Enerev Vol. 19. No. 4. cm. 415-422.

1994
Pergamon C&right @’ 1994 l&vier S&n& Ltd
Printed in Great Britain. All rights reserved
03~S442/94 $6.00+ 0.00

A NEW ADVANCED POWER-GENERATION SYSTEM

USING CHEMICAL-LOOPING COMBUSTION
MASARU ISHIDA~ and HONGGUANG JIN
Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta,
Midoriku, Yokohama, Japan 227

(Received I5 June 1993)

Abstract-A new type of power-generation system (called CLSA), with chemical-looping

combustion, air saturation and based on energy-utilization diagrams (EUDs), is proposed.
A loop of chemical reactions is substituted for conventional combustion and a process of
saturation for air is introduced for the following purposes: (1) to reduce the exergy
destruction caused by combustion and heat-exchange processes; (2) to separate CO, easily
from the exhaust gas of a gas turbine; (3) to recover the water used in this system. Exergy
analysis of a model system indicates that the expected thermal power-plant efficiency could
be as high as 55.1% (LHV). Simultaneously, the proposed system can be used to solve
environmental problems by recovering and utilizing CO2 as a by-product.

INTRODUCTION

Although the thermal efficiency of a combined cycle has become much higher than that of a
steam- or a gas-turbine cycle, there remain problems from the viewpoint of the second law of
thermodynamics. It is well known that the largest inefficiency in a gas-turbine power plant
takes place in the combustor of the gas turbine due to uncontrolled reaction between fuel and
air. One of the possibilities to lessen this high-temperature inefficiency is introduction of
chemical-looping combustion as demonstrated in a previous paper.’
To obtain a good heat-exchange match in the middle temperature range, many options have
been tried, e.g., multi-stage pressure evaporation in the heat-recovery steam generator
(HRSG) of a combined cycle, a steam-injected gas-turbine cycle (STIG),2 a regenerative
gas-turbine cycle, and a cycle (such as the Kalina cycle) with an organic working fluid used for
a bottoming cycle. All of these options contribute to the reduction of exergy destruction in the
middle temperature range. In a recent paper,3 it was found, on the basis of a graphical exergy
analysis, that a significant potential for improvement of system efficiency exists. Low-
temperature heat recovery has not been discussed because of the dew-temperature limit to
prevent the equipment from corroding. On the other hand, the production of CO2 is giving rise
to environmental concern related to the greenhouse effect. Since it is diluted by N, in air, its
recovery in conventional power-generation concepts is very difficult. No satisfactory approach
to recover CO2 effectively has been found as yet.
The objective of the present study is to develop a gas-turbine power-generation concept
which improves the overall system efficiency by applying the ideas of chemical-looping
combustion and saturation of air. This system also decreases the system cost by recovering
water. Furthermore, the CO2 in the exhaust gas of the turbine can be recovered at high
concentrations.

DESCRIPTION OF A MODEL SYSTEM

Chemical-looping combustion
Chemical-looping combustion is carried out in two successive reaction steps as shown in Fig.
1. The reduced solid product of the first reaction, Ni, is converted to NiO by oxidation in the

~To whom all correspondence should be addressed.

415
416 MASARUISHIDAand HONGGUANG
JIN

Power
Fig. 1. Schematic illustrating the concept of chemical-looping combustion.

second reaction. Here, NiO plays the role of an oxygen carrier between the two reactions. The
first reaction of metallic oxide and fuel is endothermic and absorbs low-level heat in the
temperature range 600-1000K, while the second reaction is an exothermic oxidation which
releases heat in the high-temperature region (about #IO-MOOK). The high-temperature
exhaust gas from the second reaction is utilized to drive a gas turbine.
The introduction of chemical-looping combustion into a power-generation system can reduce
the inefficiencies in the high- and middle-temperature regions (about 700-12OOK), but a large
amount of heat needs to be exchanged in the low-temperature region (about 400-600K).
Air saturation”’ used in a power-generation system has the following advantages: there is a
good match in the middle temperature range owing to smaller values of the mean-temperature
difference between heat-donating and heat-accepting streams in the heat exchangers; low-level
heat is utilized to generate the hot water used in the saturator; and there is reduced inefficiency
caused by mixing as compared to STIG.8
The system with air saturation needs a large amount of purified water. Generally this water
cannot be recovered. Since the exhaust gas from a gas turbine is stained with impurities in
fuels, heat exchangers and other facilities will be corroded when the exhaust gas is cooled to a
temperature lower than the dew temperature. Hence, unless there are sufficient water
resources, a conventional power plant utilizing saturated air may not be put into practical use.
In the present system shown in Fig. 1, the defects of the above two systems have been
removed by combining them synergistically, giving rise to reduction in inefficiencies over the
whole region from high to low temperatures.
Improvements in the high-temperature range have relied mainly on mechanical methods, i.e.
an increase of turbine-inlet temperature which is limited by the properties of the turbine
material. For synthesis of the new system proposed in this paper, the target reaction
(uncontrolled reaction of traditional combustion) is decomposed into two successive reactions,
i.e. chemical-looping combustion. When combined with air saturation, an excellent heat-
exchange match is achieved over the whole temperature range.
 Power-generation and chemical-looping combustion 417

