Comparative Study of Various Hydrogen Production Methods-68 Page

Comparative Study of Various Hydrogen Production Methods
for Vehicles
By
Fahad Suleman
A Thesis Submitted in Partial Fulfillment
of the Requirements for the Degree of Master of Applied Science
in
Mechanical Engineering
Faculty of Engineering and Applied Science
University of Ontario Institute of Technology
Oshawa, Ontario, Canada
© Fahad Suleman, December 2014

Abstract
Hydrogen as an energy carrier is a promising candidate to store green energy and it has a
potential to solve various critical energy challenges. Although, hydrogen is a clean
energy carrier, the possible negative impacts during its production cannot be disregarded.
Therefore life cycle analyses for various scenarios have been investigated in this study.
In this thesis, a comparative environmental assessment is presented for different

hydrogen production methods. The methods are categorized on the basis of various
energy sources such as renewables and fossil fuel. For the fossil fuel based hydrogen
production, steam methane reforming (SMR) of natural gas is studied. Renewable based
hydrogen production includes electrolysis using sodium chlorine cycle. Electrolytic
hydrogen production is also compared using different cells such as membrane cell,
diaphragm cell and mercury cell. Wind and solar based electricity is also used in
electrolytic hydrogen production. Furthermore, vehicle cycle is studied on the basis of
available literature to compare the hydrogen vehicle with gasoline vehicle.
The investigation uses life cycle assessment (LCA), which is an analytical tool to
identify and quantify environmentally critical phases during the life cycle of a system or a
product and/or to evaluate and decrease the overall environmental impact of the system or
product. The LCA results of the hydrogen production processes indicate that SMR of
natural gas has the highest environmental impacts in terms of abiotic depletion, global
warming potential, and in other impact categories. The abiotic depletion for SMR is
found to be 0.131 kg Sb eq. which is the highest among all methods. The second highest
abiotic depletion value comes under electrolysis using mercury cell which is 0.00786 kg
Sb eq. However, thermodynamic results suggested that SMR is the efficient method of
hydrogen production because the amount of hydrogen energy produced as output in the
system is larger than any other method. The energy efficiency of the system in this
method is about 76.8% and the exergy efficiency is about 72.4%. In terms of vehicle
cycle comparison, it is found that the gasoline vehicle appears to be the largest
contributor in energy consumption and GHGs emissions. The energy consumption of
gasoline vehicle is three times higher than hydrogen vehicle. Moreover, GHGs emissions
of the hydrogen vehicle are 8% of the gasoline vehicle.
i
Acknowledgements
First of all, I would like to thank the almighty Allah, for giving me the knowledge,
wisdom, strength and providing me with the resources to acquire education and complete
my studies in an effective manner.
I would like to express my sincere gratitude to my supervisor Dr. Ibrahim Dincer

and my co-supervisor Dr. Martin Agelin-chaab for their guidance and help that made me
overcome all the obstacles that I faced during the current research. I am indebted to them
for providing constructive criticism and illuminating views that enabled me to execute the
work to the current standard.
Furthermore, I thank my colleagues at UOIT who made an enjoyable working

environment to work. I highly appreciate the help and moral support from my friends
Farrukh Khalid, Sayantan Ghosh, and Canan Acar for their help and support during the
preparation of this thesis. I have greatly benefited from their support and will always
remember their contribution.
Last but not least, I would like to express my eternal gratitude to my parents for
their endless consistent support, patience, and encouragement throughout my life. My
Siblings, specially my elder brothers Subhan Ansari and Usman Toufiq; without their
support and motivation I would not have been able to achieve what I have so far in life.
ii
Table of Contents
Introduction ................................................................................................... 1
1.1 Motivation and Objectives ................................................................................... 4
1.1.1 Motivation ..................................................................................................... 4
1.1.2 Objectives .......................................................................................................... 4
Literature Review.......................................................................................... 6
2.1 Methods of Hydrogen Production ............................................................................. 8
2.2 Fossil Fuel Hydrogen Production ............................................................................. 8
2.3 Renewable Hydrogen Production ........................................................................... 11
2.3.1 Solar Based Hydrogen Production ................................................................... 11
2.3.2 Wind Based Hydrogen production ................................................................... 14
2.3.3 Geothermal Based Hydrogen Production ........................................................ 15
2.3.4 Biomass based Hydrogen production .............................................................. 17
2.4 Nuclear Based Hydrogen Production ...................................................................... 18
2.5 Life Cycle Assessment ............................................................................................ 19
Background ................................................................................................. 22
3.1 Hydrogen Production Methods ............................................................................... 22
3.1.1 Natural Gas Steam Reforming ......................................................................... 22
3.1.2 Coal Gasification ............................................................................................. 23
3.1.3 Partial Oxidation .............................................................................................. 24
3.1.4 Electrolysis ....................................................................................................... 25
3.1.5 Thermochemical Water Splitting ..................................................................... 26
3.2 Life Cycle Assessment Methodology ..................................................................... 27
3.2 LCA and International Standard Organization ....................................................... 29
3.4 Impact Assessment .................................................................................................. 29
iii
3.4.1 Category Definition ......................................................................................... 31
3.4.2 Characterization ............................................................................................... 31
3.4.3 Normalization .................................................................................................. 31
3.4.4 Weighting ......................................................................................................... 31
3.5 Advantages of LCA ................................................................................................ 32
Systems Studied .......................................................................................... 33
4.1 Hydrogen Production from Steam Methane Reforming ......................................... 37
4.2 Hydrogen Production via Chlorine Electrolysis Using Different Cells .................. 38
4.2.1 Mercury Cell Electrolysis ................................................................................ 38
4.2.2 Diaphragm Cell Electrolysis ............................................................................ 39
4.2.3 Membrane Cell Electrolysis ................................................................................. 40
4.3 Hydrogen Production via Wind Based Electricity .................................................. 41
4.4 Hydrogen Production via Solar Photovoltaic Based Electricity ............................. 42
Analyses ...................................................................................................... 44
5.1 Environmental Impacts Assessment using LCA..................................................... 44
5.1.1 Emissions ......................................................................................................... 45
5.1.3 Resource Depletion .......................................................................................... 46
5.2 Analysis of Hydrogen Production via Steam Methane Reforming......................... 47
5.2.1 Energy and Exergy Efficiencies ....................................................................... 48
5.3 Analyses of Hydrogen Production Methods through Electrolysis Using Different

Cell ................................................................................................................................ 50
5.4 Analyses of Hydrogen Production through Electrolysis Using Wind Electricity... 51
5.5 Analyses of Hydrogen Production through Electrolysis Using Solar Photovoltaic

Electricity ...................................................................................................................... 55
iv
Results and Discussion ............................................................................... 57
6.1 Hydrogen via Steam Methane Reforming .............................................................. 57
6.1.1 Impact Assessment Results .............................................................................. 57
6.2 Hydrogen from Chlorine Electrolysis Using Different Cells.................................. 68
6.3 Hydrogen via Electrolysis Using Wind Electricity ................................................. 77
6.4 Hydrogen via Electrolysis Using Solar Photovoltaic Electricity ............................ 88
6.5 Comparison of Various Options by CML-Method with Uncertainty Analyses ..... 98
6.5.1 Abiotic Depletion ............................................................................................. 98
6.5.2 Acidification Potential ..................................................................................... 99
6.5.3 Eutrophication .................................................................................................. 99
6.5.4 Global Warming Potential ............................................................................. 101
6.5.5 Ozone Layer Depletion .................................................................................. 101
6.5.6 Human Toxicity ............................................................................................. 102
6.5.7 Radiation ........................................................................................................ 103
5.5.8 Photochemical Oxidation ............................................................................... 104
6.6 Uncertainty Analyses of Steam Methane Reforming ........................................... 104
6.7 Uncertainty Analyses of Solar and Wind based Hydrogen Production ................ 106
6.8 Comparison of Hydrogen and Gasoline Fuels in Vehicle .................................... 107
Conclusions and Recommendations ......................................................... 115
v
7.1 Conclusions ........................................................................................................... 115
7.2 Recommendations ................................................................................................. 116
References ................................................................................................................... 118
vi
List of Figures
Figure 1.1: Estimated U.S. Energy Use in 2013: 97.4 Quads (Adapted from LLNL U.S.
Department of Energy 2013)............................................................................................... 3
Figure 2.1: Specific energies of various fuels (Modified from Sami et al., 2001). ............ 7
Figure 2.2: Five thermochemical routes for the production of solar hydrogen (Modified
from Steinfeld, 2005) ........................................................................................................ 13
Figure 2.3: A schematic illustration of a basic water electrolysis system (Modified from
Zheng et al., 2010) ............................................................................................................ 13
Figure 3.1: Steam methane reforming block flow process (Modified from Richa et al.,
2008). ................................................................................................................................ 23
Figure 3.2: Typical high temperature coal gasification process (Modified from Casper,
1978). ................................................................................................................................ 23
Figure 3.3: Block diagram of hydrogen production by partial oxidation (Modified from
Steinberg et al., 1989). ...................................................................................................... 24
Figure 3.4: Phases of LCA (Modified from Curran, 2012). ............................................. 28
Figure 3.5: Inputs and outputs in LCA (Modified from Curran, 2006) ............................ 30
Figure 4.1: System boundaries for life cycle assessment.................................................. 33
Figure 4.2: Renewable solar based hydrogen production approaches .............................. 34
Figure 4.3: Geothermal and wind based hydrogen production ......................................... 35
Figure 4.4: Fossil and nuclear based hydrogen production .............................................. 36
Figure 4.5: Steam methane reforming and water gas shift reaction (Modified from Spath
et al., 2001). ...................................................................................................................... 37
Figure 4.6: Hydrogen production via Na-Cl electrolysis using mercury cell (Adapted
from Ecoinvent report, 2007) ............................................................................................ 39
Figure 4.7: Diaphragm cell electrolysis (Adapted from Ecoinvent Report, 2007) ........... 39
Figure 4.8: Membrane cell electrolysis (Adapted from Ecoinvent report, 2007) ............. 40
Figure 4.9: Wind electrolysis system ................................................................................ 42
Figure 4.10: Schematic of solar photovoltaic based electricity (Dincer and Joshi, 2013) 43
Figure 5.1: Impact flow diagram of wind power plant. .................................................... 54
Figure 6.1: Impact flow diagram of hydrogen production via steam methane reforming. 60
Figure 6.2: Damage assessment for 1 kg of hydrogen via steam methane reforming.. .... 61
vii
Figure 6.3: Weighting results for 1 kg of hydrogen via steam methane reforming.. ........ 62
Figure 6.4: Contribution of process to total environmental impact for steam methane
reforming (CML method). ................................................................................................ 63
Figure 6.5: Effect of variation of reformer pressure on energy and exergy efficiencies. . 64
Figure 6.6: Effect of varying ambient temperature on energy and exergy efficiencies. ... 65
Figure 6.7: Effect of variation inlet pressure of reformer on mass of hydrogen............... 65
Figure 6.8: Effect of variation of ambient temperature on mass of hydrogen .................. 66
Figure 6.9: Effect of increasing hydrogen production on methane and electricity
consumption. ..................................................................................................................... 67
Figure 6.10: Effect of variation of reformer temperature on energy and exergy
efficiencies. ....................................................................................................................... 67
Figure 6.11: Damage assessment results for hydrogen production via electrolysis using
different cell. ..................................................................................................................... 69
Figure 6.12: Flow diagram of hydrogen production via electrolysis using mercury cell. 71
Figure 6.13: Impact flow diagram of hydrogen production using diaphragm cell. .......... 72
Figure 6.14: Impact flow diagram of hydrogen production using membrane cell. .......... 73
Figure 6.15: Weighting results for hydrogen production through electrolysis using
different cell. ..................................................................................................................... 74
Figure 6.16: Impact assessment chart for hydrogen production through electrolysis using
different cell (CML method). ............................................................................................ 75
Figure 6.17: Comparison of impact categories between electrolytic hydrogen production
and steam methane reforming (CML method). ................................................................. 76
Figure 6.18: Impact flow diagram of hydrogen production via wind based electricity. ... 78
Figure 6.19: Damage assessment chart for hydrogen production using wind electricity. 80
Figure 6.20: Weighting chart for hydrogen production using wind electricity. ............... 83
Figure 6.21: Impact assessment results for hydrogen production using wind based
electricity (CML method). ................................................................................................ 84
Figure 6.22: Effect of variation of inlet pressure on energy and exergy efficiencies of
wind based hydrogen production system. ......................................................................... 85
Figure 6.23: Effect of variation of ambient temperature on energy and exergy efficiencies
of wind based hydrogen production method ..................................................................... 86
viii
Figure 6.24: Effect of variation in the area of wind turbine on energy and exergy
efficiencies of wind based hydrogen production. ............................................................. 86
Figure 6.25: Effect of increasing the amount of produced hydrogen on energy and exergy
efficiencies. ....................................................................................................................... 87
Figure 6.26: Effect of variation of wind velocity on energy and exergy efficiencies....... 88
Figure 6.27: Impact flow diagram of hydrogen production via electrolysis using solar
photovoltaic electricity. ..................................................................................................... 90
Figure 6.28: Impact flow diagram of photovoltaic electricity. ......................................... 91
Figure 6.30: Damage assessment chart for hydrogen production using solar photovoltaic
electricity. .......................................................................................................................... 92
Figure 6.30: Weighting results charts for hydrogen production using solar photovoltaic.95
(CML method). ................................................................................................................. 96
Figure 6.32: Effect of variation ambient temperature on energy and exergy efficiencies of
solar based hydrogen production. ..................................................................................... 97
Figure 6.33: Effect of variation of solar irradiation on energy and exergy efficiencies of
solar based hydrogen production method. ........................................................................ 98
Figure 6.34: Abiotic depletion per kg of hydrogen for different hydrogen production
methods. ............................................................................................................................ 99
Figure 6.35: Acidification potential per kg of hydrogen for different hydrogen production
methods. .......................................................................................................................... 100
Figure 6.36: Eutrophication potential per kg of hydrogen for different hydrogen
production methods. ........................................................................................................ 100
Figure 6.37: Global warming potential per kg of hydrogen for different hydrogen
production methods. ........................................................................................................ 101
Figure 6.38: Ozone layer depletion per kg of hydrogen for different hydrogen production
methods. .......................................................................................................................... 102
Figure 6.39: Human toxicity per kg of hydrogen for different hydrogen production
methods. .......................................................................................................................... 103
Figure 6.40: Radiation per kg of hydrogen for different hydrogen production methods.103
ix
Figure 6.41: Photochemical oxidation per kg of hydrogen for different hydrogen
production methods ......................................................................................................... 104
Figure 6.42: Uncertainty analysis results of SMR method for abiotic depletion............ 105
Figure 6.43: Uncertainty analysis results of SMR method for global warming. ............ 106
Figure 6.44: Uncertainty analysis results of wind and solar based hydrogen production for
abiotic depletion .............................................................................................................. 107
global warming potential. ............................................................................................... 108
human toxicity ................................................................................................................ 109
Figure 6.47: GHG emissions of vehicle cycle ................................................................ 110
Figure 6.48: Energy consumption of vehicle cycle......................................................... 111
Figure 6.49: Energy consumption in vehicle distribution and vehicle disposal ............. 112
Figure 6.50: Fuel production comparison in terms of emission ..................................... 113
Figure 6.51: Fuel production comparison in terms of emissions .................................... 113
x
List of Tables
Table 3.1: Common thermochemical decomposition steps in S-I cycles. ........................ 26
Table 3.2: Steps and reactions in the five-step Cu-Cl cycle for thermochemical water
decomposition. .................................................................................................................. 27
Table 3.3: ISO Series for LCA ......................................................................................... 29
Table 4.1: Data inputs and assumption for 1 kg of hydrogen production via steam
methane reforming ............................................................................................................ 38
Table 5.1: Raw material inputs for the production of 1 kg of hydrogen........................... 48
Table 5.2: Water and salt consumption in different cells ................................................. 50
Table 5.3: Input values of chemical and materials used in electrolytic hydrogen
production ......................................................................................................................... 51
Table 5.4: Energy consumption for the production of hydrogen in different electrolytic
cells ................................................................................................................................... 51
Table 5.5: Material and energy consumption in wind power plant .................................. 52
Table 5.6: Inputs to solar photovoltaic based hydrogen production ................................. 55
Table 6.1: Damage assessment for 1 kg of hydrogen via steam methane reforming ....... 57
Table 6.2: Weighting results for 1 kg of hydrogen via steam methane reforming ........... 58
Table 6.3: Contribution of process to total environmental impact for steam methane
reforming (CML method) ................................................................................................. 59
Table 6.4: Damage assessment results for hydrogen production using different cells. .... 68
Table 6.5: Weighting results for hydrogen production using different cell. ..................... 70
Table 6.6: Process contribution of environmental impact categories ............................... 70
Table 6.7a: Damage assessment results for hydrogen production using wind electricity. 79
Table 6.8a: Weighting results for hydrogen production using wind electricity. .............. 82
Table 6.9: Damage assessment results for hydrogen production using solar photovoltaic
electricity. .......................................................................................................................... 89
electricity. .......................................................................................................................... 90
Table 6.11a: Weighting results for hydrogen production using solar photovoltaic
electricity. .......................................................................................................................... 93
Table 6.12: Impact assessment results for solar based hydrogen production method ...... 94
xi
Table 6.13: Impact assessment results for solar based hydrogen production using CML
method............................................................................................................................... 94
Table 6.14: Uncertainty data for hydrogen production through SMR ............................ 105
Table 6.15: Uncertainty data for hydrogen production through wind and solar energy . 106
Table 6.16: GHG emission in vehicle cycle ................................................................... 109
Table 6.17: Energy consumption in vehicle cycle .......................................................... 110
Table 6.18: Energy consumption and GHGs emission comparison in vehicle cycle ..... 111
xii
Nomenclature
A area (m2)
c specific heat (kJ/kg K)
cp specific heat at constant pressure (kJ/kg K)
cv specific heat at constant volume (kJ/kg K)
D depletion number
e specific energy (kJ/kg)
E energy (kJ)
E& energy rate (kW)
eq equivalent
ex specific exergy (flow or non-flow) (kJ/kg)
Ex exergy (kJ)
E& x exergy rate (kW)
h specific enthalpy (kJ/kg)
HHV higher heating value (kJ/kg)
KE kinetic energy (kJ)
LHV lower heating value (kJ/kg)
m mass (kg)
m& mass flow rate (kg/s)
M molecular weight (g/mol)
Pt point
R-11 refrigerant 11
Resp. respiratory
Sb stibium
V velocity (m/s)
Greek Letters
η energy efficiency
ψ exergy efficiency
ρ density (kg/m3)
xiii
Subscripts
atm Atmosphere
aq Aqueous
cyc Cycle
el Electrical
endo Endothermic
exo Exothermic
therm Thermal
Acronyms
AP Acidification Potential
BG Biomass Gasification
CG Coal Gasification
CML Centrum Milieukunde Leiden
DALY Disability-adjusted Life Years
DB Dichlorobenzene
EP Eutrophication Potential
GHGs Greenhouse Gases
GWP Global Warming Potential
IEA International Energy Agency
LCA Life Cycle Assessment
LCI Life Cycle Inventory
LCIA Life Cycle Impact Assessment
Na-Cl Sodium chloride
NREL National Renewable Energy Laboratory
ODP Ozone Depletion Potential
PAF Potentially Affected Fraction
PDF Potentially Disappeared Fraction
PV Photovoltaics
S-I Sulphur-Iodine
SMR Steam Methane Reforming
xiv
Introduction
Energy is considered as a key component of all activities and plays a major role in the
economic development of any country. Over time, energy demand in every sector keeps
increasing due to the large amount of consumption, increasing population, change in life
style and technological advancement. Almost every sector is dependent on energy which
comes mainly from fossil sources. Report by International Energy Outlook (IEO, 2013),
predicted that the world energy consumption will rise by 56% between the years 2010 to
2040. In this prediction, conventional fossil fuel will share about 78% and rest of the
number will be fulfilled by renewable and nuclear sources. The massive utilization of
fossil fuels is responsible for climate change, greenhouse gas emissions, and pollutants
(e.g. CO, CO2, SOx, NOx, ashes etc.). All these gases and air pollutants damage the
stratospheric ozone layer and create smog. This results in people getting health issues
such as lung and respiratory disorder, eye irritation and blood related disease (Granovskii
et al., 2007). The transportation sector is the second major consumer of energy where
petroleum and other liquid fuels consumption are very high after electricity generation
(industrial). Annual energy utilization in transportation sector increases 1.1 percent (IEO
2013) and majority of the energy demand is being provided by fossil fuels. Moreover, the
transportation industry is considered the most inefficient sector in the US in terms of fuel
efficiency, about 76% of supply energy is lost as heat (LLNL, U.S. Department of Energy
2013) as shown in Figure 1.1. These negative results motivate researchers to look for an
alternate of fossil fuels and a lot of work has been done in this search.
Energy strategies will play an important role for future world stability. In case of
energy consumption in transportation several renewable technologies are available in
terms of renewable biofuels, solar car, electric vehicle etc. Each of them has some
limitations for example in electric car, a battery need to charge by external electricity
which also comes from conventional method. A solar vehicle is dependent on the solar
radiation and might not work in areas where sun light is not consistent. Among various
alternatives, hydrogen as a fuel for vehicles offers the highest potential gain which can
replace petroleum products and thus decrease the Greenhouse gas (GHG) emissions and
air pollution. Due to their environmental compatible property, hydrogen possibly will
1
become one of the most feasible energy carriers in the future for various applications
(Midilli et al., 2005).
Many researchers have studied the properties and behaviour of hydrogen as a fuel.
Hydrogen can provide ecologically benign transportation systems depending on the
energy and material source (Granovskii et al., 2006). Some study focus on the
contribution of hydrogen regarding the solution of environmental problems (Dincer
2002). Environmentalists and other industrial sector professionals have encouraged the
use of hydrogen in different sectors (Gupta 2009). Hydrogen is extensively available on
earth along with different chemical composition such as water and natural gas. It is
colorless, odorless and nontoxic. It does not produce acid rain, harmful emissions and
providing 2-3 times more energy than other common fuels (Momirlan et al., 2009). In
fact, hydrogen can be produced from available abundant sources by different method.
Again majority of hydrogen is produced from fossil fuels using a process called steam
reforming of natural gas, which is responsible for massive emissions of greenhouse gases.
About 48% hydrogen demand is fulfilled by natural gas, 30% by petroleum industry,
18% from gasification of coal, 3.9% from electrolysis and remaining 0.1% from other
processes (Kalamaras et al., 2013). Scientists are still looking for renewable sources of
hydrogen production on large scale.
Renewable-based hydrogen can lead to the notably lower environmental impacts.
It depends upon many factors involved over their lifetime such as natural resource
extraction, plant construction, final product distribution and utilization. Sufficient
evaluation of environmental impact and use of energy throughout the production and
utilization from cradle to grave is critical for the proper assessment of technologies
(Granovskii et al., 2007). In order to study any operation from cradle to grave life cycle
assessment (LCA) is the methodology that represents a systematic set of procedures for
examining the inputs and outputs of materials and energy. A life cycle is the interlinked
stages of a product or service system, from the extraction of natural resources to their
final disposal.
Within a LCA, the mass and energy flows and environmental impacts related to
plant construction, operation and dismantling stages are accounted for. The determination
of all input and output flows is often very complicated, so some simplifications and
2
assumptions are often made to facilitate an LCA. The challenge is to ensure the
assumptions and simplifications (e.g., simplified models of processes) retain the main
characteristics of the actual system or process being analyzed.
Figure 1.1: Estimated U.S. Energy Use in 2013: 97.4 Quads (Adapted from LLNL U.S.
Department of Energy 2013).
3
1.1 Motivation and Objectives
1.1.1 Motivation
With the world’s increasing population and rising global energy demand, hydrogen is
considered as an ideal energy carrier due to its abundance and high energy conversion
efficiencies. However, regardless of the enormous prospective benefits of using hydrogen
as a fuel, the emissions related to its production is yet to be explored. The fundamental
motivation of this work is the potential of minimizing emissions related to different
hydrogen production methods by comparing selected methods energetically and
exergetically. For this determination, comparative assessment on different hydrogen
production methods is performed keeping in mind their respective emissions. A
significant amount of literature has been published about several hydrogen production
methods but only few of them investigated the life cycle assessment. Hence lack of
literature about the impact of different hydrogen production systems on the environment
restricts investment in this area. A different approach which makes this comprehensive
study quite interesting is to implement life cycle assessment of hydrogen production
methods using software and other available tools.
1.1.2 Objectives
The main objective of this thesis is to investigate different hydrogen production
methods/systems and implement the life cycle assessment methodology on these
hydrogen production methods.
The objective will be achieved using a commercial software (so-called: SimaPro)
which has special features of impact assessment. It can assess the life cycle inventory
data in a systematic way at all the different stages of a process/system.
This research study consists of the following sub-objectives:

