of produced (and stored) hydrogen compared to the atmospheric water
electrolysis with subsequent hydrogen compression (Onda, Kyakuno, Hattori, & Ito, 2004).
The high-temperature operation enhances both the kinetics of electrolysis reactions, thus
allowing a lower electricity demand of the process, and also the tolerance to fuel impurities;
moreover, the availability of recoverable high-temperature waste heat improves the overall
system efficiency (Ferrero & Santarelli, 2017).
The PEM Electrolyser membrane has thickness around 20–300 μm and has the following
advantages (Acar & Dincer, 2015):
 Provides high proton conductivity,

 Is compact and operates under high pressure.
 The electrolyte is thinner than the alkaline,
 Operating costs of electrolysis are smaller because the PEM can operate with high
energy density, the gases have a high purity,
 Effective at high voltages.
b) ALKALINE ELECTROLYSERS
The disadvantages in alkaline electrolyser application are (Acar & Dincer, 2015):
 the electrolyte used is corrosive;

 operating pressures are low;
47
 high cost of components,
 low durability
 Lower efficiency due to diffusion of oxygen to the cathode chamber and the diffusion
of hydrogen into the chamber of oxygen.
Character Alkaline PEM

Electrolyser Electrolyser
Temperature (oC) 40 - 90 20 - 100
Pressure (bar) < 30 < 30
Voltage (V) 1.8 – 2.4 1.8 – 2.2
Efficiency (%) 62 -82 67 - 82
H2 Production Nm3/h < 760 < 10
Decay rate (mV/h) <3 <4
Power Consumption (kW h 4.5 - 7 4.5 – 7.5
Nm3)
Table 9: Alkaline and PEM Electrolysers main characteristics (Holladay, Hu, King, &
Wang, 2009)
c) ELECTROLYSIS AND SAFETY CONSIDERATIONS
The most important consideration with electrolysers is to prevent mixing of hydrogen and
oxygen and the development of a flammable atmosphere within flammability and
detonability limits of hydrogen and oxygen mixtures. Hydrogen and oxygen are generally
separated by the membrane thus a key consideration when considering electrolyser safety is
ensuring the membrane is intact and having a strategy in place in the event that either the
membrane or a seal/gasket ruptures (Molkov V. , 2012)
Considering first the membrane several factors may contribute to its degradation or rupture
these include (Molkov V. , 2012):
 Gradual blocking up of the protonic exchange sites, this is generally as a result of

water of a poor quality being used with the electrolysers. The result of this is a
48
gradual increase in the electrolyser voltage and eventually the system will prevent the
electrolyser from operating any further.
 Uneven mechanical stresses due to stacks being unevenly tightened can also lead to
degradation.
 Contaminants in the water or uneven catalyst layer distribution (porosity, thickness
etc.) can have a negative effect on the electrolyser membrane and cause what are
known as hotspots. Hotspots ultimately may lead to thinning of the membrane or
worst case, perforations within the membrane both of which lead to an increase in the
exchange of gases across the membrane. If gases are exchanged across the membrane
there is the potential to create a potentially explosive atmosphere.
 Hotspots may also be caused by poor water management across the membrane as
insufficient water will result in parts of the membrane not being sufficiently hydrated,
leading to hotspots.
 Sub-zero temperatures can cause pinhole damage and micro-cracking of the
membrane as well as damage to other components within the stack.
 For every one mole of oxygen produced two moles of hydrogen is produced, thus
meaning either twice the volume of hydrogen or twice the pressure. This as potential
to lead to an unbalanced system, the increased pressure of the hydrogen could
potentially lead to a rupture in the membrane.
Mitigation methods should be employed to detect degradation of the membrane, or a

hydrogen leak. Sensors can be employed to detect crossover of the hydrogen to the anode of
the electrolyser. In addition to hydrogen sensors, the use of voltage and current can be used
to monitor and to detect any short circuits.
A further safety issue arises with high pressure electrolysers. Whilst they may have
advantages there are safety disadvantages in that the inventory of hydrogen in the system is
increased, this becomes significant in the case of a leak (Molkov V. , 2012).
49
Figure 11: Types of risks related to H2 production, storage and use (Dubois, et al., 2013)
Figure 11 shows a schematic and non-exhaustive representation of risks that may be

encountered along a hydrogen chain (production, storage and use). The three main control
means categories (prevention, detection and mitigation) are also represented.
2.6 HYDROGEN STORAGE
There are currently three hydrogen storage technologies namely:
i. Compressed gaseous storage

ii. Cryogenic (Liquid) storage
iii. Solid state storage
2.6.1 GASEOUS HYDROGEN STORAGE

At present hydrogen is most commonly stored as a compressed gas. Hydrogen gas
may be compressed to 20-100 MPa. This makes sense as many applications need
hydrogen at higher pressure levels anyway. Compression of hydrogen also increases
the volumetric capacity.
50
Limitations for storing hydrogen in a compressed form are the real gas effects which
make compression to even higher pressures inefficient, and the availability and
additional weight of high pressure vessels. Especially above 15 MPa the deviations
from ideal gas behaviour become evident (more than 10% in density).
The primary issues with storing hydrogen as a compressed gas are the energy required
to compress the gas, the inherent safety issues with storing hydrogen at such high
pressure and the additional cost and weight of cylinders designed to store hydrogen at
such pressures. Issues such as permeation and embrittlement are proportional to gas
pressure therefore at higher pressures these may be a greater issue.
Issues with compressed hydrogen gas tanks revolve around high pressure, weight,
volume, conformability and cost. The highest pressure gas tanks tend to be for
automotive applications where type IV tanks are currently used (Molkov V. , 2012).
SAFETY ISSUES OF GASEOUS STORAGE
a. LOSS OF CONTAINMENT
A major concern with high pressure hydrogen storage is loss of containment, either
through partial or full rupture. While it is a requirement that vehicle tanks are
equipped with pressure relief devices this is not always the case with stationary
applications. The extent of a flammable jet or a jet fire and hence the consequences is
directly proportional to the pressure of the hydrogen in the tank and thus will affect
the associated safety distances (Molkov V. , 2012).
b. MATERIALS – BLISTERING
The issue of hydrogen interaction with the materials used for hydrogen storage should
be considered. Where metallic tanks are used hydrogen attack and embrittlement are
important considerations. In type IV tanks, which are commonly used for vehicle
applications “blistering” and delamination of the polymeric liner may occur. The
51
polymeric liner is prone to permeation of the stored hydrogen and this is a result of
dissolution and diffusion in the polymer matrix. Due to this permeation, hydrogen can
accumulate between the liner and the composite and cause a blister. The accumulated
hydrogen between the liner and the composite layer will initially be at a pressure
lower than the internal pressure of the liner and thus only a blister will occur between
the liner and composite, however as the pressure within the liner is reduced the
pressure in the blister may eventually become greater than the pressure within the
liner. The result of this can be localised collapse of the liner and in extreme cases full
collapse of the liner.
The permeation issues of the liner have led to the development of polyamide liners for
use with hydrogen. These liners will minimise the permeation and reduce this effect.
Other methods of avoiding this from happening would be regular inspection of the
cylinder and/or replacement (Molkov V. , 2012).
c. FILLING ORIENTATION
Interesting work presented in the paper by Barral et al (Barral, Pregassame, &

Renault, 2004) describes experimental investigations which indicate that the
orientation of a cylinder during filling can affect the temperature rise in the tank. The
study takes the example of a cylindrical tank and considers filling in a horizontal and
vertical orientation. In the vertical case, two fill directions are considered: top to
bottom and bottom to top.
The case where the tank is orientated vertically and filled from the top shows a similar
trend in temperature rise to the case of the horizontally orientated tank. In the case of
horizontal filling small hot spots were observed for a short duration of time, this hot
spot was attributed to the fast compression of the low pressure gas present in the tank
at the beginning of the filling.
The higher the filling rate the higher the temperature of the hotspot. Similar behaviour
was observed in the vertical case whereby the cylinder was filled from top to bottom.
However, in the case where a vertical tank is filled from bottom to top a permanent
and growing temperature gradient appears. The temperature increases significantly at
52
the top of the tank, above the recommended level in the tank. The phenomenon also
depends on the filling rate. Horizontal filling or vertical filling from top to bottom are
recommended for safety purposes. When the cylinder is rapidly filled the result is near
adiabatic compression, leading to a significant increase in temperature of the gas
(Barral, Pregassame, & Renault, 2004).
d. PRESSURE RELIEF DEVICES

Thermally and pressure activated pressure relief devices are a means of addressing
safety issues. It is important to note that the inclusion of such a device can mitigate
against a potentially catastrophic scenario, indeed such safety technologies should be
considered in all forms of hydrogen storage. It is better to vent hydrogen in a
controlled manner than to have a situation where complete rupture of the tank occurs
(Molkov V. , 2012).
e. HEATING EFFECTS DURING FILLING

The rapid filling of a compressed hydrogen tank is most relevant to on-board storage,
this fast filling results in a temperature rise within the cylinder due to the heat of the
compression effects. The temperature of the gas and especially that of a vessel needs
to be closely controlled during the filling process in order to avoid detrimental effects
on the vessel materials of the vessel (85 °C is generally considered to be the
temperature limit (Wuechner, 2009).
Furthermore, without compensation, this heating effect results in reduced density of

hydrogen in storage tank. Standards allow containers to be pressurised such that,
when gas stored gas temperature stabilised, a complete fill is achieved based on the
prevailing ambient conditions. It therefore becomes necessary to dissipate the heat or
perhaps even cool the tank to enable more hydrogen to be transferred into it
(Wuechner, 2009).
53
2.6.2 LIQUID HYDROGEN STORAGE
The boiling temperature of hydrogen is 20.39 K at 0.1013 MPa for ortho-H2 and
20.26 K for para-H2. Therefore in order to store hydrogen in liquid form the
temperatures are cryogenic and the tanks must be sufficiently insulated.
Cryogenic hydrogen is the second major category of hydrogen storage. Although
volumetrically cryogenics is an excellent technology for storing and transporting
hydrogen, it does take a significant amount of energy to cool the gas down to -243 °C,
around 30% of the energy contained in the hydrogen (Aceves, et al., 2010).
Hydrogen compressed to 70 MPa has a density of about 60 g/l, while that of liquid
hydrogen is about 68 g/l. But there is a penalty to be paid by the insulated and even
more tightly sealed cryogenic tanks, reducing both volumetric and gravimetric
capacities of the system. Nevertheless, liquid hydrogen storage offers unprecedented
energy density, which makes it so popular in airspace applications. But when the
hydrogen must be justified commercially and is competing with still-cheap petrol, the
energy cost might be too high.
Hydrogen may be liquefied for a simplified transport or storage. Compared to

compressed gaseous hydrogen (CGH2), LH2 has a considerably higher volumetric
energy density. The liquefaction is achieved by cooling below the boiling
temperature. The cost and weight of suitable materials to store and maintain the
hydrogen at this temperature must also be considered. On average, 15 times more
energy is needed compared to the liquefaction of a kilogram of nitrogen. The energy
density of hydrogen can be improved by storing hydrogen in a liquid state. However,
the issues with LH2 tanks are hydrogen boil-off, the energy required for hydrogen
liquefaction, volume, weight, and tank cost. The energy requirement for hydrogen
liquefaction is high; typically 30% of the heating value of hydrogen is required for
liquefaction (Aceves, et al., 2010).
54
SOME SAFETY ISSUES LIQUID HYDROGEN STORAGE
a. LOSS OF CONTAINMENT
As with CGH2 loss of containment should be avoided wherever possible and is
mentioned here for completeness. A worst case scenario which may result in heating
and subsequent pressure rise and a loss of containment is loss of the vacuum due to
puncture of the outer tank (Molkov V. , 2012).
b. BOIL OFF
The main problem with liquid hydrogen tanks from safety perspective is hydrogen
boil-off. It must be minimised or eliminated not only for reason of cost, efficiency and
vehicle range, but also for safety, especially when the vehicle is parked in confined
spaces. The dormancy, period of inactivity before a vessel releases hydrogen to
reduce pressure build up, is 5 days at the operating pressure of today’s liquid
hydrogen tanks (~6 atm).
With liquefied hydrogen there is also an issue of boil-off and evaporation via a
pressure limiting valve. The boil-off may correspond to a loss of 1.5% of the stored
energy per day. Thus the typical stored mass of about 7kg will be lost in 2 months if
the car was not used in this phase.
The involved temperatures are demanding not only regarding the design of the actual
storage but also regarding the compatibility of all connected technologies, like
measurement techniques, armatures, valves, and piping (Molkov V. , 2012).
Boil-off losses can occur as a result of several mechanisms (Molkov V. , 2012) these
include:
i. Ortho-para conversion: The conversion of ortho-hydrogen to para-hydrogen is

an exothermic reaction. The heat of conversion is related to the change of
momentum of the hydrogen nucleus when the direction of spin changes. The
amount of heat given off in this conversion process is temperature dependent.
If the unconverted normal hydrogen is placed in a storage vessel, the heat of
55
conversion will be released within the container, which leads to the
evaporation of the liquid.
ii. Thermal stratification and self-pressurisation: Heat transfer from the sidewalls
and bottom to a liquid hydrogen storage vessel will always result in an
increase of the sensible enthalpy of the liquid. When the heat flux is small
enough and the inside wall of the vessel is smooth, boiling is unlikely to occur.
In this case, the added energy tends to get distributed non- uniformly because
the imposed heat flux usually produces a free convective flow. The warm
liquid hydrogen becomes buoyant and rises to the top.
iii. Heat leaks: This is a common cause of boil-off. The heat leakage losses are
generally proportional to the ratio of surface area to the volume of the storage
vessel (S/V).The most favourable shape of cryogenic vessel is therefore
spherical since it has the least surface to volume ratio. A big cause of heat
leaks in cryogenic storage is through the support struts in the vessel.
iv. Sloshing: Another process which leads to boil-off during liquid hydrogen
transportation by tankers is sloshing. Sloshing is the motion of liquid in a
vessel due to acceleration or deceleration. Some of the impact energy of the
liquid against the vessel is converted to thermal energy.
v. Flashing: Another source of boil-off is flashing. This problem occurs when

liquid hydrogen, at a high pressure (2.4 to 2.7 atm), is transferred from trucks
and rail cars to a low pressure Dewar (1.17 atm). This problem can be reduced
if transportation of liquid hydrogen is carried out at atmospheric pressures.
c. ICE FORMATION
The cold temperatures involved may result in ice build-up on structures (valves,
Dewar’s) which can in turn produce excessive exterior pressures, rupturing storage
systems.
56
2.6.3 SOLID STATE HYDROGEN STORAGE
Hydrogen can be stored either within the structure or on the surface of certain
materials. There are presently three generic mechanisms known for storing hydrogen
in materials: absorption, adsorption, and chemical reaction.
These methods do not require the high pressures or low temperatures of the previous
methods; this offers advantages regarding the safety of the materials. In addition solid
storage has a high volumetric energy density. Also unlike compressed and liquefied
hydrogen accidental loss of confinement may only occur if the materials are heated
and further hydrogen is released (Molkov V. , 2012).
Examples of advanced materials are metal hydrides which are based on metallic
compounds, which store hydrogen via chemical bonding. The solid reaction during
loading the hydrogen releases heat at relatively moderate pressure. To release the
hydrogen again the pressure has to be decreased and heat has to be delivered. These
loading and unloading cycles may be repeated without reducing the storage capacity.
The hydrogen storing materials are separated into three broad categories (Molkov V. ,
2012):
a. Chemical Hydrides (i.e., hydrogen containing materials with strong chemical bonding
exhibiting “irreversible” hydrogen release that usually require catalysts for desorption.
These materials typically involve off-board regeneration, requiring chemical reactions
and/or high pressure/temperature.).
b. Metallic Hydrides (i.e., materials that absorb hydrogen within the host itself by the
dissociation of hydrogen molecules and usually exhibit “reversible” reactions with
hydrogen gas under moderate conditions of temperature and pressure that can be done
on-board. These materials are typically limited by low hydrogen storage density per
unit weight.
c. Hydrogen storage via physical adsorption of hydrogen species with rather weak
bonding that generally permits storage only at much lower “cryogenic” temperatures.
57
Volumetric capacities of these materials are typically very limited at ambient
temperatures.
There are also some “borderline” materials with behaviour intermediate between any two of
these categories. The weight of the capturing element can be significant, so one of the
parameters for measurement of the effectiveness of a compound is the percentage by mass of
hydrogen that it absorbs. Common hydrides can hold about 3-8%. Any amount greater than
6% is considered attractive. It means that in order to store 4 kg of hydrogen a state-of-the-art
hydride tank would perhaps weight 80 kg (Molkov V. , 2012).
Figure 12: Hydrogen storage gravimetric capacity versus temperature for different materials
investigated within DOE programme in 2007-2009 (Energy, 2009).
SOME POTENTIAL SAFETY ISSUES OF METAL HYDRIDES
a. PYROPHORIC MATERIALS
The materials used for solid storage tend to be pyrophoric. A pyrophoric material is
one which can ignite spontaneously in air. Therefore there is a danger with solid state
58
storage that damage to the storage may results in a vigorous reaction upon exposure to
air releasing hydrogen, heat, and with probable ignition (Molkov V. , 2012).
b. RISK OF EXPLOSION
Loss of containment could lead to a potential dust cloud explosion. However, it is
worth noting that even non-pyrophoric materials, such as flour or sawdust, are prone
to deflagrate with a minimal spark energy and can cause a disastrous accident when
their fine powder forms a dust cloud in air. Complex hydrides, in general, are
powdery substances with a low density; therefore, they can easily form a dust cloud
(Molkov V. , 2012).
c. HEAT MANAGEMENT
Materials used in solid hydrogen storage typically release a lot of heat upon hydrogen
uptake. This heat must thus be managed by sound engineering and thermodynamics
applications. Thus use of a cooling fluid (oil, water) is a common approach.
d. TOXICITY
Metal hydrides can typically be toxic to humans and thus damage to the storage is
highly undesirable. They must be handled with caution and properly disposed.
2.7METAL HYDRIDE HYDROGEN COMPRESSORS
Metal hydride (MH) thermal sorption compression is an efficient and reliable method
allowing a conversion of energy from heat into a compressed hydrogen gas. The most
important component of such a thermal engine - the metal hydride material itself should
possess several material features in order to achieve an efficient performance in the hydrogen
compression. Apart from the hydrogen storage characteristics important for every solid H
storage material (e.g. gravimetric and volumetric efficiency of H storage, hydrogen sorption
kinetics and effective thermal conductivity), the thermodynamics of the metal-hydrogen
systems is of primary importance resulting in a temperature dependence of the
absorption/desorption pressures. Several specific features should be optimised to govern the
performance of the MH-compressors including synchronisation of the pressure plateaus for
multi-stage compressors, reduction of slope of the isotherms and hysteresis, increase of
59
cycling stability and life time, together with challenges in system design associated with
volume expansion of the metal matrix during the hydrogenation (Lototskyy, Yartys, Pollet, &
Bowman Jr, 2014)
Metal Hydride (MH) hydrogen compression utilises a reversible heat-driven interaction of a

hydride-forming metal, alloy or intermetallic compound with hydrogen gas to form MH and
is considered as a promising application for hydrogen energy systems. This technology,
which initially arose in early 1970s, still offers a good alternative to both conventional
(mechanical) and newly developed (electrochemical, ionic liquid pistons) methods of
hydrogen compression. The advantages of MH compression include simplicity in design and
operation, absence of moving parts, compactness, safety and reliability, and the possibility to
consume waste industrial heat instead of electricity (Lototskyy, Yartys, Pollet, & Bowman Jr,
2014).
2.7.1 METAL-HYDROGEN SYSTEM

