Chenassignment Complete

Hydrogen Production By Chemical Looping Catalytic Reactors- A.
To (z3252159)
UNSW School of Chemical Engineering

CHEN 6701 Research Report
HYDROGEN PRODUCTION BY
CHEMICAL-LOOPING CATALYTIC
REACTORS
Lecturer: Prof. A.A. Adesina
By Alice To (z3252159)
Word Count: 12400
Submitted on: 26/10/2010
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Hydrogen Production By Chemical Looping Catalytic Reactors- A. To (z3252159)
CONTENTS
ABSTRACT.......................................................................................................................................................... 3
Context of the Report .................................................................................................................................... 4
Aims of the Report ......................................................................................................................................... 7
LITERATURE REVIEW .......................................................................................................................................... 9
Conventional Hydrogen Production ............................................................................................................... 9
Alternative Hydrogen Production Processes ................................................................................................. 12
Introduction to Chemical Looping ................................................................................................................ 14
Chemical looping for Hydrogen Production .................................................................................................. 18
Syngas Chemical Looping (Developed by Ohio University) ........................................................................ 19
Coal Direct Chemical Looping (Developed by Ohio University).................................................................. 22
Unmixed Fuel Processor (from GE Global Research) ................................................................................. 26
Alstom’s Hybrid Chemical Looping Process ............................................................................................... 30
Overview of Chemical Looping Research ...................................................................................................... 33
Carbon Capture and Storage ........................................................................................................................ 34
THEORETICAL CONSIDERATIONS ...................................................................................................................... 35
AND CRITICAL ANALYSIS .................................................................................................................................. 35
Desirable Catalyst Qualities.......................................................................................................................... 36
Theoretical Considerations of Catalysts ........................................................................................................ 37
Physical Properties of Catalysts .................................................................................................................... 42
Summaries of Chemical-Looping Catalyst Research ...................................................................................... 42
Ni-based oxygen carriers: ......................................................................................................................... 43
Fe-based oxygen carriers.......................................................................................................................... 44
Cu-based oxygen carriers: ........................................................................................................................ 45
Mixed-oxide Oxygen Carriers ................................................................................................................... 47
ILLUSTRATIVE EXAMPLES ................................................................................................................................. 48
Example 1: Pilot Plant in Ohio University ...................................................................................................... 48
References:.................................................................................................................................................. 48
Summary of Work: ....................................................................................................................................... 48
Discussion of the Case Study: ................................................................................................................... 51
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Example 2: Gnanapragasam et al.’s Comparison of Syngas Chemical Looping vs. Coal Direct Chemical Looping
Using ASPEN Plus ......................................................................................................................................... 51
References: .............................................................................................................................................. 51
Summary of Work: ................................................................................................................................... 52
Example 3: Alstom Chemical Looping Pilot Plant .......................................................................................... 56
References: .............................................................................................................................................. 56
Summary of Work: ................................................................................................................................... 56
PERSONAL REFLECTIONS .................................................................................................................................. 60
CONCLUDING REMARKS .................................................................................................................................. 62
BIBLIOGRAPHY................................................................................................................................................. 64
ABSTRACT
With water as its only combustion by-product, hydrogen can meet modern society’s ever-
growing energy demand with minimal environmental impact. The main aim of this report is to
explore the potential of chemical-looping catalytic reactors for hydrogen production by
evaluating the different chemical-looping technologies and processes currently available and
identifying areas requiring further research.
Three specific catalytic chemical looping technologies for the production of hydrogen were
explored: the Syngas Chemical Looping process, the Coal Direct Chemical Looping Process
and Alstom’s Calcium Oxide Chemical Looping Process. The use of different catalysts in
these processes was also investigated.
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INTRODUCTION AND OBJECTIVES
Context of the Report

Research indicates that fossil fuels such as petroleum, natural gas and coal will provide more
than 90% of the energy needs by the year 2030 (US Department of Energy, 2006). Without
carbon capture, continued prevalent use of fossil fuels will cause widespread environmental
degradation. The Intergovernmental Panel of Climate Change (IPCC) has correlated the
increase of the Earth’s temperature with the increase in atmospheric CO 2, which is largely
due to the industrialized burning of fossil fuels (IPCC, 2007). The concentration of CO2 in the
atmosphere has risen to a value of approximately 370 ppm today from the preindustrial value
of 280 ppm. By 2030 coal is projected to be the largest source accounting for over 43% of the
total carbon dioxide emissions (EIA, 2007).
If CO2 emissions are not regulated, global warming can have severe consequences on the
natural equilibrium of the Earth’s ecosystem such as: the increase of sea and ocean levels,
ocean acidification, change in rainfall patterns, hurricanes, volcanic eruptions, earthquakes
and plant or animal extinctions (Vargas, 2007).
There are several methods of anthropogenic CO2 emissions such as: the increase of the use
of renewable sources of potential energy, such as hydro-, wind and solar power; the
promotion of CO2 uptake in biomass; the use of energy derived from biomass rather than
fossil fuels; the expansion of the nuclear power sector; and the reduction global energy
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intensity. However, the global economy revolves around fossil fuels and it is likely that society
will remain highly dependent on fossil fuels for some time to come.
The combination of fossil fuel use with CO 2 capture and storage (or CO2 sequestration) is a
method of reducing net CO2 emissions that is more feasible that the alternatives previously
listed because it requires minimal change in human behavior and is one of the more
technically and economically feasible alternatives. Implementation of CO2 capture and
storage is feasible on any large stationary point source of CO 2, e.g. power plants using fossil
fuels or biomass, steel and cement industries, refineries and natural gas processing facilities.
Storage of CO2 requires it to be separated from other components of flue gas to produce a
virtually pure CO2 stream. As a result, there has been ongoing research into CO 2 separation.
Currently, there are several technologies that are being developed for the capture and
sequestration of CO2 such as membranes, MEA absorption, PSA and Selexol. However,
these technologies are very expensive due to the large volumes they have to treat since
carbon dioxide usually is diluted. These processes also consume energy, which results in a
lower conversion efficiency of the coal (Vargas, 2007).
Chemical looping combustion is a method of CO 2 separation that has been recently
developed which requires much less additional energy compared to other CO 2 separation
technologies. In recent years, process developments in chemical looping combustion has led
to process schemes that can product a variety of products besides electricity, include liquid
fuels, chemical as hydrogen (Li, 2009).
The issue of petroleum use as an energy carrier is analogous to the issue of fossil fuel use in
power generation. Hydrogen has frequently been presented a clean and efficient alternative
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to petroleum, which releases CO2 and other undesirable gases when combusted. With water
as its only combustion by-product, hydrogen can meet modern society’s ever-growing energy
demand with minimal environmental impact. Hydrogen can be used as a transportation fuel,
for power generation and in industrial processes with no carbon dioxide emissions at the point
of use (Vargas, 2007). Hydrogen is being increasingly used in a wide variety of applications.
This is evident in world hydrogen production figures, which have been growing rapidly at 8-
10% per annum for many years (Ryu & Jin, 2007).
Since hydrogen is not a naturally occurring compound, it must be produced from a hydrogen-
containing source. More than 90% of the hydrogen currently produced is derived from fossil
fuels (Ryu & Jin, 2007). Hydrogen can also be produced from a diverse range of feedstocks
including fossil fuels (e.g. coal and natural gas), nuclear energy, and biomass. Energy
sources for production may come from wind, solar, geothermal and hydroelectric power (US
Department of Energy, 2006). Many researchers believe that hydrogen from non-fossil energy
sources will one day completely replace fossil fuels. However, such a time will not be in the
near future, because most hydrogen production process using non-fossil energy sources is
not yet commercially competitive with hydrogen produced from fossil fuels
Conventional hydrogen production occurs via the water-gas shift reaction which results in a
gaseous mixture that includes CO, CO2, H2, and methane. Further separation processes are
required to obtain pure hydrogen. These separation processes threaten the economic
competitiveness of hydrogen as a fuel: more than 22% of hydrogen generation cost is for CO 2
separation to purify hydrogen (Ryu & Jin, 2007).
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Hydrogen generation from catalytic looping reactors is a novel hydrogen production
technology with an inherent separation of CO 2.This system has the advantage of no energy
penalty for separation of CO2 and high hydrogen yield without any additional process (Ryden,
2006). Hydrogen production by chemical looping catalytic reactors simultaneous solves the
seemingly paradoxical problem of economic energy sources that is not detrimental to the
environment.
Aims of the Report

