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Pergamon Press Ltd.
1983 International Association for Hydrogen Energy.

Int. J. Hydrogen Energy, Vol. 8, No. 9, pp. 675-679, 1983.

Printed in Great Britain.

P R O D U C T I O N OF H Y D R O G E N BY DIRECT T H E R M A L
DECOMPOSITION OF W A T E R
J. Lr~D, F. LAPICQUEand J. V1LLERMAUX
Laboratoire des Sciences du G6nie Chimique, CNRS-ENSIC, 1, rue Grandville 54042, Nancy, France

(Received for publication 19 January 1983)

Abstract--This paper reports the first results of a study on the feasibility of producing hydrogen by direct thermal
splitting of water by use of concentrated radiation. Relative amounts of H, O, OH, H2, Oz and H20 have been
computed between 1500 and 4000 K at thermodynamic equilibrium. In addition, the rate of the overall reaction
has been estimated assuming a kinetic model: 90% of equilibrium concentrations are reached after about 10-z,
10-3 and 10-4s at 2200, 2500 and 3000 K respectively. The dissociation experiments have been carried out in an
image furnace, simulating the future use of a solar furnace. Water is injected through a zirconia nozzle heated
at the focus. The hot jet containing active species is then quenched by turbulent cold jets in order to minimize
recombinations. Several shapes of zirconia nozzles and quenching devices have been tested in order to maximize
the net production of hydrogen, which reaches 1.7 STP 1. h -1 in continuous operation. Modelling of the hot nozzle
allows the calculation of the gas temperature and shows that thermodynamic equilibrium conditions are reached
under certain conditions. Parallel experiments show that cooling rates up to 106 K s-1 can be obtained by quenching.
INTRODUCTION

T H E O R E T I C A L COMPOSITION OF
DISSOCIATED STEAM U N D E R
THERMODYNAMIC EQUILIBRIUM

The decomposition of water is one of the most attractive

chemical processes to get hydrogen and to achieve
energy storage in the future [1, 2]. Various ways exist
According to classical thermodynamic studies, only
to break the H20 molecule and to insure a minimum six components exist to a significant extent in dissociated
recombination of the reaction products. The most classi- steam in the range 2000-3000 K [13]: H20, H, O, OH,
cal one is probably electrolysis at ordinary or inter- H2 and 02. Other compounds such as HO2, 03 and
mediate temperature [3]. Concerning the use of solar H202 can be neglected. The thermodynamic functions
energy more specifically, other ways have been and/or of these species can be found in standard tables [14]
are presently under investigation, in which solar radia- and the calculation of the dissociated mixture compotion could be used either through quantum effects-- sition as a function of temperature and pressure, is
photolysis [4]----or as a source of thermal energy--ther- straightforward, for instance in minimizing the free
mochemical cycles [5]. Unfortunately the development enthalpy of the mixture. The calculation has been made
of a practical cycle is a difficult task due to the increas- for several pressure conditions [10, 11]. Figure 1 shows
ing complexity of the process itself, phase separation, the results expressed as a molar fraction x of the species
chemical kinetics, hot corrosion, amount of circulating (calculated on the basis of all the constituents) at thersolid yield per pass etc. It then seemed very attractive modynamic equilibrium under 1 atm. These results in
to consider another approach: the direct thermal split- good agreement with other published calculations
ring of water where two major problems must be [5, 13] show that significant amounts of hydrogen can
overcome.
be obtained only at temperatures higher than 2000 K.
Dissociation occurs at very high temperatures
(greater than 2000K): such temperatures can be
reached by concentrating solar energy on a refractory
target where steam dissociates as this has been suggested
by various authors [5-9]. It is also necessary to prevent
KINETIC MECHANISM OF T H E R M A L
recombination of the products: two possibilities can be
DECOMPOSITION
considered: use of selective membranes to eliminate
Several authors have reported elementary homoone of the products (HE or O2) as soon as it is formed
at high temperature or rapid cooling (quenching) of the geneous steps taking place by the thermal dissociation
gas mixture [10-12]. The present paper relates the first of water [15-17]. According to the literature data, four
theoretical and experimental results obtained with the elementary reactions can be retained as representative
of the overall mechanism in the range 2000-3000 K:
second technique.
(1)
HEO + M ~,~H + OH + M AH~ = 500 kJ mole-1
H20 + H ~ H 2 + OH