Applications of metal hydrides, including hydrogen compression, utilise a reversible heat-
driven interaction of a hydride-forming metal/alloy, or intermetallic compound (IMC) with
hydrogen gas, to form a metal hydride:
(24)
Where M is a metal/alloy (e.g., V or a BCC solid solution based upon it), or an intermetallic
compound (IMC; LaNi5, TiFe, etc.); (s) and (g) relate to the solid and gas phases,
respectively. The direct interaction, an exothermic formation of the metal hydride/hydrogen
absorption, is accompanied by a release of heat, Q. The reverse process, endothermic hydride
decomposition/hydrogen desorption, requires supply of approximately the same amount of
heat (Lototskyy, Yartys, Pollet, & Bowman Jr, 2014).
2.7.2 GENERAL LAYOUT OF A METAL HYDRIDE SYSTEM

The simplest apparatus realising thermally driven hydrogen compression using MH is shown
in Figure 13(a). Metal hydride material (A) thermally coupled to a heat supply/ removal
accessory (B) is placed into a pressure container (C) comprising a gas pipeline (D) which
allows supply or removal of hydrogen gas to/from MH (A). The gas pipeline (D) can have a
built-in filter element (not shown) which provides a uniform hydrogen distribution within the
60
MH bed, and also prevents contamination of gas pipelines with fine powder of the MH
(Lototskyy, Yartys, Pollet, & Bowman Jr, 2014).
The assembly A-D called the metal hydride compression element, or generator-sober,
provides periodic suction of low-pressure hydrogen (H2 @ PL) when the MH is cooled (-Q)
down to the lower temperature, TL, followed by a discharge of high-pressure hydrogen (H2
@ PH) in the course of heating (+Q) of MH to the upper temperature, TH. This solution first
patented in 1970 by Wiswall and Reilly (USA Patent No. US3516263, 1970) Allows
periodically operated hydrogen compression that restricts its application from the continuous
technological processes.
The simplest continuously-operated metal hydride hydrogen compressor (Figure 13(b))

comprises two compression elements (A1-D1, A2-D2) similar to the one shown in Figure
12(a). The gas pipelines D1 and D2 are connected to a gas distributing system (E) equipped
with a port (F) for the supply of hydrogen at low pressure, PL, and a port (G) for the output of
hydrogen at high pressure, PH. The operation of the compressor includes two steps, 1 and 2.
During Step 1 the heat supply/removal accessory (B1) of the first compression element
provides heat removal (-Q) from the MH (A1) at a lower temperature level, TL;
simultaneously, the accessory (B2) of the second compression element provides heat supply
(+Q) to the MH (A2) at a higher temperature level, TH. During the next Step 2 the
heating/cooling modes of the accessories B1 and B2 are reversed, so that B1 operates in the
heat supply, and B2 in heat removal mode. Thus, a periodic reversal of the operating modes
of the heat supply/removal accessories B1 and B2 synchronised with switching gas flows by
the gas distributing system (E) provides the continuous operation resulting in the suction of
low-pressure hydrogen to the port F and the release of high-pressure hydrogen from the port
G (Lototskyy, Yartys, Pollet, & Bowman Jr, 2014).
An approach to generate high H2 pressures at modest operating temperatures is the use of

multi-stage hydride compressors, a concept developed at Ergenics Inc. (Golben, Multi-stage
hydride hydrogen compressor, 1983). The multistage compressor uses a series of two or more
alloys differing by thermal stabilities of their hydrides. Figure 13(c) shows an example of
layout of two-stage MH compressor. The alloy forming the most stable hydride is placed in
the compression elements of the first stage (A1.1, A1.2), and other MH are loaded to the
compression elements belonging to the next stages, in the order of decrease of their thermal
61
stability (A2.1, A2.2). The multistage operation allows achievement of higher overall
compression ratios using the same or smaller temperature swing. For example, five-stage MH
compressor developed by Ergenics allows H2 compression from 7 to 250 bar in the
temperature range 30-90 C with water as a heating/cooling agent (Lototskyy, Yartys, Pollet,
& Bowman Jr, 2014).
The gas distributing system (E) can be made as a one-way (check) valve arrangement; the
periodic heating/cooling of heat supply/removal accessories (B) is conveniently controlled by
timing relays (USA Patent No. US4402187, 1983), (Patent No. EP0094202 A2, 1983), (USA
Patent No. US 4505120, 1985).
Figure 13: General layouts of MH Compressors: (a) Periodically operated, (b) One-stage
continuously operated, (c) Two stage continuously operated
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2.7.3 APPLICATION OF METAL HYDRIDE H2 COMPRESSORS
Below is the list of current applications of MH compressors
a. ISOTOPE HANDLING
Metal hydrides have been used internationally in the research laboratories, nuclear
energy and defence industries for decades to store and process hydrogen isotopes,
protium, deuterium, and tritium (Mueller, Blackledge, & Libowitz, 1968) (Beavis,
1968). Prior to 1970 the binary hydrides of titanium, zirconium, palladium, and
uranium were only utilised (Bowman Jr, Carlson, & DeSando, 1976). Often these
metal hydrides served concurrent roles of collecting, storing, purifying, transporting,
and isotope separation rather than to serve as explicit compression applications.
b. CRYOGENICS/SPACE
In 1972, van Mal was the first to report that metal hydride compressors could be used
to form liquid hydrogen via Joule Thomson (J-T) expansion (Lototskyy, Yartys,
Pollet, & Bowman Jr, 2014). Subsequently, a number of laboratory demonstrations of
hydrogen liquefaction using metal hydride compression is being practised worldwide
and is recorded in a number of journal publications.
c. UTILISATION OF LOW-GRADE HEAT
The main advantage of MH hydrogen compressors is in the conversion of waste heat

(T < 200 oC) into the energy of compressed hydrogen which can be further utilised.
In 1979 Nomura et al. (Nomura, Ishido, & Ono, 1979) developed and successfully
tested a piston engine which used one stage MH compressor on the basis of LaNi5 and
operated at 20-80 oC providing efficiency of energy conversion of 7.7%, or about
50% of the Carnot efficiency. A year later the first prototype of MH-based
(LaNi4.63Al0.37) water pump operating in the same temperature range was developed at
Sandia National Laboratories (Northrup Jr & Heckes, 1980).
63
Use of MH compressors for water pumping driven by solar heat was intensively
studied in the early 2000s. The systems were shown to be promising in distributed
stand-alone applications capable of daily pumping up to 3000 L of water over a height
of 15 m using 1 m2 solar collector area (Lototskyy, Yartys, Pollet, & Bowman Jr,
2014).
d. THERMALLY DRIVEN ACTUATORS
Developments of pneumatic actuators on the basis of MH hydrogen compression were

considered in earlier MH applications. Their advantages include compactness, ability
to develop high forces, smooth actuation, silent and vibration-free action, simplicity in
design and operation. As a rule, the actuators are driven by thermoelectric/Peltier
elements used for heating and cooling of the MH; pressure transmission from
compressed H2 to mechanical or hydraulic actuating mechanism is provided by
bellows (Lototskyy, Yartys, Pollet, & Bowman Jr, 2014).
e. HYDROGEN REFUELLING STATIONS
Hydrogen refuelling infrastructure takes a significant part of the capital investments

for the introducing fuel cell powered vehicles and must be taken into account in the
assessment of their economic feasibilities. Despite a certain number of hydrogen
refuelling stations operating worldwide, they are not introduced broadly enough,
mainly because of their high costs ranging between $500,000 and $5,000,000 per
installation (Rare, 2008). The most expensive H2 refuelling components originate
from:
i. On-site hydrogen production and
ii. Hydrogen compression.
According to techno-economic analysis presented in Reference (Weinert, Shaojun,
Ogden, & Jianxin, 2007), the contribution of hydrogen compression to the total
station cost is about 20%.
64
Cost-performance optimisation of the H2 refuelling infrastructure can be achieved by
the improvement of hydrogen compression technology. A promising way for that is
the application of thermally-driven metal hydride hydrogen compressors characterised
by simplicity in design and operation, reliability and minimum maintenance, with
potentially low price and ability to utilise waste heat, instead of electricity, for the H2
compression (Lototskyy, Yartys, Pollet, & Bowman Jr, 2014).
2.8 PHOTOVOLTAIC ELECTROLYSIS

The photovoltaic driven water electrolysis comprises photovoltaic (PV) panels, DC
bus bar, AC grid, accumulator battery set, and electrolyser and hydrogen storage
canisters. The cost of PV-generated electricity is in continuous decline. The efficiency
of the solar cell can range from 12 to 15% typically for the silicon solar cell.
However, it is as high as 25-30% for GaAs solar cells. The total efficiency of solar
radiant energy transformed to chemical hydrogen energy is nearly 16% (Yilanci,
Dincer, & Ozturk, A review on solar hydrogen/fuel cell hybrid energy systems for
stationery applications, 2009). The exergy efficiency of the PV-electrolyser
system is calculated as the product of exergy efficiency of the PV system

and the exergy efficiency of the electrolyser and it is:
(25)
Where VmIm is the electrical power accounting of all electrical losses of the PV panel,
associated electronics and electrical lines. This power is the same as that retrieved at
the input of the electrolyser. The quantity hA(Tcell - T0) represents the heat losses
between the PV panel and the ambient due to heat transfer; some exergy losses are
associated with this heat as indicated in the numerator of above equation 25 (Dincer,
Green methods for Hydrogen productions, 2012).
2.9 HYDROGEN SAFETY

Hazard can be defined as a chemical or physical condition that has the potential for
causing damage to people, property and the environment. Hydrogen accident could
have different hazards, e.g. asphyxiation due to release in closed space, frostbite by
65
liquefied hydrogen, thermal hazards from jet fire, pressure effects from deflagrations
and detonations, etc. Hazard could lead to no damage, if the proper safety measures
are applied, or could lead to costly consequences up to fatalities if the system or
infrastructure has been designed and used without professional knowledge in
hydrogen safety (Molkov V. , 2012).
The modern definition of risk is provided by ISO/IEC Guide 73:2002 (2002) stating
that it is the combination of the probability of an event and its consequence while
safety is defined as the freedom from unacceptable risk. This means that safety is a
societal category and cannot be numerically defined while risk is a technical measure
that can be calculated. Society in consequence establishes acceptable levels of risk or
risk acceptance criteria (Molkov V. , 2012).
An analysis shall be conducted to identify all fire and explosion hazards and
accomplish the following (Molkov V. , 2012):
Significant hazards shall be eliminated or reduced to acceptable risk levels
 Where the hazard cannot be eliminated or reduced, the system components associated
with the hazard shall be relocated to an area less threatening to people and property as
directed by the Authority having jurisdiction;
 Where the hazard cannot be eliminated, reduced or removed the system components
associated with the hazard shall be isolated within the facility so as not to pose a
danger to the remainder of the structure or its occupants;
 Where the hazard cannot be eliminated, reduced, relocated or isolated, protection shall
be provided to ensure adequate levels of human and structural safety. Should an
incident / accident occur, the occupants of the facility shall be provided with
protection to enable them to leave the area safety and the structure will be protected to
ensure its continued integrity
Hydrogen safety engineering (HSE) is defined as the application of scientific and

engineering principles to the protection of life, property and environment from the
adverse effects of incidents/accidents involving hydrogen. HSE can be applied to existing
and new hydrogen systems, including but not limited to stationery, e.g. Combined heat
66
and power systems, or portable e.g. mobile phones and computers, applications for indoor
and outdoor use, hydrogen transportation and refuelling infrastructures, power generation,
hydrogen production and distribution units, storage, infrastructure (Daniel & Young-Do,
2007).
A hydrogen system could be defined as an equipment dealing with hydrogen e.g. storage,
production, delivery, distribution, consumption, etc. Hydrogen should remain contained
within hydrogen system from its production/ delivery to its final use (Molkov V. , 2012) .
2.9.1 PHYSICAL AND CHEMICAL PROPERTIES OF HYDROGEN

a. BUOYANCY AS SAFETY ASSET
The main hydrogen safety assert, i.e. its highest on the earth buoyancy, confers the ability
to rapidly flow out of an incident scene and mix with the ambient air to a safe level below
the lower flammability limit (LFL) of 4% by volume of hydrogen in air. Indeed, hydrogen
has a density of 0.0838 kg/m3 (NTP) which is far below than air density of 1.205 kg/m3 at
the same conditions. The unwanted consequences of hydrogen releases into the open
atmosphere and in partially confined geometries where no conditions to allow hydrogen
to accumulate exist are drastically reduced by buoyancy (Molkov V. , 2012).
Contrary, heavier hydrocarbons are able to form a huge combustible cloud. In many
practical situations, hydrocarbons may pose stronger fire and explosion hazards than
hydrogen. Hydrogen high buoyancy affects its dispersion considerably more than its high
diffusivity.
Pure hydrogen is positively buoyant above a temperature of 22K, i.e. over almost the
whole temperature range of its gaseous state. Buoyancy provides comparatively fast
dilution of released hydrogen by the surrounding air below the lower flammability level.
In unconfined conditions, only small fraction of released hydrogen would be able to
deflagrate. Indeed a hydrogen-air cloud evolving from the inadvertent release upon the
failure of a storage tank or pipeline liberates only a small fraction of its thermal energy in
case of a deflagration which is in the range 0.1 -10% and in most cases below 1% of the
total energy of released hydrogen. This makes safety considerations of hydrogen accident
with large inventory at the open quite different from that of other flammable gases with
often less or no harmful consequences at all (Molkov V. , 2012).
67
b. DIFFUSIVITY AND VISCOSITY
Diffusivity of hydrogen is higher compared to other gases due to small size of the
molecule. Data on diffusion coefficient of hydrogen in air at Normal Temperature and
Pressure (NTP) is 6 x 10-5 m2/s. The low viscosity of hydrogen and small size of the
molecule cause a comparatively high flow rate if the gas leaks through fittings, seals,
porous material etc. This negative effect is to a certain extent offset by low energy density
(volumetric) of hydrogen in comparison with e.g. methane or other hydrocarbon gases.
Viscosity of gaseous hydrogen (µPoise): 89.48 NPT (Molkov V. , 2012).
c. INTERACTION WITH METALS

Hydrogen can cause a significant deterioration in the mechanical properties of metals.
This effect is referred to as hydrogen embrittlement. Hydrogen embrittlement involves a
large number of variables such as temperature and pressure of the environment, the
purity, concentration and exposure time of the hydrogen and the stress state, physical and
mechanical properties, microstructure, surface conditions and nature of the crack front of
the material. Many hydrogen material problems involve welds or the use of an improper
material (Molkov V. , 2012).
Many metals absorb hydrogen especially at high pressure. Hydrogen absorption by steel
can result in embrittlement, which can lead to fails in the equipment. There is an atomic
solution of hydrogen in metals. Permeated through a metal atomic hydrogen recombines
to molecules on the external surface of storage to diffuse into surrounding gas afterwards.
The choice of material for hydrogen system is an important part of hydrogen safety
(Molkov V. , 2012).
d. COMBUSTION PROPERTIES
At normal temperature hydrogen is not a very reactive substance, unless it has been
activated somehow e.g. by an appropriate catalyser. Hydrogen reacts with oxygen to form
water at ambient temperature extraordinarily slow. However if the reaction is accelerated
by a catalyser or a spark, it proceeds with high rate and explosive violence (Molkov V. ,
2012).
Hydrogen burns in a clean atmosphere with an invisible flame. It has a somewhat higher
adiabatic premixed flame temperature for a stoichiometric mixture in air of 2403 K
compared to other fuels. This temperature can be a reason for serious injury at an accident
scene, especially at clean laboratory environment where the hydrogen flame is practically
68
invisible. However hydrogen combustion and hot currents will cause changes in the
surroundings that can be used to detect the flame. Although the non-luminous hydrogen
flame makes visual detection difficult, there is a strong effect of heat and turbulence on
the surrounding atmosphere and raising plume of hot combustion products. These
changes are called the signature of the fire (Molkov V. , 2012).
e. STOICHIOMETRIC MIXTURE, EQUIVALENCE RATIO AND

