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Draft

REPORT ON

HYDROGEN PRODUCTION IN INDIA

Prepared by the

Sub-Committee on Research, Development &


Demonstration for Hydrogen Energy and Fuel Cells
Steering Committee on Hydrogen Energy and Fuel Cells
Ministry of New and Renewable Energy,
Government of India, New Delhi
March, 2016
FOREWORD

Till the end of 20th Century carbonaceous substances like coal, natural
gas, petroleum derived oils and wood have been fulfilling the of energy needs
of human society for heat, light and power (both motive and electric). With the
passage of time, the rising world population and urge for better living standards
by the people of developing regions have resulted in over exploitation of
conventional energy resources. This in turn has led to the increase in the cost
of energy and reduction in availability of conventional fuels. Emission of various
types of pollutants (such as particulates, carbon dioxide, and un-burnt
hydrocarbons) during the use of these fuels is not only affecting the health of
living beings but is also causing greenhouse effect and climate change. In view
these concerns, the focus in the futuristic energy planning and security is
shifting from carbon rich to carbon neutral new and renewable energy sources.
Hydrogen has been considered and identified as the potential energy carrier
and as a leading contender for the “ideal” energy option of the future. On
combustion it emits only water vapor. It may be produced through natural gas
reforming, coal and biomass gasification, thermo-chemical route using the heat
available at high temperature from nuclear reactors, electrolysis of water with
surplus electricity available from grid or that produced from renewable sources
of energy like hydro, wind, solar etc. Biological (fermentative and bio-
photolysis), photo-catalytic splitting of water (or photolysis), and photo-
electrochemical methods are being considered as futuristic routes of producing
hydrogen. Sufficient amount of hydrogen is also produced as by-product in
chlor alkali units and petroleum refineries

In view of the rising population and emphasis on improving the per capita
energy availability, like other countries India is also concerned about its
contribution to the climate change and is striving for developing technologies
for harnessing renewable energy sources. Therefore, hydrogen energy and
fuel cell technologies are of utmost importance, which India needs to develop
pin a mission mode. Though the Ministry of New and Renewable Energy
(MNRE) and several other government agencies at the central and state
government levels are providing support for research, development and
demonstration of hydrogen production and application, India is much behind in
the global scenario.The MNRE, Government of India constituted a high power
Steering Committee to prepare a status report and suggest the way forward for
hydrogen energy and fuel cell technologies in the country. One of the five sub-
committees was entrusted under the chairmanship of the undersigned with the
responsibility of preparing this particular document focusing on the research
and development of various hydrogen production technologies of relevance to
the country.

This document is the result of the combined effort of all the members of
the sub-committee, experts working in the area of hydrogen production, officials
and staff of MNRE.

I am indebted to all the Members of the Sub-Committee and Special


Invitees for their contribution, Dr. M. R. Nouni, Scientist ‘F’, Ministry of New and
Renewable Energy and also the officials of the Project Management Unit –
Hydrogen Energy and Fuel Cells at the Ministry, Dr. Jugal Kishor and Dr. S. K.
Sharma in particular for their active role in organizing meetings and preparing
this document.

…. March, 2016
(Prof. S. N. Upadhyay),
Chairman,
Sub-Committee on Research, Development &
Demonstration for Hydrogen and Fuel Cells
CONTENTS

Sl. No. Subject Page No.

I Composition of the Sub-Committee on Research,


Development & Demonstration for Hydrogen Energy and i
Fuel Cells
II Terms of Reference iii
III Details of Meetings iv
1 Executive Summary 1
2 Introduction 25
3 Hydrogen Production using Thermo-chemical Route from
Carbonaceous feed-stock: 34
(i) Carbonaceous feed-stock 35
(ii) Biomass feed-stock 57
4 Hydrogen Production by Electrolysis of Water 76
5 Bio-Hydrogen and Bio-Methane Production 107
6 Hydrogen Production through Thermochemical Routes 119
7 Hydrogen Production by Photo-electrochemical Water 167
Splitting
8 Hydrogen Production by Other Technologies 181
9 Action Plan 189
10 Financial Projections and Time Schedule of Project 199
Activities
11 Conclusions and Recommendations 203
12 Bibliography 213
13 Annexure 222
I Composition of Sub-Committee on Research, Development &
Demonstration for Hydrogen Energy and Fuel Cells

1. Prof. S. N. Upadhyay, Former Director, Banaras Hindu University - Institute


of Technology, Varanasi and DAE-Raja Ramanna Fellow in the Department
of Chemical Engineering, Indian Institute of Technology (Banaras Hindu
University), Varanasi - Chairman
2. Ms. Varsha Joshi, Joint Secretary / Shri A. K. Dhussa, Adviser (December,
2013 to March, 2015) / Dr. Bibek Bandyopadhyay, Adviser (upto
December, 2013), MNRE
3. Dr. Sanjay Bajpai, Scientist ‘F’, Department of Science and Technology,
Ministry of Science and Technology, New Delhi
4. Dr. Ashish Lele, CSIR-National Chemical Laboratory, Pune
5. Dr. S. Aravamuthan, Sci./ Engr.- ‘H’ & Deputy Director, Vikram Sarabhai
Space Centre, Indian Space Research Organization, Thiruvanthapuram
6. Shri A. Srinivas Rao, SO/G, Chemical Technology Division, Bhabha
Atomic Research Centre, Mumbai
7. Dr. K. S. Dhathathreyan, Head, Centre for Fuel Cell Technology, Chennai
(Retired on 31.01.2016)
8. Prof. O.N. Srivastava, Emeritus Professor, Banaras Hindu University,
Varanasi
9. Prof. B. Viswanathan, Emeritus Professor, Indian Institute of Technology
Madras, Chennai
10. Prof. Debabrata Das, Indian Institute of Technology Kharagpur, Kharagpur
11. Prof. L. M. Das, (Retired on 30.06.2014) and currently Emeritus Professor,
Indian Institute of Technology Delhi, New Delhi
12. Executive Director, Centre for High Technology, Noida
13. Dr. P. K. Tiwari, Desalination Division, Bhabha Atomic Research Centre
(BARC) as Representative of Principal Scientific Adviser to Govt. of India -
Retired on 31.01.2015 and currently Raja Ramanna Fellow at the Prof.
Homi Bhabha National Institute, BARC, Mumbai
14. Shri Sanjay Bandyopadhyay, National Automotive Testing and R&D
Infrastructure Project (NATRIP), New Delhi / Shri Neeraj Kumar, Deputy
Secretary, Ministry of Heavy Industries & Public Enterprises, (Repatriated
i
to Parent Department in January, 2015) / Shri Nitin R. Gokarn, NATRIP,
New Delhi (Repatriated in June, 2014 to Parent Cadre)

Special Invitees:

15. Prof. S. Dasappa, Indian Institute of Science, Bangalore


16. Dr (Mrs.) V. Durga Kumari, Indian Institute of Chemical Technology,
Hyderabad

Note: Since the Sub-Committees on different aspects (Fuel Cells, Hydrogen


Storage & Other Applications of Hydrogen Energy and Transportation) of
hydrogen energy and fuel cells, covered activities relating to Research,
Development & Demonstration (RD&D) in their respective areas, it was decided
that the Sub-Committee on Research, Development & Demonstration (RD&D)
would focus only on hydrogen production

ii
II Terms of Reference

1. To review national and international status of Research & Development,


Technology Development and Demonstration with a view to identify the
gaps.
2. To suggest the strategy to bridge the identified gaps and the time frame for
the same.
3. To assess R & D infrastructure in the country.
4. To identify projects and prioritize them for support with the result oriented
targets.
5. To identify institutes to be supported for augmenting R&D facilities including
setting-up of Centre(s) of Excellence and suggest specific support to be
provided.
6. To suggest strategy for undertaking collaborative R & D among leading
Indian academic institutions and research organizations and also with
international organizations.
7. To examine setting-up of a National Hydrogen Energy and Fuel Cell Centre
as an apex facility.
8. To suggest strategy to take-up projects in Public-Private Partnership mode
for the development of technologies based on transparency, accountability
and commitment for deliverables.
9. To identify the technologies, which can be adopted for applications with time
line?
10. To re-visit National Hydrogen Energy Road Map with reference to Research,
Development & Demonstration and Technology Development activities

Note: In the 5th meeting of the Steering Committee on Hydrogen Energy and
Fuel Cells held on 11.08.2015 in the Ministry of New and Renewable Energy, it
was decided that in order to fill the gap between international and national state
of art technologies, the projects may be identified in three categories viz.
Mission Mode, Research and Development and Basic / Fundamental Research
instead of re-visiting of National Hydrogen Energy Road Map.

iii
III Details of Meetings

The Sub-Committee on Research, Development and Demonstration


(RD&D) met on 09.12.2013 and had detailed presentations and discussions on
the activities relating toRD&D in the areas of hydrogen production, its storage
& applications in power generation and vehicles based on IC engine & fuel cell
technologies. The second meeting was held on 03.03.2014 for the identification
of thrust areas for hydrogen production, its storage & applications in power
generation and vehicles based on IC engine, so as the Ministry may consider
supporting projects in these areas. In the third meeting held on 18.11.2014 in
the Ministry of New and Renewable Energy, New Delhi, detailed presentations
and discussions were made on hydrogen production. Based on the input
received from the expert members of the Sub-Committee and experts outside
the Sub-Committee, a report was drafted on the Hydrogen Production. This
Draft Report was presented in the 5th meeting of the Steering Committee on
Hydrogen Energy and Fuel Cells on 11.08.2015 in MNRE, which gave some
suggestions to modify the report. The report was modified incorporating these
suggestions. The Steering Committee further requested the Chairpersons of all
the five Sub-Committees to meet and discuss uniformity of the reports and
alignment of outcome of the reports. Accordingly, the report was again modified
based on the suggestions given / decisions taken in the meetings of the
Chairpersons of the Sub-Committees held on 11.09.2015, 16.12.2015 and
18.01.2016.

iv
EXECUTIVE SUMMARY

1
1.0 Executive Summary

Preamble

1.1 Use of fossil fuels has become a part of daily energy needs and their
requirement is increasing with the passage of time. Consumption of fossil fuels
gives rise to the greenhouse gas emissions in the environment and causes
ambient air pollution, which have now become global concerns. This coupled
with the limited reserves of fossil fuels have encouraged and promoted the
development and use of new and renewable energy sources, including
hydrogen energy as an alternative clean fuel. The technologies for production
of hydrogen from new and renewable sources of energy are not yet mature and
the cost of hydrogen produced through new and renewable energy sources is
still very high and is not competitive to that produced from fossil fuels. In order
to meet the future energy demands in sustainable and environment friendly
manner, technologies are required to be developed for the production, storage
and applications of hydrogen in transportation sector as well as for portable and
stationary distributed & non-distributed power generation. In some countries
governments have started supporting these efforts.

1.2 Hydrogen is an energy carrier (a secondary source of energy) and is


available in chemically combined forms in water, fossil fuels, biomass etc. It can
be liberated with the electrical or heat energy input (generated from some
primary energy source like fossil fuel, nuclear power or a renewable energy
source such as - solar, wind, hydro-electricity, etc.). Presently the agriculture
sector is the largest user of hydrogen (as nitrogenous fertilizer), with 49% of
hydrogen being used for ammonia production (Konieczny et al., 2008)

1.3 Approximately 95% of the hydrogen produced presently comes from


carbonaceous raw material, primarily of fossil origin. About 4% is produced
through electrolysis of water.

2
1.4 Hydrogen is also produced as a by-product in chlor-alkali industries.
There are around 40 such units in India, which produced nearly 66000 tons of
by-product hydrogen during 2013-14. Around 90% of this by-product hydrogen
is utilized for captive and other uses. Only a fraction of this hydrogen is currently
used for energy purposes. Around 6600 tons of this hydrogen is still unutilized.

1.5 Hydrogen Production Technologies

a) Reforming of Carbonaceous Sources: Conventional technologies for


hydrogen production are: i) Steam Methane Reforming ii) Partial Oxidation, iii)
Auto-Thermal Reforming, iv) Methanol Reforming, v) Ammonia Cracking, vi)
Thermo-catalytic Cracking of Methane, and vii) Novel Reformer Technologies.
Steam Methane Reformers are commercially available for hydrogen
production. In the United States, most hydrogen (over 90%) is manufactured by
steam reforming of natural gas presently. High purity industrial hydrogen with
99.999% purity is produced from commercial hydrogen by pressure swing
adsorption systems or by palladium gas membranes. Technologies for coal
gasification are commercially available internationally. At national level,
hydrogen is produced commercially in fertilizer plants and petroleum refineries
by reformation of natural gas. There are extensive industry and government
programs addressing to particular technical issues for small-scale reformers,
and for syngas production in the country.

1.5.1 Compact “Fuel Cell Type” Low Pressure and Temperature Steam
Methane Reformers were developed in small sizes to produce 50 to 4000
Nm3 H2/day internationally (Halvorson, et al, 1997).These have recently been
adapted for stand-alone hydrogen production. Energy conversion efficiency in
the range of 70%-80% is possible for these units. Internationally, a novel
gasoline steam reformer with micro-channels was developed to reduce the
size and cost of automotive reformers. Another 1 kW plate reformer, a more
compact, low cost standardized design having better conversion efficiency,
and faster start-up was developed for fuel cell systems. It yielded increased
energy conversion efficiency (from about 70% to 77%) by reducing heat
losses. Its lifetime is also expected to be increased from 5 to 10 years.
3
1.5.2 Membrane Reactors for Steam Reforming is another promising
technology. Depending on the temperature, pressure and the reactor length,
methane is completely converted, and very pure hydrogen is produced. This
allows its operation at lower temperature and lower cost. A potential advantage
of this system is simplification of the process design and capital cost reduction.
Japan has built and tested a small membrane reactor for production of pure
hydrogen from natural gas (at a rate of 15 Nm3/h).

1.5.3 Partial Oxidation (POX) Reformer:Large-scale partial oxidation


systems have been used commercially to produce hydrogen from hydrocarbons
such as residual oil, for industrial applications. Small-scale partial oxidation
systems have recently become commercially available, but are still undergoing
intensive R&D. These reactors are more compact than a steam reformer with
efficiency of 70-80%. This technology is being used to install a natural gas
reformer filling station to supply hydrogen to fuel cell buses and Hythane®
buses at Thousand Palms, California. Several companies are involved in
developing multi-fuel fuel processors for 50 kW fuel cell vehicle power plants
and to develop gasoline fuel processors based on POX technology.

1.5.4 Auto-thermal reformers combine some of the best features of steam


reforming and partial oxidation systems. Several companies are developing
small auto-thermal reformers for converting liquid hydrocarbon fuels to
hydrogen for the use in fuel cell systems. The auto-thermal reformer requires
no external heat source and no indirect heat exchangers. Heat generated by
the partial oxidation is utilized to drive steam reforming reaction. This is more
compact than conventional steam reformers, and will have a lower capital cost
and higher system efficiency than partial oxidation systems. Auto-thermal
reformers are being developed for PEMFC systems by a number of groups

1.5.5 Methanol Reformation takes place with steam at moderate


temperatures (250-350oC). These reformers have been demonstrated by
several automakers in PEM fuel cell vehicles, where methanol is stored on-
4
board. But no fuel cell vehicle manufacturer is currently using this
technology.The advantages are compactness, better heat transfer, faster start-
up and potentially lower cost. Internationally, units are produced for steam
reforming of alcohols, hydrocarbons, ethers and military fuels. CJB Ltd., a
British company built and tested a plate type steam methanol reformer and
integrated the fuel cell system. A multi-fuel processor was demonstrated for
pure hydrogen production via steam reforming of methanol, using a palladium
membrane and micro-reactor technology to create a portable hydrogen source
for fuel cells.

1.5.6 Ammonia Cracking: Ammonia is widely distributed in the country and


available at low cost. It is relatively easy to transport and store, compared to
hydrogen. It can be cracked at 9000C with up to 85% efficiency. Water is not
required as co-feed. A costly separation unit Pressure Swing Adsorption unit
for separating H2 and N2 would be required. Thermo-catalytic cracking of
methane is still far from commercial application for hydrogen production. The
primary issues are low efficiency of conversion and coking but relatively low
capital costs are projected.

1.5.7 Sorbent-enhanced Catalytic Steam-reforming System: Syngas,


produced using novel reformer technologies, has a substantially higher fraction
of hydrogen than that produced in a catalytic steam-reforming reactor. Sorbent-
enhanced systems are still at the demonstration stage, and show promise for
low cost. Issues to be resolved include catalyst and sorbent lifetime and system
design.

1.5.8 Hydrogen Separation through Ceramic Membrane: Globally, some


research groups are developing ceramic membrane technology for separation
of hydrogen from syngas. The membranes are non-porous, multi-component
metallic oxides that operate at high temperature (>700 oC) and have high
oxygen flux and selectivity. These are known as ion transport membranes
(ITM). Conceptual designs were carried out for a hydrogen-refueling station
dispensing 15000 m3/day hydrogen at 350 bar. This route offers a 27% cost
savings compared to trucked-in liquid hydrogen.
5
1.5.9 Thermal plasma reformer technology can be used for the production
of hydrogen and hydrogen-rich gases from methane and a variety of liquid fuels.
Thermal plasma is characterized by temperatures of 3000-10000oC, and can
be used to accelerate the kinetics of reforming reactions even without a
catalyst. Plasma-reforming systems have been developed and used for
evaluating the potential of this technology for small-scale hydrogen production.
The best steam reforming results to date showed 95% conversion of methane
and projected that the power required can be reduced by about half.

1.5.10 Hydrogen is currently produced for industrial applications by cracking


carbonaceous fossil fuels. Natural gas reforming is currently the most
efficient, economical and widely used process for production of hydrogen and
has been utilized globally for many decades in the oil refinery and fertilizer
industries. Steam reforming (SMR) has the lowest capital costs of the hydrogen
production technologies with efficiencies in the range 60%–80%.

1.5.11 In spite of efforts to produce hydrogen by processes involving solar


energy, wind energy, nuclear energy and bio-fuels, fossilized carbonaceous
resources and their products remain the most feasible feedstock in the near
term, and for commercial scale production of pure hydrogen, steam reforming
remains the most economic and efficient route.

b) Pyrolysis of Biomass and reformation of bio-oil and gaseous


products

1.5.12 Biomass is a renewable source of energy and is available almost


everywhere on the earth. Hydrogen content in biomass is roughly 6.5% by wt.
Biomass is thermally decomposed / fast pyrolysed in the temperature range of
600 - 10000C at 1-0.5 MPa in an inert atmosphere to form vapors of dark brown
bio-oil (about 85% oxygenated organics and remaining water), other gaseous
products (H2, CH4, CO & CO2) and solid products(mainly charcoal). The bio-oil
and gaseous products are then reformed to produce hydrogen. The maximum
yield of hydrogen can reach up to 90% with the use of Ni-catalyst at 750-8500C.
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Alternatively, the phenolic components of the bio-oil can be extracted with ethyl
acetate to produce an adhesive/phenolic resin co-product; the remaining
components can be reformed as in the first option. The product gas from both
alternatives is purified using a standard Pressure Swing Adsorption (PSA)
system. National Renewable Energy Laboratory (NREL) U.S.A. has developed
a demonstration scale unit for the production of hydrogen from pyrolysis oil by
steam reformation. The pyrolysis oil is also generated from biomass (such as
peanut shells) in a fluidized bed. Slow pyrolysis gives high char yield and is
generally not considered for hydrogen production.

c) Gasification of Renewable Biomass and its Reformation

1.5.13 Biomass gasification is a sub-stoichiometric combustion process, in


which pyrolysis, oxidation and reduction take place. Pyrolysis products (volatile
matter) further react with char and are reduced to H2, CO, CO2, CH4 and higher
hydrocarbons (HHC). In this process, tar is formed, which may produce tar
aerosols and polymerized compounds. Therefore, tar formation is undesirable.
The gasifier may be so appropriately designed to reduce tar formation. Injection
of secondary air is used to reduce tar formation. Indian Institute of Science
(IISc), Bangalore has developed an open-top downdraft gasifier, in which
effects of various parameters like, equivalence ratio (ER), steam-to-biomass
ratio (SBR) residence time- temperature on efficiency are studied. Ni-based
catalysts and alkaline metal oxides are used as gasification catalysts to improve
gas product quality and conversion efficiency. The syngas yield increased from
353 g per kg of biomass to 828 g per kg of biomass by varying the pyrolysis
temperature from 600 - 10000C.

1.5.14 Internationally, many countries are involved in the development of


biomass gasification technology. The University of British Colombia, Canada
is working on fluidized bed gasification and sorbent based hydrogen separation
unit. The Gas Technology Institute (GTI), Chicago is working on a the
demonstration project for direct generation of hydrogen from a down draft
gasifier using a membrane reactor, The Energy Research Centre of the
Netherlands has developed a pilot plant scale unit of 800 kW th capacity based
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on gasification technology. The Technical University of Vienna is developing a
Fast Internally Circulating Fluidized-bed (FICB) technology for steam-blown
gasification of biomass in cooperation with Austrian Energy and Environment
agency. A combined heat and power (CHP) plant (8MW) is in operation since
2002 in Güssing, Austria. Later on, Synthetic Natural Gas (SNG) production
was also demonstrated in a methanation unit, which took a 1 MW SNG
slipstream from the Güssing plant. The targeted production cost of hydrogen
through this method is around US$ 2.5 to 3.5 /kg of hydrogen at large scale.
The Biomass Gasification project of Gothenburg, Sweden aims to construct a
synthetic natural gas (SNG) plant.

1.5.15 With the development of fuel cell systems in the country, MNRE focuses
on the generation of hydrogen rich syngas through thermo-chemical conversion
of biomass and its purification to fuel cell grade. IISchas recently concluded a
project addressing these aspects. This encouraged work on the development
of a prototype system to generate hydrogen rich syngas using oxy-steam
gasification. The entire process has been optimized to generate a maximum of
about 100 g of hydrogen per kilo gram of biomass. Syngas composition,
hydrogen yield and performance parameters have been monitored by varying
steam to biomass ratio and equivalence ratio. Results show that using dry
biomass with oxy-steam improves the hydrogen yield, efficiency and syngas
with lower heating value (LHV) compared to direct usage of wet biomass with
oxygen. With the current experience of using biomass, about 70 g of pure
hydrogen can be obtained per kg of biomass, which results in about 15 kg of
biomass for every kg of hydrogen generated.

d) Electrolysis of Water

1.5.16 Hydrogen can be generated through electrolysis of water. The water


electrolysis can be carried out in three different ways viz., alkaline water
electrolysis, acidic water (polymer electrolyte membrane based) electrolysis
8
and high temperature ceramic membranes (solid oxides membranes) water
electrolysis. Polymer electrolyte membrane (PEM) based water electrolysers
are more advantageous than conventional water-alkali electrolysers due to their
ecologically safe nature, production of hydrogen with high purity (>99.99%) and
possibility to produce at high pressure.

1.5.17 The alkaline water electrolysis is a matured technology and is


commercially available in megawatt range. It has a stack life is <90,000 h and
system life of 20-30 years, energy requirement of around 6 kWh per Nm3
hydrogen and efficiency of 60-70%. In the case of PEM based water
electrolysers stack life is <20,000 h and the system life is estimated to be
around 10-20 years. These electrolysers are smaller, cleaner and more reliable
systems than other electrolysers. Alkaline electrolysers are less expensive
than PEM electrolysers due to use of non-noble metal (nickel based) catalysts,
but consume more electricity. The major challenges of these electrolysers are
related to corrosion and poisoning of the electrolysers by inadvertent incursion
of CO2. The largest existing alkaline electrolysis plants are 160 MW plant in
Aswan, Egypt and 22 MW plant operating in Peru (pressurized operation). The
Brown Boveri electrolyser can produce hydrogen at a rate of about 4-300 m3/h.

1.5.18 The PEM water electrolyser is being deployed for the applications, where
cost is a secondary issue. The membrane material for these electrolysers is
Nafion from DuPont, USA. Besides Du Pont, Asahi Glass, Dow Chemicals and
others have also developed similar membranes either based on fluorinated or
non-fluorinated polymers, which are commercially available. The fluorinated
polymers have shown good performance for >5000 hours of operation in the
fuel cells. However, there are other issues related to its operation such as
increase of cross-permeation of gases with increase in pressure. As of now
small and medium range PEM water electrolysers are available for laboratory
use and other applications. Currently available PEM water electrolyser systems
have a hydrogen production rate that varies from 0.06 to 75 Nm³/hr whereas
alkaline electrolysers have reached the hydrogen production rate of 760
Nm³/h.Siemens, FRG plans to build an electrolyser system to store wind power
as hydrogen. The system will have a peak rating of up to 6 MW.
9
1.5.19 High temperature water electrolysis uses solid oxide electrolyte and
offers advantage over alkaline and PEM electrolysers in terms of higher
efficiency and lower capital costs. Solid oxide membranes are prepared from
calcium and yttrium stabilised zirconium oxide. These electrolysers are
operated at high temperatures (900–1000°C), which reduces the consumption
of electricity for production of hydrogen by about 30% in comparison to other
electrolysis processes at room temperature. Electricity consumed is about 2.6-
3.5 kWh/Nm3 of hydrogen produced.

1.5.20 The Bhabha Atomic Research Centre (BARC), Mumbai has developed
water electrolysers with high current density (4500 A/m2) based on indigenously
developed advanced electrolytic modules incorporating porous nickel
electrodes. A portable electrolyser of 1.5 Nm 3/h hydrogen production capacity
and large units of capacities 10 and 30 Nm3 /h hydrogen production have been
developed. BARC has also planned to develop high temperature steam
electrolyser of 1.0 Nm3/h hydrogen production capacity for technology
demonstration purposes. CSIR-CECRI has developed activated nickel
electrode for alkaline electrolyser. PEM water electrolyser of capacity 1.0 and
5.0 Nm3/h were also developed during 2012 and demonstrated with energy
consumption of about 5.75 kWh/Nm3of hydrogen at 5-10 bar pressure. These
technologies have been transferred to M/s. Eastern Electrolysers, New Delhi
for further development. In addition, CSIR-CECRI has also demonstrated solar
power integrated PEM based water electrolyser system of 0.5 Nm 3/h capacity
in 2012.The SPIC Science Foundation (SSF), Chennai has developed PEM
based water electrolysers for hydrogen production at the rates of 0.5 and 1
Nm3/h. In these electrolysers titanium plate was platinised and used as bipolar
plate. The SSF has also developed and demonstrated a PEM based water
electrolyser system with the hydrogen production capacity of 60.0 lit/h using
methanol as the depolariser. The energy consumption for hydrogen production
was 2.0 kWh/Nm3.The Institute of Science and Technology, JNTU, Hyderabad
has developed PEM based water electrolyser to produce hydrogen at the rate
of 36 L/h using Nafion membrane. The Centre of Fuel Cell Technology, Chennai
(a project of International Advanced Research Centre for Powder Metallurgy,
10
Hyderabad) has developed and demonstrated a 1.0 Nm3/h hydrogen
production capacity electrolyser using similar concept but with much lower
energy consumption of 1.40kWh/Nm3. It also demonstrated for the first time the
use of carbon based materials in its construction and thus redcuing the capaital
cost tredomnously. M/s. MVS Engineering Ltd, New Delhi are offering PEM
water electrolyser technology on turnkey basis in partnership with Proton Onsite
(USA) for hydrogen generation. Recently, such a system has been installed at
the Indian Oil’s R&D Centre, Faridabad. A number of other companies are also
reported to have commercialised alkaline water electrolyser for various
industrial applications. In general, the production of hydrogen through
electrolysis of water is a highly energy intensive (4.5-6.5 kWh/Nm3). High
energy consumption coupled with high capital investment is the reason, why
water electrolysis technology is not preferred in India for commercial purposes.

1.5.21 Acid and alkali based solid polymer electrolytes have been developed.
Alkali based electrolytes use non-noble catalysts, but face challenges such as
chemical stability in the electrochemical system. The electrolysers using acid
based solid polymer electrolyte may be deployed on a small scale for distributed
hydrogen production systems both in industry as well as remote areas for
different applications. It is suggested to setup hydrogen production plants
based on presently available technology, which can be manufactured in India
and then conventional electrolyser may be replaced by the SPE based
electrolysers in a phased manner. This will ensure the successful deployment
of technology in the times to come. The estimated cost per kg of hydrogen is
about $ 8.94, when produced on a 1 MW level.

1.5.22 The strategy to bridge the gap may be planned by identifying projects
and the institutions to work in the relevant specialized areas and demonstrate
their prototypes. Foreign collaborations may be solicited in specific areas. After
successful demonstration of the prototypes, the R&D institutions may work with
the industry through PPP Model for commercialization of the technology.
Except the electrochemical stack, couple of Indian PSUs havecore strength for
manufacturing majority of subsystems and are very much capable in system

11
engineering. Imported electrolyser stacks in different combinations may also be
used and integration can be carried in the country.

e) Bio-Hydrogen Process

1.5.23 The bio-hydrogen production may be an economical way of hydrogen


production on the ground that the process takes place at ambient temperature
and atmospheric pressure; while other processes are carried out at higher
temperatures & pressures. The major biological processes for hydrogen
production are bio-photolysis of water by algae (if the algae is deprived of
sulphur, it will switch from the production of oxygen, i.e. normal photosynthesis,
to the production of hydrogen), dark and photo-fermentation of organic
materials, usually carbohydrates by bacteria. One of the major problems faced
by photo-fermentative reactors is the light shading effect generated by
accumulation of pigment in the photo-fermentative microbes. Moreover, the rate
of hydrogen production in bio-hydrogen reactors is also considerably low when
compared with dark fermentation. Sequential dark and photo-fermentation
process is a new approach for bio-hydrogen production. Dark fermentation
reactions do not require light energy, so they are capable of constantly
producing hydrogen from organic compounds present in wastewater
throughout the day and night. Among all the biological hydrogen production
processes, dark fermentation shows highest hydrogen production rates. This
process holds promise for commercialization. Carbohydrate rich, nitrogen
deficient solid wastes such as cellulose and starch containing agricultural and
food industry wastes and some food industry wastewaters such as cheese
whey, olive mill and bakers’ yeast industry waste water can be used for
hydrogen production by using suitable bio-process technologies. Utilization of
aforementioned wastes for hydrogen production provides inexpensive energy
generation with simultaneous waste treatment. A prototype hydrogen
bioreactor using waste as a feedstock is in operation at Welch's grape juice
factory in North East Pennsylvania, USA. Another two-stage process where bio-
hydrogen production process was integrated with bio-methanation is also being
considered as a feasible option for improvement of gaseous energy recovery.
This mixture of bio-hydrogen and bio-methane may be named as “hymet”.
12
1.5.24 Major contributors in biohydrogen production research are from United
States of America, Canada, Malasiya, Indonesia, Thailand, China and India.
Different microbes have been discovered in different parts of the world, each
having unique hydrogen production ability. Shri AMM Murugappa Chettiar
Research Centre, (MCRC), Chennai was involved in the development of
hydrogen production through biological process from sugar and distillery
wastes (effluents of M/s. E.I.D. Parry Ltd., at Nellikuppam, Tamilnadu). The
Center has designed and developed a 125 m3 bioreactor, which produced
18,000 liters of gas per hour with about 60% hydrogen mixed largely with CO2
and CO. Mesophilic and thermophilic species were identified for hydrogen
production. Indian Institute of Technology Kharagpur and Indian Institute of
Chemical Technology, Hyderabad are currently setting up bio-reactors of
10m3capacity each based on distillery effluent and kitchen waste respectively
and are expected to provide hydrogen yield of 30-50 m3 / day. For bio-hydrogen
to be considered as renewable energy source, it should be produced from
renewable raw materials like waste materials. Internationally very few studies
are available on commercial level units for bio-hydrogen production. Integration
of bio-hydrogen with fuel cell was first mooted in 2012. This concept still needs
a serious consideration since this technology is capable of producing hydrogen
in a decentralized manner.

1.5.25 Hydrogen can be recovered equivalent to only 20 to 30 % of total energy


through dark fermentation and therefore has limitations in commercialization,
even though this process can be integrated with photo-fermentation.
Theoretically, 12 moles of hydrogen /mole of glucose can be recovered from
integrated dark and photo fermentation reactors but due to scaling up problem
of photo-fermentation such two-stage process cannot commercialized. The
dark fermentation for hydrogen production can be commercialized, if it is
integrated with biomethantion process. The spent media of the dark
fermentation is rich in volatile fatty acids and would be an ideal substrate for
methanogens. The integration of these two processes might lead to 50-60%
gaseous energy recovery. Most attractive point of such process is that the
reactor used for hydrogen production could be used for bio-methanation also,
13
thus separate reactors are not required. Biohymet production could be
envisioned as renewable source of energy only, when it would be produced
from renewable sources.

f) Thermochemical splitting of water

1.5.26 Water can be dissociated at very high temperatures into hydrogen and
oxygen through thermochemical splitting of water. A catalyst is required to
make the process operate at feasible temperatures. The required energy can
be either provided by nuclear energy or by solar energy, or by hybrid systems
including solar and nuclear energy. More than 356 thermo-chemical cycles
have been conceived which can be used for water splitting. Around a dozen of
these cycles such as the iron oxide cycle, cerium(IV) oxide-cerium(III) oxide
cycle, zinc-zinc oxide cycle, sulfur-iodine cycle, copper-chlorine cycle and
hybrid sulfur cycle are under research/in testing phase. The iodine-sulphur (I-
S) cycle is one of the most promising and efficient thermo-chemical water
splitting technologies for the mass production of hydrogen, on which BARC,
Trombay, Mumbai is working.

1.5.27 The I-S closed loop glass system has been operated continuously for a
period of 20 hours at hydrogen production rate of 30 Lph. India is the 5th country
to achieve I-S closed loop operation in glass system, after USA (1980), Japan
(2004), China (2010) and South Korea (2009). USA aims to demonstrate
commercial scale production of hydrogen using nuclear energy by 2017.
European Union started working in this direction in 2004 with the objective to
evaluate the potential of thermo-chemical processes, focusing on the I-S cycle
which is to be compared with the Westinghouse hybrid (HyS) cycle in view of
the 2015 target for reduction of CO2 emissions from fossil fuels by more than
25% and hydrogen production cost of less than €2/kg. It has been found that
hydrogen production costs based on small plants is most favorable using solar
energy, while nuclear energy based plants are most economical at high power
levels (> 300 MW th); hybrid systems may have their niche in the midrange of
100 to 300 MW th. Canada is investigating copper–chlorine family of thermo-
chemical cycles with energy provided by the Canadian Super Critical Water
14
Reactor and use of direct resistive heating of catalysts for SO 3 decomposition
in the I-S process. Japan has recently initiated R&D activities on the thermo-
chemical cycles based on the UT-3 and I-S processes for hydrogen production
and successfully achieved the operation of a bench-scale facility for hydrogen
production at the rate of 30 Nl/h in a continuous closed I-S cycle operation over
one week. While the efficiency was only ~10% for the bench-scale plant, the
goal for the pilot plant is ~40%. In 2005, Japan have already initiated the activity
to design and construct a pilot plant for hydrogen production at the rate of 30
Nm3/h under the simulated conditions of a nuclear reactor.

1.5.28 The Republic of Korea has targeted for 25 % (3 Mt/year) of the total
hydrogen to be supplied by advanced 50 nuclear reactors by 2040. Korea
launched its nuclear hydrogen program in 2004 targeting (i) generation of
hydrogen for fuel cell applications for electricity generation, passenger vehicles,
and domestic power and heating, and (ii) lowering hydrogen costs and
improving efficiency of the related processes. Under this programme an
underground VHT reactor of 200 MW thermal output is to be coupled with an I-
S cycle to generate hydrogen from water. In 2005 People’s Republic of China
initiated work on a demonstration project on ‘High Temperature Reactor –
Pebble Module’. Both the I-S thermo-chemical cycle and high temperature
steam electrolysis are selected as the potential processes for nuclear hydrogen
production. The target has been set for commercialization of nuclear hydrogen
production by 2020.

1.5.29 The Bhabha Atomic Research Centre has successfully demonstrated I-


S process in closed loop operation in glass/quartz material in the laboratory. It
is further planned to demonstrate closed loop operation in metallic construction.
Other institutes / organizations will also be roped in depending upon their
capabilities. Their broad plan is:

(i) Design and Demonstration of Atmospheric pressure operation all Metal


closed loop system (AMCL).
(ii) High pressure operation Bunsen reactor system has been designed
and its commissioning is underway.
15
(iii) Design and demonstration of high pressure Sulfuric acid
decomposition system.
(iv) Design and demonstration of Hydriodic acid distillation and
decomposition system.
(v) Integration of all three high pressure systems to demonstrate, High
pressure closed loop process.

1.5.30 The ONGC Energy Centre (OEC) started working on the three
thermochemical processes such as Cu-Cl closed loop cycle, I-S closed loop
cycle and I-S open loop cycle at engineering scale and all these processes will
be compared before taking-up at the commercial level. In view of expensive
and corrosive nature of materials used in these processes, OEC has planned
to study and evaluate alternative materials. New plants may then be designed
based on this evaluation of the alternative materials. CSMCRI, Bhavnagar has
been involved in the ‘development of membranes’; IIP Dehradun is engaged in
the ‘development of partially open-loop I-S cycle involving H2S incineration and
experimental studies on Bunsen Reaction & HI decomposition’; IIT-Delhi is
working on “prolonged stability tests of catalysts for HI decomposition reaction
of I-S cycle.

1.5.31 Photo-catalytic and photo-electrochemical routes for hydrogen


production are also being explored globally by several research groups. In
India also some groups, namely, Indian Institute of Chemical Technology,
Hyderabad; Institute of Minerals and Materials Technology, Bhubaneswar; Yogi
Vemana University, Kadapa; SRM University; Kancheepuram, Shiksha ‘O’
Anusandhan University, Bhubaneswar and Centre for Materials for Electronics
Technology, Pune are active in this area. Efforts are being made to come out
with effective and robust photo-catalysts and photo-electro-catalysts, electrode
materials and materials for reactors. Till date no large scale unit has been
successfully designed and demonstrated. Concerted intensive efforts,
however, are required to generate basic information and knowhow to take this
area to the production for decentralized applications.

16
1.5.32 In photo-electrochemical water splitting, hydrogen is produced from
water using sunlight and specialized semiconductors called photo-
electrochemical materials. The Institute of Minerals and Materials Technology
Bhubaneswar developed functional hybrid nano-structures for photo-
electrochemical water splitting. The different photo-catalytic materials were
developed for hydrogen production through water splitting. The developed
materials yielded hydrogen e.g. 800-1000 mg hydrogen /batch with CdS photo-
electrodes and CdS nano-crystal powder photo-catalysts, 4087 µmol
hydrogen/h/g with 0.28 wt% Poly (3-hexylthiophene-2,5-diyl) (P3HT) modified
CdS and 11,901 µmol hydrogen/h/g with CdS-NaNbO3 core-shell nano-rods.
Thus, CdS-NaNbO3 core-shell nano-rods was found to give maximum
hydrogen production.

g) Other Technologies

1.5.33 Presently, Hydrogen Production by non-thermal plasma assisted direct


decomposition of hydrogen sulphide is at research and development stage and
no commercial technology is available globally. Among the several techniques
tested for the production of hydrogen, Idemitsu Kosan Hybrid (IKC) electrolysis
process consumes 3.6 kWh/Nm3 hydrogen, whereas steam reforming of
methane, (the traditional approach for hydrogen production) demands still
higher energy of 4.3 kWh/Nm3 hydrogen. 40% conversion of hydrogen sulphide
by thermal decomposition can be achieved at temperature ~ 1500K. Most of
the research in this area in the country has been focused on catalytic/
photocatalytic decomposition of hydrogen sulphide. Hydrogen sulphide under
visible light to generate hydrogen is an attractive route of solar energy
conversion, because hydrogen is 100% environmentally clean fuel in its cycles
of generation and utilization. The Indian Institute of Technology Hyderabad
developed the process of non-thermal plasma assisted direct decomposition of
hydrogen sulphide into hydrogen and sulphur. Hydrogen production of 0.5
litre/minute was achieved in the laboratory. The reaction conditions can be still
improved to decrease the energy consumption.