The main aim of this report is to explore the potential of chemical-looping catalytic reactors for
hydrogen production by evaluating the different chemical-looping technologies and processes
currently available and identifying areas requiring further research.
Section 1 (Literature Review) provides an overview of hydrogen production and introduces
the chemical-looping concept. The review first summarizes conventional hydrogen production
methods and alternative hydrogen methods, and subsequently presents the chemical-looping
concept and the various ways the concept has been applied to produce hydrogen. In light of
its relevance to the purpose behind chemical-looping, a brief summary concerning carbon
storage was also given.
Section 2 (Theoretical Considerations and Critical Analysis) delves deeper into the
fundamentals of the chemical-looping concept for hydrogen production. In particular, the role
of the metal oxide catalysts as oxygen carriers, the theoretical considerations behind catalyst
choice and the extensive research regarding chemical-looping catalysts is explored.
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In Section 3 (Illustrative Examples), examples of chemical-looping in hydrogen production are
provided. Examples illustrating the application of chemical looping process outlined in the
literature review demonstrate that each of these processes is feasible on a technical basis.
In Section 4 (Personal Reflections), the author offers their opinion on the merits of chemical-
looping in hydrogen production and the issues surrounding the various novel chemical-
looping technologies.
In Section 5 (Concluding Remarks), key points of the report are recapitulated and areas of
further research are recommended.
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LITERATURE REVIEW
Conventional Hydrogen Production
Almost all commercial production of hydrogen is from fossil fuels. The initial step in
conventional hydrogen production is the formation of synthesis gas, a gaseous mixture of
H2and CO2. Aside from hydrogen production, synthesis gas is an important product that has
many uses, including as feedstock in the production of ammonia methanol and synthetic
fuels. Synthesis gas can be produced from all kinds of carbon-based matter (Ryden, 2006).
For light fuels such as natural gas, steaming reforming is used:
(Highly endothermic)
For heavier fuels such as oil or coal, partial oxidation or CO2 reforming is used:
(Slightly exothermic)
(Highly exothermic)
The direct oxidation of coal or biomass is also known as coal gasification. Coal gasification
produces a product gas mixture of H2, CO, carbon dioxide (CO2) and methane (CH4).
Although a mature process, coal gasification is currently more expensive than natural gas
reforming because of the gasifier and the need for O2 for the reaction process.
In particular, the majority of hydrogen is produced via steam methane reforming using natural
gas or partial oxidation, in which methane is burnt in air (US Department of Energy, 2006). In
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large scale facilities, the reaction shown below takes place in bundles of tubes packed with
catalyst, typically made up from 15-25 wt% NiO and 75-85 wt% carrier material such as
aluminium oxide or magnesia. The carrier is sensitive to sulphur, and as a result, the
feedstock must be desulfurised prior to the process. The reactor temperature is usually 800-
900°C and the pressure 15-30 bars.
Hydrogen can be formed from syngas using a water-gas shift reaction to form hydrogen and
carbon dioxide from the carbon monoxide byproduct from the previous step.
For industrial purposes, the water-gas shift reaction takes place in one or two separate
vessels. The first vessel, the high temperature shift reactor, operates at temperatures in the
region of 350-500°C and use an iron/chrome catalyst. Steam is added to achieve a H2O/CO
ratio of 1.5-4. If a high conversion of CO is needed, the high temperature shift is followed by a
second reactor operating at 180-250°C. A low reactor temperature is desirable, since the
chemical equilibrium of the water-gas shift reaction favors H2 at low temperatures.
Unfortunately, a low temperature also means a slow reaction rate, so a copper/zinc catalyst is
used in the second reactor (US Department of Energy, 2006).
The H2 rich process stream from the water-gas shift reactor also contains H2O and CO2 as
well as small amounts of other impurities such as CO and unreformed fuel. H 20 can be easily
removed via cooling in a condenser.
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However, the remaining product gas from the water shift reaction contains large amounts of
CO2 in additional to the desired H2, which must be separated and removed if high purity H2 is
to be produced. As previously stated, more than 22% of hydrogen generation cost is for CO 2
separation to purify hydrogen (Ryu & Jin, 2007).
At present, the dominating technology for production of high purity H 2 is pressure swing
adsorption, where impurities are adsorbed in a bed of solid adsorbent at elevated pressure
while highly volatile and non-polar H2 passes through the bed. Absorption, which involves the
scrubbing of the process stream with a CO 2 absorbing solvent such as MEA or MDEA, is also
frequently used. The resulting CO2 rich solvent is pumped into a separate stripper column
where CO2 is released and the solvent is regenerated. Alternative methods for H2 purification,
such as cryogenic fractionation and membranes, are currently not regarded as competitive for
industrial purposes.
Figure 1 is a schematic diagram of hydrogen production from fossil fuels, as previously
described.
Figure 1: Schematic Description of H2 Production from Fossil Fuels (Ryden, 2005)
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Alternative Hydrogen Production Processes

The production of hydrogen with carbon capture as described in the previous section is
attractive in that the hydrogen fuel produced will result in virtually zero emissions. However,
reliance on hydrogen derived from fossil fuels is not desired because of the finite nature of oil
reserves. It is much more desirable to produce hydrogen via renewable resources. This can
be done by the methods outlined below. However, the cost of hydrogen produced by these
technologies is not yet competitive with the costs via conventional methods.
Electrolysis: High purity hydrogen can be produced by the splitting of water molecules into
hydrogen and oxygen using an electrical current in an anionic transfer device. Alkaline
electrolysers with potassium hydroxide (KOH) electrolyte are commercially available.
The current can be generated by renewable energy, such as wind, solar, geothermal and
hydroelectric power, resulting in lower greenhouse emissions. Heat from a nuclear reactor
can be used to increase the temperature of water, which reduces the electricity required to
split the water molecules (US Department of Energy, 2006).
Renewable Liquid Reforming: Biomass can be processed to make renewable liquid fuels
such as ethanol, which can be reacted with high temperature steam at or near the point of
end-use to produce hydrogen (US Department of Energy, 2006).
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High Temperature Thermo-chemical Water-Splitting: High temperature generated by solar
concentrator or nuclear reactors drive a series of chemical reactions to split water using
catalyst (IEA, 2007).
Thermal Water-Splitting: Thermal water-splitting occurs at very high temperatures
exceeding 2,500°C, but thermo-chemical processes such as sulphur-iodine (S-I) or bromine–
calcium (Br-Ca) cycles may reduce temperatures to below 1,000ºC. These processes require
low-cost high-temperature heat from nuclear or solar sources, also corrosion-resistant
materials. The S-I process is the most promising, with about 43% LHV efficiency and an
operating temperature of 950ºC (IEA, 2007).
Photo Biological Systems: Green algae and cyanobacteria produce hydrogen as a
byproduct of their natural metabolic processes (IEA, 2007).
Photoelectrical Systems: Photo-electrolysis produces H2 using sunlight to illuminate a
water-immersed semiconductor that converts the light into chemical energy to split water into
H2 and O2. This method promises lower capital costs than combined photovoltaic-electrolysis
systems and it holds considerable potential for technology breakthroughs. Test-scale devices
have shown solar-to- H2 conversion efficiencies of up to 16% (IEA, 2005). But cost estimates
are premature (US Department of Energy, 2006).
Table 1 outlines the major hydrogen production processes along with the feed-stocks used,
energy generated and emissions released.
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Table 1: Major Hydrogen Production Processes (IEA, 2007)
Introduction to Chemical Looping

A given reaction step can be decomposed into multiple sub-reactions in a reaction scheme
using chemical intermediates that are reacted and regenerated through the progress of the
sub-reactions. A reaction scheme of this nature is referred to as chemical looping. An ideal
chemical looping scheme is for the sub-reactions to be designed in such a manner that the
exergy loss of the process resulting from this reaction scheme can be minimized while
allowing the separation of the desired or undesired products generated from the reactions to
be accomplished with ease, thereby yielding an overall efficient and economical process
system. (Fan L. S., 2010).
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The chemical looping concept has been widely applied to combustion processes for electricity
generation from gaseous fuels and more recently, from coal. The implementation of the
chemical looping concept in combustion enables both process intensification and carbon
capture.
Conventional CO2 capture processes techniques have large energy penalty and high costs for
separation of CO2 from the rest of the flue-gas components, resulting in a significant decrease
of the overall combustion efficiency and as a result in a price increase of the energy because
of the cost for CO2 capture. These include precombustion, in which hydrocarbon fuels are
decarbonized prior to combustion; oxyfuel combustion, which uses pure oxygen separated
from air; and postcombustion separation, which separates CO 2 from the flues gases using
different methods (Fang, Haibin, & Zengli, 2009).
Chemical Looping Combustion is a novel concept of hydrocarbon fuel energy conversion with
inherent CO2 separation. The chemical intermediate is first reduced and then combusted with
air to generate heat. In Chemical Looping Combustion, a solid oxygen carrier transports
oxygen from air to the fuel; hence air and fuel remain in separate environments and the
combustion exhaust mainly consists of CO2 and water vapour (Naqvi, 2006).
With the chemical loop, no additional CO2 separation steps are required. Since no additional
energy is required to carry out the carbon dioxide separation, carbon management in a
chemical looping system is more attractive (Vargas, 2007).Capital investments and operation
costs are reduced.
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Figure 2: Schematic Flow Diagram of Syngas Chemical Looping Combustion (Li, 2009)
Chemical Looping Combustion can be applied to both natural gas and coal. Figure 2 shows a
typical chemical looping combustion process using coal derived syngas as feedstock. Coal is
first gasified into raw syngas. A set of gas cleanup units is then used to remove the
contaminants to a level below the tolerance limit of the oxygen carrier particle used in the
process.
The cleaned syngas then reacts with the oxygen carrier particles in the first reactor which is
noted as the reducer or the fuel reactor. The syngas is oxidized to CO2 and steam by the
metal oxide particles. The main reactions in this reactor are:
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A concentrated CO2 stream can then be readily obtained by condensing out the steam in the
reducer. The CO2 stream can be further pressurized and transported for sequestration.
Meanwhile, the reduced metal oxide particles will be introduced to the second reactor, i.e. the
combustor or the air reactor, to react with air:
The oxidization reaction in the combustor is highly exothermic. As a result, a high
temperature, high pressure, oxygen depleted exhaust gas stream is generated from the
combustor. Such an exhaust gas stream is used to drive a combined cycle system for
electricity generation. Meanwhile, the particles, fully regenerated by air, are recycled to the
reducer for another redox (reduction – oxidation) cycle.
Alternatively, the coal can be directly combusted by the particles reducing the metal oxide to a
lower oxidation state, producing carbon dioxide and steam.
After the water from the product stream is condensed, a virtually pure CO 2 stream is formed.
The reduced metal oxide is subsequently regenerated with air.
In the chemical looping combustion process, because the fuel source is combusted with air
indirectly through the looping particles, i.e., metal oxide the fuel combustion products, i.e.,
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CO2 and steam are not diluted by nitrogen in the air, and the CO2 separation from nitrogen is,
therefore, avoided. Moreover, the syngas cleanup steps can potentially be simplified since the
metal oxide particles can be more robust towards contaminants when compared to
membranes, resulting in greater tolerance in contamination in the syngas compared to
membrane based systems (Li, 2009).
Chemical looping for Hydrogen Production