MIXTURE FRACTION
Stoichiometric mixture is a mixture in which both fuel and oxidiser are fully consumed to
form combustion product(s). For example, the two diatomic gases hydrogen (H2) and
oxygen (O2) can combine to form water as the only product of an exothermic reaction
between them, as described by the equation:
2𝐻2 + (𝑂2 + 3.76𝑁2 ) = 2𝐻2 𝑂 + 3.76𝑁2 26
Thus, the stoichiometric hydrogen- oxygen mixture is composed of 66.66% by volume of

hydrogen and 33.33% of oxygen. Thus the stoichiometric concentration of hydrogen in
air (assuming 21% of oxygen and 79% of nitrogen) is 29.59% by volume (2/ (2 + 1 +
3.76) = 0.2959) with air content of 70.41% (Daniel & Young-Do, 2007)
f. HEAT OF COMBUSTION
The lower heating value (LHV) (heat of combustion) of hydrogen is 241.7 kJ/mol and the
higher heating value (HHV) is 286.1 kJ/mol. The difference of about 16% is due to the
heat of condensation of water vapour and this value is larger compared to other gases
(Carmo, Fritz, & Mergel, A comprehensive review on PEM water electrolysis, 2013).
g. FLAMMABILITY LIMITS
The flammability range of hydrogen is wider compared to most hydrocarbons i.e. 4 to 75
% by volume in air at NTP. The flammability range of hydrogen expands with
temperature e.g. the lower flammability limit drops from 4% at NTP to 3% at 100 °C (For
an upward propagating flame) and depends on pressure (Molkov V. , 2012).
h. QUENCHING
Hydrogen flames are difficult to quench. For example premixed hydrogen-air combustion
can be aggravated by heavy sprays of water due to induced turbulence and ability of
69
mixture to burn around the droplets. Hydrogen has the lowest quenching distance
compared to other flammable gases. Quenching of any flame occurs when heat loses from
flame are comparable with heat generation due to combustion and then the chemical
reactions cannot be sustained. Usually quenching distance is reported as the minimum
pipe diameter through which a premixed flame can pass. The quenching distance
decreases with increase of pressure and temperature, depends of mixture composition, etc.
Hydrogen fires normally are not extinguished until the supply of hydrogen has been shut
off because of danger of re-ignition and explosion (Molkov V. , 2012).
2.9.2 HYDROGEN HEALTH HAZARDS

Hydrogen is not expected to cause mutagenicity, teratogenicity, embryo toxicity or
reproductive toxicity. There is no evidence of adverse effects if skin or eyes are exposed
to hydrogen, it cannot be ingested (unlikely route). However, inhaled hydrogen can result
in a flammable mixture within the body (Daniel & Young-Do, 2007)
Hydrogen is classified as a simple asphyxiate, has no threshold limit value (TLV) and it is
not a carcinogen. High concentration of hydrogen in air can cause an oxygen-deficient
environment. Individuals breathing such atmosphere may experience symptoms that
include headaches, dizziness, drowsiness, unconsciousness, nausea, vomiting, depression
of all the senses, etc. A victim may have a blue colour skin and under some
circumstances, death may occur. If hydrogen is inhaled and above symptoms observed,
then remove a person to fresh air give oxygen if breathing is difficult or apply artificial
respiration if not breathing (Molkov V. , 2012).
The system design shall prevent any possibility of asphyxiation of personnel in adjacent
area. The system design shall provide for prevention of personnel entering the enclosure
unless confined space entry procedures are strictly followed. It is recommended to check
oxygen content before entering an incident/accident area. Hydrogen concentrations have
to be measured with a suitable detector (Molkov V. , 2012).
Oxygen concentration below 19.5% by volume are biologically inactive for humans and
no effects of oxygen deficiency are usually observed. At concentrations below 12%,
immediate unconsciousness may occur with no prior warning symptoms. Stages of
asphyxiation have been noted based on the oxygen concentrations as follows (Molkov V.
, 2012):
70
 15-19% by volume – decreased ability to perform tasks, may induce early symptoms
in person with heart, lung or circulatory problems
 12-15% - deeper respiration, faster pulse, poor coordination
 10-12% - giddiness, poor judgement, slightly blue lips
 8-10% - nausea, vomiting, unconsciousness, ashen face, fainting, mental failure
 6-8% - death in 8 min( 50% death and 50% recovery with treatment in 6 min, 100%
recovery with treatment in 4 to 5 min)
 4% - Comma in 40 s, convulsions, respiration ceases, death
2.9.3 DETECTION AND HYDROGEN SENSORS

The addition of an odorant to hydrogen would ease the detection of small leaks. However
this is not practicable in most situations, e.g. this would poison an expensive catalyst in
fuel cells. Moreover, this is not feasible to be added to hydrogen. Hydrogen fire detection
can be based on registration of infrared radiation of flames which are not seen in a day
light (Gandia, Arzamedi, & Dieguez, 2013). They are various types of hydrogen sensors
in the market today, they include the following:
 Optical fibre hydrogen sensors

 Electrochemical hydrogen sensors
 MEMS hydrogen sensors
 Thin Film sensors
 Thick Film sensors
 Chemo chromic hydrogen sensors
 Diode based Schottky sensor
 Metallic La-Mg2-Ni hydrogen sensors
Hydrogen sensors are calibrated during manufacturing and they must be calibrated
periodically to maintain sensitivity. Depending with the operating conditions the end user
can use any type of sensor that meet his system specifications and compatibility.
71
CHAPTER 3 RESEARCH DESIGN AND METHODOLOGY
INTRODUCTION
This chapter explains in detail the research, design and methodology used in the present study.
It explains the research objectives and a suitable design and methodology to achieve these
objectives. The objectives of this study were:
i. The design of an 8.4kW Polymer Electrolyte Membrane Water Electrolyser (PEMWE)

with a hydrogen production rate of 2 Nm3/hr and hydrogen discharge pressure of 20
bars.
ii. Construction and commissioning of a 8.4kW PEMWE prototype system
iii. A HAZOP study on the integration of PEM Water Electrolyser prototype system with
the balance of plant.
iv. Integration of PEM water electrolyser prototype system with a locally developed 5
Nm3/h MH compressor.
v. Integration of PEM water electrolyser prototype system to a locally produced 4.2kW
Photovoltaic supply.
3.1PROJECT DESIGN & SPECIFICATIONS

This involves an exhaustive design process, integration and commissioning of a prototype that
has an application of hydrogen safety at its core. The produced hydrogen will be compressed
using an existing 5Nm3/h metal hydride compressor and stored in the SAIAMC gas storage
facility. An existing hydrogen dispensing system was used to refuel various FC prototypes,
amongst others the golf cart, forklift, fuel cell bicycle and fuel cell chargers. This study will
contribute in promoting use of clean fuel, hydrogen derived from renewable energy sources
that will facilitate the transition to the hydrogen economy. A crucial aspect of the study is the
establishment of design and operation protocols around hydrogen safety. The stack
specifications for the PEM water electrolyser is a hydrogen production rate of 2 Nm3/hr and
hydrogen discharge pressure of 20 bars. The project implementation summarised as follows:
 Project Design & Specifications

 Infrastructure & Integration
 Prototype Testing and commissioning
72
Figure 14: Project concept Overview
Following the project concept overview in Figure 14, a critical thinking process
begins. During this phase, the design of the PEM electrolyser system commenced.
The system is broken down into the following subsystems:
 Stack specification
 Cooling system
 Water supply
 Design of balance of plant
The PEM water electrolyser block diagram in Figure 15 evolved following the project
concept overview in Figure 14. A detailed process and instrumentation diagram
detailing all processes and controls is summarised in Figure 23.
73
Figure 15: PEMWE System Block diagram
a. STACK SPECIFICATIONS
The project specification requires a stack that can produce hydrogen at 2 Nm3/h, a
discharge pressure of 20 bars and a power rating of average of 4.3kW. The stack
specifications are specific because the hydrogen produced by the system is designed
to be consumed downstream by SAIAMC projects, FC testing systems and refuelling
fuel cell prototypes. A commercial stack with the above specification was sourced
from prospective suppliers. The specifications were given out to international
reputable companies for electrolyser suppliers namely:
 Hydrogenics,
 Proton,
 Pure Energy Centre and
 Hydron Energy B.V.
A number of challenges were encountered, some suppliers could not quote only on the
stack, and they wanted to supply a complete Electrolyser stack unit due to various
reasons which include the issue of intellectual property rights on stack design, loss of
business and after sales technical support. Only three companies managed to quote on
74
the specification provided but under different business conditions. We evaluated the
business conditions and the cost of the stack and we ominously chose the supplier
Hydron Energy B.V based on the specifications, cost and business conditions. The
specifications of the stack from Hydron is as follows:
Specifications EL100
Electrolyser type Polymer Electrolyte
Membrane
Stack model EL100
Number of cells 24
Specifications for 24
cell stack
H2 production rate ( nominal ) 1 Nm3/hr
O2 production rate ( nominal ) 0,5 Nm3/hr
Maximum H2 discharge pressure2 20 bar
Maximum O2 discharge pressure 5 bar
Beginning of life (BoL) 4,3 kW
End of life (EoL) 5,8 kW
Stack efficiency (ηth - BoL at 84% HHV
nominal operation)
Power supply requirements 30 -60 VDC 0 -150 A
Ambient temperature range 5 - 40 °C
Stack temperature range 5 - 80 °C
Process water specification (a) 18 MΩ/cm
Process water consumption 0,9 L/hr
Thermal conditioning fluid DI- water, 50/50 ethylene
3
Stack Dimensions
specifications (HxWxD) 154 4x 154
300 xglycol mm
Stack Weight 30 kg
Table 10 Stack Specifications

In order to meet the system output production of 2Nm3/H, two of the EL100 stacks were
purchased and integrated into the prototype HySA PEM Electrolyser system.
The image of the EL100 stack top view is as follows:
75
Figure 16: Process connections of the EL100 cell stack Sticker nearest to fitting designates
the process connection
The EL100 stack features 6 process connections (see Figure 16), which are identified by
stickers:
 Anode in: process water inlet

 Anode out: oxygen / process water outlet
 Cathode in: process water inlet (if cathode process water circulation is adopted,
otherwise the connection can be utilised as a hydrogen / proton water discharge)
 Cathode out: hydrogen / proton water discharge
 Coolant in: thermal exchange fluid inlet
 Coolant out: thermal exchange fluid outlet
76
Figure 17: EL 100 Stack
Figure 18: Type plate and electrical leads of the EL100 stack
77
b. COOLING SYSTEM
The cooling system is essential in order to manage heat within the stack during operation. Below is the design of the cooling system that
will ensure that the stack temperature does not go beyond 80oC in operation.
6 5 4 3 2 1
37,5 337,5
D D
375
375
294,25
262,75
COOLING FAN
485
C C
COOLANT INLET
COOLANT OUTLET
375
B B
COOLANT PUMP ELECTRICAL BOX
COOLANT RESERVOIR
TFD TF Design Matthew
1
Figure 19: Stack cooling System THERMODYNAMICS
FLUIDS & DESIGN
P.O BOX 3205
MATIELAND 7602 SHEET 1 OF 1 2016/11/25
A 1:5 A3 A
NOTE: 16085 - UWC GREEN HYDROGEN COOLING SYSTEM
1. MATERIAL: REFER TO COMPONENT DATA SHEETS. DIMENSIONS WITHOUT
TOLERANCE TO
+/-
0.1 SYSTEM ASSY
2. QTY.: 3 OFF AS PER ASSEMBLED UNIT ISO 2768m
78
3. IF IN DOUBT, PLEASE ASK. http://etd.uwc.ac.za/
6 5
The water electrolysis process generates heat as current is applied to the EL100 stack.
The production of excess heat is related to the rated current (Ohmic heating). Therefore a
thermal management subsystem should be applied in the electrolysis system. The EL100
stack features a dedicated thermal management means: the exchanging of excess process
heat is facilitated by circulating thermal conditioning fluid through the stack.
A coolant inlet and outlet process port is available on the stack. The maximum
operational temperature of the stack is 80˚C. The set points for the coolant inlet and outlet
temperature are related to the operational temperature of the stack and the flow rate of the
cooling. The heat production by the process can be calculated by assuming a thermal
efficiency of approximately 20% as specified by Hydron Energy.
c. WATER SUPPLY SYSTEM

Hydron Energy recommends to supply the anode loop with Ultra-Pure Water (UWP) of 18
MΩ/cm quality. The stack should not be operated with water with a higher conductivity
than 1, 5 µS/cm. Operation the EL100 stack with process water above this conductivity will
lead to rapid degradation of the internal parts and will irreversibly decrease lifetime of the
EL100 stack.
Continuously monitor the process water quality and trip at the threshold value of 1,5 µS/cm
once reached. A Milli-Q water purification system was used to supply water to the
Electrolyzer system. It produces Type 1 ASTM water (18 MΩ), which provides substantially
low conductivity of the water required. The water supply system design below:
79
MilliQ Water System
Prefilters
UP Water
Supply
Reservoir PLC
Figure 20: Ultra-pure water supply system
80
d. BALANCE OF PLANT
A PEM water electrolysis stack operated with Balance of Plant components.
Below a basic process and instrumentation diagram for a PEM, water electrolysis
system (Figure 21).
The prototype system is comprised of the following subsystems
 Water/oxygen subsystem
 Hydrogen subsystem
 Feed water subsystem
 Thermal management subsystem
 Electrical subsystem
 Control subsystem
 Electrical layout
81
e. HYSA SYSTEMS PEMWE PROTOTYPE P&ID
Figure 21: Process and instrumentation diagram (P&ID) PEMWE
82
f. HYSA SYSTEMS PEMWE PROTOYPE ASSEMBLY LIST AS PER
P&ID
Subassembly P&ID tag Function
0. electrolyser stack n/a PEM water electrolysis stack
1. water/oxygen subsystem
main gas solenoid valve CV-101 opens/closes off oxygen flow to application
check valve CV-102 prevents backflow into anode loop
purge solenoid valve opens/closes off oxygen flow to purge
check valve / flame arrestor CV-103 prevents backflow into anode loop/ flash back
manual drain valve water V-105 drains process water loop

pressure relief valve PR-103 prevents pressure build up in anode loop above
threshold
temperature sensor stack in TS-101A measures process water temperature entering
TS- 101B the stack
temperature sensor stack out TS-403A measures process water temperature exiting
TS-403B the stack
pressure sensor oxygen PS-103 measures oxygen/process water pressure in
anode loop
level sensor water LS-104A measures process water upper level in D-102
Level sensor water LS- 104B measures process water lower level in D-102
conductivity sensor CS-105 measures conductivity of process water

water circulation pump P-101A circulates process water through stack
water circulation pump P-101B circulates process water through stack
water/gas separator D-102 separates process water and oxygen
water polishing filter F-103 keeps water quality at specification (low
conductivity)
2. hydrogen subsystem
main gas solenoid valve SV-201 opens/closes off hydrogen flow to application
check valve check valve / flame CV-202 prevents back flow into cathode loop / flash
arrestor back
purge solenoid valve SV-203 opens/closes off hydrogen flow to purge
83
check valve / flame arrestor CV-206 prevents backflow into cathode loop/ flash back
automatic drain valve SV-301 actively drains proton water out D-202
condensate
back pressure regulator BPR-207 regulates cathode pressure in stack
pressure relief valve PR-204 prevents pressure build up in cathode loop
above threshold
temperature sensor TS-201 measures water temperature of cathode
pressure sensor hydrogen PSH-202 measures hydrogen pressure in cathode loop
hydrogen sensor HS-203 measures hydrogen concentration in process
Cabinet
water/gas separator D-202 separates proton water and hydrogen
Check Valve CV-203 Prevents backflow into water/gas separator
D202A
Check Valve CV-203 Prevents backflow into water/gas separator
D202B
Pressure Indicator PI-403A Measures pressure of hydrogen from the stack 1
Pressure Indicator PI-403B Measures pressure of hydrogen from the stack 2
ion exchange filter F-203 keeps proton water quality at specification (low
conductivity)
check valve CV-206 prevents backflow of process water
3. feed water subsystem