17
1.5.34 For the photo-splitting of hydrogen sulphide into hydrogen, extensive
work has been carried out for the development of ultraviolet driven
photocatalyst for water and hydrogen sulphide splitting. There is need to
develop prototype batch photo-reactor for hydrogen production from hydrogen
sulphide using solar energy and their field trials using gas emitted at refinery
site. Internationally, many groups in Japan, Korea, U.S, Europe are working on
development of active photo-catalysts for hydrogen generation under visible
light irradiation. The National Institute of Advanced Industrial Science and
Technology, Japan demonstrated first time in 2001 direct splitting of water by
visible light over an In1.xNixTaO4photocatalyst. Nationally, a few groups are
working on photocatalytic splitting of water and hydrogen and hydrogen
sulphide into hydrogen under visible light. BARC is working on photocatalytic
degradation of nuclear waste as well as water purification. IISc, Bangalore is
working on TiO2 based photocatalysts for organic waste degradation. IITs,
Mumbai and Madras, CECRI, Karaikudi, IICT, Hyderabad and some
universities in India are working on photodecomposition of organic pollutants.
The Centre for Materials for Electronics Technologies (C-MET), Pune is also
working on hydrogen generation by photocatalytic decomposition of toxic
hydrogen sulphide and achieved hydrogen production from hydrogen sulphide
at the rate of 8182.8 and 7616.4 µmol/h/g obtained from nanostructured
ZnIn2S4 and CdIn2S4, respectively in presence of sunlight. This design is useful
for continuous operation at large scale.

1.6.0 Suggested Action Plan

1.6.1 Based on the gap analysis undertaken between international and


national state of art of technologies and recommendations to fill the gap by
undertaking the projects as classified in the three broad categories: (a) Mission
Mode (for the technologies, which are mature or near maturity for
commercialization and with the participation of the industry); (b) Research &
Development Mode (for the technologies, which are at the stage of prototype
development, their demonstration as a proof of concept and preferably with
18
Industry participation); and (c) Basic / Fundamental Research Mode (for
advanced research on new materials and processes), the Action Plan for
hydrogen production in the country has been devised as following:

1.6.2 The unutilized (around 6600 tonnes) by-product hydrogen from the
Chlor-Alkali Units / Refineries may be used directly for the generation of power
/ in transportation applications (vehicles) based on IC engine technology. This
hydrogen may further be purified (if required) for stationary power generation
and on-board application in vehicles / material handling systems based on fuel
cell technology. To utilize this hydrogen requisite power generating system /
purification unit / compression system to fill cylinders for on-board application
of hydrogen in vehicles / material handling vehicles (based on fuel cell
technology) need to be set-up. The activity is to be completed by 2018.

1.6.3 Hydrogen has been produced from the conventional sources i.e.
carbonaceous fuels like natural gas, coal etc. Hydrogen production by
electrolysis, methanol or ammonia cracking is preferred for small, constant or
intermittent requirements of hydrogen in food, electronics and pharmaceutical
industries, while for larger capacities steam reforming of hydrocarbons /syn gas
is preferred. Renewable-based processes like solar- or wind-driven electrolysis
and photo-biological water splitting hold great promise for clean hydrogen
production; however, advances must still be made before these technologies
can be economically competitive. Thus, hydrogen production may be continued
from the conventional (carbonaceous) fuels through the most competitive
process namely auto-thermal reforming (steam reforming and partial oxidation)
process till the technologies for hydrogen production from renewable sources
become economically competitive. Scaling-up of the process of catalytic
decomposition of natural gas for the production of H-CNG for the use in H-CNG
fuelled vehicles (up to 2019), Development & demonstration of hydrogen
production by Auto-thermal Process (up to 2020) and Basic / Fundamental
Research for dissociation of gaseous hydrocarbon fuels to hydrogen using solar
energy (up to 2022) may be carried out.

19
1.6.4 Biomass has been identified as potential source of renewable energy for
hydrogen production. Biomass is gasified to hydrogen rich syngas, which may
be reformed and purified to yield pure / near pure hydrogen. The technology of
oxy-steam gasification of biomass for hydrogen products has been developed
at a small pilot scale (2 kg/hr) by the Indian Institute of Science, Bangalore. This
may be promising technology for distributed hydrogen production. However,
there are challenges associated with purification of hydrogen and scaling up.
Research and development for hydrogen production by gasification of biomass
may, therefore, be carried out including demonstration of technology at pilot
scale (up to 2020).

1.6.5 Pure hydrogen may be obtained by electrolysis for fuel cells applications.
The electrolyser system consists of various sub-systems. India is capable in
system engineering and has core strength for manufacturing majority of sub-
systems except electrochemical stack. Imported electrolyser stacks may be
used with the indigenously developed sub-systems. The Institutions / Industry
may be identified to work in PPP Model for commercialization of the balance of
plant and simultaneously, the technology for the production of stack may be
procured or developed indigenously. Solid polymer electrolyser (SPE) with
20,000 hours of operation is desirable and may have membranes based
alkaline water electrolysis system integrated with solar photovoltaic system. For
the immediate availability of hydrogen onsite, hydrogen may be produced by
deploying solar energy powered Acid / Alkali based electrolysis systems based
on available technology. Simultanously, development of (i) electrolysers based
on indigenous acid based SPE (ii) alternate alkaline membrane up to 2018 (iii)
alkaline 1 & 5 Nm3/hr high temperature steam solid polymer water electrolyser
(up to 2020) may be done and demonstrated and replaced old systems by the
newly developed systems. Hydrogen production system by splitting water using
renewable energies such as solar energy, wind energy and hybrid systems
including electrolysis, photo-catalysis and photo-electro-catalysis may also be
developed and demonstrated(up to 2022).

1.6.6 Hydrogen may be produced through dark-fermentation followed by the


photo- fermentation of solid waste from agriculture & food industry and liquid
20
waste from food industry. The integrated process is difficult to commercialize in
view of the problems associated with the photo-fermentative reactors.
Therefore, dark fermentation followed by bio-methanation may be studied,
which can recover 50 - 60% gaseous energy from the waste. Only one reactor
may be required for both processes – firstly, hydrogen production and
subsequently, bio-methanation. The mixture of hydrogen and methane, so
produced, is known as bio-hymet. The production of bio-hymet could be
envisioned as renewable source of energy. This activity has been proposed to
be taken up in Research, Development and Demonstration Mode up to 2019.
Energy balance and process economic aspects may also be studied. Biological
hydrogen production projects may also be taken up for demonstration in niche
areas.

1.6.7 Another path for hydrogen economy has been suggested by the
integration of fuel cell system with the bio-hydrogen production system. Such
setups may be put strategically near to those places where supply of feedstock
is easily available in adequate quantities. The electricity generated by such
system may be used to electrify villages in a decentralized manner. It is
suggested to take-up such activities in Mission Mode up to 2022.

1.6.8 The Bhabha Atomic Research Centre is engaged in the development of


I-S technology in-house. This process in closed loop operation has been
successfully demonstrated in glass/quartz reactor. Further, it has been planned
to demonstrate closed loop operation of I-S in metallic reactor. ONGC Energy
Centre is also working on I-S process in collaboration with IIT-Delhi, ICT
Mumbai and CECRI, Karaikudi on both I-S open & closed loop and Cu-Cl
cycles. Hydrogen generation @ 27 LPH has been achieved through Cu-Cl
process under specified operating conditions. It is suggested to continue these
activities using solar / nuclear heat in Mission Mode up to 2022.

1.6.9 Hydrogen production by water splitting through photolysis using solar


energy may be undertaken upto 2022 in Mission Mode.

21
1.6.10 Other innovative method for hydrogen production, like hydrogen
production by non-thermal plasma assisted direct decomposition of hydrogen
sulphide, Photo-splitting of Hydrogen Sulphide including developmental effort
for reduction in energy consumption for hydrogen production (up to 2022).

1.6.11 The total requirement of budget would be around Rs.285 Crore upto
2022.

1.7 Financial Projections for the Mission Mode, Research and Development
Mode and Basic / Fundamental Research Mode projects are given as under:

S. Name of Project Estimated Cost


No. Rupees in Crore
1. Setting-up of purification unit / compression 20
system to fill cylinders for power generating
system / on-board application of hydrogen in
vehicles / material handling vehicles(based on
fuel cell technology) to utilize surplus hydrogen
from the Chlor-Alkali Units / Refineries.
2. Scaling-up of the process of catalytic 40
decomposition of natural gas for the production
of H-CNG for the use in H-CNG fuelled vehicles
(up to 2019)
3. Development & demonstration of hydrogen 20
production by Auto-thermal Process (up to
2020)
4. Basic / Fundamental Research for dissociation 10
of gaseous hydrocarbon fuels to hydrogen
using solar energy (up to 2022)
5. Research and development for hydrogen 10
production by gasification of biomass including
demonstration of technology at pilot scale (up
to 2020)

22
6. Development and demonstration afresh or 10
deployment in place of old systems of
electrolyser based on indigenous acid based
SPE and alternate alkaline membrane up to
2018
7. Development and demonstration afresh or 10
deployment in place of old systems of alkaline
1 & 5 Nm3/hr high temperature steam solid
polymer water electrolyser (up to 2020)
8. Development & demonstration of efficient 10
alkaline water electrolyser (Upto 2018)
9. Development and demonstration of Hydrogen 10
production by splitting water using renewable
energies such as solar energy, wind energy
and hybrid systems including electrolysis,
photo-catalysis and photo-electro-catalysis (up
to 2022)
10. Mission Mode Project for development and 20
demonstration of biological hydrogen
production from different kinds of wastes on
bench scale, pilot scale and commercial
production up to 2022
11. Demonstration of closed loop operation of I-S 50
in metallic reactor and both I-S open & closed
loop process and Cu-Cl cycle using solar /
nuclear heat in Mission Mode up to 2022
12. Mission Mode Project for Hydrogen production 40
by water splitting using photolysis using solar
energy upto 2022
13. Hydrogen production by reformation of bio-oil 5
obtained from fast pyrolysis of biomass
14. Development of technology for production of 5
syn-gas (CO+H2)and hydrogen from

23
reformation of natural gas / biogas using solar
energy.
15. Integration of large capacity electrolysers with 5
wind / solar power units when there are not in a
position to evacuate power to grid for providing
hydrogen.
16. Other innovative method for hydrogen 20
production like hydrogen production by non-
thermal plasma assisted direct decomposition
of hydrogen sulphide, Photo-splitting of
Hydrogen Sulphide including developmental
effort for reduction in energy consumption for
hydrogen production(up to 2022)
Total requirement of budget upto 2022 285

24
INTRODUCTION

25
2.0 Introduction

2.1 Man’s dependence on fossil fuels has made a deep impact on energy
security and natural climate. This has led to exhaustion of fossil fuels, emission
of pollutants, and greenhouse gases responsible for global warming. The crude
petroleum oil output by the OPEC (Organization of the Petroleum Exporting
Countries) would not be able to meet the energy demands beyond 2045. To
address above issues, hydrogen has been considered as the potential clean
energy carrier for the future. Hydrogen may replace petrol and diesel used in
the automobiles and even coal for large scale power generation. Presently,
hydrogen production is for non-energy applications and ‘quantum of increase’
in hydrogen production will enable its mass scale utilization as a fuel. To have
sustainable hydrogen production, the energy and raw materials needed for this
purpose ought to be renewable in nature. There are various methods which
may be employed for generating hydrogen from renewable and non-renewable
resources. However, the challenge lies in the production of hydrogen in a cost
effective manner. About 95 % of the current hydrogen requirements are
produced through fossil fuel sources. Currently, the agricultural sector is the
largest user of hydrogen in the form of nitrogenous fertilizers, with 49% of
hydrogen being used for ammonia production. Being a clean energy source, its
future widespread use as fuel is likely to be in the transport and also in
distributed power generation sectors. Hydrogen may indeed emerge to be a
turning point for our nation, which is dependent heavily on the imported
petroleum crude and natural gas for meeting its energy needs. Development,
demonstration and commercialization of appropriate hydrogen production
technologies and systems are, therefore, essential in the country, since these
have advanced significantly world over.

2.2 Molecular hydrogen is not available on Earth in convenient natural


reservoirs. Most hydrogen on Earth is bonded to oxygen in water and to carbon
in live or dead and/or fossilized biomass. Currently manufacture of elemental
hydrogen requires consumption of energy generated from a fossil or an
alternative source. It produces carbon dioxide. Decomposition of water

26
requires electrical or heat input, generated from some primary energy source
(fossil fuel, nuclear power or a renewable energy- solar, wind, hydro-electricity,
etc.). The energy provided by the energy source essentially provides all of the
energy that is available in the hydrogen fuel.

2.3 Hydrogen may be produced from a variety of carbonaceous feed-stocks


and/or water using a variety of technologies. Coal, natural gas, petroleum
fractions and biomass can be converted to hydrogen through pyrolysis /
gasification and reforming using several technologies like steam methane
reforming, partial oxidation / auto-thermal reforming. About 95 % of the current
hydrogen requirements is met from fossil fuel sources.

2.3.1 Steam methane reforming (SMR) is the most common, well-developed


and fully commercialized process. It is the least expensive method of producing
hydrogen; almost 48% of the world’s hydrogen is produced from SMR. The
reforming reaction between steam and hydrocarbons is highly endothermic and
is carried out in presence of specially formulated nickel catalyst contained in
vertical tubes situated in the radiant section of the reformer. The SMR process
is popular because natural gas, commonly used feedstock has high hydrogen
content (four hydrogen atoms per carbon atom) and distribution network for the
natural gas already exists. The simplified chemical reactions are:

CH4 + H2O = CO + 3H2 delta H = + 206 kJ/mol (for methane)


CO + H2O = CO2 + H2 delta H = - 41 kJ/mol (CO shift reaction)

The Pressure Swing Adsorption (PSA) purification unit separates


hydrogen from mixture of product gases by adsorption of CO, CO2 and CH4.
This process is commonly used to supply large quantities of hydrogen gas to
oil refineries, and ammonia and methanol plants.

Cost of hydrogen production through SMR technology is highly


dependent on the scale of production. Large capacity modern SMR hydrogen
plants have been constructed with hydrogen generation capacities exceeding
480,000 kg hydrogen/day. These large hydrogen plants typically are co-located
27
with the end users in order to reduce hydrogen gas transportation and storage
costs. In addition, SMR technology is also scalable to smaller end-use
applications. SMR can also be applied to other hydrocarbons such as ethane
and naphtha. Heavier feed-stocks, however, cannot be used, because they
may contain impurities and the feed to the reformer must be in vapor form.
Other processes such as partial oxidation (POX) are more efficient with higher
hydrocarbons.

2.3.2 Hydrogen production from coal gasification is also a well-established


commercial technology, but is only competitive with SMR, where oil and/or
natural gas are expensive. Three primary types of gasifiers are used: fixed bed,
fluidized bed, and entrained flow. Because there are significant coal reserves
in many areas of the world, coal could replace natural gas and oil as the primary
feedstock for hydrogen production. However, this technology has
environmental impacts (e.g., feedstock procurement) that may prove to be a
significant impediment in the future.

2.3.3 Non-catalytic partial oxidation of a hydrogen-rich feedstock (such as


natural gas, coal, residue oil, petroleum coke, or biomass) is another pathway
for hydrogen production. With natural gas as a feedstock, the partial oxidation
process typically produces hydrogen at a faster rate than SMR, but it produces
less hydrogen from the same quantity of feedstock. The overall efficiency of
this process (50%) is less than that of SMR (65%-75%) and pure oxygen is
required. Two commercial technologies for this conversion are available (i)
Texaco Gasification Process, and (ii) Shell Gasification Process. As a result of
increasing natural gas prices, further development of natural gas partial
oxidation technology has been slowed down. The use of a solid fuel like coal is
also possible, through gasification, to produce a synthetic gas (syngas) that can
then be used in a partial oxidation process to obtain hydrogen as product.

2.3.4 Like gasification of coal, biomass may also be gasified using a variety
of methods, primarily indirect and direct gasification. Indirect gasification uses
a medium such as sand to transfer heat from the char combustor to the
gasification vessel. In direct gasification heat is supplied to the gasification
28
vessel by the combustion of a portion of the feed biomass. In general, hydrogen
produced via direct gasification is expected to cost slightly more (i.e., 5%) than
that from the indirect mode.

2.3.5 In Biomass pyrolysis, biomass may be thermally decomposed at a high


temperature (in the range of 600-10000C) in an inert atmosphere to form a bio-
oil composed of about 85% oxygenated organics and remaining water. The bio-
oil is then steam reformed using conventional technology to produce hydrogen.
Alternatively, the phenolic components of the bio-oil can be extracted with ethyl
acetate to produce an adhesive/phenolic resin as a co-product; the remaining
components can be reformed as in the first option. The product gas from both
alternatives is purified using a standard pressure swing adsorption (PSA)
system.

2.3.6 The Kvaerner-process or Kvaerner carbon black & hydrogen process


(CB&H) is a method, developed in the 1980s by a Norwegian company for the
production of hydrogen from hydrocarbons (CnHm), such as methane, natural
gas and biogas. Of the available energy of the feed, approximately 48% is
contained in the hydrogen, 40% is contained in activated carbon and 10% in
the superheated steam.

2.4 Electrolysis of Water

The Electrolysis of water uses electrical energy to split water


molecules into hydrogen and oxygen. Large-scale electrolysis of brine
(saltwater) has been commercialized for chemical applications. Some small-
scale electrolysis systems also supply hydrogen for high-purity chemical
applications, although for most medium- and small-scale applications of
hydrogen fuels, electrolysis is cost-prohibitive. For renewable technologies, the
capital costs dominate. The cost of the electricity is a major concern because it
is three to five times more expensive as “feedstock” than fossil fuels. In fact, the
high cost of the electricity is the driving force behind the development of high-
temperature steam electrolysis. In this process, some of the energy driving the

29
process can be supplied in the form of steam instead of electricity. For example,
at 1000°C, more than 40% of the energy required could be supplied as heat.

Current best process to have an efficiency of 50 - 80% and 1 kg of


hydrogen with specific energy of 143 MJ/kg (about 40 kWh/kg) requires 50 - 79
kWh electricity. At the cost of electricity as $0.08/kWh, hydrogen from
electrolysis would cost $4.00/kg hydrogen, which is 3 to 10 times the price of
hydrogen obtained from steam reforming of natural gas. The price difference is
due to the efficiency of direct conversion of fossil fuels to produce hydrogen,
rather than burning fuel to produce electricity. Hydrogen from natural gas, used
to replace e.g. gasoline, emits more CO2 than the gasoline it would replace,
and so is of no help in reducing greenhouse gases.

2.4.1 High Pressure Electrolysis

High pressure electrolysis is the electrolysis of water by decomposition


of water (H2O) into oxygen (O2) and hydrogen gas (H2) by means of an electric
current being passed through the water. This differs with the standard
electrolyser in terms of the hydrogen output at around 120-200 bar (1740-2900
psi). By pressurizing the hydrogen in the electrolyser the need for an external
hydrogen compressor is eliminated, the average energy consumption for
internal compression is around 3%.

2.4.2 High Temperature Electrolysis

Hydrogen can be generated from energy supplied in the form of heat and
electricity through high-temperature (950–1000 °C) electrolysis (HTE). The
electricity and heat generated through a nuclear reactor could be used for
splitting hydrogen from water. Research into high-temperature nuclear reactors
may eventually lead to a hydrogen supply that is cost-competitive with natural
gas-steam reforming. General Atomics predicts that hydrogen produced in a
High Temperature Gas Cooled Reactor (HTGR) would cost $1.53/kg. In 2003,
steam reforming of natural gas yielded hydrogen at $1.40/kg. HTE has been
demonstrated for hydrogen at laboratory scale (with a product having calorific

30
value of 108 MJ (thermal) per kg) but not at a commercial scale. This is lower-
quality "commercial" grade Hydrogen, which is unsuitable to use in fuel cells.

2.5 Photo-electrochemical Water Splitting

Using electricity produced by photovoltaic systems offers the cleanest


way to produce hydrogen. Water is broken into hydrogen and oxygen by
electrolysis—a photo-electrochemical cell (PEC) process which is also named
artificial photosynthesis. Research aimed toward developing higher-efficiency
multi-junction cell technology is underway by the photovoltaic industry. If this
process is assisted by photo-catalysts suspended directly in water instead of
using photovoltaic and an electrolytic system, the reaction is in just one step,
which can improve efficiency.

2.6 In photo-electro-catalytic production, a gold electrode is covered in


layers of indium phosphide (InP) nanoparticles and an iron-sulphur complex is
introduced into the layered arrangement, which when submerged in water and
irradiated with light under small electric current, produces hydrogen with an
efficiency of about 60%. The electricity production itself involves large
transformation losses, however, the efficiency of hydrogen production through
electrolysis relative to the primary energy content of the fuel input to generation
would be significantly lower. In certain cases, it may be economical to use off-
peak electricity, if it is priced well below the average electricity price for the day;
however, such market applications would have to be balanced with other
potential electricity supplies, the cost versus benefits of appropriate metering
and rate design, and the implied reduction in utilization of the electrolysis unit,
as described above. The development of such an application could also support
other technologies, such as plug-in hybrid electric vehicles.

2.7 Hydrogen through Thermal Splitting of Water:

2.7.1 Concentrated Solar Thermal Energy: Very high temperatures are


required to dissociate water into hydrogen and oxygen. A catalyst is required to

31
make the process operate at feasible temperatures. Heating the water can be
achieved through the use of concentrating solar power. Hydrosol-II is a 100-
kilowatt pilot plant in Spain, which uses sunlight to obtain the required 800 -
1,2000C to heat water. It has been in operation since 2008. The design of this
pilot plant is based on a modular concept. As a result, it may be possible that
this technology could be readily scaled up to the megawatt range by multiplying
the available reactor units and by connecting the plant to heliostat fields (fields
of sun-tracking mirrors) of a suitable size.

2.7.2 A promising long-term technology is the use of concentrated solar


energy for hydrogen production via electrolysis. Two primary process
configurations are used with this method. In the first, ambient temperature
electrolysis, concentrated solar energy is used to generate alternating current
(AC) electricity, which is supplied to the electrolyser. The second is the high-
temperature electrolysis of steam. In this system, the concentrator supplies
both heat and AC electricity to convert steam (1273 K) to hydrogen and oxygen.
In this system, an SOFC system would be operated in a reverse mode to
generate hydrogen instead of electricity. This technology is in an early stage of
development.

2.8 There are more than 356 thermo-chemical cycles for the production of
hydrogen by splitting water (without using electricity) though only around a
dozen of these cycles such as the iron oxide cycle, cerium(IV) oxide-cerium(III)
oxide cycle, zinc-zinc-oxide cycle, sulphur-iodine cycle, copper-chlorine cycle
and hybrid sulphur cycle are under research and in testing phase. These
processes can be more efficient than high-temperature electrolysis, typical in
the range from 35 - 49% (lower heating value) efficiency. Thermo-chemical
production of hydrogen using chemical energy from coal or natural gas is
generally not considered, because the direct chemical path is more efficient.
None of the thermo-chemical hydrogen production processes have been
demonstrated at production levels, although several have been demonstrated
in laboratories.

2.9 Biological Hydrogen Production

32
It is the fermentative conversion of organic substrate to bio-hydrogen
manifested by a diverse group bacteria using multi enzyme systems involving
three steps similar to anaerobic conversion. Two different fermentation routes-
dark fermentation and photo-fermentation routes are available. Dark
fermentation reactions do not require light energy, so they are capable of
constantly producing hydrogen from organic compounds throughout the day
and night. Photo-fermentation differs from dark fermentation because it only
proceeds in the presence of light. Biological hydrogen can be produced in an
algae bioreactor. In the late 1990s it was discovered that if the algae is deprived
of sulphur, it will switch from the production of oxygen, i.e. normal
photosynthesis, to the production of hydrogen.

Biological hydrogen can also be produced in bioreactors that use feed-


stocks other than algae, the most common feedstock being waste streams. The
process involves bacteria feeding on hydrocarbons and excreting hydrogen and
CO2. The CO2 can be sequestered successfully by several methods, leaving
hydrogen gas. A prototype hydrogen bioreactor using waste as a feedstock is
in operation at Welch's grape juice factory in North East, Pennsylvania.

2.10 Bio-catalyzed Electrolysis

The electrolysis using microbes provides another possibility of producing


hydrogen besides regular electrolysis of water, with bio-catalyzed electrolysis,
hydrogen is generated after running through the microbial fuel cell and a variety
of aquatic plants can be used. These include reed sweet-grass, cord-grass,
rice, tomatoes, lupines, algae.

33
HYDROGEN PRODUCTION USING
THERMOCHEMICAL ROUTE FROM
CARBONACEOUS FEED-STOCK

34
3.1 Hydrogen Production from Carbonaceous Sources

3.1.1 Introduction:

Hydrogen has been projected as one of the few long-term sustainable


clean energy carriers, emitting only water vapour as a by-product during the
combustion or oxidation process. Approximately 95% of the hydrogen produced
presently comes from carbonaceous raw materials derived primarily from a
fossilized carbonaceous feed-stock. Only a fraction of this hydrogen is currently
used for energy purposes; the bulk serves as a chemical feedstock for fertilizer,
petrochemical, food, electronics and metallurgical processing industries.
Hydrogen share in the energy market is increasing with the implementation of
fuel cell systems and the growing demand for zero-emission fuels. Hydrogen
production will need to keep pace with this growing market.

The use of hydrogen for petrochemicals, fertilizers and as clean and


renewable energy carrier will increase substantially in the next 5-10 years as
even more stringent environmental legislations are enforced. Low sulfur
gasoline and diesel fuels will become mandatory and harmful emissions will
have to be reduced drastically. Hydrogen will be required by refiners and
specialty chemical manufacturers to meet the global need for cleaner products.
The growing fuel cell market will be dependent on hydrogen as a primary fuel
source. The Hydrogen Posture Plan, published by Energy Efficiency and
Renewable Energy (EERE), USA in February 2004, envisaged a complete
transition to a hydrogen economy by 2030–2040.

However, hydrogen is not readily available in sufficient quantities and


the production cost is still high for transportation purpose. The technical
challenges to achieve a stable hydrogen economy include improving process
efficiencies, lowering the cost of production and harnessing renewable sources
for hydrogen production.

35
3.1.2 International Status & Commercialization

Conventional technologies for hydrogen production are:


a) Steam Methane Reforming
b) Partial Oxidation
c) Auto-Thermal Reforming
d) Methanol Reforming
e) Ammonia Cracking
f) Thermo-catalytic Cracking of Methane
g) Novel Reformer Technologies

A. Steam Methane Reforming

1. Process Description

Catalytic steam reforming of methane is a well-known, commercially


available process for hydrogen production. Hydrogen production is
accomplished in several steps: steam reforming, water gas shift reaction, and
hydrogen purification.

CH4 + H2O ↔ CO + 3 H2 h = +206.16 kJ/mol CH4

The steam reforming reaction is endothermic and requires external heat


input. Economics favors reactor operation at pressures of 3 to 25 atmospheres
and temperatures of 700 to 850°C. The external heat needed to drive the
reaction is often provided by the combustion of a fraction of the incoming natural
gas feedstock (up to 25%) or from burning waste gases, such as purge gas
from the hydrogen purification system. Heat transfer to the reactants is
accomplished indirectly through a heat exchanger. Methane and steam react in
catalyst filled tubes. Typically, the mass ratio of steam to carbon is about 3 or
more to avoid "coking" or carbon build-up on the catalysts.

After reforming, the resulting syngas is sent to one or more shift reactors,

36
where the hydrogen output is increased via the water-gas shift reaction which

"converts" CO to H2.

CO + H2O ↔ CO2 + H2 h = - 41.15 kJ/mol CO (2)

This reaction is favored at temperatures of less than about 600°C, and


can take place at as low as 200°C, with sufficiently active catalysts. The gas

exiting the shift reactor contains mostly H2 (70-80%) plus CO2, CH4, H2O and

small quantities of CO. For hydrogen production, the shift reaction is often
accomplished in two stages. A high temperature shift reactor operating at about
350-475°C accomplishes much of the conversion, followed by a lower
temperature (200-250°C) shift reactor, which brings the CO concentration down
to a few percent by volume or less. Hydrogen is then purified. The degree of
purification depends on the application. For industrial hydrogen, pressure swing
absorption (PSA) systems or palladium membranes are used to produce
hydrogen at up to 99.999% purity.

2. Status of Various Types of Steam Methane Reformers

a) Conventional Steam Methane Reformers

Steam methane reformers have been built over a wide range of sizes.
For large-scale chemical processes such as oil refining, steam reformers
produce 25 to 100 million standard cubic feet of hydrogen per day (1 scf =
0.02832 m3 or 28.32 L). These systems consist of long (12 meter) catalyst filled
tubes, and operate at temperatures of 850oC and pressures of 15-25 atm, which
necessitates the use of expensive alloy steels. Capital costs for a 20 million scf
H2/day steam reformer plant (including the reformer, shift reactor and PSA) are
about $200/kW H2 output; for a 200 million scf/day plant capital costs are
estimated to be about $80/kW H2 .Refinery-type (high pressure, high
temperature) long tube reformers can be scaled down to as small as 0.1-1.0
million scf/day (the scale needed for producing hydrogen at refueling stations),
but scale economies in the capital cost are significant. The capital cost is about
$750/kW H2 at 1 million scf/day and $4000/kW H2 at 0.1 million scf/day. Small-
37
scale conventional (long tube, high temperature) steam methane reformers are
commercially available from a number of companies, which normally produce
large steam methane reformers for chemical and oil industries. The main design
constraints for these systems are high throughput, high reliability and high purity
(depending on the application).

The disadvantages of conventional long tube steam reformers for


hydrogen refueling station applications are their large size (12-meter long
catalyst-filled tubes are commonly used), and high cost (which is due to costly
materials requirements for high temperature, high pressure operation, and to
engineering/installation costs for these one of kind units). For these reasons, it
is generally believed in the hydrogen and fuel cell R&D communities that a more
compact, lower cost reformer will be needed for stand-alone hydrogen
production at refueling stations.

b) Compact “Fuel Cell Type” Steam Methane Reformers with Concentric


Annular Catalyst Beds

At small sizes, a more cost effective approach is to use a lower pressure


and temperature reformer, with lower cost materials. Steam methane reformers
in the range of 2000 to 120,000 scf H2/day have been developed for use with
fuel cells, and have recently been adapted for stand-alone hydrogen
production. In these systems, the heat transfer path is properly engineered to
make the device more compact, and the reformer operates at a lower pressure
and temperature (3 atm, 700°C), which relaxes materials requirements.
Estimates of mass produced costs for small .fuel cell type. steam methane
reformers indicates that the capital cost for hydrogen production plants in the
0.1 to 1.0 million scf/day range would be $150-$180/kW H2 assuming that 1000
units were produced.

The capital costs per unit of hydrogen production ($/kW H 2) are similar
for fuel cell type small reformers and conventional, one-of-a-kind large
reformers, assuming that many small units are built. Energy conversion
efficiencies of 70%-80% are possible for these units.
38
c) Plate-type Steam Methane Reformers

Another innovation in the design of steam methane reformers for fuel cell
systems is the plate-type reformer. Plate-type reformers are more compact than
conventional reformers with long, catalyst-filled tubes or annular-type reformers
with catalyst beds. The reformer plates are arranged in a stack. One side of
each plate is coated with a steam reforming catalyst and supplied with reactants
(methane and steam). On the other side of the plate, anode exhaust gas from
the fuel cell undergoes catalytic combustion, providing heat to drive the
endothermic steam reforming reaction. The potential advantages of a plate
reformer are more compact, standardized design (and lower cost), better heat
transfer (and therefore better conversion efficiency), and faster start-up
(because each plate has a lower thermal inertia than a packed catalyst bed).

The various reactors in the steam methane reformer system (e.g.


desulfurizer, steam reformer, water gas shift reactor, and CO clean-up stage)
are made up of plates of a standard size, greatly reducing the capital cost. Heat
transfer and heat integration between reactors is facilitated.

Plate-type steam methane reformers have not yet been commercialized


for fuel cell systems, but may allow for future capital cost reduction by
simplifying system design.

d) Membrane Reactors for Steam Reforming

Another promising technology is the .membrane reactor, where the


steam reforming, water gas shift and hydrogen purification steps all take place
in a single reactor. Methane and steam are fed into a catalyst-filled reactor
under pressure. On one side of the reactor is a high selectivity palladium
membrane that is selectively permeable to hydrogen. As the steam reforming
reaction proceeds, the hydrogen is driven across the membrane by the
pressure difference. Depending on the temperature, pressure and the reactor
length, methane can be completely converted, and very pure hydrogen is
39
produced, which is removed as the reaction proceeds. This allows operation at
lower temperature, and use of lower cost materials. A potential advantage of
this system is simplification of the process design and capital cost reduction
due to the need of fewer process vessels.

There is huge spurt in industrial R&D activity on membrane technologies


for syngas and hydrogen production. Interest by major energy companies in
applying membrane technology to large-scale syngas and hydrogen production
may have significant “spin-offs” for small-scale hydrogen production as well.
Recently patents have been issued on membrane reactor reforming to a
number of companies involved in fuel processor design for fuel cells and on
related ion transport membrane technology to oil companies, Exxon, BP
Amoco, Indiana, Standard Oil, USA and other industrial gas companies like Air
Products and Praxair. Recently Praxair and Argonne National Laboratory
launched a programme to develop a compact, low-cost hydrogen generator
based on ceramic membrane technologies. Steam, natural gas and oxygen are
combined in a catalyzed auto-thermal reforming reaction. Oxygen is derived
from air, using an oxygen transport ceramic membrane (OTM) that operates at
about 800-1000oC. High purity hydrogen is removed using a high selective
hydrogen transport membrane, also operating at 800-1000oC. The OTM has
been developed by Praxair and others in the Oxygen Transport Membrane
Syngas Alliance (BP, London, Amoco, Indiana Statoil, Norway, Sasol,
Johannesburg), South Africa, since 1997, and is now undergoing Phase II pilot
demonstration. The hydrogen transport membrane is being developed at
Argonne National Laboratory, and is in an early stage of development.

In Japan, the Tokyo Gas company has built and tested a small
membrane reactor for production of pure hydrogen from natural gas at a rate of
15 Nm3/h (about 12,000 scf/d), as well as steam reforming and partial oxidation
systems. Aspen Systems has demonstrated a membrane reactor for steam
reforming methane, ethanol and gasoline.

B. Partial Oxidation

40
1. Process Description

Another commercially available method for deriving hydrogen from


hydrocarbons is partial oxidation (POX). Here, methane (or some other
hydrocarbon feedstock such as oil) is oxidized to produce carbon monoxide and
hydrogen according to

CH4 + 1/2 O2→ CO + 2 H2 h° = -36 MJ/kmol CH4

The reaction is exothermic and no indirect heat exchanger is needed.


Catalysts are not required because of the high temperature. However, the
hydrogen yield per mole of methane input (and the system efficiency) can be
significantly enhanced by use of catalysts. A hydrogen plant based on partial
oxidation includes a partial oxidation reactor, followed by a shift reactor and
hydrogen purification equipment. Large-scale partial oxidation systems have
been used commercially to produce hydrogen from hydrocarbons such as
residual oil, for applications in refineries, etc. Large systems generally
incorporate an oxygen plant, because operation with pure oxygen, rather than
air, reduces the size and cost of the reactors.

Small-scale partial oxidation systems have recently become


commercially available, but intensive R&D activities are still underway. Small-
scale partial oxidation systems have a fast response time, making them
attractive for following rapidly varying loads, and can handle a variety of fuels,
including methane, ethanol, methanol, and gasoline.

The POX reactor is more compact than a steam reformer, in which heat
must be added indirectly via a heat exchanger. The efficiency of the partial
oxidation unit is relatively high (70-80%). However, partial oxidation systems
are typically less energy efficient than steam reforming because of the higher
temperatures involved (which exacerbates heat losses) and the problem of heat
recovery. (In a steam methane reforming plant, heat can be recovered from the
flue gas to raise steam for the reaction, and the PSA purge gas can be used as
a reformer burner fuel to help provide heat for the endothermic steam reforming
41
reaction. In a POX reactor, in which the reaction is exothermic, the energy in the
PSA purge gas cannot be fully recovered).

Because they are more compact, and do not require indirect heat
exchange (as in steam reforming), it has been suggested that partial oxidation
systems could cost less than steam reformers. Although the partial oxidation
reactor is likely to be less expensive than a steam reformer vessel, the
downstream shift and purification stages are likely to be more expensive.
Developing low cost purification technologies is the key if PO X systems are to
be used for stationary hydrogen production. Another approach is using pure
oxygen feed to the POX, which incurs high capital costs for small-scale oxygen
production, but eliminates the need to deal with nitrogen downstream. Oxygen
enrichment of incoming air is another way of reducing, but not eliminating, the
amount of nitrogen. Innovative membrane technologies such as the ion
transport membrane (ITM) may allow lower cost oxygen for POX reactors. This
is being investigated by Air Products in its research related to ion transport
membranes (ITMs), and by Praxair and partners in its oxygen transport
membrane program.

2. Status of Partial Oxidation Systems

A number of companies are involved in developing small-scale partial


oxidation systems. Small partial oxidation systems have been developed, for
use with fuel cell systems, by Arthur D. Little and its spin-off companies Epyx
and Nuvera. Epyx is supplying the onboard gasoline reformer for the USDOE’s
gasoline fuel cell vehicle project. Epyx recently formed a joint company with
DeNora called Nuvera, to commercialize POX reformer/PEM fuel cell systems.
Nuvera has reportedly shipped gasoline reformers to automotive companies for
testing.

Hydrogen Burner Technology (HBT), Inc., California, USA has


developed a range of hydrogen production systems based on partial oxidation.
This includes a reformer that produces very pure H2 for cogeneration in
buildings. HBT, with funding from the California Air Resources Board, is
42
installing a natural gas reformer filling station for Sunline Transit at Thousand
Palms, CA, to supply hydrogen to fuel cell buses and Hythane® buses. HBT
has a joint venture with Gaz de France to distribute HBT’s products in Europe.
Phoenix Gas Systems (a HBT sub group) develops systems for industrial
hydrogen gas generation.

Argonne National Laboratory, Lemont, Illinois, USA has developed a


partial oxidation reformer suitable for use in vehicles. The USDOE is supporting
work on partial oxidation systems for onboard fuel processors for fuel cell
vehicles through the Office of Transportation Technologies Fuel Cell Program.
Several companies are involved in developing multi-fuel fuel processors for 50
kW fuel cell vehicle power plants. These include:

 As part of the Arthur D. Little/Epyx/Nuvera partnership, a gasoline fuel


processor built by Epyx was demonstrated with a PEM fuel cell. Plug
Power, Latham, New Yorkis building an integrated 50 kW
gasoline/PEMFC system, based on the Epyx reformer.
 McDermott Technology Inc., Alliance, Ohio, USA and Catalytica Energy
Systems Inc., Arizona are developing a multi-fuel fuel processor for a 50
kW fuel cell.
 Hydrogen Burner Technologies, Inc. is developing a multi-fuel processor
for a 50 kW fuel cell.