1. Investigate different hydrogen production methods in terms of fuel sources such as
renewables and fossil fuels.
• Conduct a comprehensive study on each method and compare different resources
which will provide source of energy to operate hydrogen production processes.
4
• Compare the energy consumption in each method which gives the better
understanding of the hydrogen production process with less environmental
impact.
2. Implement an LCA on these different methods in order to compare them in terms of

carbon dioxide equivalent emissions and other pollutants.
• Use LCA to identify the impact of a system on the environment throughout its
life cycle.
• Use LCA tool such as the SimaPro to analyse the environmental aspects of
every method in a systematic way. SimaPro covers both aspects on the
environment in term of raw material and emissions.
3. Analyse different hydrogen production methods energetically and exergetically to

provide a better understanding of the thermodynamic analysis.
• Calculate energy and exergy efficiencies of selected hydrogen production
methods.
• Performance a comprehensive assessment of hydrogen production methods
through parametric studies to examine the effects of varying environment and
other system conditions.
4. Different impact assessment methods in LCA are available such as the Eco-indicator
99, impact 2002+, CML 2 baseline 2000 etc. The Eco-indicator 99 and CML 2001
will covers major parts of this study.
5. Impact assessment was performed by considering significant environmental impacts

categories which are as follows:
• Ozone layer
• Carcinogens
• Respiratory Organics and Inorganics
• Ecotoxicity
• Acidification
• Global warming
5
Literature Review
Studies in the past have been conducted to investigate and compare the of hydrogen
production methods. Methods of hydrogen production such as steam reforming of natural
gas, thermochemical water splitting with Cu-Cl cycle and some other renewable and
nuclear based process investigated and published. Few of them implemented the LCA
methodology to carry out environmental impact assessment, air borne, water and soil
emissions. In this chapter a brief review on several LCA studies is provided.
Today’s world is in a serious need of alternate of conventional fuels. Among

various alternatives, hydrogen has the highest potential in terms of availability and
reduced emissions of pollutant and greenhouse gases. At present, hydrogen is mainly
used as a chemical substance rather than fuel despite it has a market of fifty billion US$
for 40 Mt annual production (Dincer, 2012). Several studies such as Dincer (2012),
Dincer et al. (2009), Hussain et al. (2007), Marban et al. (2006), Bockris (2002)
introduced and promoted hydrogen as a future energy and their basic remarks over
hydrogen can be drawn as follows:
• Hydrogen has a high quality energy carrier, which can be used for high efficiency
with zero or near zero emissions.
• During combustion with air or used in a fuel cell to generate electricity, only
water and small quantity of NOx is a product.
• It has been technically proven that hydrogen can be used for transportation,
heating, and power generation, and could replace current fuels in all their present
uses.
• Hydrogen exhibits the highest heating value per mass among all chemical fuels as
shown in Figure 2.1 and it is regenerative and environmentally friendly.
Moreover, hydrogen has attractive electrochemical property, which can be utilized
in a fuel cell.
• Hydrogen can be stored in different forms such as in gaseous form suitable for
large scale storage, in a liquid form which is suitable for air and space
transportation or in the form of metal hydrides to be convenient for small scale
storage requirements
6
160
141.9
140
Specific Energy (kJ/g)

120
100
80
55.8
60 45.8 46.5 47.9 50.4
39.6
40 29.7 30.2
14.9
20
Fuel
Figure 2.1: Specific energies of various fuels (Modified from Sami et al., 2001).
These aforementioned properties of hydrogen are ideally suitable for using in a

vehicle as a fuel. The technical and economic challenges of implementing hydrogen
energy are still there which need to be address properly. Michael et al. (2009) highlighted
the challenges and opportunities of promoting hydrogen as alternative fuel in the
transport sector. The major technical challenges of introducing hydrogen as vehicle fuel
includes the development of efficient and cost competitive fuel cells, designing of long
period safe structure for the hydrogen storage and large scale infrastructure for hydrogen
production, distribution and refueling. The economic analysis revealed that the
introduction of hydrogen results in positive effects for long term by assuming the same
level of difficulties as we have today. The overall impact on economic growth (GDP) into
the energy system is small. The fact that hydrogen is introduced in only part of the energy
system also helps to explain the relatively small impacts on GDP.
Dincer (2002) studied the hydrogen energy systems for the fuel cell. His study
covers the technical, environmental and exergetic aspects of hydrogen energy systems.
Exergy concept is introduced and two case studies are also discussed. Study suggested
that the environmental problems relating to energy should be understood widely and
ensures that the potential solutions are beneficial for the economy and energy systems.
Moreover, hydrogen is the most efficient and the safest fuel; it is one of the best
7
alternatives as the most versatile fuel. Lastly, exergy analysis is an effective method to
design more efficient energy systems by decreasing the inefficiencies in existing systems.
From the brief discussion above, in conclusion, hydrogen is a very promising

clean fuel. In this thesis, we will concentrate on comparison of hydrogen production
methods for vehicles.
2.1 Methods of Hydrogen Production

Production of hydrogen is one of the important aspect including the energy consumed and
emissions during the process. Currently, hydrogen that is produced covers only 2% of the
world energy demand (Gupta 2009). Hydrogen can be produced from a diversity of
energy resources such as fossil, renewable and nuclear using a variety technology which
are discussed below.
2.2 Fossil Fuel Hydrogen Production

Hydrogen can be produced from the fossil fuels by steam reforming and coal gasification.
About more than 90% of hydrogen is produced from fossil fuels and steam reforming is
the most common method (Ozbilen et al. 2011). In steam reforming of natural gas, three
steps are involved for hydrogen production. Methane is first cleaned from impurities then
mixed with steam and passed over an externally heated reactor at high temperature,
where carbon monoxide (CO) and hydrogen (H2) are produced. After this step, additional
hydrogen can be generated through a water-gas shift reaction by which carbon monoxide
and water is converted to hydrogen and carbon dioxide (CO2). Finally, the hydrogen gas
is then purified for use. Following is the chemical reaction for steam methane reforming
and water gas shift reaction, respectively.
CH4 + H2O → CO + 3H2 (2.1)
CO + H2O → CO2 + H2 (2.2)
Acar and Dincer et al. (2014) compared different hydrogen production method in
order to assess their economic, social and environmental impacts. The methods
considered in their study are natural gas steam reforming, coal gasification, water
electrolysis via wind and solar energies, biomass gasification, thermochemical water
8
splitting with a Cu-Cl and S-I cycles, and high temperature electrolysis. Environmental
impacts such as global warming potential and acidification potential, and production
costs, energy and exergy efficiencies of these eight methods are compared. Results
indicated that biomass gasification has the lowest hydrogen production cost ($/kg).
Natural gas steam reforming and coal gasification have lower costs than the rest of the
methods as well. In terms of capital costs, it can be seen that natural gas steam reforming
has lower costs than coal and biomass gasification.
Cormos (2011) analysed innovative processes for producing hydrogen from fossil
fuels conversion (natural gas, coal, lignite) using chemical looping technique. The
assessment carried out to generate hydrogen from the potential applications of natural gas
and syngas chemical looping combustion. Plant which has been investigated produce 500
MW hydrogen (based on lower heating value) by covering all ancillary power
consumptions.
Coal gasification is another major process of hydrogen production after steam

reforming of natural gas. More than 18% of hydrogen is generated by coal (Kalamaras et
al., 2013). Coal gasification comprises three principal steps. First, the conversion of coal
feedstock with steam to form a syngas and then catalytic shift conversion takes place, and
lastly, purification of final product. Initially, coal is chemically reacted with high
temperature and high pressure steam which has a temperature of approximately 1330ºC to
produce raw synthesis gas. After syngas production, the syngas passes through a shift
reactor to convert a portion of the carbon monoxide to carbon dioxide. Finally, in third
step, the hydrogen product is purified (Cohce, 2010).Coal gasification process need
gasifier and O2 for the reaction process which makes this process more expensive than
natural gas reforming (Cohce et al., 2011).
Huang et al. (2014) conducted the parametric study and assessment of coal
gasification plant for hydrogen production. The purpose of study is to show the best
steam to carbon ratio that produces the maximum system performance of an integrated
gasifier for hydrogen production. Moreover, study focuses on the energy and exergy
efficiency of the system and hydrogen production. When steam to carbon ratio feed in the
gasifier is increased, the improvement can be seen in the energy and exergy efficiency of
9
the IGHP system. The maximum efficiency is reached with a SC of 0.9 with an energy
and exergy efficiency of 53.8% and 44.8% respectively. Hydrogen production rate is at
its highest at 0.61 kg/s at the same SC value. The study also concluded that the coal
gasification is a very clean method of utilizing coal to meet their energy demands. The
process has amount of pollution compared to coal combustion. Furthermore, in this
technology the syngas can be used immediately in gas turbines, or it can be processed
into hydrogen and stored for later use.
Nirmal et al. (2010) compared the energy and exergy efficiencies of an integrated
coal-gasification combined-cycle power generation system with that of coal gasification-
based hydrogen production system which uses water-gas shift and membrane reactors.
The syngas is used to generate electricity and produce hydrogen and assessed for two
coal gasification-based energy systems. The system which is used to produce hydrogen
from syngas offers 35% higher energy and 17% higher exergy efficiencies than the
syngas-to-electricity (IGCC) system. As far as emission is concerned, specific carbon
dioxide emission from the hydrogen system was 5% lower than IGCC system. Moreover,
electrical power consumption for the IGCC system in order to compress the exhaust gases
to store CO2 is above 70% which is only 4.5% for the H2 system. To conclude, syngas-to-
hydrogen system is advantageous over IGCC system in terms of power consumption,
efficiency and emissions.
Rosen (1996) thermodynamically compared different hydrogen production

methods. The comparison is based on the energy and exergy analyses of processes which
are hydrocarbon-based such as steam methane reforming and coal gasification, non-
hydrocarbon-based and integrated SMR linked to the non-hydrocarbon based. Analysis is
performed using Aspen Plus software and result show the wide range efficiency variation.
Energy efficiency varied from 21 to 86% whereas exergy efficiency changes from 19 to
83% for the processes considered. However, most of the time the energy and exergy
efficiencies are similar because of the similarity in the magnitude of the input energy and
exergy and product energy and exergy.
10
2.3 Renewable Hydrogen Production
Hydrogen can also be produced from non-conventional renewable sources such as solar,
geothermal, biomass and wind. Renewable based hydrogen production has the advantage
of being environmentally friendly with zero or minimum greenhouse gas emissions.
Hydrogen is not available as a separate element. It is obtain from a number of sources
such as hydrocarbon, biomass, water and other chemical elements with hydrogen.
Therefore, energy is required to extract hydrogen from above mentioned sources. Dincer
et al. (2013) categorized four forms of energy: thermal, electrical, photonic and
biochemical which drive hydrogen production process. These four forms of energy can be
obtained from renewable sources that can be used to fascinate the primary energy
demands for environmentally benign hydrogen production.
2.3.1 Solar Based Hydrogen Production

Solar energy is widely used in power generation, heating and other useful products
around the world. Suleman et al. (2014) utilized solar energy in the development of
multigeneration system and in integrated solar heat pump system. Solar based hydrogen
production is one of the method by which greenhouse gases can be minimized. However,
solar photovoltaic is not a cost effective hydrogen production method as the PV
technology is costly (Joshi et al., 2009). The technology which is currently used for
hydrogen from photovoltaic electrolysis has cost about 25 times higher than that of fossil
fuel replacements. But the cost is expected to decrease due to improvement in the
photovoltaic cell. Furthermore, the factor is estimated to go down to 6 (Dell et al., 2009).
Various solar hydrogen production systems are available such as solar Photovoltaic, solar
photo electrochemical, solar photo biological and concentrated solar thermal. Under each
systems mentioned above have different processes to harvest hydrogen from water and
other chemical containing hydrogen.
Joshi et al. (2011) performed a comparative performance assessment study of

solar thermal and photovoltaic (PV) hydrogen production method. Numerous categories
of solar hydrogen production systems are studied for their performance based on energy
and exergy analysis and sustainability index. Solar thermal hydrogen production by
electricity production appears to be environmentally benign method and has greater
11
efficiency than PV hydrogen production. However, the PV hydrogen production is better
because it does not involve any moving parts. Moreover, the exergy efficiency of PV
panel alters with the concentration of solar radiation and ambient temperature which
causes lower exergy efficiency of PV hydrogen production. Proper design improvements
and use of particular technologies may increase the exergy efficiency of the system.
Ganovskii et al. (2007) used exergetic life cycle assessment on hydrogen

production from renewables such as solar and wind to evaluate exergy and economic
efficiencies and environmental impacts. Furthermore, fossil fuel technologies for
producing hydrogen from natural gas and gasoline from crude oil are compared with
options using renewable energy. Solar energy considered here comprises two main
systems: a solar photovoltaic system that produces electricity which in turn drives a water
electrolysis division to produce hydrogen. Solar energy is converted into direct current
electricity by photovoltaic elements, which is transformed by inverters to alternating
current (ac) electricity and transmitted to the power grid. The 1.231-kW photovoltaic
system combined with water electrolysis can produce 807.3 J s-1 of hydrogen exergy,
when the efficiency of electrolysis and transmission loses have considered.
Steinfeld (2005) reviewed different solar thermochemical production of hydrogen.

He divided three pathways to produce hydrogen from solar energy which are
electrochemical, photochemical and thermochemical. In thermochemical hydrogen
production, water is decomposed into hydrogen and oxygen through arrangements of
thermal driven chemical reactions. In solar thermochemical hydrogen production,
concentrated solar radiation is the energy source of high-temperature process heat for
driving an endothermic chemical reaction. Five thermochemical ways for solar hydrogen
production are illustrated in Figure 2.2.
Zheng et al. (2010) studied the progress in alkaline water electrolysis for
hydrogen production using solar energy. Study found that alkaline water electrolysis
combined with renewable solar energy can be combined into the distributed energy
system by generating hydrogen for end use and as an energy storage media. Although,
alkaline water electrolysis is less efficient, have issues in safety and durability. It is
simple in contrast to the other major methods for hydrogen production. A basic water
12
electrolysis setup is illustrated in Figure 2.3 which has an anode, cathode, power supply
and an electrolyte.
Figure 2.2: Five thermochemical routes for the production of solar hydrogen (Modified from
Steinfeld, 2005)
Figure 2.3: A schematic illustration of a basic water electrolysis system (Modified from Zheng et
al., 2010)
13
2.3.2 Wind Based Hydrogen production
Hydrogen generation from wind is also a decent option in terms of harnessing energy
from renewable source. Electricity produced by wind turbines can be used for electrolysis
for hydrogen production process. This method has the maximum potential of producing
hydrogen with minimum pollution among renewable sources (Acar and Dincer, 2014).
Wind energy technology is commercially available to provide electricity for the
electrolysis of hydrogen production. However, the production of hydrogen through
electrolysis from wind energy is not currently cost-competitive because of the cost of
wind turbines and electrolysers which make high electricity cost relative to grid
electricity.
Olateju et al. (2011) developed a detail data-intensive techno-economic model for

assessment of hydrogen production in western Canada from wind energy through the
electrolysis of water. This projected hydrogen plant is based on a current wind turbine
unit of size 1.8 MW and has a multiple function of electricity generation and hydrogen
production. During the constant flow rate electrolysers the best optimal size is found to be
240 kW (50 Nm3 H2/h) and for variable flow rate it is 360 kW (90 Nm3 H2/h). The
hydrogen production price from their study is calculated as $10.15/kg H2 and $7.55/kg
H2, respectively. As far emission is concern, emitted CO2 is found per kg of H2 is 6.35 kg
together with delivery to upgrader. Furthermore, the system produced oxygen can be
utilized commercially to reduce production price.
Akyuz et al. (2012) investigated the performance of hydrogen production from a

hybrid wind-PV system. The proposed hybrid system consisted of 10 kW wind and 1 kW
PV arrangement which is built to meet the load demand renewable energy sources. In
their study, the wind statistics of the selected region are analyzed for sizing of the
renewable energy system and performance is examined in terms of energy efficiency and
H2 production capacity. The results stated that from the month of April to July, the
average range of state of charge varies between 56.6% and 88.3%. The maximum amount
of hydrogen production is about 14.4 kg in the month of July provided by excess
electricity because of high wind speed and solar radiations. Moreover, they found out the
14
energy efficiency of the electrolyser is varying between 64% and 70% and overall energy
efficiency of wind electrolyser system varies between 5% and 14%.
Granovskii et al. (2007) studied the greenhouse gas emissions by introducing

wind and solar energies for hydrogen and electricity production. They addressed the
economic aspects of using renewable energies in place of fossil fuels to reduced
greenhouse gas emissions. Although, there are greenhouse gas emissions from renewable
technologies and are associated mainly with plant construction and the magnitudes are
considerably lower. Results showed that the prospects are good for producing clean fuel
“Hydrogen” through water electrolysis lead by renewable electricity. However, the cost
of electricity from solar and wind is higher than natural gas power plant. Their analysis
indicated that when electricity from renewable sources replaces electricity from natural
gas, the declination in the cost of greenhouse gas emissions is about four times less than
if hydrogen from renewable sources replaces hydrogen produced from natural gas.
Similarly when renewable based hydrogen is used in a fuel cell vehicle, the cost of
greenhouse gas emissions reduction tends the same value as for renewable based
electricity only if the fuel cell vehicle efficiency exceeds considerably by about two times
that of an IC engine vehicle.
2.3.3 Geothermal Based Hydrogen Production

Geothermal based hydrogen production uses geothermal energy source for hydrogen
production which is seen as an environmentally available and sustainable alternative
especially for the countries having abundant geothermal energy resources. The
technologies of hydrogen production can be combined with geothermal sources which
will help to grow hydrogen economy faster (Maack et al., 2006).
Balta et al. (2010) examined low temperature thermochemical and hybrid cycles for
hydrogen production based on geothermal energy source out of four potential methods
for hydrogen production. They are: by using steam directly from geothermal, through
conventional water electrolysis using the electricity generated from geothermal power
plant, by using both geothermal heat and electricity for high temperature steam
electrolysis and/or hybrid processes and by using the heat available from geothermal
resource in thermochemical processes to disassociate water into hydrogen and oxygen.
15
Moreover, they compared three types of industrial electrolysis for hydrogen production
with the thermochemical hybrid cycles. The findings of their study are listed as follows:
• Comparing among different thermochemical cycles, the Cu–Cl cycle acts to be

the most capable low temperature cycle to produce hydrogen efficiently.
• The energy and exergy efficiencies vary between 26% and 51%and 33% and
65%, respectively, for the Cu–Cl cycle. The energetic and exergetic renewability
ratios of Cu–Cl are obtained as 0.36 and 0.45, respectively.
• Hydrogen production from geothermal requires more research and development
on the implementation this technology cost effectively and efficiently.
Yilmaz et al. (2012) considered seven models for the production and liquefaction
of hydrogen by geothermal energy using electrolysis and high temperature steam
electrolysis. The study emphasis the development of the economic analysis methodology
and it is estimated the cost of hydrogen production and liquefaction ranges between 0.979
$/kg H2 and 2.615 $/kg H2 at a geothermal water temperature of 200 ◦C depending on the
model. Moreover, the outcome of geothermal water temperature on the cost of hydrogen
production and liquefaction is also investigated and results show the increase in the
geothermal water temperature decreases in the cost of hydrogen production and
liquefaction.
Balta et al. (2010) analysed the new four-step copper chlorine cycle for
geothermal based hydrogen. The system inspected through energy and exergy
methodology and parametric study was also implemented to investigate how individual
step of the cycle and its overall cycle performance are affected by reference environment
temperatures, reaction temperatures along with energy efficiency of the geothermal
power plant itself. The conducted study showed that the overall energy and exergy
efficiencies of the Cu-Cl cycle are found to be 21.67% and 19.35%, respectively while
the variation of energy efficiency is from 15.8% to 19.35% and exergitically it is from
16.8% to 20.5%. Furthermore, the implementation of geothermal energy through hybrid
or thermochemical cycles for green hydrogen production appears to be an eco-friendly
and sustainable option for the countries having abundant geothermal energy resources.
16
2.3.4 Biomass based Hydrogen production
Biomass based hydrogen production is a complex process and currently this process is
unable to produce hydrogen on large scale (Canan et al. 2014). Several biomaterials such
as wood waste, forestry, and agricultural remains, municipal and animal waste, and/or
crops can be used as biomass for hydrogen formation. Biomass can be converting into
useful forms of energy products by different procedure. The most approving
thermochemical conversion processes for utilizing renewable biomass energy are
pyrolysis and gasification of the waste materials (Ozbilen 2010).
Yildiz et al. (2012) performed the life cycle assessment of biomass based
hydrogen production and applied LCA analysis from the period biomass production to
the use of the produced hydrogen in Proton Exchange Membrane (PEM) fuel cell
vehicles. Two gasification system were compared through LCA and greenhouse gas
emissions are calculated. The study showed that the most energy is consumed by the
hydrogen transportation step in the DG. All values are adjusted for 1 MJ/s hydrogen
production for the comparison of two gasification system. Fossil energy consumption rate
and emissions are determined as 0.088 MJ/s and 0.175 MJ/s, and 6.27 CO2-eq. g/s and
17.13 CO2-eq. g/s for the DG and CFBG, respectively.
Jiang et al. (2013) produced hydrogen from integrated system derived from
biomass syngas by using membrane reactor. They utilized biomass efficiently by first
gasified it into syngas then processed in a water gas shift (WGS) reactor to further
enhance its hydrogen content. A single CMS membrane was used for the in situ hydrogen
separation and syngas cleanup. The process showed several advantages over traditional
reactor system such as more CO conversion and purity of hydrogen. However, reaction
took place in the presence of common impurities such as H2S, NH3 and organic vapor and
able to produce impurity free hydrogen. To conclude, the proposed system is a
multifunctional system which involves WGS reaction, the separation of hydrogen product
and the removal of syngas impurities into a single step and biomass derived hydrogen
production results in an energy saving process.
17
2.4 Nuclear Based Hydrogen Production
Nuclear energy is attractive source of energy for hydrogen production because of many
reasons defines by Dincer (2012) such as it has minimum emissions of greenhouse gases
as compared with conventional fossil fuel combustion and nuclear energy is adaptable to
large-scale hydrogen production. Thermochemical water splitting and high temperature
electrolysis are two common method of producing hydrogen using nuclear energy.
Marcus et al. (2002) defined thermochemical water splitting cycles that operates at a
temperature of 500◦C using nuclear reactors. Naterer et al. (2013) predicted five general
methods to generate hydrogen from nuclear energy through water decomposition
radiolysis, electrolysis, high temperature steam electrolysis, hybrid thermochemical water
splitting, and thermochemical water splitting.
Ozbilen (2010) assessed nuclear energy for the production of hydrogen using
copper-chlorine cycle. The life cycle methodology was implemented to explore the
environmental impacts of nuclear based hydrogen. Initially, LCA implemented on the
three-, four-, five-step Cu-Cl cycle for four different scenarios and different impact
categories are presented on the basis of four scenario. Results showed that the global
warming potential will decrease 15.8 kg to 0.56 kg CO2-eq, if electrical energy from
nuclear plant is used for all process of hydrogen production. Parametric study suggested
that the increase in plant hydrogen production capacity and lifetime does not have
substantial effects on impact categories per kg hydrogen production if the production
capacities and plant lifetimes are sufficient. Moreover, the nuclear-based sulphur-iodine
cycle and four steps Cu-Cl are the best environmentally benign hydrogen production in
terms of acidification potential and global warming potential. For the sulphur iodine
cycle, the global warming potential is 0.412 kg CO2 equivalent and for the four-step Cu-
Cl cycles it is found to be 0.559 kg CO2 -eq.
Ryland et al. (2007) investigated the technical issues and economics of hydrogen
production by integrating a steam electrolysis system with the advanced CANDU Reactor
ACR-1000 in Canada. Result proved that it is feasible to generate hydrogen by using
nuclear reactor energy and the reactor provides both thermal and electrical energy to the
steam electrolysis process. Moreover, about 15% of the steam produced by the reactor
18
would be diverted to provide thermal energy to the HTE plant. Lastly, the larger
production of the hydrogen from the plant would require more thermal energy from the
reactor, thus reducing the electrical output of the plant and would produce 275000 Nm3 h-
1
of hydrogen.
2.5 Life Cycle Assessment

