4_ hydrogen

4.1 Historical development of hydrogen as a fuel.

The historical development of hydrogen as a fuel spans several centuries and
has evolved through various stages of experimentation, discovery, and practical
applications. Here is an overview of the historical development of hydrogen as a
fuel:
1. Early Discoveries (16th-18th Century):
- Hydrogen was first discovered by the Swiss alchemist Paracelsus in the 16th
century.
- In the 18th century, the French chemist Antoine Lavoisier named the gas
"hydrogen" and described its properties.
2. Hydrogen as a Lifting Gas (18th-19th Century):
- Hydrogen gained early fame for its use in hot air balloons, particularly during
the late 18th and early 19th centuries.
- The famous Montgolfier brothers used hydrogen to lift the first piloted flight
in a balloon in 1783.
- The use of hydrogen in ballooning continued for decades until the
Hindenburg disaster in 1937, which led to safety concerns and a shift away from
using hydrogen for airships.
3. Industrial Applications (19th Century):
- In the 19th century, hydrogen found various industrial applications,
particularly in the production of ammonia and as a reducing agent in the
chemical industry.
- It was also used in the early days of electric power generation in gas-fired
engines.
4. Hydrogen Fuel Cell Concept (20th Century):
- The concept of the hydrogen fuel cell was first proposed in the 19th century,
but it gained practical attention in the mid-20th century.
- In 1959, NASA began using hydrogen fuel cells to generate electricity for
spacecraft, which laid the foundation for later developments in fuel cell
technology.

5. Hydrogen in the Space Race (20th Century):

- During the 1960s and 1970s, hydrogen played a significant role in the U.S.
space program. The Apollo missions used hydrogen fuel cells for electrical
power generation and water production.
6. Energy Storage and Fuel Cell Advancements (Late 20th Century):
- Throughout the latter half of the 20th century, hydrogen fuel cells saw
advancements in efficiency and practical applications.
- Fuel cell research expanded into areas such as transportation, including the
development of hydrogen-powered vehicles.
7. Renewed Interest in Hydrogen (21st Century): - The 21st century brought
renewed interest in hydrogen as a clean energy source.
- Countries and organizations began to focus on the potential of hydrogen as a
fuel to reduce greenhouse gas emissions and address climate change. -
Hydrogen fuel cell vehicles became commercially available in some markets,
with companies like Toyota and Hyundai leading the way.

8. Hydrogen as a Key Component of Clean Energy Transition (21st Century):

- In the early 21st century, hydrogen started gaining recognition as a key
component of the clean energy transition.
 - Governments and industries began investing in research, development, and
infrastructure for the production, storage, and use of hydrogen as a clean fuel
source.
The historical development of hydrogen as a fuel has gone through stages of
scientific discovery, practical applications, and shifts in focus, with a recent
resurgence of interest as a crucial element in the transition to cleaner and more
sustainable energy sources. It continues to be a topic of extensive research and
development in the pursuit of a greener energy future.
4.2 Various methods of hydrogen production.
Hydrogen can be produced through various methods, each with its own
advantages and disadvantages. These methods can be broadly categorized into
three main types:

1. Steam Methane Reforming (SMR):

- SMR is the most common method of hydrogen production, accounting for a
significant portion of global hydrogen supply.
- It involves the reaction of methane (CH4) with steam (H2O) in the presence
of a catalyst to produce hydrogen gas (H2) and carbon dioxide (CO2).
- It is highly efficient and cost-effective but produces CO2 emissions, making it
a source of "grey" hydrogen.
2. Electrolysis:
- Electrolysis is a method of hydrogen production that uses electricity to split
water (H2O) into hydrogen and oxygen (O2) through the process of electrolysis.

