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Chemical Engineering Science, 1966, Vol. 21, pp. 19-27. Pergamon Press Ltd., Oxford. Printed in Great Britain.

Catalytic oxidation of ammonia on platinum

E. J. NOWAK
Esso Research and Engineering Co., Process Research Division, Linden, New Jersey

(Received 19 April 1965)

Abstract-An historical background from the literature is presented and leads to a discussion of the
kinetics and mechanism of catalytic ammonia oxidation on platinum screens and gauzes. Some new
data for heat and mass transport to screens are presented and compared with a correlation for a
single infinite circular cylinder. It is shown that transport rates predicted from the correlation for
a cylinder are conservatively low, a finding which tends to confirm the adequacy of mass transport
for a solely heterogeneous mechanism. Effects of catalyst shape and roughness are also discussed, and
analysis of previous data supports an hypothesis that catalyst losses during the commercial oxidation
are due to oxidative volatilization of the platinum.

INTRODUCTION and passed normal to a bed of Pt or Pt-Rh alloy


metal gauze. Gas velocities are - 1 ft/sec, resulting
BEFORE the introduction of synthetic ammonia,
in contact times of 10m3 set or less, and gauze
nitric acid was produced commercially according
temperatures in the range 750” to 950°C. Under
to the equation:
these conditions, the oxidation to NO is nearly
NaNO, + H,SO, + HNO, + NaHS04 (1) complete. Completion of the reaction with such
short contact times requires very rapid mass trans-
The advent of synthetic ammonia made possible port of reactants to the surface if the reaction is
a commercial nitric acid process starting with solely heterogeneous, and mass transport may be
ammonia. Ammonia is oxidized with excess air or rate-limiting. Should the rate of mass transport be
oxygen over a catalyst to form nitric oxide and insufficient, then heterogeneous initiation of a
water homogeneous chain reaction is indicated. The
4NH, + 502 + 4N0 + 6H,O (2) applicability of transport estimates made from
correlations for cylinders will be discussed in the
and the nitric oxide is further oxidized to nitrogen
light of some new data for screens and grids, and
dioxide by the excess oxygen.
some effects of catalyst shape and surface roughness
2N0 + O2 = 2N02 (3) will also be presented.
The development of surface roughness and con-
The nitrogen dioxide is then absorbed by water in comitant catalyst erosion are important factors in
scrubbing towers, forming nitric acid and also the process. Fresh, smooth catalyst gauzes are only
some nitric oxide which must be oxidized by more weakly active, but soon the rate of reaction increases
excess air. to a high steady-state value as the surface roughness
develops. Activation, however, proceeds at the
3N02 + Hz0 Z$ 2HN0, + NO (4)
expense of mechanical strength, the smallest
A short historical background from the literature diameter of continuous wire metal being diminished.
will be given, with special emphasis on the platinum- Also, steady losses of costly catalyst material ac-
catalyzed oxidation reaction. company further reaction. Such losses can be of the
In the commonly used commercial catalytic order of 1 oz per 100,OOlb of ammonia oxidized.
oxidation stage, a mixture of N 10 % ammonia in Some studies of catalyst erosion will be discussed,
air at atmospheric or higher pressure is preheated and considerations based on literature data will be