AH~ = 60.1 kJ mole -1

(2)

OH+H

~-HE + O

AH~ = 8.4 kJ mole-1

(3)

OH+O

~.~-O2 + H

AH~ = - 6 5 kJ mole -1

(4)

675

J. LI~DI~, F. LAPICQUE AND J. VILLERMAUX

676

'X

Table 1. Kinetic rate constants for elementary reactions taking

place in steam dissociation
Kinetic rate constants

P:~PQ

kl = 1.3 109 exp (-52900/T)

k-1 = 8.4 109 T -2
kx = 2.2 101 exp (-52900/T)
k-1 = 1.4 10n T -2
k2 = 9 107 exp (-10250/T)
k-2 = 2.2 107 exp (-2590/T)

G1,

G01.

Units
m3.mole-1,
m 6 - mole

mole

mr

Ar

-2 s

m 3. molem 6-

l. s

H20

2. S 1

HzO

m 3 mole

~s

m 3 mole

1. s

k3 = 8.3 103 T exp (-3500/T)

k-3 = 1.8 104 T exp (-4480/T)
k4 = 2 107

m 3- m o l e

l. s- 1

k-4 = 2.2 108 exp (-8420/T)

m3.mole-1

.s

m 3" m o l e -

~s

m 3- m o l e

~s

0.0131-

librium are of the order of magnitude of 10 -2, 10 -3 and

10-4s respectively at 2200, 2500 and 3000 K.

I~0001
Fig. 1. Molar fraction x of dissociation species at thermodynamic equilibrium vs temperature at 105 Pa.

The rate constants of processes (1)-(4) found in the

literature [17, 18] or recalculated with the help of Janaf's
tables [14] are given in Table 1.
Assuming that the dissociation zone is equivalent to
a continuous stirred reactor at constant temperature,
it is possible to calculate the concentration of all the
species as a function of the m e a n residence time (Fig.
2). T h e times r e q u i r e d to reach about 90% of asymptotic
concentrations corresponding to t h e r m o d y n a m i c equi-

f_

, 't

l f

'l

Fig. 2. Molar fraction x of dissociation species as a function

of mean residence time T at 2200, 2500 and 3000 K in a stirred
reactor.

EXPERIMENTAL

(Fig. 3)

In order to prepare future experiments with a vertical

2 k W solar furnace in Odeillo the first studies are m a d e
with an image furnace consisting of a 4 k W X e n o n lamp
and two elliptic mirrors concentrating the radiation on
a 2-3 m m wide spot where the available thermal power
amounts to about 7 0 0 W . A zirconia nozzle (84%
porosity zirconia stabilized with calcia and yttria)
settled at this focus point is heated to temperatures up
to 3000 K. Liquid water is continuously injected into
the nozzle to be heated and partially dissociated. In
order to avoid recombination of the evolved species
back to water, the hot gases issued from the nozzle are
quickly cooled by mixing with four cold turbulent jets
(argon at r o o m t e m p e r a t u r e or steam at 400-450K)
inside an hemispherical Pyrex glass reactor (approx.
10 4 m3). The cold gases are then analysed by gas phase
chromatography when argon is used as a quenching gas.
It is also possible to measure their flow rate after condensing the excess of water w h e n steam is used as the
quenching gas.
Several shapes of zirconia nozzles (Fig. 4) have been
tested. These nozzles are designed to improve the
recovery of concentrated radiation, to increase the heat
transfer efficiency between the steam and the hot
zirconia walls and to minimize the energy losses by
reradiation from the hot target. Their geometry are
those of cylindrical, polytubular and annular reactors.
It is possible to recover a fraction of reradiated energy
from the nozzle by setting a concentric metallic reactor
around the zirconia working as a heat exchanger where
water is p r e h e a t e d up to 700--800 K before entering the
dissociating zone.
Two quenching devices have been tested (Fig. 5). In
the first one, the four turbulent jets are directed in such
positions that the Pyrex glass cooling reactor works as
a jet stirred reactor, whose design and operation rules
correspond to standard values [19]. In the second

PRODUCTION OF HYDROGEN BY DIRECT THERMAL DECOMPOSITION OF WATER

677

~,-~,;-t~-~
Fig. 3. Scheme of the experimental set-up.

device, the jets are positioned 4 m m downstream the

outlet of the zirconia nozzle in such positions that the
cold gases are directed perpendicularly to the hot gases
flow.
RESULTS

Fig. 4. Scheme of different shapes of zirconia nozzles (sizes

are given in mm: 10-3 m). A: Cylindrical nozzle; B: polytubular
nozzle (10 small tubes 1 nun diameter); C: annular nozzle; D:
stainless steel water preheater.