Numerous studies on life cycle assessment of different hydrogen production method have
been reported by many researchers. However, the comparison between different
hydrogen production technologies through LCA is not carefully considered. Cetinkaya et
al. (2012) reported comprehensive life cycle assessment (LCA) for five methods of
hydrogen production, which are steam reforming of natural gas, coal gasification, water
electrolysis via wind and solar electrolysis, and thermochemical water splitting with a
Cu-Cl cycle. Each method is measured and compared in terms of carbon dioxide
equivalent emissions and energy equivalents. Moreover, global warming potentials are
quantified for each method. Results show that the hydrogen production capacities of wind
turbines and PVs are comparatively less than the other methods such as, in coal
gasification the production capacity is 20,000 times the wind power production in their
study but wind electrolysis is the most environmentally benign method followed by solar
PV power.
Ozbilen et al. (2012) applied the exergetic life cycle assessment on hydrogen
production method. They examined the environmental impacts of a nuclear-based
hydrogen production via thermochemical water splitting using a copper chlorine cycle.
The parametric studies demonstrate that the effect of plant lifetime on environment per kg
hydrogen production diminishes at large-scale production capacities. Exergetic life cycle
results of their study are summarized below:
• The uranium processing is the main contributor of life cycle irreversibility of

nuclear-based hydrogen production, for which the exergy efficiency is 26.7% and
the exergy destruction is 2916.3 MJ.
• The plant capacity of 125,000 kg H2/day has the lowest global warming potential
per MJ exergy of hydrogen which is 5.65 g CO2 – eq.
19
• The lowest GWP per MJ exergy of hydrogen is 5.65 g CO2-eq, for a plant capacity
of 125,000 kg H2/day. Similarly, the equivalent CO2 for the plant capacity of
62,500 kg H2/day is about 5.75 g.
• The results also suggested that if 98% of exergy is obtained then GWP can be
reduced to as low as 5.4 g CO2-eq per MJ exergy of hydrogen. Similarly,
acidification potential can also be reduced from the value of 0.041 to 0.027 g SO2-
eq per MJ exergy of hydrogen, when the exergy efficiency is increased from 67%
to 98%.
Hajjaji et al. (2013) conducted the comparative life cycle assessment of eight
hydrogen production scenarios. The comparison analysed the sustainability performance
of different options in the production of H2 and focuses on the key factor of every
alternatives. The assessment is carried out by using impact assessment method such as
the CML baseline 2000 and the Eco-indicator 99 through the SimaPro 7.1 package. The
results indicated that the biomethane reforming systems have the lowest impact which is
0.41 pt. compare to other systems. The natural gas reforming method is not suitable in
terms of environmental pollution because it has the highest emissions of global warming
gas and has the greatest contribution to the abiotic depletion potential impact. However,
bio-ethanol which is considered to be a biofuel (wheat derived), hydrogen production
from bio-ethanol systems have a higher impact on environment than fossil CH4 on
acidification, eutrophication, ozone layer depletion and toxicological impacts. Bio-
ethanol uses excessive fertilizer and machinery, where large amount of energy is
consumed for reforming.
Koroneos et al. (2004) examined the life cycle assessment of hydrogen fuel
production processes in order to investigate the environmental aspects of hydrogen
production. The advantages and possible drawbacks of the competing hydrogen
production systems are reported which reveals that the large amount of environmental
problems result from the operation of the different hydrogen production methods.
Production from natural gas steam reforming and production from renewable sources are
analysed and compared. Results explained that the use of photovoltaic energy has the
worst environmental performance than all the other technologies due to low overall
efficiency of the photovoltaic system. However, the use of solar, wind and hydropower
20
energy routes are proved to be the most environmentally friendly because of low
equivalent emissions. Steam reforming of natural gas has the high equivalent emissions
and losses of CO2 and SO2 to the atmosphere during production and distribution which
have the major negative impact and global warming potential of the system.
21
Background
In this chapter, the background information of various hydrogen production methods is

presented. The basic option in each method is described and discussed in order to provide
an insight of different technologies. Moreover, the comparisons of various methods are
made and the possible environmental issues involved with each method are also
discussed.
3.1 Hydrogen Production Methods

Hydrogen can be generated by using diverse resources and technologies. The resources
used by different methods are fossil fuel, nuclear and renewable sources. Each source has
certain benefits and limitations. Fossil fuels are widely used all over the world in the
production of hydrogen which is also responsible for greenhouse gas emissions and other
pollution. Nuclear and renewable sources are suitable for hydrogen production in terms of
clean energy but the technology needs improvement and modification in order to reduce
cost and increase efficiency.
3.1.1 Natural Gas Steam Reforming

About, half of the hydrogen produced in the world is obtained by steam reforming of
natural gas. By this method the natural gas, methane, reacts with high temperature steam
in a catalytic converter. The process needs a nickel catalyst and temperature requirement
of above 1000 K (Brown, 2001). The steam methane reaction generates carbon monoxide
and hydrogen. The reaction is endothermic and heat is supplied externally by burning fuel
outside the reactor tube. Water gas shift reactions under high and low temperature
convert the carbon monoxide to carbon dioxide and produce additional hydrogen.
Hydrogen production is normally 72% to 85% efficient in natural-gas reformers; the
remaining is heat that may also be reusable (Tupper, 2002). The following chemical
reactions are used in the steam reforming process of methane:

3 (3.1)
The water gas shift reaction then allows water to react with carbon monoxide to produce
more hydrogen as
22
→ (3.2)
Heat H2O Heat H2O
Natural gas CH4
CH4 CO + 3H2 CO2 + 4H2 4H2 (Pure)
Pretreatment Reforming Water shift Purification
Gas impurities Heat CO2 & other impurities
Figure 3.1: Steam methane reforming block flow process (Modified from Richa et al., 2008).
3.1.2 Coal Gasification

Coal gasification is another possible technology for the production of hydrogen. In this
process coal converted from a solid to a gas and resulting gas is very similar to natural
gas which can be used to create different fertilizer, chemicals, and/or electric power. In
coal gasification coal is broken down into its basic constituents. Coal is oxidized within
the gasifier in the presence of oxygen and steam and is combined to produce synthesis
gas. The gas composition leaving the gasifier comprises 29 vol% H2, 60 vol% CO, 10
vol% CO2 and 1 vol% inert (Agnieszka, 2003).
In order to produce hydrogen, this synthesis gas is further processed using water-
gas shift reactor technology to increase hydrogen and convert carbon monoxide to carbon
dioxide. The clean gas is then sent to a separation system to recover the hydrogen
(Cormos et al., 2008)
Steam Oxygen Steam
Gasification Shift Reaction

C + 1/2O2 → CO + Heat Purification
Coal H2
C + H2O → CO + H2 CO + H2O → CO2 +H2
Ash Residue
Figure 3.2: Typical high temperature coal gasification process (Modified from Casper, 1978).
23
Sulfur
Syngas
Shift
Reaction
Desulfurization
Air N2
Raw Gas
Air Gasification
Separation Gas Purification
CO2 H2
Feed Steam Products
Figure 3.3: Block diagram of hydrogen production by partial oxidation (Modified from Steinberg
et al., 1989).
3.1.3 Partial Oxidation

Partial oxidation of hydrocarbons is another hydrogen production method. It is an
exothermic reaction with oxygen and steam at moderately high pressure with or without a
catalyst. In this process, heavy hydrocarbons are converted by superheated steam and
oxygen to a mixture of H2, CO, and CO2. This process also requires water gas shift
reaction to increase the H2 amount like in steam methane reforming. In catalytic partial
oxidation, methane to naphtha can be used and the reaction takes place at 590◦C. On the
other side, the non-catalytic partial oxidation occurs at a temperature range of 1150◦C to
1315◦C and uses methane, heavy oil and coal as feedstock. The usual composition of the
synthesis gas leaving a partial oxidation reactor is H2 46 vol%, CO 46 vol%, CO2 6 vol%,
CH4 1 vol%, and N2 1 vol% (Goswami et al. 2003). The following is the basic reaction
for partial oxidation of heavier hydrocarbon (Richa et al., 2004):
2CnHm + H2O + 23/2O2 → nCO + nCO2 + (m+1) H2 (3.4)
24
3.1.4 Electrolysis
Water electrolysis was first proposed by Michael Faraday in 1820 and today it is one of
the industrial hydrogen production processes which does not depend on fossil energy.
Electrolysis is a method of splitting chemically bonded elements and compounds by
passing an electric current through them. Water electrolysis also called solid oxide steam
electrolysis is a method in which water is separated into oxygen and hydrogen by passing
an electric current. The electrolysis process requires the implementation of a diaphragm
or separator to avoid the recombination of the hydrogen and the oxygen generated at the
electrodes (Alferedo et al., 2012). So the two electrodes separated by an ion conducting
electrolyte and two partial reactions take place at these two electrodes. Hydrogen is
produced at the cathode and oxygen is produced at the anode and the processes are
represented by the following reactions:
Cathode: 4H2O + 4 → 2H2 + 4OH (3.5)
Anode: 4OH → O2 + 2H2O + 4 (3.6)
Net: 2H2O → 2H2 + O2 (3.7)
The process system involves a water purification plant, an electrolyzer section,

gas separation, power transformer regulator, rectifiers, compressor system and the
process efficiency ranges from 85 to 95% (Theodore, 2008). Here, the efficiency is the
fraction of electrical energy used which is actually contained within the hydrogen. Some
of the electrical energy is converted to heat, a useless by-product. About 4% of hydrogen
gas produced worldwide is produced by electrolysis (Emmanuel et al., 2004). Electrolysis
is considered as one of the cleanest method to produce hydrogen, when the required
electricity is derived from renewable energy sources such as solar, geothermal and wind.
Photo-electrolysis is another method, in which the photovoltaic cells act as electrodes that
decompose water into hydrogen and oxygen gas. These methods of producing hydrogen
are favourable to reducing the environmental impact and can be stored as hydrogen
energy and used as fuel for vehicle or converted to electricity in fuel cells.
25
3.1.5 Thermochemical Water Splitting
In thermochemical hydrogen production, water is decomposed into hydrogen and oxygen
with the help of heat driven chemical reactions. When water and heat energy is given to
the system, only hydrogen, oxygen, and waste heat are generated. In solar
thermochemical hydrogen production, concentrated solar radiation is the energy source of
high-temperature process heat for driving an endothermic chemical reaction. Almost 200
thermochemical cycles are available in the literature and these cycles are composed of a
series of reactions which can help to attain to break water at lower temperatures as the
temperature requirement for splitting of water directly into hydrogen and oxygen is too
high to be practical (Serban et al, 2009). Due to economic reasons, not all the
thermochemical cycles have proceeded towards experimental demonstrations. Cycles
such as sulphur-iodine (S-I), copper-chlorine (Cu-Cl), cerium-chlorine (Ce-Cl), iron-
chlorine (Fe-Cl), magnesium-iodine (Mg-I), vanadium-chlorine (V-Cl), copper-sulfate
(Cu-SO4) and hybrid chlorine are commercially recognized after considering numerous
factors like availability and abundance of materials, simplicity, chemical viability,
thermodynamic feasibility and safety issues (Naterer et al., 2008)
Sulfur–iodine and copper–chlorine water splitting cycles are the most promising
methods of thermochemical hydrogen production. In the S–I and Cu–Cl cycles, heat is
the energy input for splitting water to produce hydrogen rather than electricity. Moreover,
both cycles have different requirements of heat quantity and source of heat flow and also
different thermal efficiencies. There are different types of S-I cycles but the following
three steps for thermal decomposition of water is common on most of the cycles (Wang et
al. 2010)
Table 3.1: Common thermochemical decomposition steps in S-I cycles.
Steps Reactions Temperature (K)

Hydrolysis I2 (l +g) + SO2 (g) + 2H2O (g) → 2HI ( g) +H2SO4 (l) (exothermic) 393
Oxygen Production H2SO4 (g) → SO2 (g) + H2O (g) + 0.5O2 (g) (endothermic) 1123
Hydrogen Production 2HI (g) → I2 (g) + H2 (g) (endothermic) 723
26
Similarly, there are also several types of the Cu–Cl cycle with various numbers of
steps from 2 to 5 depending on reaction conditions (Lewis et al., 2008). The cycle which
involves five main steps in Cu-Cl are: (1) HCl (g) production using such equipment as a
fluidized bed, (2) oxygen production, (3) copper (Cu) production, (4) drying and (5)
hydrogen production.
Table 3.2: Steps and reactions in the five-step Cu-Cl cycle for thermochemical water
decomposition.
Steps Reactions Temperature (K)
H2 Production 2Cu (s) + 2HCl (g) → 2CuCl (molten) + H2 (g) (exothermic) 723
Cu Production 4CuCl (aq) → 2Cu (s) + 2CuCl2 (aq) 303-353
Drying 2CuCl2 (aq) → 2CuCl2 (s) (endothermic) 372
2CuCl2 (s) + H2O (g) → CuOCuCl2 (s) + 2HCl
Hydrolysis (endothermic) 648
(g)
Decomposition CuOCuCl2 (s) → 2CuCl (molten) + 0.5O2 (g) (endothermic) 773
(Source: Wang et al., 2010)
3.2 Life Cycle Assessment Methodology

Life cycle assessment (LCA) is a "cradle-to-grave" methodology for assessing products,
systems and processes with the identification and evaluation of the environmental
impacts associated with a product throughout its entire life cycle. The term "life cycle"
denotes the main activities in the life-span of a specified product or process. In the LCA,
the boundaries start with the gathering of raw materials from the earth to the final product
when all materials are returned to the earth. Moreover, LCA assists the estimation of the
hidden environmental impacts resulting from entire stages in a process, the impacts of
which, are not often included in more traditional analyses (e.g., raw material extraction,
material transportation, ultimate product disposal, etc.). This broad methodology provides
a more accurate image of the true environmental balances. Figure 3.5 illustrates the
general life cycle stages that are considered during analysis (Curran, 2006). Life cycle
assessment is a systematic technique that consists of four main phases which are
described by Curran (2012) and Figure 3.4 shows the phases of an LCA:
27
1. Goal and Scope Definition:
This phase define the objective, intention and application of the product, process
or activity. Moreover, it also explains the context in which the assessment is to be
made and set the boundaries and environmental effects which are going to be
reviewed for the assessment.
2. Inventory Analysis:
The second phase collects an inventory of data of relevant energy and material
inputs and environmental releases during the life cycle. This phase often takes
more time and gathering information is difficult and not always available.
3. Impact Assessment:
This phase evaluates the human and ecological impacts that are associated with
identified inputs and environmental releases.
4. Interpretation:
The final phase interprets and communicates the results of the assessment
throughout the life cycle of the processes which are under consideration. It also
classifies and understands the uncertainty and assumptions used to create the
results. Moreover, it also discussed the recommendations to reduce the
environmental impacts of products.
Goal and scope Inventory Impact

definition Analysis Assessment
Interpretation
Figure 3.4: Phases of LCA (Modified from Curran, 2012).
28
3.2 LCA and International Standard Organization
According to the International Organization for Standardization (ISO), LCA refers to the
process of compiling and evaluating the inputs, outputs and the potential environmental
impacts of a product system throughout its life cycle (ISO 14044, 2006). The ISO has
issued a series of standards and technical reports for life cycle assessment study which
are referred to as the 14040 series of reports. This series consists of the documents listed
in Table 3.3
Table 3.3: ISO Series for LCA
Number, Year Title Description

ISO 14040 This document gives a general description and framework
(1997) Principles and of LCA. It provides an overview of the practice,
Framework applications as well as limitations of LCA
ISO 14041 Goal and scope This gives the details of the procedure for goal and scope
(1998) definition and definition including system boundary and the requirements
inventory analysis for the conduct and critical review of inventory analysis.
ISO 14042 This document provides guidance on the classification and
(2000) Life Cycle Impact evaluation of the environmental impacts those results from
Assessment the inventory analysis. Moreover, it initiate to introduce
objectivity and uniformity to the impact assessment phase.
ISO 14043 This document arranges the requirements for the analysis,
Life Cycle interpretation and presentation of LCA results in relation to
(2000)
Interpretation
the set goal and scope.
It provides the requirement and guidance on the impact
ISO 14044 Requirements and assessment as well as the nature and quality of data
(2006) guidelines
collected
(Source: Curran, 2012)
3.4 Impact Assessment

The Life Cycle Impact Assessment (LCIA) involves the analysis and interpretation of the
results of inventory analysis. It is the evaluation of potential human health and
environmental impacts of the material and energy flows which are identified and released
during the life cycle inventory (LCI). It develops a link between a process and its possible
environmental impacts. Under the impact assessment, the important aspects of measuring
environmental effects becomes significant such as the increase of carbon dioxide and
other greenhouse gas emissions which have the potential to contribute to global warming.
29
Life cycle impact assessment also provides the basis for comparison. LCIA can determine
the great potential impact among the pollutant emissions whereas inventory analysis
measures the types and amounts of pollutant emissions. Processes like power generation,
fuel production and other methods which have a global concerned of environmental
release can be assessed by an LCIA. Moreover, the results of an LCIA provide a
comparison of the relative differences in potential environmental impacts for each option.
Raw Material
Inputs Acquisition Outputs
Energy Source Manufacturing

Products
Wastes
Transportation
Air Emissions
Raw Material Use, Maintenance
Recycle,
Waste Management
Figure 3.5: Inputs and outputs in LCA (Modified from Curran, 2006)
Note that the impact assessment can help decide which electricity generation
option has the greatest potential to damage nature or contribute most to global warming
(EPA, 2004). The basic structure of the impact assessment consists of the following:
1. Category Definition
2. Characterization
3. Normalization
4. Weighting
30
3.4.1 Category Definition
Category definition considers categories to be analysed which have significant impact on
the environment. These impact categories are recommended by the goal and scope of the
study. The impact categories which are normally considered are: carcinogens,
acidification, eutrophication, respiratory organics and inorganics, ozone layer, global
warming/climate change, human toxicological impacts, land use, and work environment.
Jensen et al. (1997) recommended building a relation to the characterization and study
completeness, practicality, independence excluding dependent impact categories.
3.4.2 Characterization
Characterization measure the quantity, which gives the comparative involvement of each
input and output to the selected impact categories. The substances that contribute to an
impact category are multiplied with a characterization factor that expresses the relative
contribution of the substance. For itself it can be seen as a similarity factor. Such as, the
characterization factor for CO2 in the impact category climate change can be equal to 1,
while the characterization factor of methane can be 21. This means the release of 1.0 kg
of methane causes the same amount of climate change as 21 kg CO2 (Mark et al., 2010).
3.4.3 Normalization
Several methods allow the impact category indicator results to be compared by a
reference or normal value. This means the impact category is expressing potential
impacts in ways that can be compared such as comparing the global warming impact of
CO2 and methane for two alternative options. The reference may be chosen without
restrictions, but sometime it is the average yearly environmental load in a country or
continent, divided by the number of inhabitants is used as the reference.
3.4.4 Weighting
Weighting is a subjective process and is not essentially based on scientific facts.
Weighting highlights the most important potential impacts by assigning weights to
different impact categories based on their perceived importance or relevance.
Normalization and weighting take all environmental impacts and reduce them into a
single score.
31
3.5 Advantages of LCA
LCA can provide policy-makers with a unique technique to compare major
environmental impacts. The distinctive feature of LCA is that it incorporates all processes
and environmental emissions from the beginning of the extraction of raw materials to the
final disposal of waste products. LCA encompasses a decision between two alternatives
by determining the environmental impacts and shifting from one phase to another such as
transfer of water base emissions to soil or air emissions and without the range of LCA,
these transfers might be neglected. By performing an LCA, researchers can (Tupper,
2002):
• Identify impacts to one or more specific environmental areas of concern.