- There are two primary types of electrolysis: alkaline electrolysis and proton
exchange membrane (PEM) electrolysis.
- Electrolysis can be powered by renewable energy sources, making it a source
of "green" hydrogen with no direct emissions.
3. Biomass Conversion:
- Biomass gasification and pyrolysis processes can produce hydrogen from
organic materials, such as agricultural residues, woody biomass, or waste.
- These methods release hydrogen-rich syngas, which can be further processed
to isolate hydrogen.
- Biomass-derived hydrogen is considered a form of "green" hydrogen when
sustainable biomass sources are used.
4. Coal Gasification:
- Coal gasification involves the conversion of coal into a synthetic gas (syngas)
that contains hydrogen.
- It is used to produce "grey" hydrogen, but carbon capture and storage (CCS)
technologies can be applied to reduce CO2 emissions.
5. Nuclear Hydrogen Production:
- High-temperature nuclear reactors can generate hydrogen through
thermochemical processes.
- The sulfur-iodine and the hybrid sulfur processes are examples of nuclear-
driven methods for hydrogen production.
6. Biological Hydrogen Production:
- Some microorganisms, like certain types of bacteria and algae, are capable of
producing hydrogen through biological processes.
- This method is in the early stages of research and has potential for "green"
hydrogen production.

7. Photolytic Water Splitting:

- This method uses solar energy to split water molecules into hydrogen and
oxygen.
 - It holds promise for "green" hydrogen production but faces challenges
related to efficiency and cost.
8. Thermochemical Water Splitting:
- Thermochemical processes use heat from concentrated solar power or other
sources to drive chemical reactions that release hydrogen from water.
- Various thermochemical cycles, such as the sulfur-iodine cycle and the
copper-chlorine cycle, are being explored.
9. Hydrogen Production from Wind and Solar Power:
- Renewable energy sources, like wind and solar power, can be used to
produce hydrogen through electrolysis or other methods.
- These methods produce "green" hydrogen when the electricity source is
renewable.
The choice of hydrogen production method depends on factors such as cost,
environmental impact, availability of feedstocks, and the intended application.
The ongoing development and integration of clean and sustainable methods of
hydrogen production are crucial to the transition towards a greener and more
sustainable energy future.

4.3 Types of hydrogen (grey, blue, green)

Hydrogen comes in different types based on how it is produced, and these types
are often classified as "grey," "blue," and "green" hydrogen. These distinctions
are based on the environmental and carbon emissions profiles associated with
each production method:

1. Grey Hydrogen:
- Grey hydrogen is the most common and traditional type of hydrogen.
 - It is primarily produced through a process called steam methane reforming
(SMR), which involves reacting methane (usually derived from natural gas) with
steam to produce hydrogen and carbon dioxide (CO2).
- The key characteristic of grey hydrogen is that it is produced without carbon
capture and storage (CCS), leading to significant CO2 emissions.
- It is the least environmentally friendly type of hydrogen.

2. Blue Hydrogen:
- Blue hydrogen is produced using the same methods as grey hydrogen,
primarily steam methane reforming (SMR).
- However, the key difference is that the CO2 emissions generated during
production are captured and stored (CCS) to prevent them from entering the
atmosphere.

- The use of CCS technology makes blue hydrogen a lower-carbon option

compared to grey hydrogen.
 - It represents a transition phase toward cleaner hydrogen production.

3. Green Hydrogen:
- Green hydrogen is considered the most environmentally friendly type of
hydrogen.
- It is produced using renewable energy sources, such as wind, solar, or
hydroelectric power, to power the process of water electrolysis.

- Electrolysis splits water (H2O) into hydrogen (H2) and oxygen (O2), and when
powered by renewable energy, it generates no direct greenhouse gas emissions.
 - Green hydrogen is seen as the cleanest and most sustainable form of
hydrogen.

4.4 Hydrogen storage :

is a crucial aspect of using hydrogen as an energy carrier, given that hydrogen is
a gas at standard temperature and pressure. Effective hydrogen storage
methods are essential to ensure its availability for various applications, including
transportation, industry, and energy generation. Several hydrogen storage
technologies exist, each with its own advantages and limitations:
1. Compressed Gas Storage:
- In this method, hydrogen gas is compressed and stored in high-pressure
tanks or cylinders.
- The main advantage is that it is a simple and mature technology.