Quenching efficiency does not seem to be influenced

by the n a t u r e of the cold gas: argon or steam. The
molar fraction of hydrogen (measured among all
the active c o m p o n e n t s except the quenching gas)
increases with the volumetric flow rate of cold gas as
can be seen in Fig. 6 for a quenching device of the first
kind. The second kind of quenching is much more
efficient: as shown on Fig. 7, the molar fraction of
hydrogen evolved is increased by a factor close to 2.5.

XH.<,

S !
+ ~

1.5.

1
tlut~i~ ~ i~t
~NN:ond

'

,.,.~ - - ~ = " ~ m ~ 3 = ~ - )

~,-

(pyrex

o ~

ll, r r , , lie,s)
,I,

Q~<hnj-..

'

l">-H- t ' ' - - l t - ' t - ~ \\\

ca I ! I

#.)

Fig. 5. Schematic representation of the two quenching devices

(sizes are given in mm: 10-3 m).

ol

50

100

a~,(~-~., -')

_1

150

Fig. 6. Measured molar fraction of hydrogen Xr~2 (%) vs jet

stirring flow rate of argon QA, (cylindrical cavity and quenching
of the first kind) for several mass flow rates Q,, of
water: (+) 0.310-Skgs 1; (O) 0.9310-Skgs-X; (A)
2.83 x 10-5 kg s -].

678

J. Lt~DI~, F. LAPICQUE AND J. VILLERMAUX

.I
CSTR. . . . p
XHz(%)The*r~tic*l X~ exit hot n~l, ~--~/:~R . . . .

./.

+ .,~.. + /

+ /

+ ""-'~+~

QAr ( 10-5m3-s-l) _

Fig. 7. Influence of quenching device on the values of molar

fraction of hydrogen Xn2: (+) first kind quenching; (~): second
kind quenching. (Mass flow rate of water: Qm = 0.53
lO-Skgs-L)

15

\.'

jo"

0.5

6"

~ s

-1
~

IOo~

Qm (lO-S~.s -')

o,,.

Fig. 8. Measured molar fraction XH2 and volumetric Bow

rate Q~2 of hydrogen vs mass flow rate of water Q~
(cylindrical cavity and first kind quenching with Qar = 220 x
10-6 m3 s-I STP).

In other words, a given molar fraction of hydrogen is

obtained with a lower cold gas flow rate, leading to a
much less diluted hydrogen and then to a much higher
efficiency of the overall process. ForXn2 = 1.2%, Fig.
7 shows that the necessary flow rate of argon is divided
by a factor greater than 5.
Figure 8 shows that the molar fraction of hydrogen
diminishes as the mass flow rate of water increases in
the hot nozzle. But, owing to a compensation effect,
the net quantity of hydrogen Qn2 which is the product
of the mass flow rate by the dissociation extent increases
to a maximal value after which it diminishes, the temperature of the hot gases becoming too low to ensure
significant water splitting.
Several shapes (Fig. 4) of zirconia nozzles have been
tested. For a given cold gas flow rate, Fig. 9 shows that,
for a constant power of 700 W available at the focus,
the yield of hydrogen is higher with a po!ytubular nozzle
than with a simple cylindrical cavity. However, the best
results were obtained with an annular type reactor, net
production of hydrogen being still improved by the
presence of a concentric heat exchanger working as a
water preheater.
Figure 9 shows that in the present state of art, the
method described in this paper leads to a maximum
production of hydrogen of 4.7 x 10-Tm~s -1 STP
(1.7 STP l.h-1). This production corresponds to an
energetic yield of 0.84% (calculated on the basis of the
enthalpy of formation of liquid water and of the 700 W
thermal power available at the focus).
M A T H E M A T I C A L M O D E L L I N G OF T H E
SYSTEM
It is interesting to calculate the theoretical temperature of gases at the exit of the hot nozzle and molar
fraction of hydrogen after quenching, and to compare
the results with experience.
Taking into account the geometry of the nozzle and
the small dissociation extents, both models of Plug Flow
Reactor (PFR) and Continuous Stirred Tank Reactor

0.5 -~ ' QHz 110-sm3.sJ) STP

'T~)

Tw

2000.