level sensor feed water WLS-301A measures process water upper level in R-301
reservoir
level sensor feed water WLS-301B measures process water lower level in R-301
reservoir
feed water pump P-302 feeds anode loop with process water loop
feed water reservoir R-301 provide storage for process water
check valve CV-303 prevents back flow of process water to R-301
4. thermal management
subsystem
temperature sensor cooling in TS-401A measures coolant temperature entering the stack
1
84
temperature sensor cooling in TS-401B measures coolant temperature entering the stack
2
temperature sensor cooling TS-402A measures coolant temperature exiting the stack 1
out
temperature sensor cooling TS-402B measures coolant temperature exiting the stack 2
out
temperature sensor stack TS-403A measures stack temperature stack 1
temperature sensor stack TS-403B measures stack temperature stack 2
coolant pump P-404A circulates coolant trough stack 1 and
heat exchanger
coolant pump P-404B circulates coolant trough stack 2 and
heat exchanger
heat exchanger HE-405A radiates excess heat of stack 1
heat exchanger HE-405A radiates excess heat of stack 2
5. electrical subsystem
power supply E-501A provides DC power to stack 1
power supply E-501B provides DC power to stack 2
voltage sensor E-502A measures stack voltage Stack 1
voltage sensor E-502B measures stack voltage Stack 2
current sensor E-503A measures stack current Stack 1
current sensor E-503B measures stack current Stack 2
high power relay R-504A circuit breaker for emergency shutoff
high power relay R-504B circuit breaker for emergency shutoff
Figure 22: Equipment list
85
g. ELECTROLYSER ELECTRICAL CONNECTIONS LAYOUT
In order to supply power to the stack as per manufactures requirements and the
various balance of plant equipment they is a need of two distinct power supplies. The
first power supply is a dedicated power supply for each stack 1 & 2. The second
power supply is for the various balance of plant equipment. Below is a list of
electrical connections layout which includes:
i. Stack electrical connections

ii. Anode water supply pumps electrical connections
iii. PLC + Display & General Power supply
iv. Solenoid valves & Pressure Transducer Electrical Connections
v. Fans and Relays Electrical Connections
86
i. STACK ELECTRICAL CONNECTIONS
Figure 23: Stack Electrical Connections
87
Figure 24: Electrical leads of EL100 stack positive and negative polarity designated by sticker. Electrical grounding of stack facilitated by M6
bores of stainless steel compression plates
88
Figure 25: Cell Voltage Monitoring & thermocouples; the bores can feature voltage probes, temperature sensors
89
ii. ANODE WATER SUPPLY PUMPS ELECTRICAL CONNECTIONS
Figure 26: Anode water supply pumps Electrical connections
90
iii. PLC + DISPLAY & GENERAL POWER SUPPLY
Figure 27: PLC + Display & General Power supply
91
iv. SOLENOID & PRESSURE TRANSDUCER ELECTRICAL CONNECTIONS
Figure 28: Solenoid valves & Pressure Transducer Electrical Connections
92
v. FANS AND RELAYS ELECTRICAL CONNECTIONS
Figure 29: Fans and Relays Electrical Connections
93
3.2 INTEGRATION PHASE 1
During this phase the Prototype water Electrolyzer was constructed together with the
balance of plant as per design specifications. All material and connections are put together
and resulted in the following system:
Pressure Indicators
Control system PLC &

Components connections
Emergency shutdown button
Power supply for stack 1

Power supply for stack 2
PLC Monitor
Stack 1 Stack 2
Figure 30: HySA systems PEM Water Electrolyser Overview
94
Figure 31: HySA systems PEMWE PLC home screen
Figure 32: HySA systems PEMWE PLC- Measurement Data screen
95
Figure 33: HySA systems PEMWE PLC- Cell Voltage screen
Figure 34: HySA systems PEMWE PLC- Electrical parameters screen
96
Figure 35: HySA Systems Prototype PEMWE Overview
97
Figure 36: HySA Systems PEM Water Electrolyser prototype PLC windows
98
a. PROTOTYPE SYSTEM PLC OPERATION
The system operation window as shown in Figure 32 taken from the PLC. The prototype
system was programmed to operate in either the automatic mode or manual mode from
the PLC while an embedded data logger continually logs system data. Figure 33 shows
system parameter loggings.
b. PLC CONTROLLER WITH DEDICATED ALGORITHM

The electrolysis system managed based on an implemented Programmable Logic
Controller (PLC). It includes embedded personal Windows-based computer, signal input
and output terminals (as well as digital and analogy for connections of measurement
sensors and controlling of BoP devices), digital extension modules (including energy
meter and data acquisition unit) and communication modules as well as based on internal
communication protocol and external GSM/Ethernet-capable communication processor
for remote management. Additionally, dedicated terminal couplers and 24 VDC power
supplies installed according to the PLC architecture requirements. The basic control panel
in the form of HMI display for on-site management and maintenance integrated with PLC
controller.
PLC control algorithm written according to IEC 61131-3 standard and Structured Text
(ST) - standardized programming language (Twin CAT environment). The general
description of the algorithm structure depicted as a flowchart in Figure 38. The PLC
controller operates in a closed infinite loop. Once the electrolyser switched on, the
inspection of critical parameters takes place. This includes but is not limited to hydrogen
leaking detection, maximum allowable output pressures of gases and temperature of the
stacks, feed water pressure and temperature, cooling water presence, and PEM electrolysis
cells voltage measured independently (every three cells combined).
If the failure detected, the system reconnects to the safe operational mode and the
electrolysis process is suspended. Each cycle of the infinite loop triggers reading and
writing of PLC terminals that includes temperature and pressure readings and setting of
analog and digital voltage signals (e.g. water pumps, electric relays). Control algorithm
includes both manual and automatic operation modes. The manual mode used in case of
testing and maintenance while automatic mode is fully autonomous enabling the
uninterrupted long-term operation. The system allows on sensitive data acquisition,
99
writing CSV files as well as displaying data based on virtual or embedded HMI. Self-
testing and remote upgrading of the control algorithm implemented in the system to
optimise system efficiency.
Figure 37 Flowchart of control algorithm, PLC managed, manual or automatic operation
100
3.3 PROTOTYPE TESTING AND COMMISSIONING
After success integration of the prototype system a detailed operating manual was
complied. Emphasis has been put on safety in order to assure the user(s) of the safety of
the prototype but however common sense need to be applied in all instances.
PROTOTYPE PEMWE OPERATING MANUAL

This manual features safety guidelines and recommendations. However, it is not intended
to cover all possible operational conditions, faults, troubleshooting topics and incidents. It
is the responsibility of the user(s) of the prototype equipment to meet all local safety
requirements and to ensure safety during operation, maintenance and storage of the
prototype polymer electrolyte membrane water Electrolyzer (PEMWE) stack. Although
all efforts have been made to ensure the accuracy and completeness of the information
contained in this document, HySA systems reserves the right to change the information at
any time and assumes no liability for its accuracy.
→ WARNING: HIGH HYDROGEN CONCENTRATION
→ WARNING: HIGH OXYGEN CONCENTRATION
→ WARNING: HIGH DIRECT CURRENT
→ WARNING: HOT SURFACES
→ WARNING: PRESSURISED OPERATION
3.3.1 GENERAL INFORMATION

The prototype PEM water Electrolyzer product is a single cell /multi cell water
electrolysis stack platform developed for hydrogen (H2) and Oxygen (O2) generation.
Electrolysis of water in PEMWE cell is the decomposition of water (H2O) into oxygen
(O2) and hydrogen gas (H2) due to an electric current being passed through the water as
shown in Figure 39. The (liquid) water is supplied to the anode of the Electrolyzer and is
101
decomposed into hydrogen ions (protons: H+) and molecular oxygen (O2). This reaction is
called Oxygen Evolution Reaction (OER). The protons are transported through the
membrane from the anode to the cathode under the influence of an applied potential. At
the cathode the protons and electrons are recombined to form molecular hydrogen. This
reaction is called the Hydrogen Evolution Reaction (HER).
Figure 38: Electrolyse cell operating principle
a) SAFETY
Please read all instructions carefully prior to the HySA systems water electrolyser stack
operation and use. It is important for any operator to be aware of, understand, and follow
all safety requirements related to the handling of hydrogen, oxygen and compressed
gases. Ensure that you read the material safety data sheet (MSDS) of hydrogen and
oxygen. Familiarise yourself with the Hazard Operability study (HAZOP) of prototype
HySA systems PEM water electrolyser. The safety guidelines included here may not
cover every situation. PLEASE USE COMMON SENSE
102
b) HYDROGEN GENERATION
WARNING! FIRE OR EXPLOSION
Keep all sources of ignition away from hydrogen. The Electrolyzer generates pure
hydrogen and oxygen gas. Hydrogen is a colorless, odorless and flammable substance. It
is highly combustible in the presence of oxygen and burns with a colorless flame. The
explosion range (in air) is 4 -77% and the gas auto-ignites at 560˚C. Leaking gas may be
hot and pose a burn danger. Furthermore hydrogen is subject to igniting spontaneously if
it flows out at high speed.
If an incident with hydrogen occurs: immediately turn the electrolysis stack/system off
and - if you are not in danger - use water to cool the area. If fire occurs, do not attempt to
extinguish flames, allow the fire to burn out. Prevent personal overexposure to hydrogen.
Hydrogen is non-toxic but can act as a simple asphyxiate by displacing the oxygen in the
air. There are no warnings before unconsciousness results.
When operating the prototype Electrolyzer system in a laboratory set up:
 Ensure ventilation/extraction is on;
 Operate the system (and especially the PEMWE stack) within the temperature
and pressure limits stated in this manual;
 Never operate the system if a hazardous and/or alarm condition exists;
 If the system is operated at elevated pressures, close the process cabinet and
use personal safety glasses;
 It is highly recommended that the working area in which hydrogen is used is

equipped with safety systems (e.g. hydrogen sensor, forced ventilation etc.).
c) OXYGEN GENERATION
WARNING! FIRE OR EXPLOSION
The normal oxygen concentration in air is approximately 21% by volume. Air containing
less than 19,5% or more than 23.5% oxygen constitutes a hazardous working
103
environment. Oxygen is not combustible, but it promotes very rapid combustion of
flammable materials and some materials that are normally regarded as being relatively
non-flammable.
Although a source of ignition energy is always necessary in combination with flammable

materials and oxygen, control or elimination of flammables is a precautionary step.
Lubricating oils and other hydrocarbon materials can react violently with higher
concentrations of oxygen. Personnel should not be exposed to an oxygen-enriched
atmosphere because of increased risks of fire. As concentrations increase above 23,5%
oxygen, ease of ignition of clothing increases dramatically.
Once ignited by even a relatively weak ignition source such as a spark or cigarette,
clothing can burst into flame and burn rapidly. Above approximately 60% oxygen, the
nap on clothing and even body hair and oil are subject to flash fire that spreads rapidly
over the entire exposed surface.
d) WATER SPECIFICATIONS
The anode loop should be supplied with Ultra-Pure Water (UWP) of 18 MΩ/cm quality
(according to ISO 3696). The stack should not be operated with water with a higher
conductivity than 1, 5 µS/cm. Please note that operation the EL100 stack with process
water above this conductivity will lead to rapid degradation of the internal parts and will
irreversibly decrease lifetime of the PEM stack. Sensor CS-105 should continuously
monitor the process water quality and trip at the threshold value of 1, 5 µS/cm.
e) PROCESS WATER UTILISATION

In the water electrolysis process the rated current is directly related to the hydrogen and
oxygen production of the PEM stack. When operating the stack at 100 Ampere, a single cell
of the PEM water electrolysis stack will utilize ~0, 54 mL/min for the production of hydrogen
and oxygen (please refer to Table 11 for other current set points). To calculate the total
process water utilization in the electrolysis process, one should sum the number of cells in the
stack and multiply with the ‘process water utilization’ figure at a given current set point. For
example a 10 cell stack operated at 120 Ampere will consume 6, 5ml/min of process water.
HySA systems prototype Electrolyzer system has 24 cell stack operated at 120 Ampere will
consume 15, 6 ml/min of process water.
104
Curre H2 O2 H2O H2O Proton
nt production production utilization utilization water
[A] [LPM/cell] [LPM/cell] [λ=1]
[mLPM/cel [λ=10]
[mLPM/cel production
[mLPM/cel
0 0,00 0,00 0,00
l] 0,00
l] 0,00
l]
10 0,07 0,03 0,05 0,54 0,24
20 0,14 0,07 0,11 1,09 0,47
30 0,21 0,10 0,16 1,63 0,71
40 0,28 0,14 0,22 2,18 0,95
50 0,35 0,17 0,27 2,72 1,18
60 0,42 0,21 0,33 3,27 1,42
70 0,49 0,24 0,38 3,81 1,66
80 0,56 0,28 0,44 4,36 1,89
90 0,63 0,31 0,49 4,90 2,13
100 0,70 0,35 0,54 5,44 2,37
110 0,77 0,38 0,60 5,99 2,60
120 0,84 0,42 0,65 6,53 2,84
Table 11: Mass balance of EL100 electrolysis process
f) PROCESS WATER TEMPERATURE DIFFERENTIAL

The temperature differential between the process water entering the stack and exiting the
stack should be between 5 - 15 ˚C (5 ˚C being the most optimum value). The maximum
temperature of process water exciting the stack is 80˚C
g) PROTON WATER PRODUCTION

When performing the water electrolysis process in the PEM stack, proton water is produced
in the hydrogen compartment of the stack (cathode loop) due to a process called electro-
osmotic drag. The proton water production is - similar to the hydrogen and oxygen production
rate - directly related to the rated current (and dependent on the stack temperature). In Table
10the proton water production correlated to the rated current is given. When operating the
stack at 120 Ampere, a single cell of the PEM water electrolysis stack will produce ~2, 8
mL/min of proton water in the hydrogen compartment (please refer to Table 10 for other
current set points). To calculate the total proton water production in the water electrolysis
process, one should sum the number of cells in the stack and multiply with the proton water
production figure at a given current set point. For example a 10 cell stack operated at 120
Ampere will produce 28 ml/min of proton water. HySA systems prototype Electrolyzer
system has 24 cell stack operated at 120 Ampere will consume 68.16ml/min of proton water.
105
h) PROTON WATER RECIRCULATION
The produced proton water can be circulated back to the anode loop of the PEM stack or
drained out of the system. When recirculating the proton water to the anode loop, one
should make sure that the flow is properly degassed (and containing no gaseous
hydrogen) and sufficiently pure (low conductivity). Degassing the proton water flow in a
dedicated degassing means and purifying the proton water by means of an ion-exchange
resin filter results in the removal of all ion acquired during electrolysis. Alternatively the
proton water flow - after degassing and purification - can be circulated back to the main
process water storage vessel (R-301)
→ PLEASE NOTE THAT GASEOUS HYDROGEN MUST NEVER ENTER THE

ANODE LOOP OF THE EL100 STACK: A HIGHLY EXPLOSIVE MIXTURE OF
HYDROGEN/OXYGEN IS FORMED
i) SPECIFICATION PROCESS WATER FLOW RATE

The flow of process water by means of circulation pump P-101 will feed the electrolysis
process and in some extend influence the temperature profile and distribution within the
stack (and exchange some heat within the anode loop). Hydron Energy recommends to
utilize a stoichiometry of 10 -20 for the process water circulation flow.
To calculate the required flow at a given rated current the following calculation applies:
Process water flow rate at rated current [ml/min] = number of cell in the stack [n] *
stoichiometry (λ) * (process water utilization at rated current [ml/min] + proton water
production at rated current [ml/min])
For example, when operating a 10 cell stack at 100 Ampere and a process water
stoichiometry of λ=10 the process water flow rate should be set on: 10 * 10 * (0, 54 + 2,
37) = 291 ml/min.
HySA PEM Electrolyzer 24 *10 * (0.65 +2.84) = 837.6 ml/min
Please observe the following requirements for selecting the proper process water
circulation pump:
 Fluid compatibility: UPW

106
 Fluid temperature range: 5 - 90˚C
 Fluid flow rate range: calculate according to formula presented above -
stoichiometry flow 10-20
 Head at maximum flow rate: 6 bars
j) DC POWER SUPPLY
A DC power supply (E-501) is to be connected to the stack by means of power cables.
Magna power supply will be supplying DC power supply that can operate in both constant
current and constant voltage modus. 90 mm2 power cables are used for hooking up the
stack (in order to avoid excessive heating up of cables and current collectors/poles of the
stack).
The EL100 stack is preferably operated in a constant voltage modus. The power supply
should be shut off when the rated current exceeds 120 Ampere.
k) PRESSURE SENSORS
Pressure sensor PS-103 and PS-202 are employed to monitor the oxygen and hydrogen
pressure of the electrolysis process. When operating the EL100 stack, pressure levels
should never exceed the rated values displayed on the type plate and stack traveler.
l) TEMPERATURE SENSORS
Temperature probes (e.g. K-type thermocouple) can be placed in the empty bores of the
cell. Please note that the sensor needs to be electrically insulated from interfacing data
acquisition equipment. Hydron Energy recommends placing at least one thermocouple in
the middle cell of a multi cell stack to monitor the stack temperature. The temperature of
the stack must never exceed 80 ˚C.
m) THERMAL MANAGEMENT SUBASSEMBLY

The water electrolysis process generates heat as current is applied to the EL100 stack. The
production of excess heat is related to the rated current (Ohmic heating). Therefore a
thermal management subsystem should be applied in the electrolysis system. The EL100
stack features a dedicated thermal management means: the exchanging of excess process
heat is facilitated by circulating thermal conditioning fluid through the stack. To this
extend a coolant inlet and outlet process port is available on the stack. The maximum
operational temperature of the stack is 80˚C. The set points for the coolant inlet and outlet
temperature are related to the operational temperature of the stack and the flow rate of the
cooling. Hydron Energy recommends employing a PID type of monitoring and control
107
strategy for the thermal management subassembly (flow rate control). The heat
production by the process can be calculated by assuming a thermal efficiency of
approximately 20%.
3.4 HYSA SYSTEMS GREEN HYDROGEN SYSTEM HAZOP