In addition, a number of automotive companies are in joint ventures to


develop gasoline fuel processors based on POX technology. These include:

General Motors. USA has joined with Exxon Mobil, USA to develop an
onboard gasoline fuel processor.

International Fuel Cells, South Windsor, USA has partnered with Shell
Hydrogen, Torrance, USA to develop and market a variety of fuel
processors.

43
Projects to use partial oxidation systems in stationary fuel cells include:

Tokyo Gas Company, Japan, has demonstrated a partial oxidation


system for 1 kW fuel cell cogeneration system.

McDermott Technology, Inc. (MTI), USA and Catalytica Energy Systems


Inc.,Tempe, Arizona, United States are working together to develop
compact fuel processors for use with PEMFCs and solid oxide fuel cells
(SOFCs). This system is designed to reform gasoline and Naval Distillate
for PEMFCs.

C. Autothermal Reforming

1. Process Description

Autothermal reformers (ATRs) combine some of the best features of


steam reforming and partial oxidation systems. Several companies are
developing small autothermal reformers for converting liquid hydrocarbon fuels
to hydrogen for use in fuel cell systems. In autothermal reforming, a
hydrocarbon feed (methane or a liquid fuel) is reacted with both steam and air
to produce a hydrogen-rich gas. Both the steam reforming and partial oxidation
reactions take place. For example, with methane

CH4 + H2O ↔ CO + 3 H2 h = +206.16 kJ/mol CH4


CH4 + ½ O2→ CO + 2 H2 h° = -36 MJ/kmol CH4

With the right mixture of input fuel, air and steam, the partial oxidation
reaction supplies all the heat needed to drive the catalytic steam reforming
reaction. Unlike the steam-methane reformer, the autothermal reformer
requires no external heat source and no indirect heat exchangers. This makes
autothermal reformers simpler and more compact than steam reformers, and it
is likely that autothermal reformers will have a lower capital cost. In an
autothermal reformer all the heat generated by the partial oxidation reaction is
fully utilized to drive the steam reforming reaction. Thus, autothermal reformers

44
typically offer higher system efficiency than partial oxidation systems, where
excess heat is not easily recovered. As with a steam reformer or partial
oxidation system, water gas shift reactors and a hydrogen purification stage are
needed.

2. Status of Autothermal Reformers

Autothermal reformers are being developed by a number of groups,


mostly for fuel processors of gasoline, diesel and logistics fuels and for natural
gas fueled PEMFC cogeneration systems. These include:

Argonne National Laboratory is testing ATR systems and catalysts


International Fuel Cells(IFC), South Windsor, USA designed an ATR
that runs on logistics fuels. BWX Technologies, Inc., Lynchburg,
Virginia, and McDermott Technology, Inc. Using the IFC ATR, a
system was designed to reform Naval distillate for shipboard fuel
cells
Fraunhofer Institute for Solar Energy Systems, Freiburg, Germany is
designing ATRs for LPG and diesel fuel.
Degussa Metals Catalyst, Cardec Ag, Hanau, Germany is developing
catalysts for ATRs used with gasoline
Johnson-Matthey, Hamilton Bermuda developed a .Hot-Spot.
autothermal reformer, capable of reforming methanol and methane
Honeywell and Energy Partners, USA are developing a 50 kW
PEMFC system for buildings cogeneration. Both SMR and ATR are
being tried.
Daimler-Chrysler, USA is developing an ATR for gasoline reforming
McDermott Technology, Inc. (MTI), USA and Catalytica Energy
Systems Inc.,Tempe, Arizona, United States are developing a small
autothermal reformer for use with diesel and logistics fuels on ships,
based on an IFC design. A regenerable desulfurization stage is
important for Navy diesel fuel with 1% sulfur. Partners in this activity
are McDermott Technology, Inc. and Catalytica Advanced
Technologies, California, USA Ballard, Burnaby, Canada, BWX
45
Technologies, Lynchburg, Virginia, USA and Gibbs & Cox,
Arlington, Virginia, USA; The Idaho National Energy. USA and
Environment Laboratory (INEEL), USA with MTI and Pacific Gas
and Electric, USA have recently begun work on developing a 10 kW
ATR system for hydrogen refueling station applications. Analytic
Power, Canada has assessed multi-fuel reformer technology,
including ATR. IdaTech,Bend, Oregon, United States has
developed a multi-fuel reformer, which produces very pure
hydrogen from methane. It is likely that the reformer is either a PO X
or ATR type.
Recently, Hydrogen Burner Technologies, Inc., Long Beach,
California, US began development of an autothermal reforming system
for use with fuel cells and for hydrogen production.

D. Methanol Steam Reforming

1. Process Description

Methanol is a liquid fuel that can be more easily stored and transported
than hydrogen. Because it can be readily steam reformed at moderate
temperatures (250-350oC), methanol has been proposed as a fuel for fuel cell
vehicles. Experimental fuel cell vehicles with onboard methanol reformers have
been demonstrated by Daimler-Chrysler, USA and Toyota and Nissan, Japan.
Here a review of technologies for methanol steam reforming are presented.
Although these technologies are being developed for fuel processors onboard
fuel cell vehicles, it has also been suggested that hydrogen might be produced
by steam reforming of methanol at refueling stations (Ledjeff-Hey et al. 1998).

The reactions for production of hydrogen via methanol steam reforming


are as follows:

CH3OH ↔ CO + 2 H2, ∆H = 90.1 kJ/mol; Methanol reforming


CO + H2O ↔ CO2 + H2 ∆H=-41.2 kJ/mol; Water gas shift reaction

46
or combining these:

CH3OH + H2O ↔ CO2 + 3H2

The reaction takes place in the presence of copper/zinc catalysts in the


temperature range 200- 350°C. Overall the reaction is endothermic, requiring
the application of heat, through an indirect heat exchanger, to a catalyst filled
tube or catalyst plate. Good thermodynamic conversion has been reported for
steam-to-carbon ratios of 1.5 and temperatures of 250-350°C. Various types of
methanol steam reformers have been designed. Earlier designs use catalyst
filled tubes that are indirectly heated via combustion of some of the incoming
methanol fuel. More recently, there has been an effort to develop plate type
reformers for methanol reforming. These have a number of potential
advantages including compactness, better heat transfer, faster start-up and
potentially lower cost. Membrane reactors have also been built for steam
reforming methanol.

For refueling station applications, a hydrogen purification stage, either


pressure swing adsorption unit or a membrane separation type, unit may be
required. The cost of the hydrogen production system might be lower for a
methanol steam reformer because it would operate at much lower temperatures
than a steam methane reformer. The cost of hydrogen produced from methanol
would be higher than hydrogen from small-scale steam methane reforming,
because methanol is a more expensive feedstock than natural gas.

2. Status of Methanol Steam Reformers

Researchers at Los Alamos National Laboratory, USA have conducted


research on methanol steam reforming for PEM fuel cells. Researchers
at Argonne National Laboratory, USA have also simulated and built
methanol steam reformers.
Several automakers demonstrating fuel cell vehicles have developed
onboard steam reformers for methanol. These include Excellis Fuel Cell
Engines (DaimlerChrysler) of USA, and Toyota and Nissan of Japan.
47
The European Commission funded two projects to develop onboard fuel
processors for fuel cell vehicles as part of the JOULE II project. The
MERCATOX project had the goal of producing a prototype integrated
methanol reformer and selective oxidation system.

Wellman CJB Ltd., a British company that has produced units for steam
reforming alcohols, hydrocarbons, ethers and military fuels, coordinated the
MERCATOX project. The reformer consists of a series of catalytic plates, with
combustion of anode off-gas on one side and reforming on the other side.
Loughborough University designed the gas clean-up system. Wellmann built
and tested a plate type steam methanol reformer and integrated the system,
Rover Cars Company addressed manufacturing and vehicle design issues, and
Instituto Superior Technico undertook modeling work

 Northwest Power Systems (now called IdaTech), Thief River Falls,


Minnesota, United States has developed a multi-fuel processor. They
have demonstrated pure hydrogen production via steam reforming of
methanol, using a palladium membrane for the final purification step
 Researchers at InnovaTek, Inc., Richland, Washington, USA have
demonstrated microreactor technology to create a portable hydrogen
source for fuel cells by reforming methanol
 Researchers at Mitsubishi Electric Corporation, Japan are developing a
compact, plate-type steam methanol reformer
 Researchers at the Royal Military College, Ontario, Canada, are
studying the effects of catalyst properties on methanol reforming
 Researchers at Honeywell, USA are developing a compact plate-type
steam methanol reformer for automotive applications
 Researchers at NTT Telecommunications Laboratory, and Tokyo
University are developing a compact plate-type steam methanol
reformer for automotive applications
 Researchers at Gerhard-Mercator-Universitat, FRG, are developing
compact membrane reactors for methanol steam reforming

48
E. Ammonia Cracking

Ammonia is widely distributed to consumers today, is low cost and is


relatively easy to transport and store, compared to hydrogen. This makes it a
potential candidate for use as a hydrogen carrier for fuel cell applications.

Ammonia, NH3, can be dissociated (or cracked) into nitrogen and


hydrogen via the reaction:

2 NH3 -> N2 + 3 H2

The reaction is endothermic, and ammonia cracking takes place in indirectly


heated catalyst filled tubes. The dissociation rate depends on the temperature,
pressure and catalyst type. The reaction rate is much increased by operation

at temperatures of 700oC or above, although dissociation can occur at

temperatures as low as 350oC. The main impurities are traces of un-reacted


ammonia and nitrogen oxides. The concentration of un-reacted ammonia must
be reduced to the ppm level for use in PEM fuel cells, although alkaline fuel
cells not as sensitive to this. For PEMFC applications where low levels of
ammonia impurity are required, a recent study recommends reaction
temperatures of 900oC .The overall efficiency of fuel processor systems based
on ammonia cracking has been reported to be up to 85%. Maximum values of
about 60% were reported in another recent study, by Analytic Power, for small
ammonia crackers for PEM fuel cell applications, where up to 40% of the
product hydrogen was combusted to supply heat to drive the dissociation
reaction and to compensate for heat losses.

A potential advantage of ammonia cracking for hydrogen generation in


a fuel cell system is simplicity. Unlike a steam reformer system, water is not
required as a co-feed with the fuel, and no water gas shift reactors are needed.
When an ammonia cracker is closely coupled to a fuel cell no final hydrogen
purification stage is needed. Because nitrogen is inert and has no effect in the
fuel cell, it is simply passes through as a diluent. For pure hydrogen production

49
based on ammonia cracking, however, a costly separation of H2 and N2 would
be required, for example by using a PSA unit or a hydrogen selective
membrane. The cost of pure hydrogen production through ammonia cracking
has not yet been estimated.

F. Thermo-catalytic Cracking of Methane

In this approach, methane is broken down into carbon and hydrogen in


the presence of a catalyst at high temperature (850-1200oC), according to the
reaction

CH4 → C + 2 H2 ∆h° = 17.8 kcal/mole CH4

This reaction is endothermic, requiring energy input of about 10% of the natural
gas feedstock. Researchers at the Florida Solar Energy Center, USA have
studied thermocatalytic methane cracking. This technology is still far from
commercial application for hydrogen production. The primary issues are low
efficiency of conversion and coking (carbon fouling of the catalyst). Catalytic
cracking of other hydrocarbons has been investigated by researchers at
Gerhard- Mercator-Universitat at Duisburg, Germany. Frequent regeneration of
the catalyst is required to remove accumulated carbon, but relatively low capital
costs are projected because of the system’s simplicity.

G. Novel Reformer Technologies

1. Sorbent Enhanced Reforming

Recently several authors have investigated the possibility of sorbent


enhanced steam methane reforming. Here, an absorbent (such as calcium
oxide) is mixed with the steam reforming catalyst, removing the CO and CO 2
as the steam reforming reaction progresses. The resulting syngas has a
substantially higher fraction of hydrogen than that produced in a catalytic
steam-reforming reactor. A syngas composition was recently reported of 90%
H2, 10%CH4, 0.5% CO2 and <50 ppm CO. This reduces the need for
50
downstream processing and purification, which can be expensive in a small-
scale steam reformer. Moreover, when CO2 is removed by the sorbent, the
reaction can take place at lower temperature (400-500oC vs. 800-1000oC) and
pressure, reducing heat losses and material costs. Sorbent-enhanced systems
are still at the demonstration stage, and show promise because of their low
cost. Issues requiring further research include catalyst and sorbent lifetime and
system design.

2. Ion Transport Membrane (ITM) Reforming

Air Products, in collaboration with the USDOE and other members of the
ITM syngas team (Cerametec, Chevron, Eltron Research, McDermott
Technology, Norsk Hydro, Pacific Northwest Laboratory, Pennsylvania State
University, University of Alaska, and University of Pennsylvania, all from USA),
are developing ceramic membrane technology for generation of H2 and syngas.
The membranes are non-porous, multi-component metallic oxides that operate
at high temperature (>700oC) and have high oxygen flux and selectivity. These
are known as ion transport membranes (ITM). Conceptual designs were carried
out for a hydrogen-refueling station dispensing 0.5 million scf/day of 5000 psi
hydrogen, following work by Directed Technologies, Inc. Initial estimates show
the potential for a significant reduction in the cost of high pressure H2 produced
via this route at the 0.1 to 1.0 million scf/day size. For example, compared to
trucked-in liquid hydrogen, the ITM route offers a 27% cost savings. Oxygen
can be separated from air fed to one side of the membrane at ambient pressure
or moderate pressure (1-5 psig) and reacted on the other surface with methane
and steam at higher pressure (100-500 psig) to form a mixture of H2 and CO.
This can then be processed to make hydrogen or liquid fuels. Various
configurations for the ITM reactor were examined, and a flat-plate system was
chosen because it reduced the number of ceramic-metal seals needed. An
independent effort to develop oxygen transport membranes is ongoing at
Praxair in conjunction with the Oxygen Transport Membrane Syngas Alliance.

3. Plasma Reformers

51
Thermal plasma technology can be used in the production of hydrogen
and hydrogen-rich gases from methane and a variety of liquid fuels. Thermal
plasma is characterized by temperatures of the order of 3000-10,000oC, and
can be used to accelerate the kinetics reforming reactions even without a
catalyst. The plasma is created by an electric arc. Reactant mixtures (for
example, methane plus steam or diesel fuel plus air and water) are introduced
into the reactor and H2 plus other hydrocarbon products are formed.
Researchers at MIT, USA (Bromberg et al. 1999) have developed plasma-
reforming systems. The plasma is created by an electric arc in a plasmatron.
One set of experiments involved partial oxidation of diesel fuel. Steam
reforming of methane was also investigated. The best steam reforming results
to date have shown 95% conversion of methane and specific energy use (for
electricity for the plasmatron) of 14 MJ/kg H2 (an amount equal to about 10% of
the higher heating value of hydrogen). It is projected that the power required for
the plasmatron can be reduced by about half. With the National Renewable
Energy Laboratory (NREL) and BOC Gases, MIT researchers are evaluating
the potential of this technology for small-scale hydrogen production.
Researchers at Idaho National Energy and Environment Laboratory (INEEL),
USA and DCH are also working on plasma reforming (DOE Hydrogen R&D
Program Annual Operating Plan, March 2000).

4. Micro-channel Reformer

Researchers at Pacific Northwest National Laboratory, USA have


developed a novel gasoline steam reformer with micro-channels. The aim of
this work is to reduce the size of automotive reformers.

Over the past ten years, the rapidly growing interest in fuel cell and
hydrogen technologies has led to a variety of efforts to develop low cost small-
scale fuel processors and hydrogen production systems. The trend has been
to develop more compact, simpler and, therefore, lower cost reformers. From
the conventional long tube refinery-type steam methane reformer, fuel cell
developers moved toward more compact .heat exchange.-type steam
reformers (which are now commercialized as fuel cell components and for
52
stand-alone hydrogen production). Plate type reformers are now undergoing
development and testing for fuel cell applications and may be the next step in
compactness and simpler design. In plate reformers, each plate has a double
function (on one side, the reforming reaction take place, on the other, catalytic
heating drives the reaction.) Partial oxidation systems and auto thermal
reformers offer simpler first stages than steam reformers, but involve more
complex purification systems. Advanced purification systems are being devised
for these reformers. Sorbent enhanced reforming is another approach that
combines several steps in one reactor, with the potential of capital cost
reductions. An area of intense interest in the fuel cell and hydrogen R&D
communities is development of membrane reactors for reforming. Membrane
reactors offer further simplification, because the reforming, water gas shift and
purification step take place in a single reactor. Very pure hydrogen is removed
via hydrogen-selective permeable membranes. Membrane reactor systems are
being tested at small scale.

In parallel with fuel cell developments, there has been a growing interest
in innovative technologies for syngas production among large chemical and
energy producing companies. For example, ion transport and oxygen transport
membranes are under development for syngas applications. These are now
being applied to hydrogen production as well. Application of membrane
technology to syngas and hydrogen systems is an active area of research in
both the fuel cell R&D community and among large-scale producers of syngas
such as oil companies. In addition, oil companies such as BP Amoco, U. K.,
Shell, Houston, USA and Exxon/Mobil, Houston, Texasare involved in joint
ventures to develop fuel processors and hydrogen infrastructure
demonstrations, such as hydrogen refueling stations based on methane
reformers. The oil companies are positioning themselves to become suppliers
of hydrogen transportation fuel in the future.

3.1.3 National Status and Commercialization Efforts by industry

The focus of RD&D in India has been on production of hydrogen from


renewable sources of energy.
53
(a) Status of Hydrogen Production Technologies in India

The Indian Institute of Chemical Technology (IICT), Hyderabad designed


and developed a methanol reformer to produce around 10,000 litres/hour
hydrogen for coupling with 10 kW fuel cell. It was operated for 1000 hours and
data was collected. Based on this data a scaled up methanol reformer to
produce around 50,000 litres/hour hydrogen was designed and developed to
demonstrate the technology by coupling with 50 kW fuel cell system. The
reformed gas contained around 75% hydrogen with pre-mixed methanol and
water. The product gas was further processed to lower down CO2 and CO
content to the extent less than 10 ppm, which is suitable for the application in
PEM fuel cell system for power generation.

Indian Institute of Chemical Technology, Hyderabad developed three


catalysts viz, Ni/SiO2 (NS), Ni/ Alumina Sol [Ni/Al2O3] Ni/ Alumina Plural (NAP)
[Ni/Al2O3] for reformation of glycrol at 500-650ºC on bench scale for hydrogen
production to generate data of reaction kinetics to scale-up reformer. Based on
this data a skid mounted reactor was fabricated and installed at the institute.
The life of these catalyst lasted for several hours.

The Centre for Energy Research, SPIC Science Foundation, Chennai


(stopped R&D activities on hydrogen energy and fuel cells) designed,
developed and demonstrated a PEM methanol electrolyser for the production
of hydrogen at the rate of 1 Nm3/hour at an operating temp of 50-60oC. The
energy consumption was around 2.02 kWh/Nm3hydrogen produced. The
hydrogen gas obtained from this electrolyser contains considerable amount of
methanol, which can be removed bypassing it through water scrubber and
chiller. This hydrogen is almost free from CO2 and CO.

Central Institute of Mining and Fuel Research, Dhanbad developed


anovel process for the production of hydrogen from renewable and fossil fuel
based liquid and gaseous hydrocarbons by non-thermal plasma reformation
technique. A non-thermal plasma reactor of 0.5 litre capacity was developed for
54
reformation of hydrocarbons to produce about 12 litres/minute hydrogen
enriched gas mixture. Conversion of methane to hydrogen has been studied in
a quartz reactor by non-thermal plasma. Experiments have been conducted for
non-thermal plasma reformation of soybean oil, methanol and ethanol with both
conventional cylindrical fuel reformer as well as vortex type reformer.
Appreciable hydrogen production was also achieved with naphtha. Bio-diesel
will also be tried for hydrogen production through this process.

The Indian Institute of Technology Hyderabad is working for the


transformation of greenhouse gases like methane and CO2into for syngas/H2by
low temperature plasma catalysis. This will be achieved by optimizing
conditions like reactor design, diluting gas, discharge gap, residence time of the
gas, screening of various catalysts, etc. for a hybrid non-thermal plasma
reactor. Heterogeneous catalysts will be searched / synthesized to arrive at a
robust and cost-effective catalytic non-thermal plasma reactor for syngas
production.

b) Gap Analysis & Way Forward

There are already extensive industry and government programs


addressing particular technical issues for small-scale reformers, and for syngas
production. We have not attempted to list research priorities for each type of
reformer, or select a particular technical area for basic research. Instead, we
suggest that the International Energy Agency develop collaborative projects
aimed at enhancing interactions between researchers engaged in small-scale
hydrogen production (fuel cell and hydrogen researchers) and those engaged
in large energy production (oil and chemical companies). The purpose of the
proposed projects would be to examine the potential impact of recent technical
progress for small- and large-scale hydrogen energy production.

One project could be to identify areas where ongoing research on large-


scale syngas technologies could improve small-scale hydrogen
production systems for vehicles, and vice versa. To identify such areas,
the MNRE could convene a group of industry and academic researchers
55
from fuel cell, hydrogen and energy producing communities to discuss
issues for small-scale reformers for hydrogen production. This group
might have particular interest in technologies that could have
applications in small- and large-scale hydrogen production and could
ultimately facilitate capture ofCO2 during hydrogen fuel production.
Membrane technology would appear to be a good candidate for such an
information exchange meeting, but other areas might be identified. If
gaps in technical knowledge were identified, this could help focus future
reformer development efforts.

3.2 Hydrogen Production through Biomass Gasification

3.2.1 Biomass is a renewable source of energy and can be considered as a


large and easy source for hydrogen production. However, out of all different
routes of hydrogen production from biomass, gasification is likely to be the most
economical and sustainable process. The basic steps for getting pure hydrogen
out of biomass through gasification are similar to those for coal, methane and
naphtha reforming based processes.

3.2.2 International Status

Research & development work in the area of production of hydrogen


using biomass is being carried out at the international level by various
organizations. However, till date no technology is available for commercial use
to generate hydrogen from biomass. The reported hydrogen production is
mainly through fluidized bed gasification or conversion of pyrolytic oil. The work
done at various institutions/organizations is summarized below:

The University of British Colombia, Canada, is working on fluidized


bed gasification and sorbent based hydrogen separation unit. The National
Renewable Energy Laboratory(NREL), U.S.A. has demonstrated production
of hydrogen from pyrolysis oil by steam reforming. This pyrolysis oil was
obtained from peanut shells in a fluidized bed by pyrolysis process. Gas

56
Technology Institute (GTI), Chicago, has been working on demonstration
project for direct generation of hydrogen in a down draft gasifier using a
membrane reactor. The Energy Research Centre of the Netherlands
(ECN)has developed gasification technology, which has progressed to a pilot
plant scale (800 kW th). Currently ECN, with other partners is planning to
construct a 12 MW th synthetic natural gas (SNG) plant in Alkmaar, the
Netherlands. The gasifier has been designed with a tar scrubbing unit.
Methanation of the product gases is done after removing sulphur, chloride and
CO2. The Technical University of Vienna has developed a fast internally
circulating fluidized-bed technology for steam-blown gasification of biomass in
cooperation with Austrian Energy and Environment. This technology is being
employed in the Gothenburg Biomass Gasification (GoBiGas), project, which
aims at constructing a SNG plant in Gothenburg, Sweden. At Gussing,
Austria, an 8 MW combined heat and power plant is in operation since 2002.
Later on, SNG production was demonstrated in a methanation unit, which took
a 1 MW SNG slipstream from the Güssing plant. There has been no reported
work on fixed bed gasification. The targeted cost of production of hydrogen
was around USD 2.6/kg.

3.2.3 Biomass Pyrolysis

Pyrolysis is the heating of biomass at a temperature of 600-10000C at


0.1–0.5 MPa in the absence of air to convert biomass into gaseous compounds,
liquid oils, and solid charcoal. Pyrolysis can be further classified into slow and
fast pyrolysis. As slow pyrolysis gives high char yield, it is generally not
considered for hydrogen production. Fast pyrolysis is a process where biomass
feedstock is heated rapidly (at 150-2500C/s) in the absence of air, to form vapor
and subsequently condense it to a dark brown bio-liquid. The following products
are obtained from the fast pyrolysis process:

(i) Gaseous products include H2, CH4, CO, CO2 and other higher
hydrocarbons (HHC) depending on the organic nature of the biomass.
(ii) Liquid products include tar and oils that remain in liquid form at room
temperature like acetone, acetic acid, etc.
57
(iii) Solid products are mainly composed of char and almost pure carbon
plus other inert materials.

Although most pyrolysis processes are designed for biofuels production,


hydrogen can be produced directly through fast or flash pyrolysis if high
temperature and sufficient volatile phase residence time are allowed as follows:

Biomass +heat →H2+ CO +CH4 + HHC + C (char) - - (i)

CO, methane and other hydrocarbon are reformed catalytically in subsequent


stages to get more hydrogen. Besides the gaseous products, the oily products
can also be processed for hydrogen production. The pyrolysis oil can be
separated into two fractions based on water solubility. The water-soluble
fraction is used for hydrogen production while the water-insoluble fraction for
adhesive formulation.

Studies have shown that when Ni-based catalyst is used, the maximum
yield of hydrogen can reach 90%. Bio-oil needs to be steam reformed at 750-
850 0C in presence of nickel based catalyst followed by shift reaction. With
additional steam reforming and water–gas shift reaction, the hydrogen yield can
be increased significantly. Temperature, heating rate, residence time and type
of catalyst used are important pyrolysis process control parameters. In favor of
gaseous products especially in hydrogen production, high temperature, high
heating rate and long volatile phase residence time are required.

3.2.4 Biomass Gasification

Biomass gasification is sub-stoichiometric combustion process, in which


pyrolysis, oxidation and reduction take place. Pyrolysis products (volatile
matter)further reacts with char and are reduced to H2, CO, CO2, CH4 and HHC.

Biomass + heat + O2 → H2 +CO + CO2 + CH4 + HHC + char - (ii)

58
Unlike pyrolysis, gasification of solid biomass is carried out in the
presence of oxidiser. Besides, gasification aims to produce gaseous products,
while pyrolysis aims to produce bio-oils and charcoal. One of the major issues
in biomass gasification is to deal with the tar formation that occurs during the
process. The unwanted tar may cause the formation of tar aerosols through
polymerization to a more complex structure, which are not favorable for
hydrogen production through steam reforming. This tar formation may be
minimized by i) designing gasifier properly, ii) with controlled operation (in terms
of temperature and residence time) of gasifier and iii) with additives/catalysts.

Tar may be thermally cracked at temperature above 10000C. The two-


stage gasification and secondary air injection in the gasifier may also reduce
tar formation. The IISc, Bengaluru has developed an open-top downdraft
gasifier, where residence time of gases increases inside the reactor and high
temperature of the char bed is maintained, which improves conversion
efficiency and reduces formation of higher molecular weight compounds.
Figure 3.1 provides an input on the use of dolomite as a bed material for fluid
bed gasification system to reduce the tar levels. It can be seen that the tar level
varies from 10 to50g/m3depending upon the bed material used in typical fluid
bed gasification.

The use of some additives (dolomite, olivine and char) inside the gasifier
also helps in tar reduction. When dolomite is used, 100% elimination of tar can
be achieved. Catalysts not only reduce the tar content, but also improve the
gas product quality and conversion efficiency. Dolomite, Ni-based catalysts and
alkaline metal oxides are widely used as gasification catalysts.

H2 content in biomass is only around 6.5% (by wt.). But using steam as
the gasifying agent and air/O2 as the oxidiser enhances the H2 output
considerably. One of the major advantages of the gasification is that the
process is carbon neutral and it has flexibility in using various types of biomass
including agricultural and municipal solid waste.

59
Figure 3.1 Average benzene and tar concentration in per kg of dry gas

3.2.5 Thermo-chemical Conversion of Biomass: As a process for


hydrogen generation this route had never been a prime area of research, but
major emphasis was towards standardizing the gasification system for power
generation using reciprocating engines and for thermal applications. Biomass
gasification has been identified as a possible process for producing renewable
hydrogen. Most of the research has been stimulated by the techno-economics,
based on gasifier performance data acquired during proof of concept testing.

Some studies were done on pyrolysis and gasification of rubber, poplar


wood, yellow pinewood and residual branches of oil palm tree as fuel in a
thermally controlled environment and steam was passed at the desired flow
rate over a fixed mass of biomass for gasification. The gasifier was operated
in the temperature ranges of 600-10000Cand 800 - 9000C. Maximum yield of
hydrogen was obtained in the temperature range of 600-10000C. The hydrogen
yield was about 20 g per kg of biomass through pyrolysis and 97 g per kg of
biomass through steam gasification, with over 55% volume fraction of hydrogen
in the syngas. The influence of temperature on various performance
parameters was evaluated and analyzed. There were no significant changes in
syngas and hydrogen yield at various gasification temperatures but the
60
pyrolysis temperature had a considerable effect on the overall yield. The syngas
yield increased from 353 g per kg of biomass to 828 g per kg of biomass by
varying the pyrolysis temperature from 600 to 1000 0C with a reduction of over
50% in solid residue at the end of the process. The reaction rates enhanced
significantly with increase in temperature, 35 g of substrate took 200 min for
complete gasification at 6000C compared to 29 min at 10000C for constant flow
of steam at 3.1 g/s. The extremely slow rate of the char-steam reaction is cited
as the reason for the slow rate of gasification at low temperatures. High
temperature and long residence time were identified as important parameters
that favor higher H2 yields. Over 30% higher energy yield was reported from
gasification compared to pyrolysis due to significant contribution of the char-
steam reaction.

In recent years, many researchers have explored the gasification of


biomass for hydrogen production using different reactor configurations. In a
fluidized bed reactor steam was introduced with oxygen and nitrogen under
temperature controlled conditions. The reactor was externally heated to control
the reactor temperature and the reactant flow rates were varied to determine
the effect of the equivalence ratio and the steam to biomass ratio on the gas
quality. H2 yield showed pronounced improvement with increasing reactor
temperature. Increasing the temperature from 800 to 950 0C (at SBR = 1.8 and
ER = 0.18) doubled the yield of H2 from 28 to 61 g per kg of biomass. The effect
of increased steam to biomass ratio (SBR) and equivalence ratio (ER) on the
hydrogen yield suggests that increasing the SBR (at an ER = 0) from 1.1 to 4.7
increased the hydrogen yield from 46 to 83 g per kg of biomass, whereas
reducing the ER from 0.37 to 0 (at SBR = 1.7) enhanced the H 2 yield from 23
to 60 g per kg of biomass. The maximum H2 volume fraction in syngas is
reported as 57% at SBR of 4.7 and ER of 0, while maintaining the bed
temperature at 8000C The reported tar levels are in the range of 6 g per kg of
dry fuel, amounting to about 2500 ppm of tar and can have serious implications
on the downstream elements for hydrogen separation.

Oxygen-steam gasification has been reported using pinewood


(CH1.6O0.6) with 8% moisture as fuel in a fixed bed downdraft gasifier. The 1.3
61
m high and 35 cm diameter downdraft gasifier was preheated up to 900 0C by
igniting the feedstock and circulating the heat by a fan. Later, biomass was
placed over a bed of charcoal and oxygen was injected from multiple points.
Saturated steam at near ambient pressure was used. The oxy-steam
gasification was performed with ER varying between 0.22 and 0.26 and SBR
varying between 0.4 and 0.8 (molar basis). The maximum hydrogen yield
reported is 49 g per kg of dry biomass at ER of 0.25 and SBR of 0.8.A high tar
yield in the range of 3 to 20 g per kg of biomass was reported.

The effect of heating rate, temperature and SBR on H 2 yield, tar


reduction and char residue was also studied in a co-current flow using a 1.8 m
long downdraft reactor of 20 mm diameter with legume straw and pine sawdust
as feed-stock. Steam was injected at 3000C,keeping the reactor at the desired
temperature using electrical heating coils. SBR (on mass basis) was varied
from 0 to 1 while working in a temperature range of 700 - 8500C. Steam and
biomass flow rates were simultaneously controlled for different SBR values
keeping residence time constant. At 8000C, using legume straw as the
substrate, H2 yield peaked at SBR (mass basis) 0.6 to 40.3% (volume fraction),
reporting significant reduction in tar from 66.6 g/Nm3 at SBR of 0 to 23.1 g/Nm3
at SBR of 0.6. Reduction in char residue is reported with increase in SBR
keeping temperature constant at 8000C, resulting in 5.5 % char residue at SBR
of 0 and 2.8 % at SBR of 0.6. Increase in syngas and H2 yield with reduction in
tar and char residue is reported with increase in temperature. Keeping the SBR
(mass basis) constant at 0.6, temperature was varied and significant reduction
in tar and char residue is reported. Tar content in syngas got reduced from 62.8
g/Nm3 at 7500C to 3.7 g/Nm3 at 8500C while char residue reduced from 7% to
less than 2% in the same temperature range. Dalian University of Technology,
China inferred that addition of steam favored tar and char reduction and
subsequent increase in syngas and H2 yield due to tar steam reforming,
cracking and char gasification enhanced by higher reaction rates at higher
temperature.

Results from the previous work suggest the choice of gasification over
pyrolysis for higher hydrogen yield and efficiency. The literature has indeed
62
provided details on the various thermo-chemical conversion processes,
behavior of different reactor configurations and influence of various process
parameters like SBR, ER and temperature on hydrogen yield and overall
performance. It must be emphasized that the thermochemical conversion of
biomass to syngas, rich in hydrogen is one of the efficient processes. Steam
gasification of biomass has been studied in a batch reactor under the controlled
conditions but less exploited in a fixed bed reactor for continuous hydrogen
production. Further, the results from the literature indicate low hydrogen yield
and issues arising from the gas contaminated with higher molecular weight
compounds, i.e., the “tar”, inducing difficulty in separating hydrogen from the
syngas mixture.

Depending upon the type of fuels used, there are different kinds of
gasifier, differing in design. All these processes can be operated at ambient or
increased pressure and serve the purpose of thermo-chemical conversion of
solid biomass. Five major types ofgasifiers are- fixed-bed updraft, fixed-bed
downdraft, fixed-bed cross-draft, bubbling fluidized bed, and circulating
fluidized bed gasifiers. This classification is based on the means of supporting
the biomass in the reactor vessel, the direction of flow of both the biomass and
oxidant, and the way heat is supplied to the reactor. Fixed bed gasifiers are
typically simpler, less expensive, and produce a lower heat content producer
gas. Fluidized bed gasifiers are complicated, expensive, and produce a gas
with a higher heating value. Table 3.1 compares the advantages and limitations
of different type of gasifier designs.

Table 3.1: Relative advantages and disadvantages of different types of


gasifier

Gasifier Advantages Disadvantages


Updraft  Mature for small-scale heat  Feed size limits
fixed bed applications  High tar yields
 Can handle high moisture  Scale limitations
 No carbon in ash

63
 Low heating value
gas
 Slag formation
Downdraft  Small-scale applications  Feed size limits
fixed bed  Low particulates and low tar  Scale limitations
 Low heating value
gas
 Moisture-sensitive
Bubbling  Large-scale applications  Medium tar yield
fluid bed  Feed characteristics  Higher particle
 Direct/indirect heating loading
 Higher heating value gas
Circulating  Large-scale applications  Medium tar yield
fluid bed  Feed characteristics  Higher particle
 Higher heating value gas loading
Entrained  Can be scaled up  Large amount of
flow fluid  Low tar formation carrier gas
 Low methane content gas  Higher particle
 Higher heating value gas loading particle
size limits

The fixed bed gasifiers are broadly classified as updraft, downdraft and
cross draft depending on the direction of air flow. Downdraft type of gasifier, in
which the fuel and air move downwards, is widely used because it generates
combustible gas with low tar content. The reactor design used until recently
was the closed top, with the upper portion of the reactor acting as a storage bin
for the fuel. The air is allowed to enter at the lower part, which generally contains
charcoal. The developmental work at the Indian Institute of Science, Bangalore
(IISc) on wood gasifier has resulted in a design with an open top with air
entering both at the top and at the bottom through air nozzles. This feature has
resulted in a design which can handle wood chips of higher moisture content
up to 25%, and produce gas with low tar levels (< 30 ppm). The low tar level is
due to the stratification of the of the fuel bed helping in maintaining a large bed

64
volume at high temperature. In steady operation, the heat from the combustion
zone near the air nozzles is transferred by radiation, conduction and convection
upwards causing wood chips to pyrolyse and loose 70-80% of its weight. These
pyrolysed gases burn with air to form CO2 and H2O raising the temperature to
1000-11000C.The product gas from the combustion zone further undergoes the
reduction reactions with char, to generate combustible products like CO, H2 and
CH4.

3.2.6 Exergy and Energy Analysis

Apart from the demand and usefulness, energy efficiency is one of the
most important criteria to assess the performance and sustainability of any
technology. In the gasification process, the first law of thermodynamics permits
conservation of the total energy in the conversion of solid fuel to gaseous fuel
and the second law restricts the availability of energy (exergy) transformed to
useful form. In the case of gasification process, evolution of gaseous species
increases the entropy and introduces irreversibility in the overall thermo-
chemical conversion process. During the conversion of solid fuel to gaseous
fuel, apart from the process irreversibility, the transformation of chemical energy
in the solid fuel partly to thermal energy as sensible heat cannot be converted
to the desired output i.e., chemical enthalpy in the gaseous species. Evaluating
the energy efficiency based on the energy output to the energy input and
identifying the energy loss from the system to the environment is appropriate
while considering the device. This approach may not be sufficient while
evaluating the process and the device together as a system. Identifying the
internal losses arising due to the irreversibility is important towards
understanding any energy conversion process and probably helps in
redesigning the system elements. Exergy analysis thus helps in evaluating the
conversion process and provides an insight towards optimizing, by minimizing
the losses, if any.

The exergy efficiency of a fast pyrolysis bio-oil production plant was


analyzed using Aspen Plus software. Based on this analysis it was found that
the exergy efficiency is 71.2% and the components for the exergy losses were
65
also identified. The areas that had been identified for improvement were
biomass drier, milling process for size reduction and heat exchanger used for
pre-heating the combustion air.

In the area of biomass gasification, researchers have performed exergy


analysis based on equilibrium analysis using Engineering Equation Solver
(EES) software. With the focus on H2 production, from a gasifier reactor of 0.08
m diameter and 0.5 m height using sawdust as the fuel, exergy and energy
efficiencies were estimated. The heat loss from the reactor was modeled
assuming isothermal condition. Tar, generally an issue for gasification process
and its utilization, was considered as a useful product (fuel) and modeled as
benzene molecule in the system. Effects of varying the SBR (steam to biomass
ratio) from 0.2 to 0.6 were studied, by varying steam flow rate from 4.5 kg/s to
6.3 kg/s and biomass feed rate from 10 kg/s to 32 kg/s was considered. In the
analysis, temperature was varied between 700 and 1200 0C and its influence on
the H2 yield, exergy and energy efficiency was also studied. The maximum
exergy efficiency reported is about 65% with minimum near SBR of 0.4.It has
been shown that maximum specific entropy generation is between 0.37 and
0.42.The lower value of the exergy efficiency has been argued due to the
increase in internal irreversibility with the varying SBR. H2 yield was saturated
at around SBR of 0.7. It is evident that in the temperature range of 700-12000C,
char-steam reaction plays a significant role and H2 yield increases significantly
till carbon boundary point (at SBR of 1.5). Carbon boundary at SBR of 1.3 has
been reported in another study. The equilibrium values at higher SBR’s are not
used in the analysis performed using EES software.