19
E. J. NOWAK

presented to show that volatilization of the metal proposed hydroxylamine as the initial reaction
as oxide may adequately explain observed rates of product.
catalyst loss.
NH, + 0 + NH,OH (or NH,O) (7)
Later, BODENSTEINsummarized his work with
HISTORICAL
others [14] and concluded that hydroxylamine is
Nitric acid manufacture by catalytic oxidation the most likely first intermediate. Since then
of ammonia is a very old process. CHILTON [l] KRAUSS [15] has contributed further product
attributes the first technical description of the studies at low pressure which support BODENSTEIN’S
process to KUHLMAN[2] in 1839. He also notes conclusions.
PARTINGTONand PARKER[3] who ascribe the first Recent mechanistic studies have been reported
technical description to the Reverend I. Milner of in a fascinating paper by FOGEL,NADYKTO,RYBAL-
Cambridge (England) in 1788. The modern am- KO, SCHVACHKO and KOROBCHANSKAYA [16]. They
monia oxidation processes may be said to originate have coupled a special mass spectrometer with a low
from the work of OSTWALD[4] beginning in 1903. pressure catalytic reactor. Species on the catalytic
Special mention should also be given to PARSONS[5] platinum surface are ionized and ejected as second-
who, in 1919, contributed extensive technological ary ions by Ar+ ion bombardment. Simultaneously,
background. His work contains an historical gaseous species near the surface are ionized by a
resume, operating data, extensive descriptions of beam of electrons. The intensities of spectral lines
equipment, and a section on economics. The for ions originating on the surface and in the gas
works of CHILTON [l] and of DIXON and LONG- phase are compared as functions of temperature.
FIELD[6] both contain material similar to that given While intermediates (NH) are detected on the sur-
by Parsons. Also, both Chilton and, in a much face during ammonia decomposition [17], none are
earlier work, KRASE[7] treat extensively the engi- detected when oxygen is introduced and ammonia
neering aspects of the subsequent oxidation of NO oxidation proceeds. FOGEL,et al. conclude that the
to NO, and the absorption process to nitric acid. reaction with oxygen is direct (no intermediate
The catalytic oxidation reaction itself has been involved) on the surface and proceeds according to
the subject of extensive mechanistic research. one or both of the following equations
ANDRUSSOW [8] and BODENSTEIN [9], working in the NH, + 0, + NO + H,O + H (8)
same laboratory, proposed the nitroxyl (HNO)
scheme. In this scheme, the initial reaction between NH,+O+NO+H,+H (9)
ammonia and oxygen is written both 0, and 0 having been observed on the surface.
However, it seems rather premature to conclude
NH, + O2 fI: HNO + Hz0 (5) from the absence of detectable intermediates that no
intermediates are involved in the reaction mech-
RASCHIG[lo], in disagreement with Andrussow and
anism. In such a rapid reaction, active intermedi-
Bodenstein, set forth his own imide (NH) scheme:
ates are apt to be extremely short-lived and present
in virtually undetectable concentration. Some
NH, + 0 fI: NH + H,O (6) evidence was also found to support a Langmuir-
A published discussion [l l] of the two schemes Hinshelwood mechanism at subatmospheric pres-
ensued. Later, BODENSTEIN and BUTTNER[12, 131 sures.
studying the oxidation on platinum wire at low The striking speed of the reaction (completion
pressures, froze out reaction intermediates on the in 10e3 set or less) suggests that it may be mass
cooled walls of the reaction vessel. Their results transport-limited. ANDRUSSOW[181 derived equa-
indicated that nitrous acid (HN02)’ and hydrox- tions for the ammonia concentration gradient along
ylamine (NH,0 or NH,OH) are the principal initial a platinum capillary tube assuming oxidation reac-
products of the reaction on platinum. By slight tion only on the catalytic surface, and he compared
modification of his nitroxyl scheme, BODENSTEIN the theory with experiment. He concluded that the

20
Catalytic oxidation of ammonia on platinum

reaction is transport-limited, the concentrations of mechanism. If the maximum possible rate of am-
reactants at the surface being low compared with monia transport to the catalyst is lower than the
those in the bulk. The capillary tube, however, is observed reaction rate, a heterogeneous-homo-
not geometrically equivalent to the gauze catalyst geneous mechanism is required. On the other hand,
of commercial operation. APEL’BAUMand TEMKIN if mass transport is sufficient, a homogeneous
[19] showed that measured rates of ammonia component is not necessary to explain the reaction.
oxidation on platinum and platinum-alloy gauzes In the particular case of equal mass transport and
are essentially equal to mass transport rates calcu- observed reaction rates, a heterogeneous reaction
lated from a heat transport correlation for single rate-limited by mass transport is indicated. Such
cylinders. This work, indicating that mass trans- a case is exemplified in the work of APEL’BAUM
port is just sufficient to sustain the total reaction at and TEMKIN[19], whose calculated mass transport
the surface, will be discussed in more detail later. rates are in close agreement with their experimental
Engineering calculations for ammonia burner reaction rate data.
design based on mass transport as the rate-deter- Prediction of mass transport rates is also essential
mining factor have been demonstrated by OELE[20]. to ammonia burner design calculations in which it is
Another explanation for such rapid reaction in assumed that mass transport is rate-controlling. Such
the face of possible transport-limitation is that the calculations have been demonstrated by OELE [20].
reaction proceeds via a chain mechanism initiated Transport correlations commonly used to predict
at the catalytic surface. VLADOV[21] has published mass transport rates in ammonia oxidation may be
extensive experimental results and arguments seriously inadequate for that purpose. For example,
supporting a heterogeneous-homogeneous mechan- the transport correlations used by APEL’BAUMand
ism. VAINSHTEINand POLYAKOV [22,23] also TEMKINand by OELEare for a smooth cylinder with
conclude that the reaction is heterogeneous- flow normal to its axis. In applying this correlation
homogeneous. On the other hand, EPSHTEIN[24] to ammonia oxidation, the hydrodynamic flow about
and ATROSCHENKO [25] argue for a solely hetero- each wire of the gauze is presumed unperturbed by
geneous mechanism. adjacent wires, by surface roughness, and by fluxes
The number of materials which catalyze the of matter and heat to and from the surface. How-
ammonia oxidation reaction is impressive. SCOTT ever, the actual situation during commercial am-
[26] has compiled a list of 52 substances, elements, monia oxidation may be quite different, the catalyst
or compounds in the order of their catalytic consisting of a series of closely spaced fine-mesh
efficiency for the reaction, according to his experi- screens (or gauzes) with highly roughened surfaces.
mental observations. He found platinum to be the Mass and heat fluxes must also be very high,
most efficient, and it is still favored today. In order adding another perturbation to the system.
to maximize conversion efficiency and minimize loss Some recent transport data for screens will be
of catalyst in the product stream, moderate presented and compared with the correlation for a
amounts of other metals are alloyed with the plat- single cylinder. Then effects of catalyst shape and
inum. HANDFORTHand TILLEY [27] conducted roughness will be discussed. A discussion of the
careful tests with platinum alloy screens to show the perturbation due to very high transport rates must
effects of alloying on both conversion efficiency and await further developments in the field.
loss of platinum under typical commercial condi-
tions. Their work as well as the work of others will Recent transport data for screens
be presented later in a discussion of possible causes Since the work of APEL’BAUMand TEMKIN[19],
for platinum loss. correlations of heat and mass transport data for
screens and grids have appeared in the literature.
LONDON,MITCHELL,and SUTHERLAND [28] report
PREDICTIONOF MASS TRANSPORTRATES heat transfer data in the form of the usual Colburn
Mass transport considerations are vital to the j-factor, j,, plotted as a function of a modified
understanding of the catalytic ammonia oxidation Reynolds number, NX,. Curves generated from