The development of hydrogen economy and its growth are directly dependent on safety and
public perception and therefore safety mitigation into Electrolyzer system is of paramount
importance. Most of the hazards have been mitigated during design of the system and those
hazards that could not be eliminated by design have been mitigated by the operating
procedure and instructions. Hydrogen is a colorless and odorless gas a hydrogen detector
HS-203 has been installed in the system to detect any hydrogen leaks. Once any hydrogen
leaks are detected the PLC automatically switches to the emergency mode and the system
is intrinsically safe.
a) HYSA SYSTEMS PROTOTYPE PEMWE HAZOP

Hazard and operability study is a technique used to study the hazards of a system and
operability of a system by exploring the effects of any deviations from designed conditions.
The study will first identify and subsequently analyses possible scenarios that can cause
accidents of different severity. The following study was done our prototype PEM water
Electrolyzer:
108
b) HYSA SYSTEMS PEM WATER ELECTROLYSE HAZOP STUDY
PARAMETER DEVIATION CAUSES CONSEQUENCE EXISTING ACTION
SAFETY
MECHANISM
H2 Pressure low Electrolysis rate low Low pressure Automatic emergency  Check water supply
1
due to: hydrogen output mode activation conductivity CS-
105
 Water quality
above 1.5µS.  Check power
supply E-501A &
 Low voltage
E-501B and PLC
<1.5V per
Electrical
cell.
parameters
low Undetected leakages Low pressure Hydrogen sensor HS-  Use liquid spray to
hydrogen output 203 detect leak replace
pipe work.
installed
High  Closed Pressure built up Pressure sensor PSH-  Open the exhaust
exhaust valve 202 monitors pressure valve CV-202
109
 Closed and pressure relieve  emergency mode1
regulator valve PR-204 rapture from the PLC
outlet at 22 bars activation
 Faulty System switches into  Replace faulty

1
pressure emergency mode at pressure indicator
indicator 20.8 bars
O2 Pressure low Electrolysis rate low Low pressure Automatic emergency  Check water supply
1
due to oxygen output mode activation conductivity CS-
105
 Water quality
above 1.5µS.  Check power
supply E-501A &
 Low voltage
E-501B and PLC
<1.5V per cell
Electrical
parameters
High  Closed Pressure build up Pressure relieve valve  Open exhaust valve
exhaust PRP-103 prevent CV-101
110
pressure build up in
anode loop over 5 bars
Temperature Low H2 production very Little hydrogen PLC get into  Check the stack
low production emergency mode thermocouple TS-
403A/B and
monitor during
course of operation.
 Check the power

supply E-501A &
E-501B and
electrical
parameters on PLC
Higher >80OC Faulty temperature Damage the stack. PLC get into  Increase the speed
1
indicator emergency mode of the cooling fan
and pump P-404A
& P-404B to
maximum
 Check the stack

thermocouple TS-
403A/B and
111
monitor during
course of cooling
until 30oC
Others H2 Leak in Mechanical failure/ Potential fire and Hydrogen HS-203  Press Emergency
BOP Leaking fittings explosion installed to detect alarm button
leaks. Once leaks
detected PLC
switches to
emergency mode1
H2 leak in Overpressure causing Potential fire and Hydrogen HS-203  Press Emergency
Electrolyser rapture of membrane explosion installed to detect alarm button
leaks. Once leaks
detected PLC
switches to
emergency mode
Fire and Ignition in the Equipment damage Fire detection system  Escape the room
Explosion vicinity of H2 and O2 and possible installed which will for personal safety
mixture injuries extinguish the fire and call for
and trigger UWC Emergency
assistance X2100
112
Campus emergency
services
Short circuit Cut wires, burned Opening of safety Earth leakage will trip  Earth leakage
wires, overload valves power for the whole switch trips
system
 Emergency mode1
switched on
Alarm Gas sensor limit H2 leak PLC switches in the  System switches
reached emergency mode into emergency
mode
113
c) PROTOTYPE PEM ELECTROLYSER SYSTEM SAFETY
The system has multiple levels of built-in operator and stack safety redundancy. Control and
safety systems monitor all flows, levels and temperatures of significance. All fault
conditions are failsafe and duplicated, triggering relays, which shut the system down.
Process indicators monitor several key variables and allow operating limits to be adjusted in
response to experience of system performance automatically in the automatic mode and
manually in the manual mode.
The prototype PEM electrolyser operating system demonstrates successful integration of all
aspects of the design, including safety and control systems, into a single functioning entity
embedded in the PLC. The following safety protocols in addition to a detailed HAZOP to
mitigate any accidents, the following detailed procedures to increase prototype PEM
Electrolyser safety have been implemented:
 Pre start up
 Start up
 Shutdown
 Emergency
 Post Shutdown
 Purging the system with Nitrogen gas lead to inertisation of the Stack
Safety materials are also provided within the facility, like extinguishers, sand buckets and
fire hoses. Facility operations are supervised by a person designated by the main operator.
This will bring knowledge on the facility functioning and feedback on hydrogen and oxygen
storage in the facility housing the Prototype PEM Electrolyser.
Operation manual is in Appendix 1
114
3.5 HYDROGEN COMPRESSION AND STORAGE
Hydrogen compression technology combined with application of sound engineering practice

produced a safe and efficient hydrogen compression system. Our extensive work on
Industrial scale metal hydride hydrogen compressors developed at the South African
Institute for Advanced Material Chemistry has been developed and published (Lototskyy, et
al., 2018). The thermally driven Metal Hydride Hydrogen Compressor is intended for
compression of hydrogen gas from 3 to 200 bar with the productivity up to 5 Nm3/h.
Hydrogen compression is a main contributor in the capital and operation costs of the H2
refuelling or production infrastructure. The efficient solution to mitigate this challenge is
found in thermally driven MH compression. The success of thermally driven compressors
and has been seen in metal hydride compressor developed and commissioned at Impala
Platinum Holdings in Springs, Johannesburg South Africa. The work was published in our
article entitled Hydrogen refuelling station with integrated metal hydride compressor:
Layout feature and experience of three- year operation (Lototskyy, et al., 2019).
115
RV1
SG
CT
SP
V8
V6
Steam Water Drain 1

supply PS V7
HP LP supply Drain 2
H2 P
H2(IN)
Vent line (OUT)
F MHC
R1 V3
MFM CV1
Release
B1..4
V2 SAIAMC gas supply
V4 V5
From electrolyser
(H2 collectors 1 and 2; Fig. 15)
V1
CP
Figure 39: MH compressor (MHC) installed at SAIAMC hydrogen supply facilities; the insets show main system components. SG – steam
generator; CT – cooling tower; CP – cylinder pack
116
Figure 40: MH Heating and Cooling circuit
117
The MH compressor layout is presented in Figure 39 and the process and instrumentation
diagram of the MH compressor is presented in Figure 40. The operation of the MH compressor
and other system components results in the pressurising of hydrogen at the high pressure and a
high flow rate. In addition, the compressor uses steam (up to 10 bar / 180 °C) for the heating.
The MH compressor uses metal hydrides on the basis of AB5- and AB2 -type inter-metallide
ranging in hydrogen storage capacity from 130 to 180 NL H2 per 1 kg of the material. MH
material efficiency and performance in systems has been investigated in our work and presented
in a publication entitled Metal hydride systems for hydrogen storage and supply for stationery
and automotive low temperature PEM fuel cell power modules (Mykhaylo, et al., 2015).
The operation of the MH compressor contains a potential risk of an accident which can cause
injuries to the operator, or damage of the expensive balance of plant equipment and accessories.
A detailed system risk assessment document has been drafted and it addresses the following:
 Safety precautions;
 Start-up procedure
 Operating procedure;
 Shut down procedure;
 Emergency shut down procedure
Hydrogen from the electrolyser (see Figure 39) is supplied to the input (suction) pipeline of
the compressor (H2IN) via shut-off valves (V1, V2), buffer cylinders (B1..4), reducer (R1)
equipped with low- (LP) and high-pressure (HP) manometers, and mass flow meter (MFM).
The compressed H2 from the output (discharge) pipeline of the compressor (H2OUT)
equipped with a pressure sensor (PS), via shut-off valve (V3), check valve (CV1) and shut-
off valve (V4), is supplied to hydrogen cylinder pack (CP) and, further, via shut-off valve
(V5), to high-pressure hydrogen manifold of SAIAMC gas supply system. The cooling is
provided by a cooling tower (CT) connected to water supply and drain lines of the
compressor via shut-off valves V6 and V7, respectively. The heating steam, from steam
generator (SG) equipped with manometer (SP) and safety relief valve (RV1) is connected,
via shut-off valve (V8), to steam supply line of the compressor. Switching of the steam and
118
water flows is carried out automatically by solenoid valves in the compressor (MHC) while
switching gas flows is provided by a check valve arrangement in the compressor.
SAFETY PRECAUTIONS FOR MH COMPRESSOR
To provide safe operation, the operator and all other personnel must obey the following rules:
1. At the site, smoking, using open fire and tools that can cause sparks is STRICTLY
PROHIBITED.
2. The operation and service of the testing facility must be done ONLY by the authorised
personnel who passed the test followed by the authorisation. UNAUTHORISED
OPERATION IS STRICTLY PROHIBITED.
3. The operation must be done by the operator at the presence of at least one more person.
4. In the case of a leak, or any other hazardous situation, the operation of MH

compressor must be interrupted immediately according to emergency shutdown
procedure.
5. After service and repair work, all gas lines and connections must be carefully leak tested; the
leak tests must be repeated after reaching high H2 pressure (above 100 bar) in high-pressure
systems of the compressor after the start of its operation.
6. During routine operation of the system, the leak tests must be done periodically (2–3 times
during the shift) when the compressor is operating.
7. For the leak tests, it is recommended to use a Combustible Gas Leak Detector with H2
detection range 0-1000ppm
119
Figure 41: Summary MH Compressor operation chart
120
3.6 HYDROGEN SUPPLY, COMPRESSION AND DISTRIBUTION
Hydrogen
venting
Hydrogen SAIAMC
(80 bar)
Research
Facility
Hydrogen Fuel cell

(200 bar)
prototype
refuelling
Buffer Station
storage /
Hydrogen
Electrolyser Hydrogen MH (200 bar) Cylinder Hydrogen
(20 bar) (200 bar)
2Nm3/H Compressor pack
5Nm3/H
Cooling water
Condensate
(Tin<30C)
drain
Steam
(T=130-180 C)
Figure 42: Schematic for complete H2 supply, compression and supply

121
Figure 42 show the schematic of the complete system showing H2 production from the 2Nm3/h
PEM electrolyser, the produced hydrogen is supplied through a manifold to the 5 Nm3/h MH
compressor. The MH compressor compresses the hydrogen up to 200 bar into a buffer storage/
cylinder pack. Hydrogen is consumed from the buffer supplied to either SAIAMC research facility
or hydrogen refuelling of fuel cell prototypes.
The operation and control of the whole system is segmented into:
 PEM Electrolyser system,

 MH Compressor and
 Hydrogen distribution.
The hydrogen distribution goes either to the refuelling of fuel cell prototypes or to SAIAMC
research facility for consumption. Each subsystem has a comprehensive safe and efficient
engineering control system that allows for full mode functionality independently. Hydrogen
production from PEM electrolyser initiates the production process. The produced hydrogen is feed
into the MH compressor and the MH compressor feeds hydrogen into the buffer/cylinder pack
which then distributes the hydrogen.
122
CHAPTER 4 – RESULTS
INTRODUCTION
This chapter presents the data generated from HySA Systems prototype PEM electrolyser system
that is system operation, polarisation curves, performance, and system efficiency. Hydrogen
compression data with a 5Nm3/h metal hydride compressor is also presented in this chapter.
PROTOTYPE PEM WATER ELECTROLYSIS SYSTEM SPECIFICATION

Designed hydrogen production system uses two proton exchange membrane electrolysis cell stacks
(PEMECs). Each stack contains 24 cells capable to conduct up to 150 A of electrical current. The
stacks operate in parallel utilizing independent balance-of-plant components. The technical
specifications of the stack are in Table 12:
No Parameter Data Unit

1 Type PEMEC -
2 No of stacks 2 -
3 H2 production rate 2.0 Nm3/h
4 O2 production rate 1.0 Nm3/h
5 Max H2 pressure 20 bar
6 Nominal power 9.9 kW
7 Efficiency, HHV 70 %
8 Feed water quality <1.5 µS/cm
9 Water consumption 0.03 lpm
10 Stack Dimensions 300 x 154 x 154 mm
(HxWxD)
Table 12: Technical; parameters of 2.0 Nm3/h hydrogen production system
The operation window displayed in the HMI screen shown in Figure 43 displays process parameters
such as temperature, current, voltage, cathode & anode pressures, hydrogen production rate and
cooling system. The data shown in Figure 43 is sent to a data logger, which collects all the process
123
parameters and saves them in a CSV file. The hydrogen sensor gives a real time hydrogen
monitoring when the system is in operation.
Figure 43: PEMWE operation mode
I. HYDROGEN PRODUCTION
PEM water electrolyser produces hydrogen of very high purity, 99.999%. Water supplied on the
anode loop is oxidised into hydrogen and oxygen ions. The ultra-pure water is oxidised at the anode
to produce hydrogen ions as shown in equation 27. The hydrogen ions passes through the PEM to
the cathode were the reduction reaction occurs to produce hydrogen gas as shown in equation 28.
The overall reaction inside a PEM electrolyser is shown in equation 29.The amount of hydrogen
produced by the electrolyser can be calculated or measured.
124
Anode reaction
2𝐻2 𝑂 = 𝑂2 + 4𝐻 + + 4𝑒 − 27
Cathode reaction
4𝐻 + + 4𝑒 − = 2𝐻2 28
Overall reaction
1
𝐻2 𝑂 = 𝐻2 + 𝑂2 29
2
The amount of hydrogen produced in a PEM electrolyser is calculated using the Faradays law. The
Faradays law states that the electrolysis process is closely linked with two laws formulated by
Faraday (Millet & Grigoriev, 2013). Equation (30) presents Faraday’s first law of electrolysis.
According to this law, the mass of ions generated at the electrode is proportional to the total charge
that flows through the electrolyte.
𝑖
𝐽 = 𝑛∗ 30
𝐹
Where:
F—Faraday constant value, F= 96485.3365 C/mol;
n - Amount of electrons involved in the reaction;
i - Current in Ampere;
M – Molar mass of hydrogen, MH = 1.008
Equation (31) shows Faraday’s second law of electrolysis, which determines the charge q needed to
separate the mass of substance m.
𝑚𝐻2 = 𝑀 ∗ 𝐽 ∗ 𝑘 31
Where:
J- Amount of hydrogen flow kg/h
n - Amount of ions involved in the reaction;

125
k- Number of cells in a stack, k = 24
𝑚𝐻2 – Amount of hydrogen produced kg/h
Substituting equation (30) into equation (31), the relationship with the electrochemical equivalent
described by equation (31) is as shown in equation 32.
𝑖∗𝑛
𝑚𝐻2 = 32
𝐹
The amount of hydrogen produced by the HySA PEM Electrolyser prototype was calculated using
the Faraday’s law as shown in Figure 44.
250
44
200
42
H2 Production (g/h)
Stack Voltage (V)
150
40
100
38
Stack Voltage
H2 Production
50
36
34 0
0 20 40 60 80 100 120
Stack current (A)
Figure 44: Mass of hydrogen produced
The mass of hydrogen increased exponentially from start up until it reached the maximum stack
potential optimum temperature of 78 oC. The mass of hydrogen produced at 2Nm3/h became
constant at stack optimum conditions that is at maximum cell voltage of 2.4V.
126
II. ELECTROLYSIS SYSTEM EVALUATION AND PERFORMANCE
Constructed water electrolysis system consists of 2 Nm3/h PEM electrolyser stacks. Table
12 shows the system parameters. For the illustration of hydrogen production process in
terms of efficiency and performance, particular parameters calculated for three different
voltage points i.e. 1.4, 1.6 and 1.8 V as shown in Table 13.
Electrolysis process starts at approx. 1.4 V per cell at which low hydrogen production rate
occurs. At this voltage, the efficiency of the stack is high due to slow rate of electrochemical
reactions as well as low current density. System efficiency is low as most of the power
consumed internally by balance of plant (BoP) components. Once the voltage scaled up by
200 mV, the rate of hydrogen production increased significantly to 41 and 82 g/h for single
stack and the system, respectively. It is an optimal point in terms of system efficiency (77%)
as activation losses of the stack are only predominant. At maximum power point (11kW),
the highest long-term performance obtained (99 and 197.8 g/h of hydrogen production).
The efficiency for both the stack and the system is decreased - Ohmic and mass transport
losses become significant. The system efficiency is also affected by electrical losses
occurring at stack power supplies that generate high amount of thermal energy. The heat
removed from the system by forced circulation of air through the radiators as well as
increased flow rate of cooling water.
This also generates additional parasitic energy consumed by BoP components. Assuming a
long life-time of the system, it is advisable to operate at either low or nominal power point
(4.2 or 9.9 kW). The operation of the system at maximum performance will quickly lead to
creation of additional losses due to ageing process of the electrolysis stack. The power
required for nominal hydrogen production at BoL and EoL (beginning and end of life) for
the stack is 4.2 and 5.8 kW respectively.
127
Average cell voltage [V]
Parameter
1.4 1.6 1.8
Power [kW] 0.049 1.75 4.73
Efficiency, LHV [%] 89.0 78.4 70.0
Stack
H2 production [g/h] 1.3 41.1 99.0