Extensive analysis was carried out on the availability and irreversibility


of the biomass gasification process. The exergy efficiencies of air and steam
gasification with pyrolysis were compared. Equilibrium studies were employed
using non-stoichiometric method based on minimizing the Gibbs free energy.
Steam gasification proved to be a more efficient process compared to air
gasification and pyrolysis. Steam gasification efficiency was reported as 87.2%
compared to 80.5% for air gasification. In the case of pyrolysis, the efficiency
was 76.8%. The physical, chemical exergy and sensible enthalpy of gas and
66
their variation with SBR and ER were also analyzed. In the case of air
gasification, carbon boundary was identified at ER of 0.25 beyond which no
carbon is available for gasification. Beyond the carbon boundary point, the
efficiency decreased and losses were credited to oxidation of fuel gas to CO2
and H2O leading to higher sensible heat and lower chemical energy in the
product gas. Similarly, in the case of steam gasification, carbon boundary was
identified at SBR of 1.3 beyond which introducing extra steam led to loss in
input energy used in steam generation. The coupling of exothermic oxidation of
carbon with endothermic water-gas and Boudouard reaction was argued for the
better efficiency of gasification over pyrolysis. The researchers have not been
ableto clearly identify reasons towards higher efficiency achieved in the case of
steam gasification over air gasification.

Thermodynamic analysis was conducted for oxygen enriched air


gasification of pine wood. The oxygen fraction in gasifying media was increased
from ambient condition (21% O2) to 40% O2 on the mole basis; the balance
being N2. Increase in exergy and energy efficiencies with O 2 fraction was
observed. Exergy efficiency of 76% with 21% O2 increased to over 83% with
40% O2 while H2 and CO mole fractions in the product gas decreased from 22%
to 11% and 19% to 14% respectively. Increase in reaction zone temperature
with increase in O2 fraction was cited as the reason for higher efficiencies.
Specific reasons towards the reduction of H2 and CO with increase in O2percent
were not discussed. The higher efficiencies at higher O2fractions seems
inconsistent based on the analysis of exergy and energy efficiencies with the
variation in temperature.

It is evident from the literature on the exergy and energy analysis of


gasification systems that largely equilibrium analysis based results have been
used. The heterogeneous reaction system during gasification is very complex
and it cannot be approximated with the thermodynamic equilibrium model. The
gas composition, quality and hence the efficiency of a gasification system
depends significantly on the residence time of the reacting species at the given
temperature which inherently depends on the reactor geometry, design and

67
process parameters. The heterogeneous reactions that occur inside the reactor
are both diffusion and kinetic limited depending upon the reactants.

3.2.7 National Status (Including Commercialization Efforts by Industry)

The development of the technology (internationally), to harness this


route has taken place in spurts. The most intensive efforts were put during the
Second World War to meet the scarcity of petroleum sources for transport
needs of the civilian and military sectors. Some of the most studies on wood
gasifierswere basic as well as developmental related.

In India, during the initial developmental efforts, Department of Non-


conventional Energy Sources (now MNRE) took an important decision to field
test the technology developed by various research and industrial groups. This
was carried out during 1997 to 2000. The major emphasis was on the water
pumping application in the range of 5 to 50 HP. Around 1700 systems (35 MW
equivalent) were installed in field under the MNRE’s demonstration program on
biomass gasification.

There has been an activity for developing reliable industrial package for
both power generation and thermal application in the later period of the year
2000. In the power generation sector, the emphasis shifted from dual fuel to
pure gas engine mode; in order to compete with the grid costs as the fossil fuel
prices increased. Gas engines could not accept producer gas as a fuel as it
was not commercially available and some of the research groups carried out
the R & D to operate engines on producer gas. While various groups developed
skills to adapt natural gas engine to operate on producer gas, Indian Institute
of Science, working with Cummins India Limited (CIL) succeeded in developing
a package for producer gas engines. Currently, CIL would be the first Indian
engine manufacturer to produce engines using producer gas as fuel.

Apart from several other factors, MNRE’s role both in research,


development and implementation of the biomass gasification programme has
been very critical. There are only 4 – 5 groups involved both in the development
68
and implementation of the technology packages either directly or using
licensees. There have been differences in the technology packages developed
among these groups. M/s ASCENT, Sacramento, USA have developed
packages for woody biomass, fine biomass and a combination of the two. A
closed top gasification system has been used for conversion process. Rice
husk gasification system is designed separately to handle rice husk as
received. The Research Group at Tata Energy Research Institute has
developed technology packages for woody and briquetted biomass using
throat-less gasifier with closed top. The Sardar Patel Renewable Energy
Research Institute, Vallabh Vidhyanagar, Gujarat has been involved in the
development of technology packages for dual fuel and thermal application,
using both forced and natural drafts depending upon the requirements. Indian
Institute of Science, Bangalore has developed a multi-fuel gasification system
to accept woody biomass or biomass briquettes. The largest capacity power
plant connected to the grid using gas engines supplied by Cummins India
Limited has been built. Systems of varying capacity (up to 1 to 10 MW th) have
been developed. While there have been large numbers of gasifier systems
implemented by gasifier manufacturers, but very limited operational data is
available in the public domain for analysis and reporting, consolidating the
performance of the system/s and providing an account of operational
experience.

Use of air gasification system for power generation has been established
and options to biomass for various other outputs as indicated in the Figure 3.2
which suggests various biomass conversion process to end use energy
efficiency.

It is evident that the biomass gasification based power cycle has the
conversion efficiency in the range of 40 % while the hydrogen generation could
be in the range of 60 %.

69
Figure 3.2: Biomass to fuel efficiency for various outputs from biomass
conversion processes

As stated earlier, very limited work has been carried out in the area of
hydrogen generation from biomass. Most of the activities are at bench scale
except some of the research carried on the existing steam gasification platform,
where a small portion of the gas is being taken through the gas train for
generating pure hydrogen. The overall yield of hydrogen is about 42 g/kg of
biomass.

The National Institute of Technology, Calicut is engaged in the research


activities of hydrogen production by thermo-chemical method in fluidized bed
gasifier under catalytic support and its utilization. Under this activity a 7.5 kW
capacity bubbling ptimizat fluidised bed biomass gasifier was designed and
developed for performance evaluation. The effect of process parameters on air
gasification of rice husk and air-steam gasification of saw dust and coconut
shell were studied. Stoichiometric thermodynamic equilibrium models for air
and air-steam gasification of different biomasses were developed using
MATLAB software validated with experimental data. The developed models
were used to analyse the effect of various process parameters like gasification
temperature, steam to biomass ratio and equivalence ratio on gas composition,

70
lower heating value and yield of syngas and first and second law efficiencies.
An Eulerian-Eulerian model for air-steam gasification of sawdust was also
developed using Fluent13 software. The particle motion inside the reactor was
optimized using various drag laws derived from Kinetic Theory of Granular
Flow. In these models biomass pyrolysis was not considered.

3.2.8 Action Plan

3.2.8.1 Gap Analysis & Strategy to Bridge the Gap with Time Frame

In the recent times the focus at MNRE has beenon generating hydrogen
rich syngas through thermo-chemical conversion of biomass. Couple of
research projects has been sponsored in this sector with the focus on hydrogen
production. In view of the abundant availability of biomass in the country, work
in this area needs to be consolidated and continued to fill in the existing gaps
in R&D and design and demonstrate pilot/full size units within a reasonable time
frame.

As a part of the MNRE supported R&D activity, Indian Institute of


Science, Bangalore has completed a project addressing the above aspects of
hydrogen production through the thermo-chemical conversion of biomass. This
has resulted in developing a prototype to generate hydrogen rich syngas using
oxy-steam gasification.

The entire process has been optimized to generate a maximum of about


100 g hydrogen/kg biomass. The process has also been studied to look at
possibility of generating the hydrogen rich syngas for FT process as well with
H2:CO ratio of about 2.

Syngas composition, hydrogen yield and performance parameters were


monitored with varying steam to biomass ratio and equivalence ratio.
Experiments were conducted by varying SBR from 0.75-2.7 and ER ranging
from 0.18-0.3. Figure 3.3 shows the gas analysis data of an operation of over 4
hours.
71
Figure 3.3 : Gas composition using oxygen and superheated steam
(SBR = 1.45, ER = 0.25)

Experiments and kinetic studies in the complex heterogeneous


reacting system have been conducted with wet wood and oxygen as well as
with dry wood and oxy-steam. Table 3.2 summarizes the data from the
experimental results using wet wood with oxygen and dry biomass with
superheated steam. Results show that using dry biomass with oxy-steam
improves the H2 yield, efficiency and syngas LHV compared to direct usage
of wet biomass with oxygen.

Table - 3.2 : Results, analysis and comparison while using dry biomass with
superheated steam
Dry biomass with superheated steam
H2O to biomass ratio 0.75 1 1.4 1.5 1.8 2.5 2.7
ER 0.21 0.18 0.21 0.23 0.27 0.3 0.3
H2 yield (volume
fraction, %) on dry 41.8 45.2 43.1 45.2 49.6 51.7 50.5
basis
CO yield (volume
fraction, %) on dry 27.6 24.9 26.5 24.9 17 12.8 13
basis
66 68 71 73 94 99 104

72
H2 yield (g kg-1 of
biomass) –
Experimental result
H2 yield (g kg-1 of
biomass) – Equilibrium 87 88 102 101 99 107 117
analysis result
Percent of H2 yield from
moisture/steam (%) 21.4 20.2 28 27.7 43.7 44.3 48.1
(65.5 g H2 in biomass)
H2/CO 1.5 1.8 1.6 1.8 2.9 4.0 3.9
LHV (MJ Nm-3) 8.9 8.6 8.8 8.7 8 7.5 7.4
H2O volume fraction in
0.8 1.4 1.6 2 1.9 2.3 2.4
syngas (%)
Fraction of heat
available through
4.2 2.7 2.2 1.9 1.3 0.8 0.8
CO+CH4 in syngas for
steam generation
Hydrogen efficiency (%)
73.7 63.2 67.2 63.5 70.5 61.0 63.7

Gasification efficiency
82 73 75 74 78 67 66
(%) –
Exergy efficiency (%) - 85 81 80 77 84 78 70

Using dry wood and oxy-steam as gasifying agents, 104 g hydrogen


was obtained per kg biomass compared to a maximum of 63 g H 2 per kg
biomass with wet wood and oxygen. The gasification efficiency with oxy-
steam gasification was found to be 85.8% compared to 61.5% with wet
biomass at H2O to biomass ratio of 0.75. Hydrogen yield in syngas, as high
as, 1.3 kg/hr was achieved. Syngas with LHV of as high as 8.9 MJ Nm-3 was
obtained, which is almost twice the energy content in producer gas obtained
through air gasification. At lower SBR of 0.75, the low hydrogen yield of 66 g
per kg biomass was achieved with higher gasification efficiency of 85.8% and
higher LHV of 8.9 MJ Nm-3, and with an increase in SBR, H2 yield increased

73
to 104 g per kg of biomass with lower efficiency of 71.5% and LHV of 7.4 MJ
Nm-3. H2 fraction in syngas and H2/CO ratio is a very critical parameter for the
conversion of syngas to liquid fuel through FT synthesis. Varying the SBR
from 0.75-2.7, hydrogen fraction in syngas has been obtained ranging
from42-52% (molar basis) and H2/CO ratio is found to be varying from 1.5 to
as high as 4. At lower SBR values, the energy content in CO and CH4 yield is
sufficient for raising steam.

With the current experience of using biomass, about 70 g pure


hydrogen can be obtained per kg biomass, which results in about 15 kg
biomass for every kg of hydrogen generated.

Having generated hydrogen rich syn-gas, it is important to utilize this gas


for hydrogen production for applications like PEM fuel cells, SOFC, etc. This
calls for purification of the syngas to various levels depending upon the end
use.

3.2.8.2 Identification of the major institutions / industry for augmenting


R&D facilities including setting-up of Centre(s) of Excellence and suggest
specific support

Indian Institute of Science, which has been carrying out research activity
in the area of bio-energy for over three decades, is well positioned to take the
responsibility of Center for Excellence in the area of biomass to hydrogen
through various routes. IISc is concentrating on thermo-chemical route of
hydrogen production – Oxy–steam gasification of biomass, which has been
demonstrated with hydrogen yield of 100 gm per kg of biomass use. Apart from
the various thermo-chemical routes that are being researched, IISc also has
groups working in the area of engines, materials, storage, fuel cell, etc.

74
75
HYDROGEN PRODUCTION
BY ELECTROLYSIS OF WATER

76
4.0 Hydrogen Production by Electrolysis

4.1 Introduction

Hydrogen can be generated from water by electrolysis or thermolysis.


There are mainly three types of water electrolysis processes reported in
literature. These are classified as: alkaline, acidic (membrane based) and high
temperature ceramics (solid oxides) on the basis of electrolytes used. Of these
three types, development of the last one is still at the laboratory level. A highly
promising method of hydrogen production is electrolysis of water, using power
from solar photovoltaic cells (Figure 4.1).

Figure 4.1: Hydrogen generation using solar photovoltaic cells

4.1.1 Polymer Electrolyte Membrane based Water Electrolysis

Polymer electrolyte membrane (PEM) based water electrolysis offers a


number of advantages for the electrolytic production of hydrogen and oxygen
in comparison with the conventional water-alkali electrolysers, such as
ecological safety, high gas purity (more than 99.99% for hydrogen), the
possibility of producing compressed gases for direct pressurized storage

77
without additional power inputs and higher safety level. The membrane used in
these electrolysers is Nafion-brand perfluorinated ion-exchange membrane of
US Company DuPont (Figure 4.2). The PEM electrolysers based on solid
polymer electrolyte (SPE) technology were developed in 1966 by the General
Electric (USA) and designed for special purposes (spaceships, submarines,
etc.) as well as for industrial and analytical laboratory applications (in gas
chromatography).

Figure 4.2Schematic drawing of PEM cell

Membrane based water electrolysis can be classified on the basis of


their electrolytes as alkaline (alkali / anion exchange membrane), or based on
proton / cation exchange membrane. In water electrolysis using cation
exchange membrane the oxygen and proton are generated at anode (Equation
1), the generated proton then passes through the cation exchange membrane
and combines with electrons at the cathode to generate hydrogen (Equation 2).
The membrane acts as an electrolyte as well as a barrier for preventing mixing

78
of hydrogen and oxygen generated at cathode and anode compartments
respectively.

Anode (oxidation): 2 H2O(l) → O2(g) + 4 H+(aq) + 4e− --(1)

Cathode (reduction): 2 H+(aq) + 2e− → H2(g) --(2)

The electrode reactions in case of alkaline electrolysis are different from


those of acid electrolysis as shown in Equations 3 and 4. Here, cathodic
reduction of water generates hydrogen and hydroxyl ion (Equation 3), which
passes through an anion exchange membrane. At the anode hydroxyl ions are
oxidized (Equation 4) generating oxygen.

Anode (oxidation): 4 OH- (aq) → O2(g) + 2 H2O(l) + 4 e− --(3)

Cathode (reduction): 4 H2O(l) + 4e− → 2H2(g) + 4 OH-(aq) --(4)

The hydrogen thus produced in the process needs to be utilized in a


device that will convert it into electricity, e.g., fuel cells or it can also be utilized
in internal combustion engine.

Specifications of State-of-the-Art Alkaline and PEM Electrolyzers as


reported in the NOW-study are given in Table 4.1.

Table 4.1: Specifications of State-of-the-Art Alkaline and PEM Electrolyzers


as reported in the NOW-study.

Specifications Alkaline PEM electrolysis


electrolysis

Cell temperature (0C) 60-80 50-80

Cell pressure (bar) <30 <30

Current density (mA/cm-2) 0.2-0.4 0.6-2.0

79
Cell voltage (V) 1.8-2.4 1.8-2.2

Power density (mW cm-2) <1 <4.4

Voltage efficiency HHV (%) 62-82 67-82

Specific energy consumption: 4.2-5.9 4.2-5.6


Stack (kW h Nm-3)

Specific energy consumption: 4.5-7.0 4.5-7.5


System (kW h Nm-3)

Lower partial load range (%) 20-40 0-10

Cell area (m2) >4 <0.03

H2 production rate: Stack- <760 <10


system (Nm3 h-1)

Lifetime stack (h) <90000 <20000

Lifetime system (y) 20-30 10-20

Degradation rate (mV h-1) <3 <14

Advantages and Disadvantages of Alkaline and PEM Electrolysis are


given in Table 4.2.

Table 4.2: Advantages and Disadvantages of Alkaline and PEM Electrolysis.

80
The PEM electrolyzers offer smaller, cleaner and more reliable systems
than competing electrolysis systems based on other technologies. Alkaline
electrolysers are relatively less expensive but consume more electricity
compared to PEM electrolysers wherein highly precious metals are being used
in PEM cell stack.

4.2 Alkaline Water Electrolysis

Electrolysis phenomenon was discovered by Troostwijk and Diemann in


1789. Alkaline water electrolysis is one of the earliest methods employed for
hydrogen production. Sodium hydroxide or potassium hydroxide are used as
electrolytes and the cell is normally operated at about 70 0C. The alkaline
electrolyser cell consists of two nickel based electrodes separated by a gas-
tight diaphragm. This assembly is immersed in a liquid electrolyte that is usually
a highly concentrated aqueous solution of KOH (25–30 wt.%). It uses
81
microporous diaphragm to separate cathode and anode chambers. The
product gases are completely prevented from cross diffusing through
diaphragm. This results in the reduction of efficiency of the electrolyser. The
three major issues associated with alkaline electrolysers are i) low partial load
range, ii) limited current density, and iii) low operating pressure. The energy
required to produce 1 nM3 hydrogen /hr is around 6 kWh. This is a matured
technology with a large number of industries supplying these electrolyser units
for a wide variety of applications. These electrolysers are less expensive as
non-noble metal catalysts are normally used. Alkaline electrolysis has been
used extensively for hydrogen production commercially up to the megawatt
range.

4.2.1 Challenges

The major challenges with alkaline water electrolyzer (AWE) are


corrosion related issues and poisoning of the electrolytes by inadvertent
incursion of CO2. The energy required to produce hydrogen is still high
compared to the theoretical requirements. The other issue is developing high
pressure systems. Present method involves a separate receiver and
compressor sections in the electrolysis plant. This requires development of
polymeric membranes with anion exchange capability.

4.2.2 Current Technology

 State of the Art Alkaline Electrolyser, Efficiency: 60-70% (LHV)

 Operating temperature: up to 80oC

 Operating pressure: 1 – 25 atm

 Cost: ~$1000 - 2500/kW

4.2.3 Future Technology: Increasing the Capacity & Efficiency and


Reduction in Cost

82
 System efficiency should reach 70-80% (LHV) by advanced electrolyser
technology

 Industrial size electrolyser (MW level)

 Cost should be reduced to $300 - 500/kW (Cost of Hydrogen at $2/kg)

4.3 Polymer Electrolyte Membrane (PEM) based Water Electrolysis

The drawbacks of alkaline electrolysers were overcome by the


development of solid polymer electrolyte concept by General Electric, USA, in
the 1960’s. The membranes used were sulfonated polystyrene membrane. This
concept is also referred to as proton exchange membrane or polymer
electrolyte membrane (both with the acronym PEM) water electrolysis, and less
frequently as solid polymer electrolyte (SPE) water electrolysis. The polymeric
membrane based water electrolysers till now have used cation exchange
membrane. Water electrolysis with a polymer electrolyte membrane (PEM) cell
possesses certain advantages compared with the classical alkaline process like
increased energy efficiency and specific production capacity and simplicity in
construction with a solid electrolyte operating at a low temperature. Direct
application to water electrolysis was not possible at that time because available
Solid polymer electrolytes (SPEs) were lacking sufficient chemical stability. This
was mainly due to very oxidizing conditions found at the anode of water
electrolyser where oxygen is evolved at high electrode potential values (close
to +2 V vs. NHE). At the end of the sixties, more stable sulfonated
tetrafluoroethylene based fluoropolymer-copolymers, (E.I. DuPont Co.,
Nafion®) products were made available for water electrolysis applications. This
membrane exhibits high chemical stability both in strong oxidizing and reducing
conditions up to 1250C.

Ultra-pure water is fed to the anode compartment of the electrolysis cell,


which is made of porous titanium and activated by a mixed noble metal oxide
catalyst. The membrane conducts hydrated protons from the anode to the
cathode side. Appropriate swelling procedures have led to low ohmic

83
resistances enabling high current density of the cells. The standard membrane
material used in PEM water electrolysis units is Nafion® 117 and is
manufactured by DuPont, USA. The cathode of such an electrolyser consists
of a porous current collector with either Pt or, in more recent designs, a mixed
oxide as electro-catalyst. Individual cells are stacked into bipolar modules with
titanium based separator plates providing the manifolds for water feed and gas
evacuation.

The polymer electrolyte membrane (Nafion, Fumasep) have high proton


conductivity, low gas crossover, compact system design and high pressure
operation. The low membrane thickness (~20-300 m thick) is in part the reason
for many of the advantages of the solid polymer electrolyte.

PEM electrolyzers can operate at much higher current densities, capable


of achieving values above 2 A cm-2, this reduces the operational costs and
potentially the overall cost of electrolysis (Tables 4.1 and 4.2). Ohmic losses
limit maximum achievable current densities, with a thin membrane capable of
providing good proton conductivity (0.1 - 0.02 S cm-1), higher current densities
can be achieved. The solid polymer membrane allows for a thinner electrolyte
than the alkaline electrolyzers.

The low gas crossover rate of the polymer electrolyte membrane results
in yielding hydrogen with high purity, as described in Table 4.2 and allows for
the PEM electrolyser to work under a wide range of power input. This is due to
the fact that the proton transport across the membrane responds quickly to the
power input, not delayed by inertia as in liquid electrolytes. As discussed above,
in alkaline electrolysers operating at low load, the rate of hydrogen and oxygen
production reduces while the hydrogen permeability through the diaphragm
remains constant, yielding a larger concentration of hydrogen on the anode
(oxygen) side thus creating a hazardous and less efficient conditions. In
contrast with the alkaline electrolysis, PEM electrolysis covers practically the
full nominal power density range (10-100%). PEM electrolysis could reach
values over 100% of nominal rated power density, where the nominal rated

84
power density is derived from a fixed current density and its corresponding cell
voltage. This is due to low permeability of hydrogen through Nafion (less than
1.25 x 10-4 cm3s-1cm-2 for Nafion- 117, standard pressure, 800C, 2 mA cm-2).

4.3.1 Drawbacks

Problems related to higher operational pressures in PEM electrolysis are:

1. Cross-permeation phenomenon, which increases with pressure.


2. PEM membranes being highly acidic are corrosive and require use
of distinct materials. These materials must not only resist the harsh
corrosive low pH condition (pH ~ 2), but also sustain the high
applied over-voltage (~2 V), especially at high current densities.
3. The catalysts used, current collectors and separator plates also
need to be corrosion resistive.
4. Only a few materials can be selected in this harsh environment,
such as noble catalysts (platinum group metals-PGM e.g. Pt, Ir and
Ru), titanium based current collectors and separator plates (Figure
4.3).

Figure 4.3: Component overview for a typical PEM water electrolyser.

85
Numbers of publications as a percentage of total publications directly
related to PEM water electrolysis over the years including the percentage
published related specifically to modeling (source: ISI web of knowledge) are
given in Figure 4.4.

Figure 4.4 : Number of publications as a percentage of total publications directly


related to PEM water electrolysis over the years including the
percentage published related specifically to modeling (source: ISI web
of knowledge).

Performance range of published polarization performance curves from


2010 to 2012 for a PEM electrolysis single cell operating with Ir anode, Pt
cathode, and Nafion membrane at 800C is given in Figure 4.5.

86
Fig. 4.5 : Performance range of published polarization performance curves from
2010 to 2012 for a PEM electrolysis single cell operating with Ir anode,
Pt cathode, and Nafion membrane at 800C

4.4 Hydrogen Utilization

Fuel cells have emerged as an alternative source of energy/energy


conversion devices in portable as well as stationary mode. A variety of fuel cells
such as phosphoric acid fuel cell (PAFC), alkaline fuel cell (AFC), molten
carbonate fuel cell (MCFC), solid oxide fuel cell (SOFC) etc. have been
developed and a few of them are commercially available. Other than PAFC, all
the commercially available fuel cells such as MCFC or SOFC operate at high
temperatures and therefore their use remains limited to stationary power
generation applications. Electrolyte leakage is a major drawback of the liquid
electrolyte fuel cells. Proton Exchange Membrane(PEM) Fuel Cells otherwise
known as solid polymer electrolyte fuel cells can operate at temperatures close
to 800C has large number of applications in civil, aviation and military areas
both in portable and stationary power generation mode. Constant research and
development activities across different laboratories of the world are in progress
to prepare cost effective eco-friendly membranes to make affordable PEMFCs.

87
4.5 High Temperature Water Electrolyser (HTWE)

Using solid oxide fuel cells (SOFC) in the reverse mode is a recent trend
in hydrogen generation. The HTWE has an advantage over alkaline and PEM
electrolysers, because they can achieve a higher efficiency and lower capital
costs over a wider range of current densities and cell voltage. The high
temperature electrolysis splits steam at a temperature above 800 oC. This
process uses calcium and yttrium stabilised zirconium oxide (YSZ) membranes.
Operation of the cell at high temperatures (900–1000°C) reduces the amount
of electricity needed to produce hydrogen by about 30% as compared to
electrolysis process at room temperature. Electricity consumed is about 2.6-3.5
kWh/Nm3 of hydrogen produced. Nuclear reactors operating in the same
temperature range are ideally suited for this purpose.

4.6 International Status

International status of the published work available in open literature is


summarized in Table 4.3.

Table 4.3: List of Companies Manufacturing Alkaline Electrolysers


Manufacturer Cell Type Rated Location
production
(Nm3/hr)
AccaGen alkaline (bipolar) 1-100 Switzerland
Avalence alkaline 0.4-4.6 USA
Claind (monopolar) 0.5-30 Italy
ELT alkaline (bipolar) 3-330 Germany
ELT alkaline (bipolar) 100-760 Germany
Erredue. alkaline (bipolar) 0.6-21 Italy
NEL Hydrogen alkaline (bipolar) 10-500 Norway
Hydrogenics alkaline (bipolar) 10-60 Canada
H2 Logic alkaline (bipolar) 0.66-42.62 Denmark
Idroenergy alkaline (bipolar) 0.4-80 Italy
alkaline (bipolar) 110-760 Switzerland

88
Industrie Haute alkaline (bipolar) 5-250 Germany
Technologie alkaline (bipolar) 0.4-16 Italy
Linde alkaline (bipolar) 1-5 France
PIEL, division of ILT alkaline 2.8-56 USA
Technology (monopolar) Upto 485 Norway
Sagim alkaline (bipolar)
Teledyne Energy alkaline (bipolar)
Systems Upto 50 USA
Norsk Hydro ( 0.5 to1
bar, 61-72 LHV alkaline (bipolar)
efficiency)
Stuat Energy ( 1 to 25
bar ; 73-75% LHV
efficiency)

The largest existing alkaline electrolysis plants are: KIMA fertilizer plant
in Aswan, Egypt with a capacity of 160 MW and 132 modules, and a 7 module
22 MW plant in Peru (pressurized operation). Another highly modularised unit
is the Brown Boveri electrolyser, which can produce hydrogen at a rate of about
4–300 m3/h.

The PEM water electrolyser was developed before 1966 and introduced
by General Electric Corporation, USA. In 1979 the cells operating at 1A.cm -2
800C at 1.8V was reported. Based on this technology high pressure electrolysis
cells were designed and tested. All these efforts were basically for NASA, US
Navy aircraft carriers and nuclear submarines for hydrogen generation and
oxygen supply for life support systems. Several types of cell and system
configurations were evaluated and an ultimate size of one cell unit was found
to be 0.23 ft2. The Nafion-120 membranes with catalysts of platinum, platinum-
iridium-tantalum etc. were used for the membrane-electrode assembly. The
preparation of the membrane–electrode composites was very expensive. By
the end of this project economic evaluation indicated a prohibitively high cost
of such units. This system was suitable only for specific applications, where

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cost is secondary and so the technology could not attain commercial status for
large scale hydrogen generation.

Billings Energy Corporation, Provo, Utah, USA also described their


version of PEM electrolyser having Nafion membrane coated with lead-dioxide
anode and nickel cathode catalysts, the performance of which was very poor.
The cell showed about 5.0V at 400mA/cm-2 at 500psig. On using platinum for
both anode and cathode they could improve the performance to about 3.25V at
600 mA/cm2with an efficiency of efficiency of 45%. Because of the high loading
of the noble-metal catalysts and the higher resistance of the membranes, the
efficiency and economics were far from acceptable standard.

United Technologies Corporation, East Hartford, USA was reported


to be engaged in the development of PEM electrolyser modules, probably with
the GE concept, with 22 cells of 0.23ft2 each for US navy and space applications
and also described a regenerative fuel cell unit of 1-2 kW capacity.

ABB Switzerland was also active in the PEM electrolyser development


during 1976 to 1998. The ABB technology has been demonstrated in two
commercial versions of 100kW capacity at Stellram SA, Nyon, Switzerland and
Solar-Wasserstoff-Bayern GmbH. The general design features are: Nafion-117
with platinum cathode catalyst and graphite current collector and the anode was
Ru-Ir mixed oxide with porous titanium anode current collector. At 1 A.cm -2 and
800C, the cells exhibited 1.75V. Both plants had to be stooped after three years
of operation from 1987 due to the high level of hydrogen in oxygen (>3%) and
the membrane was found to have been damaged in part of the cells. The cells
were refurbished and operated till 1998. The cause of failure of the cells was
found to be related to the assembling faults causing mechanical stresses and
also due to the membrane degradation.

The Electrolysis 2000 project was initiated in France and different


aspects of the system were investigated at various laboratories during the 90’s.
Laboratory cells have been tested with typical voltage of 2.1V at 1 A.cm-2. The
European Commission (EC) is actively supporting different projects within the
6th and 7th Framework Programmes. The main deliverable of the GenHyPEM

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project was on the development of a PEM water electrolyser with a hydrogen
production capacity ranging from 0 up to 1 Nm3H2/hour, operating in the 0-90oC
temperature range and the 1-50 bars pressure range and this project was
carried out by the Institut de Chimie Mole´culaire et des Mate´riaux, France
in 2008. Apart from these developments, many research laboratories and
academic institutions and universities are engaged in studies on both the
fundamental and applied aspects of the PEM water electrolyser system.

The recent reports of the commercial availability of small and medium


range PEM water electrolysers for laboratory utility and for other applications
are from three major industries.

Proton Energy Systems, USA is currently offering 0.5, 1 and 10 m3 per


hour hydrogen delivery systems, suitable for power generation through fuel
cells. This may be the so called state-of the-art hydrogen generator with a
number of advanced features for safe and efficient generation of hydrogen. The
system delivers hydrogen at a high purity (99.999%) and pressure of 170 to 200
psi with an overall average energy requirement of 5.7 to 6.4 kWh/Nm 3 H2 for
the 1 Nm3/hr H2 generators. M/s ITM power, UK is also offering PEM based
Water electrolyser system in the range of 11- 75 Nm3 H2/hr capacity. Hamilton
Sundstrand, a subsidiary of United Technology Corporation,East Hartford, USA
has reported to be offering a system containing stacks upto 65 cells of 0.23 ft 2
active area, operating upto 3 A.cm -2 that can deliver hydrogen up to 750 psig.
This system is intended mainly for strategic applications.

The third report is from Fuji Electric Corporate Research and


Development, Japanis about the development of 25 dm2 PEM water
electrolyser under the WE-NET program. The electrolytic cells were fabricated
with their own experimental membranes with low equivalent weight, low
thickness & high ionic conductivity and reports a test cell performance of 1.555
to 1.58V at 1 A.cm-2 and 80oC. All the cell hardware are based on the most
improved structure and fabrication techniques.

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Siemens, FRG plans to build an electrolyser system to store wind power
as hydrogen. The system will have a peak rating of up to 6 MW. The project,
which will cost 17 million, is being financed with the support of the German
Federal Ministry of Economics and Technology as part of the Energy Storage
Funding Initiative. The system involves highly dynamic PEM high-pressure
electrolysis that is particularly suitable for high current density and can react
within milliseconds to sharp increases in power generation from wind and solar
sources.

Currently available PEM water electrolyser systems have a hydrogen


production rate that varies from 0.06 to 75 Nm³/hr. This is very low in
comparison to alkaline electrolyser production rates that have already reached
500 Nm³/h. With regard to the lifetime, the membrane represents the critical
component of PEM system. Even though the lifetime of PEM electrolysis
systems were significantly improved in the last 10 years, it is still limited due to
the nature of solid polymer electrolyte membrane, and it is below 20,000 h. PEM
electrolysers are less mature, produced in smaller quantities, and therefore
more expensive than alkaline electrolysers. It is expected that the lifetime will
be prolonged up to 60,000h in the long term predictions. Even though there is
no clear relation between operating conditions and degradation processes of
the stack, in some cases operating conditions can lead to membrane
perforation.

The concept of high-temperature electrolysis production of hydrogen


from steam was investigated first in the 1980s by Dornier System GmbH,
Friedrichshafen, Postfach, Germany in the project called ‘‘High Operating
Temperature Electrolysis, HOT ELLY’’. After that Westinghouse Electric Co.
and Japan Atomic Energy Research Institute (JAERI) made efforts to carry out
HTWE experiment through tubular single cells and planar cells. Then the
research and development efforts on HTWE became slow due to the cheap and
sufficient supply of fossil energy. Now once again the HTWE technology for
hydrogen production is becoming popular again, because of two major context
changes the prospects of transition to a hydrogen-based economy due to the

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shortage of fossil energy and the prospects for the development of advanced
primary energy to supply highly efficient heat sources. In 2004, researchers at
the U.S. Department of Energy’s Idaho National Laboratory (INL) and
Ceramates, Inc. of Salt Lake City, USA announced a breakthrough
development in hydrogen production from nuclear energy. They have
demonstrated a 15 kW integrated laboratory scale (ILS) facility with a hydrogen
production rate of 0.9 Nm3/h.

They achieved the highest-known production rate of hydrogen by HTSE


with an electrolysis efficiency of almost 100%. This development is viewed as
a crucial first step toward large-scale production of hydrogen from water, rather
than fossil fuels and a milestone in the hydrogen energy research field.
Department of Energy (DOE) of the United States hoped that INL can
commercially produce hydrogen production by HTSE before 2017 to reduce the
dependence of fossil fuel. In Jan, 2005, the news of large-scale hydrogen
production through HTSE by nuclear reactor was voted by 584 Chinese
academicians and chosen as one of the ten biggest scientific news of the world
in 2004, which indicated the deep concern about the hydrogen and nuclear
energy development progress in China. Subsequently, GE Company, a joint
effort of University of Nevada, Las Vegas and Argonne National Laboratory,
European Union (the coordinator including European Institute for Energy
Research, Swiss Federal Laboratories for Materials Testing and Research,
Deutsches Zentrum fur Luft- und Raumfahrt and Rise National Laboratory, the
University of Iceland and Icelandic New Energy, French CEA, Japan and Korea
successively initiated HTWE research programs around 2005.

Institute of Nuclear and New Energy Technology (INET), China started


R&D projects for nuclear hydrogen production in 2005. Thermo-chemical water
splitting by an iodine-sulfur (IS) process and HTSE process using SOEC are
mainly concerned currently with the heat utilization system of nuclear reactor
(HTR-10). In the last three years, HTWE research group experienced
preliminary investigation, feasibility study, equipment development and
hydrogen production technology.

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Cylindrical design was favored for the prototypes model in the 1980s.
Current investigations focus on planar designs. Planar type HTWE technology
is being utilized, because it has the best potential for high efficiency due to
minimized voltage and current losses. These losses also decrease with
increasing temperature.

Perflurosulfonated membranes were synthesized from


tetrafluoroethylene as the starting material. These membranes have a PTFE
like back bone with side chains terminating with sulfonic acid groups. Besides
Du Pont, Asahi Glass and Dow Chemical’s also developed similar membranes.
However, the length of the side chains and the distance between the side
chains were different (Table 4.4). The equivalent weight of these electrolyte
membranes ranged from 800 to 1200g equivalent of protons in dry form.
Thickness was in the range of 50 to 260 m. Apart from perfluorosulfonated
membrane like Nafion there are several other electrolyte membranes made
from either from perfluorinated or non-fluorinated chemicals and are
commercially available. Some of these electrolyte membranes are given in
Table 4.5. The hydrophilic region having sulfonic acid groups forms clusters in
the presence of water. The overlapping clusters form a transport channel
responsible for the proton transport in the membrane. Since the proton
transport takes place through the cluster region, the conductivity is highly
sensitive to the water content of the membrane. The fluorinated polymers have
shown the best of the performance in the fuel cells (>5000 hrs of operation).
However, there is a need to develop alternate non fluorinated polymers.
Besides high cost, the fluorinated membranes contribute to environmental
burden during their preparation as well as disposal of the polymers. It is recently
reported that fluorinated compounds such as hydrofluoric acid and other
fluorinated fragments are released in the water during operation. There has
been constant effort to develop alternate polymers by various researchers
around the world and their method of preparation is tabulated in Table 4.6.

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Table 4.4: Schematic structure of perfluorosulfonic acid membranes manufactured by different companies.

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Table 4.5: Commercially Available SPE Materials

96
Table 4.6: Different Membranes and their Detailed Description.

Sl.No. Membrane Description

Perfluorinated Membranes/Partially Fluorinated Polymers


1 Gore-Select Membrane Composite membrane; a base
material preferably made of expanded
PTFE that supports perfluorinated
sulfonic acid resin, PVA etc.
2 BAM3G (Ballard Inc) Polymerization of ,,-
trifluorostyrene and subsequent
sulfonation

Grafted Polymers
3 ,, - Trifluorostyrene Grafting of ,,-trifluorostyrene and
grafted membrane PTFE/ethylene copolymers
4 Styrene grafted and Pre-irradiation grafting of styrene onto
sulfonated poly(vinylidene a matrix of PVDF after elec-tron beam
fluoride) membranes [PVDF- irradiation. The proton conductivity
g-PSSA] can be increased by crosslinking with
DVB

Non-fluorinated
5 -methyl styrene blend Partially sulfonated -methyl styrene
PVDF composite with PVDF
6 Sulfonated poly(ether Direct sulfonation of PEEK in conc.
etherketone) (SPEEK) sulfuric acid medium
7 Sulfonated poly(ether Partially sulfonated polysulfones
sulfone)
8 Sulfophenylatedpolysulfone Sulfophenylation of polysulfone
9 Methylbenzenesulfonated These alkylsulfonated aromatic
PBI/methylbenzenesulfonate polymer electrolyte posses very good
thermal stability and proton

97
poly(p- phenyleneterephthal conductivity when compared to PFSA
amide) membranes membranes, even above 80 ◦C
10 Sulfonated napthalenic Based on sulfonated aromatic
polyimide membrane diamines and dihydrides. Its
performance is similar to PFSA
11 Sulfonated poly(4- Derived from poly(p-phenylene) and
phenoxybenzoyl-1,4- structurally similar to PEEK. Direct
phenylene) (SPPBP) sulfonation to produce the electrolyte.
12 Poly(2-acrylamido-2- Made from polymerization of AMPS
methylpropanesulfonic acid) monomer. AMPS monomer is made
from acrylonitrile, isobutylene and
sulfuric acid

Acid Base Blends


13 Imidazole doped sulfonated Complexation with imidazoles to
polyether ketone (SPEK) obtain high proton conductivities
14 Sulfonated poly(ether ether Sulfonated poly(ether ether ketone)
ketone) (SPEEK)-PEI (SPEEK)-Poly ethylene imine (PEI)
blended
15 Sulfonated poly(ether ether Composite membranes based on
ketone) (SPEEK)-PBI blend highly sulfonated PEEK and PBI
16 PBI-H3PO4 PBI doped with phosphoric acid

4.7 National Status

R&D on alkaline electrolysers in India dates back to early eighties.


