The document provides an overview of hydrogen production methods, highlighting processes like steam methane reforming and biomass gasification, with steam reforming being the most commonly used method. It details current hydrogen production statistics, predominant uses, and emerging technologies, particularly focusing on Germany's future hydrogen strategy and efforts to incorporate green hydrogen into sectors like transport and steel production. Additionally, it discusses the potential of electrolysis and photobiological methods for producing pure hydrogen.

1. Hydrogen Production
Dr. Snunkhaem Echaroj
ดร. สนันตน์เขม อิชโรจน์

2. One Advantage of using hydrogen
 One advantage is that it stores approximately
2.6 times the energy per unit mass as
gasoline, and the disadvantage is that it
needs about 4 times the volume for a given
amount of energy.
 A 15 gallon automobile gasoline tank contains
90 pounds of gasoline. The corresponding
hydrogen tank would be 60 gallons, but the
hydrogen would weigh only 34 pounds.

3. Current global hydrogen production
 48% from natural gas
 30% from oil
 18% from coal
 4% from electrolysis of water

4. Primary Uses for Hydrogen Today
 1. About half is used to produce ammonia
(NH3) fertilizer.
 2. The other half of current hydrogen
production is used to convert heavy
petroleum sources into lighter fractions
suitable for use as fuels.

5. Hydrogen Production Processes
 Steam Methane Reforming
 Coal Gasification
 Partial Oxidation of Hydrocarbons
 Biomass Gasification
 Biomass Pyrolysis
 Electrolysis

6. Steam Methane Reforming
 Most common method of producing
commercial bulk hydrogen.
 Most common method of producing
hydrogen used in the industrial synthesis
of ammonia.
 It is the least expensive method.
 High temperature process (700 – 1100 °C.
 Nickel based catalyst (Ni)

7. The Steam Methane Reforming
Process
 At 700 – 1100 °C and in the presence of a nickel
based catalyst (Ni), steam reacts with methane
to yield carbon monoxide and hydrogen.
 CH4 + H2O → CO + 3 H2
 Additional hydrogen can be recovered by a
lower-temperature gas-shift reaction with the
carbon monoxide produced. The reaction is
summarized by:
 CO + H2O → CO2 + H2

8. Purification of Hydrogen
 Carbon dioxide and other impurities are
removed from the gas stream, leaving
essentially pure hydrogen.
 Endothermic reaction (Heat must be
added to the reactants for the reaction to
occur.)

9. Schematic of the SMR Process
REMOVAL OF CO
AND CO2
REFOR MER
10%
CO
2,000ppm
CO
WATER GAS SHIFT
REACTOR
Water
Methane
Gasoline
Ethanol
Methanol
<100ppm
CO
O2
H2O
H2
FUEL CELL
STACK

10. Coal Gasification
 well-established commercial technology
 competitive with SMR only where oil and/or
natural gas are expensive.
 coal could replace natural gas and oil as the
primary feedstock for hydrogen production,
since it is so plentiful in the world.

11. Partial Oxidation Hydrocarbons
 process can be used to produce hydrogen
from heavy hydrocarbons such as diesel
fuel and residual oil.
 Any hydrocarbon feedstock that can be
compressed or pumped may be used in
this technology.

12. Partial Oxidation
 Methane and other hydrocarbons in
natural gas are reacted with a limited
amount of oxygen (typically, from air) that
is not enough to completely oxidize the
hydrocarbons to carbon dioxide and water.
 CH4 + ½O2 → CO + 2H2 (+heat)
 Exothermic reaction (heat is evolved)

13. Schematic of Partial Oxidation
Partial Oxidation Plant Diagram

14. Thermochemical Production of
Hydrogen
 When water is heated to above 2500 oC, it
separates into oxygen and hydrogen in a
process known as thermolysis.
 However, at such high temperatures, it is
difficult to prevent the oxygen and
hydrogen from recombining to form water.

15. Thermochemical Production of
Hydrogen
 Thermochemical water-splitting cycles can lower
the temperature and help separate oxygen and
hydrogen products to produce pure hydrogen
gas.
 These cycles can improve the efficiency of
hydrogen production from 30% for conventional
electrolysis to around 50% efficiency
 One of the most promising cycles so far is the
sulfur-iodine (S-I) cycle.

16.  Sulfur dioxide (SO2 ) and iodine (I2) are fed
into the cycle as chemical catalysts..
 A catalyst lowers the activation energy of a
reaction without being used up by the
reaction.

17. Sulfur-Iodine Thermochemical
Cycle
 In this cycle, sulfur dioxide (SO2) and
iodine (I2) are feed into the cycle as a
chemical catalyst.
 A catalyst lowers the temperature at which
the reaction will occur without being used
up by the reaction.