In recent times, the chemical looping concept has been applied to hydrogen production from
fossil fuels. Several chemical looping systems have been developed. These include: the
Syngas Chemical Looping process and the Coal Direct Chemical Looping process (both
developed by the Ohio State University) as well as GE’s Unmixed Fuel Processor and the
ALSTOM’s Hybrid Combustion-Gasification Chemical Looping process. Literature abounds in
papers explaining other, very similar processes.
The advantage of the chemical looping processes, compared with the traditional method of
hydrogen generation via the water gas-shift reaction, is that separate high-pressure streams
of CO2 and H2 can be produced at high temperatures, thereby eliminating the costly and
energy intensive carbon dioxide separation units. As a result, the hydrogen can be produced
at higher efficiencies.
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Syngas Chemical Looping (Developed by Ohio University)
The Syngas Chemical Looping process co-produces hydrogen and electricity from syngas
based on the cyclic reduction and oxidation of specially developed metal oxide composite
particles. The main advantage of the Syngas Chemical Looping process is that it produces a
pure hydrogen stream and a concentrated carbon dioxide stream in two separate reactors. In
additional, the Syngas Chemical Looping offers process flexibility; electricity can be efficiently
co-generated with hydrogen in the ratios desired.
The Syngas Chemical Looping process consists of five major components: an air separation
unit, a gasifier, a gas clean-up system, a reducer and an oxidizer. Figure 3 shows a simplified
block diagram of the Syngas Chemical Looping process (Fan, Li, & Ramkumar, 2008).
Figure 3: Simplified Schematic of the Syngas Chemical Loop Process (Fan, et al., 2008)
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In the Syngas Chemical Looping process, a high-purity oxygen stream (oxygen concentration
>95%) from an air separation unit is sent to the gasifier, which partially oxidizes coal to form a
high temperature raw syngas. The raw syngas is cleaned using process steps used for
conventional coal gasification to hydrogen such as quenching, particulate removal, acid gas
removal and mercury removal.
The syngas is converted to hydrogen in three major units, i.e. a reducer, an oxidizer, and a
combustion train. For the purposes of illustrating the process, iron oxide has been used as the
catalyst. However, there are a plethora of catalyst options (this will be further discussed in the
Theoretical Considerations and Critical Analyses section of the report).
Reducer: The purified syngas from the gas cleanup units is introduced into the reducer,
which consists of a moving bed of iron oxide composite particles, 2–10mm in diameter, at
750–900 ◦ C and 30 atm. In this reactor, the syngas is completely converted into carbon
dioxide and water while the iron oxide composite particles are reduced to a mixture of Fe and
FeO via the reactions below. The specific thermodynamics of the overall reaction is
dependant on the syngas composition, reaction temperature and particle reduction rate which
determines whether the overall reaction is slightly endothermic or slightly exothermic.
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The exhaust gas from the reducer contains only CO 2 and steam. The steam is easily removed
via condensation, resulting in a high-pressure CO2 stream that can be directly transported for
sequestration (Fan, Li, & Ramkumar, 2008).
Oxidiser: The particles reduced in the reducer are introducer to the oxidiser where they are
reacted with steam to produce a gas stream that contains solely H 2 and unconverted steam at
30 atm and 500–750 ◦C. The steam is easily removed via condensation, resulting in a H 2
stream with a very high purity (>99.7%). The reactions involved in the oxidizer are slightly
exothermic and include:
The steam used in the oxidizer is produced from the syngas cooling units and
reducer/oxidizer exhaust gas cooling units. The oxidiser is kept thermally neutral by adjusting
the temperature of the pressurized steam introduced into the system.
Combustion Train: The Fe3O4 formed in the reducer reactor is regenerated to Fe2O3 in the
combustion train. The combustion train is a pneumatic conveyor (pressure in beginning of the
train is 30 atm in order to compensate for pressure drop) that transports solids discharged
from the oxidizer reactor to the inlet of the reducer reactor. It also serves as a heat generator
for the reducer, since significant amounts of heat is produced during the oxidation of Fe 3O4 to
Fe2O3:
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The byproduct of the above reaction is a high pressure high temperature spent air (mainly N2)
stream, which is used to drive a gas turbine-steam turbine combined cycle system to
generate electricity for the system’s energy requirements.
To provide more energy, a portion or all of the reduced particles from the reducer reactor can
undergo full chemical looping combustion; the particles are directly sent to the combustion
train without reacting with steam in the oxidizer reactor. By doing this, more heat would be
available for power generation at the expense of decreased hydrogen production. The
utilization of both chemical looping reforming and chemical looping combustion concepts in
the Syngas Chemical Looping system makes it flexible. The operator is able to adjust the ratio
between H2 and electricity product as required.
Coal Direct Chemical Looping (Developed by Ohio University)