• Develop a systematic evaluation of the environmental consequences associated with a
product.
• Measure environmental releases to air, water, and land in relation to each life cycle
stage and/or major contributing process.
• Assist in classifying significant shifts in environmental impacts between life cycle
stages and environmental media.
• Measure the human and ecological effects of material consumption and
environmental releases to the local community, region, and world.
• Compare the health and ecological impacts between two or more rival
products/processes or identify the impacts of a specific product or process.
32
Systems Studied
In this study, various hydrogen production systems are studied in order to compare them
on the basis of environmental impact and efficiency. There are hundreds of methods
available for hydrogen production but we categorized them on the basis of energy sources
such as the energy from the fossil fuel source, renewable energy and the nuclear energy
sources. Figure 4.2 to Figure 4.4 show different hydrogen production approaches on the
basis of energy source and technology. This chapter presents the methods for comparison
which we have considered for hydrogen production. The LCA of hydrogen production
via steam reforming of natural gas has been done by several researchers and
organizations. However, this study will compare SMR with other methods by utilizing
renewable energy sources such as wind electricity, solar photovoltaic and nuclear energy.
This study quantifies and analyses total environmental aspects of producing hydrogen via
different sources. LCA is a “cradle to grave” approach, for this reason, energy
requirement and production for each process is examined so that total environmental
scenario and efficiencies could be presented. The general system boundaries for LCA are
shown in Figure 4.1.
Figure 4.1: System boundaries for life cycle assessment
33
Renewable
Solar 1 Solar 2 Solar 3 Solar 4 Solar 5 Solar 6 Solar 7 Solar 8 Solar 9 Solar 10
Thermal Thermal Thermal Thermal Electrical Electrical Electrical Electrical Photonic Photonic
High Photo-
Hybrid Plasma arc PV- Photo-
Thermocatalysis Thermolysis Thermochemical Electrolysis Temperature
Thermochemical decomposition electrolysis electrolysis catalysis
Electrolysis
H2O →OH+H Thermal +

H2S Cracking Water Splitting Electricity Electricity + H2O + PV Panels +
OH → H + O H2O + Photo electrodes Catalysts
with Cu-Cl, S-I, Water Splitting Electricity + Water
2H →H2 Electricity
CH4 → C +
+ electricity +photo-initiated
H2S →H2 + S Na-Cl, Na-OH with Cu-Cl, S-I, electrolyzer→H2
2H2 Heat electrons
2O →O2 Na-Cl, Na-OH
34
Hydrogen
Figure 4.2: Renewable solar based hydrogen production approaches

Renewable
Geothermal 1 Geothermal 2 Geothermal 3 Geothermal 4 Geothermal 5 Geothermal 6 Geothermal 7 Wind 1 Wind 2
Thermal Thermal Thermal Electrical Electrical Electrical Electrical Electrical Electrical
High High
Hybrid Plasma arc PV-
Thermocatalysis Thermolysis Electrolysis Temperature Electrolysis Temperature
Thermochemical decomposition electrolysis
Electrolysis Electrolysis
Thermal + H2O →OH+H

Electricity H2S Cracking OH → H + O Electricity + H2O + PV Panels + H2O +
H2O + H2O +
Water Splitting 2H →H2 CH4 → C + Electricity + Water Electricity +
with Cu-Cl, S-I, H2S →H2 + S Electricity Electricity
2H2 Heat electrolyzer→H2 Heat
Na-Cl, Na-OH 2O →O2
35
Hydrogen
Figure 4.3: Geothermal and wind based hydrogen production

Renewable Fossil Fuels Nuclear
High High High

Biomass 1 Biomass 2 Biomass 3 Natural gas Coal Temperature Temperature Temperature
Heat Heat Heat
Biochemical Thermal Thermal Thermal Thermal Electric Power Electric Power Electric Power
High
Biomass Steam Thermo- Hybrid Thermo-
Dark Fermentation Pyrolysis Gasification Temperature
Gasification Reforming chemical cycle chemical cycle
Electrolysis
Fermentative C + 1/2O2 → CO + H2O + Cu-Cl, Water + Cu-Cl,

Bio-oil+H2 O→CO + H2 Water +
Biomass + O2 → Heat S-I, Na-Cl
bacteria + CO + H2O → CO 2 + H2 CH4 + 2H2O → C + H2O → CO + H2 S-I, Na-Cl,
CO + H2 + CO2 CH 1.9O0.7 + 1.26H2O → electrolyte +Heat
Biomass → H2 + + Energy CO2 + 4H2 CO + H2O → CO2 + Na-OH electrolyte +Heat
CO 2 + 2.21H2
CO2 H2
36
Hydrogen
Figure 4.4: Fossil and nuclear based hydrogen production
4.1 Hydrogen Production from Steam Methane Reforming
The most common method of producing hydrogen is steam reforming of natural gas and
therefore this study analyzes this process first. For hydrogen production from steam
methane reforming, the method is divided into a basic subsystem which is shown in
Figure 4.5 The cycles and data used in the study are obtained from several studies in the
literature such as Spath et al. (2001, 2004), and Ray (2010). The process starts in
reforming reactor where natural gas and steam react under high temperature and pressure.
After the reaction, the products passed through high and low temperature shift reactor
where water-shift gas reaction occurred to produce more hydrogen. Finally, the
separation of hydrogen from CO2 takes place by the process called pressure swing
adsorption method. The system considered here depicts a true picture of SMR plant
except several assumptions. The energy, raw material and other basic necessities are
assumed for the production of 1 kg of hydrogen.
Flue Gas
Natural
Gas
CO2
Steam
Reforming
Reactor High Low
Hydrogen
Temperature Temperature
Purification
Shift Reactor Shift Reactor
Hydrogen
Figure 4.5: Steam methane reforming and water gas shift reaction (Modified from Spath
et al., 2001).
The calculated commodities for 1 kg of hydrogen are shown in Table 4.1. The
input values calculated on the basis of the available data such as Spath et al. (2001) which
is similar to the typical plant available at today’s major oil refineries. The considered
37
hydrogen plant which has a production capacity of 135000 kg per day and the purity of
hydrogen on industrial grade is about 99 mol% H2.
Table 4.1: Data inputs and assumption for 1 kg of hydrogen production via steam methane
reforming
Plant Inputs Values

Hydrogen Purity Industrial grade ( >99.95% mol% H2)
Natural gas requirement (methane) 3.4 kg
Steam requirement 9.4 kg
Electricity consumption 1.13 MJ
4.2 Hydrogen Production via Chlorine Electrolysis Using Different Cells

Electrolysis is another method of producing hydrogen using different chemicals. In this
system, Na-Cl and Na-OH is used for electrolysis using different cells. Hydrogen is
produced by the electrolysis of salt solution. Technologies which are mainly used are
mercury, diaphragm and membrane cell electrolysis. Each of these technologies signifies
a different method to deposit the produced hydrogen at the cathode separate from the
chlorine produced at anode. In all of the cell technologies the following basic principle is
used.
At cathode: In a diaphragm and membrane cells, water decomposes to form
hydrogen (H2) and hydroxide ions (OH-). In the mercury cell, a sodium/mercury amalgam
is formed at anode. This reacts with water in the decomposer cell at cathode to form H2
and OH-. The chemical reaction at the cathode is:
2 Na+(aq) + 2H2O(l) + 2 e- H2(g) + 2 Na+ (aq) + 2 OH- (aq) (4.1)
At anode: chlorine is formed at anode by oxidized chlorine ions and the chemical
reaction is given by:
2 Cl- (aq) Cl2 (g) + 2 e- (4.2)
4.2.1 Mercury Cell Electrolysis

A mercury cell comprises two cells: the electrolyser and the decomposer as shown in
Figure 4.6. Anodes are generally composed of graphite or titanium and a mercury cathode
which flows along the bottom of the cell. When a direct electric current flows on a salt
38
solution, chlorine is liberated at the anode while sodium dissolves into the mercury
cathode to form an amalgam. In the decomposer, the hydrogen and a 50% sodium
hydroxide solution is produced when amalgam reacts with water. The regenerated
mercury is reverted to the electrolyser and this whole process is very energy intensive.
Figure 4.6: Hydrogen production via Na-Cl electrolysis using mercury cell (Adapted from
Ecoinvent report, 2007)
4.2.2 Diaphragm Cell Electrolysis

This technology mainly developed in the U.S at the end of 19th century. It consists of a
cell with a typically asbestos diaphragm applied to an iron grid cathode which prevents
the chlorine and sodium hydroxide from mixing. Again, hydrogen is produced together
with the formation of sodium hydroxide. This method requires less energy than mercury
cell; however the sodium hydroxide solution has a concentration of only 10 to 12%.
Figure 4.7: Diaphragm cell electrolysis (Adapted from Ecoinvent Report, 2007)
39
4.2.3 Membrane Cell Electrolysis
In membrane cell electrolysis which was developed around 1970, the cell is separated
into two sections by a membrane that performance as an ion exchanger. Initially, the
ionic compartment is filled with saturated salt brine and the cathode department filled
with only water. The main advantages of membrane type electrolysis is their moderate
energy consumption which is less than the diaphragm cell, more pure sodium hydroxide
is produced in this technology as compared to the diaphragm cell and very small amount
of environmental impacts such as no Hg and asbestos emissions.
Brine is a basic chemical used in the production of hydrogen through electrolysis.

Before electrolysis, all three types of cells require few similar supplementary processes
for preparation of the brine. The preparation of the salt brine can be divided in the
following steps:
Figure 4.8: Membrane cell electrolysis (Adapted from Ecoinvent report, 2007)
Brine production: Generally fresh salt is dissolved in water or in depleted brine from
mercury or membrane process. So the basic raw material is solid salt.
Brine purification: After the brine production step brine purification is require to
remove undesirable elements from the brine that affect the electrolytic process. Different
chemicals are added to eliminate the various undesirable components specially, for the
membrane cell, a more precise purification is needed and therefore this technology has a
40
second purification step composed of a filter and a softening step using an ion exchange
unit.
Brine re-saturation: In a recirculation circuit, the brine leaving the electrolysis cell is
first de-chlorinated which is the extraction with air in case of mercury and membrane
cells, then the saturation with salt is prepared. In case that impure salt is used, the pH of
the solution is brought to an alkaline level with caustic soda which helps to reduce the
solubility of impurities. However, in order to protect the anode coating, hydrochloric acid
is added to bring the pH to an acidic value. This process sometime produces carbon
dioxide emissions in cases where carbonates are introduced into the brine as impurities of
the added salt. The process can occur in open or in closed vessels.
After the electrolysis, the final products are hydrogen, chlorine and sodium
hydroxide which are separated through several processes. Hydrogen leaves the cell with
high concentration, therefore does not require major process. It is just cooled in order to
remove moisture and other small impurities such as Na-OH, salt and Hg in case of
mercury cell.
4.3 Hydrogen Production via Wind Based Electricity

The wind energy capacity around the world has been growing at an annual rate of 28%
(Rifkin, 2002). According to the European Wind Association, wind energy can produce
about 10% of electricity around the world by 2020. The wind/electrolysis system studied
here is the same as Na-Cl electrolysis but electricity used in this system is renewable and
generated from wind turbine. In case of wind, the kinetic energy per unit mass of air in
motion is proportional to the square of its velocity. The electricity from the wind power
plant is wheeled to a hydrogen production system where the electrolyzer converts the
electricity to hydrogen. The power depends upon energy multiplied by the mass flow rate
of the air which gives the cubic relationship between the power and the wind velocity.
Figure 4.9 shows the simple wind turbine electricity flow for hydrogen production.
41
Water (H2O)
H2
O2
Electrolyser
Figure 4.9: Wind electrolysis system
An eco-invent model is used for the electrolysis system for wind generated
electricity from an 800 kW wind power plant. In the, electricity is wheeled from the wind
power plant to system where the electrolyzer converts the electricity to hydrogen. Some
electrical losses were neglected from the final electricity produced by the wind turbines.
Such as the transmission losses, electricity needed, to pump the deionized water and
finally, the power requirement for compression of the product hydrogen.
4.4 Hydrogen Production via Solar Photovoltaic Based Electricity

Solar radiation is a source for renewable energy. One possible use is the production of
electricity in photovoltaic appliances (PV) for hydrogen production. The most common
method of solar based hydrogen production uses photovoltaic cells in combination with
water electrolysis. In solar photo photovoltaic based hydrogen production, electricity
requirement is fulfilled by solar photovoltaic electricity. In this study all the inputs and
system requirements are similar as sodium chlorine electrolysis as we have used similar
system for hydrogen production but electricity is obtained from solar photovoltaic cell
instead of fossil fuel electricity from grid. PV cells are used to create electrical energy.
Photovoltaic cells convert photon energy into electrical energy. During

conversion two conditions exist inside a PV material: the striking light energy must be
sufficiently high to break a chemical bond in the material and thus create a free
electron/hole pair, and the presence of an electrical asymmetry in the form of a p–n
junction.
42
Figure 4.10: Schematic of solar photovoltaic based electricity (Dincer and Joshi, 2013)
43
Analyses
In this section, systems are analysed on the basis of LCA, energetically and exergetically.
For the life cycle analysis, only environmental impacts are considered in each process
mentioned here. For the goal and scope of the life cycle analysis, the functional unit is to
produce one kg hydrogen. So, all calculations will be based on 1 kg hydrogen production.
Moreover, some inputs and outputs data are obtained from literature for the processes.
This chapter provides the inventory data which are overall inputs and outputs of all steps.
The reference data obtain from different literature is used to calculate the basic
requirement for the processes. Environmental impacts, energy and exergy efficiencies are
calculated for the studied systems. The following assumptions are made for analyses:
• The reference environment temperature (T0) and pressure (P0) are 25°C and 1
atm, respectively.
• The processes are adiabatic.
• The analysis considers one kg of hydrogen produced per system, so all emissions
and other quantities are provided in terms of per kg of hydrogen produced.
• All processes occur at steady state.
• The natural gas is composed of methane, ethane, propane, butane, hydrogen
sulphide and other gases. Only methane gas is used in the LCA analyses.
5.1 Environmental Impacts Assessment using LCA
For the environmental impacts calculation, the LCA software, SimaPro, is used which
contains a number of impact assessment methods. In this study, the Eco-indicator 99 is
used which has the damage-oriented approach (Mark et al., 2010). Impact categories are
expressed in terms of three damage categories:
1. Damage to human health; this category is responsible for damage to human

health which is expressed as the number of year life lost and the number of years
lived disabled. The index used to evaluate is called as Disability Adjusted Life
Years (DALYs) which is also used by other international organization such as the
World Bank and World Health Organization (WHO).
44
2. Damage to ecosystem quality; this damage is responsible for destroying our
ecosystem in terms of loss of species over certain region and time. This damage is
expressed in Potentially Disappeared Fraction (PDF*m2*year) per kg of emission.
3. Damage to resources; the surplus energy required for the extractions of minerals
and fossil fuel in future. It expressed in MJ of surplus energy.
These damages are further divided to other impact categories such as emissions,
land use and resource depletion.
5.1.1 Emissions
All the emissions which come under damage to human health, damage to ecosystem and
the damage to resources are also analysed. Following are the impact categories for the
emissions:
• Carcinogens: Carcinogenic affects due to emissions of carcinogenic substances

to air, water and soil. Damage is expressed in DALY/ kg emission
• Respiratory Organics: Respiratory effects resulting from summer smog, due to
emissions of organic substances to air, causing respiratory effects. Damage is
expressed in DALY / kg emission.
• Respiratory Inorganics: Respiratory effects resulting from winter smog caused
by emissions of dust, sulphur and nitrogen oxides to air. Damage is expressed in
DALY / kg emission.
• Climate Change: Damage, expressed in DALY/kg emission, resulting from an
increase of diseases and death caused by climate change.
• Radiation: Damage expressed in DALY/kg emission, resulting from radioactive
radiation.
• Ozone layer: Damage expressed in DALY/kg emission due to increased UV
radiation as a result of emission of ozone depleting substances to air.
The effect score for ozone layer depletion is given kg as calculated by
Ozone layer depletion (kg) = (ODP (ozone depletion potential) × airborne emission
(kg)) 4
45
• Ecotoxicity: It is responsible to cause damage to ecosystem quality, as a result of
emission of ecotoxic substances to air, water and soil.
Damage is expressed for per kg of emission:
= Potentially Affected Fraction (PAF) × area × time = PAF × m2 × year
• Acidification/ Eutrophication: Damage to ecosystem quality, as a consequence

of emission of acidifying substances to air. They are produced by depositions of
inorganic substances into the water and through the air affecting the soil. The
source of the damage is due to several sulphates, nitrates and phosphates.
Damage is expressed for per kg of emission:
= Potentially Disappeared Fraction (PDF) × area × time = PDF × m2 × year
• Land Use: The impact of a land use on the environment also affects the
surrounding regional area with the local area used because the number of species
increases with area size. Damage cause by land use is expressed in Potentially
Disappeared Fraction (PDF) multiplied with the area and time span:

EQ = PDF × area × time = × ×

where Sref is the species diversity on the reference area type, Suse is the species diversity
on the converted or occupied area, A is the area in m2, and T is the time in years
5.1.3 Resource Depletion

In the extraction of resources, the best quality resources are in general extracted first and
the remaining lower quality resources are kept for future extraction. These resources will
create more problems which will be experienced by future generations, as they will have
to use more effort to extract remaining resources. This extra effort is expressed as
“surplus energy”.
• Minerals: Surplus energy per kg mineral or ore, as a result of decreasing ore

grades.
46
• Fossil Fuels: Surplus energy per extracted MJ, kg or m3 fossil fuel, as a result of
lower quality resources.
5.2 Analysis of Hydrogen Production via Steam Methane Reforming

Analysis of hydrogen production from SMR is presented here. Only methane gas is
assumed in our LCA analyses. For 1 kg of hydrogen the energy requirement from natural
gas to hydrogen plant is about 159.6 MJ (Spath et al., 2001). So the amount of methane
can be calculated as follows:
Energy in the natural gas to hydrogen plant = 159 MJ / kg of H2
For 1 kg of methane = 47.13 MJ (LHV)
The amount of methane required for 1 kg of H2 is
MJ /0
= 159.6 &' () * /47.13 &' () 1*
+ 2
&' () 1*2
= 3.4 &' () *+
The steam requirement for hydrogen plant which has a capacity of 135000 kg/day
is about 1290 ton per day.
So, the amount of steam required for 1 kg of hydrogen is

/' &'
= 1290 / 135000
456 456
&'
= 9.5 &' () 7648('9:
The electricity requirement for the hydrogen production is also fulfilled by

consuming natural gas and the impact flow diagram for 1 kg of hydrogen is shown in
Figure 4.7. The electricity requirement for assumed plant is about 153000 MJ per day, so
for 1 kg of hydrogen it is calculated as:
MJ kg
= 153000 day /135000 day
Therefore, the electricity requirement for 1 kg of hydrogen is
47
MJ
= 1.13
kg of hydrogen
The consumption of raw material inputs, energy and other chemicals for the
production 1 kg of hydrogen the environmental impacts are shown in Table 5.1. The
water consumption is divided into water gas shift reactions and steam production.
Table 5.1: Raw material inputs for the production of 1 kg of hydrogen
Inputs Amount Unit

Coal, hard (in ground) 159.2 gram
Crude oil (in ground) 16.4 gram
Iron ore (in ground) 10.3 gram
Limestone (in ground) 16 gram
Water unspecified natural origin 0.0198 m3
Water consumed in reforming and shift reactions 0.0048 m3
Water consumed in steam production 0.0141 m3
Natural gas, at production 5 m3
Electricity, production mix 0.314 kWh
Steam 8 Kg
5.2.1 Energy and Exergy Efficiencies

Energy and exergy analyses were performed on the steam methane reforming process.
The general equation for energy efficiency is defined as:
HIJKLM NI OPJ QKRSTUO

η= (5.1)
HIJKLM NIQTO OR OPJ VMVOJW
The hydrogen plant energy efficiency is defined as the total energy produced by
the hydrogen plant divided by the total energy input to the plant which is determined by
the following formula energy.
HIJKLM NI QKRSTUO PMSKRLJI

η = XYOTKYZ LYV JIJKLM[JZJUOKNUNOM (5.2)
The performance of a system is usually assessed by the thermal efficiency of the

system. The thermal efficiency of the system is based on a first-law energy balance and is
given by:
W]^+ _à^+
η\PJKWYZ = W] (5.3)
b^2 _àb^2 [ c]defge [ c]gfg
48
The exergetic efficiency of the system is given by using the same formula as for
energy efficiency but in this case the exergetic LHV value is used for hydrogen and
natural gas. Moreover, in the calculation of pump and compressor work input exergy
analysis is also applied. The exergetic efficiency of the steam methane reforming for
hydrogen production is given as follows:
W]^+ Ji_à^+
h = (5.4)
W]b^2 _àb^2 [ c]defge [ c]gfg
In SMR of natural gas to produce hydrogen, energy input considered here comes
in two forms. First is the energy content in methane gas and we have considered LHV
value for methane in our system. Second energy considered here comes in form of
electricity which is utilized to operate pumps and compressor in the plant. The hydrogen
production process begins by compressing the natural gas and pumping the inlet water to
the reformer.
For steady-state process, respective general balances for mass, energy and exergy
can be written as follows:
∑N k] l = ∑J k] J (5.5)
∑N m]l + n] = ∑J mJ] + o] (5.6)
\
∑N mp] l + ∑N q1 − s u n]N = ∑J mp] J + o] + mpSJVO (5.7)
\ t
Applying the balance equations on the pump of the water gas shift reaction, it gives
mass balance equation:
k]`+ v,NI = k]`+ v,RTO (5.8)
Energy balance equation for the pump of the of the water gas shift reaction can be
written as
k]`+ v,NI ℎ`+ v,NI + o]QTWQ = k]`+ v,RTO ℎ`+ v,RTO (5.9)
The exergy balance equation for the pump used in SMR can be written as
k]`+ v,NI p`+ v,NI + o]QTWQ = k]`+ v,RTO p`+ v,RTO + m] pSJVO,QTWQ (5.10)
49
Methane gas is utilized as source of hydrogen production and dissociate when
react with high pressure and temperature steam in reformer. The hydrogen production
process starts from compressing the natural gas to the reformer. The mass balance
equation for compressor is given as follows:
k]y`2 ,NI = k]y`2 ,RTO (5.11)
Energy balance equation for the compressor of the reformer can be written as
k]y`2 v,NI ℎy`2 ,NI + o]URWQKJVVRK = k]y`2 ,RTO ℎy`2 ,RTO (5.12)
Similarly, the exergy balance equation for the compressor of reformer can be
written as
k]y`2 ,NI py`2 ,NI + o]URWQKJVVRK = k]y`2 ,RTO py`2 ,RTO + m] pSJVO,URWQKJVVRK (5.13)
5.3 Analyses of Hydrogen Production Methods through Electrolysis

Using Different Cell
Analyses for hydrogen production through electrolysis of sodium chloride (Na-Cl) are
presented here. The material consumption for the production of 1 kg of hydrogen through
Na-Cl electrolysis is obtained from the library of SimPro and several other literatures.
Different types of salts are used in the preparation of the salt brine which is utilized
within the electrolysis cell such as vacuum crystallized salt from solution-mining, rock
salt and solar salt. Another, essential raw material used in the hydrogen production
through electrolysis is water. In the process, water is used in different unit such as in the
preparation of the brine and for keeping the water ratio in the reaction to produce sodium
hydroxide. Moreover, water is also used in the chlorine absorption unit. Water and salt
consumption in the production of 1 kg of hydrogen is shown in Table 5.2.
Table 5.2: Water and salt consumption in different cells
Resource (g/kg of H2) Mercury Cell Diaphragm cell Membrane Cell

Salt 1750 1750 1750
Water 1.9 1.9 1.9
50
In the examined method, the input values of other materials for 1 kg of hydrogen
used in the system is shown in Table 5.3. Materials consumed in the system have
particular use in the process, such as soda powder used in the precipitations of calcium
ions, barite used in the precipitation of sulphates, calcium chloride used in the
precipitation and elimination of sulphates, hydrochloric acid and sodium sulphite used in
the de-chlorination of brine, sodium hydroxide is used to remove magnesium and heavy
ions.
Table 5.3: Input values of chemical and materials used in electrolytic hydrogen production
Materials per kg of
Unit Mercury Cell Diaphragm Cell Membrane Cell
hydrogen
Sodium chloride
kg 0.9125 0.9125 0.9125
powder
Asbestos g . 0.2 -
Mercury mg 3.133 - -
Soda powder kg 0.00533 0.00533 0.00533
Barite kg 0.001625 0.001625 0.001625
Calcium chloride kg 0.00826 0.00826 0.00826
Hydrochloric acid kg 0.0116 0.0116 0.0116
Sodium sulphite g 0.1 0.1 0.1
Sodium hydroxide g 3 2 20
The energy consumption in the electrolytic hydrogen production varies with types
of cells used. Table 5.4 gives an overview of the energy demand in different electrolytic
cells.
Table 5.4: Energy consumption for the production of hydrogen in different electrolytic cells
Energy (kwh/kg of hydrogen) Mercury Cell Diaphragm cell Membrane cell