- However, it requires strong and heavy tanks to withstand high pressures, and
energy is needed for compression.
 - Compressed gas storage is suitable for stationary applications with ready
access to infrastructure.
2. Liquid Hydrogen Storage:
- Hydrogen can be cooled and liquefied at extremely low temperatures
(around -253°C or -423°F) and stored in insulated containers.
- Liquid hydrogen has a higher energy density compared to gaseous hydrogen.
- However, the extreme cryogenic conditions require specialized containers
and result in energy losses during liquefaction and transportation.
- It is commonly used in space applications and specialized transport.
3. Metal Hydride Storage:
- Metal hydrides are compounds formed when hydrogen is chemically bonded
with certain metals.
- They can absorb and release hydrogen reversibly under controlled
conditions, making them suitable for on-demand hydrogen release.
- Metal hydrides can store hydrogen at moderate pressures and temperatures,
making them safer than gas or liquid storage.
- However, metal hydride systems can be heavy and may have limited
hydrogen storage capacities.
4. Chemical Hydrogen Storage:
- Chemical hydrogen storage involves the use of chemical reactions to release
and store hydrogen.
- Ammonia (NH3) is one example; it can release hydrogen when heated and
can be used as a carrier for hydrogen.
- While chemical storage can provide high hydrogen density, it can be complex
and may involve toxic or hazardous substances.

5. Carbon Nanotube and Nanostructured Materials:

 - Nanostructured materials and carbon nanotubes have been studied for their
potential to store hydrogen through adsorption on their surfaces.
- They offer the potential for high hydrogen storage densities at lower
pressures, but challenges related to stability and reversibility remain.
6. Solid-State Hydrogen Storage:
- Solid-state hydrogen storage materials, such as complex metal hydrides and
covalent organic frameworks, have been researched for their ability to store and
release hydrogen.
- They offer the potential for safe and efficient storage, but research is ongoing
to improve their properties.
7. Hydrogen Liquefaction for Long-Term Storage:
- For long-term storage, surplus renewable energy can be used to produce
hydrogen via electrolysis and then liquefied for storage and transport.
- This method can be applied to balance the variability of renewable energy
sources and ensure a stable hydrogen supply.
Hydrogen storage technologies are continually evolving, with ongoing research
and development aimed at improving efficiency, safety, and practicality. The
choice of storage method depends on factors such as the application, energy
efficiency, safety, and infrastructure availability. Different storage methods may
be suitable for various use cases, from portable applications like fuel cell
vehicles to large-scale energy storage and industrial processes.
4.5 Horse power output ranges for hydrogen-powered engines
1. Automotive Fuel Cells:
Hydrogen fuel cells used in hydrogen fuel cell vehicles (FCVs) typically provide
power in the range of 80 to 200 kilowatts (kW), which is approximately
equivalent to 107 to 268 horsepower (hp). These vehicles use electric motors
driven by fuel cell stacks to propel the vehicle.

2. Marine Engines:
In maritime applications, the power output can vary significantly based on the
size and design of the ship's engine. Some hydrogen-powered ship engines can
produce thousands of kilowatts (kW), equivalent to several thousand
horsepower (hp).
3. Aircraft Engines:
Hydrogen can also be used in aviation. Hydrogen-powered aircraft engines can
provide a wide range of power, depending on the aircraft's size and purpose.
Small hydrogen-powered drones might have power outputs in the tens of
kilowatts, while larger aircraft could have power outputs in the thousands of
kilowatts.
4. Industrial and Power Generation:
Hydrogen is used in industrial processes, and it can also be used to generate
electricity. Power plants using hydrogen can have a wide range of power
outputs, from a few megawatts to hundreds of megawatts or more.
It's important to note that the power output of hydrogen-based engines is
influenced by factors like the efficiency of the engine, the type of fuel cell or
combustion technology used, and the amount of hydrogen available.
Additionally, advancements in hydrogen technology and engine design may lead
to higher power outputs in the future.
Hydrogen has the potential to play a significant role in a wide range of
applications, including transportation, power generation, and industrial
processes, where power requirements can vary greatly. The specific power
output will depend on the application's requirements and the technology used.
4.6 Hydrogen combustion equations.
Hydrogen combustion reactions can be summarized with a series of equations,
taking into account various forms of hydrogen and the resulting products. Here
are some common hydrogen combustion reactions:
1. Complete Combustion of Hydrogen:
- Balanced Equation: 2H2 + O2 -> 2H2O
 - This equation represents the complete combustion of hydrogen, forming
water as the only product.
2. Incomplete Combustion of Hydrogen:
- Balanced Equation: 2H2 + O2 -> 2H2O + Energy
- Incomplete combustion can occur when there is an insufficient supply of
oxygen, leading to the release of energy and the formation of water vapor and
unburned hydrogen.
3. Combustion of Hydrogen with Air:
- Balanced Equation: 2H2 + O2 + N2 -> 2H2O + N2
- In real-world combustion processes, hydrogen typically burns with
atmospheric air, which contains nitrogen (N2). The reaction forms water and
nitrogen as the products.
4. Hydrogen Combustion with Carbon:
- Balanced Equation: 2H2 + C + O2 -> 2H2O + CO2
- When hydrogen burns in the presence of carbon, as in a hydrocarbon fuel, it
produces water and carbon dioxide (CO2) as the primary products.
These equations represent different scenarios in which hydrogen can undergo
combustion. In each case, hydrogen combines with oxygen to produce water,
and other reactants may also be involved, depending on the specific conditions
and reactants present.
4.7 The economic impact of hydrogen on the world in the future.
The economic impact of hydrogen on the world in the future is expected to be
significant:
1. Job Creation: The hydrogen industry is likely to create jobs in production,
infrastructure development, and research, stimulating economic growth.