Unlike the Syngas Chemical Looping process which uses a conventional gasification system
to generate syngas feedstock, the iron based Coal Direct Chemical Looping process takes
coal directly as feedstock rather than syngas. This offers several advantages such as the
reduction in O2 consumption and process intensification. As for the Syngas Chemical Looping
process, a myriad of metal oxide catalysts can be used.
Figure 4 shows a simplified flow diagram of the coal direct chemical looping process, which
has three main reactors: the coal reactor, the hydrogen reactor, and a combustion reactor.
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Figure 4: Simplified Schematic of the Coal Direct Chemical Looping Process (Fan, et al., 2008)
The coal reactor converts the coal into CO2 and H2O while reducing Fe2O3 to a mixture of Fe
and FeO, the hydrogen reactor oxidizes the reduced Fe/FeO particle to Fe3O4 using steam
while producing a H2 rich gas stream. The combustion reactor pneumatically transports the
Fe3O4 particles from the H2 reactor outlet to the fuel reactor inlet using air, the Fe 3O4 particles
are reoxidized to Fe2O3 during the conveying process (Fan, Li, & Ramkumar, 2008).
Fuel Reactor: The fuel reactor is a countercurrent moving bed reactor operating at 750–
900C, 1–30 atm. The desirable reaction in the fuel reactor is:
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The conversion of coal to water and carbon dioxide is highly endothermic with a heat of
reaction of 1794 kJ at 900C. Therefore, heat is provided to the first reactor by partially
combusting coal with oxygen in the reactor. In order to balance the heat, coal is partially
combusted in situ by sending sub-stoichiometric amounts of O2 (according to coal) into the
fuel reactor. The overall reaction, with negligible heat of reaction, is given as:
Since the amount of oxygen required for the above reaction is significantly less than that for
conventional coal gasification reactions, a smaller air separation unit is required, resulting in
reduced costs.
Fresh Fe2O3 composite particles are fed from the top of the fuel reactor while coal is
introduced in the middle section of the reactor. This configuration allows the volatiles from the
coal to react with Fe2O3 particles to form CO2 and H2O as they move upward.
The devolatilized coal char, however, move downwards along with the partially reduced Fe 2O3
particles.
The coal char is gradually gasified by the CO2 and H2O formed at the lower part of the reactor.
Provided enough residence time, which is estimated to be 30–90 min depending on the
operating temperature and pressure, coal char can be converted fully, while the Fe2O3
reduces to a mixture of metallic iron and FeO. Coal ash will come out along with the particles.
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Thus, the product from the fuel reactor is a solid stream with Fe, FeO, and coal–ash and a
gas stream with mainly CO2 and H2O. The steam is easily removed via condensation,
resulting in a high-pressure CO2 stream that can be directly transported for sequestration
(Fan, Li, & Ramkumar, 2008).
In order to promote the reaction rate between solids, a small quantity of hydrogen gas (<5%)
produced from the hydrogen reactor is recycled to the bottom of the fuel reactor. By doing
this, the steam formed from the reaction between hydrogen and FeO at the bottom of the fuel
reactor would enhance char gasification.
Figure 5: Reactions in the Fuel Reactor (Fan, et al., 2008)
Hydrogen reactor: the Fe and FeO mixture from the fuel reactor reacts with steam in a
countercurrent mode in the hydrogen reactor, a moving bed reactor that operates at 700–
900C, and 1–30 atm. It is identical to the oxidizer outlined in the section about Syngas
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Chemical Looping. As with the oxidizer in Syngas Chemical Looping, steam is easily removed
via condensation, resulting in a H2 stream. The reaction product is Fe3O4 particles.
Combustion reactor: The combustion reactor is analogous to the combustion train in the
syngas looping process. The combustion reactor, a fluidized bed reactor operated at a
pressure similar to that of both the fuel reactor and the hydrogen reactor in an adiabatic
mode. Air is used to simultaneously oxidize and pneumatically convey the Fe3O4 particles
from the outlet of the hydrogen reactor to the fuel reactor inlet, resulting in Fe2O3 for use as
feedstock in the fuel reactor. The oxidization reaction is the same as that for the Syngas
Chemical Looping and is likewise highly exothermic, which is beneficial as the heat of the
Fe2O3 product partially compensates for the heat needed to convert the coal in the Fuel
Reactor.
The coal ash, being composed of smaller particles, is separated from the Fe2O3 composite
particles via cyclone. Some oxygen carrier will be lost and thus makeup oxygen carrier
particles being added to the regenerated Fe2O3 for entry into the Fuel Reactor.
Unmixed Fuel Processor (from GE Global Research)
The Unmixed Fuel Processor technology, developed by GE Global Research, makes use of
three circulating fluidized bed reactors containing CO 2 absorbing material (CAM) and oxygen
transfer material (OTM), as shown in Figure 6.
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Figure 6: Conceptual Design of the UFP Technology (Andrus H. E., 2009)
The GE process differs from the Syngas Chemical Looping process and the Coal Direct
Chemical Looping process in that two separate looping particles are used, i.e., an oxygen
carrier and a CO2 sorbent, to carry out the coal conversion. Thus, there are two separate
looping schemes involved in the production of hydrogen using these systems.
In the GE process, the CO2 sorbent is used to enhance the hydrogen generation while the
oxygen carrier is either used for indirect combustion of fuel to provide the heat needed for
spent sorbent reactivation or used for coal gasification. These processes can convert coal into
a variety of products with in-situ carbon dioxide capture. The mixing between the oxygen
carrier particles and sorbent particles as well as significantly large solid handling requirements
render these processes more difficult to operate as compared to chemical looping processes
that involve single chemical reaction loop (Rizeq, Kulkarni, Wei, Frydman, McNulty, & Shisler,
2005).
27
From reading GE’s technical report concerning the Unmixed Fuel Processor (Rizeq, Kulkarni,
Wei, Frydman, McNulty, & Shisler, 2005), it is evident that GE has withheld information
concerning the specifics of their process from the public. Nevertheless, a brief overview of
their process has been given for completeness.
CAM is a sorbent that absorbs CO2 to form CAM-CO2, OTM is a metal oxide, which can be
oxidized to form OTM-O. A mixture of the bed materials and coal ash is present in each
reactor, and the bed materials undergo a variety of transformations and reactions as they
move from one reactor to another. Each reactor serves a different key purpose: gasification,
CO2 release, or oxidation.
Gasification Reactor: Coal is fed to the gasification reactor together with steam, producing
H2, CO and CO2. CO2 is absorbed by the CAM by the reaction:
The reduction in gas-phase CO2 concentration shifts the equilibrium of the water-gas shift
reaction to deplete CO from the gas phase:
The removal of both CO and CO2 from the gasification reactor results in a H2-rich product
stream suitable for use in liquefaction, fuel cells, or turbines.
28
Regeneration Reactor: Spent CAM is transferred to the regeneration reactor, where it is
regenerated via heat provided by the transfer of hot bed material (oxidized OTM) from the
Oxidation Reactor:
A CO2rich stream that is suitable for sequestration is produced.
Simultaneously, the oxidized OTM is reduced in order to provide the oxygen needed to
oxidize CO to CO2 and H2 to H2O:
The regenerated CAM sorbent is recycled for use in the gasification reactor.
Oxidation Reactor: Air fed to oxidation reactor re-oxidizes the OTM via a highly exothermic
reaction that consumes most of the oxygen in the air fed. Thus, the oxidation reactor
produces high-temperature, high-pressure oxygen-depleted (vitiated) air for a gas turbine
expander as well as generating heat that is transferred to the gasification reactor and the
regeneration reactor via solids transfer.
Periodically, ash and bed materials will be removed from the system and replaced with fresh
bed materials to reduce the amount of ash in the system and increase the effectiveness of the
bed materials.
29
Alstom’s Hybrid Chemical Looping Process
Alstom’s limestone based chemical looping process uses calcium sulfide as the oxygen
carrier. It is similar to the GE process in that an oxygen carrier and a CO2 sorbent, to carry
out the coal conversion with a similiar looping scheme. However, in the Alstom process, the
oxygen and CO2 sorbent functions are performed by the same particle, limestone.
The Alstom process uses air, coal, limestone and steam to produce product gas and capture
CO2. Depending on the system configuration, the Product Gas can be hydrogen, syngas (CO
and H2) and/or CO2. Heat and product gas produced by the process can be directly used to
produce electricity via Rankine cycle, Brayton/Rankin cycle and/or fuel cell cycles in retrofit,
repowered or new capacity power plants. The general process is outlined in Figure 7.
Figure 7: ALSTROM Chemical Looping Process (Andrus H. E., 2008)

30
The chemical and thermal looping technology can be alternatively configured in several different ways,
as demonstrated in Figure 8.
Figure 8: Different Configurations for the Alstom Chemical Looping Process (Andrus H. E., 2008)
Option 1-Chemical Looping Combustion Steam Power Plant with CO2 capture: In this
configuration, only the bottom loop of Figure 6 is used. The process burns coal by using air
indirectly as follows: Limestone added to the process captures the sulfur in the coal forming
CaSn (calcium sulfide) in the Reducer reactor. The CaS is burned in a heat liberating reaction
with air in the Oxidizer reactor, producing hot CaSO 4 (calcium sulfate). The hot CaSO4 is
cycled to the Reducer supplying the oxygen and heat to burn the coal and reduce the CaSO 4
to CaS for continuous recycle. An excess air-to-coal ratio of about 1.2 (air-rich) is used. The
31
carbon and hydrogen in the coal leave the Reducer as CO 2 and H2O (the Product Gas).
Water can be removed from this gas stream, and the CO 2 directed for sequestration. Heat
produced by the process is used to make high pressure superheated steam for power
generation. CaSO4, coal ash and some unused CaO are bled from the system to prevent
sulfur and ash from building up. Fresh limestone (CaCO 3) is added to replace the calcium
thus removed (Andrus H. E., 2009)
Option 2 -Chemical looping Gasification with downstream CO2 capture: The
configuration is identical to Option 1 but with a lower air-to-coal ratio of about 0.3 (fuel-rich) is
applied, resulting in a product gas of CO and H2 (syngas). This product gas can be shifted to
hydrogen and CO2 followed by CO2 separation. The resulting hydrogen can be used for
feedstock to a wide range of product applications, or can be burned in a gas turbine,
comparable to a conventional IGCC plant. The separated CO 2 would be directed for
sequestration (Andrus H. E., 2009).
Option 3 -Chemical looping Gasification with inherent CO2 capture: Option 3 operates at
the same low air-to-coal (fuel-rich) ratio as Option 2, but includes inherent CO 2 capture. To
accomplish CO2 capture, a Calciner is added to the system. Steam (H2O) is added to the
Reducer, which oxidizes the CO in the syngas to CO2 while reducing the H2O to H2. The CO2
is captured by the excess CaO (calcium oxide) which is in the circulating solids, forming
CaCO3 (calcium carbonate). The CO2 is released from the CaCO3 in the Calciner with heat for
the reaction supplied by hot solids from the Oxidizer, forming CaO for recycle and reuse in the
Reducer (Andrus H. E., 2009).
32
Overview of Chemical Looping Research

Since the conception of the chemical looping concept in the utilization of fossil fuels, numerous studies have
been conducted. These have been summarized in a table by Go et al (Go, 2009). In the table, Class A refers to
catalytic chemical looping systems whilst Class B refers to sorbent chemical looping systems. Conceptual
studies are those involving Aspen simulations and calculations, whereas experimental studies were more
focused on laboratory results.
Table 2: Overview of Chemical Looping Research (Go, 2009)
33
Carbon Capture and Storage