BARC and CECRI were very active in developing materials for this type of
electrolysers as well as stacks. Compact alkaline electrolysers have been
designed and demonstrated in Chemical Engineering Group (ChEG), BARC in
the late eighties. BARC has developed water electrolysers with high current
density based on indigenously developed advanced electrolytic modules
incorporating porous nickel electrodes. A 40-cell electrolysis module
incorporating Porous Nickel Electrode operates at a high current density of

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4500 A/m2 which is much higher than conventional cells in the market (1500
A/m2 or below). The electrolyser operates at 550C and 0.16 MPa to produce 10
Nm3/h of hydrogen. They have also now developed 30 Nm 3/hr capacity alkaline
water electrolyser and this technology is available for production.

In 1990’s CSIR-CECRI had reported a new Lanthanum Barium


Manganate based oxygen evolution catalyst and Nickel-Molybdenum-Iron
based composite based cathode materials for alkaline water electrolysis. They
also developed a monopolar unit alkaline water electrolytic cell and
demonstrated the performance of 1.8 V at 300 mA.cm -2 in 6 M KOH at 303 K.
In 2008, CSIR-CECRI transferred a process know-how for development
activated nickel electrode for alkaline water electrolysis to M/s/ Eastern
electrolyser, Noida.

Energy Research and development association (ERDA), Vadadora has


demonstrated the concept of wind hydrogen using commercial alkaline water
electrolyser (AWE) for practical distribution generation system in 2013. This
project was financially supported by MNRE. The integrated system consists of
wind turbine (2X5kw), alkaline water electrolyser (1.1Nm3/hr), hydrogen storage
tank (1Nm3, at 5kg/cm2), battery bank (6x 200Ah at 12 V) and IC engine
(650VA) and it was installed at Savli (about 30 km away from Vadodara,
Gujarat). The battery was used to provide consistent electrical power output
and avoid short term intermittent fluctuations. Hydrogen fuelled IC engine was
operated when wind along with battery is not able to meet the load demand.

The National Institute of Solar Energy, Gwalpahari, Gurgaon has


installed a 120 kW solar photovoltaic systems to produce electricity for
generation of hydrogen through the water electrolyser andis geared up to
demonstrate and evaluate the performance of various technologies of hydrogen
energy. The hydrogen, so generated will be stored in high pressure cylinders.
As and when required, it would be utilized for stationary power generation
through fuel cell and dispensed through the dispenser unit into fuelled vehicles
(3-wheelers & 4-wheelers), meant for demonstration.

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The following companies are reported to be engaged in manufacturing
AWE for various industrial applications:

Company Production capacity


M/s. Sam Gas Projects Pvt. Ltd., Ghaziabad - 201
015, Uttar Pradesh 1 to 50 Nm3 / hr.
M/s. Rak Din Engineers, New Delhi 0.072Nm3/hr
M/s. Vaayu Tech Engineering, Ghaziabad, Uttar
Pradesh 50 Nm3/hr
M/s. S. S. Gas Lab Asia, Delhi - 110 095 10Nm3/hr
M/s. Vemag Engineers Private Limited, Baroda,
Gujarat 1-50 Nm3/hr
M/s. Eastern Electrolyser limited, Noida, Uttar
Pradesh 201301 --

The CSIR-CECRI developed a PEM based hydrogen production


(capacity 40 and 80 litres/hr) water electrolyser system under a MNRE funded
project during 2003-2006. Subsequently they have developed 1.0 and 5.0
Nm3/hr capacity PEM water electrolyser under 11th Five year plan CSIR
Network Project during 2012 and demonstrated the same with the energy
consumption of 5.75 kWh/Nm3 of hydrogen. The electrolyser was designed
using circular type platinum coated titanium flow field plate, platinum black
cathode and iridium oxide anode. The developed electrolyser stack can deliver
the hydrogen at 5-10 bar pressure. Recently this technology has been
transferred to M/s. Eastern electrolyser, New Delhi and this company has
started to work with CSIR-CECRI for further development. In addition, CSIR-
CECRI has also demonstrated solar power integrated PEM based water
electrolyser system of 0.5 Nm3/hr capacity in 2012.

SPIC Science Foundation ( SSF) was also engaged in development of


PEM based water electrolyser for hydrogen generation and developed
electrolyser stacks of capacity 500 lit/hour (0.5 Nm3/hour) Hydrogen and 1000
lit/hour (1 Nm3/hour) Hydrogen, under DST-TIFAC funded project . They used

100
platinised Titanium plate as bipolar plate. The proto-type 0.5 Nm3/hr capacity
hydrogen generator was demonstrated at the Indian Meteorological
Department (IMD), Thiruvananthapuram in Feb’ 2006, to utilise the hydrogen
for lifting the weather balloons used to collect atmospheric data.

Centre for environment, Institute of Science and technology, JNTUH,


Hyderabad has also developed indigenous PEM based water electrolyser of 36
lit/hr Hydrogen Production capacity using Nafion 115 under BRNS funded
project in 2010.

Hydrogen generation using PEMWE concepts using depolarisers have


also been reported from some Indian labs. This types of work has also been
reported from some labs in USA. For the first time, SSF developed and
demonstrated PEM based water electrolyser system, which used methanol as
a depolariser. In this method, pure hydrogen can be generated with a much
lower energy consumption compared to water electrolysis. Electrolyser stack
was developed using titanium flow field plate, carbon supported Pt-Ru and
Carbon supported Platinum catalyst for anode and cathode respectively. This
was demonstrated with the hydrogen production capacity of 60.0 lit/hr under
MNRE funded project during 2006. The energy consumption for hydrogen
production was 2.0 kWh/Nm3.

In 2012, The Centre of Fuel Cell Technology, Chennai (a project of


International Advanced Research Centre for Powder Metallurgy, Hyderabad)
demonstrated of 1.0 Nm3/hr hydrogen production capacity electrolyser using
similar concept but with much lower energy consumption of 1.40 kWhr/Nm 3. It
also demonstrated for the first time use of carbon based materials in its
construction and thus redcuing the capaital cost tredomnously. ARCI-CFCT is
carrying out a large amount of work in identifying suitable depolaisers, which
can redcue the cost of hydrogen .

Sea water electrolsyis to produce hydrogen is being pursued at CSIR-


CECRI and the Centre of Fuel Cell Technology, Chennai (a project of
International Advanced Research Centre for Powder Metallurgy, Hyderabad).

101
Novel electrocatalayts have been developed . However the energy cost
remains still high .

M/s. MVS engineering Ltd , New Delhi offer turnkey supply for PEM
technology in partnership with proton onsite (USA) for customers looking for
non-alkaline solution for hydrogen generation by water electrolysis.

Indian Oil’s R&D Centre recently commissioned India’s first Hydrogen-


CNG fuel dispensing station at its R&D Centre at Faridabad. The pilot station
provides a hands-on experience with on-site Hydrogen production, storage,
distribution and supply. The hydrogen is being produced by water electrolysis
method using imported electrolyser system.

In general, the production of hydrogen through electrolysis of water is a


highly energy intensive method (4.5-6.5 kWh/Nm3). Because of its high energy
consumption and also of the quite substantial investment, water electrolysis
technology is not widely used in India for commercial purposes. The challenges
for widespread use of water electrolysis are also the durability.

BARC has a roadmap for development of solid oxide fuel cell and
development of materials and methods are underway for SOFC power packs.
They have a plan to utilise this development for the development of High
temperature steam electrolyser of 1.0 Nm3/hr hydrogen production capacity for
technology demonstration purposes. Development of proton conducting high
temperature materials is another major R&D thrust. Besides BARC, CGCRI,
IIT-D has initiated some work in this area recently.

4.8 Gap Analysis & Strategy to Bridge the Gap

 Identification of projects and prioritize them for support with the result
oriented targets.
 Identification of the major institutions / industry for augmenting R&D
facilities including setting-up of centre(S) of excellence and suggest
specific support.
 Partnership with foreign institutions including technology adaption from
abroad.

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 Identification of the institutions for setting up of demonstration plants.
 Identification of institutions / industry to work on PPP model for
commercialization of the developed processes.
 Identification of technologies for adoption in specific applications with
time line.
 The electrolyser system consists of various subsystems like
electrochemical stack, power rectifiers, control systems, instrumentation
for monitoring various processes, water purification, pumps, multistage
compressors, pressure vessels, and multiple number of other
engineering subsystems involved while integration as per customer
requirements to develop complete system. Except for the
electrochemical stack, couple of PSU’s in India has core strength for
manufacturing majority of aforementioned subsystems and very much
capable in system engineering. Imported electrolyser stacks in different
combinations may be used and integration can be carried in the country.

4.9 Action Plan

Development of alternate solid polymer electrolytes that are stable in the


electrolysis cells more than 5000 hrs of operation would be of desirable. The
SPE is either acid or alkaline based, the acid based electrolysis system requires
noble metal catalysts, and alkaline membrane based electrolysis require
cheaper electro-catalyst like nickel. It is ideal to have alkaline membranes
based water electrolysis system that works on the solar energy derived from
solar cells. However, presently alkaline based SPE faces numerous challenges
such as chemical stability in the electrochemical device. These challenges are
lesser for either phosphoric acid based electrolysis cells or alkali based
electrolysis systems using diaphragm. Due to this the following path is
suggested with an idea of immediate goals of onsite hydrogen production using
presently available technology and replacement of the traditional technology
with the membrane based electrolyser in a phase wise manner. Following steps
are envisaged.
(i) Solar energy based
(a) Acid based electrolysis system

103
(b) Alkali based electrolysis system
(ii) Development of electrolysers based on indigenous acid based SPE
(iii) Development of alternate alkaline membrane
(iv) Development of alkaline SPE based electrolyte system
(v) Replacement of traditional systems as in 1 by the new membrane based
system

4.10 Possible Incentives Plan to Promote Industry Participation

Industry participation is the most essential factor for the successful


implementation as well as utilisation of the hydrogen produced using the
electrolysis method. Currently industry uses other methods for the production
of hydrogen; such industries can earn carbon credits by use of electrolysis
based hydrogen production.

(i) To begin with government can set up few demonstration plants in an


industrial area to augment the hydrogen produced by these industries
for their own production.
(ii) A comparative study of this method with the age old methods can
carried out and an educative program can be undertaken to show the
techno-economic feasibility of the electrolysis method.
(iii) Subsidy may be provided or the industry may earn carbon credits for
putting up such plants.

4.11 Summary & Conclusions

Solid polymer electrolyte (SPE) based electrolysis process is a clean


process of hydrogen production when coupled with photovoltaic based solar
cells. Development of solid polymer electrolytes both acid and alkali based
would be the key for successful development of these systems. Alkali based
electrolytes are preferred over the acid based ones due to the use of non-noble
catalysts, however alkali based SPE faces challenges such as chemical
stability in the electrochemical system. The acid SPE based electrolyser may
be deployed on a small scale in a distributed hydrogen production systems both
in industry as well as for remote areas. It is suggested to setup hydrogen

104
production plants based on presently available electrolysers which can be
manufactured in India and then replace these conventional electrolyser with the
SPE based electrolysers in a phase wise manner. This will ensure the
successful deployment of technology in time to come.

4.12 Cost Estimate of Hydrogen Generation

Hydrogen Generation on a 1 MW system

Assumptions
Utilization
factor 75% Plug
Cost of
Electricity ($/kW) $ 0.12 Plug
Efficiency % 77% Calculated
Efficiency kWh/kg 51.0 Plug

CapEx
10 year program
kg / Day Cost kg of H2 $ / kg
1 MW System 450 $ 1,975,000 1,231,875 1.603247

Opex
Cost Total Cost $ / kg
Maintenance per year $ 35,000 $ 350,000 0.28412
Spare Parts over proyect $ 60,000 $ 600,000 0.487062
Electrical Cost $ 753,908 $ 7,539,075 $ 6.12
Water Cost $ 54,750 $ 547,500 $ 0.44
Total Cost of per kg of H2 produced $ 8.94

105
BIO-HYDROGEN AND BIO-METHANE
PRODUCTION

5.0 Bio-Hydrogen and Bio-Methane Production

106
5.1 Biological H2 production process has gained importance in recent years.
In early 90s biological hydrogen production came in lime light in energy policy
of many government institutions throughout the world. Biological H2 production
takes place mainly at ambient temperature and atmospheric pressure which
makes this process less energy intensive than other conventional processes
(chemical or electrochemical process). Microbial species capable of producing
H2 belong to different taxonomic and physiological types. Pivotal enzyme
complex involved in H2 production are hydrogenase or nitrogenase. These
enzymes regulate the hydrogen production process in prokaryotes and some
eukaryotic organisms including green algae. The excess electrons generated
during catabolism inside the cells are disposed in the form of H2 by the action
of hydrogenase protein.

The biohydrogen production process can be classified into two broad


group viz. light dependent and light independent process. Light mediated
processes include direct or indirect biophotolysis performed by algal species
and photo-fermentation performed by purple non-sulphur bacteria. Dark
fermentation is performed by heterotrophic organotrophic microbes. The algae
use their photo-synthetic apparatus and solar energy to convert water into
chemical energy. In this process, oxygen is produced as by-product. This
oxygen acts as inhibitor of enzyme system responsible for hydrogen production.

The coupling of two separate stages of micro-algal metabolism i.e


photosynthesis and fermentation for hydrogen production is termed as indirect
‘bio-photolysis'. The fixation of CO2 into storage carbohydrates (e.g. starch in
green algae, glycogen in cyanobacteria) is coupled with fermentation of these
stored energy reserve for H2 production under anaerobic conditions. This
process is not marred with the problem of oxygen accumulation. Thus it is
considered more efficient than direct photolysis of water. To compete with
alternatives sources of renewable H2 production process, such as photovoltaic
electrolysis, the bio-photolysis processes must achieve close to an overall 10%
solar energy conversion efficiency. To achieve high solar conversion
efficiencies, certain biotechnological steps are required. One of such steps

107
could be reduction of number of light harvesting pigments or use of
metabolically engineered cell that are more efficient in fermentation of stored
carbohydrates to H2.Improvement of bioprocess parameters could lead to the
solution of scaled up operation of photo bioreactor for hydrogen production.

Among all the biological H2 production processes, dark fermentation


shows highest H2 production rates. This process holds promise for
commercialization. If evolution of microbes is considered, as the availability of
organic matter on earth varied, the fermentative microbes capable of H 2
production i.e.fermentative bacteria evolved with the appearance of organic
material on earth. These microbes adapted themselves to different growth
conditions (mesophilic temperatures, thermophilic temperatures, etc.) and
complexity of the substrate. They are heterotrophic in nature and produce H2
under anaerobic conditions. The metabolism of these microbes involves
utilization of simple sugars and production of electron donors in terms of NADH.
The substrate-level phosphorylation is the only way of ATP production under
anaerobic conditions. The NADH thus produced is used by Fe-Fe H2ase
enzyme complex to produce molecular hydrogen in obligate anaerobes. In case
of facultative anaerobes, the format lyase enzyme breaks format to molecular
hydrogen and carbon dioxide. Format lyase is also known as Ni-Fe
hydrogenase whose turnover number is lower than Fe-Fe H2ase. Thus obligate
anaerobes are reported as highest H2 producing organisms. Theoretical
maximum yield for hydrogen production is 4 moles / mole of glucose.
Fermentative microbes growing at thermophilic temperatures are reported to
produce hydrogen at high rate. There are many advantages of thermophilic
bioH2 production viz. at thermophilic temperature the thermodynamics of H 2
production is more favorable. Moreover, temperatures greater than 600C lead
to pathogen destruction and reduce the chances of unwanted contaminations.
Very few end-metabolites are produced under thermophilic regime. These end-
metabolites are generally composed of ethanol, acetate, butyrate, propionate,
etc. The presence of these molecules in the spent media leads to extra burden
of waste disposal.

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The photoheterotrophic process converts the volatile fatty acid rich spent
media of dark fermentation to hydrogen. Photo-fermentative bacteria such as
Rhodopseudomonas, Rhodobactersp, Rhodospirullum sp., etc. are the major
photo-fermentative bacteria. Light intensity, light wavelength and illumination
protocol are the major factors that drive the photo-fermentation. Theoretically,
H2 production from 1 mole of acetate, propionate and butyrate are 4, 7 and 10
moles, respectively. Thus integration of photo-fermentation with dark
fermentation was considered for the maximization of gaseous energy recovery
(Figure 5.1). But there were many operational challenges of using photo-
fermentative bacteria. One of the major problems faced was the light shading
effect generated by accumulation of pigment in the photo-fermentative
microbes. Moreover, the rate of H2production was also considerably low when
compared with dark fermentation. Photo-bioreactor design and scale up
challenges have hampered the implementation of integration of photo-
fermentation with dark fermentation. Poor light conversion efficiency of these
organisms and requirement of external light source made this process energy
intensive.

Another two-stage process where bioH2 production process was


integrated with bio-methanation was also considered as a feasible option of
improvement of gaseous energy recovery. Since bio-methanation process is a
well-established process, the implementation of such integrated process holds
a lot of promise. Scaling up of biomethantion process is relatively easy and less
costly. Thus the mixture of bio-hydrogen and bio-methane can be collectively
called under the eponym of “HyMet”.

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Figure 5.1 Gaseous Energy Recovery in Two-stage Integrated Process.

5.2 International status: First review on bio-hydrogen production was


published in Nature Biotechnology as “Bio-hydrogen production deserves
serious funding”. Subsequently, impetus on bio-hydrogen gained momentum in
early 21st century. Major contributors in bio-hydrogen production research were
from United States of America, Canada, Malaysia, Indonesia, Thailand, China
and India. National Renewable Energy Laboratory (NREL), Oak Ridge USA,
funded initial bio-hydrogen studies in USA. Enzymatic bio-hydrogen
productionand bio-hydrogen from waste paper was the major initiative taken by
NREL. Different microbes were discovered in different parts of the world, each
having unique hydrogen production ability. Potential of E. coli in bio-hydrogen
production and its metabolic engineering was explored by Hellenbeck in the
year 2006. Many mesophilic species were explored for hydrogen production.
Enterobacteraerogenes was one of the commonly studied facultative
anaerobes. Obligate hydrogen producing microbes were popular species due
to their higher H2 yields. Thermophilic bio-hydrogen research gained

110
importance by 2004. Thermophilic Clostridium thermolacticumwas reported for
the first time for bio-hydrogen production. Pusan National University, Pusan,
South Korea studied Thermophilic H2 production from glucose at 55-64 oC
using a continuous trickling biofilter reactor (TBR) packed with a fibrous support
matrix. The biogas composition was around 53 % of H2 and 47 +/- 4% of CO2
by volume. The thermophilic TBR is superior to most suspended or immobilized
reactor systems reported thus far. This is the first report on continuous H2
production by a thermophilic TBR system. As time passed on, need of
renewable feedstock for bio-hydrogen production was realized, as for bio-
hydrogen to be considered as renewable energy source, it should be produced
from renewable raw materials only. The concept of waste management coupled
with energy generation was popularized. In 2003, Logan et al. first reported the
possibility of wastewater management along with hydrogen production. Major
surge in bio-hydrogen research was in the year 2004. Dark fermentative H2
production using packed bed reactor was first explored by Logan et al.in 2004.
Up till now significant research has been done on bioH2 production. Many
studies were done in pilot scale units. Internationally very few studies are
available for commercial H2 production. Integration of bio-hydrogen with fuel
cell was first mooted by Marta S. Basualdo in 2012.This concept still needs a
serious consideration since this technology can produce H2 in decentralized
manner for low and medium level electricity needs.

5.3 National Status

In India, first dedicated pilot-scale bio-hydrogen production unit using


distillery effluent was reported by Shri AMM Murugappa Chettiar Research
Centre (MCRC) using defined bacterial co-culture. MCRC has developed a
biological process for generation of hydrogen from sugar and distillery wastes
using the effluents at M/s. E.I.D. Parry Ltd., at Nellikuppam, Tamilnadu. MCRC
has been working on scaling this technology using a 125 m3 bioreactor which
has produced 18,000 liters of total gas per hour with about 60% hydrogen mixed
largely with CO2 and CO. Under the road map of hydrogen economy projected
by Ministry of New and Renewable energy, India (MNRE), few Institutes were
recognized as centre of excellence for bio-hydrogen production. Indian Institute
of Technology Kharagpur was one of the leading institutions involved in bio-
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hydrogen research for more than a decade. IIT Kharagpur demonstrated high
rate of hydrogen production in packed bed reactor configuration in a pilot scale
unit. Its main emphasis was on utilization of organic wastes for energy
generation. Under the leadership of IIT Kharagpur an attempt for
commercialization of bio-hydrogen production was envisioned through the
mission mode project “Biohydogen through Biological Routes” sponsored by
MNRE. IIT Kharagpur is also involved in development of novel and cheap
media composition which would make the product cost effective. It is mainly
focused on the identification of cheap nitrogen sources that can replace the
need of yeast extract and tryptone in the fermentation media. Moreover, it is
also involved in waste to energy concept. Use of distillery effluent, starchy
wastewater and lignocellulosic biomass as substrates arereceiving more
attention. Other collaborators in this group include institutions with varied
experiences in bio-hydrogen production. Indian Institute of Chemical
Technology, Hyderabad has developed rapid screening methodology for
selecting organic waste for bio-hydrogen production. Jawaharlal Nehru
Technological Institute, Hyderabad has developed mixed consortia from
mangroves sludge and hot spring for hydrogen production. The Tata Energy
Research Institute (TERI), New Delhi has a well-established large scale
bioreactor facility for bio-hydrogen production. It is involved in thermophilic H2
production process. Banaras Hindu University and Allahabad University were
chosen for photo-fermentation studies.

Under a Mission Mode Project on Biological Hydrogen Production


sanctioned by MNRE in 2009, two 10 m3 capacity reactors are under installation
at IIT Kharagpur and IICT Hyderabad using distillery effluent and kitchen waste
respectively. These bio-reactors are expected to produce 30-50 m3 of
hydrogen per day. In addition, technical document for setting up an industrial
level reactor will also be developed under this project. In collaboration with IIT
Kharagpur, Naval Material Research Laboratory (NMRL), Mumbai has been
planning to integrate bio-hydrogen with chemical fuel cells for electricity
generation. Other institutions/universities such as Anna University, Institute of
Genomics and Integrative Biology India, New Delhi, etc. are also actively
involved in bio-hydrogen production.
112
The National Institute of Technology, Raipur recently started working on
the development of Microbial Electrolytic Cell for economic and energy efficient
bio-hydrogen production from leafy biomass by electro-hydro-genesis.

Indian Association for the Cultivation of Science, Kolkata is working on


the development of a bio inspired catalyst that would efficiently catalyse
hydrogen evolution and give better understanding about the mechanism of the
hydrogen evolution reaction (HER) by the [Fe-Fe]- Hydrogenase enzymes
which will in turn be helpful in the development of better HER catalyst in terms
of performance and turnovers. Novel hydrogenase model complexes
(catalysts) have been synthesized with a clickable alkyne group. For robust and
successful immobilization of the catalyst onto the electrode surface, the
graphene oxide is modified with aza-amine with azide group to get aza
terminated ITO supported graphene as electrode material and the alkyne end
of the catalyst is clicked onto electrode with Cu(I) as the catalyst. The catalysts
so developed will be used for production of H2 from H2O.

5.4 Action Plan and Suggestions

Hydrogen production through dark fermentation has certain limitations.


Gaseous energy recovery in terms of only H2 might not be sufficient to make
this process commercially viable. Only 20 to 30 % of total energy can be
recovered through H2 production. Even though integration with photo-
fermentation, theoretically, 12 moles of H2 /mole of glucose can be recovered
but due to scaling up problem of photo-fermentation such a two-stage process
is difficult to commercialize. To make the dark fermentative hydrogen
production worthy of commercialization, it should be integrated with the bio-
methantion process. The spent media of the dark fermentation is rich in volatile
fatty acids that would be an ideal substrate for methanogens. Bio-methantion
technologies are well established and are easy to scale up. The integration of
these two processes might lead to 50-60% gaseous energy recovery (Figure
5.2). Most attractive point of such a process is that the reactor used for H2
production could be used for bio-methanation. So, separate reactor is not
required. This would lead to decrease in operational cost of the entire process.

113
Bio-hymet production could be envisioned as renewable source of energy only
when it would be produced from renewable sources. Any organic compound
which is rich in carbohydrates, fats and proteins could be considered as
possible substrate for bio-hymet production.

The advent of technology, such as fuel cell that converts hydrogen to


electricity has infused new life to the implementation of hydrogen based
economy. The path of hydrogen economy would be realized through the
implementation of fuel cell system with the bio-hydrogen production systems.
The efficient fuel cells, that would be able to perform at ambient temperatures
and would require minimum maintenance, are the major advantages towards
their commercialization. Till now very few steps have been taken on
demonstration of integration of bio-hydrogen production with fuel cells. It would
be interesting to see the performance of continuous bio-hydrogen production
when connected to fuel cells.

The bio-hydrogen setup should be put strategically near to those places


where supply of feedstock is cheap and easily available. The electricity
generated by such process could be helpful for rural electrification.
Development of such process would lead to decentralized use of hydrogen.

114
Figure 5.2 Bio-hymet Concept for Maximum Gaseous Energy Recovery

International and National status and gaps of technologies of bio-


hydrogen production routes have been compared in Table 5.1.

Table 5.1 Comparison of Bio-hydrogen Production Routes

Technology International National Technology Suggestions


Status status Gaps
Direct Techno- Techno- Expensive and Development of
Biophotolysis logical logical difficulty in mutant strains
advancement advancemen scaling up of resistant to O2
was not t was not photo- toxicity,
encouraged encourage bioreactor, Development of
inhibition of H2 cheap material of
production due

115
to oxygen construction for
toxicity, photobioreactors
H2 production
rate are not
encouraging
Indirect Technological Technologic Expensive and Development of
Biophotolysis advancement al difficulty in strains that are
was not advancemen scaling up of more efficient in
encouraged t was not photo- starch
encourage bioreactors, accumulation
H2 production and
rate are not fermentation,
encouraging Development of
cheap material of
construction for
photobioreactors
Photo- Scale up pilot Lab scale Expensive and Development of
fermentation plant of 100 L stage difficulty in mutant strains
was scaling up of having low
developed photo- pigment content,
bioreactors, heterologous
Shading effect over expression
of pigments of
produced by clostridialH2ase,
the microbes, Development of
poor cheap material of
photosynthetic construction for
efficiency, photobioreactors
H2 production
rate are not
encouraging

116
Dark Pre Pre Scale up Use of
fermentation commercial commercial problem, customized
stage stage development packed bed
of large scale reactor systems
bioreactors, for high rate of
screening of H2 production,
potential Use of organic
microbes, raw industrial and
material household waste
availability, as feedstock,
Storage of H2, Development of
Purity of H2 cheap gas
produced is scrubbing
not sufficient technologies
to be supplied such as water
to fuel cells scrubbing

117
HYDROGEN PRODUCTION THROUGH
THERMOCHEMICAL ROUTES

118
6.0 Hydrogen Production through Thermo-chemical Route

6.1 Introduction

Thermo-chemical splitting of water to produce hydrogen was considered


as one of the potential methods which can be scaled up for large scale
generation. In this context to provide quality heat for the process use of energy
sources such as nuclear and solar etc., was considered, as these sources
were being envisaged by these sources for input heat were attracting
worldwide attention. With regard to the choice of likely process routes for
development the iodine-sulfur (I-S) and copper-chlorine (Cu-Cl) cycles were
considered having potential for scale up hydrogen generation, however, the
process was complex and required multi-disciplinary approach to develop
suitable technology. Currently globally, these cycles are at different stages of
development and are yet to be commercially proven.

The iodine-sulfur (I-S) cycle is one of the most promising and efficient
thermo-chemical water splitting technologies for the massive production of
hydrogen. As competing processes, other options such as HTSE, hybrid sulfur
cycle and Cu-Cl cycle are also being studied for the production of hydrogen.

Schematic of thermo-chemical water splitting cycle is shown in Figure


6.1.

Figure 6.1: Schematic of thermo-chemical water splitting cycle

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Schematic and conditions of a typical Cu-Cl closed loop is shown in
Figure 6.2 and Figure 6.3.

Figure 6.2: Schematic of a typical Cu-Cl closed loop

Figure 6.3 Schematic and conditions of a typical I-S closed loop

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6.2 International Status

Integrated I-S loop cycle has been demonstrated in the following


countries:

Country Year

USA : 1980

European Union : NA

Canada : NA

Japan : 2004

South Korea : 2009

China : 2010

India : 2013

Country wise status and plan on I-S process is discussed below.

6.2.1 United States of America: The Nuclear Energy Research Initiative


(NERI) was established with the goal to demonstrate the commercial scale
production of hydrogen using nuclear energy by 2017. The modular helium
reactor (MHR) has been suggested as the Generation IV reference concept for
nuclear hydrogen generation on the basis of either the I-S thermo-chemical
cycle or HTSE.As part of the national hydrogen research programme, the US
DOE created the Nuclear Hydrogen Initiative (NHI) with the objective to
advance nuclear energy for the support of a future hydrogen economy. The
frame was widened with the start of the International Nuclear Energy Research
Initiative (I-NERI) for bilateral or multilateral international cooperation
supporting R&D activities for Generation IV reference concept of the NHI and
the advanced fuel cycle R&D. The objectives of I-NERI include the development
and demonstration of technologies which enable the nuclear power based
production of hydrogen by non-fossil based water splitting hydrogen production
processes. The I-S cycle development project has been taken up by an
international consortium led by General Atomics and comprising also the

121
Sandia National Laboratory (SNL), USA and the French Commissariat of
Atomic Energy (CEA). Between 2003 and 2008, the US DOE promoted nuclear
hydrogen programmes in the USA which concentrated on:

- Hybrid sulphur thermo-chemical cycle development at the Savannah


River National Laboratory (SRNL);
- High temperature electrolysis development at the Idaho National
Laboratory (INL);
- I-S process development at the General Atomics.

Through a down selection activity led by INL and carried out in 2009to
systematically evaluate and select the best technology for deployment with
NGNP (Next Generation Nuclear Plant), the HTSE was adjudged as the most
appropriate advanced nuclear hydrogen production technology that presents
the greatest potential for successful deployment and demonstration at NGNP.
But it was also stated that both HyS and I-S processes exhibit attractive
attributes for hydrogen production, which supports not abandoning either
technology for future consideration.

6.2.2 European Union: High Temperature Thermo-chemical Cycles


(HYTHEC) was a STREP (Specific Targeted Research Project) with six
partners starting in 2004 and running over almost four years. Its main objective
was to evaluate the potential of thermo-chemical processes, focusing on the I-
S cycle to be compared with the Westinghouse hybrid (HyS) cycle.

Nuclear and solar were considered as the primary energy sources, with
a maximum temperature of the process limited to 950°C. A preliminary
reference sheet of the I-S cycle has been conceptualized and optimized to a
‘reference’ flow sheet by coupling to a single 600 MW indirect cycle VHTR
(Very-High-Temperature Reactor). The reactor, fully dedicated to hydrogen
production, is designed as a ‘self-sustaining concept” delivering both electricity
to meet the plant’s own total power demand and heat to run the Hydrogen
production process at a rate of 110 t/d and an overall plant efficiency of ~35%.

A preliminary evaluation of the hydrogen production costs based on


solar, nuclear and hybrid operation led to following results: small plants are

122
powered most favorably by solar energy, while nuclear plants are most
economical at high power levels (> 300 MW(th)); hybrid systems may have their
niche in the midrange of 100 to 300 MW(th).

The 2015 targets defined for high temperature thermo–electrical–


chemical processes with solar–nuclear heat sources are reduction of CO2
emissions for fossil reforming by more than 25% and hydrogen production cost
of less than €2/kg

HycycleS is a new European project that started in 2008 involving nine


European and four associated international partners. Following in the footsteps
of the HYTHEC project, the three year project HycycleS (2008–2010) was
aimed at the qualification of ceramic materials and reliability of components for
the essential reactions in thermo-chemical cycles. The focus was on the
decomposition of sulphuric acid as the central step of the hybrid-sulphur (HyS)
cycle and the I-S cycle.

The final aim was to bring thermochemical water splitting closer to


realization by improving the efficiency, stability, practicability and economic
viability.

6.2.3 Canada: In close cooperation with the Argonne National Laboratory


(ANL) in the USA and the University of Ontario, Institute of Technology (UOIT)
and other universities, Atomic Energy of Canada Limited (AECL) is
investigating the copper–chlorine family of thermo-chemical cycles with
maximum temperatures that can be provided by the CANDU Mark 2 SCWR
(Super Critical Water Reactor). But apart from this cycle, AECL research
includes investigating the use of direct resistive heating of catalysts for SO 3
decomposition in the I-S process.

6.2.4 Japan: In recent years, JAEA has undertaken extensive R&D on the
thermo-chemical cycles based on the UT-3 and I-S processes for H2
production. It is most advanced in the study of the I-S cycle, with the successful
operation of a bench-scale facility having achieved a hydrogen production rate
of 30 NL/h in continuous closed cycle operation over one week. This process is

123
now considered the prime candidate for the demonstration of nuclear assisted
hydrogen generation.

The next step, which started in 2005, is the design and construction of a
pilot plant with a production rate of 30 Nm3/h of H2 under the simulated
conditions of a nuclear reactor. While the efficiency was ~10% for the bench-
scale plant, the goal for the pilot plant is ~40%.

As a backup hydrogen production method, thehigh temperature


electrolysis has also been investigated, but has not yet gone beyond lab-scale
testing (Figure 6.4)

Figure 6.4: Plan of proposed R&D activities

6.2.5 South Korea: The projected hydrogen economy in the Republic of


Korea requires that 25 % of total hydrogen be supplied by advanced nuclear
reactors by 2040. This amount of hydrogen is around 3 Mt/year and it is
expected to be produced in 50 nuclear hydrogen units. The nuclear policy in
Korea is led by its Atomic Energy Commission (AEC) which collaborates with
the Korean Institute of Energy Research (KIER), Korean Atomic Energy
Research Institute (KAERI), and the Korean Institute of Science and
Technology (KIST).

Korea launched its nuclear hydrogen program in 2004 with two targets
as under:

(1) Generation of hydrogen for fuel cell applications such as electricity


generation, passenger vehicles, and residential power and heating,
and

124
(2) Lowering hydrogen costs and improving efficiency of the related
processes.

The following nuclear hydrogen programs were approved by AEC:

 NHDD—“Nuclear Hydrogen Development and Demonstration” program


which started after 2011 and go up to 2030

(Milestones: 2022—prototype construction, 2026—technology


demonstration, 2030—technology commercialization).

 Hydrogen production program with two phases:

– I: Hydrogen production from natural gas, petroleum naphtha, and


electricity (ending in 2025)

– II: Hydrogen production from coal, nuclear energy and renewable


energy (ending in 2040)

 For the reference case design of the VHTR-H2 system, an underground


VHTR reactor of 200 MW thermal output will be coupled with an I-S
cycle to generate hydrogen from water

 I-S cycle development. It runs in parallel with NHDD (Nuclear


Hydrogen Development and Demonstration) and GIF (Generation IV
International Forum) programs and it has two phases:

– I: 2006–2011 for development of key technologies

– II: 2012–2017 for performance improvement and validation

I-NERI-Korea participates in the I-NERI program of DOE with joint


projects with the Idaho Nuclear Laboratory and Argonne National Laboratory.
Korea also established two major joint research agreements, namely:

(1) Nuclear Hydrogen Joint Development Centre (NHDC) with General


Atomics,

(2) Nuclear Hydrogen Joint Research Centre with China (via INET).

125
6.2.6 China: R&D on hydrogen production through water splitting using HTGR
as a process heat source was initiated in 2005 as one component of China’s
HTR-PM (High Temperature Reactor – Pebble Module) demonstration project.
Both the I-S thermo-chemical cycle and high temperature steam electrolysis
have been selected as potential processes for nuclear hydrogen production.

Beginning with preliminary studies, the R&D programme, now part of the
HTR-PM project, will be conducted in phases as under:

– Phase one (2005–2009): verification of nuclear hydrogen production;

– Phase two (2010–2012): bench-scale testing;

– Phase three (2013–2020): pilot-scale testing, R&D on coupling


technology with reactor, nuclear hydrogen safety;

– Phase four (after 2020): commercialization of nuclear hydrogen


production.

Other countries such as Italy, South Africaand France are also working
on different thermo-chemical cycles including I-S and Cu-Cl processes.

6.3 National Status

6.3.1 Work Done by Bhabha Atomic Research Centre

R & D for the Production of Hydrogen by Splitting Water using


nuclear Heat: Successful feasibility demonstration of cyclic operation of the
process provided fillip to intensify the development effort for tackling variety of
issues like efficient integrated process schemes, equipment, materials and
analytical techniques etc. Efforts are also on to demonstrate the operation
under prototypical conditions to generate data for assessing the viability of the
process for large scale deployment.

The road map for I-S process development is shown in Figure 6.5.

126
Material Studies

Experimental Research Design and

Validation and Development Simulation

Bench Scale Demonstration

150 Lit H2/Hr

Pilot Scale Demonstration

3
13 M H2/Hr

Demonstration with 600 MWth HTR

3
80,000 M H2/Hr

Figure 6.5: Road Map for I-S Process

High temperature reactor based iodine-sulfur (IS) thermo-chemical cycle


offers a promising approach to the high efficiency production of large volumes
of hydrogen from water.

127
The I-S cycle consists of three sections as expressed in following
equations:

SO2 + I2 + 2H2O = 2HI + H2SO4 (25 – 120oC) -------- (i)


H2SO4 = H2O + SO2 + 0.5O2 (800 – 900 oC) -------- (ii)
2HI = H2 + I2 (350-450 o C) --------- (iii)

The Equation (i) is the Bunsen reaction where water is split by sulphur-
dioxide (SO2) & iodine (I2) at relatively low temperature. Equation (ii) is the
highest temperature reaction of the cycle where high temperature is achieved
using Nuclear (High Temperature Reactors) / Solar heat. Equation (iii) is
hydrogen iodide (HI) decomposition reaction, where HI is decomposed into
hydrogen (H2) & iodine by heating at intermediate temperatures. The I-S
process is a closed loop process as the chemicals SO2 & I2 are recycled back
to the system, water & heat are the only input and the output is hydrogen (H 2)
as product and oxygen (O2) as the by-product.

Initially Bunsen reaction studies were carried out at Chemical


Technology Division of BARC to study the overall reaction kinetics. A sketch of
the apparatus used in the experiments of SO 2 chemical absorption in water
containing iodine is shown in Figure 6.6.

128
Figure 6.6: Schematic of Bunsen Reactor Setup

The experimental results for the SO2 absorption into aqueous solution
containing iodine are shown in Figure 6.7&6.8.

129
Figure 6.7: SO2 Inlet Partial Pressure Vs Absorption Rate

130
Figure 6.8: Batch Time (Experimental) Vs Batch Time (Calculated)

The other reactions of I-S process require catalyst. In house catalysts are
developed and tested in BARC. Chemistry Division, BARC has developed
catalyst for sulfuric acid decomposition and Heavy Water Division, BARC has
developed catalyst for HI decomposition reaction. The test facility and
characterization is shown in the Figure 6.9& 6.10.

