Solar Thermochemical Process Technology

ENCYCLOPEDIA OF PHYSICAL SCIENCE & TECHNOLOGY Solar Thermochemical Process Technology
1

ENCYCLOPEDI A OF PHYSI CAL SCI ENCE & TECHNOLOGY
R. A. Meyers Ed., Academic Press, Vol. 15, pp. 237-256, 2001.

SOLAR THERMOCHEMICAL PROCESS TECHNOLOGY

Aldo Steinfeld
Institute of Energy Technology
Department of Mechanical and Process Engineering
ETH Swiss Federal Institute of Technology
CH-8092 Zurich, Switzerland

Robert Palumbo
Laboratory for Solar Technology
Department of General Energy Research
Paul Scherrer Institute
CH-5232 Villigen, Switzerland

Outline:
I. Introduction
II. Principles of Solar Energy Concentration
III. Thermodynamics of Solar Thermochemical Conversion
IV. Solar Thermochemical Processes
V. Solar Thermochemical Reactors
VI. Outlook
VII. References
2

Glossary

aperture opening of a solar cavity-receiver
Carnot efficiency the maximum efficiency for converting
heat from a high-temperature thermal reservoir at T
H
into
work in a cyclic process and rejecting heat to a low-
temperature thermal reservoir at T
L
, given by 1-T
L
/T
H

CPC (Compound Parabolic Concentrator) a non-
imaging concentrating device that is usually positioned in
tandem with the primary parabolic concentrating system
for further augmentation the solar concentration ratio
detoxification a process in which hazardous materials are
decomposed to harmless and environmentally compatible
compounds
endothermic absorbs heat
exothermic rejects heat
exergy efficiency (for a solar thermochemical process)
the efficiency for converting solar energy into chemical
energy. It is given by the ratio of the maximum work (e.g.,
electrical work) that may be extracted from a solar fuel to
the solar energy input for producing such a fuel
normal beam insolation power flux of direct solar
irradiation on a surface perpendicular to the sun rays
solar cavity-receiver a well-insulated enclosure, with a
small opening to let in concentrated solar energy, which
approaches a blackbody absorber in its ability to capture
solar energy
solar chemical heat pipe concept for storing and
transporting solar energy using a reversible endothermic
reaction
solar concentration ratio non-dimensional ratio of the
solar flux intensity (e.g., in suns) achieved after
concentration to the normal insolation of incident beam
solar fuels fuels produced with solar energy
solar thermochemical process any endothermic process
which uses concentrated solar energy as the source of
high-temperature process heat
specular (mirror-like) - the angle between the incident ray
and the normal to the surface equals the angle between the
reflected ray and the normal to the surface
syngas synthesis gas (a mixture of primarily hydrogen
and carbon monoxide), which serves as the building block
for a wide variety of synthetic fuels including Fischer-
Tropsch type chemicals, hydrogen, ammonia, and
methanol
water-splitting chemical process or cycle aimed at
obtaining hydrogen and oxygen from water

Nomenclature

A
aperture
area of reactor aperture
C solar flux concentration ratio
I normal beam insolation
Irr
quench
irreversibility associated with quenching
Irr
reactor
irreversibility associated with the solar
reactor
n& molar flow rate of reactant
Q
aperture
incoming solar power intercepted by the
reactor aperture
Q
FC
heat rejected to the surroundings by an
ideal fuel cell
Q
quench
heat rejected to the surroundings by the
quenching process
Q
reactor,net
net power absorbed by the solar reactor
Q
solar
total solar power coming from the
concentrator
T nominal solar cavity-receiver temperature
T
stagnation
maximum temperature of a blackbody
absorber
T
optimum
optimal temperature of the solar cavity-
receiver for maximum
exergy,ideal

W
FC
work output by an ideal fuel cell
eff
effective absorptance of the solar cavity-
receiver
eff
effective emittance of the solar cavity-
receiver
G Gibbs free energy change per mole of
reactant
H enthalpy change per mole of reactant
S entropy change per mole of reactant
reflectivity
angle subtended by the sun at the earths
surface (approximately 0.0093 rad)
absorption
solar energy absorption efficiency
Carnot
efficiency of a Carnot heat engine
operating between T
H
and T
L

exergy
exergy efficiency
exergy,ideal
exergy efficiency of an ideal system
rim
rim angle of a parabolic concentrator
Stefan-Boltzmann constant (5.670510

-8

Wm
-2
K
-4
)

3
I. INTRODUCTION

One of the most abundant resources on the surface of
the earth is sunlight. Yet we do not typically think of
this resource as the solution to any upcoming energy
crisis or as the fuel that will bring clean air to our
cities. We just cannot see ourselves driving into the
local gasoline station and filling our cars up with
sunlight. Perhaps it is for this reason that this
resource does not capture our imagination as the
ingredient that could help us deal with two of the
most pressing problems that we will meet head-on in
the 21
st
century, namely, the impending shortage of
crude oil and environmental pollution. A number of
scientists and engineers from around the world are
intrigued by a rather staggering fact: using only 0.1%
of the earths land space with solar collectors that
operate with a collection efficiency of merely 20%,
one could gather more than enough energy to supply
the current yearly energy needs of all the citizens of
the planet. Furthermore, the solar energy reserve is
essentially unlimited. No particular individual or
government owns it. And its utilization is
ecologically benign. Good enough reasons to expect
increasing utilization of solar energy, if it were not
for the following very serious drawbacks: solar
radiation reaching the earth is very dilute (only about
1 kW per square meter), intermittent (available only
during day-time), and unequally distributed over the
surface of the earth (mostly between 30 north and
30 south latitude). Scientists ask themselves how
can we get hold of solar energy such that it can be
stored and transported from the sunny and
uninhabited regions of the earths sunbelt to the
worlds industrialized and populated centers outside
the earths sunbelt, where much of the energy is
required?
This question has motivated the search for recipes
that convert sunlight into a fuel that one can use to
propel not only our cars but the entire world
economy. In other words, these investigators are
looking for processes (and reactors for conducting
these processes) that can convert intermittent solar
radiation falling in the deserts of the world into
storable chemical energy, in the form of fuels, that
can be transported to the population centers. Cars
running on fuels produced from such a recipe would
be, in fact, running on solar energy, even if it
happens to be a rainy evening.
The means by which sunlight can be used to produce
fuels for the 21
st
century can be found in the writings
of two of the prominent scientists of the 19
th
century,
Carnot and Gibbs. They created the discipline of
thermodynamics, which is the study of how energy
can be converted from one form to another, for
example, from solar to chemical energy. In very
simple terms, thermodynamics tells us that the higher
the temperature at which we supply solar energy to
our process, the more creative we can be with what
comes out as a final product. For example, if we use
sunlight in a typical flat-plate solar collector, we can
produce warm water that could be used for taking
baths or supplying space heat. Although this type of
device can make a great deal of sense for certain
local conditions, it will not enable solar energy
collected in Australia to be transported to Japan. But
if we supply solar energy to a chemical reactor at
very high temperatures near 2300 K, we open up the
possibility for such a feat: solar energy collected in
Australia can heat homes, supply electricity, propel
cars, and more ... in Tokyo.

Solar Fuels Reactants
Concentrated
Solar Energy
Heat Absorption
Q
H
,T
H
Chemical
Reactor
Fuel Cell
Q
L
,T
L
Transportation
&
Power
Generation
Solar Fuels Reactants
Concentrated
Solar Energy
Heat Absorption
Q
H
,T
H
Chemical
Reactor
Fuel Cell
Q
L
,T
L
Transportation
&
Power
Generation

Figure 1. Schematic of solar energy conversion into solar fuels.
Concentrated solar radiation is used as the energy source for high-
temperature process heat to drive chemical reactions towards the
production of storable and transportable fuels.

Figure 1 illustrates the basic idea. If we concentrate
the diluted sunlight over a small area with the help of
parabolic mirrors and then capture that radiative
energy with the help of suitable receivers, we would
be able to obtain heat at high temperatures for
driving a chemical transformation and producing a
storable and transportable fuel. Regardless of the
nature of the fuel, the theoretical maximum
efficiency of such an energy-conversion process is
limited by the Carnot efficiency of an equivalent heat
engine. With the suns surface as a 5800 K thermal
reservoir and the earth as the thermal sink, 95% of
the solar energy could, in principle, be converted into
the chemical energy of fuels. It is up to us to design
4
and develop the technology that approaches this
limit.
This article develops some of the underlying science
and describes some of the latest technological
developments for achieving this goal. The reader is
first introduced to the principles of solar energy
concentration and to the thermodynamics of solar
thermochemical conversion. State of the art reactors
are described as well as the most promising solar
thermochemical processes.