In order to produce hydrogen with zero carbon emissions, CO 2 needs to be prevented from
reaching the atmosphere. In order to be transported and stored, CO 2 needs to be
compressed. A pressure in the order of 100 bar would be sufficient. This can be achieved by
intercooled multi-stage compression (Ryden and Lyngfelt, 2005).
Available options for the final handling of produced CO2 include underground geological
storage, ocean storage and mineral carbonation. Geological storage, which presently seems
to be the most plausible alternative, basically means returning the carbon to whence it came.
Potential geological storage sites include depleted oil and gas reservoirs, deep unmineable
coal seams, deep unused saline water-saturated reservoir rocks (aquifers), and sites where
enhanced oil recovery using CO2 is practiced. The engineered injection of CO 2 into
subsurface geological formations has been undertaken since the 1970s for the purpose of
enhanced oil recovery (Linderholm, 2008)
Transportation of CO2 from production site to storage site should constitute no major
obstacle. Large-scale transportation of CO2 has already been practiced for decades for use in
enhanced oil recovery. (Linderholm, 2008).
34
THEORETICAL CONSIDERATIONS
AND CRITICAL ANALYSIS
The focal areas of the research and development activities on the chemical looping processes
are on the oxygen carrier particle design and synthesis, looping reactor design and operation,
and looping process analysis and demonstration. Various types of oxygen carrier particles,
including the oxides of Ni, Fe, Mn, Cu, and Co, have been investigated.
The chemical looping process depends heavily on the proper selection of oxygen carrier
particles. The function of the oxygen carrier particle is to continuously deliver the maximum
amount of oxygen to the fuel for oxidation. In combustion processes, this oxygen comes from
air. In gasification processes, oxygen comes from water and occasionally, from carbon
dioxide. Hence, for a hydrogen production process, the selection of the oxygen carrier’s
principal metal oxide depends primarily on its ability to transport oxygen from water to fuel.
Incomplete conversion of the fuel or gases would require the addition of separation and/or
post-treatment systems, which increases production costs while decreasing the overall
process efficiency.
The principal metals that have been investigated as oxygen carriers are oxides of Mn, Fe, Co,
Ni and Cu, each with its own characteristics. Typically the oxygen carriers have been tested
via bench scale experimental using temperature programmed thermogravimetric analysers
(TGA), pulse reactors, and small-scale fluidized beds. X ray-diffraction (XRD) and scanning
electron microscopy (SEM) equipments is used to gather information concerning the surface
35
and physical properties of the carrier particles, prior to and after the redox process (Vargas,
2007).
Past research indicates that pure carrier particles are unsuitable for extended use in chemical
looping systems due to their poor reactivity, chemical stability and mechanical durability. The
addition of inert support materials such as silica, alumina, yttria stabilized zirconia (YSZ),
kaolin and various metal aluminates acts to enhance the mechanical strength and reactivity of
carrier particles by improving particle porosity and surface characteristics (Mattisson,
Johansson, & Lyngfelt, 2003).
Desirable Catalyst Qualities

Not all metal oxides are suitable for the production of hydrogen. The choice in materials
suitable for use can be significantly reduced by going through the checklist below (Wall, Liu, &
Moghtaderi, 2007):
1. Favourable thermodynamic characteristics to ensure complete fuel conversion
2. High reactivity which guarantees faster reactions and lowers the amount of catalyst
required
3. High degree of conversion, which is closely linked to the carrier particle’s
thermodynamic equilibrium with other gases present.
36
4. Good selectivity
5. High oxygen transfer capacity
6. Good chemical stability to avoid degradation of redox properties during repeated redox
cycles. In order for the chemical looping process to be economical, these particles
should be regenerable for at least 100 cycles (Gupta, 2007)
7. High mechanical strength so that particle fragmentation and sintering can be avoided
8. Low cost
9. Sound environmental characteristics
Theoretical Considerations of Catalysts
Mattison and Lyngfelt (2001) reported a possible choice of oxygen carrier materials based on
thermodynamics. Most of previous technical literature on chemical looping has been focused
on the development of suitable oxygen carrier materials. Transition metal oxides such as
nickel, copper, cobalt, iron and manganese are good candidates given their favorable
reductive/oxidative thermodynamic properties. In this section, the physical properties affecting
the thermodynamics of catalysts will be explored.
37
Melting Point:
Since the chemical looping gasification reaction is usually undertaken at high temperature, the
melting point of the metal oxide must be considered. If the melting point of the oxygen carrier is
within the range of operation temperature, agglomeration and decrease in reactivity may occur
during the reaction. Table 3 shows the melting points for some metals and metal oxides.
Table 3: Properties of Suitable Metal/Metal Oxides for Chemical Looping
38
It can be seen from Table 3 that Mn, Fe, and Ni-based particles have very high melting points
in both reduced and oxidized forms that exceed the operating temperature of the chemical
looping process; therefore, the risk of agglomeration or low activity in the reaction is
minimized. In contrast, Cd, Zn and Ce with melting points below than or close to 600C, are as
a result unsuitable oxygen carriers. Cu has also a relatively low melting point (1085C) and as
a consequence, cannot be used above 900C.
Oxygen Transfer Capacity:
The oxygen transfer capacity of an oxygen carrier determines its utilization efficiency. Table 4
lists the oxygen carrying capacity (moles of oxygen per mole of metal) of various metal
oxides. Among the candidate metal oxides Co 3O4 offers the highest oxygen transfer capacity
(Andrus H. E., 2009).
Table 4: Oxygen Carrying Capacity of Various Metal Oxides (Hossein et al., 2008)
To increase their reactivity, durability and fluidizability oxygen carrier particles can be
prepared by depositing the active metal oxide(s) phase on an inert support such as SiO 2,
TiO2, ZrO2, Al2O3, YSZ and bentonite (Vargas, 2007).
39
In the case of a supported metal oxide oxygen carriers, the oxygen carrying capacity is a
strong function of the metal loading and of the stability of the carrier over repeated reduction–
oxidation cycles. In addition, different oxygen carriers may be reduced to different states
depending upon the metal dispersed on the support materials. As a result of this it is quite
common to observe a reported mass-based conversion (oxygen ratio) to express the oxygen
carrying capacity of a given carrier (Hossein et al., 2008)
Recyclability: Particle recyclability can be testing by reacting particles in a thermogravimetric
analyzer (TGA) under reducing and oxidizing gas environments at various temperatures.
Particles that reduce and oxidize over many cycles are said to be recyclable. Although the
presence of ceramic inert support materials reduces the oxygen-carrying capacity of the
solids, the recyclability of the particles is usually enhanced by them.
Equilibrium Constant: A high log K value is desirable as it means greater reactivity. Figure
8 reports the equilibrium constant K (logarithmic scale) versus 1/T plots for the reduction of
some common materials arbitrarily using methane as the reducing agent fuel.
It is apparent from Figure 8 that MnO2/Mn2O3, Mn2O3/Mn3O4, Co3O4/CoO and CuO/Cu2O
have greater tendency to react with methane as compared to Fe 2O3/Fe3O4 and NiO/Ni.
However, MnO2, Mn2O3, Co3O4 and CuO decompose into Mn2O3, Mn3O4, CoO and Cu2O,
respectively, at low temperatures and thus are not suitable as oxygen carriers.
40
Figure 8: Log K vs. 1/T for Various Metal Oxide Systems (Mattisson and Lyngfelt, 2001)
Conversion: Complete conversion of fuel is another important characteristic for an oxygen
carrier. The degree of conversion can be calculated by using the method of minimization of
Gibbs free energy (Mattisson and Lyngfelt, 2001). From Figure 9, Mn2O3/Mn3O4, CuO/Cu2O,
Fe2O3/Fe3O4 and NiO/Ni carriers are able to convert methane to CO 2 almost completely.
Figure 9: Conversion vs. Temperature for Various Metal Oxides (Mattisson and Lyngfelt, 2001)
41
Physical Properties of Catalysts

Apart from thermodynamics, some physical properties such as density, active surface area,
pore volume, particle size and crushing strength are also important parameters for a
successful oxygen carrier material (Adanez et al., 2004).
Density and Particle Size: The density and particle size not only determine the fluidizability
of the oxygen carrier but also may affect the overall reaction rate, given their influence on
mass and heat transfer inside the particles. According to the literature, oxygen carriers with
particle sizes ranging from 0.08 to 2mm are suitable for chemical looping.
Mechanical Strength: The crushing strength of the particle is also an important property due
to the physical stresses associated with fluidization. For most of the available oxygen carriers,
the crushing strength is in the range of 3.7–5.2N (Mattisson et al., 2003).
Summaries of Chemical-Looping Catalyst Research