2. Reduced Energy Costs: Hydrogen can help stabilize energy costs and promote
energy independence, benefiting various industries and consumers.
3. Exports: Countries with abundant renewable energy resources can become
hydrogen exporters, boosting their economies.
4. Industrial Growth: Hydrogen use in sectors like transportation, industry, and
power generation can drive economic development and innovation.
5. Energy Security: Diversifying energy sources through hydrogen can enhance
national energy security and resilience.
6. Innovation and R&D: Investment in hydrogen technologies will foster
innovation, making economies more competitive in the global energy market.
7. Carbon Emissions Reduction: Hydrogen can help meet emissions reduction
targets and avoid associated costs of climate change.
8. Hydrogen Economy: A mature hydrogen economy could result in trillions of
dollars in economic activity.
While the economic impact of hydrogen is promising, it depends on factors like
technological advancements, supportive policies, and infrastructure
development.
4.8 Compare between diesel powered ship and hydrogen powered ship
4.9 Hydrogen types and fuel cells
4.9.1 Proton Exchange Membrane Fuel Cells (PEMFC):
Proton Exchange Membrane Fuel Cells (PEMFC) are based on an aqueous electrolyte—a
polymer—that transports hydrogen ions thanks to the presence of liquid water on the
component itself. The main components of PEMFC are as follows the Membrane Electrode
Assembly (MEA) which includes the Polymer Electrolyte Membrane (PEM), the catalyst
layers, and gas diffusion layers. There are other components to integrate MEA into the fuel
cell, such as the gaskets that give a seal around the MEA to avoid gas leakage and bipolar
plates which assemble the single PEMFC into a fuel cell stack. The hydrogen enters the anode
side, which is oxidized to produce protons and electrons; the protons diffuse through the PEM
to the cathode; the electrons travel through the MEA to the cathode; the oxygen reduction
reaction takes place at the cathode, where the oxygen is reduced. The unreacted oxygen and
the water produced in the reaction exit PEMFCs are the most diffused type of fuel cell and
one of the most promising technologies for decarbonizing the transportation sector, as they
employ high-purity H2, with only water emissions in the energy generation. They operate at
low temperatures (60–85) C° {14}
Equation: Cathode: 2H2(g) + 4e- + 4H+ --> 4H2O(l)
Anode: 2H2(g) --> 4H+ + 4e-
Overall reaction: 2H2(g) + O2(g) --> 2H2O

Proton Exchange Membrane Fuel Cells (PEMFC)