II. PRINCIPLES OF SOLAR ENERGY CONCENTRATION

The conventional method for concentrating solar
energy, i.e. collecting solar energy over some large
area and delivering it to a smaller one, is by
parabolic-shaped mirrors. A parabola focuses rays
parallel to its axis into its focal point. However, sun
rays are not parallel. To a good approximation they
can be assumed to originate at a disk which subtends
the angle =0.0093 radian. When a perfectly
specular reflective paraboloid of focal length f and
rim angle
rim
is aligned to the sun, reflection of the
rays at the focal plane forms a circular image
centered at the focal point (shown in Fig. 2). It has
the diameter,

) cos 1 ( cos
f
d
rim rim

(1)

rim
f

Figure. 2. Concentration of sunlight by a parabolic dish of focal
length f and rim angle rim. When the dish is aligned toward the
sun, reflection of sun rays at the focal plane forms a circular image
centered at the focus of diameter d.

On this circle, the radiation flux intensity is
maximum and uniform in the paraxial solar image
(the hot spot). It decreases for diameters larger
than f as a result of forming elliptical images. The
theoretical concentration ratio C at the hot spot is
defined as the ratio of the radiation intensity on the
hot spot to the normal beam insolation, and is
approximately

rim
2
2
sin
4
C
(2)
For example, for a rim angle of 45, the theoretical
peak-concentration ratio exceeds 23,000 suns, where
1 sun refers to the normal beam insolation of 1
kW/m
2
. The thermodynamic limit for solar
concentration is given by the factor sin
-2
46,000
suns. In practice, the achievable concentration ratios
are much smaller. Losses in power and concentration
are due to geometrical imperfections (such as a
segmented approximation to the exact parabolic
profile, facet misalignments, structural bending and
deformations), optical imperfections (such as poor
reflectivity and specularity of the mirrors and glass
absorption), shading effects (such as shading caused
by the receiver and the non-reflective space or frame
around each mirror facet), and tracking
imperfections.
Three main optical configurations based on
parabolic-shaped mirrors are commercially available
for large-scale collection and concentration of solar
energy. These are the trough, tower, and dish
systems. These three systems are shown
schematically in Fig. 3 (Tyner et al., 1999). Trough
systems use linear, 2-dimensional, parabolic mirrors
to focus sunlight onto a solar tubular receiver
positioned along their focal line. Tower systems use
a field of heliostats (two-axis tracking parabolic
mirrors) that focus the sun rays onto a solar receiver
mounted on top of a centrally located tower. Dish
systems use paraboloidal mirrors to focus sunlight on
a solar receiver positioned at their focus. The total
amount of power collected by any of these systems is
proportional to the projected area of the mirrors.
Their arrangement depends mainly on the
concentrating system selected and on the site
latitude. Trough systems are usually arranged in
rows along the east-west direction and track the sun
along the south-north direction, as is the case for the
SEGS plant at Kramer Junction, USA. Tower
systems, which are also referred to as central-
receiver systems, may have instead a circular field of
heliostats with a centred receiver on top of the tower,
as for the Solar-Two plant at Barstow, USA, or may
also have an asymmetric field, as for the south-
facing plant at Plataforma Solar de Almeria, Spain.
A recently developed Cassegrain optical
5
configuration for the tower system at the Weizmann
Institute of Sciences, Israel, makes use of a
hyperboloidal reflector at the top of the tower to re-
direct sunlight to a receiver located on the ground
level (Yogev, 1998).

(a)

(b)

(c)

Figure 3. Schematic of the three main optical configurations for
large-scale collection and concentration of solar energy: (a) the
trough system, (b) the tower system, and (c) the dish system.

The solar flux concentration ratio C typically
obtained at the focal plane varies between 30-100
suns for trough systems, 500-5,000 suns for tower
systems, and 1000-10,000 for dish systems. Higher
concentration ratios imply lower heat losses from
smaller receivers and, consequently, higher
attainable temperatures at the receiver. To some
extent, the flux concentration can be further
augmented with the help of non-imaging secondary
concentrators, e.g., a compound parabolic
concentrator, which is usually referred to as CPC
(Welford and Winston, 1989). They are positioned in
tandem with the primary concentrating systems.
Figure 4 shows a schematic of a 2-dimensional CPC
that can be applied to primary concentrating trough
systems, and also a 3-dimensional CPC that can be
applied to primary concentrating tower and dish
systems. With such an arrangement, the power flux
concentration can be increased by a factor
(sin
rim
)
-1
for 2D-CPC and by (sin
rim
)
-2
for 3D-
CPC, where
rim
is the rim angle of the primary
concentrating system and is the inner wall total
hemispherical reflectance of the CPC. Other
geometries for non-imaging concentrators based on
total internal reflection of a dielectric-filled CPC
have also been developed (Welford and Winston,
1989).
3D - CPC 2D - CPC

Figure 4. Schematic of a 2-D and 3-D compound parabolic
concentrator (CPC). CPCs have specular reflective inner walls and
can be used to augment the solar flux concentration of the primary
concentrator. The arrows represent concentrated solar radiation
arriving from the primary concentrator (from trough systems for
the 2D-CPC and from tower or dish systems for the 3-D CPC).

Solar furnaces are concentrating facilities in which
high-flux solar intensities are usually obtained at a
fixed location inside a housed laboratory. They are
experimental platforms for conducting research with
high radiation fluxes and at high temperatures. The
traditional design consists of using a sun-tracking,
flat heliostat on-axis with a stationary primary
paraboloidal concentrator (Haueter et al., 1999); off-
axis configurations have also been designed. A
recent survey of solar furnace installations
(SolarPACES, 1996) lists the test facilities presently
in operation.
The solar concentrating systems described have been
proven to be technically feasible in large-scale
experimental demonstrations aimed mainly at the
production of solar thermal electricity in which a
working fluid (typically air, water, helium, sodium,
or molten salt) is solar-heated and further used in
traditional Rankine, Brayton, and Stirling cycles
(Tyner et al., 1999). Solar thermochemical
applications, although not developed as far as solar
thermal electricity generation, will make use of the
same solar concentrating technology.
6
III. THERMODYNAMICS OF SOLAR THERMOCHEMICAL CONVERSION

Because thermodynamics is the science that
describes the conversion of one form of energy into
another form, it is germane to the field of Solar
Thermochemistry. Solar thermochemical processes
convert radiant energy into chemical energy. The
two fundamental thermodynamic laws that give
practical information with regard to any solar
thermochemical process are the 1
st
and 2
nd
laws.
Using the 1
st
law, one establishes the minimum
amount of solar energy required to produce a
particular fuel or chemical species. The 2
nd
law
indicates, among other things, whether or not the
chosen path for producing the fuel is physically
possible. Both types of information are required for a
process designer.
We consider as an example a generic solar process in
which one wishes to effect the following chemical
transformation:
reactants products . (3)

Temperature
Energy Requirement
H
rxn
G
rxn
S
rxn
0
300 K

Figure 5. Variations of Hrxn, Grxn, and TSrxn with temperature
for a generic solar chemical reaction. Hrxn is the total energy
required to effect the transformation. Grxn is the portion of energy
that must be supplied as high-quality energy in the form of work,
for example, in the form of electrical work. The remainder TSrxn
is the amount of energy that can be supplied as process heat for
the completely reversible process in the form of solar thermal
energy.

Figure 5 shows the energy requirements to effect this
transformation as a function of temperature. The
total energy required is the enthalpy change H
rxn
for
the reaction. Of this total, an amount of energy equal
to the Gibbs free energy for the reaction, G
rxn
, must
be supplied as high-quality energy in the form of
work, for example in the form of electric work. The
remainder, TS
rxn
, is the amount of energy that can
be supplied as process heat for the completely
reversible process in the form of solar thermal
energy. G
rxn
decreases with temperature.
Consequently, the ratio of work (e.g., electrical
energy) to thermal energy, G
rxn
/TS
rxn
, decreases
as the temperature is increased. At temperatures for
which G
rxn
0, the reaction proceeds spontaneously
to the right when supplying only solar process heat.
The 1
st
law is also applied to calculate the solar
energy absorption efficiency of a solar reactor,
absorption
. It is defined as the net rate at which energy
is being absorbed divided by the solar power coming
from the concentrator. Solar reactors for highly
concentrated solar systems usually feature the use of
a cavity-receiver type configuration, i.e. a well-
insulated enclosure with a small opening (the
aperture) to let in concentrated solar radiation. At
temperatures above about 1000 K, the net power
absorbed is diminished mostly by radiative losses
through the aperture. For a perfectly insulated cavity-
receiver (no convection or conduction heat losses), it
is given by