18. There are three steps in the S-I
cycle
 Step 1:
 I2 + SO2 + 2H2O 2HI + H2SO4
 The reaction is run at 120 degrees C.
 The hydrogen iodide and sulfuric acid are
separated, usually by distillation.

19.  Step 2:
 Generation of oxygen and regeneration of
SO2.
 H2SO4 H2O + SO2 + 1/2 O2
 This reaction is run at 850 degrees C.

20.  Step 3: Generation of hydrogen and
regeneration of I
 2HI H2 + I2
 This reaction is run at 450 degrees C.

21. Sulfur—Iodine Cycle
 These reactions can reduce the high
temperature demands of the thermolysis
of water for the production of hydrogen
gas and can provide a mechanism for the
separation of oxygen and hydrogen
products to prevent recombination.
Source: Office of Nuclear Energy, Science and Technology

22. Biomass Production of Hydrogen
 Hydrogen can be produced numerous ways
from biomass.
 Biomass is defined as a renewable resource
made from renewable materials. Examples of
biomass sources include:
>switchgrass
>plant scraps
>garbage
>human wastes
 Gasification of biomass could be a way of
extracting hydrogen from these organic sources.

23. Biomass Production of Hydrogen
 The biomass is first converted into a gas through
high-temperature gasifying.
 The hydrogen rich vapor is condensed in
pyrolysis oils.
 These oils can be steam reformed to generate
hydrogen.
 This process has resulted in hydrogen yields of
12% - 17% hydrogen by weight of the dry
biomass.
 When biological waste material is used as a
feedstock, this process becomes a completely
renewable, sustainable method of hydrogen
generation.

24. Hydrogen from Fossil fuels
 The production of Hydrogen can also take place
from fossil fuels, and steam reforming process is
used to carryout the process.
 95% prefers production of Hydrogen through
steam reforming
 Steam reforming also known as Steam methane
reforming, a method to produce Syngas (H2 and
CO) by reacting of hydrocarbons with H2O. The
reaction proceed as follows:
CH4 + H2O ⇌ CO + 3H2

25. Step 1) Furnace - Steam Production
The steam reforming will take place in 5 steps.

26. Steps of Steam reforming
 2. Reforming: Involves the
catalytic reaction of
methane with steam(H2O)
at very high temperatures of
1400 – 1500 F. The reaction
will be:
CH4 + H2O ⇌ CO + 3H2
The reaction is endothermic
and it takes place through
catalyst filled tubes in a
furnace. It consist of 25 – 40%
Nickel oxide which will be
deposited on a low silica
refractory base.

27. Steps of Steam reforming
 3. WaterS-hift Conversion: The CO of the
previous process is further reacted with steam
to produce Hydrogen which result in the
following reaction:
CO + H20  CO2 + H2
The excessive heat will be produced and the
reaction will be exothermic and carried out at a
temperature of 650 deg F in a fixed bed catalytic
converter. The catalyst is also used to speed up
the reaction which is a mixture of Chromium and
iron oxide.

29. Steps of Steam reforming
 4. Gas Purification: The carbon dioxide is further removed
from the system of gases by absorption in a circulating
amine or hot potassium carbonate solution. We will also add
treating solutions which will contact the H2 and CO2 in the
absorber containing about 24 trays. Carbon dioxide will be
absorbed by the solution which will send for regeneration.
 5. Methanation: In this step the small amount of that
remaining CO and CO2 are converted to methane gas to get
back to the initial step for further production of H2.
CO + 3H2  CH4 + H2O
CO2 + 4H2  CH4 + 2H2O
This process also takes place in fixed-bed catalytic reactor at
temperature of about 700 to 800 deg F. Both reactions are
exothermic.

30. Steam Reforming Process

31. Steam Reforming Process
The H2 gas from Steam Reforming may includes small
amount of CO, CO2, H2S as impurities and we must have to
remove them in order to get pure H2 gas. Two steps can be
taken:
 Feedstock purification: Using this process, we will
remove poison, including sulphur, chloride to increase the
life of catalyst.
 Product purification: The CO2 will be removed. The
product gases undergoes a methanization step to remove
residual traces of carbon oxides.
New SMR are using Pressure Swing Absorption (PSA) units
which produces 99.9% pure H2 gas

32. Advantages for the process of
Steam Reforming
I. The process is highly economical, efficient, environmental
friendly and widely used for H2 production.
II. The efficiency of the process is 65 to 75%
III. It is the cheapest of all above discussed processes, since the
production depends on the cost of Natural gas(methane)
which is readily available.
IV. Relatively stable during transition operation