131
HI Catalyst Characterized and tested at 350°C

Catalyst HI decomposition
temperature fraction

%
423 K 0.4

523 K 3 %

623 K 14 %

Figure 6.9: HI Decomposition Test Facility and Catalyst Characterization

Fresh catalyst
Used catalyst

SO2 yield: as a function of acid flux

Cr0.2Fe1.8O3 more
active than Fe2O3

Figure 6.10: Catalyst Characterization for Sulfuric Acid Section

132
As a first step to demonstrate the I-S process and feasibility of closing
the loop, Chemical Technology Division, BARC has initiated the efforts for the
same. The I-S closed loop system has been worked out in glass/quartz
equipment, operating at atmospheric pressure and prototypical temperature
conditions.

Figure 6.11: Layout of Closed Loop Figure 6.12: Boxed up Arrangement


Glass System (CLGS) for CLGS.

The closed loop glass setup (Figure 6.11 and Figure 6.12) is divided into 3
sections as given below:

1. Bunsen Section
a. Bunsen Reaction
b. Liquid-Liquid Separation
c. Acid Purification

2. Sulfuric Acid Section


a. Sulfuric Acid Concentration
b. Sulfuric Acid Decomposition

133
3. HI Section
a. HIx Distillation
b. HI Decomposition and HI Recovery
c. Hydrogen Purification

The pictures of various equipment/systems during operation are given in


Figures 6.13 to 6.17.

Interface of two phases

Figure 6.13: Bunsen Reactor during Operation & Liquid- Liquid Phase
Separation

134
Figure:6.14 SO3 Decomposition Experiment

Figure 6.15: HIx Distillation Equipment

135
Fig 6.16: Sulfuric Acid Concentrator and Decomposer

Fig 6.17: HI Decomposition System

136
The closed loop glass system is operated continuously for a period of 20
hours at the hydrogen production rate of 30 lph. India is the 5 th country in the
world to achieve I-S closed loop operation in glass system, after USA, Japan,
China and South Korea. The Chemical Technology Division, BARC is also
pursuing the studies on Bunsen reaction and phase separation at high
pressures in Metallic Bunsen System (MBS) and sulfuric acid decomposition
studies in High Pressure Sulfuric acid Decomposition System (HSDS). This will
give substantial inputs for the closed loop metallic system at higher pressures
(Figure 6.18 and Figure 6.19).

Figure 6.18: Reactor & Separation System

137
Figure 6.19: Feed System

Schematic of Operations Envisaged in Integrated Reactor of HSDSis


given in Figure 6.20.

138
Figure 6.20: Schematic of Operations Envisaged in Integrated Reactor
of HSDS

Cut View of Integrated Reactor of HSDSis shown in Figure 6.21.

139
Figure 6. 21: Cut View of Integrated Reactor of HSDS

Heavy Water Division, BARC is working on reactive distillation route to


produce hydrogen by splitting of HI acid. Desalination Division, BARC is
working on alternate route for HI decomposition section studies using electro-
electro dialysis for concentration and membrane reactor for decomposition of
HI to produce hydrogen. Alumina Supported Silica Membraneis shown in Figure
6.22.

Figure 6.22: Alumina Supported Silica Membrane

140
Membrane Reactor for HI Decompositionis shown in Figure 6.23.

Figure 6.23: Membrane Reactor for HI Decomposition

Chemical Technology Division, BARC has taken the initiative to carry out
the I-S process demonstration in engineering material of construction. For that
purpose Atmospheric Metallic Closed Loop (AMCL) is being taken up by the
division. The P&ID is ready for the setup. Process designing for the setup is
underway.

The Chemical Engineering Division, BARC has started working on 3-


step Copper Chlorine (Cu-Cl) process. The Chemistry Division, BARC along
with Chemical Technology Division, BARC have started working on Hybrid
Sulfur (Hy-S) process.

6.3.2 Work Done by ONGC Energy Centre

ONGC Energy Centre (OEC) is working on sections of I-S process


through IIT-Delhi, CECRI Karaikudi. ONGC is working on Cu-Cl process

141
through ICT-Mumbai. They have demonstrated proof of principle experiments
and are going ahead with design to demonstrate 25 NL/h Hydrogen production
capacity lab-scale unit. OEC started several sub-projects in collaboration with
some of the leading research institutions for research on the initial proof of
principle process development, which were to be followed up by further
development work to scale up the process.

In case of Cu-Cl cycle, the originally proposed five step cycle by Argonne
National Laboratories, USA has been modified and established. Several novel
designs especially in electrochemical section were made to improve the
system. The energy calculations showed that there is no additional energy
requirement in the modified cycle as compared to originally reported ANL cycle
and also reconfirmed that it is a non-catalytic process. Efforts made to cross-
confirm the data generated in electrochemical cell parameters generated in the
studies at ICT, Mumbai confirmed further that the data is in the range reported
in a parallel project study undertaken at CECRI, Karaikudi.

Based on proof of concept studies, a conceptual closed-loop Cu-Cl


process for hydrogen generation@ 25L/h was developed to design and
fabricate a metallic lab-scale engineering process facility with indigenous
sources. A model metallic reactor fabricated initially helped freezing the design
and fabrication of hydrogen generation, CuCl2 hydrolysis, decomposition and
oxygen generation reactors. This approach has resulted in considerable time
and cost saving in the project besides instilling confidence in indigenous
capability development. A spray drier system was designed and fabricated for
drying CuCl2 to produce very fine and pure CuCl2 powder. The electrochemical
set up required in the integrated closed-loop operation was developed using
the data generated through series of electrochemical cells of varying capacities
viz., 2A, 5A, 12A finally leading to design/fabrication of 60 A stack with improved
designs and indigenous fabrications using commercially available materials
viz., electrodes, membranes, cell materials etc. During the studies, a novel
method was developed for complete conversion of CuCl after electrolysis

142
reaction based on which a suitable process gadget was designed to enable
trouble free closed-loop operation of the cycle.

In the integrated facility indigenously developed for closed-loop


operation all reactors viz., hydrogen, oxygen generation, CuCl2-hydrolysis and
decomposition along with electrochemical system were individually checked for
their performance and found to be working as per desired specifications.
Several facilities required for transfer of solids between individual units were
developed with a newly designed and fabricated flexible screw conveyor along
with provision for liquid transportation between various units across the loop.

The engineering scale process plant, now installed at ICT, Mumbai is


proposed to be shifted to OEC project site in Panvel.

In the I-S cycle, electrochemical Bunsen reaction and electro dialysis


technique for HI enrichment were established at lab-scale with minimum cross-
contamination levels across membrane and without any side reactions. Model
codes were developed in simulation work undertaken to address scaling up and
issues related to integration with the remaining sections of the cycle. In H2SO4
decomposition section of this cycle, a cost-effective, high performing and highly
stable non-Pt-based catalyst system was developed and tested in an in-house
designed, fabricated pilot scale metallic reactor system equivalent to 150 L/h of
H2 generation. Performance of selected catalyst system under lab stage was
evaluated further in this reactor at 900±50°C and 10-15 bars and found to be
highly satisfactory. Mechanistic studies on catalytic decomposition of
H2SO4were completed. In HI decomposition section, a highly performing
transition metal based catalyst system was developed that yields conversion
being close to equilibrium values at 500-550°C. The catalysts were stable for
over 100 hrs. Through a short study techno-economic feasibility of open loop I-
S cycle was also evaluated.

The research work performed by OEC and the collaborating institutions


have thus been able to successfully establish the proof of concept for
developing both Cu-Cl and I-S cycles and has led to setting up metallic closed

143
loop lab scale engineering facility in Cu-Cl cycle. These accomplishments are
major steps in technology development for these two processes and achieved
for the first time in the country.

ONGC Energy Centre has been able to successfully develop the


indigenous process, several process equipment and trained manpower in the
country. The collaborative R&D on both cycles has resulted in
publications/presentations of 46 technical papers in national / international
conferences and Journals. The research work has also resulted in filing of 7
Indian patents. In addition, keeping in view the recent international
developments in research in Cu-Cl cycle, which is considered most potential for
scale up, OEC has filed 3 international patents related to Cu-Cl cycle in six
countries (UK, USA, Canada, Japan, Korea and China). In the last few months
USA and Japan have accepted our patent application on multi-step Cu-Cl cycle
and patent has been granted in these two countries.

Scheme of R&D activities related to I-S cycle at OEC, Mumbai is given


in Figure 6.24.

144
Figure 6.24 Scheme of R&D activities related to I-S cycle at OEC, Mumbai

6.3.3 Highlights of the R&D Work

The OEC had planned to implement the project work in two distinct
stages viz., establish the proof of concept, followed by the lab-scale
development in association with collaborative research group for the selected
process route and thereafter, setting up of the pilot plant at OEC premises at
appropriate time to transform the developed knowledge and expertise to further
scale up. In this context, a total of 16 collaborative sub-projects and 1 in-house
project were undertaken as per details given below:

145
 8 sub-projects to establish proof of principle of both the Cu-Cl and I-S
cycles

 3 sub-projects to establish alternate paths for these cycles

 1 sub-project to establish closed-loop operation of Cu-Cl cycle

 1 sub-project to establish techno-economic feasibility of open-loop cycle

 3 sub-projects to addresses various issues related to simulations /


modeling, scale up / bridging the gaps for achieving closed loop
operations

 1 In-house sub-project on simulation of I-S and Cu-Cl Cycle

The details of various collaborative sub-projects / in-house projects undertaken


in line with the scope of the work are given in Table 6.1:

Table 6.1 List of Collaborative Sub- projects in I-S and Cu-Cl Cycles

1 Proof of Principle of Cu-Cl Cycle (3 Sub-projects)


Sl. Title of the Project Institute Amount Amount Status
No Duration / Start committed Released
Date / End Date (Rs in Lakh) (Rs in
Lakh)
1.1 Preliminary ICT, 80.40 80.40 Completed
process analysis Mumbai
for copper-chlorine
(Cu-Cl)
thermochemical
hydrogen
production process
42 months /
01.07.07 /
31.12.10
1.2 Experimental data CECRI, 6.23 6.23 Completed
collection on Karaikudi

146
oxidation of CuCl
and recovery of Cu
10 months /
28.04.08 /
28.02.09
1.3 Studies on the CECRI, 10.70 10.70 Completed
electrolysis of Karaikudi
CuCl& recovery of
Cu – Energy
Optimisation –
Phase II
9 months /
27.02.10 /
26.11.10
Sub Total-1 97.33 97.33
2 Proof of Principle of I-S Cycle (5 Sub-projects)

2.1 Studies on the IIT-Delhi 107.74 107.74 Completed


catalytic
decomposition of
Sulfuric acid in the
I-S process for
Hydrogen
production
57 months /
11.01.08 /
11.10.12
2.2 Studies on IIT-Delhi 102.77 102.77 Completed
Bunsen reactor for
production of
sulfuric acid and HI
using
electrochemical
cell48 months /

147
21.01.08 /
21.01.12
2.3 Concentration of IIT-Delhi Completed
HIx Solution Using
Electroelectrodialy
sis
48 months /
21.01.08 /
21.01.12
2.4 Catalytic IIT-Delhi 45.63 45.63 Completed
Decomposition of
Hydrogen Iodide
(HI) into I2 and H2
57 months /
29.09.08 /
30.06.13
2.5 Development of IIT-Delhi 31.64 31.64 Completed
Hydrogen
Transport
Membrane
Reactors for
Hydrogen Iodide
decomposition
followed by
hydrogen removal
36 months /
29.09.08 /
28.09.11
Sub Total -2 287.78 287.78
3 Simulation of I-S Cycle (1 Sub-project)

3.1 Simulation studies Dr. 4.09 4.09 Completed


on the sulphur- Babasahe
iodine (I-S cycle) b

148
closed loop Ambedkar
thermochemical Univ.
process for Lonere,
production of Maharasht
hydrogen using ra (BATU)
suitable simulation
and application
software
24 Months /
15.12.09 /15.12.11
Sub Total -3 4.09 4.09
4 Design, Installation and Lab Scale Demonstration of Closed Loop
Operation (1 Sub-Project)
4.1 ICT – OEC ICT, 767.87 767.87 Completed
Process for Mumbai
Copper-Chlorine
(Cu-Cl) Thermo-
chemical Hydrogen
Production –
Phase-II
30 months /
23.02.12 /
22.08.14
Sub Total -4 767.87 767.87
5 Additional Studies / Alternate paths in Cu-Cl Cycle and I-S Cycles
Cu-Cl Cycle (1 Sub-Project)
5.1 Electrolysis of CECRI, 25.91 25.91 Completed
CuCl – HCl system Karaikudi
for the preparation
of CuCl2& H2 - A
Feasibility Study

149
23 months /
05.04.10 /
04.03.12
Sub Total -5 25.91 25.91
I-S Cycle (2 Sub-Projects)
5.2 Experimental ICT, 2.20 2.20 Completed
Studies for Mumbai
Reaction of Metals
with HI 1.5
months / 10.01.11 /
23.02.11
5.3 Experimental ICT, 9.85 9.85 Completed
Studies for Mumbai
Reaction of Metals
with Hydroid Acid
&Detailed Studies
on Decomposition
of Certain
Transition Metal
Iodides
5 months /
14.09.11 /
13.02.12
Sub Total -6 12.05 12.05
Techno-economic Studies on Partially Open-loop I-S Cycle (1 Sub-
project)
5.4 Techno Economic CSIR-IIP, 13.47 13.47 Completed
Feasibility of Open Dehradun
Loop Thermo-
chemical S–I cycle
of H2S split for
Carbon-Free
Hydrogen

150
Production in
Petroleum Refinery
4 months /
10.01.12 /
09.05.12
Sub Total -7 13.47 13.47
Additional studies to address scaling up issues in I-S Cycle (2 Sub-
projects)
5.5 Modeling of IIT, Delhi 10.86 7.61 Completed
Membrane
Electrolysis Cell for
Bunsen Reaction
and Electro-
Electrodialysis Unit
for concentration of
Hix Solution
9 Months /
08.02.13 /
07.11.13
5.6 Mechanistic IIT, Delhi 17.48 11.19 Completed
Studies on the
Catalytic
Decomposition of
Sulfuric Acid in the
I-S Cycle for
Hydrogen
Production
12 months /
25.02.13 /
24.02.14
Sub Total -8 28.34 18.80
Grand Total (Sub 1236.84 1236.84
Total 1-8)

151
6.0 Simulation Studies OEC - - Completed
on (In-house)
Thermochemical
Iodine-Sulfur&
Copper-Chlorine
Cycle for Hydrogen
Production
5 Years / May
2010 – Sept. 2015)

The linkage between various sub-projects is shown in Figure 6.25.

Figure 6.25 Linkage between various sub-projects

152
6.3.4 Highlights of the R&D Work

(i) Cu-Cl Cycle

 The proof of principle experiments for all reactions of Cu-Cl cycle have
been successfully completed, using a combination of thermo-chemical
and electrochemical routes. This has resulted in development of a ICT-
OEC modified and patented Cu-Cl cycle.

 In modified cycle; hydrolysis step was suitably modified to overcome


problems faced in formation and characterization of copper oxychloride.

 Detailed thermo-chemical calculations of the modified route indicated


that there is no excess heat demand in the modified route.

 Analytical test methods and procedures to facilitate trouble free


operations during closed-loop operations have been standardized

 In the electrochemical reaction, based on a novel cell design 2A cell has


been fabricated. It resulted in low cell voltage of 0.7 ± 0.1V along with
>90% current efficiency, 5-10μ particle size of copper generated in the
process under operating conditions that could be directly used as feed /
reactant in the Cu-HCl-Hydrogen generation reaction.

 Kinetic studies for all reaction steps of the Cu-Cl cycle have been
performed and from the activation energy value it has been confirmed
that this is a non-catalytic reaction process.

 Based on the experimental data generated in the proof of principle


experiments, a basic flow sheet has been initially developed for the
closed-loop experiment to generate hydrogen @ 2.73 liters per hour
(lph), subsequently revised to 5 L/h and finally to @ 25 L/h to align with
market supply of various process gadgets.

 Detailed studies on flow simulations, cold flow experiments etc., have


been performed to finalize the reactor configuration.

 A 5 Ampere electrochemical cell has been fabricated. The performance


of the cell showed that cathodic current density of 133mA/cm 2 at a cell
voltage of 0.7 ± 0.1 V.

153
 Further scale up to a 12A electrochemical system was done with
improved design. A cathodic current density of 187 mA/cm2 at 0.7 ± 0.1V
could be achieved.

 Aerial oxidation of CuCl solutions has been found to be a major issue in


electrochemical step. A novel method has been developed for complete
conversion of CuCl after electrolysis reaction. Accordingly a suitable
process gadget has been designed and fabricated for onsite application
during closed-loop operation.

 Based on the outcome of electrochemical studies, a 60A stack has been


developed to integrate with thermal reactors.

 Initially a representative metallic model reactor system for hydrogen


generation @ 25 L/h has been designed and fabricated to study all
thermal reactions based on which design /fabrication of all the other
reactors viz., hydrolysis, decomposition and oxygen generation reactors
has been taken up. This approach has helped in reducing the cost and
meeting the project time line.

 Hydrogen generation @ 27 L/h in the hydrogen generation reactor has


been achieved under specified operating conditions.

 Hydrolysis reactor has been operated at 450°C and the reactor is


behaving ideally. When the oxygen generation reactor was run at 500°C;
the experimental data indicated oxygen production @ 13.7 L/h.

 CuCl2 decomposition reactor has yielded fine CuO powder and Cl2 gas
at 475oC.

 Experimental runs on commissioned spray drier system have been


performed for drying CuCl2 at 140°C and the units have delivered desired
results. Data generated on the dryer unit have resulted in encouraging
results in which very fine and pure CuCl2 powder has been obtained as
confirmed by UV-Visible spectroscopy, iodometric and titrimetric
methods.

 Simulations / Modeling studies in Cu-Cl cycle have been performed on


Aspen Plus simulator. Flow sheets for individual sections/ process

154
leading to integrated system / process have been developed. Energy
balance and mass balance has been calculated and compared with
theoretical values.

 Proof of principle of alternate electrochemical reaction pathway has been


established at CECRI, Karaikudi. The studies have shown that 100%
efficiency at low cell voltage (0.8V) and 250A/m2 current density at 80°C
under ambient pressure conditions could be achieved. Based on lab
studies, a 25A scale electrochemical cell has been designed to work
under specified operating conditions. The study has enabled further
modification in Cu-Cl cycle in reducing number of steps/ processes.

 Solid handling problems in various sections for transfer of solid copper


and copper oxide between individual units have been achieved with a
newly fabricated flexible screw conveyor based on a novel ICT- design.
Provision for liquid transportation between various units across the loop.
Facility for Integration of various individual reactors leading to form a
closed-loop has been completed.

The details the reactions in ICT-OEC route of Cu-Cl cycle is given in


Table 6.2:

Table 6.2: The ICT-OEC route of Cu-Cl cycle

S. No. Reactions ICT-OEC route : Cu-Cl Cycle

1 Hydrogen Generation 2Cu(s) + 2HCl(g) → 2CuCl(l) + H2(g)


2 Electrochemical 4CuCl(l) → 2CuCl2(aq) + 2Cu(s)
3 Drying 2CuCl2(aq) → 2CuCl2(s)
4 Hydrolysis CuCl2(s)+H2O(g) → CuO(s)+ 2HCl(g)
5 Decomposition CuCl2(s) → CuCl(l)+½ Cl2(g)
6 Oxygen Generation CuO(s)+½ Cl2(g) → CuCl(l) +½ O2(g)

155
(ii) I-S Cycle

 Proof of concept of complete cycle has been established using a


combination of electrochemical and thermo-chemical reactions.

 Bunsen reaction has been successfully carried out at lab-scale using a


two-compartment membrane electrolysis cell consisting of graphite
electrodes and Nafion-117 membrane.

 Excess iodine used could be reduced by 75% compared to direct contact


mode. The current efficiency close to 100% has been achieved and
absence of side-reactions has been confirmed

 Cross-contamination has been found to be much lower than the direct


contact mode; loss of sulfate ions to HIx section (~12%) has been
noticed due to limitation on membranes.

 Electro-Electro Dialysis (EED) technique has been established and


demonstrated in lab-scale to concentrate HIx solution beyond its
azeotropic concentration.

 Only Nafion membranes have been found useful In electrochemical work

 Model codes for simulation work on electrochemical Bunsen and EED


sections for I-S cycle has been successfully developed to address scale-
up issues and integration with the remaining sections of the cycle.

 In H2SO4 decomposition study, a lab-scale model quartz reactor system


has been designed and assembled to screen various catalysts. Several
transition metal/metal oxide based catalysts viz., Fe 2O3/Al2O3,
Fe2O3/ZrO2, CoO/Al2O3, CuO/ZrO2, Fe2O3, Cr2O3, CuFe2O4, ZnCr2O4,
FeCr2O4, NiCr2O4, CuxCr3-xO4 etc. were screened and relative
performance of some of these catalysts were determined.

 Detailed kinetic and thermodynamic studies have been performed on


promising catalyst systems. Based on the studies, a cost-effective, high
performing and highly stable non-Pt-based catalyst system for catalytic
decomposition of H2SO4 has been developed.

 For the decomposition of H2SO4, High Temperature-High Pressure


(HTHP) bayonet type metallic reactor for pilot scale operation equivalent

156
to 150 mph in terms of H2 generation was successfully designed,
fabricated & commissioned at IIT-Delhi using in-house expertise and
indigenous resources.

 The proven catalyst system under lab-stage evaluation has been further
evaluated under high pressure (10-15 bars) - high temperature
(900±50°C) experimental conditions for 24hrs. Results of this study have
indicated encouraging trend with the conversions in the order of ~90%.

 The developed catalyst has been found to be stable for longer durations
under the actual operating conditions. It is relatively cost-effective and
superior to the available products reported. Data generated for high
pressure high temperature (HP-HT) operation is suitable for onsite
application and integration in closed loop operation.

 Mechanistic studies on catalytic decomposition of H2SO4 have been


completed to address scaling up issues and integrate this step with
remaining sections of the cycle.

 A lab-scale model quartz reactor system has been designed and


assembled to screen various catalysts under operating conditions of HI
decomposition.

 Several transition metal (Fe, Co, Ni) based catalysts and mixed metal
catalysts like Pt-Ni combinations have been synthesized and screened
over various catalyst beds viz., Alumina, Vanadia, Molybdina, Zirconia,
Activated Carbon, and SiC in the temperature range 400-550°C.

 The generated data have indicated that nickel based catalysts worked
better with the conversion being close to equilibrium values (~22%) at
500-550°C.The catalyst deactivation studies performed over 100 hrs
also indicate a marginal decrease of nickel based system activity to
~20% at the end of the test.

 Studies on alternate pathways in I-S cycle for HI decomposition involving


Metal – HI reaction has also been established to explore the possibility
of ease of operation by avoiding less energy efficient distillation
processes.

157
 Techno economic feasibility of open loop thermo-chemical I-S cycle has
been successfully evaluated.

 Simulation / modeling studies of I-S open/closed-loop cycle and alternate


routes have been successfully carried out using Aspen simulator.
Individual flow-sheets have been developed leading to Integration of
different sections with one another. Energy requirement based on
theoretical basis and efficiency calculations has been performed.

Cu-Cl Cycle, I-S Cycle and I-S Cycle Open Loop for Hydrogen
Generation are compared in Table 6.3.

Table 6.3. Comparison of Cu-Cl Cycle, I-S Cycle and I-S Cycle Open Loop
for Hydrogen Generation

Sl. Attributes Cu-Cl Cycle I-S Cycle I-S Cycle


No. Open Loop
1 No. of Steps 6 Step Process 3 Step Process 2 Step Process
(Combination of (Combination of (Combination of
Electrochemical & Electrochemical & Classical Bunsen
Thermochemical Thermochemical & Hi
Reactions) Reactions) Decomposition
of HI with
Reactive
Distillation step)
2 Establishment Proof of concept Proof of concept Collaborative
of Proof of for all 6 steps for all 3 steps Work is in
Concept have been have been Progress
established (OEC established (OEC
and Collaborators) and
Collaborators)
3 Maximum 550°C 900°C 500°C
Temperature (O2 Generation) (H2SO4 Section) (Oxidation of
Encountered H2S)

158
4 Total Energy 668 kJ/molH2 675 kJ/molH2 562 kJ/mol
Requirement

5 MoC Relatively Lower Higher Relatively Lower


Temperature (Max Temperature Temperature
5500 C) (Max 9000 C) (Max 5000 C)
6 Catalyst Not catalytic Catalysts required Catalysts
process for both H2SO4 required for HI
and HI Decomposition
Decomposition
7 Separation Solid – Liquid Liquid – Liquid Separation by
Liquid – Liquid Separation of Reactive
Gases Separation complex distillation in HI
azeotrope decomposition
step
8 Membranes Imported Imported Not Required
(Required in (Required for EBR (when Classical
electrochemical and EED steps) Bunsen Reaction
step) is followed)

9 Electrodes Required Required Not Required


(when Classical
Bunsen Reaction
is followed)
10 Process 5 Step = 52.57% Using Reactive 51%
Efficiency 4 steps distillation = 51%
 Nuclear Energy: (GA)
Generation IV
Supercritical EBR & EED (Ideal
Water Cooled case) = 46.5%
Reactor (SCWR)
= 51%

159
Solar Energy:
Using molten salt
= 70%
3 Step = 40%
11 By-products / No waste as all No waste as all H2SO4 which can
Wastes products are products are be sold for
recycled recycled industrial use

7. Indigenous Equipment Development

Hydrogen Generation Reactor System is shown in Figure 6.26.

Figure 6.26: Hydrogen Generation Reactor System

12A Electrochemical Cell with perforated Pt plate as anode is shown in


Figure 6.27.

160
Figure 6.27: 12A Electrochemical Cell with perforated Pt plate as anode

Spray Dryer System is shown in Figure 6.28.

161
Spray Nozzle:
Hastelloy C

Control
Panel

Drying
Pump Chamber

Blower
Scrubber

(SS 316)

Cyclones

(Borosilicate

Figure 6.28 Spray Dryer System

CuCl2 Decomposition Reactor is shown in Figure 6.29 and Hydrolysis


Reactor is shown in Figure 6.30.

162
Figure 6.29: CuCl2 Decomposition Reactor

Figure 6.30: Hydrolysis Reactor

163
Oxygen Generation Reactor is shown in Figure 6.31.

Figure 6.31: Oxygen Generation Reactor

Cu-Cl closed loop facilty is shown in Figure 6.32.

Figure 6.32:. Cu-Cl closed loop facilty

164
High Temperature-High Pressure Reactor for H2SO4 Decomposition is
shown in Figure 6.33.

Figure 6.33: High Temperature-High Pressure Reactor for H2SO4


Decomposition

H2SO4pilot plant facility is shown in Figure 6.34.

Figure 6.34: H2SO4pilot plant facility

165
HYDROGEN PRODUCTION BY

PHOTO-ELECTROCHEMICAL WATER
SPLITTING

166
7.0 Hydrogen Production by Photo-electro-chemical Water
Splitting

7.1 Introduction

The ever increasing energy demands and rapid consumption of fossil


fuels has triggered urgent need of sustainable and renewable sources of
energy. A lot of research and its commercialization have already been done in
the areas of solar photovoltaic, however, it requires storage of energy due to its
limited operation in day-time only. Hydrogen is one of the most promising fuels
due to its highest energy density (120 MJ/Kg). Environment and energy crisis
issues can be addressed if Hydrogen can be produced in a clean and efficient
manner. Steam methane reforming is most commonly used for Hydrogen
production in industries. Source for methane reforming is a fossil fuel and
moreover CO2 gas is emitted as shown in reaction 1 & 2.

CH4 + H2O → CO + 3H2 ------- (1)

CO + H2O → CO2 + H2 -------- (2)

Renewable production of Hydrogen through solar energy is essential


considering environmental issues and can also cater to the energy needs.
There are several ways of Hydrogen production through solar energy. However
water splitting is considered as the “Holy Grail” of sustainable hydrogen
economy. Water splitting phenomenon was first observed by Researchers in
Kanagawa University, Yokohamaduring1972 where TiO2 electrode was
irradiated with UV light and Hydrogen was produced by reduction reaction at
cathode and oxygen is produced at anode by oxidation reaction.

University of Notre Dame, Notre Dame, Indiana worked on photocatalytic


water splitting. Photocatalytic water splitting consists of a powder catalyst
dispersed in water or in some suitable solution. Catalyst used in this process
needs to be photoactive and should be capable of generating necessary charge
particles to activate redox reactions. Minimum bandgap required to split water
can be calculated from the relation in between Gibbs free energy and potential
as given below:

167
ΔG =-nFE

Where ΔG is the change in Gibbs free energy, n is number of electrons


transferred in chemical reaction, F is faraday constant and E is the bandgap.
For water splitting, ΔG = 237KJ/mol, n=2 and F=96500 C/mol. Therefore “E =
1.23V”, is the minimum potential and hence minimum bandgap of 1.23eV is
required to split water. Thermodynamic bandgap requirement for water splitting

Figure 1: Thermodynamic bandgap requirement for water splitting.

Solar hydrogen production from direct photo electrochemical (PEC)


water splitting is the ultimate goal for a sustainable, renewable and clean
hydrogen economy. In PEC water splitting, hydrogen is produced from water
using sunlight and specialized semiconductors called photo electrochemical
materials, which use light energy to directly dissociate water molecules into
hydrogen and oxygen. This is a long-term technology pathway, with the
potential for low or no greenhouse gas emissions. While there are numerous
studies on solving the two main photo-electrode (PE) material issues i.e.
efficiency and stability, there is no standard photocell or photo reactor used in
the study. The main requirement for the photocell or photo-reactor is to allow
maximum light to reach the PE.

The PEC water splitting process uses semiconductor materials to


convert solar energy directly to chemical energy in the form of hydrogen. The

168
semiconductor materials used in the PEC process are similar to those used in
photovoltaic solar electricity generation, but for PEC applications the
semiconductor is immersed in a water-based electrolyte, where sunlight
energizes the water-splitting process. PEC reactors can be constructed in panel
form (similar to photovoltaic panels) as electrode systems or as slurry-based
particle systems, each approach with its own advantages and challenges. To
date, panel systems have been the most widely studied, owing to the similarities
with established photovoltaic panel technologies.

Photo-electrochemical process consists of an electrode of


semiconductor material, which is photoactive and is capable of generating
electron hole pair when light (photons) is incident on its surface. One of the
advantages of photo-electrochemical cells is reduction and oxidation reaction
happens at different electrodes eliminating the need for separation of gases.
However, chemical stability of materials inside electrolyte solution or water is a
challenging issue.

Schematic diagram of a typical photo-electrochemical cell consisting of


n-type semiconductor photoanode, reference (SCE) and metal cathode for
water splitting is shown in Figure 2.

US DoE has set following benchmarks for commercialization of PEC


water splitting technology for hydrogen production.

 Criteria 1: 10% Solar to Hydrogen conversion efficiency.

 Criteria 2: Stability against Chemical, electrochemical and photo-


corrosion. Working time of at least 1000-hour without significant
degradation.

 Criteria 3: Cost of hydrogen production should be economical.

169
Figure 2: Schematic diagram of a typical photo-electrochemical cell
consisting of n-type semiconductor photo anode, reference (SCE)
and metal cathode for water splitting.

7.2 Process of water splitting

The crux of water splitting process lies in the redox reaction with the
participation of generated charge carriers through solar radiation at catalyst
surface (or active sites). Materials used for catalysts or electrode preparation
are semiconductor in nature. Therefore, they have a defined band gap which is
a result of the separation of conduction and valence band. Moreover band
edges also play an important role in the selection of the material. Conduction
band edge should be more negative than the reduction potential of the
hydrogen and valence band edge should be more positive than the oxidation
potential of oxygen for water splitting. When light of a particular wavelength is
incident on the catalyst, electron-hole pair is generated only if the photon
energy is more than the band gap of the material. Electron is then migrated to
the conduction band leaving a hole in the valence band.

Next step is separation of charge carriers and their movement to the


surface of the catalyst. For an efficient process, mean life time of the generated
carriers should be high or recombination rate should be low. Recombination

170
rate in a semiconductor material is affected largely by crystal defects. Crystal
defects acts as electron traps which neutralizes holes. To inhibit recombination
of electron-hole pair, a co-catalyst is generally used. Generally used co-
catalysts are platinum, nickel, ruthenium, rhodium, palladium, iridium and
rhodium. Another requirement of co-catalysts is to impede the back reaction in
between hydrogen and oxygen. However, in photo-electrochemical, charges
are separated by putting a separate electrode of aforementioned noble metals.

A research group in Kyoto University, Kyoto, Japan worked on the non-


equilibrium interfacial phenomena occurring under microgravity in water
electrolysis.Once separated electron and hole pair is available, redox reaction
can be conducted on the surface of catalyst/co-catalyst. Hydrogen ion is
reduced to hydrogen gas by the transfer of trapped electron and hydroxyl ion is
reduced to oxygen gas by neutralizing the hole in valence band. Oxidation
reaction in water splitting is a 4-electron transfer process and therefore, valence
band has to be deep enough for transfer of charges.

Reduction at cathode: 2 H+(aq) + 2e− → H2(g)

Oxidation at anode: 2 H2O(l) → O2(g) + 4 H+(aq) + 4e−

7.3 Evaluation Parameters

Evaluation of a water splitting system is done on the basis of amount of


gas (hydrogen and oxygen) evolved in due course of time. Amount of gas is
measured in moles and therefore unit for rate of evolution is mol per unit time
(for instance; µmol/hour). Parameter Quantum Yield can be used to compare
different photoactive material under similar operating conditions (Modern
Aspects of Electrochemistry, New York).

Number of reacted electrons


Quantum Yield =  x 100%
Number of absorbed photons

Actual quantum yield is usually more than the quantum yield mentioned above.
This difference can be computed if the incident light spectrum and absorption

171
spectrum of the material is known. Overall efficiency can be computed on the
basis of total input energy versus total output energy. In case of solar hydrogen
production, input energy is the incident Sun’s energy and output energy is the
energy content of evolved hydrogen gas.

Output energy of hydrogen


Solar to hydrogen efficiency =  x 100%
Energy of incident solar light

(mol H2/s) x (237kJ/mol)


=  x 100%
(Inc Power W/m2) X Area (m2)

In photo-electrochemical, another term specified as ‘applied bias photon


to current efficiency’ is more suitable as an external source is usually required
for transfer of charge particles from main electrode to counter electrode [5].

Applied Bias solar to hydrogen efficiency

Current density (mA / cm2) x (1.23 – Vbias) (V)


=  x 100%
Ptotal (mW/cm2) at AM 1.5G

7.4 National and International Status

Photo-electrochemical water splitting for hydrogen generation is based


on solar energy and water, both of which are renewable sources. Energy for
stationary and transportation applications can be retrieved from hydrogen with
low carbon foot print and climate impact. Ever since in the first report,
Researchers in Kanagawa University, Yokohamaduring1972 demonstrated the
feasibility of hydrogen generation via photo-electrochemical splitting of water,
lot of efforts have been made by different workers across the globe to exploit
this process for commercial production of hydrogen. Main focus of this research
has been to search for an ideal semiconductor that can be used as efficient
photo-electrode in this process. However, the long cherished goal of reaching
at least 10% conversion efficiency has so far remained unachieved. Working at
this efficiency, with photo-current generation at the rate 10-15 mA cm-2, would
imply that the cost of hydrogen production would be economical. This would be

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a cost competitive against the existing costs of conventional fuels and would
make this process commercially viable. Another issue important in the process
is of semiconductor material durability in contact with PEC cell electrolyte. It is
desired that the material should remain stable at least for 2000 working hours.

Researchers in Yerevan State University, Armeniain2005 has concluded


that among different semiconductors used for PEC water splitting, the best
efficiency is detected in metal oxide photo-electrodes, which were partially
reduced and contained an optimal concentration of impurities. In the ongoing
search for a material with above desired characteristics, in recent years several
new dimensions have been added (plate 1). Use of mixed oxides,
Combinatorial approach and designing of high throughout fast screening
procedures, adoption of density functional theory to screen the materials, Use
of phosphides, Selenides, Graphene and CNT based systems and layered
structure are some recent developments in this field of research. Besides above
mentioned work, research pertaining to geometry orientation and shaping of
nanomaterial (by orthogonalizing direction of light absorption, charge collection,
charge separation/ transportation), exploring bandgap and band alignment as
a function of composition, doping and morphology for engineering structures,
which have features favorable for water photolysis, are also being explored.

Few of the promising material(s) system for application in PEC water


splitting are given in Plate 1.

The Institute of Minerals and Materials Technology (IMMT),


Bhubaneswar developed functional hybrid nano structures for photo
electrochemical water splitting. The different photo-catalytic materials
developed for hydrogen production through water splitting, which were
continuously operated for 6-7 hours. Among the developed materials like CdS
photo-electrodes and CdS nano-crystal powder photo-catalysts with yield of
800-1000 mg/batch, 0.28 wt% P3HT modified CdS with yield of 4087 µmol/h/g
and CdS-NaNbO3 core-shell nano-rods with yield of 11,901 µmol/h/g, the CdS-
NaNbO3 core-shell nano-rods was found to give maximum hydrogen
production.

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Strategies being
Properties required?
tried
 Band gap energy ≈ 2 eV PEC
 Strong optical absorption Water  Doping
 Long life time of charge Splitting
carriers  Surface
 Conduction and Valance Material Modifications
band edges to straddle water Issues
redox potentials  Layered
 High Stability in electrolytes Structures
 Non Toxic & Economical
 Dye
Sensitization
Systems Investigated:
ResultHighlights

New concepts/ Emerging Trends ………..

Nanocomposites Bio inspired Quantum Metal Ion


catalysts Dots Implantatio
n

Fe2O3- Bio-inspired Co- CdSe QD electro- ZnO modified


Graphene catalyst CoPi on deposited on α-Fe2O3 with Cu ion
Nano- the surface films implantation
composite
Plate 1: Few of the promising material(s) system for application in PEC
water splitting

7.5 Action Plan

Action plan consists of two main activities: (i) basic R & D towards the
identification, synthesis and laboratory-scale PEC measurements on
prospective materials/material systems; (ii) up-scaling of the materials/systems
found promising with respect to their solar-to-hydrogen conversion efficiency
and stability under longer illumination time. Research will be conducted under
following lines:

I. Laboratory-scale studies on prospective materials and their


performance evaluation

Core activity 1: Exploration on promising semiconductors/systems

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Extensive R & D is required to be undertaken concerning the photo-
electrochemical measurements for hydrogen generation via photo-splitting of
water by employing the promising semiconductors. Thin films of the
semiconductors would be converted into electrode by adopting the standard
procedure and used in PEC water splitting studies. For converting films into
electrode, initially an electrical contact would be generated using silver paint
and copper wire. The Ohmic contact so prepared and all the sides of film
(except the front side) would be sealed with the coating of an opaque and non-
conducting epoxy. So prepared thin film working electrodes would be used as
photo-sensitive working electrode, in conjunction with platinum counter
electrode and saturated calomel electrode (SCE, as reference electrode), at
varying electrolyte conditions. Nature and concentration of the electrolyte and
its pH would also be varied in order to optimize the conditions of hydrogen
evolution. Current (I) – Voltage (V) characteristics of PEC cell would be studied,
both under darkness and illumination. By observing the I-V plots, onset voltage
for photo-current would be determined, and based on these measurements the
performance of PEC cell would be evaluated. As mentioned above this
constitutes the core activity in the proposal. The sustained R & D effort in this
direction by the investigators for the past 15 years has led to few of the
promising material-options in this regard that need to be tested at the next level,
which involves their integration with pilot-scale hydrogen generation reactor and
the performance evaluation of such reactors both under controlled conditions
as well under real-time solar illumination. However, as is evident from the
literature survey and the recent emerging trends in this vital area of research,
the material issue is yet not finally settled. As a matter of fact, each of the
existing material-options has its own drawbacks and the researchers are trying
to crack those issues.

