Int. 1. Hydrogen Energy, Vol. 6, No. 6, pp. 601~08, 1981. 0360-3199/81/060601--08 $02.

00/0
Printed in Great Britain. Pergamon Press Ltd.
International Association for Hydrogen Energy.

CATALYTIC COMBUSTION OF H Y D R O G E N I--ITS R O L E IN

H Y D R O G E N U T I L I Z A T I O N SYSTEM A N D SCREENING OF
CATALYST MATERIALS
M. HARUTA and H. SANO
Government Industrial Research Institute of Osaka, Midorigaoka 1, Ikeda, Osaka 563, Japan

( Receioed for publication 6 January 1981)

Abstract--The role which low-temperature catalytic combustion should play in the future hydrogen energy
system is discussed in comparison with those of conventional flame-type combustion and fuel cells. A hybrid
of catalytic and flame combustion is also referred to in the comparison. Screening of catalyst materials proved
that several inexpensive oxides of the 3d transition metals were active at intermediate temperatures around
150C. A volcano-like relation was observed between the catalytic activity and the heat of formation of metal
oxides per gram-atom of oxygen. Platinum-group metals supported on a carrier were active enough to initiate
hydrogen combustion even at temperatures below 0C. The effect of hydrogen concentration and space velocity
on combustion rate was also investigated.

INTRODUCTION
HYDROGEN has been proposed as one of the most desirable and clean forms of secondary energy
that can supplement and replace fossil fuels in commercial, residential, and industrial utilization.
However, our recent work has revealed that the conventional flame-type combustion of hydrogen
produces large amounts of nitrogen oxides in a diffusion flame, while it suffers from the danger
of backflash in a premixed flame where NOx emission level is very low [1]. Safe and clean
combustion of hydrogen requires the solution for the hydrogen flame of this dilemma between
NOx emission and flashback. In residential utilization of hydrogen, where high temperatures are
not usually necessary, low-temperature flameless combustion over the catalyst surface appears to
be the best solution, in consideration of the fact that hydrogen is much more readily oxidizable
than any other fuels. The catalytic combustion technique itself has already been utilized, since it
has been applied to space heaters with LPG in European countries [2]. Its application to hydrogen
fuel was first proposed by Sharer [3], but not much experimental and developmental work has
been published except for the fundamental work on platinum-plate catalysts [4,5], and the
developmental work on catalytic-combustion appliances by I G T in the U.S.A. [6, 7].
Since 1975, we have been carrying out research and development work in catalytic combustion
of hydrogen as one of the research programmes of a national project for hydrogen energy systems
in Japan. We have been working on the development of inexpensive oxide catalysts and the
fabrication of several prototype catalytic burners [8]. As the first publication of our still-continuing
work, the present paper deals with the comparative evaluation of catalytic combustion techniques
with flame combustion and fuel cells, and the results of screening of catalyst materials. Succeeding
papers will cover the developmental work on composite oxide catalysts and fundamental studies
for burner construction.

C H A L L E N G I N G ASPECTS O F C A T A L Y T I C COMBUSTORS IN H Y D R O G E N
U T I L I Z A T I O N SYSTEMS
Hydrogen can be converted to thermal energy by combustion or to electric energy by fuel cells
in industrial, commercial, and residential utilization. Conventional flame-type combustion has to
cover the industrial demands for high-temperature heat, despite the problems of high NOx emission
and the occurrence of flashback. In residential utilization, low-temperature catalytic combustion
is more favorable than flame combustion because safety from fire hazards and elimination of
pollutants are required. However, the heat output obtainable from low-temperature catalytic
combustion is limited to a certain range and is small in comparison with flame combustion, since
combustion takes place only on the surface of a catalyst.
601
602 M. HARUTA AND H. SANO
The hybrid of the above two types of combustion, so called catalytically supported thermal
combustion [9, 10, 11, 12], would be quite effective in providing a large heat output with a minimum
NOx emission. Fuel cells can be regarded as a kind of catalytic device for cold-type combustion
which mainly produces electrical energy, with accompanying heat generation. The comparison of
the characteristic features of the four types of hydrogen conversion is summarized in Table 1.