Power [kW] 0.37 4.23 11.01
System
Efficiency, HHV [%] 28.7 76.7 70.9

H2 production [g/h] 2.7 82.2 197.8
Table 13: The comparison of parameters recorded and calculated at different cell’s voltage for
single electrolysis stack and whole electrolysis system consisting of 2 stacks
The characterisation of electrolysis stack is crucial from the system design point of view. In
Figure 45 there is stack power and efficiency depicted as a function of stack current. The
nominal power point (at BoL) for the stack is at the voltage of 42 V and current of 100 A. At
this point the efficiency calculated for the lower heating value of hydrogen (LHV, 33.4
kWh/kg) is around 86%.
This allows on the generation of low amount of thermal energy in the consequence of small
electrochemical losses and changes of entropy for given reactants and products of hydrogen
and oxygen evolution reactions. The maximum power point is achieved at the point of 44 V,
120 A (5.3 kW). Lifetime of the PEM electrolysers was taken into consideration during
development process of the system, as at EoL the power requirement of the stack might
exceed the available resources.
128
Figure 45 Electrical characterization of the 1.0 Nm3/hr PEMWE stack; lower heating value
of hydrogen taken for calculation of efficiency
Total energy consumption of the electrolysis system is an aggregation of the utilization by

two stacks and BoP components. The latter includes high power supplies, water and cooling
pumps, cabinet and cooling fans and PLC controller with its dedicated hardware
(programmable voltage sources, input/output terminals, etc.). Calculation of total energy
utilization includes all internal consumption in order to obtain reliable dependency of system
efficiency.
Figure 46 describes the system performance as a function of total power. At slow hydrogen
production rate (less than 12 g/h), the system efficiency is low due to BoP requirements.
Increasing the production rate increases also the efficiency maximally up to 77% (3.7 kW).
It is an optimal point of operation for the system at which the ratio of hydrogen energy
produced to the total energy consumed has the highest value. Above this point, the
efficiency is still high (around 70%) however, it is linearly decreasing.
129
Figure 46: Electrolysis system performance, including Balance of Plant and two stacks under
operation
Taking into account the higher heating value of hydrogen (39.49 kWh/kg) and recording the
energy utilization for electrolysis system, the energy input/output dependency was obtained.
In Figure 47, chemical energy of produced hydrogen is shown as a function of total energy
consumption. The amount of hydrogen generated in electrolysis process calculated based on
Faraday’s law assuming there were not any electrochemical losses nor internal currents.
Hydrogen mass (mH2) calculated from the following equation 33:
𝑀𝐻2 ∙𝐼∙𝑁𝑜
𝑚𝐻2 = 33
𝑛𝐹
Where MH2 is molecular mass of H2,
I – electrical current,
130
N0 – number of cells in the stack,
n – Number of electrons per hydrogen molecule,
F – Faraday’s constant.
Hydrogen production method via the electrolysis is an energy-consuming process. For the
designed system, at least 30% of energy has to be lost. The system can operate the most
effectively at the efficiency of 77%, which means a constant utilization of 3.7 kWh of
electricity corresponding to 2.85 kWh of hydrogen produced (HHV). However, it is
relatively slow production rate. At the nominal point of operation, this relation is 9.9 vs. 7.1
kWh, while at maximum power point 12.2 vs. 8.5 kWh.
hydrogen, Calculated based on the higher heating value of this fuel (39.49 kWh/kg)
131
III. EFFICIENCY
A PEM electrolyser system for hydrogen production is established and the corresponding
efficiency is derived. Based on semi-empirical equations, thermodynamic-electrochemical
modelling of water splitting reaction is systematically carried out. It is confirmed that the Joule
heat resulting from the irreversibility inside the PEM electrolyser is larger than that needed in
the water splitting process in the whole region of the electric current density. Some alternative
configurations are designed to improve the overall performance of the system and the
corresponding expressions of the efficiency are derived (Zhang, Su, Lin, & Chen, 2012).
The efficiency of an electrolyser is inversely proportional to the cell potential, which in turn is
determined by the current density, which in turn directly corresponds to the rate of hydrogen
production per unit of electrode active area. A higher voltage would result in more hydrogen
production, but at a lower efficiency. Typically, cell voltage is selected at about 2V, but a lower
nominal voltage (as low as 1.6V) may be selected, if the efficiency is more important than the
size (and capital cost) of the electrolyser (Kwaka, Chaeb, & Kanga, 2014).
Another ‘‘source’’ of inefficiency is hydrogen permeation (loss) through the polymer

membrane. This is typically insignificant at low operating pressures, but it may significantly
affect the overall efficiency at very high pressures (>100bar).In addition, there are power losses
in voltage regulation and some power is required for the auxiliary equipment (pumps, fans,
solenoid valves, instrumentation and controls). Typical industrial electrolysers have electricity
consumption between 4.5 and 6.0kWh/Nm3, corresponding to the efficiency of 65–80% (Zhang,
Su, Lin, & Chen, 2012).
PEM electrolyser efficiency calculation using some electrochemical calculations based on the
hydrogen Higher Heating Value (HHV) of H2 was applied in this study. Electrolyser efficiency
using HHV of H2 in equation 34:
𝑊𝐻2
𝜂𝑃𝐸𝑀𝑊𝐸 = 34
𝑊𝑒𝑙
Where:
𝜂𝑃𝐸𝑀𝑊𝐸 – Efficiency of PEMWE
132
𝐻𝐻𝑉𝐻2 – High Heating Value of hydrogen
𝑊𝑒𝑙 – Electric energy used to produce hydrogen (kWh)
Hydrogen energy is calculated by the equation 35:
𝐽
𝑊𝐻2 = 𝐻𝐻𝑉𝐻2 ∙ 𝑁𝐻2 [𝑠] 35
𝑘𝐽
Where, HHV – higher heating value of hydrogen,𝐻𝐻𝑉𝐻2 = −286.02 [𝑚𝑜𝑙]
NH2 – the amount of hydrogen produced [mol/s].
Based on Faraday’s law:
𝐼
𝑁𝐻2 = 𝑛𝐹 36
Where 𝑁𝐻2 – Molecular mass of hydrogen
F – Faradays law
And n – number of Hydydgen ions = 2
Hydrogen energy can be calculated from:
𝐼
𝑊𝐻2 = 𝐻𝐻𝑉𝐻2 ∙ 𝑛𝐹 37
Energy utilized to produce hydrogen:
𝐽
𝑊𝑒𝑙 = 𝐼 ∙ 𝑉 [𝑠] 38
Combining the equations 34, 35, 36 and 37, the thermodynamic efficiency of electrolysis can be
described by equation (39) written as:
𝐼
𝑊𝐻2 𝐻𝐻𝑉𝐻2 ∙ 𝑛𝐹 𝐻𝐻𝑉𝐻2
𝜂𝑃𝐸𝑀𝑊𝐸 = = =
𝑊𝑒𝑙 𝐼∙𝑉 𝑛𝐹𝑉
286.02 ∙ 103 1
𝜂𝑃𝐸𝑀𝑊𝐸 = ∙
2 ∙ 96485.33 𝑉
133
1.482
𝜂𝑃𝐸𝑀𝑊𝐸 = 39
𝑉
The system efficiency is affected also by electrical losses occurring at stack power supplies
that generate high amount of thermal energy. The heat is removed from the system by forced
circulation of air through the radiators as well as increased flow rate of cooling water. This
also generates additional parasitic energy that is consumed by BoP components.
Assuming long life time of the system, it is advisable to operate at either low or nominal
power point (4.2 or 9.9 kW). The operation of the system at maximum performance will
quickly lead to creation of additional losses due to ageing process of the electrolysis stack.
The power required for nominal hydrogen production at BoL and EoL (beginning and end of
life) for the stack is 4.2 and 5.8 kW respectively.
Figure 48: System Stack power and Efficiency

134
The characterisation of electrolysis stack is crucial from the system design point of view. In
Figure 48 there is stack power and efficiency depicted as a function of stack current. The
nominal power point (at BoL) for the stack is at the voltage of 42 V and current of 100 A. At
this point the efficiency calculated for the lower heating value of hydrogen (LHV, 33.4
kWh/kg) is around 86%.
This allows on the generation of low amount of thermal energy in the consequence of small
electrochemical losses and changes of entropy for given reactants and products of hydrogen
and oxygen evolution reactions. The maximum power point is achieved at the point of 44 V,
120 A (5.3 kW). Lifetime of the PEM electrolysers was taken into consideration during
development process of the system, as at EoL the power requirement of the stack might
exceed the available resources.
Total energy consumption of the electrolysis system is an aggregation of the utilization by

two stacks and BoP components. The latter includes high power supplies, water and cooling
pumps, cabinet and cooling fans and PLC controller with its dedicated hardware
(programmable voltage sources, input/output terminals, etc.). Calculation of total energy
utilization includes all internal consumption in order to obtain reliable dependency of system
efficiency.
135
Figure 49: Hydrogen production versus System Efficiency
Figure 49 describes the system performance as a function of total power. At slow hydrogen
production rate (less than 12 g/h) the system efficiency is low due to BoP requirements.
Increasing the production rate increases also the efficiency maximally up to 77% (3.7 kW).
It is an optimal point of operation for the system at which the ratio of hydrogen energy
produced to the total energy consumed has the highest value. Above this point, the
efficiency is still high (around 70%) however it is linearly decreasing.
136
hydrogen, calculated based on the higher heating value of this fuel (39.49 kWh/kg)
In Figure 50, chemical energy of produced hydrogen is shown as a function of total energy
consumption. The amount of hydrogen generated in electrolysis process calculated based on
Faraday’s law assuming there were not any electrochemical losses nor internal currents.
Hydrogen mass (mH2) calculated from the following equation
𝑀𝐻2 .𝐼 .𝑁𝑂
𝑚𝐻2 = 35
𝑛𝐹
Where MH2 is molecular mass of H2,
I – electrical current,
N0 – number of cells in the stack,
n – Number of electrons per hydrogen molecule,
137
F – Faraday constant.
Hydrogen production method via the electrolysis is an energy-consuming process. For the
designed system, at least 30% of energy has to be lost. The system can operate the most
effectively at the efficiency of 77%, which means a constant utilization of 3.7 kWh of
electricity corresponding to 2.85 kWh of hydrogen produced (HHV). However, it is
relatively slow production rate. At the nominal point of operation, this relation is 9.9 vs. 7.1
kWh, while at maximum power point 12.2 vs. 8.5 kWh.
IV. POLARISATION CURVES

A polarisation curve is a plot of cell voltage against current density, it is a standard
electrochemical technique used to characterise the performance of electrochemical cells
(Baniasadi, Dincer, & Naterer, 2012). Current- voltage polarisation curve for HySA
PEMWE prototype in Figure 51 is a commercial stack operated at stack temperature 78 oC,
process feed water flow 60 LPH; anode pressure 2 bars and cathode pressure two bars:
46 Polarisation Curve
44
42
Stack Voltage (V)
40
38
36
34
0 20 40 60 80 100 120
Stack current (A)
Figure 51: Voltage-current characteristics (Polarisation Curve)
138
V. PEM COST ANALYSIS
The cost analysis of the produced prototype PEM electrolyser system compared to a
commercially produced system from one commercial supplier called Proton. Both systems have
the same hydrogen productivity of 2 Nm3/h. Table 14 show the capital, installation and
maintenance costs of both systems.
Hysa Systems Proton

System ( 2 System ( 2
Type of cost Unit Nm3/h) 20 bar Nm3/h) 30 bar
1. Capital Cost
Equipment Cost
1.1 Electrolyser stack R R 841 080,00 R -
1.2 Power supply R R 245 100,00 R -
1.3 UP water supply R R 200 000,00 R 126 529,30
1.4 Cooling system R R 116 475,00 R -
1.5 BOP R R 549 344,08 R -
1.6 Chiller for H2 (cooling) R 150 000,00 R 276 150,00
1.7 Stack, BOP Proton HS40 series R - R 2 226 952,50
Sub total R 2 101 999,08 R 2 629 631,80
Installation Cost
Installation cost ( 20% of
1.4 Equipment Cost) R R 236 700,00
Total (Equipment + Installation) R R 2 101 999,08 R 2 866 331,80
2. Operational Cost
2.1 Water
Cost per litre R/L R 0,02 R 0,02
2.2 Electricity
Grid Cost per kWh R/kWh R 2,67 R 2,67
PV cost per kWH R/kWh R 0,62 R 0,62
3. Maintenance Cost
Maintenance Total Cost (2%
3.1 of Capital Cost per Annum) R/year R 42 039,98 R 52 592,64
3.2 UP water supply consumables R/year R 25 000,00 R 25 000,00
3.3 Routine manifold maintance R/year R 5 000,00 R 5 000,00
Table 14: System Capital, Installation and Maintenance Costs
139
Operational costs
Yearly 1 Yearly 2
Description Capacity Unit Capacity Unit Stack Stacks
Production capacity 2 Nm3/h 3,970378 kg/d 1449 2898
mol
Production capacity 82,1 H2/h 1969,433 718843,22 1437686,45
Water requirement 1477,1 g/h 35,45 12939,18 25878,36
Sufficient capacity
for purifier 0,9 l/h 21,6 7884,00 15768
Water cost(Schools
& Sport Bill) 50 R/kL 473,04 946,08
Power consumption
BoT 206,4 kWh/day
Power consumption
BoT 227,04 kWh/day
Power consumption
EoT 247,68 kWh/day
Grid power Cost 2,67 R/kwh 606,1968 221261,832 442523,664
PV power Cost 0,62 R/kwh 14,88 5431,2 10862,4
Ave Electrical cost 2,242916667 R/kwh 509,2318 185869,607 371739,214
Table 15: System Operation Costs
140
Table 17 shows the standard operational cost involved in operating the systems during the 2
year life span of the Stack. The Stack life span determines the amount of hydrogen that can
be produced before the stack can be refurbished and given another new life span. Table 16
shows the standard International units used in the calculation of the total cost of hydrogen
produced.
Hydrogen Production Unit Value

Faraday Constant C/mol 96485,34
Number of H2 ions (n) 2
Current (i) A 100
Number of cells in a stack (k) 24
Amount of H2 flow (J) mol/s 0,000518213
Molecular mass of H2 (M) g 2,016
Amount of H2 produced (mh2) g/h 90,26366078
Amount of H2 produced/ day kg/day 2,166327859
Total H2 produced by 2 stacks kg/day 4,332655717
Table 16: System units and standards
141
Total Cost of H2
Hysa Systems Proton
Equipment( E ) + Installation R 2 101 999,08 R 2 866 331,80
Interest R 210 199,91 R 286 633,18
Maintenance (M) R 42 039,98 R 52 592,64

Water cost (W) R 946,08 R 946,08
Electrical R 371 739,21 R 371 739,21
E+Inst+Interest + M+W R 2 726 924,26 R 3 578 242,91
Utilization factor 1 1
Total Cost of H2 per Kg R 940,85 R 1 234,57
Table 17: Total Cost of H2 per Kg
PEM hydrogen production is still expensive mainly because of the cost of the electrolyser stack.
In Table 17 prototype PEM electrolyser system is found to be cheaper than the PEM
electrolyser system from the commercial supplier when comparing the cost of hydrogen per kg.
The cost of hydrogen per kg compared to fossil fuel is still expensive, considerable work need
to be done in renewable energy technology development to bring comparative cost to the
existing fossil fuel market.
142
Figure 52: Breakdown of the incurred cost for the integration and commissioning of Prototype
PEM water Electrolyser (Cost in South African Rand 2016-2019)
Figure 52 show the cost breakdown for the complete prototype system. Considerable cost of up
to 47% went for the PEM electrolyser stack procurement. Extensive research still needs to be
explored in order to bring down the cost for the Electrolyser stack if the hydrogen economy is to
take centre stage in the global market compared to fossil fuels. Government and private equity
funding is key to the success of hydrogen economy.
VI. HYDROGEN COMPRESSION AND SUPPLY

The produced hydrogen form the prototype PEMWE was supplied to a 5 Nm3/H Metal Hydride
(MH) compressor. The industrial scale metal hydride hydrogen compressor was developed at
South Africa Institute of Advanced Material Chemistry that we published in (Lototskyy, et al.,
2018) was used for hydrogen compression.
The three-stage compressor supplied with hydrogen form the electrolyser at 20 bar (further
reduced to 3–5 bar to minimise influence of the operation of the compressor on performance of
the electrolyser) and compressed to 180–200 bar. The commercial refuelling fuel cell station
and SAIAMC research facility had hydrogen supplied at 180–200 bar from the MH compressor.
143
They made use of high-pressure regulators to step down the pressure to their optimum
operational pressure.
Hydrogen compression is carried out by the periodic heating (TH=130 °C) and cooling (TL=25
°C) of metal hydride materials disposed in metal hydride containers for hydrogen compression.
The compression is carried out in three stages using:
 AB5 material (LaNi4.9Sn0.1) for stage 1,

 AB5 material (La0.8Ce0.2Ni5) for stage 2 and
 AB2-type material (C14-Ti0.65Zr0.35(Mn,Cr,Fe,Ni)2+x) for stage 3.
In Figure 54, hydrogen is absorbed in the cooled MH container of stage 1 at 3-5 bar, desorbed
from the heated MH container of stage 1 to the cooled container of stage 2 at 15-20 bar, then
desorbed from the heated MH container of stage 2 to the cooled container of stage 3 at 50-80
bar.
When MH container of stage 3 is heated, it desorbs hydrogen to a receiver (cylinder pack) at a

pressure up to 200 bar. The amount of hydrogen compressed per unit weight of the MH ( C)
depends on both the operating temperatures and pressures and varies between 100 and 145 NL
H2 per 1 kg of the MH material.
144
PH 3d
C=100.7
100
2d
PM2
3a
C=131.6
1d
PM1
2a
P [atm]
10
C=145.6
PL
1a
0 20 40 60 80 100 120 140 160 180 200

CH [NL/kg]
Figure 53: Pressure – composition isotherms for H absorption at TL=298 K (a) and
H desorption at TH=403 K (d) for MH H2 compression alloys: LaNi4.9Sn0.1 (1),
La0.8Ce0.2Ni5 (2) and C14-Ti0.65Zr0.35 (Mn, Cr, Fe, Ni) 2+x (3).
From Figure 53 it can be seen that hydrogen compression by a MH material takes
place when the H2 suction pressure is higher than the plateau pressure for hydrogen
absorption in the MH at T=TL and the discharge pressure is lower than the plateau
pressure for hydrogen desorption from the MH at T=TH. The amount of hydrogen
compressed per unit weight of the MH (C) depends on both the operating
temperatures and pressures and can be estimated as the difference of hydrogen
concentrations, CH (P, T).
The MH materials are loaded in MH containers each able to absorb and desorb up
to 2 Nm3 H2. The containers belonging to stages 1, 2 and 3 have the same design
differing only by the length when the MH container belonging to the next
compression stage is 10% shorter than the container of the previous compression
stage. The operation and performance of the MH compressor has been presented in
145
our paper entitled industrial scale metal hydride compressors developed at the
South African Institute of Advance Material Chemistry (Lototskyy, et al., 2018).
A typical cyclogram of the compressor operation is presented in figure 55.

