Hydrogen Generation
A
Pillar of Hydrogen Economy
by
Prof. (Dr.) P. Muthukumar
Department of Mechanical Engineering
Indian Institute of Technology Tirupati
Email:
[email protected] Thermolysis Technology for Hydrogen Production
Direct dissociation of water to produce hydrogen and oxygen
H2O → H2 + ½ O2
Stable compound and complete dissociation around 4500 K
Only 50% of water dissociated at 3000 K
Only 3% at 2500 K
Several challenges like material selection, heat input, etc., for such high temperature.
Because of high heat input, thermolysis can be broken down to multiple steps
using comparatively low heat and intermediate chemical reactions and the
modified process is known as Thermo-chemical hydrogen production process
Thermo-Chemical Cycle for Hydrogen Production
Basics of working of Thermo-Chemical Cycle
Heat (Nuclear; CSP, etc) Hydrogen
Thermo-Chemical
Output
Input
Cycles
Water Oxygen
Heat (Nuclear; CSP, etc) Hydrogen
Hybrid Thermo-
Output
Input
Electricity
Chemical Cycles
Water Oxygen
Thermo-Chemical Cycle for Hydrogen Production
Simplest (2-Step) Thermo-Chemical Cycle Endothermic
Reduction Process
Advantage
Less no of steps and simple in operation Energy O2
Challenges
T = 1700 – 3000 K MOx → MOx-y + y/2 O2
CSP
Low Efficiency (because of high temperature heat losses)
For this temperature range various metal oxide redox pair are available:
Fe3O4/FeO, ZnO/Zn, CeO2/Ce2O3, GeO2/GeO, etc. MOx MOx-y
Fe3O4 → 3FeO + ½ O2 ; T > 1873 K MOx-y + Y H2O → MOx + y H2
3FeO + H2O → Fe3O4 + H2 ; Exothermic reaction
Iron(II,III) oxide / Magnetite or Magnetic oxide.
H2O H2
• To avoid energy and oxide losses, Fe can be replaced by Ni, Co, Mn
• Theoretical efficiency of such system is 50-60%, however due to Hydrolysis (Exothermic
losses, actual efficiency is 20-25%. Oxidation Process)
Thermo-Chemical Cycle for Hydrogen Production
Simplest (2-Step) Thermo-Chemical Cycle Endothermic
Reduction Process
2CeO2 → Ce2O3 + ½ O2 ; T > 2200-2400 K 2000-2300 K O2
Ce2O3 + H2O → 2CeO2 + H2 ; 700-900 K
ZnO → Zn + 1/2 O2
Need for multistage Thermochemical Process
ZnO Zn
• In all the 2-step Thermochemical Cycle, the temperature requirement
is very high
Zn + H2O → ZnO + H2
• Redox pair undergoes stoichiometric phase change (ZnO, Ce 2O3,
CeO2), which shows high specific energy storage but slow kinetics.
• If redox pair undergoes partial reduction, shows faster kinetics but H2O H2
have lower specific energy storage.
Hydrolysis (700-800 K)
Thermo-Chemical Cycle for Hydrogen Production
3-step Thermo-Chemical Cycle
Sulphur-Iodine Cycle (Most common 3-step TCC); T >1000 K O2
Originally proposed by General Atomics and further
studied by several other laboratories. Step 2 H2SO4 → H2O + SO2 + 1/2 O2
Challenges:
• Still higher temperature (⁓1000 K)
Step 1 H2O I2 +SO2 + 2H2O → 2HI + H2SO4 T ⁓ 400
• Reactants are corrosive and reactive K
• Separation of HI from sulphuric acid in presence of T > 570 K
Iodine leading to significant loss in iodine
Step 3 2HI → I2 + H2 H2
Thermo-Chemical Cycle for Hydrogen Production
4-step Thermo-Chemical Cycle
Step 4 T >900 K O2
H2O
Cl2 +H2O → 2HCl + 1/2 O2 Step 2
Cl2
T ⁓ 900
2FeCl2 K
Step 3 2 FeCl3 → 2FeCl2 + Cl2 3FeCl2 + 4H2O → Fe3O4 + 6HCl + H2 H2
T > 700 K
2HCl
FeCl2 + 4H2O
2FeCl3 Fe3O4 + 6HCl
Step 1 Fe3O4 + 8HCl → FeCl2 + 2FeCl3 + 4H2O
T > 400 K
Other similar cycle could be : Ce-Cl, Cu-Cl, Fe-Cl, Mg-Cl, V-Cl cycle, etc
Thermo-Chemical Cycle for Hydrogen Production
Hybrid Thermo-Chemical Cycle
Westinghouse cycle/2-Sep hybrid sulphur cycle/ISPRA Mark 11 Cycle
Step 1
T >1000 K O2
Electrochemical Thermochemical combined cycle (as both
Heat H2SO4 → H2O + SO2 + 1/2 O2
heat and electricity is used)
Theoretical thermal efficiency is 40% and actual is 28%
Modified is mark V2 (hydrogen bromide was use), Mark H2O SO2 + 2H2O → H2SO4 + H2 H2
13A (SO2 taken from flue gases), HySA Cycle etc.