Electricity 1.65 1.38 1.29
Heat (steam) - 0.61 0.18
5.4 Analyses of Hydrogen Production through Electrolysis Using Wind

Electricity
In the analyses of hydrogen production from electrolysis by using wind power plant
electricity, all data used is similar as Na-Cl electrolysis except electrical energy. In this
analysis, fossil fuel electrical energy is now replaced by electricity which is generating
51
from renewable wind energy. In the development of wind based electricity, a wind power
plant is considered which have a capacity of 800kW. The electricity from the wind power
plant is wheeled to a hydrogen production system where the electrolyzer converts the
electricity to hydrogen. The inputs and raw material utilization in the arrangement of
wind based electricity is shown in Table 5.5
Table 5.5: Material and energy consumption in wind power plant
Material Amount Unit

Electricity, medium voltage 17500 kWh
Aluminium 207 kg
Cast iron 6480 kg
Chromium steel 14500 kg
Copper 1460 kg
Glass fibre reinforced plastic 9660 kg
Lead 0.5 kg
Lubricating oil 58.8 kg
Polyethylene, HDPE, granulate 621 kg
Polypropylene, granulate 20 kg
Polyvinylchloride, bulk polymerised 434 kg
Steel, low-alloyed 3750 kg
Synthetic rubber 100 kg
Tin, at regional storage 0.5 kg
Section bar rolling, steel 10200 kg
Sheet rolling, aluminium 207 kg
Sheet rolling, chromium steel 14400 kg
Wire drawing, copper 1460 kg

The energy analysis of wind turbine system depends on several factor such as the wind
velocity, and the area of wind turbine. The mass of air passes through the wind turbine
which causes the rotation of the blade and the conversion of kinetic energy to electrical
energy occurred. The mass of air is conserved in the wind turbine, so the mass balance
equation for the wind turbine can be written as
k]YNK,NI = k]YNK,RTO (5.14)
where
52
k]YNK = zYNK {O |] (5.15)
The energy balance equation for the wind turbine is the energy in the incoming air
stream striking the wind turbine and leaving after certain change in temperature and
velocity. The output of the wind turbine is electricity which is a function of voltage and
current. Ghosh et al. (2014) analyse the wind turbine and their energy balance on wind
turbine is given as
∆ = k] ~Q (RTO − NI ) (5.16)
The exergy balance equation of the wind turbine for hydrogen production can be
written as
\
m]i = m]LJIJKYOJS + k] ~Q (RTO − NI ) + k]YOW (~Q e − + − e ) (5.17)
\t \f
The energy efficiency of the wind turbine is the useful work output from the
turbine to the input energy to run the turbine and it can be written as
c]t t,e
JIJKLM = (5.18)
IQTO JIJKLM
where o]{NIS OTKNIJ,RTO = kYNK |] (5.19)
and k]YNK = zYNK {O |] (5.20)
Here, the area of wind turbine can be calculated by simple mathematical formula and can
be written as
+
{O =
, D is the diameter of the rotor.
The energy efficiency of the wind based hydrogen production system is the amount
of energy content in the produced hydrogen to the energy input to the system in terms of
wind electricity and sodium chloride powder which can be written as
W]^+ _à^+
`+ ,JZJUOKRZMVNV = (5.21)
H]tg
The exergy efficiency of the system of hydrogen production using renewable wind
based electricity can be written as
53
W]^+ Ji^+
h{NIS = (5.22)
H] itg
1 MJ
Electricity, at
0.0006 Pt
9.92E-9 p 4.94E-9 p
Wind power Wind power
0.000454 Pt 0.00014 Pt
0.000152 kg 1.57E-5 kg 9.58E-5 kg 0.000384 kg

Chromium Copper, at Glass fibre Steel,
0.000226 Pt 0.000114 Pt 7.66E-5 Pt 0.000104 Pt
9.58E-5 kg 5.63E-5 kg 2.66E-6 kg 0.000101 kg 0.000242 kg

Steel, Steel, Copper, Nylon 66, Steel,
0.00014 Pt 8.1E-5 Pt 6.13E-5 Pt 6.36E-5 Pt 8.31E-5 Pt
4.82E-5 kg 6.02E-5 kg 1.01E-5 kg 0.000416 kg

Ferrochromi Ferronickel, Copper Pig iron, at
9.2E-5 Pt 0.000165 Pt 5.25E-5 Pt 5.72E-5 Pt
0.00171 kg
Disposal,
7.52E-5 Pt
Figure 5.1: Impact flow diagram of wind power plant.
54
5.5 Analyses of Hydrogen Production through Electrolysis Using Solar
Photovoltaic Electricity
In the analysis of hydrogen production from electrolysis by using solar photovoltaic
electricity, all data used is similar as Na-Cl electrolysis except electrical energy. In this
analysis, fossil fuel electrical energy is now replaced by electricity which is generating
from renewable solar energy. In the development of solar based electricity, a solar power
plant is assumed to have power production of 1 kWh. The electricity from the solar
photovoltaic is brought to a hydrogen production system where the electrolyser converts
the electricity to hydrogen with other chemical reaction. The inputs and raw material
utilization in the solar based hydrogen production is shown in Table 5.6
Table 5.6: Inputs to solar photovoltaic based hydrogen production
Materials per kg of hydrogen Amount Unit

Sodium chloride, powder 0.8125 kg
Soda, powder 0.0053 kg
Barite 0.0016 kg
Calcium chloride, CaCl2 0.0083 kg
Hydrochloric acid, 30% in H2O 0.0011 kg
Sulphite 4.643E-05 kg
Sodium hydroxide, 50% in H2O 0.0195 kg
Electricity, photovoltaic 1.2940 kWh
Tap water 0.0037 kg

The energy analysis of solar photovoltaic system depends on several factor such as the
solar radiation and the area of solar panel. All the solar radiation emitted from the sun is
assumed to be incident on the panel. Since no mass exchange occurs at the boundary of
the photovoltaic panel, therefore, the input to the concentrator is fully defined by
expressing its energy and exergy equation which can be written as
m]NIUNSJIO = QYIJZ VRZYK

] (5.22)
where; m]NIUNSJIO is the energy with respect to solar radiation entering the system, QYIJZ
]
is the total effective area of the panel and VRZYK is the direct solar radiation intensity from
55
the sun which can be obtain from standard solar spectrums if the total intensity of a
location is known. The exergy equation of the solar panel can be written as
\s
m] pNIUNSJIO = m]NIUNSJIO (1 − ) (5.23)
\tdt
The energy efficiency of the solar based hydrogen production system is the
amount of energy content in the produced hydrogen to the energy input to the system in
terms of solar photovoltaic electricity. The energy efficiency of the solar based hydrogen
production can be written as:
W]^+ _à^+
`+ ,VRZYK = H]tg
(5.24)
The exergy efficiency of the solar based hydrogen production is also the amount
of exergy content in the produced hydrogen to the input exergy of the system which can
be written as:
W]^+ Ji^+
hVRZYK = (5.25)
H] itg
56
Results and Discussion
This chapter consists of the results from the analysis showed in the previous chapter. In
addition, there are some further discussions and comparisons among the systems
described. The results and discussion are divided according to the system studied. Under
each system, environmental results are discussed and then thermodynamic analyses
results are presented. The environmental results are calculated using two methods such as
the Eco-indicator 99 (H) and CML 2001. Impact categories of both methods are
considered in each hydrogen production method considered in the previous chapter.
Thermodynamic analyses results of the methods are also discussed in terms of energy and
exergy efficiencies.
6.1 Hydrogen via Steam Methane Reforming
6.1.1 Impact Assessment Results
In the analysis of the hydrogen production from steam methane reforming, the method is
divided into four sections in order to see the environmental impact of each section
through several impact categories. Figure 6.1 shows the impact flow diagram of hydrogen
production via steam methane reforming. In that flow diagram, maximum parts to the
environment are due to the utilization of natural gas. Four sections which are evaluated
here are hydrogen production, natural gas, electricity production and steam production for
the process. Table 6.1 shows the damage assessment results for producing 1 kg of
hydrogen using the Eco-indicator method. For better presentation of the result, these
numeric values are plotted as bar chart in terms of percentage. Figure 6.2 shows the chart
diagram of damage assessment of producing 1 kg of hydrogen SMR.
Table 6.1: Damage assessment for 1 kg of hydrogen via steam methane reforming
Impact category Unit Hydrogen Natural gas Electricity Steam
-9 -8 -8
Carcinogens DALY 3.50×10 1.57×10 5.56×10 5.49×10-8
-8 -8 -11
Resp. organics DALY 2.29×10 3.29×10 6.65×10 9.64×10-10
Resp. inorganics DALY 1.83×10-6 8.4×10-8 1.24×10-7 5.69×10-7
-6 -7 -8
Climate change DALY 1.73×10 6.10×10 4.95×10 4.64×10-7
Radiation DALY 0 3.27×10-10 1.46×10-9 6.76×10-10
-9 -12
Ozone layer DALY 0 3.09×10 6.56×10 2.88×10-10
Acidification PDF* m2yr 8.02×10-2 4.64×10-2 0.0004 0.0147
2 -2
Land use PDF* m yr 0 3.90×10 0.188 0.0014
Minerals MJ surplus 2.99×10-4 3.42×10-3 7.3×10-4 3.33×10-3
Fossil fuels MJ surplus 1.28×10-1 30.1 0.135 4.98
57
The hydrogen production process has maximum impact on the environment in
terms of climate change, respiratory inorganics, organics and acidification which covers
60%, 55%, 40% and 55% respectively. Natural gas utilization in the process has
maximum effect in the ozone layer which is 90% among the different sectors and about
85% in fossil fuels which has a value in the Table 6.1 of 30 MJ surplus. This surplus
energy shows that a large amount of better quality natural gas is extracted for hydrogen
production and that the rest is left for future extraction and use. Moreover, natural gas
contribution in land use, minerals and respiratory inorganics is also worthy of mention
here. The land use impact of natural gas is about 75% (3.90×10-2 PDF*m2 yr) which is
affecting local and surrounding regions. The electricity used in the process has maximum
points on radiation and carcinogenic categories which is about 60% (1.46×10-9 DALY)
and 42% (5.56×10-8) respectively, among different section of the process. In the steam
production minerals and energy are used and because of this utilization it has emissions
almost in all impact categories but carcinogens, minerals and ecotoxicity are worthy of
mention. About 75% (3.57×10-2 PDF*m2yr) of ecotoxicity is due to steam production and
about 40% for carcinogens and minerals.
Table 6.2: Weighting results for 1 kg of hydrogen via steam methane reforming
Impact Category Unit Total Hydrogen Natural gas Electricity Steam

Total Pt 1.64 1.34×10-1 1.25 1.39×10-2 2.40×10-2
Carcinogens Pt 4.44×10-3 1.20×10-4 5.39×10-3 1.90×10-3 1.88×10-3
Resp. organics Pt 1.95×10-3 7.85×10-4 1.12×10-6 2.27×10-6 3.30×10-5
Resp. inorganics Pt 0.115 6.26×10-2 2.88×10-2 4.23×10-3 1.95×10-3
Climate change Pt 9.79×10-2 5.94×10-2 2.09×10-2 1.69×10-3 1.59×10-2
Radiation Pt 8.42×10-5 0 1.12×10-5 4.99×10-5 2.31×10-5
Ozone layer Pt 1.16×10-4 0 1.06×10-4 2.25×10-7 9.85×10-6
Ecotoxicity Pt 3.04×10-3 2.69×10-7 3.457×10-3 2.01×10-4 2.49×10-3
Acidification Pt 1.02×10-2 5.60×10-3 3.24×10-3 2.80×10-4 1.03×10-5
Land use Pt 3.59×10-3 0 2.73×10-3 1.31×10-4 7.29×10-4
Minerals Pt 3.09×10-4 1.19×10-5 1.35×10-4 2.90×10-5 1.33×10-4
Fossil fuels Pt 1.40 5.10×10-3 1.19 5.36×10-3 0.198
Among all impact categories presented in damage assessment have values based
on their units and different categories. Weighting expressed these results as a single part
irrespective of their category. Figure 6.3 shows the weighting results for 1 kg of hydrogen
58
via steam methane reforming which tells that in this process major impact on
environment is due to the natural gas consumption and steam production. In terms of
impact categories, fossil fuels have maximum number of parts for natural gas which is
1.2 and for steam is about 0.2.
Table 6.3: Contribution of process to total environmental impact for steam methane reforming
(CML method)
Impact category Unit Total Hydrogen Natural gas Electricity Steam

Abiotic depletion kg Sb eq 0.130 0.0025 0.1088 0.0018 0.0179
Acidification kg SO2-eq 0.028 0.0176 0.0042 0.0018 0.0054
Eutrophication kg PO4-eq 0.003 0.0016 0.0012 0.0004 0.0004
Global warming kg CO2 eq 11.956 7.426 2.1542 0.2287 2.1474
Ozone layer kg R-11 eq 3.0×10-6 0 2.65×10-6 1.9×10 -9
3.5×10-7
Human toxicity kg 1,4-DB eq 3.2 2.675 0.033 0.0541 0.4084
The same process is also analysed by using the CML 2001 method. The CML
2001 impact categories which are abiotic depletion (AD), acidification potential (AP),
eutrophication potential (EP), global warming potential (GWP), ozone layer depletion
potential (ODP) and human toxicity potential (HP) are taken into consideration. Again,
natural gas consumed in the hydrogen production by this process has maximum
percentage in abiotic depletion of 0.1088 kg Sb eq and ozone layer depletion 2.65E-06 kg
R-11 eq. Figure 6.4 also shows that the steam consumed in the steam methane reforming
has minimum emissions in all six impact categories as followed by the electricity
consumption. Table 6.3 has the numerical values for each category along with units for
comparison.
59
1 kg
Hydrogen,
1.64 Pt
5 m3 9.5 kg
Natural gas, Steam, for
1.25 Pt 0.24 Pt
19.6 MJ 24.8 MJ 5.99 MJ

Natural gas, Natural gas, Heavy fuel
0.147 Pt 0.175 Pt 0.0648 Pt
24.8 MJ 0.156 kg
Natural gas, Heavy fuel
0.162 Pt 0.0469 Pt
0.68 m3 0.158 kg
Natural gas, Heavy fuel
0.162 Pt 0.0466 Pt
0.233 m3
Natural gas,
0.062 Pt
0.272 m3
Natural gas,
0.0598 Pt
Figure 6.1: Impact flow diagram of hydrogen production via steam methane reforming.
60
100
95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Carcinogens Resp. organics Resp. inorganics Climate change Radiation Ozone layer Ecotoxicity Acidification Land use Minerals Fossil fuels
/ Eutrophication
Hydrogen, SMR Natural gas, at production/NG U Electricity, production mix US/US U Steam, for chemical processes, at plant/RER U
Analyzing 1 kg 'Hydrogen, SMR';

Method: Eco-indicator 99 (H) V2.08 / Europe EI 99 H/H / Damage assessment
Figure 6.2: Damage assessment for 1 kg of hydrogen via steam methane reforming..
61
1.4
1.3
1.2
1.1
0.9
0.8
Pt
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
/ Eutrophication

Method: Eco-indicator 99 (H) V2.08 / Europe EI 99 H/H / Weighting
Figure 6.3: Weighting results for 1 kg of hydrogen via steam methane reforming..
62
100
95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Abiotic depletion Acidification Eutrophication Global warming 500a Ozone layer depletion Human toxicity 100a
steady state
Method: CML 2001 (all impact categories) V2.05 / World, 1990 / Characterization
Figure 6.4: Contribution of process to total environmental impact for steam methane reforming
(CML method).
63
A thermodynamic analysis of hydrogen production through steam methane reforming is
presented here. The energy efficiency for the process is calculated as 76.8% while exergy
efficiency is about 72.4%. Figure 6.5 shows the effect of changing the inlet reformer
pressure on energy and exergy efficiencies. Increasing the reformer pressure from 800
kPa to 1200 kPa, the energy efficiency decreases from 76% to 72% and exergy efficiency
decreases from 72.6% to 72.3%, because of the amount of power requirement in the
compressor to compress natural gas. A similar case is presented in Figure 6.6 where
changing the ambient temperature also decreases the energy and exergy efficiencies.
However, this decrease in efficiencies is not large as compare to pressure variation.
0.7695 0.7255
Energy
Exergy
0.725
0.769
Exergy efficiency
0.7245
Energy efficiency
0.7685
0.724
0.768
0.7235
0.7675
0.723
0.767 0.7225
800 900 1000 1100 1200
Inlet pressure of reformer [kPa]
Figure 6.5: Effect of variation of reformer pressure on energy and exergy efficiencies.
The inlet pressure of the reformer also affects the mass of hydrogen production as
well as mass of natural gas consumption. Increasing the pressure from 800 kPa to 1200
kPa, the mass of hydrogen production reduces to 0.31 kg from 0.4 kg. While mass of
methane also decreases from 1.35 kg to 1 kg which is shown in Figure 6.7. Similarly,
Figure 6.8 shows the declination of masses of hydrogen and natural gas as the ambient
temperature increases.
64
0.7683 0.7245
Energy
Exergy
0.7682
Exergy efficiency
0.7244
Energy efficiency
0.768
0.7242
0.7679
0.7241
0.7677
300 315 330 345 360
T ο [K]
Figure 6.6: Effect of varying ambient temperature on energy and exergy efficiencies.
1.35 0.38
m CH4
mH
2
1.3
0.36
mH2 [kg]
mCH4 [kg]
1.25
0.34
1.2
1.15 0.32
800 900 1000 1100 1200
Inlet pressure of reformer [kPa]
Figure 6.7: Effect of variation inlet pressure of reformer on mass of hydrogen.
65
1.26 0.346
CH4
H2
1.254
0.344
1.249
mH2 [kg]
0.342
mCH4 [kg]
1.243
0.34
1.238
1.232 0.338
1.227
0.336
290 300 310 320 330 340 350
T ο [K]
Figure 6.8: Effect of variation of ambient temperature on mass of hydrogen
Figure 6.9 shows the increase in the amount of hydrogen production with respect to
electricity and natural gas consumption. From this method of hydrogen production
natural gas is the major raw material on which hydrogen depends along with energy and
other source. With the increase in hydrogen production from 0.4 to 3 kg, there is an
increase in the consumption of natural gas from 2 to 11 kg. In SMR of natural gas large
amount of natural gas is consumed which is also shown in impact assessment results. It is
calculated and also confirmed from the past studies that 1 kg of hydrogen needs about
more than 3 kg of natural gas.
The electricity consumption also increases as amount of hydrogen production

increases. Large amount of fossil fuels are consumed in this method of hydrogen
production which has effect on the environment in terms of human health, misbalance in
ecosystem and declining the fossil fuel reserve which can be seen in the results of
environmental impact. The last parameter which affects the values of energy and exergy
efficiency is the reformer temperature. Increasing the reformer temperature from 600 to
800K, there is a minor decrease in the energy and exergy efficiency. However this
66
increase in temperature might increase the hydrogen production but this rate is not that
much as the increase in energy consumed to increase the temperature.
12 30000
Electricity m CH
4
10 25000
Electricity consumption [kJ]

8
20000
mCH4 [kg]
6
15000
4
10000
2
5000
0.4 0.8 1.2 1.6 2 2.4 2.8
mH [kg]
2
Figure 6.9: Effect of increasing hydrogen production on methane and electricity consumption.
0.7685 0.7248
Exergy Energy
0.7245
Exergy efficiency
Energy efficiency
0.768
0.7242
0.7675 0.7239
0.7236
0.767
600 650 700 750 800
Reformer Temperature [K]
Figure 6.10: Effect of variation of reformer temperature on energy and exergy efficiencies.
67
6.2 Hydrogen from Chlorine Electrolysis Using Different Cells
In the analysis of the hydrogen production from Na-Cl electrolysis, we analyse this
method using different cells used in the system. The diaphragm cell, membrane cell and
mercury cell which are commercially used in the electrolysis of Na-Cl for chlorine,
sodium hydroxide and hydrogen production. Impact assessment results are discussed for
the preparation of 1 kg of hydrogen using these three cells. Figure 6.12 to Figure 6.14
show the impact flow diagram of hydrogen production using different cells.