4.9.2 Solid Oxide Fuel Cells (SOFC):
Solid Oxide Fuel Cells (SOFC) work at very high temperatures, the highest among all the
fuel cell types (around 800–1000). They have an efficiency of up to 55–60% when converting
fuel to electrical energy; the high operating temperature gives the possibility of employing
SOFC in hybrid systems with gas turbines (GT) and for Combined Heat and Power (CHP)
applications. The hybrid system can achieve very high performance. SOFCs use a solid
ceramic electrolyte, such as zirconium oxide stabilized with yttrium oxide, instead of a liquid
(used for alkaline cells) or aqueous membrane (used for PEMFC). The main components of
planar SOFC are an anode, solid ceramic electrolyte, cathode, and bipolar separator plate.
The molecular oxygen becomes oxide ions (O2) and combines with hydrogen to form water
while simultaneously producing electrical energy, Fuel flexibility is one of the advantages of
solid oxide fuel cells: thanks to their high operating temperature, the fuel can be reformed
within the fuel cell itself, eliminating the need for an external reformer and allowing the units
to operate with a variety of hydrocarbon fuels. They are also relatively resistant to small
quantities of sulfur in the fuel compared to other fuel cells. A further advantage of the high
operating temperature is that the reaction kinetics are improved, removing the need for noble
metal catalysts. The high temperatures and absence of a metal catalyst allow for higher
tolerance to impurities in the reactants.

Solid Oxide Fuel Cells (SOFC)

Equation: Cathode: 1/2O2(g) + 2e- + 2H+(aq) --> H2O

Anode: H2(g) --> 2H+(aq) + 2e-
Overall reaction: H2(g) + 1/2O2(g) --> H2O
 4.9.3 Molten carbonate fuel cells (MCFCs):
MCFCs are high-temperature fuel cells that use an electrolyte composed of a molten
carbonate salt mixture suspended in a porous, chemically inert ceramic lithium
aluminum oxide matrix. Because they operate at high temperatures of 650°C (roughly
1,200°F), non-precious metals can be used as catalysts at the anode and cathode,
reducing costs. Improved efficiency is another reason MCFCs offer significant cost
reductions over phosphoric acid fuel cells. Molten carbonate fuel cells, when coupled
with a turbine, can reach efficiencies approaching 65%, Unlike alkaline, phosphoric
acid, and PEM fuel cells, MCFCs do not require an external reformer to convert fuels
such as natural gas and biogas to hydrogen. At the high temperatures at which MCFCs
operate, methane and other light hydrocarbons in these fuels are converted to hydrogen
within the fuel cell itself by a process called internal reforming, which also reduces
cost. The primary disadvantage of current MCFC technology is durability. The high
temperatures at which these cells operate and the corrosive electrolyte used accelerate
component breakdown and corrosion, decreasing cell life. Scientists are currently
exploring corrosion-resistant materials for components as well as fuel cell designs that
double cell life from the current 40,000 hours (~5 years) without decreasing
performance.

Equation: Cathode: 1/2O2(g) + CO2(g) + 2e- --> CO3^2-(aq)

Anode: H2(g) + CO3^2-(aq) --> H2O(l) + CO2(g) + 2e-
Overall reaction: H2(g) + 1/2O2(g) + CO2(g) --> H2O(l) + CO3^2-

Figure 10 Molten carbonate fuel cells (MCFCs)

4.9.4 Phosphoric acid fuel cells (PAFCs):
Phosphoric acid fuel cells (PAFCs) use liquid phosphoric acid as an electrolyte—the acid is
contained in a Teflon-bonded silicon carbide matrix—and porous carbon electrodes
containing a platinum catalyst. The PAFC is considered the "first generation" of modern fuel
cells. It is one of the most mature cell types and the first to be used commercially. This type
of fuel cell is typically used for stationary power generation, but some PAFCs have been used
to power large vehicles such as city buses. PAFCs are more tolerant of impurities in fossil
fuels that have been reformed into hydrogen than PEM cells, which are easily "poisoned" by
carbon monoxide because carbon monoxide binds to the platinum catalyst at the anode,
decreasing the fuel cell's efficiency. PAFCs are more than 85% efficient when used for the
co-generation of electricity and heat but they are less efficient at generating electricity alone
(37%–42%). PAFC efficiency is only slightly more than that of combustion-based power
plants, which typically operate at around 33% efficiency. PAFCs are also less powerful than
other fuel cells, given the same weight and volume. As a result, these fuel cells are typically
large and heavy. PAFCs are also expensive. They require much higher loadings of expensive
platinum catalyst than other types of fuel cells do, which raises the cost.