The majority of the previous works consider Fe, Cu and Ni for use as oxygen carriers, due to
their favorable thermodynamics, abundant availability and low cost. Both iron- and copper-
based oxygen carriers attracted significant number of research studies. Although nickel-based
materials are more expensive, they possess superior reactivity, thermal stability, negligible
volatility, and so is also the subject of vigorous research. Hossain et al has written an
extensive literature review, “Chemical-Loping Combustion (CLC) for Inherent CO 2
Separations”. The summaries of the research into oxygen carriers provided below are
largely based on Hossain’s work. Consult Hossain’s article for references of the research
summarized.
42
Ni-based oxygen carriers:
Both bulk and supported nickel-based materials have been tested as oxygen carriers by
Ishida and Jin . Usually unsupported NiO displays poor reoxidation over repeated reduction
and oxidation cycles, due to agglomeration. As a result, supported NiO/Ni materials are
preferred. Among available support materials, alumina (Al2O3) has received the highest
attention given its favorable fluidization properties and thermal stability. However, Cho et al
found that these benefits come at the disadvantage of the formation of some nickel aluminate,
which does not carry oxygen well and hence the reactivity of the oxygen carrier material
decreases with time, and thus obtained a stable Ni/Al2O3 carrier after few reduction and
oxidation cycles. X-ray diffraction (XRD) analysis of the used sample shows that during the
initial cycles the excess nickel reacts with Al 2O3 forming NiAl2O4,and this helps to improve
oxygen carrier stability. This led to the suggestion of the use of NiAl2O4 as a support instead of
Al2O3. The Ni on Ni/NiAl2O4 approach presents, however, the negative feature that it requires
more nickel than the one required for Ni/Al2O3.
Recently Ni/MgAl2O4 has also been investigated as an alternative to Ni/NiAl2O4 by researchers
such as Villa, Mattisson, Johansson, Zafar and Ryden. The addition of Mg limits the sintering
of NiO and stabilizes the Ni2+ in cubic NiO and NiAl2O4 phases, resulting in stable redox cycles
at very high temperatures (above 1300C).
Ishida and his group and Ryu and his collaborators also considered YSZ as support for
oxygen carriers. Ni/YSZ displayed excellent reactivity and regenerability given the abundant
availability of NiO sites with no metal support complexes detected.

43
Ryu and his coworkers also investigated NiO on bentonite as oxygen carrier which
demonstrated good activity and stability under repeated redox cycles. Unfortunately,
bentonite possesses limited thermal stability and thus is unstable for high temperature
applications.
Several researchers also focused on Ni/TiO2 materials without much success due to the
material’s tendency to form nickel titantate and coke. Similarly, nickel supported on SiO2 and
ZrO2 showed a decrease in reactivity with time.
In summary, it can be concluded that despite some of the described limitations nickel
supported on alumina holds significant promise as a potential oxygen carrier material for large
scale chemical looping applications.
Fe-based oxygen carriers

If technically feasible, iron would be extremely attractive for large scale chemical looping
systems, due to its abundance and low price in addition to its favorable thermodynamics.
Mattison et al investigated the use of naturally occurring iron ores such as hematite in
chemical looping. Hematite is a non-porous smooth textural material of low surface area. He
found that the surface of the hematite particles changes to a coarser texture with cracks and
fissures being formed as it was exposed to alternating reduction and oxidation. In addition,
the reaction rate of hematite to metallic iron is slow and the material agglomerates at high
temperatures.
44
Hence, alternative approaches consider iron dispersion on a number of supports. Iron on
Al2O3 is a CLC support of choice with the reduction rates substantially increased but
agglomeration was still an issue. Although Fe2O3 is considerably less reactive with Al2O3 than
other transition metals such as nickel, copper and cobalt, Bolt et al. demonstrated the
existence of Fe2O3–Al2O3 interactions leading to FeAl2O4.
Hence, Zafar et al and Mattison et al. conducted studies investigating MgAl2O4 has also been
considered as a support for Fe2O3 to avoid aluminate formation. MgAl2O4 offers a combination
of chemical resistance and thermal stability. When loaded with Fe 2O3, the resultant material
displays high reactivity and stability up to 1100C. Particle agglomeration was still observed.
Ishida et al experimented with TiO2, and SiO2 as potential oxygen carrier supports. These
proved less effective than aluminium based supports.
Fe2O3 on YSZ was studied by a number of authors. These oxygen carriers showed no metal
support interaction and stable activity over repeated reductions and oxidations. The reduction
rates of Fe2O3/YSZ were, however, slower than that for iron supported on alumina.
Cu-based oxygen carriers:
Copper has several favorable features over other oxygen carrier materials such as Ni and Fe
which include its high reactivity in redox cycles and the exothermic nature of these redox
reactions which eliminate the need for energy supply in the reduction reactor, along with its
45
favorable price. Despite the abovementioned advantages, CuO has not received significant
attention due its tendency to decompose and agglomerate at comparatively low temperatures.
De Diego et al demonstrated that at 950C CuO/Cu displayed very high reactivity in both
reduction and oxidation cycles which reduced dramatically after a few cycle due to particle
agglomeration. Cao et al. considered low temperature operation as a means of utilizing the
benefits of CuO, using a fluidized bed CLC process at 600C using gasified solid fuels along
with CuO. No particle agglomeration was observed and the use of excess air in the re-
oxidation minimized CuO decomposition.
Similarly at what was observed in the case of nickel and iron, supported Cu-based oxygen
carriers are considered a better choice than bulk CuO. Cu/Al2O3 is an oxygen carrier
frequently considered in literature, but research shows that agglomeration and aluminate
formation is a especially significant drawback, given copper’s comparative lower melting
point. Cho et al. unsuccessfully tried to obtain a stable carrier using CuAl2O4 as a support.
Studies show that particle reactivity of SiO2 supported copper was reasonable but inferior to
those found with Ni supported on SiO2. Particles showed as well, better stability over repeated
reduction and oxidation cycles. However, the prepared sample suffered from CuO
decomposition to Cu2O. Finally, the usage of TiO2 as a Cu support by de Diego resulted in the
formation of CuTiO4.
46
Mixed-oxide Oxygen Carriers
There are, in the open literature, a limited number of studies focused on using mixed metal
oxygen carriers for chemical looping combustion. In fact, some supported mixed metallic
materials have demonstrated better reactivity in comparison to their monometallic
counterparts.
Recently, Adanez et al. reported a stable bimetallic Cu–Ni/Al2O3 oxygen carrier. It was
claimed that Cu and Ni stabilized each other, providing an improved performance at higher
reaction temperatures and higher oxygen carrying capacity. Johansson et al. also reported a
similar result with a mixed iron and nickel oxygen carrier.
Recently, Hossain et al demonstrated the excellent reactivity and stability of a Co modified
Co–Ni/Al2O3 oxygen carrier No metal sintering or agglomeration was observed. The addition
of Co resulted in higher dispersion. According to Bolt et al., the promotional effects of Co have
been explained by applying the site-preference energy concept. The site preference concept
is based on the assumption that metal cations in their oxidized states (Ni++ or Co++) with
lower bonding energies are the favored species to interact with Al 2O5. Co, having a bonding
energy of 13 kJ/mol is likely to compete more effectively for the Al2O3 sites than Ni, with a 50
kJ/mol bonding energy. Thus, in a bimetallic CoNi/Al2O3 sample, the addition of Co enhances
the CoAl2O4 abundance minimizing the NiAl 2O4. The addition of Co also diminishes the metal-
support interactions and the binding energy between the metals and the H2 molecules and
thus increases the availability of the reactive species in a Co–Ni/Al2O3 sample (Hossain &
Lasa, 2008)
47
ILLUSTRATIVE EXAMPLES
Many studies have been conducted to establish the technical and economic feasibility of the
chemical-looping technologies outlined in the Literature Review. Key findings from selected
studies have been summarized in this section. Case studies demonstrating operational pilot
plants utilizing Syngas Chemical looping, coal direct chemical looping and the ALSTROM
chemical looping process demonstrate the technical feasibility of these technologies.
Since chemical looping technology for hydrogen production has not yet been commercialized
in a full-scale plant, the economic feasibility of full scale chemical looping process has only
been conducted using simulation models such as Aspen.
Example 1: Pilot Plant in Ohio University
References:
 Li, F. (2009). Chemical Looping Gasification Process. Ohio: The Ohio State University.
 Vargas, L. G. (2007). Development of Chemical Looping Gasification Processes for the
Production of Hydrogen from Coal. Ohio: Ohio State Univeristy.
Summary of Work:
Extensive studies on the syngas chemical looping gasification process and the coal direction
gasification process has been conducted under a bench scale (2.5 KWth) and a sub-pilot
scale (25 KWth) unit using coal as feedstock at Ohio University. Both processes have been
48
described in the literature review. Hence this case study presents the key results of the
research done in Ohio University as well as their future direction.
Li chosen a 60 wt. % Fe2O3 particle supported by TiO2 was chosen for use in their pilot
testing, because he found that it possessed superior recyclability, while maintaining
satisfactory reaction rates. iron oxide particles supported by TiO2 are cheaper, easier to
synthesize, and more resistant to attrition. They have also developed a kinetics model for the
particle chosen in order to aid future reactor design.
Figure 8 shows the pilot plant facilities in Ohio University. On the left is the bench scale unit
(2.5 KWth), on the right is the sub-pilot scale (25 KWth) unit.
Figure 10: Ohio Pilot Plant Facilities
49
Ohio University has extensively studied both the syngas chemical looping process both
analytically and experimentally. Li et al determined by thermodynamic analysis that a
countercurrent moving bed design is suitable for both the reducer and the oxidizer. ASPEN
Plus® simulation were used to determine the optimum operating conditions and pollutant
control techniques for the syngas chemical looping process. Experiments are carried out in a
2.5 kWth bench scale reactor. More than 99.5% of the syngas was converted during the
reducer test. The hydrogen generated during the oxidizer test has an average purity higher
than 99.95%. ASPEN Plus® simulation showed that the syngas chemical looping process
offers a 4-10% efficiency improvement compared to the current conventional method of
producing hydrogen from coal.
The bench scale moving bed reactor has also been used to study the coal direct chemical
looping process. More than 90% conversions for various types of coal char were achieved.
Process simulation using ASPEN Plus® showed that the hydrogen production efficiency for
the CDCL process can reach nearly 80%.
A 25 kWth sub-pilot scale chemical looping unit has been designed and constructed, however
no studies utilizing this unit could be found by the author. It is anticipated that further studies
will be conducted by Ohio University. Technical Review states that with the help of a $5
million grant from the U.S. Department of Energy's new Advanced Research Projects
Agency-Energy, Ohio University is planning the production of a 250-kilowatt, pilot-scale power
plant (Bullis, 2009).
50
Discussion of the Case Study:
The high level of conversion using the Ohio University patented iron oxide catalyst is very
promising for the future success of their ingenious chemical looping processes. With an eye
for commercialization, they have selected one of the more inexpensive metal oxides for use
and have begun to upscale their experiments.
However, as stated by David Thimsen, a senior project manager for advanced coal
generation at the Electric Power Research Institute, the approach being taken by the Ohio
State researchers may not prove to be the best version of chemical looping due to the
expensive nature of any specially designed metal oxide.
Ohio University publications have estimated the price of hydrogen produced by a full-scale
version of their chemical looping process at $0.83/kg, which is a very competitive number in
today’s market. However, it is unclear how this price estimate was made.
Example 2: Gnanapragasam et al.’s Comparison of