_______________-_____-___--q
Reduction reactor
f-_-__-__-_--_

I
I
I
I saturator I
I
I
I
I
I
I
I
I
I
I
I
Air I
’L____L______A
@120018
tz7
PG.
~~t~~=~=~=~-=~=~=~=~=~____-_-~_
L-_-m-_
_-_ ______-_-_-_-_-_
BT--* @55
i

Fig. 2. A process flow diagram for CLSA. The first number given for a stream corresponds to the
temperature (in “C) and the second number to pressure (in atm).

Model description
A schematic flow diagram representative of the proposed system is shown in Fig. 2. In the
present example, the following two reactions are carried out in the reduction and the oxidation
vessels, respectively:
CH,+4NiO+C0,+2HZO+4Ni, (1)
4Ni+20,-*4NiO. (2)
In the reduction reactor, methane reacts with a metallic oxide (NiO) instead of burning with
the oxygen in air. In the oxidation reactor, a reduced product (Ni) reacts with the oxygen
contained in air.
The gases formed in the two reactors are utilized in gas turbines 1 (GT 1) and 2 (GT 2),
respectively. The gases discharged from GT 1 and GT2 are cooled in a series of heat
exchangers; water vapor is condensed and utilized in the system. The exhaust gas from the
reduction reactor is mainly CO* while that from the oxidation reactor is mainly Nz and is
discharged into the atmosphere.
Let us follow the main streams. Methane at 25°C and 20 atm is preheated by the exhaust gas
from GT 2 to raise its temperature to 530°C at 19 atm and is then introduced into the reduction
reactor. Here, NiO particles at 1200°C are introduced by gravity from the oxidation reactor
(the NiO and Ni streams are shown by broken lines). The NiO is reduced to Ni by the
endothermic reaction (1) and the Ni is then fed to the oxidation reactor.
The gas product discharged from the reduction reactor consists mainly of CO;! and water
vapor. This exhaust gas generates power in GT2. It is further cooled by releasing heat to
methane and process water (shown by dash-dot lines). Liquid water is removed in a condenser
and CO* at 70°C and 1.1 atm is recovered.
On the other hand, the air at 25°C and 1 atm is compressed to 20 atm by means of
multi-stage compressors. This procedure reduces the compression power and provides part of
the thermal energy to be utilized in a saturator, which needs a large amount of water at 186°C.
The compressed air is saturated with this hot water and results in a state at 142°C and 19 atm
418 MASARU ISHIDA and HONGGUANG JIN

’ Aed

0 800 1600
AHea ( kJ/mol-CH4)
Fig. 3. EUD for the reaction subsystem.

(the mole fraction of water vapor is about 0.25). The saturated air is further heated to 530°C by
the exhaust gas from the oxidation reactor before it is introduced into the oxidation reactor.
Here, Ni supplied from the reduction reactor is oxidized by the saturated air.
Since the reaction in the oxidation reactor is exothermic, an exhaust gas at 1200°C can be
obtained. This gas at 1200°C is introduced into GT 1. The exhaust gas from GT 1 is utilized to
preheat the saturated air and is then cooled, releasing heat to the process water. Water vapor is
condensed in a condenser and recovered. The rest of the gas is discharged into the atmosphere
and consists mainly of N2 at 40°C and 1.1 atm; 27.45 mol of air are supplied for every mol of
CH,.
Water vapor in the exhaust gases from both reactors is condensed in the condensers and the
condensed liquid water is cooled by using a heat exchanger. It is utilized as process water for
cooling the exhaust gases from both reactors and for cooling the air in intercoolers between the
compressors. Its stream is shown by dash-dot lines. Some additional processing of water may
be required to remove the impurities accumulated in its recycle use.