33. Demerits for the process of
Steam Reforming
I. Excess amount OF CO2 is produced.
II. The impurities of Chlorides, CO, CO2 and sulphides
are also present which may damage the catalyst in the
reactor which must be removed.
III. External heat transfer device is required and hence
result in system complexity and potential higher cost

34. Hydrogen Production in Germany
 The current production of H2 gas in
Germany is almost 20billion cubic
centimeters annually.
 5% of H2 is produced from green
resources, while 95% is produced from
fossil fuel such as Natural gas or coal

35. Possible Hydrogen applications in
Germany
 Rail transport line, hydrogen could be effective for tracks that have no overload contact line.
 Hydrogen may also be attractive for public road and freight road transport because in
comparison with electric vehicles, the charging times and weight of the batteries needed for
electric vehicles are not always economically feasible
 Thyssen-Krupp is aiming to produce climate-neutral steel by 2050 and has begun a project
on the use of green hydrogen in blast furnaces
 Uniper is also focusing to increase the use of hydrogen in electricity production and, in
cooperation with Siemens, is examining how gas power plants can become more
environmentally friendly. Converting excess green electrical energy into enrich hydrogen and
methane that can be stored and then used to power fuel cells.

36. Possible Hydrogen applications in
Germany

37. Germany’s future strategy for
production of Hydrogen
 Germany plans to built hydrogen production plant with a total
capacity of 5GW, and by 2035 to 2040 it will expand to 10GW.
 The 5GW of energy will still not be able to meet the demands in
2030, so focus on import of H2 will be emphasized, and it will also
be urged.
 Opportunities for new businesses and cooperation models between
operators of electrolysers and TSOs in line with the regulatory
unbundling regime will be developed

38. References
1.Kamran Ashraf, (2015), Steam Methane Reforming, https://urlzs.com/tswds
2.Anupam Basu, (Oct, 2009), Hydrogen Production in Refinery, https://tinyurl.com/yafxeegh
3.S. Shiva Kumar, V. Himabindu, (March, 2019), Hydrogen Production by PEM Water Electrolysis, Material Science for
Energy Technologies, Vol 2, Issue 3 https://tinyurl.com/y6upx9d3
4.Hydrogen Production:Biomass Gasification, Office of U.S. Department of Energy, https://tinyurl.com/yxfbqtbk
5.Meng Ni, Dennis Y.C. Leung, Michael K.H. Leung, (May 2006), An overview of Hydrogen production from biomass, Fuel
Processing Technology, Vol 87, Issue 5, Pages: 461-472
https://tinyurl.com/y8mzhzx3
6.N.Z Muradov, (March 1993), How to produce Hydrogen from fossil fuels without CO2 emission, Vol: 18, Issue 3, pg: 211-
215 https://tinyurl.com/ybp6j9qm
7.M. Steinberg, Hydrogen Production from fossil fuels, Energy carriers and conversion system, Vol:1,
https://tinyurl.com/y9rcm628
8.L Garcia, (2015), Hydrogen production by steam reforming of natural gas and other nonrenewable feedstocks,
Compendium of Hydrogen Energy, pg 83-107
https://tinyurl.com/yan24jk8
9.Isabelle Huber, Germany’s Hydrogen industrial strategy, (Oct 2021), Centre for Strategic & International Studies
https://tinyurl.com/ya3b8qq2
Opportunities for Hydrogen Energy Technologies considering the National Energy & Climate Plans
https://tinyurl.com/yanyc233

39. Electrolysis
 Electrolysis is the technical name for using electricity to
split water into its constituent elements, hydrogen and
oxygen.
 The splitting of water is accomplished by passing a DC
electric current through water.
 The electricity enters the water at the cathode, a
negatively charged terminal, passes through the water
and exists via the anode, the positively charged terminal.
 The hydrogen is collected at the cathode and the
oxygen is collected at the anode. Electrolysis produces
very pure hydrogen for use in the electronics,
pharmaceutical and food industries

40. Electrolysis
 The hydrogen is collected at the cathode
and the oxygen is collected at the anode.
 Electrolysis produces very pure hydrogen
for use in the electronics, pharmaceutical
and food industries.

41. Photobiological
 This method involves using sunlight, a biological
component, catalysts and an engineered
system.
 Specific organisms, algae and bacteria, produce
hydrogen as a byproduct of their metabolic
processes.
 These organisms generally live in water and
therefore are biologically splitting the water into
its component elements.
 Currently, this technology is still in the research
and development stage and the theoretical
sunlight conversion efficiencies have been
estimated up to 24%.