T ⁓ 400
Step 2 K
Other example Cu-Cl cycle, UT 3 cycle (University of
Tokyo), Power : 0.17 V.
Electrolysis : 1.23 V
Photo Electrochemical Hydrogen Production
Technology is still under developmental stage, only few Anode Cathode
prototype laboratory scale models are available.
It is inspired by Photosynthesis in Plants
In 1971 (Phosusema and Honda) first came up with the
technology, using Titanium di oxide as material.
The principle of photo electrochemical water decomposition
is based on the conversion of light energy into electricity with
a cell involving two electrodes (or three), immersed in an 2H2O + 4H+ + 4e- → 2H2 + O2 (g)
aqueous electrolyte of which at least one is made of a
semiconductor exposed to light and able to absorb light. This Cathode: 2H+ + 2e- → H2
electricity is further used for water electrolysis
Anode: 2H2O → O2 + 4H+ + 4e-
The photo-electrolysis technology is based on solar energy wherein water is splitting into
hydrogen and oxygen using solar energy which is renewable energy source.
Photons provides 1.7 eV
(1.23 eV + over potential using
PEC technology is safe and environmental friendly
photoelectrocatalysis) per e-h pair
It is a simple technology that can be from small to large scale hydrogen production
Photo electrochemical Hydrogen Production
The energy conversion efficiency of water photo-electrolysis is determined mainly by the properties of the materials
used as electrodes in the photo-electrochemical cell.
• Photo electrodes with required band gap (band gap matches with the redox potential of water)
• Suitable electrolyte and charge conducting surfaces (semiconductor materials).
• Energy required for non spontaneous process (because of water splitting)
• Oxygen evolution step thermodynamically and kinetically more challenging (focus on photo anode)
• Electrodes: stable, high surface area, good crystallinity and electrical conductivity
Lower edge of CB
> potential of HER
(-4.6 eV)
Upper edge of VB < Conduction band
redox potential of
OER (-5.9 eV)
Valance band
Photo electrochemical Hydrogen Production
Most of the materials are not suitable due to their band gap or conduction band location or valance band
locations
TiO2 is most studied material as it has adequate band gap, required energy band position, stability against
light induced corrosion, non toxicity, availability, cost, etc.
However, because of wide band gap (3 to 3.2 eV) of TiO 2, absorption is restricted to UV (4% of entire
solar spectrum)
High recombination rate
Other substitute could be: GaN, SiC, C3N4, GaxIn1-xN
TiO2 can be modified or low band gap material can be used
Hybrid material can be manufactured/tailored and tested
Photo electrochemical Hydrogen Production
Principle of working of PEC Cell
CB being more negative than water reduction potential and VB should be more positive than the
water oxidation potential
Photons energy > Band gap, so as to create electron-hole pair (charge carriers generated)
The charge carrier need to be effectively separated. Or else, they combine and produce energy.
Efficient and effective separation of charge carriers is essential, hence use of photocatalyst are
considered (Ru, Pt).
Separated charges reach surface of semiconductors for PEC reaction at interface (electrode and
electrolyte)
Electrocatalysts reduces activation energy by providing active sites.
Thickness of photocatalyst- diffusion length of the charge carrier should be more than thickness of
photocatalyst (recommendation length)
Optimum surface area. High surface area may lead to recombining of e-hole