System presentation in a graphical exergy analysis

Our model system may be described in terms of EUD (energy-utilization diagram)
methodology in which inefficiencies are displayed graphically as exergy destruction or loss. The
procedure for use of this methodology was demonstrated in detail in a previous paper.3 Hence
only key points in this system will be briefly discussed based on the EUDs shown in Figs. 3, 4,
and 5.
Reaction subsystem. The reduction of NiO in the first reactor occurs at 530°C [ATI =
1 - (298/803) = 0.6291. The energy level of the endothermic reaction is denoted by Aeal in Fig.
3. The shaded area between AT, and Aeal in Fig. 3 then represents exergy destruction in the
reduction reactor when the heat at 530°C is used as heat donor. The exergy destruction is
38.4 kJ/mol-CH,.
Air saturation with a phase change of liquid water to water vapor is included in the reaction
1
1

0
800

AHea ( kJ/mol-CH4)
Fig. 4. EUD for the heat exchange subsystem.
 Power-generation and chemical-looping combustion 419

Aed gas turbines

lf’x”‘:x\\““, I
//&
Aea -net work 4
compressors

A -----------------~---------~--~---.--~--~-----~------~-

0 1
0 800 1600

‘*ea ( kJ/mol-CH4)
Fig. 5. EUD for the power subsystem.

subsystem in the graphical analysis. This process consists of two stages: adiabatic evaporative
cooling and humidification by obtaining heat from the liquid water. In the former, the
compressed air is cooled adiabatically and acts as an energy donor, whereas the evaporation of
water is an energy acceptor. In the latter, the hot water supplied at 186°C becomes the energy
donor, and the donated heat is used to saturate the compressed air and to raise the
temperature of the gas stream from 112°C (A = 0.226) to 142°C (A = 0.282). The detailed
analysis of the saturator was discussed in another paper.6 The difference in the energy levels of
Aedl and Aeaz is rather small because of direct contact of compressed air and liquid water, and
hence the exergy destruction in the saturator is only 9.7 kJ/mol-C&.
The exothermic oxidation of Ni in the oxidation reactor to form a chemical loop takes place
at 1200°C. The energy level of this temperature [AR = 1 - (298/1473) = 0.7981 is plotted as a
dash-dot line. The energy level of the exothermic reaction is represented by the line AedZ, and
the released heat is used to raise the temperature of the saturated air and the Ni particles. The
energy levels for preheating the saturated air and the Ni particles are shown by Aed and Aea4 in
Fig. 3, respectively. The exergy destruction in the oxidation reactor is 158.8 kJ/mol-CH,.
Hence the total exergy destruction of the reaction subsystem is 207 kJ/mol-CH, as shown in
Table 1.
Table 1. Operating condition and calculated results. The fuel
is 1 mole of methane at 25°C and 20 atm; the adiabatic
efficiencies are 86% for the air compressors, 88.5% for the gas
turbine; the LHV of methane is 802.6 kJ. CLSA = chemical-
looping combustion with air saturation; STIG = steam-injected
gas-turbine cycle.
420 MASARU ISHIDA and HONGGUANG JIN

In our analysis, reduction and oxidation are assumed to proceed at 530 and 1200°C
respectively. These may be nonisothermal reactions. The outlet temperature of Ni from the
reduction reactor is then 530°C while 1200°C is the outlet temperature of NiO from the
oxidation reactor.
Heat-exchanger subsystem. Figure 4 shows the composite curves for the heat-donating
streams Aed and the heat-accepting streams A,,. The shaded area between Aed and A,,
represents the amount of exergy destruction in the heat-exchange subsystem and equals
91.4 kJ/mol-CH,. As seen from Table 1, this value is less than that of the STIG (steam-injected
gas-turbine cycle). The value for the STIG is based on the result given in the previous paper.3
To make the comparison fair, the minimum temperature difference at pinch is decreased to the
level adopted in this study.
Power subsystem. The energy-utilization diagram for the power subsystem is shown in Fig.
5. The abscissa of this diagram indicates the work. The energy levels for the expansion in the
two turbines are represented by the curves Aedgasturbines+ The work generated is equal to the
width of this curve and its energy level is unity. The shaded area between the curve Aed and the
horizontal line A,, = 1 represents the exergy destruction in the turbine. Gas compression is an
energy acceptor and the energy levels of the three compressors correspond to the curves
A eacompressors.
The work required is equal to the width of the curves and its energy level is unity.
Hence, the shaded area between the horizontal line with Aed = 1 and the curves A,, represents
exergy destruction in the compressors.
For this system, the polytropic efficiency for the turbines is set at 88.5% and that for the
compressor is 86%. The exergy destruction shown by the shaded area in Fig. 5 is
58.4 kJ/mol-CH,.
Figure 5 indicates that the total power generation for the CLSA system is 758.8 kJ/mol-CH,
as shown on the abscissa. By subracting the consumption power for the compressors, the net
output power is found to be 442.1 kJ/mol-CH,, resulting in a thermal efficiency of 55.1% based
on LHV.