(Fletcher and Moen, 1977)

solar
4
aperture eff aperture eff
absorption
Q
T A Q
(4)
where Q
solar
is the total power coming from the
concentrator, Q
aperture
the amount intercepted by the
aperture of area A
aperture
,
eff
and
eff
are the effective
absorptance and emittance of the solar cavity-
receiver, respectively, T is the nominal cavity-
receiver temperature, and the Stefan-Boltzmann
constant. The first term in the numerator denotes the
total power absorbed and the second term denotes
the re-radiation losses Q
rerad
. Their difference yields
the net power absorbed by the reactor, which should
match the enthalpy change of the chemical
reaction n& H
rxn
per unit time. The incoming solar
power is determined by the normal beam insolation
I, by the collector area, and by taking into account
the optical imperfections of the collection system
(e.g., reflectivity, specularity, tracking
imperfections). The capability of the collection
system to concentrate solar energy is often expressed
in terms of its mean flux concentration ratio

C over
an aperture normalized with respect to the incident
normal beam insolation as follows:

.
A I
Q
C
~
aperture
aperture
(5)
For simplification, we assume an aperture size that
captures all incoming power so that Q
aperture
= Q
solar
.
With this assumption and for a perfectly insulated
isothermal blackbody cavity-receiver (
eff
=
eff
=1),
Eqs. (4) and (5) are combined to yield

.
4
absorption
C
~
I
T
1

,
_
(6)
7
The absorbed concentrated solar radiation drives an
endothermic chemical reaction. The measure of how
well solar energy was converted into chemical
energy for a given process is the exergy efficiency,
defined as

,
Q
G n
solar
K 298
rxn
exergy

&
(7)
where G
rxn
is the maximum possible amount of
work that may be extracted from the products as they
are transformed back to reactants at 298 K. The 2
nd

law is now applied to calculate the maximum exergy
efficiency
exergy,ideal
. Since the conversion of solar
process heat to G
rxn
is limited by both the solar
absorption and Carnot efficiencies, the maximum
overall efficiency is

1
1
]
1
,
_

1
1
]
1
,
_

H
L
4
H
Carnot absorption ideal , exergy
T
T
1
C
~
I
T
1

(8)
where T
H
and T
L
are the upper and lower operating
temperatures of the equivalent Carnot heat engine.
exergy,ideal
is plotted in Fig. 6 as a function of T
H
for
T
L
= 298 K and for various solar flux concentrations.

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 500
Temperature [K]
1000 1500 2000 2500 3000 3500 4000
Carnot
T
optimum
1000
5000
10000
20000
40000
exergy,ideal

Figure 6. The ideal exergy efficiency exergy,ideal is shown as a function of the operating temperature TH, for a blackbody cavity-receiver
converting concentrated solar energy into chemical energy [Eq. (8); TL = 298 K]. The mean solar flux concentration is the parameter:
1000, 5000, ...40000. Also plotted is the Carnot efficiency and the locus of the optimum cavity temperature Toptimum (Eq. 11).

Because of the Carnot limit, one should try to
operate thermochemical processes at the highest
upper temperature possible; however, from a heat-
transfer perspective, the higher the temperature, the
higher the re-radiation losses. The highest
temperature an ideal solar cavity-receiver is capable
of achieving, defined as the stagnation temperature
T
stagnation
, is calculated by setting
exergy,ideal
equal to
zero, which yields

.
C
~
I
T
25 . 0
stagnation

,
_
(9)
At this temperature,
exergy,ideal
= 0 because energy is
being re-radiated as fast as it is absorbed.
Concentration ratios of 10,000 and more have been
achieved using paraboloidal primary reflectors and
non-imaging secondary concentrators (such as CPCs),
which translate to stagnation temperatures above 3600
K. However, an energy-efficient process must run at
temperatures that are substantially below T
stagnation
.
There is an optimum temperature T
optimum
for maximum
efficiency obtained by setting

. 0
T
ideal , exergy
(10)
8
Assuming a uniform power-flux distribution, this
relation yields the following implicit equation for
T
optimum
:
( ) . 0
4
C
~
I T
T T 75 . 0 T
eff
L eff
4
optimum L
5
optimum

,
_
(11)
Equation (11) was solved numerically (Steinfeld and
Schubnell, 1993) and the locus of T
optimum
is shown in
Fig. 6. The optimal temperature for maximum
efficiency varies between 1100 and 1800 K for
uniform power-flux distributions with concentrations
between 1000 and 13,000. For example, when

C =
2000 and I = 900 W/m
2
, the maximum efficiency
corresponds to about 1250 K. For a Gaussian
incident power-flux distribution having peak
concentration ratios between 1000 and 12,000 suns,
the optimal temperature varies from 800 to 1300 K.
In practice, when considering convection and
conduction losses in addition to radiation losses, the
efficiency will peak at a somewhat lower
temperature.
The pertinent questions that follow from the
preceding arguments are the following: (1) What are
the best chemical systems for solar thermochemical
processing? (2) What are the optimum temperatures
for these processes? One criterion for making
comparative judgments of various solar processes is
the ideal exergy efficiency [see Eq. (7)]. To help
apply this term, one can think of solar processes that
lead to fuels as ideal cyclic processes like that shown
in Fig. 7, which uses a solar reactor, a quenching
device, and a fuel cell.
The complete process is carried out at constant
pressure. In practice, pressure drops will occur
throughout the system. If one assumes, however,
frictionless operating conditions, no pumping work
is required. The reactants may be pre-heated in an
adiabatic heat exchanger where some portion of the
sensible and latent heat of the products is transferred
to the reactants; for simplicity, a heat exchanger has
been omitted. The reactor is assumed to be a perfect
blackbody cavity-receiver. The reactants enter the
solar reactor at T
L
and are further heated to the
reactor temperature T
H
. Chemical equilibrium is
assumed inside the reactor. The net power absorbed
in the solar reactor should match the enthalpy change
per unit time of the reaction,
H L
T @ Products T @ Reactants
net , reactor
H n Q

& (12)
Irreversibilites in the solar reactor arise from the
non-reversible chemical transformation and re-
radiation losses to the surroundings at T
L
. It is found
that
,
_
,
_
,
_
H L
T @ Products T @ Reactants
L
rerad
H
solar
reactor
S n
T
Q
T
Q
Irr
&
. (13)
Products exit the solar reactor at T
H
and are cooled
rapidly to T
L
. The amount of power lost during
quenching is
L H
T @ Products T @ Products
quench
H n Q

& . (14)
The irreversibility associated with quenching is

,
_
,
_
L H
T @ Products T @ Products
L
quench
quench
S n
T
Q
Irr
& (15)

Concentrated
Solar
Energy
Q
solar
Q
rerad
Reactants
@ T
L
Products
@ T
H
Quench
Products
@ T
L
Q
quench
Ideal
Fuel
Cell
W
FC
Q
FC
T
Concentrated
Solar
Energy
Q
solar
Q
solar
Q
rerad
Reactants
@ T
L
Products
@ T
H
Quench Quench
Products
@ T
L
Q
quench
Ideal
Fuel
Cell
Ideal
Fuel
Cell
W
FC
Q
FC
T

Figure 7. Schematic of an ideal cyclic process for calculating the
maximum exergy efficiency of a solar thermochemical process.

The cycle is closed by introducing a reversible, ideal
fuel cell, in which the products recombine to form the
original reactants and thereby generate electrical power
in the amount
. G n W
L L
T @ ts tan ac Re T @ oducts Pr
FC

&
(16)
W
FC
is the maximum amount of work that the products
leaving the reactor could produce if they combined at
9
T
L
and a total pressure of 1 bar. This work value is
also known as the exergy of the products at ambient
temperature. The fuel cell operates isothermally;
where the amount of heat rejected to the
surroundings is
. S n T Q
L L
T @ ts tan ac Re T @ oducts Pr
L FC

&
(17)
The exergy system efficiency of the closed-cycle is
then calculated using Eq. (7) as

.
Q
W
solar
FC
exergy

(18)
Check This thermodynamic analysis is verified by
performing an energy balance and by evaluating the
maximum achievable efficiency (Carnot efficiency)
from the total available work and from the total
power input. The energy balance confirms that

) Q Q Q ( Q W
FC quench rerad solar FC
+ +
. (19)
The available work is calculated as the sum of the
fuel-cell work plus the lost work due to
irreversibilities in the solar reactor and during
quenching. Thus,

.
Q
) Irr Irr ( T W
solar
quench reactor L FC
max
+ +

(20)
This maximum efficiency must be equal to that of a
Carnot heat engine operating between T
H
and T
L
, i.e.