TABLE1. Comparisonof characteristicfeatures of hydrogenutilizationmethods

Temperature Output
Features (C) (kcalcm-2 h -1) Advantages*& Disadvantagest Appliedsectors

* large heat output

ca t high NOx emission
Flame combustion 2,100-1,200 1,000 t danger of backflash industrial
industrial
CatalyticCombustion * low NOxemission (commercial)
hybrid 1,200-500 1,000-10 t danger of fire (residential)
low-temp. 500-room temp. 3-0.3 t smallheat output residential
* no NO, emission commercial
* safety from fire (industrial)
Fuel cells 900-room temp. 1-0.03 t smalloutput small community
* electricitygeneration residential

The low-temperature catalytic combustion to which the present paper is devoted has the following
advantageous features over the conventional flame combustion [3, 13]:
(1) The desired temperature can be readily obtained from room temperature up to about 500C
by controlling the feed rate of hydrogen.
(2) There is no danger of starting a fire and no emission of nitrogen oxides.
(3) A lean hydrogen mixture outside the flammability limit is utilizable as a fuel.
(4) A large fraction of heat output is generated as radiant heat, which permits us to construct
effective and comfortable space heaters.
These advantages of catalytic combustion will develop its application to the following fields:
(1) Heaters--Safe, clean and temperature-controllable heaters will be available for heating
spaces, floors and walls. The energy demand in this field is expected to increase most
appreciably in Japan.
(2) Cooking devices--Temperatures suitable for cooking can be chosen with ease.
(3) Drying and heating processe .sv-Industrial application is also expected in paint drying and
heating plastic pipes as well as in the food industry and the pharmaceutical industry.
(4) Road-heating systems--Catalytic combustors buried under the ground are effective and
convenient to prevent freezing and wetting on the public roads and around the entrances
of buildings.
We planned to construct prototypes of space heaters and cooking devices until 1980. The likely
economic obstacles to the widespread application of catalytic combustors are the cost and the
availability of catalyst materials. Another problem may be the designing of the optimum burner
construction which facilitates high combustion-efficiency and uniform temperature-distribution
over the catalyst surface. From this point of view, a literature survey of work on the catalytic
oxidation of hydrogen was carried out and this has been summarized elsewhere [14]. Since most
of the previous work was of an academic nature and was mainly concerned with platinum-group
metals, it was felt necessary to start our study with catalyst screening experiments.

SCREENING OF CATALYST MATERIALS

Experimental
Catalyst screening was conducted by using a small fixed-bed reactor made of Pyrex glass. The
reactor shown in Fig. 1 had an inside diameter of 6 mm. A sample of desiccated catalyst (0.30 g
 CATALYTIC COMBUSTION OF HYDROGEN I 603

3 4 5 6

FIG. 1. Schematic diagram of catalyst-screening apparatus: 1--standard gas (H2, 1

vol. % + air); 2--vacuum pump; 3--flow controller; 4---gas reservoir; 5--silica get;
6--P2Os granules; 7--catalyst; 8---porous glass sheet; 9--heaters.

of 42-70 mesh granules) was loaded into the reactor. A standard gas of 1 vol. % hydrogen balanced
with air was passed through the catalyst bed at a flow rate of 100 ml min-L The rising-temperature
technique, described by Jennings et al. [15], was adapted for a simple and rapid measurement of
catalytic activity. The inlet gas was preheated by passing it through a long coiled tube covered
with an electrical heater. The heater operation was controlled by a thermal program controller
HPC 5000 (SINKU RIKO, JAPAN) so that the temperature of the catalyst bed increased at a
constant rate.
A thermowell with an outside diameter of 2.5mm was positioned within a region 3-5 mm below
the top of the catalyst bed. Temperature was measured for both the catalyst bed and the inlet gas
(A and B respectively in Fig. 1). No appreciable difference in temperature measured at A was
observed through the catalyst bed with a length ranging from 15 to 20 mm except for few cases
with highly active platinum metal catalysts. Since the catalyst bed was heated by the heat released
from the oxidation of hydrogen, the onset of catalytic combustion was readily detected by the
differential thermal analysis (DTA) between the catalyst bed and the inlet gas.
In addition to DTA, the change of hydrogen concentration in the effluent gas was monitored
by automatic gas chromatography. Fig. 2 shows typical examples of the relation between percentage

100 , . . ~__,~ . .~,.~r ~.~....~_~r~7._~./

o 7 / o,~" t
. I/ 2/ %,~5 j
f- / / //g/"
t . o] ~
? ~ ,,I/ /o /
I I ,~i_~ ,o'"
I I ,'/," o-'"
E 50 / / ~..o-
o / .s ......