Periodic heating and cooling of two compression modules in the opposite phase
(T1, T2) results in the increase of H2 pressure from 3–5 bar in the suction line (P
(in)) to 20–30 bar between stages 1 and 2 (P1–2), 40–80 bar between stages 2 and
3 (P2–3) and higher, up to 200 bar at the output of the compressor (P (out)).
In doing so, the H2 flow rate at the input of the compressor periodically changes
between 0 and 3–4 Nm3/h. The values of H2 flow rate (up to 6 Nm3/h) and the
average compressor productivity (1–4 Nm3/h) depend on the duration of the
heating / cooling cycle (20–35 minutes), steam temperature (120–150 °C) and, in
the lesser extent, the suction (above 3 bar) and discharge (up to 200 bar) H2
pressures.
146
5
Pressure (bar), Temperature (oC) 140
P(out)
T2 P(2-3)
120 T1 H2 flow 4
100
H2 flow (Nm3/h)
3
80
60 2
40
1
20
0
P(1-2) P(in) 0
12:00 13:00 14:00 15:00 16:00

Time (hh:mm)
Figure 54: Typical operation of MH compressor at SAIAMC; heating / cooling

time 25 minutes, average productivity 1.2 Nm3/h. Left Y-axis: T1, T2 –
temperatures in the first and the second compression modules, respectively; P(in)
– H2 suction pressure; P(out) – H2 discharge pressure; P(1-2) – H2 pressure
between stages 1 and 2; P(2-3) – H2 pressure between stages 2 and 3. Right Y-
axis: H2 flow in the suction line of the compressor.
The compressed hydrogen is supplied to either SAIAMC Research facility for

consumption, or for refuelling fuel cell vehicle prototypes.
VII. PEM STACK FAILURE

During the system operation, as seen in the screen shot (Figure 56), it was
discovered that both our stacks had low voltage. Individual cell voltages for
each stack were tested and it was discovered that all the cells had low voltage
of an average of 0.7V/ cell except two cells, which had 2.2V/cell in each stack
and current less than 10A (measured separately). Therefore, it was concluded
that most of the cells were broken or damaged.
147
The possible reasons for the damage were:
 Possibly some corrosion in the cooling loop which might have filtered
some ions to the stack
 The metal profile that was used to support the PEM stacks to stand in
upright position might have had a contact with the current collectors that
might have resulted in a short circuit that might have damaged the PEM
stacks.
Figure 55: PEMWE readings indicating failure of the stacks
The most possible reason as to why both electrolyser stacks failed at the same time
due to metal bar which physically "switched off" some of the cells in the stack.
The graph in Figure 56 indicated of one of the stack when the failure happened.
The data for second electrolyser are very relevant. At that time metal bars were not
148
isolated as is visible in the picture. Once we put isolation and started the
electrolysers these cells that were covered and "protected" by metal bar were also
destroyed due to over-voltage (as some of the cells were already damaged). It was
interesting that two cells in each stack survived and were working, however their
maximum current (measured independently) is just around 10 A @ 2.4 V.
Figure 56: Stack Current/ Voltage when failure occurred
a) ANALYSIS OF DEFECTIVE STACKS

The following activities were carried out to ascertain the defective stacks:
I. STACK HYDROSTATIC TEST,

The hydrostatic test revealed that both stacks were leaking internally: with
the anode and cathode header capped off on one side, a pressurised water
flow (~2 bar), resulted in a water discharge at the cathode header indicating
a “macro leak” across the membranes/MEAs;
149
II. STACK DISASSEMBLY AND INSPECTION OF
COMPONENTS
Both stacks were disassembled and all the components have been
inspected. It immediately became clear that the MEAs were severely
damaged. Figure 57 shows typical damaged MEA out of the stack.
Furthermore, unfortunately the ‘flow fields’ were also damaged (see Figure
58). One current collector was bent; perhaps this happened when
dismounting the stack out of the system. All other stack components were
approved to be usable.
Figure 57: Damaged MEAs
Figure 58: Damaged Flow Fields
150
b) PLAN FOR REFURBISHMENT
The good news are that the cell plates and compression assembly can be cleaned
and re-used. The MEAs, flow fields and sealing have to be renewed or
refurbished. The plan for refurbishment of both stacks is quite extensive and
account for over 50% of the total stack cost: ~€24.000 for the two 1Nm3/h PEM
stacks. The refurbishment cost funding will be co-funded by HySA systems and a
private company, Isondo Precious Metals.
VIII. QUANTITATIVE RISK ASSESSMENT
The prototype PEMWE system has been equipped with hydrogen sensors and
cathode exhaust line connected to a flame arrestor. The oxygen from the anode
loop connected to an exhaust line that takes produced oxygen outside the building
into the environment in order to avoid high concentration of oxygen inside the
location of the electrolyser. Safety procedures were implemented to protect the
stacks following sound engineering practice. BoP, cooling system and power
supply units were integrated with the PLC to protect the entire prototype system.
Modelling of the facility housing prototype PEMWE was carried out using
Hydrogen Risk Assessment Model. The HyRAM toolkit is the first-ever software
toolkit that integrates deterministic and probabilistic models for quantifying
accident scenarios, predicting physical effects, and characterizing hydrogen
hazards’ impact on people and structures.
HyRAM incorporates generic probabilities for equipment failures and probabilistic

models for heat-flux impact on humans and structures, with computationally and
experimentally validated models of hydrogen release and flame physics.
Modelling of the facility housing prototype PEMWE was modelled using HyRAM
and the following was obtained:
151
Figure 59: PEMWE System H2 release scenarios
Application of HyRAM modelling software on the facility housing the PEMWE
system revealed the hazard scenarios in Figure 59. Hydrogen leak triggers
complete system shutdown and no ignition. In cases of hydrogen ignition it will
result in either a jet fire or explosion in worst case scenario. Dedicated engineering
controls embedded in the PLC mitigate hydrogen fires risks.
IX. HYDROGEN PRODUCTION, COMPRESSION AND SUPPLY TO

SAIAMC FACILITY & FUEL CELL PROTOTYPE REFUELLING
The testing has been done in separate subsystems (results presented above)
namely:
 Hydrogen production – 2Nm3/h HySA Systems Prototype PEM

Electrolyser system
 Hydrogen compression – 5 Nm3/h Metal hydride compressor
Though the detailed testing of the complete system was not done due to the PEM
stack failure, this study (including the collected experimental data) allowed to
152
show technical feasibility of the system and to develop detailed safety protocols
presented above.
Note that after the stack failure the incomplete system including MH compressor,
dispensing station and H2 distribution between refuelling and SAIAMC research
facilities (Figure 14) continued to operate. The operation was provided by the
connection of hydrogen cylinder packs from H2 suppliers to the input of the MH
compressor instead of the output collectors of the electrolyser (Figure 41). It
allowed to maintain the pressure in the high pressure buffer (CP in Figure 39)
above 180 bar thus providing the operation of both fuel cell prototype refuelling
station (required H2 pressure 180–200 bar) and SAIAMC research facility
(required H2 pressure 80 bar; see Figure 42). At the same time, the pressure in the
source cylinder pack could drop down to 5–10 bar without interruption of the main
operations requiring the higher H2 pressures. In doing so, the hydrogen
compression part of developed system allowed to utilise most of the delivered
hydrogen resulting in significant costs savings.
153
CHAPTER 5 – CONCLUSIONS AND
RECOMMENDATIONS
INTRODUCTION
This study aimed at the integration of hydrogen production and storage technologies
into one large project, demonstrating South African competencies in the renewable
energy space and technological development towards the growing hydrogen
economy. This study developed a safe, green hydrogen production, compression and
distribution system for fuel cell applications and general hydrogen consumption in
SAIAMC research facility.
GENERAL CONCLUSIONS
Hydrogen economy has become a necessary action for our civilization due to
environmental issues such as global warming effect, air pollution, and depletion of
fossil fuels. During this study, the renewable hydrogen production autonomous
system was developed including its engineering, testing and analysis. The produced
hydrogen was fed to a prototype 5 Nm3/h Metal Hydride compressor. Hydrogen
safety was also taken into consideration as one of the most important issue arising
when it comes to development of practical hydrogen production and compression
systems.
Public acceptance of hydrogen as a clean reliable energy source is still a challenge

mainly because of previously publicized hydrogen accidents like the Hindenburg
disaster of 1937. Public awareness of the clean energy hydrogen is a key to the
success of hydrogen economy. This may imply that there is a need to the
establishment of a new hydrogen safety culture in the society, development of
innovative safety strategies and breakthrough engineering solutions that mitigate
hydrogen accidents or incidents.
154
PEM electrolysis is a commercially viable hydrogen production method that has
potential to produce green energy of high purity (99.999%). PEM Electrolyzer has a
low gas crossover rate that result in yielding hydrogen of high purity. PEM
Electrolyzer have the ability to operate with a wide range of power input like the grid,
wind and solar. This is due to the fact that the proton transport across the membrane
responds quickly to the power input. PEM electrolysis covers practically the full
nominal power density range (10 -100%).
PEM electrolysis system efficiency, performance and cell degradation are keys to the
development of clean hydrogen production. The concern related to high cost of
catalysts used has opened research for alternative catalyst loading or substituting the
expensive noble metals like platinum and iridium. The promising alternatives are
core-shell catalysts, bulk metallic glasses and nanostructured thin films.
Hydrogen compression technology using MH compressors is a mature technology

that has been published in many publications. MH compressors have been developed
that can compress hydrogen to pressure >700 bars safely.
GAPS FROM THE LITERATURE RELATED TO THE CURRENT

STUDY
Water electrolysis is a mature technology, and it is being used for hydrogen

production capacities ranging from few cm3/min to thousands m3/h today. It is
relatively efficient (>70%), but because it needs high quality energy (electricity)
hydrogen produced by water-electrolysis is expensive. There is a potential to
generate relatively inexpensive hydrogen from hydropower and nuclear plants
during off-peak hours.
155
Hydrogen could be economically produced from large PV power plants if the cost
of PVs could be brought to US$0.2 to US$0.4/Watts Peak. PEM electrolysers
produce hydrogen with very high purity (up to 99.999), which may be used in a
fuel cell directly without purification process.
Voltage increase is steeper in the first couple of thousands of hours of operation,

20–50lV/h, but then it levels off (<3lV/h), mainly because of electrolyser initial
conditioning and equilibration of the complete system. The reasons for voltage
increase are equilibration of water content in the membrane, and oxidation of
catalyst and other metallic components. With good design and careful selection of
materials, this performance degradation may be minimized.
The efficiency of an Electrolyser is inversely proportional to the cell potential,

which in turn is determined by the current density, which in turn directly
corresponds to the rate of hydrogen production per unit of electrode active area of
the cell. A higher voltage would result in more hydrogen production, but at a lower
efficiency. Typically, cell voltage is selected at about 2V, but a lower nominal
voltage (as low as 1.6V) may be selected, if the efficiency is more important than
the size (and capital cost) of the electrolyser system.
In addition there are power losses in voltage regulation and some power is needed
for the auxiliary equipment (pumps, fans, solenoid valves, instrumentation and
controls). Typical industrial electrolysers systems/ units have electricity
consumption between 4.5 and 6.0kWh/Nm3, corresponding to the efficiency of 65–
80%.
Metal Hydride (MH) hydrogen compression utilises a reversible heat-driven

interaction of a hydride-forming metal, alloy or intermetallic compound with
156
hydrogen gas to form MH and is considered as a promising application for
hydrogen energy systems.
The advantages of MH compression include simplicity in design and operation,

absence of moving parts, compactness, safety and reliability, and the possibility to
consume waste industrial heat instead of electricity.
The major factor affecting hydrogen compression efficiency of the MH materials

is the plateau slope. Hydrogen compression performances of the real MH systems
are significantly affected by hysteresis, as the values of plateau pressures for
hydrogen absorption/hydrogenation are higher than the ones for hydrogen
desorption/ dehydrogenation. Efficient metal hydride compression process requires
a high compression ratio, high productivity and efficiency, long and reliable
operation.
157
FINDINGS OF THIS STUDY
Designed prototype had a productivity of 2 Nm3/h. PEM Electrolyzer system had a
power rating of 8.6 kW PEM stacks managed by Beckhoff PLC controller. The
Electrolyzer had a discharge output pressure of 20 bars. The prototype system was
capable of working with the efficiency of 77% at optimal conditions. Its efficiency
depended on selected power point therefore this value can vary significantly.
Hydrogen production method, electrolysis is an energy-consuming process.
For the designed system, at least 23% of energy has been lost as a heat and due to
internal consumption. Thermal energy generated due to stack electrochemical
losses and BoP electrical losses accounts for approximately 33% increase of
energy consumed. The PLC controller operated in a closed infinite loop, this
enabled system safety that protected the whole system and ensured reliable
operation.
PEM electrolysis cells characteristically operate between about 1.4 V at zero

current and 1.9 V at full current. The lower voltage defines the energy required for
electrochemical hydrogen conversion whilst voltages greater than that may be
associated with internal resistive cell losses and consequent heat dissipation. These
characteristics suggest a design configuration of 24 cells operating in series at 100
A, with a peak dissipation of 3.8 kW to achieve an efficiency of approximately
80%, with a 38 V total stack voltage.
Prototype PEMWE electrolysis process started at approximately 1.4 V per cell at

which low hydrogen production rate occurs. At this voltage, the efficiency of the
stack is high due to slow rate of electrochemical reactions as well as low current
density. System efficiency is low as most of the power is consumed internally by
balance of plant (BoP) components.
158
Once the voltage is scaled up by 200 mV, the rate of hydrogen production
increases significantly to 41 and 82 g/h for single stack and the whole system,
respectively. It is an optimal point in terms of system efficiency (77%) as
activation losses of the stack are predominant. At maximum power point (11kW),
the highest performance is obtained (99 and 197.8 g/h of hydrogen production).
The efficiency for both the stack and the system is decreased - Ohmic and mass
transport losses become significant.
Average cell voltage [V]

Parameter
1.4 1.6 1.8
Power [kW] 0.049 1.75 4.73
Stack
Efficiency, LHV [%] 89.0 78.4 70.0