.
T
T
1
H
L
Carnot max

(21)
Example: The ZnO/Zn-Cycle
In order to illustrate the use of equations (1)-(21), we
consider as an example a solar process in which the
following chemical transformation occurs

K 298
2
K 298
O
2
1
) s ( Zn ) s ( ZnO + (22)
The variations of H
rxn
, G
rxn
, and TS
rxn
for
reaction (22) with temperature are shown in Fig. 8.
At 2235 K, G
rxn
= 0. Above 2235 K, G
rxn
<0 and
the reaction proceeds spontaneously to the right by
supplying H
rxn
solar process heat. Table 1 gives a
numerical description for the components shown in
Fig. 7 for the ZnO thermal dissociation as an
example of how one evaluates the exergy efficiency
of a process as well as how one quantifies the
intrinsic entropy production of the process. The
analysis of this particular system is relatively simple.
The reader is referred to Steinfeld et al (1996) for a
more complex system. This kind of process
modeling establishes a base for evaluating and
comparing different solar thermochemical processes
for ideal, closed cyclic systems that recycle all
materials and also for open systems that allow for
material flow into and out of the system.
Table I. Exergy analysis of the solar thermal dissociation of ZnO
using the process modeling depicted in Fig. 7. The ZnO molar rate
n& is assumed 1 mol/s.
Assumptions T
L
= 298 K, T
H
= 2300 K,
p=1 bar, C=5000, n& =1 mol/s
Q
solar
815 kW
Q
rerad
258 kW
Q
reactor,net
557 kW
Irr
reactor
0.81 kW/K
Q
quench
209 kW
Irr
quench
0.52 kWK
Q
FC

30 kW
W
FC

318 kW
absorption

68 %
Carnot

87 %
exergy,ideal

59 %
exergy

39 %

0
100
200
300
400
500
200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400
Temperature [K]
H
G
TS
Zn m.p. Zn b.p.
kJ/mol

Figure 8. Energy requirements for ZnO(s) Zn + 0.5 O2.

All solar thermal chemical processes can be thought of
in this manner, and their exergy efficiencies can be
compared as one criterion for judging their relative
industrial potential. The higher the exergy efficiency,
the lower is the required solar collection area for
producing a given amount of solar fuel and,
consequently, the lower are the costs incurred for the
solar concentrating system, which usually correspond
to half of the total investments for the entire solar
chemical plant. Thus, high exergy efficiency implies
favorable competitiveness. It is important to note that
we have a thermal cycle receiving thermal energy from
a high-temperature reservoir and rejecting it to a low-
10
temperature reservoir. If we pick a chemical system
where everything in the cycle could be done
perfectly, the maximum efficiency would be the
Carnot efficiency. Thus, the higher the temperature
at which one supplies process heat, the more work-
like and thus the more valuable the process heat. But
there is an important caveat. A Carnot cycle is one
where there are no internal sources of entropy-
production. When entropy is produced one looses
some capacity for doing useful work. Examples of
common entropy production mechanisms are
friction, heat transfer across temperature differences,
and most chemical reactions. The moment one
selects a specific solar process, one inherits the
intrinsic process entropy-production mechanisms.
Some processes have higher exergy efficiencies than
others, and any individual process has some
preferred operating temperature. Furthermore, the
entropy production calculations guide ones thinking
in creating process ideas. The lost work calculations
tell the solar process designer the potentially most
thermodynamically profitable places for creating
new concepts. In the above example, the quench can
reduce the process efficiency by as much as 33%. The
lost-work calculation suggests finding an alternative
method for separating the products. This fact was the
impetus for research into electrolytic methods for
separating the gas phase products at high temperatures.
One will recognize that thermodynamics is a powerful
tool used in the field of solar thermochemistry. But it
does not tell the entire story with regard to the potential
performance of a solar process. Specifically, it does not
give insight into the rates of the chemical reactions. It
is beyond the scope of this review to go into much
detail on the importance of chemical kinetics in the
field of solar thermochemistry. Understanding the
complex interactions between solar flux, reactant feed
conditions, and chemical kinetics is important for
designing reactors that convert solar energy efficiently
into chemical fuels. Low activation energy to favor
kinetics, large enthalpy change to maximize energy-
conversion capacity, and small molar volume of
products to minimize handling/storage volume are
some of the general guidelines for the selection of solar
chemical processes.

IV. SOLAR THERMOCHEMICAL PROCESSES

IV.1. Solar Hydrogen:
The Direct Thermal Dissociation of H
2
O
Some of the earliest work in solar thermochemistry
was dedicated to the direct thermal dissociation of
water, also known as thermolysis of water, i.e.
H
2
O H
2
+ O
2
(23)
The processes investigated to date used a zirconia
surface, solar-heated to temperatures of or above
2500 K, and subjected to a stream of water vapor.
The gaseous products that result from the water
thermolysis need to be separated at high-
temperatures to avoid recombination or ending with
an explosive mixture. Among the ideas proposed for
separating the H
2
from the products are effusion
separation (Fletcher and Moen, 1977; Kogan, 1998),
and electrolytic separation (Ihara, 1980; Fletcher,
1999). Rapid quench by injecting a cold gas or by
expansion in a nozzle, followed by a low-
temperature separation, are simpler and workable
(Diver et al., 1983; Ld et al., 1987), but the quench
introduces a significant drop in the exergy efficiency
of the process. Furthermore, the very high
temperatures demanded by the thermodynamics of
the process pose severe material problems and can
lead to significant re-radiation from the reactor,
thereby lowing the absorption efficiency and,
consequently, further lowing the exergy efficiency.
These obstacles pushed research in the direction of
water-splitting thermochemical cycles (see Section
IV.5).
Thermal Decomposition of H
2
S
Several papers describe solar chemical processes for
producing H
2
and S
2
by thermally decomposing H
2
S,
from which this discussion is extracted (Noring and
Fletcher, 1982; Kappauf et al., 1985; Kappauf and
Fletcher, 1989; Harvey et al., 1998; Diver and
Fletcher, 1985). H
2
S is a highly toxic industrial
product recovered in large quantities in the
sweetening of natural gas and in the removal of
organically bound sulfur from petroleum and coal.
Current industrial practice uses the Claus process to
recover the sulfur from H
2
S, but the process wastes
H
2
by oxidizing it to H
2
O to produce low-grade
process heat. In 1979, the amount wasted in the US
and Canada alone amounted to the equivalent of 17
million barrels of gasoline. Furthermore it has been
pointed out that some natural gas wells throughout
the world are so rich in H
2
S that they are not used. A
solar process that converted the highly toxic material
into a useful fuel would make a substantial
contribution to the world's energy pipeline. In one
such process, H
2
S is fed to a solar thermal chemical
reactor operating at temperatures near 1800 K and
pressures between 0.03- 0.5 bar. At these operating
conditions, the sulfide is cracked into H
2
and S on a
hot Al
2
O
3
surface, viz.,
H
2
S H
2
+ S
2
(24)
The product gas mixture is quenched at the exit of
the reactor in a water-cooled heat exchanger,
11
producing liquid and ultimately solid sulfur and
thereby separating the H
2
from the S
2
. Experimental
evidence suggests that the quench is relatively easy;
the reverse reaction between the products seems to
be unimportant at temperatures as high as 1500 K. A
recent study delineating the chemical kinetics of the
decomposition reaction gives a quantitative rate
expression for H
2
S decomposing in an alumina
reactor in the temperature range of 1350 - 1600 K.
(Harvey et al., 1998). An economic analysis
indicates that, assuming H
2
S has zero value (this is a
conservative choice) and a price for electric energy
of $0.05/kWh, the solar thermal decomposition of
H
2
S could have a pay-back time as short as 6.3 years
(Diver and Fletcher, 1985).
IV.3. Solar Chemical Heat Pipes
Solar chemical heat pipe refers to the solar energy
conversion concept depicted in Fig. 9. High-
temperature solar process heat is used for driving an
endothermic reversible reaction in a solar chemical
reactor. The products can be stored long-term and
transported long-range to the customer site where
the energy is needed. At that site, the exothermic
reverse reaction is effected, yielding process heat in
an amount equal to the stored solar energy H
AB
.
This high-temperature heat may be applied for
example to generate electricity using a Rankine
cycle. The chemical products for the reverse reaction
are the original chemicals; they are returned to the
solar reactor and the process is repeated. Two
reverse reactions that have been extensively
investigated for application in chemical heat pipes
are the CH
4
reforming-methanation and the NH
3

dissociation-synthesis.