i t/' 3- ~"f'
~__ t ~...o" . . / ~._.~
o { ~ - ~ ~ . . . . , . . . . ,
100 150 200 25(
CotQ[yst t e m p e r a t u r e , C
FIG. 2. Relation between percent combustion of hydrogen and temperature of catalyst
bed: 1--Hopcalite I (commercial); 2--Co304; 3--MnO2; 4--NiO; 5--CuO; 6--Hopcalite
II (commercial).
604 M. HARUTA AND H. SANO
combustion of hydrogen and temperature of the catalyst bed. The temperature for 50% combustion
of hydrogen (T1;2) was used as a parameter for catalytic activity. Thus, the material with a lower
value of 50% combustion temperature has a higher catalytic activity.
Fig. 3 shows the dependence of the obtained value of Tt/2 on the programmed heating rate of
the catalyst bed. The value of T~/2 at a rate of 2C min-! is only slightly higher than the value
obtained under the steady-state conditions, namely at a constant temperature, for most of the

i i i

900/~~ 200 , , ,

150 ~~---5 0 ~ "

E 200

o~ NnO2 Co304

! i 1001() I
1
I
2

Heating rate, *C/min.

FIG. 3. Dependence of 50% and 90% combustion temperatures on heating rate.

materials except for manganese dioxide. In the case of manganese dioxide, which exhibited
appreciable dependence of T1/2 on heating rate, percentage combustion increased only gradually
with increasing temperature, as shown in Fig. 2. Since most of the materials screened had as steep
an increase of percentage combustion with temperature as cobalt oxide had, the value of Tta thus
obtained could be used as an effective and reliable parameter for catalytic activity.

Results of Catalyst Screening

Several types of material were screened for the search of inexpensive catalysts. Part of the results
are well summarized in Fig. 4. Catalytic activities of metal oxides expressed in terms of T~/2 have

I !

PdO

~02~o Ru02
lO0
o/
CAu
NiO o %
200 0 o~os
CuO
Fe=Os o ~ Cr=Os
\ 0
I , , , , I , .v=o. ~,\ ,
300
0 50 1O0
Heat of formation, kcal/g.atom oxygen
FIG. 4. Dependence of hydrogen oxidation activities of metal oxides on their heat of
formation per gram-atom of oxygen.
 CATALYTIC COMBUSTION OF HYDROGEN I 605

a volcano-like relationship with the heats of formation of oxides per gram-atom of oxygen.
Boreskov has already reported the right-side linear portion of this relation for the 3d transition
metal oxides [16]. Similar volcano-like relations were also reported in other reactions such as the
perfect oxidation of ethylene [17] and the partial oxidation of propylene [18].
The volcano-like relation with palladium oxide at the top of the graph in Fig. 4 can be interpreted
by considering that the catalytic activity of metal oxides for hydrogen combustion is associated
with the magnitude of metal-oxygen (M-O) bond energy. Activity increases with decreasing bond
energy on the right arm of the volcano-shaped curve, whereas the opposite is the case for the left
arm. For oxides located on the right arm, the breaking of the M - O bond is the slowest step and
thus the catalytic activity decreases with increasing bond energy. On the other hand, the formation
of the M - O bond is slower than the bond breaking for oxides on the left arm, and therefore the
activity increases with increasing bond energy.
It should be noted that oxides of inexpensive transition metals such as Co, Ni, Mn, and Cu were
active at intermediate temperatures although they required a little preheating for the initiation of
hydrogen combustion.
Pd and Pt metals supported on a carrier could initiate hydrogen combustion even at a temperature
below 0C. Fig. 5 shows a combustion efficiency curve together with a corresponding DTA curve

100 I I I
o .
I
o - - o - - .
I
- o . . o ~

f
/
E
0
/
-Q g o
E
0
U o
/
o
/
E

~ 0

DTA
I [ 51 i I
-50 0 0 100 150
Temperature, C

FIG. 5. DTA and percentage combustion curves for Pd supported on silica gel (0.1 wt%).