DISCUSSION

Performance improvement
When only saturated air is used, exergy destruction becomes small in the middle- and
low-temperature regions. However, the inefficiency in the high-temperature region remains.
On the other hand, when only chemical-looping combustion is used, exergy destruction
becomes small in the high- and middle-temperature regions. However, the inefficiency in the
low-temperature region is now not removed. When both technologies are combined, the
thermal efficiency may become much greater than that obtained from each individual process.
The synergistic effect of combining these two key technologies is reminiscent of the
improvement achieved when a combined system was designed as a new power-generation
system by combining a gas turbine with a steam turbine.
For the model system, a power-generation efficiency of 55.1% is obtained when the process
water is recovered and a value of 56.7% is obtained when water is not recovered. These
power-generation efficiencies are approximately by 7-8% points greater than the efficiencies of
comparable combined cycles or STIG systems.

CO, recovery
A new environmental concern has emerged as a result of the gradual increase of CO* in the
atmosphere and anticipated greenhouse effects or climatic changes. At present, reductions in
CO2 emitted from fossil-fuel combustion must be achieved mainly by increasing the thermal
efficiency. Recovery of COZ is currently being investigated by applying existing chemical and
physical technologies such as gas absorption or membrane separation. However, a large
 Power-generation and chemical-looping combustion 421

amount of energy is consumed in the recovery of CO*. This loss inevitably reduces the
overall-system thermal efficiency.
A significant advantage of the CLSA system is that CO;? can easily be recovered. The CO*
produced in the reduction reactor is not diluted by air since air and fuel enter different
reactors. This is quite different from the traditional combustor in which CO;? is diluted in air
and hence cannot be concentrated and separated efficiently or economically. In our system,
since the exhaust gas from the reduction reactor is only composed of high-concentration COz
and water vapor, CO2 can easily be recovered by cooling the exhaust gas and removing the
liquid water, i.e. very little energy expenditure is required for recovering CO* from the exhaust
gas.
The recovered CO2 may be utilized, for example, in biological or artificial photosynthesis as
in the technology using a high-CO,-concentration plantation to enhance the rate of plant
growth.

Water recovery

Another significant characteristic of the CLSA system is that most of the water vapor in the
exhaust gas can be recovered by cooling the exhaust gas from the oxidation reactor. In
chemical-looping combustion, fuel is not burned directly and the gas discharged from the
oxidation reactor has no impurities from the fuel. Hence, there will be no corrosion of the
apparatus when the exhaust gas is cooled to a very low temperature and inexpensive materials
can be utilized for the heat exchangers. Because of the recycling of water, the CLSA system
can be used in locations with limited water resources.

Basic experiments and applications

To put the CLSA system into practice, basic experiments were performed on chemical-
looping combustion at atmospheric pressure by using an electrobalance and NG as fuel. It was
found that the rate of reduction of NiO [Reaction (l)] is fast because the gases from the
reactants and products diffuse easily through the porous structure of the solid product Ni. For
oxidation of Ni [Reaction (Z)], the rate is fast at the initial stage when Ni at the outer surface of
the particle reacts with oxygen. However its rate becomes significantly slower and complete
conversion from Ni to NiO cannot be obtained because the rate of O2 diffusion through the
dense units NiO layer is very slow.
Increasing the oxidation rate is very important because the size of the reactor depends on the
reaction rate. We have solved this problem by adding yttria-stabilized zirconia (YSZ) (ZrO,
stabilized by the addition of 8% Y203) to the NiO during particle preparation. The weight ratio
of NiO to YSZ is 3 to 2 and the particle diameter is approximately 1 mm. YSZ is known as an
oxygen-permeable material and can carry oxygen into the interior of the particle. The results
revealed that the addition of YSZ has significantly improved the rate of oxidation and complete
conversion from Ni to NiO can be obtained. Moreover, as the result of the addition of this
ceramic medium, the Ni or the NiO particles had sufficient physical strength for repeated
cycling in the reactors.

REFERENCES

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422 MASARUISHJDA and HONGGUANG JIN

Gas-Turbine system with a New Method of Heat Recovery with Water Injection,” pp. 297-303, 1983
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