Endothermic Reactor
Storage & Transport
A B
Exothermic Reactor
A B
Heat Exchangers
Power Generation
A
B
H > 0 H < 0
Endothermic Reactor
Storage & Transport
A B A B
Exothermic Reactor
A B A B
Heat Exchangers Heat Exchangers
Power Generation Power Generation
AA
BB
H > 0 H < 0

Figure 9. Solar chemical heat pipe for the storage and
transportation of solar energy. High-temperature solar process
heat is used to drive the endothermic reversible reaction AB.
The product B may be long-term stored and long-range
transported to the site where the energy is needed. At that site, the
exothermic reverse reaction BA is effected and yields high-
temperature process heat in an amount equal to the stored solar
energy HAB. The chemical product of the reverse reaction A is
returned to the solar reactor for reuse.
Methane undergoes reforming to synthesis gas
(syngas), a mixture of primarily H
2
and CO, when
using either H
2
O or CO
2
as the partial oxidizing
agent as follows
CO H 3 O H CH
2 2 4
+ + (25)
CO 2 H 2 CO CH
2 2 4
+ + (26)
Reactions (25) and (26) are endothermic by 206 and
247 kJ/mol, respectively, and proceed catalytically
above 1100 K. Reaction (26) has been studied in
solar furnaces with small-scale solar reactor
prototypes using an Rh-based catalyst (Levy et al.,
1992; Muir at al., 1994), and recently scaled-up to
power levels of 300 - 500 kW in a solar tower
facility using a high-pressure (8-10 bar) tubular
reactor and a low-pressure (1-3 bar) volumetric
reactor (Epstein and Spiewak, 1996; Abele et al.,
1996).
The dissociation of ammonia

2 2 3
N
2
1
H
2
3
NH + (27)
is endothermic by 70 kJ/mol and proceeds
catalytically at high-pressures (50-200 bar) and at
temperatures above 700 K. It is being investigated
for application in a distributed-dish concentrating
system with the reverse synthesis reaction delivering
heat to a Rankine cycle. A techno-economic
feasibility study for a 10-MW power-plant design,
with a net solar-to-electric conversion efficiency of
18% and a capacity factor of 80%, indicates a
levelized energy cost of 0.16 US$1999 per kWh
(Lovegrove et al., 1999, Luzzi et al., 1999).
IV.4. Solar Thermal, Electrothermal, and
Carbothermal Reduction of Metal Oxides
Metals are attractive candidates for storage and
transport of solar energy. They may be used to
generate either high-temperature heat via combustion
or electricity via fuel cells and batteries. Metals can
also be used to produce hydrogen via a water-
splitting reaction; the hydrogen may be further
processed for heat and electricity generation. The
chemical products from any of these power-
generating processes are metal oxides which, in turn,
need to be reduced and recycled. The conventional
extraction of metals from their oxides by
carbothermic and electrolytic processes is
characterized by its high energy consumption and its
concomitant environmental pollution. The extractive
metallurgical industry discharges vast amounts of
greenhouse gases and other pollutants to the
environment, derived mainly from the combustion of
fossil fuels for heat and electricity generation. These
emissions can be substantially reduced, or even
completely eliminated, by using concentrated solar
energy as the source of high-T process heat.
12
The thermal and electrothermal reduction of metal
oxides without using a reducing agent and the
carbothermal reduction of metal oxides using C(gr)
and CH
4
as reducing agents may be represented as
follows:

2 y x
O
2
y
xM O M + (28)
yCO xM ) gr ( yC O M
y x
+ + (29)
) CO H 2 ( y xM yCH O M
2 4 y x
+ + + (30)
where M denotes the metal and M
x
O
y
the
corresponding metal oxide. The Gibbs free energy of
formation of many stable metallic oxides such as
ZnO, MgO, SiO
2
, CaO, Al
2
O
3
, and TiO
2
are large
negative numbers that decrease in magnitude with
temperature, while their enthalpy of formation
remains relatively independent of temperature. The
variation of the energy requirement for the thermal
and electrothermal dissociation of these metal oxides
with temperature is depicted in Fig. 5 for a generic
solar chemical reaction, and in Fig. 8 for the thermal
dissociation of ZnO. Table II lists the approximate
temperatures at which the standard G
rxn
for
reactions (28), (29), and (30) equals 0 for various
metal oxides of interest (JANAF, 1985; Steinfeld et
al., 1998a).
The solar thermal dissociation of ZnO is among the
most promising metal oxide processes. A simplified
exergy analysis for this process has been presented in
Section III. A kinetic study reported an apparent
activation energy in the range 310-350 kJ/mole
(Hirschwald and Stolze, 1972, Palumbo et al., 1998).
The product gases need to be quenched to avoid re-
oxidation, which introduces irreversibilities and may
be a factor of complexity in large-scale utilization. In
particular, the quench efficiency is sensitive to the
dilution ratio of zinc and oxygen in an inert gas flow
and to the temperature of the surface on which the
products are quenched. Maximum exergy
efficiencies exceeding 50% are possible for a molar
ratio of an inert gas to ZnO(s) less than 1 (Palumbo
et al., 1998). The condensation of Zn(g) in the
presence of O
2
was studied by fractional
crystallization in a temperature-gradient tube
furnace. The oxidation of Zn is a heterogeneous
process and, in the absence of nucleation sites, Zn(g)
and O
2
can coexist in a meta-stable state
(Weidenkaff et al., 1999).
Except for the thermal dissociation of ZnO, the
required temperature for effecting reaction (28)
exceeds 3500 K. Although it is possible to attain
such stagnation temperatures with high-flux solar
concentrating systems that deliver concentration
ratios above 10,000 [see Eq. (9)], practical
engineering and heat-transfer considerations suggest
operation of solar reactors at substantially lower
temperatures, especially when the process is to be
conducted with high energy absorption efficiency
[see Eq. (6)]. Under these circumstances, solar
process heat alone will not make the reaction
proceed; some amount of high-quality energy is
required in the form of work. It may be supplied in
the form of electrical energy in electrolytic processes
or in the form of chemical energy by introducing a
reducing agent in thermochemical processes.

Table II. Approximate temperatures for which Grxn of reactions
(28), (29), and (30) equals zero.
Metal
Oxide
G
rxn28
=0
@
G
rxn29
=0
@
G
rxn30
=0
@
Fe
2
O
3
*
3700 K 920 K 890 K
Al
2
O
3
> 4000 K 2320 K 1770 K
MgO 3700 K 2130 K 1770 K
ZnO 2335 K 1220 K 1110 K
TiO
2
*
> 4000 K 2040 K 1570 K
SiO
2
*
4500 K 1950 K 1520 K
CaO 4400 K 2440 K 1970 K
*Fe2O3, TiO2, and SiO2 decompose to lower-valence oxides before
complete dissociation to the metal.

An example of a solar electrothermal reduction
process that has been demonstrated experimentally in
a solar furnace is the electrolysis of ZnO. As shown
in Fig. 8, at 1000 K up to 30% of the total amount of
energy required to produce Zn could be supplied by
solar process heat. In such an electrochemical
process, an electrolytic cell is housed in a solar
cavity receiver that is irradiated with concentrated
solar energy. ZnO(s) is dissolved into an electrolyte
composed of a combination of sodium, aluminum
and/or calcium fluoride with a melting point near the
process temperature. This choice prevents excess
loss of electrolyte due to evaporation. Electric energy
is then supplied to two electrodes immersed in a
saturated solution. If the electrodes are made of
graphite, the products are essentially CO and Zn
(Fletcher et al., 1985, Fletcher, 1999). If the anode is
made of Pt and the cathode is made of Mo the
products are Zn and O
2
(Palumbo and Fletcher,
1988). ZnO(s) can also be dissociated thermally in a
cell. The O
2
is then separated from the Zn vapor by
pumping it electrolytically through a cell wall made
of zirconia sandwiched between two Pt surfaces
(Parks et al., 1988). Solar electrochemistry research
in this field has to date been almost exclusively
dedicated to ZnO and H
2
O, but one can extend the
thinking to the high-temperature electrolysis or
13
quasi-electrolysis of MgO, Al
2
O
3
, and other
interesting candidate materials (Fletcher, 1999).
If one wishes to decompose metal oxides thermally
into their elements without the application of
electrical work, a chemical reducing agent is
necessary to lower the dissociation temperature. Coal
as coke and natural gas as methane are preferred
reducing agents in blast-furnace processes because of
their availability and relatively low price. In the
presence of carbon, the uptake of oxygen by the
formation of CO brings about reduction of the oxides
at much lower temperatures. While reactions (29)
and (30) have favorable free energies above the
temperatures indicated in Table II, a more detailed
calculation of the chemical equilibrium composition
shows that only the carbothermic reduction of Fe
2
O
3
,
ZnO, and MgO will result in significant free metal
formation below about 2000 K. The carbides TiC,
SiC, Al
3
C
4
, and CaC
2
are thermodynamically stable
in an inert atmosphere; the nitrides TiN, Si
3
N
4
, and
AlN are stable in N
2
atmosphere. Examples of
carbothermic reduction processes that have been
carried out in solar furnaces include the production
of Fe, Mg, and Zn from their metal oxides in Ar
atmospheres, the production of AlN, TiN, Si
3
N
4
, and
ZrN from their metal oxides in N
2
atmospheres, and
the production of Al
4
C
3
, TiC, SiC, and CaC
2
from
their metal oxides in Ar atmospheres (Steinfeld and
Fletcher, 1991; Murray et al., 1995; Duncan and
Dirksen, 1980).
Using natural gas as a reducing agent combines in a
single process the reduction of metal oxides with the
reforming of methane for the co-production of
metals and synthesis gas (syngas), [see Eq. (30)].
The resulting syngas mixture has a molar ratio of H
2