for Pd supported on silica gel with a metal loading of 0.1 wt%. In the DTA curve, the steep
exothermic increase ends at around 0C and turns rapidly toward the endothermic direction. This
is because the frozen water produced by the combustion of hydrogen at lower temperatures begins
to melt and vaporize from the catalyst, absorbing heat.
Some commercially available tungsten carbides which were recently reported as good oxidation
catalysts [19, 20] did not show any activity up to 250C. Neither bronzes nor oxides of tungsten
were active in the temperature range investigated. As other current likely candidates for combustion
catalysts, Hopcalite catalysts used for carbon monoxide oxidation were also examined. Hopcalite
I (MnO2, 50%: CuO, 30%: Co203, 15%: Ag2O, 5% by wt) had TI/2 = 108C, Hopcalite II (MnO2,
60%: CuO, 40% by wt) had Tla = 181C. The former one containing silver oxide was rather active
but its activity did not exceed that of simple silver oxide.
606 M. HARUTA AND H. SANO
Activities of metal oxides generally depended on the preparative methods and conditions, for
instance, oxide precursors, calcination temperature and atmosphere. The results shown in Fig. 4
were obtained for oxides prepared from carbonates or hydrates precipitated from the corresponding
aqueous solutions of nitrates. The calcination temperature of oxide precursors was varied from
120C to 500C depending on the types of oxides. Detailed information on the effect of preparative
methods and conditions will be reported in subsequent papers.

Effect of Hydrogen Concentration and Space Velocity

When hydrogen concentration was high, the temperature of the platinum metal catalyst instan-
taneously rose after a certain temperature, as shown in Fig. 6. This temperature could be easily

Equi va[ent air ratio

50 10 5 2 1

t.
i

CRITICAL TEMP. i/
j so
uo 60

D 40
~5 ~-50 _ __DTA . . . .

Q_ TIME
E
20
i--

I I t I I I

0 10 20 30
Concentration of H2, vot/o

FIG. 6. Dependence of auto-initiation temperature on hydrogen concentration over Pd

supported on asbestos (10 wt%): x---critical auto-initiation temperature; 0----90%
combustion temperature; 0---50% combustion temperature.

determined by observing the instantaneous jump of the D T A curve. This critical temperature for
commercially available Pd/asbestos (10 wt.%) is plotted against hydrogen concentration in the
lower part of Fig. 6. At an equivalent air ratio (3,) of 1, the temperature for auto-initiation was
around 0C and it rose gradually with decreasing hydrogen concentration. At 3, = 10, the auto-
initiation temperature became higher than room temperature. At 3, = 50, no rapid rise in catalyst
temperature was observed and therefore 50% and 90% combustion temperatures were measured.
On the other hand, a different features was observed for cobalt oxide. Fig. 7 shows a slight rise
in auto-initiation temperature with decreasing hydrogen concentration below 15 vol. %. The
temperatures for 50% and 90% combustion were parabolic functions of hydrogen concentration.
It appeared interesting that the most suitable concentration of hydrogen for oxide catalysts was
about 18 vol. %, which corresponded to an equivalent air ratio of 2.0. This value of air ratio was
far leaner than the optimum air ratio in flame combustion, usually around 1.0-1.2.
The effect of space velocity on temperature for 50% and 90% combustion is shown in Fig. 8.
Temperature for 90% combustion rose appreciably, by about 50C with increased space velocity
from 104 to 105 hr-~; while temperature for 50% combustion rose only by 15C. Consequently,
complete combustion of hydrogen would require either a much smaller space velocity or a higher
catalyst temperature.
 CATALYTIC COMBUSTION OF HYDROGEN I 607
Equivatent air r a t i o
20050 10 5 2 1 0.6
I I

E
I---
o_ 100! i I

10
Concentration
i I

20
,

of H2, vot/o
30
I ,

FIG. 7. Dependence of 50% and 90% combustion temperatures on hydrogen concentration

over Co304: x----critical auto-initiation temperature, 0--90% combustion temperature;
(5)---50% combustion temperature.

90 %

O
200
Ct_

E ~ 50O/o~ - - - ----''~
/

150 ' i .... ; .... 1; . . . . 1;' '

Space veracity, xl04 hr -1
FIG. 8. Dependence of 50% and 90% combustion temperatures on space velocity over
Co304 .

CONCLUSION
Low-temperature catalytic combustion is potentially advantageous over the conventional
flame-type combustion in residential utilization of hydrogen because of its safety from fire hazards
and the elimination of pollutants. Several inexpensive oxides of transition metals such as Co, Ni,
Mn, and Cu were proved to be active at around 150C and might possibly replace platinum-group
metals as practical catalysts if developmental work is done on the composite oxides of these metals.
Such work is in progress in the authors' laboratory.

Acknowledgement--Grateful acknowledgement is made to Mr Y. Bando for experimental assistance.

608 M. HARUTA AND H. SANO

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