H2 production [g/h] 1.3 41.1 99.0
Power [kW] 0.37 4.23 11.01
Efficiency, HHV [%] 28.7 76.7 70.9
System
H2 production [g/h] 2.7 82.2 197.8
Table 18: The comparison of parameters recorded and calculated at different cell’s
voltage for single electrolysis stack and whole electrolysis system consisting of 2
stacks
The system efficiency is decreased by electrical losses occurring at power supplies
that generate high amount of thermal energy. The heat is removed from the system
by forced circulation of air through the radiators as well as increased flow rate of
cooling water. This also generates additional parasitic energy consumed by BoP
159
components. For long lifespan of the system, it is advisable to operate at either low
or nominal power point (4.2 or 9.9 kW).
The operation of the system at maximum performance will quickly lead to creation
of additional losses due to ageing process of the electrolysis stack. The power
required for nominal hydrogen production at BoL (Beginning of Life) and EoL
(End of life) for the stack is 4.2 and 5.8 kW respectively.
In this work, we reported the hydrogen production autonomous system including

its engineering, safety, testing and analysis. Designed electrolysis system operated
based on an 8.6 kW PEM stack managed by safely integrated PLC controller. The
system achieved an efficiency (HHV) of 82% at optimal conditions. Its efficiency
depends on selected power point therefore this value can vary significantly in
operation.
The calculations based on system lifespan indicate high productivity and efficiency
at BoL 8.6kW and decreased production and efficiency at EoL 11.6kW. The power
requirement of the stack might exceed the available resources hence trigger system
decommissioning or stack refurbishment.
The system has multiple levels of built-in operator and stack safety redundancy.
Control and safety systems monitor all flows, levels and temperatures of
significance. All fault conditions are failsafe and are duplicated, triggering latching
relays which shut the system down. Process indicators monitor several key
variables and allow operating limits to be easily adjusted in response to experience
of system performance gained in the field.
The prototype PEM electrolyser operated from a power supply with a capability of
up to 100 A and up to 38 V corresponding to a power input of 8.6 kW at full load.
The system has an extensive monitoring, control and safety system which
160
encompasses all process values relevant to its safe operation. These include
pressures, temperatures, flow rates and water levels at various locations, stack
voltage and stack current, and hydrogen gas leakage detection.
The system is highly configurable but the usual consequence of detecting any
abnormal value or fault is to remove power and shut down the system. Design
details of the electrolysis stack itself was not considered in this study, it was a
commercial stack supplied by Hydron Energy.
The design, integration and commissioning of the prototype PEMWE system was a
critical part of this study. System testing and operation of the prototype PEMWE
was an integral part of the study.
To facilitate comprehensive monitoring and control, the Beckhoff Twin CAT

software, windows based with a multi-PLC system with on board data logging was
employed on the prototype PEMWE. The prototype PEMWE was housed, in an
equipment cabinet of modest size, the balance-of-plant incorporated a relatively
sophisticated control and monitoring system providing emphasis on flexible
operation and high levels of system safety and redundancy.
An attempt was made to achieve a compact package at this stage, resulting in a

cabinet of generous size which was straightforward to assemble and is easy to
service. Considerable size reduction would be possible for similar future designs.
PEM Water Electrolyser prototype system was subjected to a quantitative risk

assessment method called Hazard Operability Study (HAZOP). The purpose of the
HAZOP study was to investigate the complete prototype system, identify potential
hazards and operability challenges. Appropriate remedial measures were
highlighted, mitigated and integrated in the prototype system. Pre-start-up, start-
up, shut-down and emergency procedures were formulated.
161
The production of hydrogen by electrolysis is an initiative aimed at reducing
global warming by reducing toxic gas emissions which is a key to the
establishment of clean environment. The waste product of electrolysis is oxygen.
Oxygen is an environmentally friendly gas. This is in support of the South Africa’s
economy, a drive to reduce carbon footprint through initiatives like the White
Paper on Renewable Energy of 2003 released by the department of energy.
Application of Hydrogen Risk Assessment Model modelling software on the

facility housing the PEMWE system on H2 release revealed some hazard scenarios.
Hydrogen leak can either triggers complete system shutdown with no ignition or
can result in a jet fire or explosion in worst case scenario. Dedicated engineering
controls embedded in the PLC mitigate hydrogen fires risks.
The hydrogen produced by PEM electrolyser was feed to a 5 Nm3/h 3-stage MH

compressor. Hydrogen was compressed from 3 bar to 200 bars. The compressor fed
the compressed hydrogen to a buffer - 12 cylinder pack (supplied by Air Products).
Extensive work on the industrial MH compressors has been done and published as
part of this project. Also the author has been able to demonstrate metal hydride
compression technology, its performance, reliability, productivity and efficiency in
other related publications.
SAIAMC research facility and HySA systems commercial fuel cell refuelling station
were supplied with hydrogen from the buffer cylinder pack at high pressure of 200
bars. The refuelling infrastructure is a commercial refuelling equipment that is
intrinsically safe and the hydrogen distribution infrastructure is certified and
maintained by certified gas installers.
The project demonstrated South Africa’s capabilities in hydrogen production and

compression technologies embracing the emerging Hydrogen economy. This
162
renewable energy technology initiative reduces the carbon footprint and addresses
global warming challenges facing the world today.
Hydrogen production, compression and dispensing technology developed during

this study can be used extensively in emerging Hydrogen economy in South Africa,
creating employment opportunities to talented scientists and engineers. Application
of hydrogen safety and sound engineering practise mitigated all safety related issues
resulting in an intrinsically safe operating system.
This thesis was focused on proof of concept of the integrated hydrogen production,
compression, storage and dispensing system, by the development of a prototype
system and its trial operation at SAIAMC with a special focus on the establishment
on design and operation protocols around hydrogen safety. The system modelling is
indeed critical for the system optimisation and upscaling, but it is a subject of a
separate study presently commenced with the participation of the candidate on the
basis of the research outputs from his PhD thesis.
It has to be noted that though the modelling was not a part of this study, some results
including detailed consideration of the operation of the PEM electrolyser (pages
133-139 and 147-152), as well as experimental study of the operation of the metal
hydride compressor (pages 144-147) provide important starting data for the future
modelling activities
163
RECOMMENDATIONS
Further investigations are highly recommended as a follow up to the research and
results obtained in this PhD study:
 Integration & Testing of a locally (HySA Systems) produced 1Nm3h PEM

stack into the Prototype HySA PEM electrolyser system.
 Automation of all manual valves and the Ultra-Pure water supply system.
 Integration of prototype HySA PEM electrolyser system with a 5.2kW
Photovoltaic supply (This objective was not achieved due to lack of funding
for the purchase of a 5.2 kW photovoltaic supply system).
 Testing of the complete integrated subsystems, PEM electrolyser and 5
Nm3/h Metal hydride compressor
 Design of a centralised PLC that controls and monitors all subsystems that
is the hydrogen production (PEM Electrolyser), hydrogen compression
(MH Compressor) and hydrogen distribution system.
 Mathematical modelling and simulation of complete system- hydrogen
production, compression and dispensing
164
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2. APPENDIX 1
PEM ELECTROLYSER OPERATION MANUAL
SYSTEM OPERATION
I. PRE-START UP PROCEDURE
After the stack is properly installed in the test set up / system and all the
process lines are connected and inspected, the operator should check the
following items prior to operation:
 Check if the stack is properly assembled and leak tight by turning

on the process water pump (P- 101). No water should be leaking to
the outside of the stack. Furthermore check if water is flowing in
the anode loop (it should be safeguarded that a water flow is present
when operating the stack e.g. by visual inspection of transparent
tubing).
 Check if the stack is properly assembled and leak tight by turning

on the thermal management subsystem. No heat transfer fluid
should be leaking to the outside of the stack. Furthermore check if
heat transfer fluid is flowing in the thermal management loop.
 Make sure the power supply sensing probes are connected to the
designated cell plates (the cell plates that are next to the current
collectors).
II. STARTUP CHECK LIST

 Is the extraction / ventilation switched on in the test bench /
electrolysis system?
 Is the hydrogen sensor (HS-203) online and calibrated?
 Are all process connections and fittings properly tightened?
173
 Are the power cables and power supply probes properly connected?
Are the ‘live parts’ not touching other components and/or frames?
 Are there no tears and/or ruptures visible in the installed piping

(hoses of rigid piping)?
 Is the process water in R-301 clean? No dirt/particles in the water

observed?
 Is the water quality of the process water below 1, 5 µS/cm?
 Is the temperature of the process water below 50 ˚C?
 Is the temperature of the EL100 stack below 50 ˚C?
 Is there no water on the surface on which the stack is installed

indicating a leakage in stack, process piping and/or appendages?
 Is there any water in D-102 (as indicated by level sensor EIZA-104)?
 Is the temperature sensor of the stack (TIZA-403) properly fitted in the

bore of the middle cell of the EL100 stack?
 Check all hoses and cables of the system. Check the stack. Is everything
looking OK?
III. ELECTROLYSIS SYSTEM START UP SEQUENCE AND

OPERATION
1. Switch on magna power supply 1 and 2. They must be in standby mode.
2. Switch on the PLC.
 From the desktop click the icon Green Hydrogen system

 From the main menu of Green Hydrogen system:
174
 Click manual control, open system P&ID
 Switch on cabinet fans
 Check the water level sensor for D-102A and D-102B
 Switch on water pump P-101A and P-101B,
 Circulate water in stack 1 and 2 for 2 minutes at 30 LPH
 Check water
3. Start pumps P-101A and P-101B from the PLC. Make sure the flow is
between 50 ml/min and 2000 ml/min.
4. Check the water temperature entering the stack (sensor TS-403A and TS-
403B). The value should be between 5 and 60 ˚C.
5. Check the water temperature exiting the stack (TS-401A and TS-401B).
This should be between 5 and 70 ˚C.
6. Turn on the power supply (PS-501). Set the voltage level to 1, 5 V/cell
(calculate the specific set voltage by the number of cells in the stack) (24
x 1.5) = 36V. Set the current to 100 A. Turn on the output of the power
supply: the power supply is now operating in a constant voltage modus.
7. The stack is now performing the water electrolysis process: hydrogen and
oxygen is now being produced (when transparent hoses are utilized
bubble formation can be detected).
8. After 5 minutes raise the stack potential to 2 V/cell (calculate the specific
set voltage by the number of cells in the stack) (24 x2) = 48V. The
current set point is still 100 A.
9. The drawn current starts to increase as the stack heats up. When a current
of 100 A is achieved, the stack voltage starts to decrease and stabilizes
when the stack temperature (TS-403A and TS- 403B) of max 80˚C is
reached.
175
10. Monitor the following process parameters:
 Stack temperature (TS-403A and TS-403B),
 The stack voltage Stack 1 and Stack 2 from PLC and magna
power source 1 & 2,
 Stack current Stack 1 and Stack 2 from PLC and magna power
source 1 & 2,
 Anode pressure (PS- 103),
 Cathode pressure (PSH – 202 ),
 Process water temperature entering the stack (TS-101A and TS-

101B)
 Process water exiting the stack (TIZA-102),
 Coolant temperature entering the stack (TS-402A and TS-402B),
 Coolant exiting the stack (TS-401A and TS-401B),
 Proton water temperature (TIZA-201),
 Process water conductivity (EIZA-105),
 Hydrogen concentration in cabinet (HS-203),
 Water level in D-102 (LS-104A and LS-104B).
11. Make sure that the following maximum threshold (trip) values are
observed for:
a. Stack temperature (TS-403A and TS-403B): 80˚C
176
b. Stack voltage PLC electrical parameters: maximum individual
cell voltage of 2,4V/cell times the number of cells in the stack
c. Stack current PLC Stack 1 and 2 electrical parameters: 120 A
d. Anode (oxygen/process water) pressure (PS-103): 5 bar
e. Cathode (hydrogen) pressure (PSH-202): 20 bars
f. Process water temperature exiting the stack (TIZA-102): 80˚C
g. Coolant temperature exiting the stack (TS-401A and TS-401B):

80˚C
h. Proton water temperature (TIZA-201): 70˚C
i. Process water conductivity (EIZA-105): <1,5 µS/cm
j. Hydrogen concentration in cabinet (HS-203): 75% of LEL (lower

explosive limit : 4% H2 in air)
k. water level in D-102 (LS-104A and LS-104B): low water level in

separator (D-102)
12. Adjust the set points for the actuators (e.g. the flow rate of pump P-101
and/or P-404 or the stack current and/or potential (E-501) when an alarm
value (defined as a percentage of the threshold trip value) is reached.
13. The electrolysis process utilizes process water as a reactant. Make sure
the process water reservoir (R-301) contains enough water at all time, the
process water loop is replenished according to the process water
utilization and the process water is continuously circulated through the
stack according to the specified flow set point at a rated current. Note
that adding cold process water to the reservoir R-301 will influence the
stack performance.
177
14. As described in chapter 4, the proton water can be recirculated back to
the process water loop (please provide means for recirculation) in order
to decrease the process water consumption of the process.
15. EMERGENCY SHUT DOWN: WHEN A THE THRESHOLD OF A

TRIP VALUE IS REACHED THE POWER SUPPLY TO THE STACK
MUST BE TURNED OFF INSTANTENOUSLY BY MEANS OF
OPENING THE ELECTRICAL LOOP E.G. BY MEANS OF A
RELAY/CONTACTOR (R-504). TURNING OFF THE POWER OF
THE ELECTROLYSIS PROCESS WILL STOP THE PRODUCTION
OF GASSES.
IV. SYSTEM SHUT DOWN
When the system needs to be shut down (after operation or in case of emergency
shutdown) the following sequence need to be initiated:
1. Open electrical parameters
Set Voltage and current on both power supply 1 and 2 to zero and click stop
2. Turn off the power supply into standby mode
3. Increase the cooling pumps P-404A and P-404B to 200 LPH and the fan
speed to 100
4. Monitor the decreasing pressure in the cathode compartment with sensor

PSH-202.
5. Monitor the decreasing pressure in the anode compartment with sensor

PS-103.
6. Allow pump P-101A and P-101B to pump at a minimum flow rate of 150
ml/min for approximately 5 min.
178
7. Turn off the pump P-404A and P-404B when the stack 1 & 2 temperature
is between 25-30 oC
8. As the power to the stack is off and the water pump is no longer
operational, the electrolysis process is fully stopped.
9. Please note that a potential is still present at the poles/current collectors

of the stack.
10. Open Nitrogen, 2 bar through the cathode compartment of the stack to
flush the system. This process will enable the inertisation of
electrochemical reactions within the stack by replacing residual hydrogen
by nitrogen.
DO NOT TOUCH OR IN ANY OTHER MEANS SHORT CIRCUIT THE

POLES AS DANGEROUS CURRENTS CAN BE DRAWN.
V. CHECKLIST AFTER OPERATION
The following checklist need to be followed before operation:
 Is there enough process water present in the anode loop?
 Is the water clean? No particles in the water observed?
 Is there no water on the surface where the stack is placed upon indicating
a leakage in stack, process piping and/or appendages?
 Check all hoses and cables of the system. Is everything looking OK and
not detached
179
Figure 60: Summary of Prototype PEM Electrolyser operation chart
180

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Green Hydrogen Production for Fuel Cell Applications and Consumption in SAIAMC

Supervisor: Dr Mykhaylo Lototskyy

Co-Supervisors: Prof Sivakumar Pasupathi,

Prof Bernard J Bladergroen

PhD Thesis, Department of Chemistry, University of the Western Cape

Stanford Chidziva. 18 May 2020

My mother Cornelia Chidziva and late father Richard Garikayi Chidziva

Firstly, I would like to express my sincere gratitude to my supervisor Dr Mykhaylo Lototskyy

Besides my supervisor, I would like to thank my core supervisors Professor Bernard

KEY WORDS ........................................................................................................................................ iii

LIST OF FIGURES ............................................................................................................................. xiii

LIST OF TABLES ................................................................................................................................xvi

ACADEMIC OUTPUT REPORTED IN THIS RESEACH ................................................................xvii

PUBLISHED PAPERS ....................................................................................................................xvii

CHAPTER 1 – GENERAL INTRODUCTION ...................................................................................... 1

1.1 INTRODUCTION .................................................................................................................. 1

2.1WHAT IS HYDROGEN? .................................................................................................................. 9

a) HYDROGEN AS FUEL ........................................................................................................... 10

a. ENERGY AND EXERGY EFFICIENCIES COMPARISON OF HYDROGEN

2.6.1 GASEOUS HYDROGEN STORAGE ............................................................................. 50

2.7.1 METAL-HYDROGEN SYSTEM .................................................................................... 60

2.9 HYDROGEN SAFETY ............................................................................................................ 65

2.9.1 PHYSICAL AND CHEMICAL PROPERTIES OF HYDROGEN .................................. 67

3.1 PROJECT DESIGN & SPECIFICATIONS ............................................................................. 72

a. STACK SPECIFICATIONS ..................................................................................................... 74

CHAPTER 4 – RESULTS .................................................................................................................. 123

INTRODUCTION .............................................................................................................................. 123

PROTOTYPE PEM WATER ELECTROLYSIS SYSTEM SPECIFICATION ................................ 123

I. HYDROGEN PRODUCTION ............................................................................................... 124

IX. HYDROGEN PRODUCTION, COMPRESSION AND SUPPLY TO SAIAMC FACILITY &

CHAPTER 5 – CONCLUSIONS AND RECOMMENDATIONS .................................................... 154

INTRODUCTION .......................................................................................................................... 154

CHAPTER 6 – REFERNCES AND APPENDIX .............................................................................. 165

1. REFERENCES ............................................................................................................................ 165

2. APPENDIX 1 .......................................................................................................................... 173

SYSTEM OPERATION ....................................................................................................................... 173

2. Mykhaylo Lototskyy, Moegamat Wafeeq Davids, Dana Swanepoel, Gerhard Louw,

3. Mykhaylo Lototskyy, Moegamat Wafeeq Davids, Ivan Tolj, Yevgeniy Klochko,

PEM – Proton Exchange Membrane

Figure 1: Current main hydrogen production routes (Molkov V. , 2012).

Hydrogen production from renewable energy sources is an environmental friendly

Cathode: 2H+ + 2e- → H2 (g) (2)

Full reaction H2O (L) → H2 (g) + 1/2O2 (g) (3)

1.5 HYPOTHESIS OF THE STUDY

1.6 NOVELTY OF THE STUDY

1.8 RESEARCH QUESTIONS

Figure 3: Research Framework

1.11 THESIS STRUCTURE

b) ADVANTAGES OF USING HYDROGEN AS A FUEL

Fuel HHV (kJ/g) LHV (kJ/g)

Here, we go further to compare hydrogen with other conventional fuels in terms of

2.2 HYDROGEN PRODUCTION METHODS

Hydrogen can be produced by a number of technologies using renewable and non-renewable

Figure 5: Selected hydrogen production methods (Dincer, 2012).

Figure 5 summarises the current methods used to produce hydrogen. Hydrogen is an

Method Source Brief Description

Primary energy Material

Direct current is used to split water

Cleaned natural gas is passed through