Phosphoric acid fuel cell

Equation: Cathode: 1/2O2(g) + 2H+(aq) + 2e- --> H2O(l)
Anode: H2(g) --> 2H+(aq) + 2e-
Overall reaction: H2(g) + 1/2O2(g) --> H2O(l)
4.9.5Alkaline fuel cells (AFCs):
These fuel cells use a solution of potassium hydroxide in water as the electrolyte and can use
a variety of non-precious metals as a catalyst at the anode and cathode. In recent years, novel
AFCs that use a polymer membrane as the electrolyte have been developed. These fuel cells
are closely related to conventional PEM fuel cells, except that they use an alkaline membrane
instead of an acid membrane. The high performance of AFCs is due to the rate at which
electro-chemical reactions take place in the cell. They have also demonstrated efficiencies
above 60% in space applications.
this fuel cell type is that it is susceptible to poisoning by carbon dioxide (CO2). In fact, even
the small amount of CO2 in the air can dramatically affect cell performance and durability
due to carbonate formation. Alkaline cells with liquid electrolytes can be run in a
recirculating mode, which allows for electrolyte regeneration to help reduce the effects of
carbonate formation in the electrolyte, but the recirculating mode introduces issues with shunt
currents. The liquid electrolyte systems also suffer from additional concerns including
wettability, increased corrosion, and difficulties handling differential pressures. Alkaline
membrane fuel cells (AMFCs) address these concerns and have lower susceptibility to CO2
poisoning than liquid-electrolyte AFCs do. However, CO2 still affects performance, and
performance and durability of the AMFCs still lag that of PEMFCs. AMFCs are being
considered for applications in the W to kW scale. Challenges for AMFCs include tolerance
to carbon dioxide, membrane conductivity and durability, higher temperature operation,
water management, power density, and anode electro catalysis. {14}

Equation: Figure 12 Alkaline fuel cells (AFCs)

Cathode: 1/2O2(g) + 2H2O(l) + 4e- --> 4OH-(aq)
Anode: 2H2(g) + 4OH-(aq) --> 4H2O(l) + 4e-
Overall reaction: 2H2(g) + 1/2O2(g) --> 2H2O(l)

4.10 Hydrogen production systems

4.10.1Solid Oxide Electrolyzer Cell (SOEC)

Bloom Energy | 1.8 MW module

System Efficiency = 37.5 kWh/kg
Warm Start-up = 10 min
Power consumption:
H2 output (mt*/day) = 1.2
H2 output (kg/hr) = 48
H2 output (Nm3/hr) = 534
- Steam input:
Pressure = 4.5-5.5 bar (g)
Temperature = 150-200°C
Volume = 10.51 of H20/ka of H2

4.10.2 Proton exchange membrane (PEM) electrolyzer

Nel Hydrogen | M5000

- Net Production Rate = 4,920 Nm3/h = 10,618
kg/24h
Production Capacity Dynamic Range = 10 to 100%
Average Power Consumption at Stack = 4.5
kWh/Nm3
Delivery Pressure = 30 barg
Feed Water Consumption = 0.9 I/Nm3

4.10.3 Anion Exchange Membrane (AEM)

Enapter | AEM Flex 120

H2 nominal flow = 25 Nm3/h / 53.9 kg/24h
H2 outlet pressure =< 35 barg
Nominal power consumption = 120 kW - 150
H20 nominal consumption = 23 L/h Purified
water
- H20 inlet quality → Minimum ASTM D1193-06
Type IV or recommended Type II or Type IlI
- Operational flexibility = 12% - 100% Of
nominal H2 fowrate
- Specific power consumption (Efficiency) = 4.8
kWh/Nm3H2 - 53.3 kWh/kgH2, 62.5% (LHV)
Cold startup = 0 - 100% in 30 min
Hot startup = 0 - 100% in 100 sec
Weight ~ 3,700 kg