to CO equal to 2, which makes it especially suitable
for methanol synthesis. Since the evolved product
gases are sufficiently valuable commodities to justify
their collection, discharge of gaseous reaction
products to the environment is eliminated. Thermal
reductions of Fe
3
O
4
and ZnO with CH
4
to produce
Fe, Zn, and syngas have been demonstrated in solar
furnaces using fluidized bed and vortex type reactors
(Steinfeld et al., 1993; Steinfeld et al., 1995;
Steinfeld et al., 1998b). These reactions are
endothermic by 333 kJ/mol Fe

and 442 kJ/mol Zn,
respectively, and proceed to completion at
temperatures above about 1250 K.
H
2
O-splitting thermochemical cycles
Single-step (direct) thermal water dissociation,

although conceptually simple, has been impeded by
the need to use very high temperatures and an
effective technique for separating H
2
and O
2
. Water-
splitting thermochemical cycles have been proposed
to bypass the H
2
/O
2
separation problem. Multi-step
thermochemical cycles also allow the use of
relatively moderate operating upper temperatures,
but their overall exergy efficiency is limited by
irreversibilities associated with heat transfer and
product separation. A status review on multi-step
cycles was given in 1992 by Serpone et al. and
includes a 3-step cycle based on the solar
decomposition of H
2
SO
4
at 1140 K and a 4-step
cycle based on the solar hydrolysis of CaBr
2
and
FeBr
2
at 1020 K and 870 K, respectively. Two-step
water-splitting cycles, based on metal oxides redox
systems, require much higher temperatures, but,
when using high solar concentration ratios and heat-
recovery systems, have the potential of achieving
efficiencies above 30% (Steinfeld et al., 1998a). The
first, endothermic step is the solar thermal
dissociation of metal oxides [see Eq. (28) in Section
IV.4]. The second, non-solar, exothermic step is the
hydrolysis of the metal at moderate temperatures
(below about 800 K) to form molecular hydrogen
and the corresponding metal oxide, i.e.

2 y x 2
yH O M O yH xM + + (31)
The products have a natural phase separation. The
liberated heat may be used to effect the reaction in an
auto-thermal reactor. This 2-step solar
thermochemical cycle is shown schematically in Fig.
10. The net reaction is H
2
O H
2
+ 0.5O
2
.
Hydrogen and oxygen are formed in different steps,
thereby eliminating the need for high-temperature
gas separation.
H
2
H
2
O
Concentrated
Solar Energy
WATER-SPLITTING
REACTOR
xM + yH
2
O = M
x
O
y
+ yH
2
O
2
SOLAR
REACTOR
M
x
O
y
= xM+ y/2 O
2
M
x
O
y
M
M
x
O
y
recycle

Figure 10. Schematic of a two-step water-splitting
thermochemical cycle using metal oxides in redox systems. In the
first, endothermic, solar step, the metal oxide MxOy is thermally
decomposed into the metal M and oxygen. Concentrated solar
radiation is the energy source for the required high-temperature
process heat. In the second, exothermic, non-solar step, the metal
M reacts with water to produce hydrogen. The resulting metal
oxide is then recycled back to the first step. The net reaction is
H2O H2 + 0.5 O2. Since hydrogen and oxygen are produced in
different steps, the need for high temperature gas separation is
eliminated.

14
In some cases, a lower-valence metal oxide is
capable of splitting water, so that complete reduction
of the metal oxide to the metal is not necessary.
These cycles have been examined
thermodynamically and tested in solar reactors for
ZnO/Zn and Fe
3
O
4
/FeO redox pairs (Bilgen et al.
1977; Nakamura, 1977; Palumbo et al., 1998;
Sibieude et al., 1982; Steinfeld et al., 1998a;
Steinfeld et al., 1999). Other redox pairs, such as
TiO
2
/TiO
x
, Mn
3
O
4
/MnO, and Co
3
O
4
/CoO have also
been considered, but the yield of H
2
in reaction (31)
has been too low to be of any practical interest.
Partial substitution of iron in Fe
3
O
4
by other metals
forms mixed metal oxides of the type (Fe
1-x
M
x
)
3
O
4

that may be reducible at lower temperatures than
those required for the reduction of Fe
3
O
4
, while the
reduced phase (Fe
1-x
M
x
)
1-y
O remains capable of
splitting water (Ehrensberger et al., 1995).
IV.6. Solar Upgrade and Decarbonization of Fossil
Fuels
The replacement of fossil fuels by solar fuels, e.g.,
solar hydrogen and solar metals, is a long-term goal.
It requires the development of novel technologies
and it will take time before these methods are
technically and economically ready for commercial
applications. Thus, from a strategic point of view, it
is desirable to consider a mid-term goal that aims at
the development of hybrid solar/fossil processes.
Any endothermic process that uses fossil fuels
exclusively as chemical reactants and solar energy as
the source of process heat qualifies as an hybrid
solar/fossil process. The products are fuels whose
quality has been upgraded by solar energy, i.e. the
calorific value is increased above that of the fossil
fuel by solar energy input equal to the enthalpy
change of the reaction. Increased energy content
means extended fuel life and reduced pollution of the
environment. Therefore, these fuels are cleaner
fuels. The mix of solar and fossil energies creates a
link between current fossil-fuel-based technologies
and future solar chemical technologies. This
approach builds bridges between present and future
energy economies. Solar technologies will represent
viable economic paths earlier if the costs of fossil
energy account properly for environmental
externalities arising from the burning of fossil fuels.
The transition from fossil to solar fuels can occur
smoothly, and the lead time for transferring
important solar technology to industry can be
reduced. Figure 11 illustrates the research strategy
which is aimed at both the long-term goal of using
solar fuels and at the mid-term goal of applying
solar-fossil fuel mixtures.
Fossil Fuels
Fossil & Solar
Energy Mix
Solar Fuels
PRESENT
FUTURE TRANSITION
Fossil Fuels
Fossil & Solar
Energy Mix
Solar Fuels
PRESENT
FUTURE TRANSITION

Figure 11. Strategy for replacement of fossil fuels by solar fuels,
which involves research on two paths: a long-term path for a
completely sustainable energy supply, and a mid-term path for
mixing fossil and solar energies.

Examples of processes involving mixed fossil and
solar energies are the carbothermic reduction of
metal oxides using coke or natural gas as chemical
reducing agents. Use of these types of processes will
substantially reduce greenhouse-gas emissions. For
example, a life cycle analysis indicates that replacing
conventional fossil-fuel-based zinc production by a
solar-based CH
4
-thermal reduction process results in
CO
2
-equivalent emission reductions of 59% (Werder
and Steinfeld, 2000).
Another important category of thermochemical
processes for mixing fossil and solar energies is the
decarbonization of fossil fuels, i.e. the removal of
carbon from fossil fuels prior to their combustion so
that no CO
2
is discharged during combustion. Two
methods have been considered (Steinberg, 1999): (1)
the solar thermal decomposition of fossil fuels and
(2) the steam-reforming/gasification of fossil fuels.
The thermal decomposition of natural gas, oil, and
other hydrocarbons may represented by
. H
2
y
) gr ( xC H C
2 y x
+ (32)
Other compounds may also be formed, depending on
the reaction kinetics and the presence of impurities in
the raw materials. But the thermal decomposition
yields basically two distinct products that have a
natural phase separation, namely, a carbon-rich
condensed phase and a hydrogen-rich gas phase. The
carbonaceous solids can either be sequestered or
used as material commodities under less severe CO
2

constraints. The hydrogen-rich gas mixtures may be
further processed to high-purity hydrogen that is not
contaminated by carbon oxides and that can be used
in fuel cells without inhibiting the use of platinum-
made electrodes. H
2
-rich mixtures can also be
adjusted to yield high-quality syngas.
The steam-reforming of natural gas, oil, and other
hydrocarbons is represented by
xCO H x
2
y
O xH H C
2 2 y x
+
,
_
+ + (33)
15
and the steam-gasification of coal by
CO , H O H coal
2 2
+ (34)
As in thermal decompositions, other compounds may
also be formed, especially from coal. Some
impurities contained in the raw materials such as
sulfur compounds are removed prior to
decarbonization by using conventional technologies.
The principal product is syngas of different H
2
:CO
mole ratios. The CO content in the syngas may be
shifted toward H
2
via the catalytic water-gas shift
reaction