Syngas Chemical Looping vs. Coal Direct Chemical
Looping Using ASPEN Plus
References:
Gnanapragasam, N., Reddy, B., & Rosen, M. (n.d.). Hydrogen production from coal using
coal direct chemcial looping and syngas chemical looping combsution systems: Assessment
of system operation and resource requirements.
51
Summary of Work:
In Gnanapragasam’s work, operating conditions were assessed for coal direct chemical
looping and syngas chemical looping for hydrogen production from coal using ASPEN Plus
simulations. The main objective of his study was to increase the overall H2/CO2 ratio for a
given amount of coal, based on the various conditions.
He compared the resource utilization in combustion direct chemical looping and syngas
chemical looping systems in producing hydrogen using coal, iron oxide (sorbent), air and
water. The operating variables considered as part of his resource optimization analysis
included: inlet conditions to the primary reactors, minimum resource requirements (air, steam
and iron oxide), hydrogen-to-component ratios, and effect of coal carrier gas.
The range for the air inlet mass flow rate was 15–25 kg/s, which was chosen to maintain the
corresponding fuel reactor operating temperature range (700–950C). The oxygen inlet to the
primary reactors ranges from 3.49 to 5.82 kg/s for the corresponding air inlet range of 15–25
kg/s, respectively, for both systems. The pressure in all the reactors is set at 30 bar. The coal
inlet rate is fixed at 5 kg/s.
52
Figure 9: Schematic of Gnanapragasam’s ASPEN Plus Model for Syngas Chemical Looping
Figure 10: Schematic of Gnanapragasam’s ASPEN Plus Model for Coal Direct Chemical Looping
53
From his simulations, Gnanapragasam made the following inferences:
1. The CDCL has fewer unit operations (at least by one, gasifier) than the syngas
chemical looping system.
2. Gasification in the syngas chemical looping has better solids handling compared to the
coal direct chemical looping system where two solid groups (coal and iron oxide) are
mixed in the same unit operation.
3. The coal direct chemical looping process produces the most hydrogen at the lowest
oxygen and steam requirements with the lowest CO 2generation. The SCL system
consumes additional steam in the gasifier which is lost as water while reducing the iron
oxide with hydrogen in the syngas.
Gnanapragasam concluded from his simulations that the coal direct chemical looping system
has the overall advantage based on resource requirements and specific hydrogen produced.
However, he also noted that more systems have merit in being able to mitigate carbon dioxide
emissions in the utilization of coal as an energy source.
Gnanapragasam’s insightful work must be extremely helpful to his colleagues in that it
comprehensively compares the coal direct chemical looping process with the syngas
chemical looping process on a common basis. However, some may disagree with his
54
assessment that the coal direct chemical looping process is superior to the syngas looping
process.
As mentioned in the body of his work, syngas chemical looping has the advantaged of better
solids handling and more effective iron oxide recovery compared to coal direct combustion
looping due to the removal of coal ash during the gasification process. In solely assessing
hydrogen production based on oxygen and steam requirements, Gnanapragasam disregards
the greater costs of catalyst loss in the coal direct chemical looping system. This is
understandable, because his ASPEN Plus simulations assume complete recovery of solids by
the addition of bag filter after cyclone separation. However, zero losses of resources is
unrealistic, and the increased losses of one of the most expensive and integral components in
the coal direct chemical looping process must surely increases the attractiveness of the
syngas chemical looping process in comparison.
In additional, Gnanapragasam was very enthusiastic about the comparative configurationally
simplicity coal direct chemical looping process due to the elimination of an additional
gasification unit prior to the looping system. However, the benefits of configurational simplicity
may come at the cost of increased operational difficulty; Laboratory studies show that
catalysts are more adept in dealing with the operational conditions of syngas chemical
looping. ASPEN Plus simulations do not account for operational problems, so this is not a
flaw in Gnanapragasam’s work. However, issues such as these demonstrate the limitations of
models.
55
Example 3: Alstom Chemical Looping Pilot Plant