Implementing the life cycle assessment methodology on the hydrogen production from
electrolysis, different cells are analysed and environmental results are calculated which
are shown in Table 6.4. Bar chart diagram based on these results is presented in Figure
6.11. In this calculation results of the mercury cell are set as the benchmark and it can be
seen that all results of mercury cell is 100%. Electrolysis using the mercury cell has the
maximum percentage of emissions and energy consumption as compare to diaphragm and
membrane cell. After mercury, and diaphragm cell also effect the environment.
Moreover, in this electrolysis the energy consumption in terms of electricity is also
fulfilled by fossil sources. Damage assessment results shows that almost all impact
categories has percentage more than 80% with maximum value located with land use and
minerals.
Table 6.4: Damage assessment results for hydrogen production using different cells.
Impact category Unit Diaphragm cell Membrane cell Mercury cell

-7 -7
Carcinogens DALY 4.91×10 4.86×10 5.42×10 -7
Resp. organics DALY 2.78×10 -10 2.78×10 -10 3.12×10 -10
Resp. inorganics DALY 5.34×10 -7 5.25×10 -7 6.10×10 -7
Climate change DALY 1.96×10 -7 1.92×10 -7 2.27×10 -7
Radiation DALY 1.42×10 -8 1.37×10 -8 1.66×10 -8
Ozone layer DALY 6.39×10 -11 6.36×10 -11 7.08×10 -11
Ecotoxicity PAF*m2yr 0.042 0.042 0.046
2
Acidification PDF* m yr 0.013 0.013 0.015
2
Land use PDF* m yr 0.009 0.009 0.010
Minerals MJ surplus 0.062 0.063 0.064
68
100
95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
/ Eutrophication
Hydrogen, liquid, diaphragm cell, at plant/RER U Hydrogen, liquid, membrane cell, at plant/RER U Hydrogen, liquid, mercury cell, at plant/RER U
Comparing 1 kg 'Hydrogen, liquid, diaphragm cell, at plant/RER U', 1 kg 'Hydrogen, liquid, membrane cell, at plant/RER U' and 1 kg 'Hydrogen, liquid, mercury cell, at plant/RER U';
Figure 6.11: Damage assessment results for hydrogen production via electrolysis using
different cell.
69
After implementing weighting criteria a better picture of the impact on the
environment can be seen. In the damage assessment almost all values have similar
contribution. However, weighting results have different pictures as shown in Figure 6.15.
The major impact of this process is done by the category of fossil fuels extraction in all
types of cells. Second category which has 0.0313 parts in mercury cell, 0.269 part in the
membrane cell and 0.0273 part in the diaphragm cell.
Table 6.5: Weighting results for hydrogen production using different cell.
Impact category Unit Diaphragm cell Membrane cell Mercury cell
Total Pt 0.0766 0.0756 0.0867

Carcinogens Pt 0.0168 0.0166 0.0186
-6 -6
Resp. organics Pt 9.50×10 9.51×10 1.07×10-5
Resp. inorganics Pt 0.0183 0.0180 0.0209
Climate change Pt 0.0067 0.0066 0.0078
Radiation Pt 0.0005 0.0005 0.0006
-6 -6
Ozone layer Pt 2.19×10 2.18×10 2.42×10-6
Ecotoxicity Pt 0.0029 0.0029 0.0032
Acidification Pt 0.0009 0.0009 0.0011
Land use Pt 0.0007 0.0007 0.0007
Minerals Pt 0.0025 0.0025 0.0025
Fossil fuels Pt 0.0273 0.0269 0.0313
Table 6.6: Process contribution of environmental impact categories
Hydrogen, Hydrogen, Hydrogen,

Impact category Unit
diaphragm cell membrane cell mercury cell
Abiotic depletion kg Sb-eq 6.78×10-3 6.61×10-3 7.86×10-3
Acidification kg SO2-eq 4.60×10-3 4.50×10-3 5.30×10-3
Eutrophication kg PO4-eq 3.18×10-3 3.10×10-1 3.67×10-3
Global warming kg CO2-eq 9.09×10-1 8.87×10-1 1.05
Ozone layer kg R-11-eq 5.99×10-8 5.95×10-8 6.65×10-8
Human toxicity kg 1,4-DB-eq 4.22×10-1 4.23×10-1 4.49×10-1
The CML method results have similar results about mercury cell which has
maximum amount of damage on human health, human welfare and ecosystem.
Membrane cell has the minimum impact on the environment as compare to other two
70
cells. However, if we compare electrolytic hydrogen production method with steam
methane reforming, strong difference can be seen in all impact categories. Only
eutrophication potential have enormous amount of impact which can be compared with
steam methane reforming. Figure 6.15 shows the comparison between electrolytic
hydrogen production and steam methane reforming. The eutrophication depletion in case
of SMR is about 0.00364 kg PO4 eq. While for electrolytic hydrogen its values are
0.00367 kg PO4 eq. for mercury cell, 0.0031 kg PO4 eq. for membrane cell and 0.00318
kg PO4 eq. for diaphragm cell.
1 kg
Hydrogen,
0.0867 Pt
0.842 kg 6.77 MJ
Sodium Electricity,
0.0183 Pt 0.0669 Pt
5.33E-10 p 6.92 MJ
Chemical Electricity,
0.0164 Pt 0.066 Pt
8.76E-5 m3 0.00672 kg 6.99 MJ

Building, Facilities, Electricity,
0.00701 Pt 0.00928 Pt 0.0659 Pt
0.0163 kg 0.00113 kg 1.6 MJ 0.742 MJ 0.799 MJ

Brick, at Copper, at Electricity, Electricity, Electricity,
0.00028 Pt 0.00817 Pt 0.0121 Pt 0.00896 Pt 0.0123 Pt
0.000399 MJ 0.0241 kg 0.362 MJ

Pulverised Heavy fuel Electricity,
1.74E-6 Pt 0.00727 Pt 0.00685 Pt
0.36 kg 0.0246 kg 0.966 MJ

Lignite, at Heavy fuel Natural
0.0068 Pt 0.00727 Pt 0.00685 Pt
Figure 6.12: Flow diagram of hydrogen production via electrolysis using mercury cell.
71
1 kg
Hydrogen,
0.0766 Pt
0.84 kg 5.77 MJ
Sodium Electricity,
0.0183 Pt 0.0571 Pt
5.32E-10 p 5.9 MJ
0.0164 Pt 0.0563 Pt
8.73E-5 m3 0.00671 kg 5.96 MJ

0.00699 Pt 0.00926 Pt 0.0562 Pt
0.0162 kg 0.00111 kg 1.36 MJ 0.633 MJ 0.682 MJ

0.000279 Pt 0.00799 Pt 0.0103 Pt 0.00764 Pt 0.0105 Pt
0.0207 kg 0.000707 kg
Heavy fuel Copper
0.00624 Pt 0.00369 Pt
0.0211 kg 0.149 kg
Heavy fuel Disposal,
0.00624 Pt 0.00654 Pt
Figure 6.13: Impact flow diagram of hydrogen production using diaphragm cell.
72
1 kg
Hydrogen,
0.0867 Pt
0.842 kg 6.77 MJ
Sodium Electricity,
0.0183 Pt 0.0669 Pt
5.33E-10 p 6.92 MJ
0.0164 Pt 0.066 Pt
8.76E-5 m3 0.00672 kg 6.99 MJ

0.00701 Pt 0.00928 Pt 0.0659 Pt
0.0163 kg 0.00113 kg 1.6 MJ 0.742 MJ 0.799 MJ

0.00028 Pt 0.00817 Pt 0.0121 Pt 0.00896 Pt 0.0123 Pt
0.0241 kg
Heavy fuel
0.00727 Pt
0.0246 kg
Heavy fuel
0.00727 Pt
Figure 6.14: Impact flow diagram of hydrogen production using membrane cell.
73
30
28
26
24
22
20
18
16
m Pt
14
12
10
0
/ Eutrophication
Figure 6.15: Weighting results for hydrogen production through electrolysis using different cell.
74
100
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90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Abiotic depletion Acidification Eutrophication Global w arming 500a Ozone layer depletion 40a Human toxicity 500a
Figure 6.16: Impact assessment chart for hydrogen production through electrolysis using different cell
(CML method).
75
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95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Abiotic depletion Acidification Eutrophication Global warming 500a Ozone layer depletion 40a Human toxicity 500a
Hydrogen, liquid, diaphragm cell, at plant/RER U Hydrogen, liquid, membrane cell, at plant/RER U Hydrogen, liquid, mercury cell, at plant/RER U Hydrogen, SMR
Comparing 1 kg 'Hydrogen, liquid, diaphragm cell, at plant/RER U', 1 kg 'Hydrogen, liquid, membrane cell, at plant/RER U', 1 kg 'Hydrogen, liquid, mercury cell, at plant/RER U' and 1 kg 'Hydrogen, SMR';
Figure 6.17: Comparison of impact categories between electrolytic hydrogen production

and steam methane reforming (CML method).
76
6.3 Hydrogen via Electrolysis Using Wind Electricity
In the analyses of hydrogen production using wind electricity, the same electrolytic
process is assumed. In this case membrane cell is used instead of mercury and diaphragm
cell because it has minimum impact on the environment. Figure 6.18 shows the impact
flow diagram of hydrogen production through wind based electricity.

In the environmental assessment of hydrogen production through wind based electricity,
major chemicals and energy and waste is considered. In this manner the process will be
evaluated more carefully.
Table 6.7 shows all the major contributors in the production of 1 kg of hydrogen
through electrolysis. Figure 6.19 depicted the values of these tables in a bar chart format
which shows that the major influence on environment is due to the sodium chloride
powder and from the chemical plant. For the chemical plants the value for carcinogens
particle which are danger for human health causing cancer is 3.70×10-7 (DALY). The
chemical plant has also major effect on ecosystem and the value for ecotoxicity is about
0.038 PAF*m2yr. The third large impact category under the chemical plant is minerals
which have effect of future energy deficiency of 0.104 MJ surplus.
The second most dominant material which covered almost every impact category
is sodium chloride powder. Sodium chloride is essential components in the electrolysis
for hydrogen production. The radiation value (comes from radioactive radiation) for
sodium chloride powder is the largest area covered in the bar of radiation as shown in
Figure 6.19. Fossil fuel category for sodium chloride also contain significant amount of
impact which is about 0.128 MJ surplus of energy. Transportation is another category in
this process which also contributes emissions and other impacts on the environment. The
significant percentage values for transportation come under fossil fuels, acidification,
ozone layer and respiratory organics. The effect of transportation in fossil fuels is 0.0291
MJ surplus of energy which covers about 18% among other different process. The ozone
layer effect for transport through the truck is about 2.42×10-12 DALY and for rail transport
is about 2.79×10-14 DALY. Other process chemicals such as sodium hydroxide can be
seen in all impact categories. Sodium hydroxide is also a product of Na-Cl electrolysis for
77
hydrogen production. In this process, electricity is generated through renewable wind
power options which have less impact on environment shown in Figure 6.19.
1 kg
Hydrogen
0.0562 Pt
0.847 kg 1.35E-9 p
Sodium Chemical
0.0184 Pt 0.0415 Pt
1.16 MJ 0.00022 m3 0.017 kg

Electricity, Building, Facilities,
0.0114 Pt 0.0176 Pt 0.0235 Pt
1.22 MJ 0.00256 kg 0.0051 kg 0.000734 kg

Electricity, Copper, at Chromium Electronics
0.0116 Pt 0.0185 Pt 0.00757 Pt 0.00631 Pt
1.24 MJ 0.000432 kg 0.00322 kg 0.000104 kg

Electricity, Copper, Steel, Printed
0.0117 Pt 0.00997 Pt 0.00471 Pt 0.00549 Pt
0.00163 kg 0.00193 kg 5.18E-5 kg

Copper Ferronickel, Printed
0.00853 Pt 0.00528 Pt 0.00474 Pt
0.352 kg
Disposal,
0.0154 Pt
Figure 6.18: Impact flow diagram of hydrogen production via wind based electricity.
78
Table 6.7a: Damage assessment results for hydrogen production using wind electricity.
Impact Calcium
Unit Na-Cl Soda Barite HCl Sulphite
category chloride
Carcinogens DALY 1.56×10-7 1.15×10-9 1.35×10-6 3.54×10-9 5.65×10-10 3.17×107

Resp. organics DALY 6.2×10-11 7.66×10-13 9.74×10-6 2.70×10- 3.66×10-13 2.5×10-14
Resp. DALY 9.82×10-3 2.0×10-9 1.77×10-6 6.53×10-9 5.9×10-10 1.2×10-10
Climate change DALY 3.06×10-3 4.9×10-10 6.38×10-6 1.54×10-9 1.9×10-10 1.3×10-11
Radiation DALY 1.60×10-9 8.35×10-12 4.81×10-6 2.80×10- 1.2×10-11 7.4×10-13
Ozone layer DALY 9.2×10-12 5.80×10-14 1.53×10-6 2.10×10- 1.5×10-12 4.8×10-15
Ecotoxicity PAF* m2yr 0.0152 0.0001 9.75×10-6 0.0003 5.39×10-45 3.01×10-6
Acidification PDF* m2yr 0.0023 9.92×10-5 4.59×10-6 0.0003 1.45×10-5 2.47×10-6
Land use PDF* m2yr 0.0033 4.19×10-7 3.13×10-6 0.0001 1.21×10-5 7.46×10-7
Minerals MJ surplus 0.0352 0.0002 1.01×10-5 0.0006 9.53×10-5 5.02×10-7
Fossil fuels MJ surplus 0.1287 0.0010 0.0002 0.0034 0.0009 6.56×10-5
Table 6.7b: Damage assessment results for hydrogen production using wind electricity.
Electricity
Impact Transport Transport
Unit Na-OH Chemical wind
category truck train
power
Carcinogens DALY 1.06×10-8 1.41×10-9 1.07×10-11 3.70×10-7 1.36×10-8

Resp. organics DALY 6.15×10-12 2.37×10-11 3.09×10-13 8.60×10-11 1.08×10-11
Resp. DALY 1.20E-08 1.56×10-8 3.61×10-10 1.48×10-7 1.88×10-8
inorganics
Climate change DALY 4.47×10-9 3.01×10-9 8.07×10-11 2.58×10-8 3.03×10-9
Radiation DALY 3.27×10-10 2.75×10-11 4.22×10- 1.03×10-9 5.31×10-11
Ozone layer DALY 1.39×10-12 2.42×10-12 2.79×10-14 8.27×10-12 8.29×10-13
Ecotoxicity PAF*m2yr 0.0009 0.0004 1.33×10-5 0.0382 0.0047
Acidification PDF* m2 yr 0.0003 0.0006 1.16×10-5 0.0025 0.0002
Land use PDF* m2yr 0.0002 0.0002 1.15×10-5 0.0079 0.0009
Minerals MJ surplus 0.0012 0.0002 2.14×10-5 0.1043 0.0139
Fossil fuels MJ surplus 0.0155 0.0291 0.00040 0.1152 0.0153
79
100
95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Climate change Fossil fuels Minerals Land use Acidification Ecotoxicity Ozone layer Radiation Resp. inorganics Resp. organics Carcinogens
/ Eutrophication
Hydrogen via electrolysis (wind) Sodium chloride, powder, at plant/RER U
Soda, powder, at plant/RER U Barite, at plant/RER U
Calcium chloride, CaCl2, at regional storage/CH U Hydrochloric acid, 30% in H2O, at plant/RER U
Sulphite, at plant/RER U Sodium hydroxide, 50% in H2O, production mix, at plant/RER U
Transport, lorry >16t, fleet average/RER U Transport, freight, rail/RER U
Chemical plant, organics/RER/I U Electricity, at wind power plant 800kW/RER U
Disposal, sludge, NaCl electrolysis, 0% water, to residual material landfill/CH U Disposal, paper, 11.2% water, to sanitary landfill/CH U
Analyzing 1 kg 'Hydrogen via electrolysis (wind)';

80
Figure 6.19: Damage assessment chart for hydrogen production using wind electricity.
The weighting values for impact categories are shown in Table 6.8. Weighting of
impact categories shows that the chemical plant in the hydrogen production process has
most impact on the environment. Figure 6.20 shows the weighting bar chart for wind
based hydrogen production method in which the chemical plant contribution can be seen
in almost all impact categories. The carcinogen particulates from the chemical plant hold
the maximum number of part which is about 0.0127 Pt. On the other side sodium chloride
which is another main contributor in the hydrogen production through wind electricity
has also maximum value in carcinogen with 0.0053 parts. This carcinogen is affecting the
human health in terms of life threatening disease cancer. Sodium chloride also has
significant weight on fossil fuel and respiratory inorganics with 0.0051 parts and 0.0034
parts respectively.
The same process is analysed using the CML method to examine the damage in
terms of abiotic depletion, global warming potential, ozone layer and other. Table 6.10
show the values for the impact categories. The CML method also shows that the chemical
plant and sodium chloride are major contributors of environmental impact in the
production of 1 kg hydrogen. Chemical plants have large impact under human toxicity
which has a value of 0.506 kg 1.4-DB eq. Sodium chloride has abiotic depletion values of
9.82×10-4 kg Sb eq. which is about 45% among other processes and material. The second
large contributor in abiotic depletion is the chemical plant which has a value of 8.47×10-4
kg Sb eq. and covers 35% of chart area as shown in Figure 6.21. The global warming
potential, ozone layer depletion and eutrophication values for sodium chloride are 1.4×10-1
kg CO2 eq., 8.59×10-9 kg R-11 eq and 5.43×10-4 kg PO4 eq. respectively. For the chemical
plant values are 0.12 kg CO2 eq. 7.96×10-9 kg R-11 and 6.62×10-4 kg PO4 eq. respectively.
The electricity generated by wind source which is used in this method has very little
impact on environment. The global warming potential for wind electricity is 1.38×10-2 kg
CO2 eq. which covers only 5% among other impact categories. The abiotic depletion for
wind based electricity is about 1.06×10-4 kg Sb eq. which also covers 5% of the bar area
among other category. These results reveal that electricity from wind nearly free from
environmental pollution which is a better option of hydrogen production using this
electricity in the process of electrolysis.
81
Table 6.8a: Weighting results for hydrogen production using wind electricity.
Calcium
Impact category Unit Na-Cl Soda Barite HCl Sulphite
chloride
Climate change Pt 0.0010 1.68×10-5 2.18×10-4 5.29×10-5 6.72×10-6 4.61×10-7
Fossil fuels Pt 0.0051 3.82×10-6 8.88×10-4 0.00013 3.75×10-5 2.61×10-6
Minerals Pt 0.0014 7.66×10-6 4.00×10-7 2.36×10-5 3.79×10-6 1.99×10-7
Land use Pt 0.0002 2.93×10-6 2.19×10-7 9.47×10-6 8.43×10-7 5.22×10-8
Acidification Pt 0.0002 6.94×10-6 3.21×10-7 2.17×10-5 1.02×10-6 1.73×10-7
Ecotoxicity Pt 0.0011 7.08×10-9 6.82×10-7 2.21×10-5 3.77×10-6 2.10×10-7
Ozone layer Pt 3.17×10-7 1.98×10-9 5.24×10-10 7.19×10-9 5.46×10-8 1.65×10-10
Radiation Pt 5.49×10-5 2.86×10-7 1.65×10-7 9.58×10-7 4.13×10-7 2.55×10-8
Resp. inorganics Pt 0.0034 7.05×10-5 6.06×10-4 0.00022 2.05×10-5 4.03×10-6
Resp. organics Pt 2.14×10-6 2.62×10-8 3.34×10-9 9.24×10-8 1.25×10-8 8.06×10-6
Carcinogens Pt 0.0053 3.95×10-5 4.63×10-4 0.00012 1.93×10-5 1.09×10-6
Table 6.8b: Weighting results for hydrogen production using wind electricity.
Impact Transport, Transport, Electricity Disposal,

Unit NaOH Chemical
category truck rail wind power electrolysis
Climate change Pt 0.0002 0.0001 2.76×10-7 0.0009 0.0001 1.67×10-5

Fossil fuels Pt 0.0006 0.0012 1.61×10-7 0.0046 0.0006 5.28×10-5
Minerals Pt 4.92×10-5 1.04×10-5 8.51×10-7 0.0041 0.0006 5.57×10-7
Land use Pt 1.40×10-5 1.56×10-5 8.05×10-7 0.0006 6.54×10-7 2.93×10-6
Acidification Pt 2.11×10-5 4.86×10-5 8.12×10-7 0.0002 1.62×10-7 1.96×10-6
Ecotoxicity Pt 6.31×10-5 2.99×10-3 9.27×10-7 0.0027 0.0003 1.45×10-6
Ozone layer Pt 4.76×10-8 8.30×10-8 9.55×10-10 2.83×10-7 2.84×10-7 4.16×10-9
Radiation Pt 1.12×10-5 9.40×10-7 1.44×10-7 3.51×10-7 1.82×10-7 1.57×10-7
Resp. Pt 0.0004 0.0005 1.24×10-5 0.0051 0.0006 2.42×10-5
Resp. organics Pt 2.11×10-7 8.12×10-7 1.06×10-8 2.94×10-7 3.70×10-7 3.58×10-8
Carcinogens Pt 0.0004 4.82×10-7 3.66×10-6 0.0127 0.0005 5.75×10-5
82
19
18
17
16
15
14
13
12
11
10
m Pt
9
8
7
6
5
4
3
2
1
0
Climate change Fossil fuels Minerals Land use Acidification Ecotoxicity Ozone layer Radiation Resp. inorganics Resp. organics Carcinogens
/ Eutrophication

Method: Eco-indicator 99 (H) V2.08 / Europe EI 99 H/H / Weighting Figure 6.20: Weighting chart for hydrogen production using wind electricity.
83
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95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Abiotic depletion Acidif ication Eutrophication Global warming 500a Ozone layer depletion 40a Human toxicity 500a

Sulphite, at plant/RER U Sodium hydroxide, 50% in H2O, production mix , at plant/RER U

Figure 6.21: Impact assessment results for hydrogen production using wind based electricity
(CML method).
84
Thermodynamic analysis of hydrogen production through sodium chlorine electrolysis
using wind electricity is presented here. The energy efficiency for the process is
calculated as 67.98% while exergy efficiency is about 60.57%. Figure 6.22 shows the
effect of changing the inlet pressure on energy and exergy efficiencies. Both efficiencies
are decreasing on increasing the pressure at which Na-Cl is coming towards the
electrolyser. The energy efficiency decreases from 67% to 56% while exergy efficiency
reduced to 55% from 66% as pressure rose to 120 kPa.
0.68 0.6
Energy
Exergy
0.66
0.58
Exergy efficiency
0.64
Energy efficiency
0.56
0.62
0.54
0.6
0.52
0.58
0.56 0.5
104 108 112 116 120
Inlet pressure [kPa]
Figure 6.22: Effect of variation of inlet pressure on energy and exergy efficiencies of wind based
hydrogen production system.
In general, surrounding conditions also play an effective role on the efficiencies of

the system. Figure 6.23 shows the effect of variation of ambient temperature on energy
and exergy efficiencies. At operating condition the energy efficiency is about 68% which
decreases to 48% as temperature rose to 310K. Similar results can be seen for exergy
efficiencies, with the increase of ambient temperature the exergy efficiency decreases
from 60% to 43%. During the electrolysis, the surrounding temperature should be
85
moderate, high temperature might affect the efficiency of the system which can be seen
by our result.
0.7 0.65
Energy
Exergy
0.65 0.6
Exergy efficiency
Energy efficiency
0.6 0.55
0.55 0.5
0.5 0.45
0.45 0.4
298 302 306 310
Tο [K]
Figure 6.23: Effect of variation of ambient temperature on energy and exergy efficiencies
of wind based hydrogen production method
0.72 0.64
Energy
Exergy
0.7
0.62
Exergy efficiency
0.68
Energy eficiency
0.6
0.66
0.58
0.64
0.56
0.62
0.6 0.54
300 310 320 330 340 350
Area of Wind Turbine [m2]
Figure 6.24: Effect of variation in the area of wind turbine on energy and exergy efficiencies of
wind based hydrogen production.
86
Figure 6.23 shows the effect of changing the area of wind turbine on energy and
exergy efficiencies. In this study, when the area of wind turbine increases both energy
and exergy efficiencies decrease, which is opposite what is expected. Generally,
whenever the area of wind turbine increase, the electricity production also increases to be
used for the hydrogen production. But during the electrolysis optimum amount of voltage
and current is required. After that condition, a saturation point occurs and no further
voltage or current effect the electrolysis process. In other words, the hydrogen production
might increase with the increase in the area of wind turbine but that rate is not that much
as increase in energy input to the system in terms of electricity. Similar results can be
seen in Figure 6.26 where efficiency is decreasing by increasing the wind velocity.
The above discussion is also verified by the result shown in Figure 6.25 where
both the efficiencies increase by the increase in the amount of hydrogen production.
When the mass of hydrogen increases from 0.3 kg to 1 kg, energy efficiency increases
from 26% to 87% and the exergy efficiency increases from 30% to 82%. This result is
obvious as previously defined efficiency by hydrogen as a potential useful product.
0.9
Energy
0.9 Exergy 0.8
0.7
0.75
Exergy efficiency
Energy efficiency
0.6
0.6
0.5
0.45
0.4
0.3 0.3
0.2
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mH [kg]
2
Figure 6.25: Effect of increasing the amount of produced hydrogen on energy and exergy
efficiencies.
87
0.8 0.7
Energy
Exergy 0.65
0.7
0.6
Exergy efficency
Energy efficiency
0.6
0.55
0.5
0.5
0.45
0.4
0.4
0.3 0.35
4.8 5.2 5.6 6
Velocity of Wind [m/s]
Figure 6.26: Effect of variation of wind velocity on energy and exergy efficiencies.
6.4 Hydrogen via Electrolysis Using Solar Photovoltaic Electricity

In the analyses of hydrogen production using solar photovoltaic electricity, the same
electrolytic process is assumed as studied in the wind based hydrogen production. Among
three cell, membrane cell is used instead of mercury and diaphragm cell because it has
minimum impact on environment. Figure 6.27 shows the impact flow diagram of
hydrogen production using solar photovoltaic electricity.