2 2 2
CO H O H CO + + (35)
CO
2
is separated from H
2
, for example, by pressure
swing adsorption (PSA).
Reactions (32) to (34) proceed endothermically in
the 800-1500 K range. Several chemical aspects of
these reactions have already been studied (Ullmann,
1996). Reaction (32) has been effected catalytically
by using solar process heat at about 823 K for the
production of filamentous carbon (Meier et al.,
1999). Reaction (33) has been demonstrated in a
solar tower using natural gas (see Section IV.3) and
is currently being considered for the use of low
petroleum gas (a gas mixture that results from
petroleum distillation containing mainly propane and
butane) using the same reactor technology (Epstein
and Spiewak, 1996; Abele et al., 1996). Reaction
(34) has also been performed using solar energy in
early exploratory studies, for example, with oil shale
(Ingel et al., 1992, Fletcher and Berber, 1988). Some
of these processes are currently practiced at an
industrial scale and the energy required for heating
of the reactants and for the heat of reaction is
supplied by burning some portion of the feedstock.
As an example, to crack methane according to Eq.
(32), at least 20% of the higher heating value of the
feedstock is used. For methane reforming according
to Eq. (33), about 40% of the feedstock needs to be
burned to supply process heat. Internal combustion
results in contamination of the gaseous products
while external combustion results in reduced thermal
efficiency because of the irreversibilities associated
with indirect heat transfer via heat exchangers. The
use of solar energy for process heat has the following
advantages: (1) the discharge of pollutants is
avoided; (2) gaseous products are not contaminated;
and (3) the calorific value of the fuel is upgraded by
adding solar energy in an amount equal to the H of
the reaction.
The two solar thermal decarbonization methods are
shown schematically in Fig. 12 in the form of
simplified process flow diagrams.
Solar
Chemical
Reactor
Fossil Fuels
Concentrated
Solar Energy
H
2
-rich
gas-phase mixture
C(gr)-rich
condensed-phase mixture
Solar
Chemical
Reactor
Fossil Fuels
Concentrated
Solar Energy
Water
Syngas
Shift
Reactor
Water
PSA
Separation
H
2
CO
2
(a)
(b)

Figure 12. Simplified process flow diagram for the solar thermal
decarbonization of fossil fuels. Two methods are considered: (a)
solar thermal decomposition and (b) solar thermal steam-
reforming/gasification. Omitted are the formation of by-products
derived from impurities present in the feedstock and the pre-
treatment of the fossil fuels (e.g., by desulfurization).

The two methods have been compared (Steinberg,
1999). From the point of view of carbon
sequestration, it is easier to separate, handle,
transport and store solid carbon than gaseous CO
2
.
The steam-reforming/gasification method requires
additional steps for shifting CO and separating CO
2
,
while thermal decomposition accomplishes the
removal and separation of carbon in a single step. In
contrast, the major drawback of the thermal
decomposition method is the energy loss associated
with the sequestration of carbon. For this approach,
the type of feedstock is of crucial importance when
selecting the decarbonization method. For example,
thermal decomposition may be the preferred option
for gaseous hydrocarbons because of the high H
2
/C
ratio. But for coal and other solid carbonaceous
materials, the residual of energy after
decarbonization may be too low for industrial
application. Gasification of coal via reaction (34) has
the additional advantage of converting a relatively
dirty solid fuel, which is traditionally used to
generate electricity in steam-turbine cycles at about
16
35% efficiency, into a cleaner fluid fuel when using
solar process heat that can be used in gas-turbine or
combined cycles with over 55% efficiency.
Many fossil fuel reserves exist in regions with high
solar insolation. Thermochemical processes that mix
fossil fuels with solar energy, such as those
described here, are important intermediate solutions
towards a sustainable energy-supply system.
IV.7. Solar thermal production of chemical
commodities
Concentrated solar energy may be used for the
processing of high-temperature and energy-intensive
commodities. Examples are the following. (a)
Syngas may be produced by solar reforming or solar
gasification of fossil fuels according to Eqs. (33) and
(34) (see Section IV.6). Syngas is the building block
for a wide variety of synthetic fuels, including
Fischer-Tropsch type chemicals, hydrogen,
ammonia, and methanol (which is a possible
substitute for gasoline in vehicles). (b) Biomass and
other carbonaceous materials may be converted in
different solar thermochemical routes into bio-oils,
charcoal, and syngas (Ld, 1999). A significant
advantage of using biomass is that the process has a
zero net release of CO
2
. (c) Fullerenes and carbon
nanotubes can be produced by sublimation of
C(graphite) above 3000 K or by catalytic thermal
decomposition of hydrocarbons according to Eq.
(32), (Guillard et al., 1999; Meier et al., 1999). (d)
Metallic carbides and nitrides can be produced by
the solar carbothermic reduction of metal oxides as
in Eqs. (29) and (30), (see Section IV.4). These
ceramics are valuable materials for high-temperature
applications because of their high hardness,
excellent corrosion resistance, high melting points,
and low coefficients of thermal expansion. They
may also be incorporated in cyclic processes of the
type shown in Fig. 10; their hydrolysis yields
hydrocarbons and ammonia (Murray et al., 1995).
(e) Zinc, iron, magnesium, and other metals can be
produced by the carbothermic reduction of their
metal oxides (see Section IV.4). Aluminum-silicon
alloys may be produced by the carbothermic
reduction of Al
2
O
3
and SiO
2
at 2300 K, thus
providing an alternative route to the Hall-Hroult
electrolytic process (Murray, 1999). (f)
Decomposition of limestone, the main endothermic
step in the production of cement, may be effected
using solar process heat at 1300 K.
IV.8. Solar thermal detoxification and recycling of
waste materials
Solid waste materials from a wide variety of sources
(e.g., municipal waste incineration residuals,
discharged batteries, dirty scraps, contaminated soil,
dusts and sludge, and other by-products from the
metallurgical industry) contain hazardous
compounds that should not be discharged into the
environment. They are usually vitrified in a non-
leaching slag and finally disposed of at hazardous
waste-storage sites. However, limited storage space,
increasing storage costs, and environmental
regulations have led to the urgent need of
developing technologies that recycle these toxic
materials into useful commodities rather than
deposit them in dump sites for an undetermined
period of time. Chemical transformations of these
materials into their elemental components offers the
possibility of converting waste materials into
valuable feedstock for processes in closed materials
cycles. Thermal processes are well suited for the
treatment of complex solid waste materials. Waste
materials containing carbonaceous compounds can
be converted by thermal pyrolysis and gasification
into syngas and hydrocarbons that can be further
processed into other valuable synthetic chemicals.
Waste materials containing metal oxides may be
converted by carbothermal reduction into metals,
nitrides, carbides, and other metallic compounds.
The chemical products from such transformations
are feedstock for a variety of manufacturing
processes and may also be used as fuels.
Closed cycles of materials require high-temperature,
energy-intensive recycling processes. The
commercial recycling techniques by blast, induction,
arc, and plasma furnaces are major consumers of
electricity and high-temperature process heat and,
consequently, major contributors of greenhouse-gas
emissions and other pollutants. Concentrated solar
radiation supplies clean thermal energy at high
temperatures to drive these complex processes that
usually involve gases, solids, and melts. Preliminary
feasibility tests with aluminium melts were
conducted in a solar furnace with a rotary-kiln solar
reactor (Funken et al., 1999).
17
V. SOLAR THERMOCHEMICAL REACTORS