Core Activity 2: Scale-up studies and related issues

Moving towards solar energy fed pilot-scale hydrogen generation


reactors such that it can perform efficiently under field conditions, this core
activity has been chalked out. The above mentioned two semiconductor
systems would be investigated for this purpose in the beginning. However, any

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new material/ system that promises to be even better as observed under core
activity 1, would also be incorporated in the work-plan under this activity. Key
work elements involved, especially pertaining to the synthesis of large area
electrodes would be as:

 Suitable synthesis methods as described in objectives to be used for


preparation of electrodes.

 First-level up-scaling studies with existing facilities at Dyalbagh


Educational Institute, Agra. Electrodes of at least 3 different dimensions
to be fabricated and tested under controlled laboratory conditions.

 Scaling of electrodes from 1cm2 to 150 cm2 active area. Feasibility of


maximum area of electrode (150 cm2) to be determined by conducting
experiments. These experiments will be conducted with state of the art
instruments at IOC-R&D which is a part of the procurement activity of
the present project plan. Two routes of large area electrodes shall be
explored – one having single large area electrode and the other – several
small electrodes connected in suitable configuration so as to result into
large area exposure

 Empirical modeling of performance versus increase in the area of


electrodes. Determining maximum feasible size of the electrode that can
be incorporated in the reactor.

 Study on scaling of counter electrode with respect to increase in the area


of working electrode.

 Optimization of interconnection design for working and counter


electrodes.

II. Studies on reactor design and fabrication.

Core Activity 3: Designing the Reactor

Designing reactor: Theoretical modeling and testing

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 Study of different losses associated with electrode and electrolyte
interfaces.

 Qualitative and quantitative study of electrolyte and electrode resistance


components.

 Study on feasibility of packaging electrodes in parallel connections, their


associated losses and optimum size possible for a reactor.

Core Activity 4: Fabrication of Reactor

Actual design of the reactor will be taken up after study on electrodes.


Key step of the work planned are mentioned below:

 A lab scale reactor will be fabricated to support scale-up activities for


performance evaluation of electrodes of different sizes. Basic design
would be similar to that of a twin compartment reactor. Separate
compartments will be available for working and counter electrode. This
will eliminate need for the separation of evolved gases (hydrogen and
oxygen). Moreover, reactor will be air tight and provision will be made to
sample evolved gases for analysis. Furthermore, an additional provision
will be provided to input feed without opening the reactor or without
interrupting the ongoing process.
 An electronics circuit will be designed to supply constant external bias to
the electrodes. Initially battery will be used for supply and subsequently
efforts will be laid to try to use photovoltaic panel for supplying external
bias to electrodes.
 A bigger bench scale reactor will also be fabricated as a part of the
project. This bench scale reactor will exhibit a maximum active area of ~
900cm2. All the challenges faced in the lab scale reactor will be
addressed in the design of this reactor. Bench scale reactor will also
have the provision of two compartments wherein both the hydrogen and
oxygen gases can be separated. Benchmark data will be generated by
controlled indoor testing with large area illumination continuous light
solar simulator.

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Core Activity 5: Fabrication of Reactor

Performance evaluation

Under controlled laboratory conditions

 It is proposed to set up a continuous solar simulator in laboratory which


can illuminate electrodes up to a maximum area of~ 900 cm 2.

Under real-time solar illumination outdoor field conditions

 Real-time testing will be taken up after laboratory testing. Performance


will be evaluated with respect to the real time data obtained from a
weather station already in place at IOC-R&D.

7.6 Summary and Recommendations

Among the various material groups for the photo-electrodes,


semiconductor metal oxides are relatively inexpensive and have a better photo-
chemical stability, many metal oxides have been extensively studied and
significant progress has been achieved in past two decades both nationally and
internationally.

Among the metal oxides; Iron, copper, bismuth vanadium and zinc have
been researched globally for their performance in photo water splitting.
Promising results have been achieved with aforementioned metal oxides; nano-
wire arrays of hematite has shown a promising current density of 3.44 mA/cm 2,
oxides of Bismuth has been reported with current density up to 2.3 mA/cm 2,
current density of the order of 2.34 mA/cm2 for Cu2O sample (1 at. % Ag) under
visible light illumination at 0.8 V/SCE has been reported.

While the search for new and more efficient semiconductor


materials/systems for above application would continue, studies are also
needed on upscaling the device by initiating R & D efforts in this direction. Metal
oxides, viz. Fe2O3, TiO2, ZnO, CuO, Cu2O, SrTiO3, BaTiO3 etc are important
class of semiconductors, viewed largely as prospective material systems for
PEC applications. Further, in order to overcome certain limitations associated
with these metal oxides, these were subjected to various modifications viz.

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doping, swift heavy ion irradiation, dye sensitization etc., yielding varied
improvements on their performances. Nanocomposites, bio-inspired systems,
quantum dots, and ion implantation are amongst the different newly emerged
concepts that have drawn the attention of researchers and are being
investigated with lot of hope and expectations.

Research on scale-up and reactor is equally important as that of the


material research. Efficient and reliable materials need to be studied further for
scalability. Demonstration at lab scale and pilot scale can be significant towards
realizing the ultimate potential of the technology.

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HYDROGEN PRODUCTION
BY OTHER TECHNOLOGIES

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8.0 Hydrogen Production by Other Technologies

8.1 Hydrogen Production by non-thermal plasma assisted direct


decomposition of hydrogen sulphide

8.1.1 Hydrogen Sulfide is an inorganic compound that causes severe odor


problems. The emission of Hydrogen Sulfide from petroleum industry, coal
gasification and animal industry has to be regulated as the odor threshold for
Hydrogen Sulfide is 1 ppbv. Hydrogen sulphide occurs as a by-product in the
production of coke form sulfur- containing coal, the refining of Sulphur-
containing crude oils, the production of carbon disulphide, the manufacturer of
viscose rayon, and in the Kraft process for producing wood pulp. Hydrogen
sulphide is the most dangerous of the gases produced by the anaerobic
decomposition of manure. Large amounts of Hydrogen Sulfide are produced
worldwide, mostly from natural gas production and oil refining. Yearly tonnages
of H2S can be deprived from sulfur production, 14.4 million tons from sour gas
and 9.6 from refineries, worldwide. This sour gas potentially contained about
342, 000 tons (3.8 billion cubic meters) of hydrogen. Oil refineries and
upgraders use hydrogen as well as make H2S, and for this reason constitute a
logical location for a H2S dissociation plant.

Conventional methods to controls hydrogen Sulfide include absorption


(wet scrubbing), absorption, incineration (thermal and/or catalytic), and bio-
filtration. The widely employed Claus method is based on partial combustion of
hydrogen sulfide into sulfur dioxide followed by the catalytic conversion of H 2S
+ SO2 mixture into elemental sulfur and water. Earlier methods were focused
on recovery of elemental sulfur, however the desired reaction would be the
production of hydrogen by direct oxidation of hydrogen Sulfide, which is
endothermic and thermodynamically unfavorable.

An alternative approach is to use Non-thermal Plasma (NTP) generated


at atmospheric pressure and room temperature. NTP, the fourth state of the
matter consists of energetic electrons, radicals, atoms and molecules. At low
consumption of energy, NTP produces highly energetic electrons that initiate
the chemical reaction leaving the background gas nearly at room temperature.

181
Recently dielectric barrier discharge (DBD) reactor with catalytic sintered metal
fibre (SMF) electrode has been tested for the abatement of volatile organic
compounds. It was demonstrated that the metal oxide modified SMF
electrodes, performance of the NTP technique could be improved.

8.1.2 International Status

It is known since long that strong healing decomposes hydrogen


sulphide. Thermal decomposition has recently been implemented at the pilot
scale at a gas plant in Alberta. Conversions close to equilibrium have been
observed. An economic study showed that costs for thermal decomposition
would be close to those for conventional processes. Improvements in
separation technologies are needed to enable commercial implementation of
thermal decomposition.

As of today there is no commercial technology for the production of


hydrogen from hydrogen sulphide. The conventional method for hydrogen
sulphide removal is the Claus process, which produces sulfur and water instead
of hydrogen and sulfur that are beneficial. Besides sulfur recovery limitations,
major disadvantage of the Claus process is that the valuable product hydrogen
is converted into water. Moreover, the cost of tail gases cleanup from Claus
plant can exceed the value of sulfur recovered if the environmental regulations
become more stringent. Regarding the catalytic process, only limited
information has been reported, where none of the catalysts was promising. One
of the reasons could be the severe reaction conditions like high operation
temperature (>2000K). Among the several techniques tested for the production
of hydrogen, Idemitsu Kosan Hybrid (IKC) electrolysis process has been
considered as feasible. It is based on absorption of hydrogen sulphide by Ferric
chloride aqueous solution followed by electrolysis to generate hydrogen and
sulfur. IKC process consumes 3.6 kWh/Nm3 hydrogen, whereas steam
reforming of methane, the traditional approach for hydrogen production
demands still higher energy of 4.3 kWh/Nm 3hydrogen. Like-wise, 40%
conversion of hydrogen sulphide by thermal decomposition can be achieved at
temperature ~ 1500K, which is equivalent to 2.76kWh/Nm3 of hydrogen. At this

182
temperature considerable amount of by-products like SH were produced.
Formation of pure Sulphur and hydrogen was observed only above 2273K. The
practical limitation of this technique is the operating conditions and separation
of products at this temperature. The main advantage of carrying out hydrogen
sulphide decomposition in the novel DBD reactor is the production of hydrogen
in an economically feasible manner under ambient conditions.

8.1.3 National Status

Most of the research in this area has been focused on


catalytic/photocatalytic decomposition of hydrogen sulphide. However, in both
the cases, catalyst deactivation due to the deposition of sulphur decreases the
efficiency. But, photocatalytic decomposition of hydrogen sulphide to hydrogen
and sulphide offers some promise. Hydrogen sulphide under visible light to
generate hydrogen is an attractive route of solar energy conversion, because
hydrogen is 100% environmentally clean chemical fuel in its cycles of
generation and utilization. Although hydrogen generation from water in visible
light represents a potentially viable route of solar energy conversion, till date
only marginal conversion efficiency has been achieved (5.1% quantum yield
with sacrificial agents and 2.5 % from pure water. Obviously, the difficulty in
achieving high efficiency is attributed to the involvement of many high energetic
reactive species in the thermodynamically uphill water spilling reaction.

The Indian Institute of Technology Hyderabad developed the process of


non-thermal plasma assisted direct decomposition of hydrogen sulphide into
hydrogen and sulphur. This process is feasible and advantageous over Claus
process where sulphur alone is recovered from hydrogen sulphide. It is possible
to achieve hydrogen production at about 160 kJ/mole that corresponds to
energy conversion of 2 kWh/Nm3 of hydrogen, which is less than the energy
required for hydrogen production from SMR (about 346 kJ/mole of hydrogen).
A packed bed configuration with glass tubes reactor showed best performance
of the reactor which was attributed to the change in discharge properties. MoO x
supported on Al2O3 catalysts showed better conversion compared to CoOx and
NiO due to deactivation of CoOx and NiO quickly due to sulphur poisoning.
Hydrogen production of 0.5 litre/minute was achieved in the laboratory.

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The NTP technology is environmentally friendly and operationally
simple. Another advantage of the suggested process is that the hydrogen
produced is free from impurities, hence secondary purification can be avoided.
The reaction conditions can be still improved to decrease the energy
consumption.

8.2 Hydrogen Production by Photo-splitting of Hydrogen Sulphide

8.2.1 Hydrogen sulphide is a toxic gas occurs widely in natural gas fields and
is produced in large quantities as a byproduct in the coal and petroleum
industry. Currently this toxic gas is converted into sulphur using Claus’s process
or released into the atmosphere. Photo-splitting of hydrogen sulphide into
hydrogen can be an attractive option by conventional the Claus’s process.
Hydrogen sulphide Cleavage process might be used in industrial procedures
where hydrogen sulphide or sulphides are formed as a waste whose rapid
removal and conversion into hydrogen is desired. Currently, for this application
oxide catalysts have been studied but due to certain limitations, researchers
are trying to develop catalyst which can absorb maximum part of solar radiation
and are active under natural solar light. Extensive work has been carried out in
the development of ultraviolet driven photocatalyst for water and hydrogen
sulphide splitting. However, there is a demand for highly efficient photocatalyst
for photo production of hydrogen under visible light irradiation. Stability and
efficiency of these catalysts still low and need improvement. There is need to
develop prototype photoreactor for hydrogen production from hydrogen
sulphide using solar energy and field trials using gas emitted at refinery sites
using a batch type photo reactor.

8.2.2 International Status

Semiconductors mediated heterogeneous photo catalysis has become


an attractive technology for environmental pollution remedy, particularly due to

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its potential to degrade a wide range of inorganic and organic compounds in
both waste gases and water. The initial reaction step consists of electron-hole
pair’s production by irradiating the semiconductor with light having an energy
content equal to or higher than the band-gap of semiconductor. After separation
of photo generated electrons and holes due to trapping by species adsorbed
on the semiconductor, redox reactions occur between trapped electrons and
holes and adsorbate. Most of the semiconductor photo catalysts investigated
are metal oxides (e.g. TiO2, ZnO, SnO2, WO3) and chalcogenides (e.g. CdS,
ZnS, CdSe, ZnSe, CdTe) [1-5]. As hydrogen-based power and transportation
technologies develop the need for an effective hydrogen source to power fuel
cells in the hydrogen economy. Hydrogen from photo-electrochecmical cells is
believed to offer the prospect of such a source. Photocatalytic splitting of water
using n-type TiO2 under UV illumination was first reported over 30 years ago by
Researchers in Kanagawa University, Yokohama. Since then a number of
photocatalytic compounds have been investigated with the aim of improving
catalyst activity and stability in the irradiated aqueous environment. In 2001 Zou
et al. first demonstrated the direct splitting of water by visible light over an
In1.xNixTaO4 photocatalyst. As energy conversion devices, water-splitting
photoelectrochecmical cells convert photon energy to the Gibbs free energy of
hydrogen and Oxygen via excited electron states in the photocatalyst. These
excited electron states result from the promotion of valance band electron to a
level above the conduction band edge on the absorption of an incident photon.
In practice, any energy in the excess of the bandgap energy will be dissipated
as heat since electrons promoted to higher states readily thermalise to the
conduction band edge. Internationally, the research on hydrogen generation
from hydrogen sulfide and water is still at academic level. No commercial
process has been developed yet. Many groups in Japan, Korea, U.S, Europe
is working on development of active photo catalysts for hydrogen generation
under visible light irradiation. University of Tokyo, Japan has done extensive
work on photocatalysts for water splitting and recently has reported many UV
and visible light catalysts.

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Considering the depletion of other energy sources, it is quite essential to
develop new sources of energy. Development of active photocatalyst for photo-
hydrogen generation will be advantageous for future energy demand.

8.2.3 National Status

In India, large number of groups is working on photocatalytic


decomposition of organic waste and toxic materials. Very few groups are
working on photocatalytic splitting of water and hydrogen and hydrogen
sulphide into hydrogen under visible light. Few research group in BARC are
working on photocatalytic degradation of nuclear waste as well as water
purification. Some research teams in IISc, Bangalore are working on TiO2
based photocatalysts for organic waste degradation. In addition to this, some
researchers in IIT, Mumbai and Madras, CECRI, Karaikudi, IICT, Hyderabad
and few universities in India are working on photodecomposition of organic
pollutants. But the photo catalysis work has not crossed the development of
other possible new active photocatalyst other than TiO2andCdS. The current
trend in the country is only the degradation of waste or organic using TiO2/Cds
photocatalyst. Only C-MET Pune is working on hydrogen generation by
photocatalytic decomposition of toxic hydrogen sulphide. In India, the
development of active photocatalyst for pure hydrogen generation by water and
hydrogen sulphide splitting is still at academic level. It is essential to develop
catalysts useful under solar light for the decomposition of water/hydrogen
sulphide into hydrogen. The hydrogen sulphide from the refineries and mines
is continuously emitted into the atmosphere as a result air in the bin such areas
is highly polluted. C-MET is developing new class of photocatalysts which are
stable and active under sunlight.

The Centre for Materials for Electronics Technologies (C-MET), Pune


has developed the prototype photo reactor for hydrogen production from
hydrogen sulphide at the rate of 8182.8 and 7616.4 µmol/h/g was obtained from
nanostructured ZnIn2S4 and CdIn2S4, respectively under Natural Sunlight (UV
optical absorption edge at 557nm for ZnIn 2S4 and 576nm for CdIn2S4). The
reactor has been designed for the facile operation and considering the safety
186
aspects. The sparger was fixed as a H2S distributer, which also acts as a
particle disperser. This design is useful for continuous operation at large scale.

187
ACTION PLAN

9.0 Action Plan

9.1 Hydrogen is a byproduct along with the production of caustic soda and
chlorine in the chlor-alkali units. These units are continuously working towards

188
better utilization of hydrogen and have succeeded in achieving 90% utilization
during 2014-15. The remaining hydrogen amounting to around 6600 tonnes
may be utilized in energy related applications, since it emits no pollution except
water and heat. This hydrogen may be used directly for the generation of power
/ in transportation applications (vehicles) based on IC engine technology. For
fuel cell application, hydrogen may further be purified (if required),for use in
stationary power generation and on-board application in vehicles / material
handling systems (based on fuel cell technology), etc.

9.2 Hydrogen has been produced from the conventional sources i.e.
carbonaceous fuels like natural gas, coal etc. For small capacities hydrogen
production by electrolysis, methanol or ammonia cracking for small, constant
or intermittent requirements of hydrogen in food, electronics and
pharmaceutical industries and for larger capacities steam reforming of
hydrocarbons / syngas are preferred. These sources release CO2 in the
atmosphere. The average rate of growth of CO2 in the atmosphere is around
2.1 ppm per year and its concentration in air has increased from 381.90 ppm in
2006 to 398.55 ppm in 2014. India has proposed to reduce emissions by 33-
35% by 2030 over the 2005 levels by boosting clean (non-fossil & including
renewable) energy in electricity generation to 40% (at least another 150GW)
and by adding sinks through trees and forests. Renewable-based processes
like solar- or wind-driven electrolysis and photo-biological water splitting hold
great promise for clean hydrogen production; however, advances must still be
made before these technologies can be economically competitive. Thus,
hydrogen production may be continued from the conventional (carbonaceous)
fuels through the most competitive process namely auto-thermal reforming
(steam reforming and partial oxidation)process till the technologies for
hydrogen production from renewable sources become economically
competitive.

9.3 Biomass has been identified as potential renewable source for hydrogen
production. It is carbonaceous source and produce CO2, which is released to
the atmosphere. Biomass is gasified to hydrogen rich syngas, which may be
reformed and purified to yield pure / near pure hydrogen. The technology is

189
being developed in the country by IISc, Bangalore. Some other institutes like
NIT, Rourkela and NIT Cochin have also been engaged in R&D work for
hydrogen production through gasification of biomass. IISc developed a
prototype for production of 2 kg/hr hydrogen through Oxy-steam gasification
process with hydrogen yield of 100 gm/kg of biomass used.

9.4 Electrolysis is a method by which hydrogen may be obtained in pure


form. This hydrogen may be used directly in the fuel cells applications. The cost
of hydrogen production by this method is high due to high capital investment
and operating cost (i.e. electricity consumption). Electricity generated by the
solar energy / wind energy / hydro resource may be used to nullify carbon
emission in the atmosphere, but these technologies require high capital
investment. The electrolyser system consists of various subsystems like
electrochemical stack, power rectifiers, control systems, instrumentation for
monitoring various processes, water purification, pumps, multistage
compressors, pressure vessels, and multiple number of other engineering
subsystems involved and requires integration as per customer requirements to
develop complete system. Except an electrochemical stack, India has core
strength for manufacturing majority of aforementioned subsystems and very
much capable in system engineering. Imported electrolyser stacks in different
combinations may be used and integration can be carried in the country. The
institutions / industry may be identified to work in PPP Model for
commercialization of the balance of plant and simultaneously, the technology
for the production of stack may be procured or developed indigenously.

9.5 Solid polymer electrolyzer (SPE) with 20,000 hours of operation are
desirable. SPE is either acid or alkal based, the acid based electrolysis system
requires noble metal catalysts, and alkaline membrane based electrolysis
require cheaper electro catalyst like Nickel. It is ideal to have membranes based
alkaline water electrolysis system integrated with solar photovoltaic system.
However, alkaline based SPE faces numerous challenges such as chemical
stability in the electrochemical device. These challenges are lesser for either
phosphoric acid based electrolysis cells or alkali based electrolysis systems

190
using diaphragm. Due to these problems, the following steps are suggested in
the sequential order:

(i) Deployment of solar energy powered


a. Acid based electrolysis system
b. Alkali based electrolysis system
for immediate onsite hydrogen production using available technology.
(ii) Development of ectrolysers based on indigenous acid based SPE
(iii) Development of alternate alkaline membrane
(iv) Development of alkaline SPE based electrolyte system
(v) Replacement of old systems by the newly developed systems

9.6 Hydrogen may be produced through dark and photo-fermentation


process. The dark fermentation has certain limitations and can yield hydrogen
in terms of energy recovery ranging 20 to 30 % of total energy. This process
may be integrated with photo fermentation, but such a two-stage process is
difficult to commercialize. However, theoretically, 12 moles of H2 /mole of
glucose can be recovered. If the dark fermentation followed by bio-methantion
process may lead to gaseous energy recovery ranging from 50 to 60%. In this
process the same reactor may be used for H2 production and later for bio-
methanation, which would curtail the operational cost. The mixture of hydrogen
and methane so produced is called bio-hymet. The production bio-hymet could
be envisioned as renewable source of energy only when it would be produced
from renewable sources. Any organic compound which is rich in carbohydrates,
fats and proteins could be considered as possible substrate for bio-hymet
production. Another path of hydrogen economy has been suggested by the
integration of fuel cell system with the bio-hydrogen production system. Such
setups may be put strategically near to those places where supply of feedstock
is easily available in adequate quantities. The electricity generated by such
system may electrify villages in a decentralized manner.

9.7 Bhabha Atomic Research Centre has successfully demonstrated I-S


process in closed loop operation in glass/quartz material in the laboratory. It is
further planned to demonstrate closed loop operation in metallic construction.

191
Other institutes / organizations will also be roped in depending upon their
capabilities. The broad plan is given below:

(i) Design and demonstration of atmospheric pressure operation all metal


closed loop system (AMCL).
(ii) High pressure operation Bunsen reactor system has been designed and
its commissioning is underway.
(iii) Design and demonstration of high pressure sulfuric acid decomposition
system.
(iv) Design and demonstration of hydroiodic acid distillation and
decomposition system.
(v) Integration of all three high pressure systems to demonstrate, high
pressure closed loop process.

The following challenges have been envisaged for the metallic system,
which are to be dealt with in this endeavor:

(i) Fabrication of exotic material based equipment, such as Tantalum,


Hastelloy, Silicon Carbide etc.
(ii) Development of special seals, compatible for high temperature, high
pressure and corrosive chemicals for metallic system.
(iii) Development of special instrumentation and controls for metallic
system.

9.8 ONGC Energy Centre (OEC) is of the view that three potential thermo-
chemical processes (Cu-Cl closed loop cycle, I-S closed loop cycle and I-S
open loop cycle) first be studied at engineering scale and compared before
deciding to take up at the commercial level. The OEC has planned to study and
evaluate alternative materials used in process and plant design, keeping in view
the corrosive nature and use of expensive materials in the process. The
following work has been undertaken by the Centre:

(i) Indigenous membranes are being developed with CSMCRI, Bhavnagar


and expected to be completed by January, 2018.

192
(ii) Development of partially open-loop I-S cycle involving H2S incineration,
experimental studies on Bunsen reaction and HI decomposition would
be completed within two years with IIP Dehradun.
(iii) Work on “Prolonged stability tests of catalysts for HI decomposition
reaction of I-S cycle have recently been taken-up jointly with IIT-Delhi.
(iv) Suitable materials for design and development of process reactors for I-
S cycle are being identified. The work is in progress.

The OEC has planned to start research on identification, development


and testing of suitable materials for design and construction of large size
indigenous reactors for Cu-Cl process, keeping in view the corrosive nature of
materials used in the Cu-Cl process.

9.9 Photo-electrochemical Water Splitting

Indian Oil Corporation Limited Research and Development Centre,


Faridabad made a plan to conduct laboratory-scale studies on prospective
materials and their performance evaluation. The details are given below:

Core activity 1: Exploration on promising semiconductors/systems:


Extensive R & D is required to be undertaken concerning the photo-
electrochemical measurements for hydrogen generation via photo-splitting of
water by employing the promising semiconductors. Thin films of the
semiconductors would be converted into electrode by adopting the standard
procedure and to be used in PEC water splitting studies. These thin film working
electrodes would be used as photo-sensitive working electrode, in conjunction
with platinum counter electrode and saturated calomel electrode (SCE, as
reference electrode), at varying electrolyte conditions. Current (I) – Voltage (V)
characteristics of PEC cell would be studied, both under darkness and
illumination. The performance of PEC cell would be evaluated. Promising
material-options in this regard that need to be tested at the next level, which
would be involved their integration with pilot-scale hydrogen generation reactor
and the performance evaluation of such reactors both under controlled
conditions as well under real-time solar illumination.

193
Core Activity 2: Scale-up studies and related issues: Solar energy fed
pilot-scale hydrogen generation reactors to perform efficiently under field
conditions will be developed. The above mentioned two semiconductor
systems would be investigated. New promising material/ system would also be
incorporated in the work-plan under this activity. Key work elements involved
the synthesis of large area electrodes including suitable synthesis methods for
preparation of electrodes. First-level up-scaling studies with existing facilities at
Dyalbagh Educational Institute, Agra will be done. Electrodes of different
dimensions need to be fabricated and tested. Feasibility for scaling of
electrodes from 1cm2 to 150 cm2 active area is to be determined by conducting
experiments with state of the art instruments at IOCL - R&D. Two routes of large
area electrodes shall be explored – one having single large area electrode and
the other – several small electrodes connected in suitable configuration.
Empirical modeling of performance versus increase in the area of electrodes
will be done. Maximum feasible size electrode will be determined that can be
incorporated in the reactor. Study on scaling of counter electrode with respect
to increase in the area of working electrode and optimization of interconnection
design for working and counter electrodes would be done.

III. Studies on reactor design and fabrication.

Core Activity 3: Designing the Reactor: Theoretical modeling of reactor will


be designed and tested. Different losses associated with electrode and
electrolyte interfaces will be studied. Qualitative and quantitative study of
electrolyte and electrode resistance components will be taken up. Feasibility of
packaging electrodes in parallel connections, their associated losses and
optimum size possible for a reactor will be studied.

Core Activity 4: Fabrication of Reactor: Actual design of the reactor will be


taken up after study on electrodes. A lab scale reactor with a twin compartment
reactor will be fabricated to support scale-up activities for performance
evaluation of electrodes of different sizes. Separate compartments will separate
the evolved gases (hydrogen and oxygen).An electronics circuit will be
designed to supply constant external bias to the electrodes. Initially battery will

194
be used for supply and subsequently efforts will be laid to try to use photovoltaic
panel for supplying external bias to electrodes. A bigger bench scale reactor
having the provision of two compartments will also be fabricated with a
maximum active area of ~ 900cm2. Benchmark data will be generated by
controlled indoor testing with large area illumination continuous light solar
simulator.

Core Activity 5: Fabrication of Reactor: Performance is to be evaluated


under controlled laboratory conditions. It is planned to set up a continuous solar
simulator in laboratory which can illuminate electrodes up to a maximum area
of~ 900 cm2.

Under real-time solar illumination outdoor field conditionstesting will be


taken up after laboratory testing. Performance will be evaluated with respect to
the real time data obtained from a weather station at IOCL-R&D.

9.10 Presently, Hydrogen Production by non-thermal plasma assisted direct


decomposition of hydrogen sulphide is at research and development stage and
no commercial technology is available. Electrolysis process consumes 3.6
kWh/Nm3 hydrogen, whereas steam reforming of methane, the traditional
approach for hydrogen production demands still higher energy of 4.3 kWh/Nm 3
hydrogen. 40% conversion of hydrogen sulphide by thermal decomposition can
be achieved at temperature ~ 1500K. Nationally, most of the research in this
area has been focused on catalytic/ photocatalytic decomposition of hydrogen
sulphide. Hydrogen sulphide under visible light to generate hydrogen is an
attractive route of solar energy conversion, because hydrogen is 100%
environmentally clean chemical fuel. The Indian Institute of Technology
Hyderabad developed the process of non-thermal plasma assisted direct
decomposition of hydrogen sulphide into hydrogen and sulphur. Hydrogen
production of 0.5 litre/minute was achieved in the laboratory. The reaction
conditions can be still improved to decrease the energy consumption. Further
R&D is required in this area.

9.11 For the photo-splitting of hydrogen sulphide into hydrogen, extensive


work has been carried out in the development of ultraviolet driven photocatalyst

195
for water and hydrogen sulphide splitting. There is need to develop prototype
photo reactor for hydrogen production from hydrogen sulphide using solar
energy and field trials using gas emitted at refinery sites using a batch type
photoreactor. The research on hydrogen generation from hydrogen sulfide and
water is still at research level. No commercial process has been developed yet.
Nationally, very few groups are working on photocatalytic splitting of water and
hydrogen and hydrogen sulphide into hydrogen under visible light. Few
research group in BARC are working on photocatalytic degradation of nuclear
waste as well as water purification. Some research teams in IISc, Bangalore
are working on TiO2 based photocatalysts for organic waste degradation. In
addition to this, some researchers in IIT, Mumbai and Madras, CECRI,
Karaikudi, IICT, Hyderabad and few universities in India are working on
photodecomposition of organic pollutants. The Centre for Materials for
Electronics Technologies (C-MET), Pune is working on hydrogen generation by
photocatalytic decomposition of toxic hydrogen sulphide. C-MET is developing
new class of photocatalysts which are stable and active under sunlight. C-MET,
Pune has developed the prototype photo reactor for hydrogen production from
hydrogen sulphide at the rate of 8182.8 and 7616.4 µmol/h/g was obtained from
nanostructured ZnIn2S4 and CdIn2S4, respectively under Natural Sunlight. This
design is useful for continuous operation at large scale. There is a scope to
carry R& D in this area.

9.12 The Institute of Minerals and Materials Technology (IMMT),


Bhubaneswar developed functional hybrid nano structures for photo
electrochemical water splitting. The different photo-catalytic materials
developed for hydrogen production through water splitting, which were
continuously operated for 6-7 hours. Among the developed materials like CdS
photo-electrodes and CdS nano-crystal powder photo-catalysts with yield of
800-1000 mg/batch, 0.28 wt% P3HT modified CdS with yield of 4087 µmol/h/g
and CdS-NaNbO3 core-shell nano-rods with yield of 11,901 µmol/h/g, the CdS-
NaNbO3 core-shell nano-rods was found to give maximum hydrogen
production. Research & Development may be continued in this area.

196
197
FINANCIAL PROJECTIONS AND TIME
SCHEDULE OF PROJECT ACTIVITIES

198
10.0 Financial Projections

10.1 Hydrogen Production from Carbonaceous Feed-stock like Natural Gas,


Coal etc. using Thermo-chemical Route

(i) Mission Mode Projects: Scaling-up of the process of catalytic


decomposition of natural gas for the production of H-CNG for the
use in vehicles (Upto 2019) - Rs.40 Crore
(ii) Research and Development Projects: Development &
demonstration of hydrogen production by auto-thermal process
(Upto 2020) - Rs. 20 Crore
(iii) Basic / Fundamental Research Projects: Dissociation of gaseous
hydrocarbon fuels to hydrogen using solar energy (Upto 2022)
- Rs. 10 Crore

10.2 Hydrogen Production from Carbonaceous Source like Biomass Feed-


stock as Renewable Source using Thermochemical Route

(i) Mission Mode Projects: Research and development for hydrogen


production by gasification of biomass, including demonstration of
technology at pilot scale (Upto 2020) - Rs. 10 Crore

(ii) Research and Development Projects: Hydrogen production by


reformation of bio-oil obtained from fast pyrolysis of biomass(Upto
2020) - Rs.5 Crore

10.3 Hydrogen Production using Electrolytic Processes - Low and High


Temperature Electrolyzers

(i) Research and Development Projects: Development &


demonstration of 1 Nm3/h high temperature steam electrolyser and
5 Nm3/h indigenously developed solid polymer water electrolyser
(Upto 2020) - Rs. 10 Crore

199
(ii) Research and Development Projects: Development &
demonstration of efficient alkaline water electrolyser (Upto 2018)
- Rs. 10 Crore
(iii) Research and Development Projects: Development and
demonstration of clean and sustainable hydrogen production by
splitting water using renewable energies such as solar energy, wind
energy and hybrid systems. This also includes electrolysis, photo-
catalysis and photo-electro-catalysis (Upto 2022)
-Rs. 10 Crore
iv) Integration of large capacity electrolysers with wind / solar power
units when there are not in a position to evacuate power to grid for
providing hydrogen. -Rs. 5 Crore

10.4 Bio-Hydrogen Production

i) Mission Mode Projects: Development and demonstration of


biological hydrogen production from different kinds of wastes like
effluents from distillery, brewery, paper mills, wastewater from city,
dairy, tannery, slaughter house, chemical & pharmaceutical
industries, agro / food processing industry residues like cane
molasses, noodle and potato processing, poultry litter, de-oiled algal
cakes, food (canteen) waste through dark or/and photo
fermentation. Demonstration of prototypes at various levels followed
by bench scale and pilot plant. After successful demonstration
commercial production may be commenced (Upto 2022)
-Rs.20 Crore
ii) Mission Mode Projects: Hydrogen production by water splitting
using photolysis using solar energy (Upto 2022) -Rs.40 Crore
iii) Research and Development Projects: Hydrogen production
together with methane through biological processes from different
kinds of organic wastes, including industrial effluent. Energy balance
and process economic aspects may also be studied (Upto 2019)
- Rs.10 Crore

200
iv) Research and Development Projects:Development of technology
for production of syn-gas (CO+H2)and hydrogen from reformation of
natural gas / biogas using solar energy.
- Rs.5 Crore

10.5 Hydrogen Production through Thermochemical Cycles

Mission Mode Projects: Hydrogen production by water splitting using


thermo-chemical route (open / closed loop Iodine-Sulphur cycle and
Copper – Chlorine cycle) using solar / nuclear heat (Upto 2022)
- Rs.50 Crore

10.6 Other innovative method for hydrogen production such as hydrogen


production by non-thermal plasma assisted direct decomposition of
hydrogen sulphide, Photo-splitting of Hydrogen Sulphide including
developmental effort for reduction in energy consumption for hydrogen
production (up to 2022).
-Rs.20 Crore

10.7 Projects for utilization of byproduct hydrogen at chlor-alkali units /


refineries: Development and demonstration of prototype systems for
purification of by-product hydrogen from chlor-alkali units / refineries for
the use in fuel cells to generate power for captive use or its compression
for filing in cylinders to use them on-board in hydrogen fueled vehicles /
material handling systems (based on fuel cell technology) (Upto 2018)
- Rs.20 Crore
_______________
Total requirement (Upto 2022) -Rs.285 Crore
______________

201
CONCLUSIONS AND RECOMMENDATIONS

202
11.0 Conclusions and Recommendations

11.1 Conclusions

11.1.1 Hydrogen has been widely used in chemical industries to manufacture


fertilizers, chemicals, ammonia, saturated fatty acids (vanaspati ghee), etc. Its
use in non-energy applications is expected to increase further in coming years
substantially. It is an energy career and not a primary source of energy. It is
gaining importance as a futuristic clean (pollution free) and sustainable (on the
basis of its production from renewable sources of energy) fuel for stationary
power generation and transportation. Hydrogen may be produced from direct
or indirect source of energy and hydrocarbon. The fossilized carbonaceous
feed stocks, like natural gas, naphtha or coal, etc., (source of hydrocarbon and
chemical energy) are being used for producing hydrogen through steam
reforming, plasma reforming, coal gasification, partial oxidation, and co-
conversion using steam. Hydrogen is also being produced from electrolysis of
water.

11.1.2 The conventional carbonaceous feed stocks are limited. The non-
fossilized renewable carbonaceous materials, such as biomass, agro-waste,
rubber wastes, urban solid waste, de-oiled seed cakes, waste cooking oil etc.
contain carbon and may be used for producing hydrogen. All these feed-stocks
emit CO2 (a greenhouse gas) and other polluting gases. Hydrogen is also
produced through low or high temperature electrolysis of water, which is
abundantly available on earth. The electricity used for this process may be
generated using fossil fuels or through the use of solar energy / wind energy.

11.1.3 In view of the current developments and efforts at the national level for
the deployment of fuel cells as the back-up power system for the telecom towers
and demonstration of vehicles based on the hydrogen IC engine technology as
well as fuel cells, it is the right time to set-up hydrogen production facilities on
small, medium and large scales to derive meaningful insights regarding
realisation and management of hydrogen energy infrastructure in the country.

203
11.1.4 Substantial quantity of surplus hydrogen is available as byproduct
hydrogen. It may be tapped to meet immediate requirement for research,
development and demonstration of various hydrogen based projects. The
Government may consider extending support to create facilities for tapping this
hydrogen. In India, currently the byproduct hydrogen amounting to around 6600
tonnes hydrogen (10% of total byproduct hydrogen) is available as unutilized
with the chlor-alkali units. This hydrogen may be further purified (if required),
compressed, bottled and transported to the sites for use in stationary power
generation and on-board application in vehicles / material handling systems,
etc. This surplus volume of by-production hydrogen is, however, quite small to
meet the future needs of the gas for energetic uses. A concerted effort is
required to transform the laboratory results into hydrogen production facilities.

11.1.5 Biomass can be processed (pyrolysed / gasified) for obtaining hydrogen


rich syn-gas. The hydrogen needs to be separated out and purified to different
levels of purity depending on the application needs from the hydrogen rich syn-
gas. The biomass is considered to be easily available in large quantities. The
research outcome of biomass gasification suggests addressing to the need of
hydrogen generation from biomass through the thermo-chemical conversion
process. The R&D experience in the country on the biomass gasification is rich
and can be utilized for technology development of hydrogen production.
Internationally, hydrogen generation by gasification is being pursued and
shortlisted as an economical way to address to hydrogen production problem.

11.1.6 Water can be decomposed into hydrogen and oxygen through


electrolysis. It is an energy intensive process. The available technologies in the
world’s market are alkaline and solid polymer electrolyte (SPE) based water
electrolyser. Alkaline water electrolysis is cheaper due to use of nickel catalysts,
but efficiency is lower (60-75%) than that (65–90%) of SPE water electrolysers,
which are expensive due to the use of noble metal catalyst (e. g. platinum) and
are operated at higher current densities. The SPE water electrolysers are
possibly, capable of producing cheaper hydrogen, if its production is taken up
on large scale. The efficiency of SPE water electrolyser is more at higher
temperature and pressure (around 120-200 bar). In high pressure electrolysis

204
external hydrogen compressor is eliminated and hence around 3 % as average
energy consumption for compression of hydrogen is saved. This SPE based
electrolysis process can also be operated with the electricity generated from
the solar photovoltaic systems or wind mills, which have large potential. Several
large installations coupling solar energy or wind farms with water electrolysers
have come up world over. Most of these are implemented through consortium
of several companies. SPE technology up to 1 Nm 3/h has been developed
indigenously and its technology has been transferred to industry.