In the environmental assessment of hydrogen production through solar photovoltaic
electricity, major chemicals and energy and waste is considered. In this way the process
will be evaluated more carefully.
Table 6.9 and Table 6.10 show the all major contributor in the production of 1 kg
of hydrogen through electrolysis using solar energy. Figure 6.29 depicted the values of
these tables in bar chart format which shows that the major influence on environment is
due to the sodium chloride powder, from the chemical plant. Moreover, solar based
electricity has also impacts on environment which can be seen in the bar chart. In this
method electricity from solar is the third large process of contributing overall emissions.
88
For the chemical plants the value for carcinogens particle which are danger for human
health causing cancer is 3.70×10-7 (DALY). The chemical plant has also major effect on
ecosystem and the value for ecotoxicity is about 0.038 PAF*m2yr. These results are
almost similar to the result of wind based hydrogen production except for power
requirement which is electricity. The values for solar electricity are more than wind
electricity which can be seen in Figure 6.29.
The second most dominant material in solar based hydrogen production which has
covered almost every impact category is sodium chloride powder. Sodium chloride is
essential components in the electrolysis for hydrogen production. The radiation value for
sodium chloride powder is the 1.6×10-9 DALY which covers about 45% of area in the bar
of radiation as shown in Figure 6.29. The maximum value for electricity from solar
photovoltaic comes under ozone layer and respiratory organics which are 1.25×10-11 and
9.55×10-11 DALY respectively. These categories can be seen on the damage assessment
chart which covers 35% among all categories.
electricity.
Impact Sodium Calcium

Unit Soda Barite HCl Sulphite
category chloride chloride
Carcinogens DALY 1.56×10-7 1.15×10-9 1.35×10-10 3.54×10-9 5.65×10-10 3.17×10-11
Resp. organics DALY 6.24×10-11 7.66×10-13 9.74×10-14 2.70×10-12 3.66×10-13 2.35×10-14
Resp. inorganics DALY 9.82×10-8 2.06×10-9 1.77×10-10 6.53×10-9 5.99×10-10 1.18×10-10
Climate change DALY 3.06×10-8 4.90×10-10 6.38×10-11 1.54×10-9 1.96×10-10 1.35×10-11
Radiation DALY 1.60×10-9 8.35×10-12 4.81×10-14 2.80×10-11 1.21×10-11 7.46×10-13
Ozone layer DALY 9.27×10-12 5.80×10-14 1.53×10-14 2.10×10-13 1.59×10-12 4.81×10-15
Ecotoxicity PAF*m2yr 0.0152 0.0001 9.75×10-6 0.0003 5.39×10-5 3.01×10-7
Acidification PDF* m2yr 0.0023 9.92×10-5 4.59×10-6 0.0003 1.45×10-5 2.47×10-6
Land use PDF*m2yr 0.0033 4.19×10-5 3.13×10-6 0.0001 1.21×10-5 7.46×10-7
Minerals MJ surplus 0.0352 0.0002 1.01×10-5 0.0006 9.53×10-5 5.02×10-6
Fossil fuels MJ surplus 0.1287 0.0010 0.0002 0.0034 0.0009 6.56×10-5
89
electricity.
Sodium
Impact Transport, Transport, Chemical Electricity,
Unit hydroxide,
category truck rail plant photovoltaic
50% in H2O
Carcinogens DALY 1.06×10-8 1.41×10-9 1.07×10-10 3.70×10-7 8.19×10-8
Resp. organics DALY 6.15×10-12 2.37×10-11 3.09×10-13 8.60×10-11 9.55×10-11
Resp. inorganics DALY 1.20×10-8 1.56×10-8 3.61×10-10 1.48×10-7 4.17×10-8
Climate change DALY 4.47×10-3 3.01×10-9 8.07×10-11 2.58×10-8 1.28×10-8
Radiation DALY 3.27×10-10 2.75×10-11 4.22×10-12 1.03×10-9 3.89×10-10
Ozone layer DALY 1.39×10-12 2.42×10-12 2.79×10-14 8.27×10-12 1.25×10-11
Ecotoxicity PDF*m2yr 0.0009 0.0004 1.33×10-5 0.0383 0.0058
Acidification PDF*m2yr 0.0003 0.0007 1.16×10-5 0.0026 0.0010
2 -5
Land use PDF*m yr 0.0002 0.0002 1.15×10 0.0080 0.0008
Minerals MJ surplus 0.0012 0.0003 -5 0.1044 0.0160
2.14×10
Fossil fuels MJ surplus 0.0155 0.0292 0.0004 0.1153 0.0759
1 kg
hydrogen
0.0622 Pt
0. 848 kg 1. 35E-9 p 4. 66 MJ
Sodium Chemical Electricity,
0. 0184 Pt 0.0415 Pt 0.00887 Pt
1. 27 MJ 0. 000221 m3 0. 017 kg
Electricity, Building, Facilities,
0. 0125 Pt 0.0176 Pt 0.0235 Pt
1. 33 MJ 0. 00287 kg 0. 00443 kg 0. 000734 kg

Electricity, Copper, at Chromium Electronics
0. 0127 Pt 0.0208 Pt 0.00657 Pt 0. 00632 Pt
1. 35 MJ 0.000486 kg 0. 000104 kg
Electricity, Copper, Printed
0. 0127 Pt 0.0112 Pt 0. 0055 Pt
0. 00184 kg
Copper
0.00959 Pt
0.395 kg
Disposal,
0.0174 Pt
Figure 6.27: Impact flow diagram of hydrogen production via electrolysis using solar
photovoltaic electricity.
90
1 MJ
Electricity,
0.0019 Pt
5.55E-7 p 7.55E-7 p
3kWp 3kWp
0.000454 Pt 0.000595 Pt
1.91E-5 m2 5.72E-6 p 2.77E-5 m2

Photovoltaic Inverter, Photovoltaic
0.000365 Pt 0.000423 Pt 0.000455 Pt
8.38E-5 kg 0.00377 MJ 2.75E-5 m2 7.19E-8 kg

Copper, at Natural gas, Photovoltaic Nickel,
0.000606 Pt 2.73E-5 Pt 0.000332 Pt 6.49E-7 Pt
1.42E-5 kg 0.0467 MJ 0.0111 kg

Copper, Natural gas, Disposal,
0.000327 Pt 0.000305 Pt 0.000487 Pt
Figure 6.28: Impact flow diagram of photovoltaic electricity.
91
100
95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
/ Eutrophication
hydrogen via electrolysis using photovoltaic Sodium chloride, powder, at plant/RER U
Chemical plant, organics/RER/I U Electricity, production mix photovoltaic, at plant/US U
Analyzing 1 kg 'hydrogen via electrolysis using photovoltaic';

electricity.
92
According to the weighting Figure 6.30, the processes which have major weight
are the chemical plant, sodium chloride and solar electricity. The maximum parts can be
seen under the category of carcinogens in which the chemical plant has 0.0127 parts,
sodium chloride has 0.0053 parts, and solar electricity has 0.0028 parts and the remaining
for others. The second maximum parts can be seen under the category of fossil fuels in
which sodium chloride has 0.0051 parts, the chemical plants has 0.0046 parts and another
mentionable process contributor is solar electricity which has 0.003 parts. The third
category which has maximum number of parts is respiratory inorganics in which the
chemical plant has maximum parts of 0.0051 with sodium chloride of 0.0034 parts and
solar electricity has 0.0014 parts.
Table 6.11a: Weighting results for hydrogen production using solar photovoltaic electricity.
Impact Calcium
Unit NaCl Soda Barite HCl Sulphite
category chloride
Carcinogens Pt 0.0053 3.95×10-5 4.63×10-6 0.0001 1.93×10-5 1.1×10-5
Resp. organics Pt 2.14×10-6 2.62×10-8 3.34×10-9 9.24×10-8 1.25×10-8 8.1×10-10
Resp. Pt 0.0034 7.05×10-5 6.06×10-6 0.0002 2.05×10-5 4.0×10-6
Climate change Pt 0.0010 1.68×10-5 2.18×10-6 5.29×10-5 6.72×10-6 4.6×10-7
Radiation Pt 5.49×10-5 2.86×10-7 1.65×10-7 9.58×10-7 4.13×10-7 2.5×10-8
Ozone layer Pt 3.17×10-7 1.98×10-9 5.24×10-10 7.19×10-9 5.46×10-8 1.6×10-10
Ecotoxicity Pt 0.0011 7.08×10-6 6.82×10-7 2.21×10-5 3.77×10-6 2.1×10-7
Acidification Pt 0.0002 6.94×10-6 3.21×10-7 2.17×10-5 1.02×10-6 1.7×10-7
Land use Pt 0.0002 2.93×10-6 2.19×10-7 9.47×10-6 8.43×10-7 5.2×10-8
Minerals Pt 0.0014 7.66×10-6 4.00×10-7 2.36×10-7 3.79×10-6 1.9×10-7
Fossil fuels Pt 0.0051 3.82×10-5 8.88×10-6 0.0001 3.75×10-5 2.6×10-6
The CML method shows the same results as wind based hydrogen production
except the electricity results. In the solar based hydrogen production, the abiotic depletion
is about 4.30×10-4 kg Sb eq, which was 1.06×10-4 kg Sb eq. In the wind based electricity,
global warming potential is 5.88×10-2 kg CO2 eq which was 1.38×10-2 kg CO2 eq. In the
wind based electricity and ozone layer depletion is 1.52×10-8 kg R-11 eq. which was
5.95×10-10 kg R-11 eq.
93
Table 6.13b: Weighting results for hydrogen production using solar photovoltaic electricity.
Chemical
Transport Transport, Electricity
Impact category Unit Na-OH plant,
, truck rail photovoltaic
organic
Carcinogens Pt 0.0004 4.82×10-5 3.66×10-6 0.0126 0.0028
-7 -7 -8 -6
Resp. organics Pt 2.11×10 8.12×10 1.06×10 2.94×10 3.27×10-6
Resp. inorganics Pt 0.0004 0.00053 1.24×10-5 0.0051 0.0014
-6
Climate change Pt 0.0002 0.00010 2.76×10 0.0009 0.0004
Radiation Pt 1.12×10-5 9.40×10-7 1.44×10-7 3.51×10-5 1.33×10-5
Ozone layer Pt 4.76×10-8 8.30×10-8 9.55×10-10 2.83×10-7 4.29×10-7
Ecotoxicity Pt 6.31×10-5 2.99×10-5 9.27×10-7 0.0026 0.0004
-5 -5 -7
Acidification Pt 2.11×10 4.86×10 8.12×10 0.0001 6.86×10-5
Land use Pt 1.40×10-5 1.56×10-5 8.05×10-7 0.0006 5.93×10-5
Minerals Pt 4.92×10-5 1.04×10-5 8.51×10-7 0.0041 0.0006
-5
Fossil fuels Pt 0.0006 0.0012 1.61×10 0.0046 0.0030
Table 6.12: Impact assessment results for solar based hydrogen production method
Sodium Calcium
Impact category Unit Soda Barite HCl
chloride chloride
Abiotic depletion kg Sb-eq 9.82×10-4 1.56×10-5 2.34×10-6 4.94×10-5 7.06×10-6
Acidification kg SO2-eq 7.29×10-4 2.20×10-5 1.51×10-6 6.79×10-5 4.92×10-6
Eutrophication kg PO4-eq 5.43×10-4 6.41×10-6 1.02×10-6 2.00×10-5 2.95×10-6
Global warming kg CO2-eq 1.42×10-1 2.25×10-3 2.96×10-4 7.10×10-3 9.09×10-4
Ozone layer kg R-11-eq 8.59×10-9 5.30×10-11 1.45×10-11 1.91×10-10 1.45×10-9
Table 6.13: Impact assessment results for solar based hydrogen production using CML method
Impact Sodium Transport, Chemical Electricity,

Unit
categories hydroxide truck plant photovoltaic
Abiotic
kg Sb-eq 1.55×10-4 1.04×10-4 8.47×10-4 4.30×10-4
depletion
Acidification kg SO2-eq 1.04×10-4 7.80×10-5 8.27×10-4 2.98×10-4
Eutrophication kg PO4 -eq 7.21×10-5 2.07×10-5 6.62×10-4 1.88×10-4
Global warming kg CO2-eq 2.07×10-2 1.40×10-2 1.20×10-4 5.88×10-2
Ozone layer kg R-11-eq 1.31×10-9 2.08×10-9 7.96×10-4 1.52×10-8
94
21
20
19
18
17
16
15
14
13
12
11
m Pt
10
9
8
7
6
5
4
3
2
1
0
/ Eutrophication

Figure 6.30: Weighting results charts for hydrogen production using solar photovoltaic.
95
100
95
90
85
80
75
70
65
60
55
%
50
45
40
35
30
25
20
15
10
5
0
Abiotic depletion Acidification Eutrophication Global warming 500a Ozone layer depletion 40a


96
(CML method).
Thermodynamic analysis of hydrogen production through sodium chlorine electrolysis
using solar electricity is presented here. The energy efficiency for the process is
calculated as 46.34% while exergy efficiency is about 45.41%. These efficiencies are less
than the efficiencies in steam methane reforming and wind based hydrogen production.
Figure 6.32 shows the effect of changing the ambient temperature on energy and
exergy efficiencies. Both efficiencies are decreasing on increasing the ambient
temperature. However, this decrease in the efficiencies are not that much significant. The
energy efficiency decreases slightly from 46.34% to 46.29% while exergy efficiency also
increased to 45.41% from 45.38% as pressure rose to 350 K from 300 K. Figure 6.33
shows the effect of increasing the solar irradiation on energy and exergy efficiency of the
solar based hydrogen production method. Irradiation is proportional to the power
generation and increasing the electricity corresponds to increase in the input energy. This
increase in the input energy causes both efficiencies to decrease because most of the
photovoltaic cell has an efficiency of 20% and the rate at which input energy increases is
greater than the rate of output.
0.4634 0.4542
Energy
Exergy
0.4633 0.4541
Exergy efficiency
Energy efficiency
0.4632 0.454
0.4631 0.4539
0.463 0.4538
0.4629 0.4537
300 310 320 330 340 350
Tο [K]
Figure 6.32: Effect of variation ambient temperature on energy and exergy efficiencies of
solar based hydrogen production.
97
0.54 0.52
Energy
Exergy
0.52 0.5
0.5
Exergy efficiency
Energy efficiency
0.48
0.48
0.46
0.46
0.44
0.44
0.42 0.42
0.4 0.4
14000 15000 16000 17000 18000
Iο [W/m2]
Figure 6.33: Effect of variation of solar irradiation on energy and exergy efficiencies of solar
based hydrogen production method.
6.5 Comparison of Various Options by CML-Method with Uncertainty

Analyses
In this section, environmental impacts of for one kilogram of hydrogen production for
different processes are compared. The CML 2001 impact categories which are abiotic
depletion potential, acidification potential, eutrophication potential, global warming
potential, ozone depletion potential and human toxicity are considered for comparison
purposes.
6.5.1 Abiotic Depletion

Abiotic depletion potential is related with effect on non-living natural resources. It can be
observed from Figure 6.34 that the abiotic depletion potential for steam methane
reforming is much higher than all other methods. Using large amount of fossil fuels in
SMR is responsible for this amount of depletion. From the Figure 6.34, abiotic depletion
for SMR method is about 0.1309 kg Sb-eq. In other process such as electrolysis using
mercury, diaphragm and membrane cell, abiotic depletion is almost similar with mercury
98
on top with a figure of 0.0079 kg Sb-eq. diaphragm cell with 0.0068 kg Sb-eq. and
membrane cell with 0.0066 kg Sb-eq. In the solar photovoltaic electrolysis, abiotic
depletion is least with 0.00026 kg Sb-eq after wind electrolysis with 0.0002 kg Sb-eq.
0.1400
0.1309
Abiotic depletion (kg Sb eq )
0.1200
0.1000
0.0800
0.0600
0.0400
0.0200
0.0068 0.0066 0.0079
0.0002 0.0026
0.0000
Electrolysis Electrolysis Electrolysis Electrolysis Electrolysis SMR
wind photovoltaic diaphragm membrane mercury cell
cell cell
Figure 6.34: Abiotic depletion per kg of hydrogen for different hydrogen production methods.
6.5.2 Acidification Potential

Acidification potential comes as a result of acid deposition of acidifying pollutants on
soil, water, biological organisms, ecosystems and materials. Figure 6.35 depicted that the
acidification potential for steam methane reforming is the highest among all other
methods. The value of acidification for SMR in the Figure 6.35 is about 0.0289 kg SO2-
eq. The second highest acidification potential is for electrolysis using mercury cell with
0.0053 kg SO2-eq. and then for diaphragm and membrane cell with a difference of 0.0001
kg SO2-eq. From the results of acidification potential it can be seen that wind based
hydrogen production is most effective method of hydrogen production with minimum
impact result. The acidification potential for wind based hydrogen is about 0.0002 kg
SO2-eq. After wind based hydrogen production, solar photovoltaic hydrogen is an
efficient way of hydrogen production with an acidification potential of 0.0021 kg SO2eq.
6.5.3 Eutrophication
Results of eutrophication are quite different than abiotic depletion and acidification. From
Figure 6.36, hydrogen production using mercury cell contain the highest value of
99
eutrophication with 0.0037 kg phosphate-eq. SMR is the second highest method in terms
of eutrophication potential with 0.0036 kg phosphate-eq. only 0.0001 value less than the
mercury cell electrolysis. The membrane cell electrolysis has a value of 0.0032 kg
phosphate-eq. followed by the diaphragm cell with 0.0031 kg phosphate-eq. Again wind
based electrolysis has a minimum impact on the environment with eutrophication value
0.0001 kg phosphate-eq.; followed by the solar based hydrogen with an eutrophication
impact of 0.00015 kg phosphate-eq.
0.0350
0.0289
0.0300
Acidification (kg SO2 eq)
0.0250
0.0200
0.0150
0.0100
0.0046 0.0045 0.0053
0.0050 0.0021
0.0002
0.0000
cell cell
Figure 6.35: Acidification potential per kg of hydrogen for different hydrogen production
methods.
0.0040
0.0037 0.0036
Eutrophication (kg phosphate-eq )
0.0035 0.0032 0.0031

0.0030
0.0025
0.0020
0.0015
0.0015
0.0010
0.0005 0.0001
0.0000
cell cell
Figure 6.36: Eutrophication potential per kg of hydrogen for different hydrogen production
methods.
100
6.5.4 Global Warming Potential
Global warming potential (GWP) is the result of human emissions on the radioactive
forcing of the atmosphere which is responsible for temperature rise at the earth’s surface
and this is generally related to ‘greenhouse effect”. It can be observed from Figure 6.37
that the most important contributions for global warming potential come from utilization
of natural gas in steam methane reforming method. SMR has the value of 11.956 kg CO2-
eq. The rest of the methods are far behind than SMR. The lowest value of global warming
potential comes under the wind based electrolysis with 0.0325 kg CO2-eq. After wind
solar based electrolysis can be seen in the Figure 6.37with an amount of 0.37 kg CO2-eq.
Hydrogen production through electrolysis using mercury contain relatively higher amount
of global warming potential than diaphragm and membrane cell. The value of mercury
cell is about 1.051 kg CO2-eq, for diaphragm cell it is 0.909 kg CO2-eq. and for
membrane cell the value of global warming potential is about 0.8872 kg CO2-eq which is
minimum among three cells.
14.0000
11.9567
12.0000
Global warming (kg CO2 eq )
10.0000
8.0000
6.0000
4.0000
2.0000 0.9090 0.8872 1.0510

0.0325 0.3700
0.0000
cell cell
Figure 6.37: Global warming potential per kg of hydrogen for different hydrogen production
methods.
6.5.5 Ozone Layer Depletion

Ozone layer depletion is the weakening of the ozone layer as a result of emissions. This
thinning of ozone layer is responsible for a greater portion of solar UV-B radiation reaching
the earth’s surface. From Figure 6.38, almost all of the method has minimum contribution on
101
ozone layer depletion except steam methane reforming with a value of 3.0 x 10-06 kg R-11-eq.
The hydrogen production via wind based electrolysis contributes the minimum ozone layer
depletion with 2.24 × 10-09 kg R-11-eq.
3.50E-06
3.00E-06
3.00E-06
Ozone layer depletion (kg R11-eq )
2.50E-06
2.00E-06
1.50E-06
1.00E-06
5.00E-07
2.24E-09 3.70E-08 5.99E-08 5.95E-08 6.65E-08
0.00E+00
cell cell
Figure 6.38: Ozone layer depletion per kg of hydrogen for different hydrogen production
methods.
6.5.6 Human Toxicity

Human toxicity category deals with the effects of toxic substances on the human
environment. Figure 6.39 shows the values of human toxicity of different hydrogen
production methods. It can be seen that steam methane reforming and photovoltaic
electrolysis contributed large amount of human toxicity with SMR 3.179 kg 1, 4-
dichlorobenzene equivalents and for photovoltaic based hydrogen it is 0.8034 kg 1, 4-
dichlorobenzene eq. Diaphragm cell and membrane cell sharing almost equal amount of
human toxicity of 0.4221 kg 1,4 DB-eq. and 0.4229 kg 1,4 DB-eq. Again the wind based
electrolysis has the minimum contribution in environmental impact which is 0.0782 kg 1,
4 DB-eq. in this case.
102
3.5000 3.1796
Human toxicity (kg 1,4-DB eq )

3.0000
2.5000
2.0000
1.5000
1.0000 0.8034
0.4221 0.4229 0.4489
0.5000
0.0782
0.0000
cell cell
Figure 6.39: Human toxicity per kg of hydrogen for different hydrogen production methods.
6.5.7 Radiation
Radiation includes impacts arising from releases of radioactive substances along with
direct exposure to radiation, such as building materials. If the radiation level is high, it
can be harmful to both human as well as animals. Figure 6.40 show the radiation results
for different hydrogen production methods. The main contributor in the radiation is the
hydrogen production form electrolysis using mercury cell with 1.66 x 10-08 DALY.
1.80E-08
1.66E-08
1.60E-08
1.42E-08 1.37E-08
1.40E-08
Radialtion (DALY)
1.20E-08
1.00E-08
8.00E-09
6.00E-09
4.00E-09 3.10E-09 3.43E-09

2.46E-09
2.00E-09
0.00E+00
Hydrogen via hydrogen via Hydrogen Hydrogen Hydrogen Hydrogen,
electrolysis eletrolysis diaphragm membrane mercury cell SMR
(wind) photovoltaic cell cell
Figure 6.40: Radiation per kg of hydrogen for different hydrogen production methods.
103
5.5.8 Photochemical Oxidation
Photo-oxidants formed by the influence of ultraviolet light, through photochemical
oxidation of Volatile Organic Compounds (VOCs) and carbon monoxide in the presence
of nitrogen oxides. Figure 6.41 show the photochemical oxidation for different hydrogen
production methods in which SMR is the largest contributor of photochemical oxidation
with 1.98 x 10-03 kg Ethene-eq. The minimum contributor in this category is the wind
based hydrogen methods where renewable energy is utilized to reduced pollution and
other impacts. The photochemical oxidation for wind hydrogen production is 9.04 x 10-05
kg Ethene-eq. These results encouraged that renewable based hydrogen has minimum
environmental emissions as compared to fossil fuel based hydrogen production.
2.50E-03
Photochemical Oxidation (kg Ethene-eq)
1.98E-03
2.00E-03
1.50E-03
1.00E-03
5.00E-04
1.85E-04 1.81E-04 2.12E-04
9.04E-05 1.04E-04
0.00E+00
Hydrogen via hydrogen via Hydrogen Hydrogen Hydrogen Hydrogen,
electrolysis eletrolysis diaphragm cell membrane cell mercury cell SMR
(wind) photovoltaic
Figure 6.41: Photochemical oxidation per kg of hydrogen for different hydrogen production
methods
6.6 Uncertainty Analyses of Steam Methane Reforming