,e

Qm (I0 -s Kg.s-~)

Fig. 9. Volumetric flow rate QH2 of hydrogen produced vs

water mass flow rate (quenching of the second kind with
OAr = 100 10-6m 3 s-ISTP): ((D) cylindrical cavity; (&)
polytubular cavity; (x) annular cavity; (D) annular cavity with
preheater.

1500

Qm(lO-SN.sJL
0

Fig. 10. Theoretical temperature of steam at the exit of a

cylindrical cavity vs mass flow rate of water a m (for a mean
wall temperature of 2560 K and inlet temperature of 600 K)
for a Plug Flow Reactor Model (PFR) and a Continuous Stirred
Tank Reactor model (CSTR).

PRODUCTION OF HYDROGEN BY DIRECT THERMAL DECOMPOSITION OF WATER

(CSTR) can be a priori used for representing the hot
dissociation nozzle.
Mass balances have been written for the P F R model
with the assumption of flat radial profiles of velocity,
concentration and temperature and for the CSTR model
in transient regime. The four differential equations
(corresponding to the four kinetic processes), depending on the rate extents and the concentration of the six
constituants have been solved with the help of a Runge
Kutta integration method.
The heat balance has been written in assuming a
Nusselt number depending on the abscissa, in nonestablished regime, given by Kays [20] for the PFR and
a Nusselt number proposed by David [21] for the CSTR.
Figure 10 shows that for small massic flow rates of
steam, both models give the same values of T. For
instance for Qm = 5.33 x 10 -6 Kg s -1, Twall = 2560 K and
To = 600 K, we obtain:
PFR: T = 2370 K
CSTR: T = 2350 K

Xm = 2.37%
XH2 = 2.65%.

Figure 1 and these values show that, in these conditions, the thermodynamic equilibrium is reached at
the exit of the cylindrical nozzle (theoretical XH2 =
2.5%).
For Q,~ > 7 10-rkg s -L, the temperature given by
the P F R model rapidly drops even for Q,, values with
which appreciable amounts of hydrogen are still experimentally measured. Two explanations can be given: the
first one is that the P F R model is not representative
and that the CSTR model should be preferred; the
second one is that a whole homogeneous kinetic model
for the dissociation is insufficient, and that at low temperature, a heterogeneous step for water dissociation
at the hot walls becomes predominant.
It can be interesting to compare the values of Xu~
measured outside the reactor with the values predicted
by a convenient theory. The study of a model representing the quenching zone must take into account
the fact that quenching is the result of two phenomena:
rapid cooling of the hot gas and dilution of reactive
species in the inert gas. Taking into account only the
thermal effect it is possible to show that for Qm =
5.33 10 -6 Kg s -1 the necessary cooling rate to bring
the gases from 2400 to 800 K with an 80% quenching
efficiency (percentage ratio of XH2 after and before the
quenching zone) is of the order of 106 K s -1. Assuming
now that quenching is the result of both cooling and
dilution, the calculations show that the rate of cooling
is reduced to 2 105 K s -~. This last value has been
confirmed by experimental studies of the efficiency of
mixing of two gases.

CONCLUSION
The present paper has shown the feasibility of direct
thermal water splitting with an energetic yield close to
1%. The main advantages of the described process are:
simplicity and cleanliness. The type of reactor described

679

can be used for other highly endothermic reactions such

as carbon dioxide thermolysis for example. The concentrated radiative energy used was delivered by an
image furnace showing that such an experimental device
could be used with solar furnaces.
In the present state of art, the method described
delivers a stoichiometric mixture of hydrogen and
oxygen. The separation of hydrogen could be carried
out by using porous ceramics, metallic membranes [22]
or hollow fibers made of polysulfone [23].
In the overall energy balance of the system, losses
due to reradiation of the hot target and forced convection inside and outside the quenching reactor, are very
important (of the order of 65% of available power).
Better recovery of these losses for efficient preheating
of steam could perceptibly improve the yield of the
process.
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