11.1.7 The thermo-chemical cycles are processes, where water is decomposed


into hydrogen and oxygen via a series of chemical reactions using
intermediates, which are recycled. As the heat can be directly used, these
cycles have the potential of a better efficiency than alkaline electrolysis. The
required energy can be either provided by nuclear energy / solar energy. The
iodine-sulfur closed & open loop (I-S) cycle and Cu-Cl closed loop cycle are
most promising and efficient thermo-chemical water splitting technologies for
the massive production of hydrogen. BARC has successfully demonstrated in
the I-S closed loop operation in glass / quartz materials in the country. It has
been planned to take-up demonstration of the same process in metal
construction. The ONGC Energy Centre (OEC) has set-up an engineering scale
plant for Cu-Cl closed loop cycle process, which will be operated for one year
and alternative materials for platinum as electrode has been undertaken for
development at this plant. OEC is also working with CSMCRI, Bhavnagar on
indigenous development of polymeric charged membranes for thermochemical
hydrogen generation processes; with IIP, Dehradun for the development of
partially open-loop I-S cycle involving H2S incineration & experimental studies
on Bunsen reaction and HI decomposition and with IIT Delhi on prolonged
stability tests of catalysts for HI decomposition reaction of I-S cycle. OEC has
also planned to carry out research on identification, development and testing of
suitable materials for design and construction of large size indigenous reactors
for Cu-Cl process, keeping in view the corrosive nature of materials used in the
Cu-Cl process.

205
11.1.8 Hydrogen can be produced from dark fermentation (equivalent to 20 to
30% of the total energy content of the feed). This process followed by photo
fermentation, 12 moles of H2 /mole of glucose can be recovered theoretically,
but it is difficult to integrate the two processes for commercialization. The dark
fermentation can be integrated with the bio-methantion process (to yield 50-
60% gaseous energy recovery), where methane may be produced from the
spent media of the dark fermentation, which is rich in volatile fatty acids that is
an ideal substrate for methanogens. The most attractive point of such a
process is that both the processes may be carried out one after the other in the
same reactor (H2 production followed by bio-methanation. So, separate reactor
is not required. This would lead to decrease in operational cost of the entire
process. Bio-hythane production may be envisioned as renewable source of
energy only when it would be produced from renewable sources. Any organic
compound which is rich in carbohydrates, fats and proteins could be considered
as possible substrate for bio-hymet production.

11.1.9 Steam-methane reforming (SMR) and coal gasification are the


technologies established globally for hydrogen production. They are
commercially ready, though the cost is high. Still there is scope for carrying out
R&D activities for coming out with cheaper catalysts and efficient reforming
units.

11.1.10 Auto-thermal reformers (ATRs) combine some of the best features of


steam reforming and partial oxidation systems. Several companies are
developing small auto-thermal reformers for converting liquid hydrocarbon fuels
to hydrogen for the use in fuel cell systems. The auto-thermal reformer requires
no external heat source and no indirect heat exchangers. Heat generated by
the partial oxidation is utilized to drive steam reforming reaction. This is more
compact than steam reformers, and it will have a lower capital cost and higher
system efficiency than partial oxidation systems. Auto-thermal reformers are
being developed for PEMFC system by a number of groups.

11.1.11Solar hydrogen production from direct photo electrochemical (PEC)


water splitting is the ultimate goal for a sustainable, renewable and clean

206
hydrogen economy. In PEC water splitting, hydrogen is produced from water
using sunlight and specialized semiconductors called photo electrochemical
materials, which use light energy to directly dissociate water molecules into
hydrogen and oxygen. Indian R & D organisations are engaged in the extensive
R & D of photo-electrochemical technology.

11.1.12 The efforts are required to develop other/new innovative methodfor


hydrogen production,like hydrogen production by non-thermal plasma assisted
direct decomposition of hydrogen sulphide, Photo-splitting of Hydrogen
Sulphide including developmental effort for reduction in energy consumption for
hydrogen production

11.1.13 To start with, the country may adopt technologies from abroad,
especially to build large installations, for which we may not have the expertise
straightaway. For medium and small installations, Indian R & D organisations
and industries could chip in well.

11.1.14 The Ministry may constitute a group of experts, which may review from
time to time, the plan and actual development and deployment of hydrogen
based systems and devices in the field in order to assess the future hydrogen
requirement. The group will then suggest ways and means to fulfil hydrogen
requirement through various technologies being developed in the country or to
be imported from abroad.

11.2 Recommendations

11.2.1 India has announced its Climate Action Plan for reduction of emissions
by 33-35% by 2030 over the 2005 levels, boosting clean (non-fossil & including
renewable) energy in electricity generation to 40% (at least another 150GW),
while adding carbon sinks — tree and forest cover to remove carbon dioxide
from the atmosphere — amounting to 2.5-3 billion tonnes of CO2 by 2030.
Thus, the country has targeted to enhance nuclear power from 5 GW to 63 GW
by 2032 and doubling wind capacity to 60 GW by 2022, solar capacity from 4
GW to 100 GW by 2022.
207
11.2.2 In view of the India’s Climate Action Plan, the technologies for hydrogen
production may be targeted accordingly. The first target may be focused on the
efficient utilization of byproduct hydrogen of the chlor-alkali units. At the end of
the financial year 2014-15, only 10% of byproduct hydrogen is available.
Remaining 90% byproduct hydrogen is being utilized,~40% in chemical
industries,~37% as fuel in boiler heating for captive use and ~13% being bottled
for sale. After utilization of surplus un-utilized 10% byproduct hydrogen, next
target may be made to utilize ~37% hydrogen efficiently, which is currently
being used as fuel in boiler heating for captive use. Alternate sources may be
used for heating purpose. In-house stationary power generation may be one
of the most effective ways of utilizing hydrogen. The government may consider
incentivizing this application of hydrogen for its cost effective utilization.

11.2.3 The present facilities of hydrogen production may be utilized to supply


hydrogen for purpose of carrying out the activities on the research,
development and demonstration for hydrogen production and its applications
for stationary power generation and vehicles.

11.2.4 From the gap between international and national state of art of
technologies, it has been visualized that India has to take a leapfrog to come at
par with the international level. This gap is to be planned in time bound project
mode (with foreign collaboration, if required) and therefore, the projects may be
classified in the following three categories viz. National Mission Projects,
Research & Development projects and Basic / Fundamental Research projects:

11.2.5 The National Mission Projects may cover projects with the participation
of the industry for the technologies, which are mature or near maturity for
commercialization after the short development time and those may be taken up
on large scale demonstration. Such projects would be multi-disciplinary in
nature. These projects may involve more than one institution (with a lead
institution), which are already involved in the implementation of research &
development activities. The outcome of such projects should be a compact,
comprehensive, marketable and user friendly product. The resources and the

208
infrastructure facilities of the involved institutions may be pooled together to
achieve the common goal.

11.2.6 The Research & Development projects may include the projects in which
the technology is at the stage of prototype development and its demonstration
as a proof of concept. Industry participation should be preferred for these
projects. Such projects may be undertaken on different subjects like design,
research & development of the individual system components, sub-systems,
integration of systems after the basic research has shown encouraging
results. Engineering research and development must be a part of such
projects.

11.2.7 The Basic / Fundamental Research projects will cover search /


development of new materials for the development of components, catalysts
and new processes in the area of hydrogen production.

11.2.8 These categories may be further elaborated as under:

a) Mission Mode Projects

(i) Development and demonstration of biological hydrogen


production from different kinds of wastes like effluents from
distillery, brewery, paper mills, wastewater from city, dairy,
tannery, slaughter house, chemical & pharmaceutical
industries, agro / food processing industry residues like cane
molasses, noodle and potato processing, poultry litter, de-
oiled algal cakes, food (canteen) waste through dark or/and
photo fermentation. Demonstration of prototypes at various
levels followed by bench scale and pilot plant. After successful
demonstration commercial production may be commenced.
(ii) Research and development for hydrogen production by
gasification of biomass, including demonstration of technology
at pilot scale.
(iii) Hydrogen production by water splitting using photolysis and
thermo-chemical route using solar and nuclear heat.
209
b) Research and Development Projects

(i) Hydrogen production together with methane through


biological processes from different kinds of organic wastes,
including industrial effluent. Energy balance and process
economic aspects may also be studied.
(ii) Development & demonstration of 1 Nm3/hr high temperature
steam electrolyser (HTSE) and 5 Nm3/hr indigenously
developed solid polymer water electrolyser (SPWE).
(iii) Development & demonstration of efficient alkaline water
electrolyser.
(iv) Development and demonstration of clean and sustainable
hydrogen production by splitting water using renewable
energies such as solar energy, wind energy and hybrid
systems. This also includes electrolysis, photo-catalysis and
photo-electro-catalysis.

c) Basic / Fundamental Research Projects

(i) Dissociation of gaseous hydrocarbon fuels to hydrogen using


solar energy.
(ii) Any other innovative method for hydrogen production, like
hydrogen production by non-thermal plasma assisted direct
decomposition of hydrogen sulphide, Photo-splitting of
Hydrogen Sulphide, including developmental effort for
reduction in energy consumption for hydrogen production

(d) Projects for Utilization of Byproduct Hydrogen at Chlor Alkali


Units / Refineries

Development and demonstration of prototype systems for


purification of by-product hydrogen from chlor-alkali units /
refineries for the use in fuel cells to generate power for captive

210
use or its compression for filing in cylinders to use them on-board
in hydrogen fueled vehicles / material handling systems (based
on fuel cell technology).

211
BIBLIOGRAPHY

212
12.0 Bibliography

12.1 Hydrogen Production from Carbonaceous Biomass Feed-stock


using Thermochemical Route

1. Konieczny A, Mondal K, Wiltowski T, Dydo P.,Catalyst Development


for Thermocatalytic Decomposition of Methane to Hydrogen. 33,
2008, Int J Hydrogen Energy, pp. 264–272.
2. Meng Ni, Dennis Y.C. Leung, Michael K.H. Leung, K. Sumathy. An
Overview of Hydrogen Production from Biomass. Fuel Processing
Technology 87 (2006) 461 – 472
3. Sandeep K, Dasappa S. Oxy–steam Gasification of Biomass for
Hydrogen Rich Syngas Production using Downdraft Reactor
Configuration. International Journal of Energy Research, 2014, 38,
pp. 174–188.
4. Mukunda H S, Dasappa S, Shrinivasa U. Open-Top Wood Gasifier
(Renewable Energy – Sources for Fuels and Electricity). S. l. : Island
Press. pp. 699-728.
5. Dasappa S, Paul, P J Mukunda, H S, Rajan, NKS, Sridhar, G.,
Sridhar. H V., Biomass Gasification Technology – A Route to Meet
Energy Needs, Current Science, 2004, 87( 7), pp. 908-916.
6. Tuomi, S., Kurkela, E., Simell, P., and Kaisalo, N., Gasification
Concept Testing for Dual Fluidized-bed based SNG Process, VTT
Technical Research Centre of Finland, POB 1000, FI-02044 VTT,
Espoo, Finland. Proceedings of the ICPS – 2013, pages 397-472.
7. Bridgewater, A. V., Renewable Fuels and Chemicals by Thermal
Processing of Biomass, Chemical Engg. Journal, 2003, 91, pp. 87-
102.
8. Ahmed, I., Gupta, A. K., Characteristic of Hydrogen and Syngas
Evolution from Gasification and Pyrolysis of Rubber., Int J Hydrogen
Energy, 2011, 36, pp. 4340–4347.
9. Ahemad, I., Gupta, A. K., Kerdsuwan, S., Nipattulmmakul, N.,
Hydrogen and Syngas Yield from Residual Branches of Oil Palm

213
Tree Using Steam Gasification, Int J Hydrogen Energy 2011, 36, pp.
3835–3843.
10. Turn, S., Kinoshita, C. Zhang, Z., Ishimura, D., Zhou. J., An
Experimental Investigation of Hydrogen Production from Biomass
Gasification, Int J Hydrogen Energy , 1998, Vol. 23(8), pp. 641-648.
11. Pengmei L V, Yuana Zhenhong, Longlong Maa, Chuangzhi Wua,
Yong Chena, Jingxu Zhu, Hydrogen-rich Gas Production from
Biomass Air and Oxygen/Steam Gasification in a Downdraft Gasifier.
Renewable Energy 10/2007; 32(13):2173-2185.
12. Wei, L., Xu, S., Zhang, L., Liu, C., Zhu, H., Liu, S., Steam
Gasification of Biomass for Hydrogen-rich Gas in a Free-fall Reactor,
Int J Hydrogen Energy , 2007, 32, pp. 24–31.
13. Pereira, E. C., Silva, J. N., de Oliveira, J. L., Machado, C. S.,
Sustainable Energy: A Review of Gasification Technologies,
Renewable and Sustainable Energy Reviews, 2012, 16, pp. 4753–
4762.
14. Arnavat, M. P., Bruno, J. C., Coronas, A., Review and Analysis of
Biomass Gasification Models, Renewable and Sustainable Energy
Reviews, 2010, 14, pp. 2841–2851.
15. Dasappa, S. Shrinivasa, U., Baliga, B. N., Mukunda, H. S., Five Kilo
Watt Wood Gasifier Technology: Evolution and Field Experience,
Sadhana , 1990, Vol. 14(3), pp. 187-212.
16. Peters, J. F., Petrakopoulou, F, Dufour J., Exergetic Ananlysis of a
Fast Pyrolysis Process for Bio-oil Production, Fuel Processing
Technology, 2014, 119, pp. 245–255.
17. Abuadala, A, Dincer, I., Naterer, G. F., Exergy analysis of hydrogen
production from biomass gasification, International Journal of
Hydrogen Energy , 2010, 35, pp. 4981–4990.
18. Prins, M. J.,Ptasinski,, K. J., Janssen, F. J. J. G., Thermodynamics
of Gas-Char Reactions: First and Second Law Analysis, Chemical
Engineering Science, 2005, 58, pp. 1003 – 1011.
19. Silva V B, Rouboa A., Using a Two-stage Equilibrium Model to
Simulate Oxygen-Air Enriched Gasification of Pine Biomass
Residues., Fuel Processing Technology, 2013, 109, mpp. 111–117.
214
20. Ptasinski K J, Prins M J, Pierik A., Exergetic Evaluation of Biomass
Gasification, Energy, 2007, Vol. 32 (4), pp. 568–74.
21. Karamarkovic R, Karamarkovic V., Energy and Exergy Analysis of
Biomass Gasification at Different Temperatures. Energy, 2010, 35,
pp. 537–549.
22. Sues A, Juras M, Ptasinski K J., Exergetic Evaluation of 5 Biowastes-
to-Biofuels Routes via Gasification, Energy, 2010, 35, pp. 996–1007.
23. Lucasa, C.,Szewczyka, D., Blasiaka, W., Mochida, S., High
Temperature Air and Steam Gasification of Densified Biofuels. 27,
2004, Biomass and Bioenergy, pp. 563–575.
24. Umeki, K., Yamamoto, K., Namioka, T., Yoshikawa. K, High
Temperature Steam-only Gasification of Woody Biomass. 87, 2010,
Applied Energy, pp. 791-798.
25. Dasappa, S., Experimental and Modeling Studies on the Gasification
of Wood-char. Ph.D. thesis. Indian Institute of Science, India. 1999.
26. Generator Gas "The Swedish Experience from 1938-1945
(translation)", Solar Energy Research Institute, Colorado,
NTIS/Sp.33-140. SERI, 1979
27. http://mnre.gov.in/
28. www.ankurscientific.com/
29. http://www.teriin.org/
30. http://www.spreri.org/
31. CGPL–2009 http://cgpl.iisc.ernet.in/site/Home/tabid/36/Default.aspx
32. Fail S., Diaz, N., Konlechner, D., Hackel, M., Sanders, E., Rauch,
R., Harasek, M., Bosch, K., Schwenninger, F., Zapletal, P., Schee,
Z., and Hofbauer, H., .An Experimental Approach for the Production
of Pure Hydrogen Based on Wood Gasification, Presented at the
13th International conference on Polygeneration Strategies, Vienna,
Austria 2013.

12.2 Gasifiers, Reformers and Electrolysers

1. Winter C. J., International Journal of Hydrogen Energy 34(2009),


S1-S52
215
2. Bastien J. and Handler C., IEEE 2006, 1-4244-0218-2/06
3. www.eai.in
4. Nouni M. R., Green Power 2008, Intenational Conference cum
Exhibition on Renewable Energy Technologies, 2008
5. www.ITM–power.com
6. Wendt H. Water Splitting Methods. In: Winter C.-J., Nitsch J,
editors. Hydrogen as an Energy Carrier – Technologies, Systems,
Economy, Springer Verlag; 1988
7. www.hysolar.com
8. LIrong Ma, Sheng Sui, Yuchun Zai, International Journal of
Hydrogen Energy, 2009, 34:678-84
9. Rubin E. S., 4th Annual SECA, 2003
10. www.thuega.de
11. www.dvnkema.com
12. www.afhypac.com
13. Fuel Cell Industry Review 2012 (www.fuelcelltoday.com)
14. National Hydrogen Energy Board, Ministry of New and Renewable
Energy, New Delhi, National Hydrogen Energy Road Map – 2006
(abridged report – 2007)
15. Nouni M. R., Akhshay Urja (Renewable Energy) News Letter 5(5),
2012, 10-15,
16. Minsitry of New and Renewable Energy, Presentation to IPHE
Steering Committee, 2012
17. Central Electrochemical Research Institute, Kraikkudi – Brochure,
PEM based Hydrogen Generator
18. Rengarajan Balaji, Natarajan Senthil, Subramanyan Vasudevan,
Subbiah Ravichandran, Swaminathan Mohan, Ganapathy Sozhan,
Sonanatha Madhu, Jeevarathanam Kennedy, Subramanian
Pushpavanam, Malathy Pushpavanam, International Journal of
Hydrogen Energy, 36 (2011), 1399 – 1403
19. Venkatkarthick R., Elamathi S., Sangeetha D., Balaji R., Suresh
Kannan B., Vasudevan S., Jonas Davidson D., Sozhan G.,
Ravichandran S., Journal Electroanalytical Chemistry, 697, 2013, 1
–4
216
20. www.newIndpress.com
21. International Symposium & Exhibition on Fuel Cell Technologies,
FUCETECH 2009, 11th - 13th November, 2009, Nehru Centre,
Worli, Mumbai
22. Basu, S., Second International Conference on Hydrogen and Fuel
Cells, Dec 1 - 3, 2013, Goa
23. Basu, S., Workshop on On-board Power Source for Defense and
Aerospace applications, R C I Hyderabad, DRDO, June 2014
24. UKH2 Mobility: Synopsis of Phase 1 Results, February 2013
25. http://energy.gov/articles/energy-department-launches-public-
private-partnership-deploy-hydrogen-infrastructure

12.3 Hydrogen Production using Electrolytic Processes - Low and High


Temperature Electrolysers

1. Magnet, H. R., and Berger, C., "Handbook of Fuel Cell Technology,"


Prentice- Hall, Englewood Cliffs, NJ, USA, p. 425, 1968.
2. Bockris, J. O., and Srinivasan, S., Fuel Cells: Their
Electrochemisry, New York: McGraw-Hill, 1969.
3. Smitha, B., Sridhar, S., and Khan, A. A., Journal of Membrane
Science, vol. 259, pp. 10-26, 2005.
4. Yoko, , H., Sodaye, H., Shibahara, Y., Honda, Y., Tagawa, S., and
Nishijima, S., Polymer Degradation and Stability, vol. 95, no. 1, pp.
1-5, 2010.
5. B. Bahar, A. R. Hobson, J. A. Kolde and D. Zuckerbrod, U.S. Patent
5,547,551 (1996).
6. Wei, J., Stone, C., and Steck, A.,.Patent 5422411, June 1995.
7. S. Heitala, S., M. Paronen, M., S. Holmberg, S., J. Nasman, J.,
Juhanoja, J., Karjalainen, M., Serimaa, R., Tivola, M., Lehtinen, T., .
Parovuori, K., Sundholm, G., Ericson, H., Mattsson, B., Torell, L.,
and F. Sundholm, F., Journal of Polymer Science, vol. 37, pp. 1474-
1753, 1999.

217
8. Sodaye, H. S., Prabhakar, S., and Tewari, P. K., in National
Seminar on Membrane Science & Technology: Challeges and
Opportunities, Jorhat, 2004.
9. Wang, F., Hickner, M., Kim, Y. S., Zawodzinski, T. A., and
McGrath, J. E., Journal of Membrane Science, vol. 197, pp. 231-
242, 2002.
10. Lafitte, B., Karlsson, L. E., and Jannasch, P., Rapid Macromol
Commun, vol. 23, pp. 896-900, 2002.
11. Rikukawa, R., and Sanui, K., Progress Polymer Science, vol. 25,
pp. 1463-1502, 2000.
12. Genies, C., Mercier, R., Sillion, B., Corner, N., Gebel, G. and
Pineri, M., Polymer, vol. 42, pp. 359-373, 2001.
13. Lawrence, R., USA Patent 4214969, July 1980.
14. K. D. Kreuer, Journal of Membrane Science, vol. 185, p. 13, 2001.
15. Jochen, K., Andreas, U., Frank, M., and Thomas, H., Solid State
Ionics, vol. 125, no. 1-4, pp. 243-249, 1999.
16. Haiqui, Z., Li, X., Zhao, C., Fu, T., Shi Y., and. Na, H., Journal of
Membrane Science, vol. 308, no. 1-2, pp. 66-74, 2008.
17. Thomas, T., and Jari, I. K., Journal of Membrane Science, vol. 313,
no. 1-2, pp. 86-90, 2008.
18. Haubold, H. G., Vad, T., Jungbluth, H., and Hiller, P., Electrochim
Acta, Vol. 46, pp. 1559-1563, 2001.

12.4 Bio-Hydrogen Production

1. Armor, J. N., “The Multiple Roles for Catalysis in the Production of


H2”, Applied Catalysis A: General. 1999; 176: 159-176.
2. Benemann J R. Hydrogen Biotechnology: Progress and Prospects.
Nature Biotechnol 1996; 14:1101–3.
3. Momirlan M, Veziroglu T N. Current Status of Hydrogen Energy.
Renewable Sustainable Energy Rev. 2002; 6:141–179.

218
4. Collet C., Adler N., Schwitzguébel J P., Paul Péringer P., Hydrogen
Production by Clostridium thermolacticum during Continuous
Fermentation of Lactose, Int J Hydrogen Energy. 2004; 29(14): 1479-
1485.
5. Oh, Y. K., Kim S. H., Kim, M. S., and Park, S., Thermophilic
Biohydrogen Production from Glucose with Trickling Biofilter. Biotech
Bioengineering. 2004; 88(6): 690–698.
6. Potential for Wastewater Treatment Systems Based on Microbial
Fuel Cells and Biological Hydrogen Production. ACS, Division of
Environmental Chemistry - Preprints of Extended Abstracts. 2004;
44(2):1474-1477.
7. Zangh H., Logan B., Biological Hydrogen Production from an
Unsaturated, Packed-bed Bioreactor. ACS National Meeting Book of
Abstracts 2004: 228(1); 300. Abstracts of Papers - 228th ACS
National Meeting; Philadelphia
8. Degliuomini L.N., Biset S., Luppi P., Marta S. Basualdo, A Rigorous
Computational Model for Hydrogen Production from Bio-ethanol to
Feed a fuel Cell Stack, Int J Hydrogen Energy. 2012; 37(4): 3108-
3129.
9. Vatsala, T.M., Raj, M., Manimaran, A., A Pilot-scale Study of
Biohydrogen Production from Distillery Effluent using Defined
Bacterial Co-culture. Int J Hydrogen Energy. 2008; 33(20): 5404-
5415.

12.5 Hydrogen Production through Thermochemical Cycles (Iodine-


Sulphur Cycle)

1. Zhang, P., et al., Overview of Nuclear Hydrogen Production


Research through Iodine-Sulfur Process at INET, International
Journal of Hydrogen energy, 35 (2010 ) 2883 – 2887.
2. IAEA Nuclear Energy Series, No. NP-T-4.2 Hydrogen Production
Using Nuclear Energy, 2013
3. Status of HTTR Project in JAEA, Hirofumi OHASHI, Technical
Meeting on the Safety of High Temperature Gas Cooled Reactors in
219
the Light of the Fukushima Daiichi Accident, 8 - 11 April 2014, IAEA
Headquarters, Vienna, Austria
4. Greg F. Naterer, Ibrahim Dincer, Calin Zamfirescu Hydrogen
Production from Nuclear Energy, Springer, 2013

12.6 Hydrogen Production by Photo-electrochemical Water Splitting

1. Kudo, A., Miseki, Y. Heterogeneous photocatalyst materials for water


splitting. Chem. Soc. Rev. 2009, 38, 253–278.
2. Kamat, P.V. Graphene-based nano architectures. Anchoring
semiconductor and metal nano particles on a two-dimensional
carbon support. J. Phys. Chem. Lett. 2010, 1, 520–527.
3. H. Matsushima, T. Nishida, Y. Konishi, Y. Fukunaka, Y. Ito and K.
Kuribayashi, Electrochim. Acta, 48 (2003) 4119.
4. Guttman F and Murphy OJ, Modern Aspects of Electrochemistry.
New York: Plenum Press, 1983.

220
ANNEXURE

221
13.0 Publications and Patents pertaining to Hydrogen
Production through Thermochemical Routes
(I-S & Cu-Cl)

13.1 Publications

1. G. D. Yadav, P.S. Parhad, A. B. Nirukhe and S. B. Kamble. Study of


Hydrogen Generation using Copper and Hydrochloric Acid. Presented at
Chemcon-2008, IIChE Annual congress held in Chandigarh, India during
December 27-30, 2008.
2. D. Parvatalu, A. Bhardwaj and B.N. Prabhu. Technical challenges in
generation of Hydrogen through thermo-chemical processes: ONGC
perspective. Poster paper presented at PETROTECH-2009 held in Delhi,
India during January 11-15, 2009.

3. A. Bhardwaj, D. Parvatalu, and B.N. Prabhu. Closed-loop Thermo-


chemical Cycles for Hydrogen Production: Fuel for Tomorrow. Poster
paper presented PETROTECH-2009 held in Delhi, India during January
11-15, 2009.

4. A. Bhardwaj, D. Parvatalu, and B.N. Prabhu. Hydrogen Production by


Closed-loop Thermo-chemical Cycles: A Review of S-I Process. Paper
presented at the National Conference on Energy held at Punjab
University, Chandigarh, India during March, 2009.

5. V. Immanuel, K. U. Gokul, S. Sant and A. Shukla. Membrane Electrolysis


of Bunsen Reaction. Presented at CHEMCON-2009, IIChE annual
congress held in Visakhapatnam, India during December 27-30, 2009,

6. D. Parvatalu, A. Bhardwaj and B. N. Prabhu. Electrochemical Routes


Need Better Understanding in Managing Closed- loop Hybrid Thermo-
chemical Hydrogen Generation Cycles. Paper presented at 15 th National
convention of Electrochemists held at VIT-University, Vellore, India during
February18-19, 2010.

222
7. A. Bhardwaj, D. Parvatalu, and B.N. Prabhu. Study of the Alternate Route
in Closed-loop Thermo-chemical Cycles for Hydrogen Production: fuel for
tomorrow. Poster presentation at PETROTECH-2010 held in Delhi, India
during October 31-November 4, 2010.

8. A. Bhardwaj, D. Parvatalu, B.N. Prabhu and N.J. Thomas. Future Energy


and Hydrogen. Oral presentation at 17th IORS, held in Mumbai, India
during September 9-10, 2010.

9. D. Parvatalu, Anil Bhardwaj and B.N. Prabhu. Impact of Electrochemical


Routes on thermochemical Hydrogen Generation Technologies. Poster
presentation at ISAEST-9, held in Chennai, India during December 2-4,
2010.

10. V. Immanuel, K. U. Gokul and A. Shukla. Membrane Electrolysis of


Bunsen Reaction for the Iodine-Sulfur Process for Water Splitting.
Presented at ISAEST-9, held in Chennai, India during December 2-4,
2010.

11. P. K. Sow and A. Shukla. Investigations on Electro-electrodialysis Cell for


Concentration of HIx. Presented at ISAEST-9, held in Chennai, India
during December 2-4, 2010.

12. G. D. Yadav, A. B. Nirukhe and P.S. Parhad. Kinetic Study of Hydrolysis


of Cupric Chloride in Cu-Cl Thermochemical Hydrogen Production.
Presented at CHEMCON-2010, IIChE annual congress held at Annamalai
University, Chidambaram, India during December 27-29, 2010.

13. G. D. Yadav, P.S. Parhad and A. B. Nirukhe. Study of Electrolysis of


Cuprous Chloride. Presented at CHEMCON-2010, IIChE annual congress
held at Annamalai University, Chidambaram during December 27-29,
2010.

14. P. K. Sow, S. Santand A. Shukla. EIS Studies on Electro-electrodialysis


Cell for Concentration of Hydroiodic Acid. Int J Hydrogen Energy, 2010;
35: 8868–8875.

223
15. D. Parvatalu, Anil Bhardwaj and B.N. Prabhu. Development of
thermochemical Hydrogen Production by Closed-loop Cycles: ONGC
initiatives. Oral presentation at ICRE-11 held at CNRE, Univ. Rajasthan,
Jaipur, India during January 17-21, 2011.

16. D. Parvatalu, A. Bhardwaj and B.N. Prabhu. Gearing up for Large Scale
Thermochemical Hydrogen Generation Technologies: ONGC Initiatives.
Oral presentation at ICSN 2011 held at Univ. Mumbai, Mumbai, India
during February 14-16, 2011.

17. D. Parvatalu, A. Bhardwaj and B.N. Prabhu. Opportunities and Challenges


Associated with Thermochemical Hydrogen Generation Technologies: A
Perspective in Indian Context. Presented at ICAER 2011 held at IIT-
Bombay, Mumbai, India during December 9-11, 2011.

18. D. Parvatalu, A. Bhardwaj and B.N. Prabhu. Application of


Electrochemical Technologies in Establishing Closed-loop
Thermochemical Hydrogen Generation Cyclic Processes: ONGC
Initiatives. Oral Presentation at NCE-16 (National Convention of
Electrochemists) held at P.S.G.R.K. College, Coimbatore, India during
December 15-16, 2011.

19. K. Kondamudi, P. Kotari and S. Upadhyayula. Numerical Study of Sulfurtri


Oxide Decomposition over Complex Catalyst Shapes and Sizes in S-I
Cycle for Hydrogen Production. Presented at Europacat X held at
University of Glasgow, Glasgow, UK during August 28 – September 2,
2011.

20. K. Kondamudi, A.N. Bhaskarwar, S. Upadhyayula, B.N. Prabhu, Anil


Bhardwaj and D. Parvatalu. Kinetic Studies of Sulfuric Acid Decomposition
over Alumina Supported Iron (III) Oxide Catalyst in the SI Cycle for
Hydrogen Production. Presented at ICRE-2011, held in Jaipur, India
during January 17-21, 2011.

21. K. U. Gokul, V. Immanuel, S. Sant and A. Shukla. Membrane Electrolysis


for Bunsen Reaction of S-I Cycle. J. Membr. Sci., 2011, 380, 13-20.

224
22. V. Immanuel, K. U. Gokul and A. Shukla. Membrane Electrolysis of
Bunsen Reaction in the Iodine – Sulfur Process for Hydrogen Production.
Presented at ICRE-2011 held in Jaipur, India during January 17-21, 2011

23. P. K. Sow and A. Shukla. Electro-Electrodialysis for Concentration of


Hydroidic Acid. Presented at ICRE-2011 held in Jaipur, India during
January 17-21, 2011.

24. K. Kondamudi and S. Upadhyayula. Kinetic Studies of Sulfuric Acid


Decomposition over AL–Fe2O3 Catalyst in the Sulfur-iodine Cycle for
Hydrogen Production. Int. J. Hydrogen Energy, 2012, 37(4), 3586–3594.

25. P. K. Sow and A. Shukla. A Chronopotentiometry based Identification of


Time-varying Different Transport Resistances of Electro-electrodialysis
Cell used for Concentration of HIx Solution. Int. J. Hydrogen Energy. 2013,
38, 3154-3165

26. P.K. Sow, D. Parvatalu, A. Bhardwaj, B. N. Prabhu and A. N. Bhaskarwar.


Impedance spectroscopic determination of effect of temperature on the
transport resistances of an electro-electrodialysis cell used for
concentration of Hydroidic Acid. J. Applied Electrochem, 2012, 43 (11) 31-
41.

27. P. K. Sow and A. Shukla. Effect of Asymmetric Variation of Operating


Parameters on EED Cell for HI Concentration in I-S Cycle for Hydrogen
Production. Int. J. Hydrogen Energy, 2012, 37(19), 13958-13970.

28. V. Immanuel, D. Parvatalu, A. Bhardwaj, B. N. Prabhu, A. N. Bhaskarwar


and A. Shukla. Properties of Nafion 117 in Highly Acidic Environment of
Bunsen Reaction of I-S Cycle. J. Membr. Sci., 2012, 409-410, 137-144.

29. V. Immanuel and A. Shukla, “Effect of Operating Variables on


Performance of Membrane Electrolysis Cell for Carrying Out Bunsen
reaction of I-S Cycle” Int. J. Hydrogen Energy, 2012, 37, 4829-4842.

30. P. K. Sow and A. Shukla. Electro-electrodialysis for Concentration of


Hydroidic Acid. Int. J. Hydrogen Energy, 2012, 37, 3931-3937.

225
31. V. Immanuel, K. U. Gokul and A. Shukla. Membrane Electrolysis of
Bunsen Reaction in the Iodine-Sulfur Process for Hydrogen Production.
Int. J. Hydrogen Energy, 2012, 37, 3595-3601.

32. P. K. Sow and A. Shukla. A Chronopotentiometry based Identification of


Time-varying Different Transport Resistances of Electro-electrodialysis
Cell Used for Concentration of HIx Solution. Int. J. Hydrogen Energy,
2013, 38(8), 3154-3165.

33. D. Parvatalu, S. Banerjee and B.N. Prabhu. Envisaged Technical Barriers


in Converting Electrochemical Solutions to Hybrid-Thermochemical
Technologies: ONGC Perspective. Paper presented at ISAEST-10held in
Chennai, India during January 28-30, 2013.

34. A.B. Nirukhe, P.S. Parhad, A. Bhardwaj, D. Parvatalu and G. D. Yadav.


Hydrogen Production by Non-Catalytic Decomposition of Hydroidic Acid.
Paper accepted for presentation at the International Conference on
Advances in Chemical engineering (ICACE-2013)to be held at NIT,
Raipur, India during March, 8-9, 2013.

35. S. Kamini, S. Banerjee, D. Parvatalu and B.N. Prabhu. Hydrogen


Production by Thermochemical Iodine-Sulfur Cycle: Process Simulation
Studies of Bunsen Section. Paper presented at the International
Conference on Advances in Chemical engineering (ICACE-2013)held at
NIT, Raipur, India during April 5-6, 2013.

36. K. Kondamudi and S. Upadhyayula, “Decomposition of Sulfuric Acid over


Mixed Metallic Oxides - A Comparative Study for Oxygen Evolving Step in
S-I Cycle for Hydrogen Production”, EUROPACAT XI Conference, LYON,
France, September 1-6, 2013.

37. D. Parvatalu and B.N. Prabhu. Material Issues Dictate Hydrogen


Generation by Thermochemical Water Splitting Technologies: ONGC
Energy Center Perspective. Presented at CORCON-2013, New Delhi.

38. D. Parvatalu, S. Banerjee and B.N. Prabhu. Recent Developments in


Hydrogen Generation using Iodine- Sulfur Thermochemical Water

226
Splitting Cycle: ONGC Energy Center efforts, PETROTECH-2014held in
Delhi, India during January 12-15, 2014.

39. D. Parvatalu. Development of Thermochemical Hydrogen Generation


Technologies using Water Splitting Processes: ONGC Energy Center
Perspective. Invited lecture at National workshop on “Fuel Cell
Technology: Basic science to Application” held at MANIT, Bhopal during
March 24-25, 2014

40. D. Parvatalu. Hydrogen is the Key to Success of Renewable Energy


Campaign: ONGC Energy Centre perspective. Invited talk at the National
Seminar during 17-18th November 2014 at Univ. Kerala, Trivandrum
organized by Indian Association for Hydrogen Energy and Advanced
Materials

41. Kamini Shivakumar, S. Banerjee and D. Parvatalu. Simulation studies on


HI Decomposition in Thermochemical Iodine-Sulfur Cycle. Paper
presented at CHEMCON-2014, the 67th Annual Session of the Indian
Institute of Chemical Engineers to be held at Punjab University,
Chandigarh, from 27th – 30th December, 2014.

42. D. Parvatalu, An Overview of Material Requirements for Copper-Chlorine


Thermochemical Cycle: ONGC Energy Centre Perspective. Paper
published in Society for Materials Chemistry Quarterly Bulletin issued by
BARC, 2014

43. D. Parvatalu. Development of Closed-loop Thermochemical Water


splitting Processes for Hydrogen Generation: ONGC Energy Centre
Initiatives. Presentation at 3rd International Conference on Hydrogen and
Fuel Cell during 7-9 December 2014 at Udaipur.

44. D. Parvatalu. Role of Catalysts in the Development of the Iodine-Sulfur


and Copper-Chlorine Thermochemical Hydrogen Generation
Technologies. Presented at 22nd National Symposium on Catalysis
(CATSYMP 22) during 7-9.01.2015 at CSMCRI Bhavnager.

227
45. N. Sathaiyan, V. Nandakumar, G. Sozhan, J. GhandhibaPackiaraj, E.T.
Devakumar, D. Parvatalu, Anil Bhardwaj and B.N. Prabhu. Hydrogen
Generation through Cuprous Chloride-Hydrochloric Acid Electrolysis.
International Journal of Energy and Power Engineering, 27 January 2015.
[Pages 15-22]

13.2 Details of Patents

Sl. Patent title Institutions Patent Details


No.

1 Hydrogen Production Method by OEC and ICT, National and


Multi-Step Copper-Chlorine Mumbai International*
Thermochemical Cycle
2 Electrochemical Cell Used for the OEC and ICT, National and
Production of Copper Using Cu-Cl Mumbai International*
Thermochemical Cycle

3 Effect of Operating Parameters on OEC and ICT, National and


the Performance of Mumbai International*
Electrochemical Cell in Copper-
Chlorine Cycle
4 High Performance Supported OEC and IIT, National*
Metallic/Mixed Metallic Catalyst Delhi
for Sulfuric Acid Decomposition in
Sulfur-Iodine (SI) Cycle for
Hydrogen Production
5 Process for Catalytic OEC and IIT, National*
Decomposition of Sulfuric Acid Delhi
over High Performance Supported
Metallic/Mixed Metallic Catalyst in
SI Cycle
6 Highly active supported bimetallic OEC and IIT, National*
(Ni-Pt) catalyst for hydrogen Delhi
iodide (HI) decomposition and
synthesis procedure thereof

228
7 Vanadia supported Pt catalyst OEC and IIT, National*
and use thereof for hydrogen- Delhi
iodide decomposition in sulfur-
iodine (I-S) cycle for hydrogen
production.

The US and Japan patents on “Hydrogen Production Method by Multi-Step


Copper - Chlorine Thermochemical Cycle” have been granted.

*********

229