The chemical thermodynamics and kinetics of the
reaction place important constrains on the size, type,
materials of construction, and modes of operation of
reactors. The species involved and their phases,
temperature requirements, enthalpies, and rates of
reaction are among essential information required for
reactor design. The design of a multi-purpose reactor
that optimizes every reaction is an impossible task.
However, reactors may be classified according to
general types that will guide their designs. They may
be reactors for homogeneous and heterogeneous
chemical systems, for batch, semi-batch and steady-
flow operations, for plug or mixed flows, etc. We
refer the reader to the introductory book of
Levenspiel (1992) for a comprehensive treatment on
chemical reactor engineering.
A unique feature of solar chemical reactors is that
the source of process heat is concentrated solar
energy. Therefore, the heat transfer characteristics of
a solar reactor may differ significantly from those
existing in conventional designs. We have found it
useful to classify solar reactors into two groups: (i)
Indirectly-irradiated reactors, i.e. reactors in which
the opaque external walls of the reactor are exposed
to concentrated solar radiation and transfer the
absorbed heat to the chemical reactants. (ii) Directly-
irradiated reactors, i.e. reactors in which the
chemical reactants (or catalysts) are directly exposed
to the concentrated solar radiation.
There are benefits and drawbacks associated with
both concepts. Indirectly-irradiated reactors have the
advantage of eliminating the need for a transparent
window. Disadvantages are linked to limitations
imposed by the materials of construction of the
reactor walls such as the maximum operating
temperature, thermal conductivity, radiative
absorptance, inertness, resistance to thermal shocks,
and suitability for transient operation. Directly-
irradiated reactors have the advantage of providing
efficient radiation heat transfer directly to the
reaction site where the energy is needed and thereby
by-passing the aforementioned limitations imposed
by indirect heat transport through the reactor walls.
Furthermore, under proper conditions, direct
irradiation may enhance photochemical kinetics. The
major drawback, when working with reducing or
inert atmospheres, is the requirement for a
transparent window, which is a critical and
troublesome component in high-pressure and severe
gas environments. Both directly- and indirectly-
irradiated reactors suffer intrinsic losses in energy
conversion efficiency as the result of re-radiation
losses. Since these losses are proportional to the re-
radiation area, they can be minimized by using
cavity-type solar receivers.
A solar cavity-type receiver is basically a well-
insulated enclosure designed to capture effectively
the incident solar radiation by allowing entry of
radiation only through a small opening [the aperture
(see Section III)]. Because of multiple internal
reflections, the fraction of the incoming energy
absorbed by the cavity greatly exceeds the simple
surface absorptance of the inner walls. This effect is
called the cavity effect and may be expressed as an
apparent absorptance which is defined as the fraction
of energy flux emitted by a blackbody surface
stretched across the cavity opening that is absorbed
by the cavity walls. The apparent absorptance has
been calculated for cylindrical, conical and spherical
geometries having diffuse and specularly reflecting
inner walls (Siegel and Howell, 1972). The larger the
ratio of the cavity diameter or depth to the aperture
diameter, the closer the cavity-receiver approaches a
blackbody absorber. Smaller apertures also serve to
reduce re-radiation losses. However, they intercept a
reduced fraction of the sunlight reflected from the
concentrators. Consequently, the optimum aperture
size is a compromise between maximizing radiation
capture and minimizing radiation losses. The
optimum aperture radius r
optimum
for a Gaussian
power flux distribution according to F
peak
exp(-
r
2
/2
2
), where F
peak
is the peak solar flux intensity at
r=0 and denotes the radius corresponding to one
standard deviation for the power flux distribution, is
(Steinfeld and Schubnell, 1993)
.
F
T
ln 2 r
5 . 0
peak
4
2
optimum
1
1
]
1
,
_

(36)
The optimal aperture radius varies from 2.6 to 2.9
for peak solar flux intensities between 1,000 and
12,000 suns.
The following is an example of a directly-irradiated
solar chemical reactor for high-temperature solid-gas
processes (Haueter et al., 2000). Other examples of
solar chemical reactor for various thermochemical
applications may be found in the cited literature.
Figure 13 is a detailed schematic of a directly-
irradiated reactor concept designed for the solar
thermal dissociation of ZnO(s) into Zn(g) and O
2
at
temperatures above 2000 K [Eq. (22), see Section
III].
It is a reactor closed to air. The main component is a
rotating conical cavity-receiver (#1) made of inconel
steel that contains the aperture (#2) for access of
concentrated solar radiation through a quartz window
(#3). Because of multiple reflections at the inner
walls of the cavity, the cavity approaches a
blackbody absorber that captures and absorbs
incoming solar energy efficiently. The solar flux
18
concentration may be further augmented by
incorporating (see Section II) a CPC (#4) in front of
the aperture. Both the copper-made window mount
and the aluminum-made CPC are water-cooled and
integrated into a concentric (non-rotating) conical
shell (#5). The reactants are ZnO particles which are
fed continuously along the axis into the rotating
cavity by means of a screw powder feeder located at
the rear of the reactor (#6). The centripetal
acceleration forces the ZnO powder to the wall
where it forms a thick layer of ZnO (#7) that
insulates and reduces the thermal load on the inner
cavity walls. The gaseous products Zn and O
2
are
swept out of the chamber by a continuous flow of
inert gas

that enters the cavity-receiver tangentially at
the front (#8) and exits via an outlet port (#9) to a
quench device (#10). The purge gas also keeps the
window cool and clear of particles or condensable
gases.

Figure 13. Schematic of a solar chemical reactor for the thermal
decomposition of ZnO [Eq. (22)]. 1= rotating cavity-receiver, 2 =
aperture, 3 = quartz window, 4 = CPC, 5 = outside conical shell, 6
= reactant feeder, 7 = ZnO layer, 8 = purge-gas inlet, 9 = product
outlet port, 10 = quench device.
With this arrangement, concentrated sunlight
impinges directly on the top surface of the ZnO
layer. This efficient heating condition leads to a
system with a low thermal inertia and excellent
thermal shock resistance. The ZnO serves
simultaneously as radiation absorber, thermal
insulator, and chemical reactant. An indirectly-
irradiated version of this reactor may be obtained by
incorporating a graphite cavity at the aperture.
Concentrated solar radiation is then absorbed by the
cavity and further transferred to the reactants by
combined conduction, convection, and radiation heat
transfer.
Other directly-irradiated reactor concepts have been
demonstrated experimentally with gas-particle
suspensions, fluidized beds, perforated graphite
disks, ceramic honeycombs and foams, and other
radiation absorbers for transferring heat to reactants
and/or catalysts (Kappauf et al., 1985; Ingel et al.,
1992; Levy et al., 1992; Abele et al., 1996, Muir at
al., 1994; Steinfeld et al., 1998b). Most of these solar
experiments were performed with small-scale
prototype reactors at an early stage of R&D.
Especially the window technology requires further
development and feasibility demonstration at a larger
scale. In contrast, the indirectly-irradiated reactor
concept uses well-established engineering practices
and has already been demonstrated at 0.5 MW for a
tubular solar reformer operating at 1100 K (Epstein
and Spiewak, 1996). For large-scale applications at
moderate temperatures, it may be preferable over the
near term to apply the indirectly-irradiated concept
for the reactor design. Over the long term, directly-
irradiated reactors for advanced applications at
temperatures exceeding 1500 K may prove to have
superior performance.

VI. OUTLOOK

After the 1973/74 Middle East oil crisis, the world
community began to appreciate its dependence on a
precarious supply of crude oil. The International
Energy Agency was created to help ensure the
development of cheap and stable energy-resource
options. The agency's objectives continue to makes
sense. It has been pointed out that a country's
national security and control of its own political
destiny depend on access to energy. Unfortunately,
access to conventional sources of energy for a nation
are not secure and could be cut off. Whether it be a
war, depletion of a major energy source such as
crude oil, or a threat to the environment such as the
greenhouse effect, these are sound reasons for
countries to invest in the development of energy
options. From this perspective, solar energy research
is preventive medicine for the health of a country
(Fletcher, 1996).
This view leads to a profound change in the role of
economics in guiding research. Rather than
evaluating solar chemistry technology options by
how well they compete economically against
conventional fossil-fuel-based technologies in the
current market place, economic arguments would
challenge new sustainable energy technology options
to be more economical than the best current ones. If
the goal were to produce H
2
, the economic
competition should properly be between sustainable
concepts for producing it. If solar energy is to be
used to reduce CO
2
emissions, the solar process
should be more cost effective than all other options
19
that bring atmospheric CO
2
levels to sustainable
values.
If solar thermochemical or other renewable energy
technologies for producing fuels and chemical
commodities are required to compete with all other
production technologies, the cost of fossil-fuel-based
materials and processes involved in those
technologies must be forced to account for the
externalities of burning fossil fuels such as the cost
of CO
2
mitigation and pollution abatement. These
external costs may be assessed by conducting a life
cycle analysis (LCA) which is a method for
evaluating the environmental burdens associated
with a product, process, or activity by identifying
and quantifying energy and materials used and
wastes released to the environment during the entire
life cycle. When the external costs are internalized,
renewable energy technologies may well become
competitive with conventional technologies.
Solar-made electricity is a key form of clean energy
based on an unlimited resource, but it cannot be
stored or transmitted over long distances more
conveniently than electricity produced from any
other energy sources. Solar-made chemical fuels
overcome these limitations to a large extent. They
are solar energy carriers that can be used for heat and
electricity generation to match the customers energy
demands. Solar thermochemical processes are
thermodynamically favorable paths for producing
solar fuels because of the potential for converting
unlimited solar energy into chemical energy
efficiently. Thus, solar thermochemical process
technology is a promising long-term prospect for
delivering clean, efficient, sustainable energy
services.

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Solar Thermochemical Process Technology

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ENCYCLOPEDIA OF PHYSICAL SCIENCE & TECHNOLOGY Solar Thermochemical Process Technology

Stefan-Boltzmann constant (5.670510

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