References:
Andrus, H. E. (2008). Hybrid Combustion-Gasification Chemical Looping PHASE III - FINAL REPORT. Windsor,
Connecticut: Coal Power Technology Development.
Summary of Work:
Alstom Power Inc, with major funding from the DOE, has just started Phase IV of a
multiphase program to develop an entirely new, ultra-clean, high efficiency power plant
process for the global power market. This Alstom chemical process has been outlined in the
Literature Review. Alstom is a major, worldwide supplier of power plant equipment, with over
40% of the world’s power plant steam generators are of Alstom design. Environmentally,
Alstom has pioneered the development of power plant SO2 scrubbers, CO, NOx and
particulate control and most recently mercury capture systems.
In Alstom’s process, the limestone not only transports oxygen, but also captures and purges
all of the sulfur in the fuel, captures nearly all (>95%) of the carbon in the coal (as CO 2) and
produces CO2-free hydrogen, all within the chemical looping process. All other metal-oxide-
based chemical looping processes only transport oxygen. They can be used for chemical
looping combustion or to make syngas (CO/H2), but they cannot capture the sulfur in the fuel
or produce CO2-free hydrogen without additional equipment.
56
Alstom has chosen to use limestone as the oxygen carrier in their chemical looping process,
citing the following reasons: limestone is less costly than the prepared sorbents by orders of
magnitude, limestone transfers more oxygen per pound of sorbent then any of the metal oxide
sorbents, sorbent re-activation can be done at very low cost.
Alstom has been developing the Chemical Looping Process for almost fifteen years and has
designed and built a small-scale pilot plant at its Windsor Ct. site, shown in Figure 11. The
pilot plant has been used in the first three phases of the current development program with
the DOE. The first three phases investigated the chemical and mechanical processes that are
involved in chemical looping as well as the solids transport control. The recently started
Phase IV program will build and test an integrated prototype chemical looping plant with an
auto-thermal capability that is roughly the size of a 3Mw thermal plant. Below is an overview
of the research activities that have been conducted from Alstom in collaborations with DOE.
In Phase I the pilot plant was used to develop the indirect combustion loop, including the
oxidizer and reducer with CO2 separation. Syngas production from coal was demonstrated
with calcium sulfide (CaS) and calcium sulfate (CaSO 4). Cold flow modeling of the solids flow
characteristics was preformed.
In Phase II, the pilot plant was used to develop the carbonate loop, this lime (CaO) and
calcium carbonate (CaCO3) loop was integrated it with the gasification loop from Phase I and
ultimately demonstrated the feasibility of hydrogen production from the combined loops.
Additional cold flow modeling was performed.
57
Figure 11: Schematic of Alstom’s Chemical Loop Test Facility for Phase III (Andrus H. E., 2008)
In Phase III, the pilot plant was used to obtain engineering information to design a prototype
of the commercial Chemical Looping concept. The work included modifications to and testing
with the pilot plant, solids transportation studies, control and instrumentation studies and
additional cold flow modeling. The pilot plant was run to test the feasibility of using automatic
controls to control two separate outlet streams, automatically control fluidizing air and
transport air to the solids control main air flow with temperature changes and load changes
and control start-ups, shut-downs and emergency plant shut-downs. These tests were
successful and showed that there was a feasible method for automatic control.
58
Alstom has also developed a design for the Phase IV Prototype. The proposed 3 MWt
prototype plant was sized to run auto-thermally, without external heating as needed in the
Process Development Unit. Heat transfer studies were done to determine that the heat loss
was small enough to achieve this condition. It was also determined that the prototype could
be heated up in a reasonable time.
Alstom’s process is very promising, in particular because of the ready availability and low
price of its limestone oxygen carrier as well as the easy disposal options for the byproduct
Calcium sulfate formed. Limestone at less than $20/ton delivered (world-wide) is at least 10
to 100 times less expensive than other oxygen carriers. In addition, Alstom has a very large
experience base in the coal conversion.
There are also some disadvantages to the process. Carbon dioxide is delivered at low
pressure and thus must be pressurized further before sequestration. The multiple flows from
and to the various component reactors of the process, as established in the literature review,
may be difficult to control.
59
PERSONAL REFLECTIONS
The three main chemical looping processes for the production of hydrogen each possess
inherent advantages and disadvantages. The one that is superior is the one that is
commercially viable and will work on a large scale. None of the processes have been proven
on a large scale, but Alstom’s chemical looping process appears at this time to be the nearest
to commercialization.
A key issue in chemical looping is the choice of oxygen carrier. There are a myriad of options
but no perfect solution: no one oxygen carrier possess all the desirable qualities. For
instance, copper based oxygen carriers have excellent reactivity but a low melting point;
nickel based catalysts possess excellent durability but are less reactive; iron is less expensive
and durable but not as reactive. It seems that at present, the oxygen carrier chosen will be the
one that gives what the researcher deems as the best combination. As seen from numerous
studies involving the use of different oxygen carriers, it is very much up to preference.
There are strong fundamental differences in the Chemical Looping concept between metal
oxides and limestone based CaS/CaSO 4 looping. The durability issue with metal oxides is
that metal oxides are expensive and therefore need to last in the process for a large number
of cycles. In contrast, the length of time that the bed material in the calcium based Chemical
Looping concept needs to be retained in the system is on the order of hours instead of
60
months as in the metal oxide case. Therefore, the durability of the oxygen carrier is not an
issue in Alstom’s DOE project.
Another major issue is the disposal of spent oxygen carrier. Metal oxide looping produces
less waste, which is also a desirable trait. However, where calcium sulfate is a benign, safe
waste, some metal oxides such as nickel are hazardous and thus disposal is costly.
Another fundamental difference between metal oxide chemical looping and calcium sulfide
chemical looping is that only one chemical loop is used in the former, which simplifies the
reaction scheme and thus simplifies the engineering required.
Conducting this research has made me consider the effects of the developed world’s energy
use and realized that chemical engineers have a valuable role to play in minimizing the
damage cause by anthropogenic activities. It is clear that using chemical looping or other
carbon dioxide separation techniques, carbon dioxide emissions can be mitigated without
damaging quality of life or the development of growing economies. The technology for the
mitigation of carbon dioxide emissions and the preservation of the natural habitats is only not
economically viable because of the low value society places upon environmental well-being. If
a high carbon tax was imposed, as was proposed in Australia a short time ago, carbon
dioxide sequestration would become more attractive.
61
CONCLUDING REMARKS
The chemical looping process is a novel way producing H2 from carbon sources such as
methane, coal and biomass which also produces a pure stream of CO 2 by design. The H2
produced can be used as a transportation fuel as well as for central station power generation.
The high H2 production efficiency of chemical looping processes place it at the forefront of
future energy management. Chemical looping processes are inherently much simpler than
conventional gasification schemes which use a greater number of reactors/reaction schemes
to produce H2/electricity.
Chemical looping technology has applications in a number of markets including oil refining,
fertilizers, H2 for transportation and electricity production using turbines and fuel cells.
Chemical looping process is a direct substitute for the traditional gasification technologies and
provides an alternative pathway to gasify coal to H 2 without CO2 emissions. along with
substantially reduced emissions and integrated CO 2 separation. Successful deployment of the
technology will allow the quicker advent of the hydrogen economy.
From the research done for the preparation of this report, it is evident that several promising
methods of chemical looping for hydrogen production exist. These include Syngas Chemical
Looping, Coal Direct Chemical Looping and privately developed chemical looping processes
such as GE’s chemical looping process and Alstom’s chemical looping process. However,
62
none of these processes have yet been used on a commercial scale, although Alstom’s
process seems to be approaching commercial viability.
From this research study, it is evident that there are areas in which further research is very
much needed. In the past, much of the research concerning chemical looping has been in
developing superior oxygen carriers and in theoretical simulations of various chemical looping
concepts. This research was extremely useful for establishing the chemical looping concept
and generating industrial interest. Now that the technical feasibility and the efficiency on
chemical looping for hydrogen production has been established, it is crucial to conduct
research that will make chemical looping commercially viable. Specifically, there needs to be
studies involving larger chemical looping plants and a focus on developing affordable oxygen
carriers. The chemical looping process developed by Alstom demonstrates that the
recyclability of the catalyst becomes less important if the said catalyst is inexpensive and can
be disposed of easily and safely.
Currently, the widespread use of chemical looping catalytic reactors is prevented by a lack of
full scale experimental examples. As the technology matures and carbon emissions become
more important, chemical looping technology for hydrogen production may one day become
the conventional process for hydrogen generation rather than a novel technology.
63
BIBLIOGRAPHY
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Connecticut: Coal Power Technology Development.
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looping and syngas chemical looping combsution systems: Assessment of system operation and resource
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Dioxide. Goteburg, Sweden: Department of Energy and Environment, Chalmers University of Technology.
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of the Scandinavian-Nordic Section of the Combustion Institute. Goteburg, Sweden.
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Hydrogen Production By Chemical Looping Catalytic Reactors- A.

UNSW School of Chemical Engineering

explore the potential of chemical-looping catalytic reactors for hydrogen production by

identifying areas requiring further research.

these processes was also investigated.

INTRODUCTION AND OBJECTIVES

Context of the Report

total carbon dioxide emissions (EIA, 2007).

ocean acidification, change in rainfall patterns, hurricanes, volcanic eruptions, earthquakes

and plant or animal extinctions (Vargas, 2007).

technically and economically feasible alternatives. Implementation of CO2 capture and

lower conversion efficiency of the coal (Vargas, 2007).

Chemical looping combustion is a method of CO 2 separation that has been recently

fuels, chemical as hydrogen (Li, 2009).

separation to purify hydrogen (Ryu & Jin, 2007).

Hydrogen generation from catalytic looping reactors is a novel hydrogen production

Aims of the Report

hydrogen production by evaluating the different chemical-looping technologies and processes

currently available and identifying areas requiring further research.

Section 1 (Literature Review) provides an overview of hydrogen production and introduces

storage was also given.

choice and the extensive research regarding chemical-looping catalysts is explored.

In Section 3 (Illustrative Examples), examples of chemical-looping in hydrogen production are

further research are recommended.

conventional hydrogen production is the formation of synthesis gas, a gaseous mixture of

For light fuels such as natural gas, steaming reforming is used:

900°C and the pressure 15-30 bars.

chemical equilibrium of the water-gas shift reaction favors H2 at low temperatures.

used in the second reactor (US Department of Energy, 2006).

removed via cooling in a condenser.

separation to purify hydrogen (Ryu & Jin, 2007).

Figure 1 is a schematic diagram of hydrogen production from fossil fuels, as previously

Figure 1: Schematic Description of H2 Production from Fossil Fuels (Ryden, 2005)

Alternative Hydrogen Production Processes

electrolysers with potassium hydroxide (KOH) electrolyte are commercially available.

split the water molecules (US Department of Energy, 2006).

end-use to produce hydrogen (US Department of Energy, 2006).

High Temperature Thermo-chemical Water-Splitting: High temperature generated by solar

catalyst (IEA, 2007).

Thermal Water-Splitting: Thermal water-splitting occurs at very high temperatures

exceeding 2,500°C, but thermo-chemical processes such as sulphur-iodine (S-I) or bromine–

low-cost high-temperature heat from nuclear or solar sources, also corrosion-resistant

operating temperature of 950ºC (IEA, 2007).

Photo Biological Systems: Green algae and cyanobacteria produce hydrogen as a

byproduct of their natural metabolic processes (IEA, 2007).

Photoelectrical Systems: Photo-electrolysis produces H2 using sunlight to illuminate a

are premature (US Department of Energy, 2006).

energy generated and emissions released.

Table 1: Major Hydrogen Production Processes (IEA, 2007)

Introduction to Chemical Looping

sub-reactions. A reaction scheme of this nature is referred to as chemical looping. An ideal

system. (Fan L. S., 2010).

different methods (Fang, Haibin, & Zengli, 2009).

costs are reduced.

metal oxide particles. The main reactions in this reactor are:

combustor or the air reactor, to react with air:

The oxidization reaction in the combustor is highly exothermic. As a result, a high

reducer for another redox (reduction – oxidation) cycle.

lower oxidation state, producing carbon dioxide and steam.

The reduced metal oxide is subsequently regenerated with air.

membranes, resulting in greater tolerance in contamination in the syngas compared to

membrane based systems (Li, 2009).

Chemical looping for Hydrogen Production

ALSTOM’s Hybrid Combustion-Gasification Chemical Looping process. Literature abounds in