Data used in the LCA have uncertainties and the result will slightly deviate from actual
value. For example, SOx emission during burning of 1 kg of heavy oil is about 10 grams.
However, in 95% of the cases the value lies between 5 and 15 grams, depending on the
sulphur content of the oil. For this purpose, uncertainty analysis of results is necessary.
The uncertainty data for producing 1 kg of hydrogen through steam methane

reforming are shown in Table 6.14 and all the values are calculated at the 95%
104
confidence level. The original abiotic depletion value for SMR method is about 0.1309 kg
Sb-eq. and uncertainty analysis calculated the error chances of 95% surety. The minimum
and maximum values at 95% confidence interval are shown in Figure 6.42 which result in
0.1309 ± 0.040 kg Sb-eq. The measured standard error of mean for ADP is about 0.005
with coefficient of variation is 15.50%.
Table 6.14: Uncertainty data for hydrogen production through SMR

Impact Coefficient of Std. err. of
Unit Mean Median SD
category Variation mean
Abiotic depletion kg Sb eq 0.132 0.130 0.020 15.50% 0.005
Acidification kg SO2 eq 0.029 0.028 0.004 13.80% 0.004
Eutrophication kg PO4 eq 0.004 0.003 0.001 15.60% 0.005
Global warming kg CO2 eq 12 12 0.439 3.67% 0.001
Human toxicity kg 1,4-DB eq 3.19 3.14 0.244 7.63% 0.002
Ionising
DALYs 2.5E-09 1.45E-09 3.93E-09 153% 0.049
radiation
Ozone layer kg CFC-11eq 3.E-06 2.31E-06 2.28E-06 75.60% 0.024
Photochemical
kg C2H4 eq 0.002 0.002 0.000277 13.90% 0.004
oxidation
Characterization Abiotic depletion
0.024
0.022
0.02
0.018
0.016
P ro b a b ility
0.014
0.012
0.01
0.008
0.006
0.004
0.002
0
0.096 0.099 0.102 0.104 0.107 0.109 0.112 0.114 0.117 0.119 0.122 0.124 0.127 0.13 0.132 0.135 0.137 0.14 0.142 0.145 0.147 0.15 0.152 0.155 0.158 0.16 0.163 0.165 0.168 0.17 0.173 0.175 0.178
kg Sb eq
Figure 6.42: Uncertainty analysis results of SMR method for abiotic depletion.
For the global warming potential, the mean and median value is 12 which has a
coefficient of variation of about 3.67% and from Figure 6.43 it can be written as 11.957 ±
0.8 kg CO2-eq. at 95% confidence interval. This slight variation in value is due to the
difference in maintenance and other operating parameters of the process.
105
0.024
0.022
0.02
0.018
0.016
0.014
P ro b a b ility
0.012
0.01
0.008
0.006
0.004
0.002
0
11.2 11.2 11.3 11.4 11.4 11.5 11.5 11.6 11.7 11.7 11.8 11.8 11.9 11.9 12 12 12.1 12.1 12.2 12.2 12.3 12.3 12.4 12.5 12.5 12.6 12.6 12.7 12.7 12.8 12.9 12.9 13 13 13 13.1
kg CO2 eq
Figure 6.43: Uncertainty analysis results of SMR method for global warming.
6.7 Uncertainty Analyses of Solar and Wind based Hydrogen

Production
The comparison of uncertainty analysis between wind and solar based hydrogen
production is conducted on the 95% confidence level. The uncertainty value is given in
Table 6.15 where A represents the data of wind based electrolysis and B is the solar based
hydrogen production. The difference of the abiotic depletion potential values is about
29.2% where mean and median values are -0.0003. From the probability of getting -3.6e-
4 kg Sb-eq. is 0.07 which is the maximum. These uncertainties results are because of the
slight difference in the assumed data. However, this minor difference indicated that the
results of the impact categories give the real picture of the emissions.
Table 6.15: Uncertainty data for hydrogen production through wind and solar energy
Impact Coefficient Std. err. of

A >= B Mean Median 2.50%
category of Variation mean
Abiotic depletion 29.20% -0.0003 -0.0003 -310% -0.00212 -0.0979
Acidification 34.60% -0.0002 -0.0002 -456% -0.00201 -0.144
Eutrophication 36.70% -0.0001 -0.0001 -588% -0.00156 -0.186
Global warming 29.40% -0.0412 -0.0413 -314% -0.292 -0.0993
Human toxicity 48.90% 0.0002 -0.0109 3.67E+03 -1.09 116
-10 -10 -9
Ionising radiation 31.90% -3.4×10 -1.82×10 -562% -3.76×10 -0.178
Ozone layer 2.90% -2.32×10-8 -2.28×10-8 -57.80% -4.95×10-8 -0.0183
106
0.08
0.075
0.07
0.065
0.06
0.055
0.05
P ro b a b ility
0.045
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
-2.33e-3 -2.17e-3 -2e-3 -1.84e-3 -1.59e-3 -1.35e-3 -1.1e-3 -9.39e-4 -6.93e-4 -5.3e-4 -3.66e-4 -1.21e-4 4.31e-5 2.07e-4 3.7e-4 5.34e-4 6.97e-4 8.61e-4 1.02e-3 1.19e-3 1.35e-3 1.52e-3 1.68e-3
Uncertainty analysis of 1 kg 'Hydrogen via electrolysis (wind)' (A) minus
1 kg 'hydrogen via electrolysis using photovoltaic' (B),
Figure 6.44: Uncertainty analysis results of wind and solar based hydrogen production for abiotic
depletion
The comparison between wind and solar hydrogen based on global warming
potential is also conducted. The uncertainty data for global warming potential is also
shown in Table 6.15 and Figure 6.44 shows the uncertainty bar diagram. The maximum
probability difference is about 0.085 on the value of -0.046 kg CO2 emissions. For human
toxicity, the mean and median values are 0.0002 and -0.0109 kg CO2-eq. Moreover, the
maximum probable value is around -0.01 kg CO2-eq.
6.8 Comparison of Hydrogen and Gasoline Fuels in Vehicle

Energy consumption in vehicle is developing large amount of pollution level on
environment and about 26.6% of energy is consumed in the transportation sector all over
the world. Researchers have been investigating various options for alternatives to fossil
fuels and propose hydrogen as a potential one to replace conventional fuels for vehicles.
In this section, a case study is presented on the basis of the fuels used in vehicle. The
selected fuels are hydrogen and gasoline. The vehicle cycle are studied from literature
such as Weiss et al. (2000), Hussain et al. (2007) and Sorensen (2004). The vehicle cycle
has major stages in its production such as vehicle material production, vehicle assembly
and vehicle use.
107
In vehicle material production, all the greenhouse gas emissions and energy use in
the material production are evaluated. Regular automobile consume about 890 kg of
ferrous metals, 100 kg of different plastics, roughly 80 kg of aluminum, and about 200 kg
of other materials (Weiss et al., 2000). Furthermore, PEM fuel cell powered automobile
incorporates polymer membrane, platinum, graphite, etc. In vehicle assembly, greenhouse
gases and energy requirement in the supply chain of vehicle parts are included. All the
automobile parts are assembled and this process is associated with several difficult steps.
In the use of vehicle, all the emissions and energy consumption are taken into account
including vehicle maintenance throughout its life. Specific distance value is required for
the life of automobile and Sorensen (2004) assumed the distance of 300,000 km. For
comparison purposes, the assumption is made for energy consumption in PEMFC
powered automobile is 650 kJ/km and for internal combustion engine it is about 2730
kJ/km.
0.085
0.08
0.075
0.07
0.065
0.06
0.055
0.05
P ro b a b ility
0.045
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
-0.324 -0.301 -0.278 -0.255 -0.232 -0.209 -0.186 -0.163 -0.14 -0.117 -0.093 -0.07 -0.047 -0.024 -0.001 0.022 0.045 0.068 0.091 0.114 0.137 0.16 0.184 0.207 0.23
Uncertainty analysis of 1 kg 'Hydrogen via electroly sis (wind)' (A) minus
Figure 6.45: Uncertainty analysis results of wind and solar based hydrogen production for global
warming potential.
108
Table 6.16: GHG emission in vehicle cycle
Hydrogen Vehicle Gasoline Vehicle

Vehicle Cycle
(Tons of CO2) (Tons of CO2)
Vehicle material production 3.63 3.52
Vehicle assembly 1.65 1.76
Vehicle use 0 59.03
Total 5.28 64.31
0.075
0.07
0.065
0.06
0.055
0.05
0.045
P ro b a b ilit y
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
-1.26 -1.16 -1.06 -0.96 -0.86 -0.76 -0.66 -0.56 -0.46 -0.36 -0.26 -0.16 -0.06 0.03 0.13 0.23 0.33 0.43 0.53 0.63 0.73 0.83 0.93 1.03 1.13
Uncertainty analysis of 1 kg 'Hydrogen via electrolysis (wind)' (A) minus
Figure 6.46: Uncertainty analysis results of wind and solar based hydrogen production for human
toxicity
The greenhouse gas emission from both types of vehicle is compared on the basis
of available literature. Vehicle cycle related emissions are listed in Table 6.16 based on
300,000 km and it shows the gasoline vehicle has the highest emission of 59 tons of CO2.
While on the other hand, hydrogen vehicle has no emission on the environment
throughout its life cycle. However, in the vehicle material production, the hydrogen based
vehicle has more emissions than the gasoline vehicle. This is due to the platinum and
graphite conventional material consumption in the manufacturing of hydrogen vehicle as
shown in Figure 6.47.
109
Hydrogen Vehicle (Tons of CO2) Gasoline Vehicle (Tons of CO2)
70
64.31
59.03
60
GHG emissions, Tons of CO

50
40
30
20
10 5.28
3.63 3.52
1.65 1.76 0
0
Vehicle material production
Vehicle assembly Vehicle use Total
Figure 6.47: GHG emissions of vehicle cycle
The energy consumption data listed in Table 6.17 and Figure 6.53 show that the
gasoline vehicle has the highest energy consumption throughout its life when it covered
the distance of 300,000 km. This 819 GJ of energy is responsible for large amount of
emissions in terms of CO2, SO2 and NOx. The difference in the amount of energy
consumed between the hydrogen vehicle and gasoline vehicle is about 624 GJ of energy.
Table 6.17: Energy consumption in vehicle cycle
Vehicle Cycle Hydrogen Vehicle (MJ) Gasoline Vehicle (MJ)
Vehicle material production 54600 49800

Vehicle assembly 24300 25500
Vehicle use 195000 819000
Total 273900 894300
(Source Hussain et al., 2007)
Energy consumption in vehicle assembly step is higher for the gasoline vehicle
which is 255 GJ as compared to the hydrogen vehicle which is 243 GJ energy as shown
in Figure 6.48. Several complex parts are assembled for internal combustion engine such
as piston, combustion system etc. However, the hydrogen vehicle consumed more energy
in the vehicle material production cycle. About 48 GJ more energy is consumed in the
material production for the hydrogen vehicle.
110
1000000
Hydrogen Vehicle (MJ) Gasoline Vehicle (MJ) 894300
900000 819000
Energy Consumption (MJ)

800000
700000
600000
500000
400000
273900
300000
195000
200000
100000 54600 49800 24300 25500
0
Vehicle material Vehicle assembly Vehicle use Total
production
Figure 6.48: Energy consumption of vehicle cycle
Other steps of vehicle cycle include vehicle distribution and vehicle disposal. In
the vehicle distribution all the energy requirement and GHGs emission are incorporated
during the transport of vehicles from manufacturing and assembly center to the dealers.
On the other hand, in the vehicle disposal, the vehicle is disposed for scrap. The overall
energy required in this process is the sum of all energy needed to move all scrap material
to the shredder and other disposal material. The energy consumption in vehicle
distribution requires more energy than the vehicle distribution. This step consumes about
6 times more energy than vehicle disposal as shown in Table 6.18.
Table 6.18: Energy consumption and GHGs emission comparison in vehicle cycle
Hydrogen Gasoline Hydrogen Vehicle Gasoline Vehicle

Vehicle Cycle
Vehicle (MJ) Vehicle (MJ) (Tons of CO2) (Tons of CO2)
Vehicle distribution 2100 2100 0.11 0.11
Vehicle disposal 300 300 0 0
111
2500
Vehicle distribution Vehicle disposal
2000
Energy consumption (MJ)

1500
1000
500
0
Hydrogen Vehicle (MJ) Gasoline Vehicle (MJ)
Figure 6.49: Energy consumption in vehicle distribution and vehicle disposal
Fuel cycle is another important process which involves several steps for the
production of fuel. Emission throughout the production of hydrogen fuel is calculated in
the previous section, where several processes are studied. This fuel cycle is studied by
Weiss et al. (2000) and Hussain et al., (2007) which include the energy consumption in
the conversion of natural gas to hydrogen and crude oil to gasoline. Moreover, total
greenhouse gases emission is also compared between hydrogen and gasoline for vehicle.
In this thesis, the damage on the environment is measured in different impact categories
and comparison is made between 1 kg of hydrogen through wind electrolysis with 1 kg of
gasoline produced in refinery.
Figure 6.50 shows the comparison between hydrogen and gasoline production.
The emissions are calculated on the bases of 1 kg of fuel. Abiotic depletion is 100 times
higher in gasoline production as compared to hydrogen through wind electrolysis. Large
amount of non-living natural resources are consumed in gasoline production such as
crude oil, coal, heavy metals in the refinery and raw material extraction. The acidification
emission is also higher in gasoline production in comparison with hydrogen production.
About 0.0031 kg SO2-eq. is emitted and deposited on the environment in gasoline fuel
production. Acidification is the acidifying pollutants deposit on the soil, surface and
112
ground water and other biological organisms. However, eutrophication emissions are
comparatively higher in hydrogen fuel production which is about 0.0014 kg PO4-eq.
Eutrophication measure the excess nutrients in terms of NOx and PO4 and all the excess
nutrients emitted on the environment is also damaging the ecosystem quality.
0.0300
0.0246
0.0250
0.0200
Emissions (kg)
0.0150
0.0100
0.0050 0.0031
0.0023 0.0019 0.0014
0.0005
0.0000
Abiotic depletion (kg Sb-eq.) Acidification (kg SO2-eq) Eutrophication (kg PO4-eq.)
Hydrogen wind electrolysis Gasoline at Refinery
Figure 6.50: Fuel production comparison in terms of emission
0.9000
0.7815
0.8000
0.7000 0.6402
0.6000
Emissions (kg)
0.5000
0.4000
0.3250
0.3000
0.2000 0.1532
0.1000
0.0000
Global warming (kg CO2-eq.) Human toxicity (kg DB-eq.)
Hydrogen wind electrolysis Gasoline at Refinery
Figure 6.51: Fuel production comparison in terms of emissions
113
The global warming potential in gasoline production is greater than hydrogen fuel
production. The value of global warming potential is about 0.6402 kg CO2-eq. whereas in
hydrogen it is about 0.325 kg CO2-eq. All the greenhouse gases emissions are higher in
crude oil distillation which is also an energy intensive process. Again in this process,
large amount of fossil fuel resources are burnt to produce gasoline fuel. On the other side,
human toxicity values are higher in hydrogen fuel production which is about 0.7815 kg
dichlorobenzene equivalent. Toxic chemicals which are hazardous to the human health
includes heavy metals, benzene emissions etc.
The benefit of using hydrogen based vehicle is presented through vehicle cycle case
study. Several previous studies are combined for energy consumption and GHGs
emission to give comparison between hydrogen vehicle and gasoline vehicle. Different
periods of vehicle cycle are also compared. It is found that during the vehicle cycle of an
automobile, energy consumption and GHGs emissions of gasoline vehicle are higher than
that of hydrogen automobile and the largest contributor to the energy consumption and
GHGs emissions is the vehicle use stage of the gasoline vehicle cycle.
114
Conclusions and Recommendations
7.1 Conclusions
This thesis study investigated the environmental impacts of hydrogen production using
different methods. Even though hydrogen is a clean energy carrier, the negative impacts
during its production cannot be disregarded, and therefore life cycle analyses for various
scenarios were implemented.
LCA methodology was implemented in order to calculate the environmental

impact of the hydrogen production. LCA software called SimaPro is used in which
several methods are available. In this study, the Eco-indicator 99 and CML 2001 methods
are implemented. Three damage categories were expressed such as damage to human
health, damage to ecosystem quality and damage to resources. After analyzing the
systems in terms of environmental impacts, thermodynamic analyses were conducted to
study the systems energetically and exergetically. The vehicle cycle was studied in order
to compare the hydrogen fuel based vehicle with conventional vehicle using several steps.
The systems energy and exergy efficiencies were calculated. Moreover, parametric
studies were also conducted to examine the effects of different parameters on the system.
The study concluded that hydrogen production from steam methane reforming has
the maximum load on the environment in terms of emissions and other impact categories.
However, this method has the highest energy and exergy efficiencies because large
quantity of hydrogen is produced with almost an equal quantity of input energy
(electricity) as compared to other methods. The comparative environmental impact
findings of the studied system are concluded below;
• Using the CML method for impact categories, the abiotic depletion for SMR is
found to be 0.131 kg Sb eq. which is the highest among all methods. The second
highest abiotic depletion value comes under electrolysis using the mercury cell
which has 0.00786 kg Sb eq. and then with the diaphragm cell with 0.00678 kg Sb
eq, the membrane cell with 0.0061 kg Sb eq., the solar electrolysis with 0.0026
and the wind electrolysis with 0.00228 kg Sb eq.
115
• The global warming potential is highest in SMR of hydrogen production which is
12 kg CO2 eq. After SMR method, electrolysis using the mercury cell has 1.05 kg
CO2 eq. but in the diaphragm cell with 0.909 kg CO2 eq. the membrane cell with
0.887 kg CO2 eq, the solar based hydrogen with 0.37 kg CO2 eq. and the wind
based with 0.325 kg CO2 eq.
• The thermodynamic results suggested that steam methane reforming is the most
efficient method of hydrogen production because the amount of hydrogen energy
produced as output in the system is larger than any other method. The energy
efficiency of the system in this method is about 76.8% and the exergy efficiency
is about 72.4%.
• During the vehicle cycle, the gasoline vehicle has the highest energy consumption
throughout its life when covered a distance of 300,000 km. Moreover, it also has
the highest GHGs emission which is about 50 tons of CO2. On the other hand, a
hydrogen vehicle has no emission on the environment throughout its life cycle.
In summary, hydrogen energy is projected to play a key role in a pollution free

environment. However, the negative impacts during its production cannot be disregarded.
This thesis investigated the environmental impact of hydrogen which shows that steam
methane reforming of natural gas has the highest emissions which is responsible for
damage to human health, damage to ecosystem quality and damage to resources. In order
to replace this method, renewable based hydrogen production was also studied which
suggested that solar and wind based hydrogen production have minimum effects on the
environment.
7.2 Recommendations
This study might help policy makers to put more effort in hydrogen production using
renewable energy, since this thesis found that hydrogen production from renewable
sources is a sustainable way. The following recommendations are provided for future
works:
• Methods such as coal gasification, plasma gasification, partial oxidation,

thermochemical, gasification of biomass and photochemical hydrogen production
should be investigated through life cycle analysis.
116
• Geothermal, tidal and other renewable energy based hydrogen production
methods should also be studied by using life cycle assessment methodology.
• More detailed LCA models should be designed to get more accurate results of the
studied systems.
• Exergoenvironmental and exergoeconomic analysis should be performed for
different hydrogen production methods.
• Specific
• Comprehensive optimization studies should be conducted to determine optimum
operating parameters for hydrogen production.
• Other types of vehicles for different life times should also be studied for
comparison purposes.
117
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Comparative Study of Various Hydrogen Production Methods

A Thesis Submitted in Partial Fulfillment

of the Requirements for the Degree of Master of Applied Science

Faculty of Engineering and Applied Science

University of Ontario Institute of Technology

Oshawa, Ontario, Canada

© Fahad Suleman, December 2014

In this thesis, a comparative environmental assessment is presented for different

I would like to express my sincere gratitude to my supervisor Dr. Ibrahim Dincer

Furthermore, I thank my colleagues at UOIT who made an enjoyable working

1.1 Motivation and Objectives ................................................................................... 4

1.1.1 Motivation ..................................................................................................... 4

1.1.2 Objectives .......................................................................................................... 4

2.1 Methods of Hydrogen Production ............................................................................. 8

2.2 Fossil Fuel Hydrogen Production ............................................................................. 8

2.3 Renewable Hydrogen Production ........................................................................... 11

2.3.1 Solar Based Hydrogen Production ................................................................... 11

2.3.2 Wind Based Hydrogen production ................................................................... 14

2.3.3 Geothermal Based Hydrogen Production ........................................................ 15

2.3.4 Biomass based Hydrogen production .............................................................. 17

2.4 Nuclear Based Hydrogen Production ...................................................................... 18

2.5 Life Cycle Assessment ............................................................................................ 19

3.1 Hydrogen Production Methods ............................................................................... 22

3.1.1 Natural Gas Steam Reforming ......................................................................... 22

3.1.2 Coal Gasification ............................................................................................. 23

3.1.3 Partial Oxidation .............................................................................................. 24

3.1.4 Electrolysis ....................................................................................................... 25

3.1.5 Thermochemical Water Splitting ..................................................................... 26

3.2 Life Cycle Assessment Methodology ..................................................................... 27

3.2 LCA and International Standard Organization ....................................................... 29

3.4 Impact Assessment .................................................................................................. 29

3.4.2 Characterization ............................................................................................... 31

3.4.3 Normalization .................................................................................................. 31

3.4.4 Weighting ......................................................................................................... 31

3.5 Advantages of LCA ................................................................................................ 32

Systems Studied .......................................................................................... 33

4.1 Hydrogen Production from Steam Methane Reforming ......................................... 37

4.2.1 Mercury Cell Electrolysis ................................................................................ 38

4.2.2 Diaphragm Cell Electrolysis ............................................................................ 39

4.2.3 Membrane Cell Electrolysis ................................................................................. 40

4.3 Hydrogen Production via Wind Based Electricity .................................................. 41

4.4 Hydrogen Production via Solar Photovoltaic Based Electricity ............................. 42

5.1 Environmental Impacts Assessment using LCA..................................................... 44

5.1.1 Emissions ......................................................................................................... 45

5.1.3 Resource Depletion .......................................................................................... 46

5.2 Analysis of Hydrogen Production via Steam Methane Reforming......................... 47

5.2.1 Energy and Exergy Efficiencies ....................................................................... 48

5.3 Analyses of Hydrogen Production Methods through Electrolysis Using Different

5.4 Analyses of Hydrogen Production through Electrolysis Using Wind Electricity... 51

5.4.1 Energy and Exergy Efficiencies ....................................................................... 52

5.5 Analyses of Hydrogen Production through Electrolysis Using Solar Photovoltaic

5.5.1 Energy and Exergy Efficiencies ....................................................................... 55

6.1 Hydrogen via Steam Methane Reforming .............................................................. 57

6.1.1 Impact Assessment Results .............................................................................. 57

6.1.2 Energy and Exergy Efficiencies ....................................................................... 64

6.2 Hydrogen from Chlorine Electrolysis Using Different Cells.................................. 68

6.2.1 Impact Assessment Results .............................................................................. 68

6.3 Hydrogen via Electrolysis Using Wind Electricity ................................................. 77

6.3.1 Impact Assessment Results .............................................................................. 77

6.3.2 Energy and Exergy Efficiencies ....................................................................... 85

6.4 Hydrogen via Electrolysis Using Solar Photovoltaic Electricity ............................ 88

6.4.1 Impact Assessment Results .............................................................................. 88

6.4.2 Energy and Exergy Efficiencies ....................................................................... 97

Cathode: 4H2O + 4 → 2H2 + 4OH (3.5)

Anode: 4OH → O2 + 2H2O + 4 (3.6)