21
E. J. NOWAK

j++neml mnge of connwcial opemtion -4


Lominar flow Tmnshon frcm larntn~~ to fully developed wake flow Fully de&aped wake,laminor boundwy layer up
(infInite cylinder1 (Infinite cylinder) of separation
+- + (Infinik cylinder)

FIG. 1

their data appear in Fig. 1. Each curve of the family With these new data for screens, it is now pos-
is for a matrix of 20 or more screens or grids having sible to assess the applicability of transport corre-
the labeled porosity, p. For matrices of fewer than lations for single cylinders to the screen geometry.
20 grids or screens, the heat transfer coefficient is The Nusselt number correlation [30] used by
reduced by an empirical factor to be determined APEL’BAUMand TEMKINhas been converted to a
from Fig. 2. Extrapolating their data to a single j-factor correlation for air by assuming a constant
screen (dotted line in Fig. 2) shows the factor to be Prandtl number of 0.71 and using the following
never much smaller than 05 relationship :
Mass transport data for single screens have been
reported by GAY and MAUGHAN[29]. They meas-
ured rates of mercury vapor transfer from a mercury-
coated copper screen to a gas flowing normal to the
screen, but the measured rates were very low and
therefore do not strictly apply to the rapid ammonia
oxidation reaction. The j-factor correlations of
GAY and MAUGHANare plotted in Fig. 1 along with
the heat transfer correlations of LONDON,et al. for
comparison. The two sets of correlations are
relatively close in the range of Reynolds numbers
l-100, but they diverge at higher Reynolds numbers.
GAY and MAUGHANbelieve that heat transfer stud-
ies are influenced by longitudinal conduction of
heat, causing discrepancies relative to their own
mass transfer data.

22
Catalytic oxidation of ammonia on platinum

The usual Reynolds number, NRe, for cylinders was commercial ammonia oxidation processes lie in the
used in place of the modified Reynolds number used transition range, as indicated in Fig. 1.
for screens. The resulting calculated j-factors are With the breakup of laminar flow, regions of
plotted in Fig. 1 for comparison with the other boundary-layer separation and reverse flow develop
transfer correlations. Comparison shows that, in on the cylinder, as shown in Fig. 3. There is also a
the Reynolds number range of interest for ammonia point of stagnation on the front portion of the cyl-
oxidation, mass transfer coefficients predicted for inder normal to the direction of flow and a build-up
screens are larger than those predicted for corre- of the laminar boundary layer downstream from
sponding cylinders from the heat transfer corre- that point. At some point downstream, the bound-
lation. Therefore the calculations by APEL’BAUM ary-layer separates from the surface. Here the re-
and TEMKINappear to be conservative. That is, the gion of reverse-flow begins. The higher the Rey-
sufficiency of mass transport to support strictly nolds number, the smaller the angle 8 determined
heterogeneous ammonia oxidation seems confirmed. by the separation point, the center of the cylinder
However, effects of surface roughness and flow cross section, and the stagnation point. At fully-
perturbations due to high transport rates must be developed wake flow 8 = 95”. Finally, there is a
evaluated before a firm conclusion can be drawn. relatively turbulent region on the down-stream side
Roughness effects might be determined experimen- of the cylinder directly opposite from the forward
tally by measuring heat transport to activated plat- stagnation point.
inum screens under flow conditions (e.g. experi- The non-uniformity of flow leads to unequal
ments similar to those of LONDON,MITCHELLand transport rates around the surface of the cylinder.
SUTHERLAND).Some effects of roughness and cata- For example, ECKERTand SOEHNGEN [31] measured
lyst shape on transport properties will be discussed the local Nusselt numbers for heat transport to
in the following section. Treatment of very high air flowing past a heated cylinder at Reynolds num-
transport rates must await further developments bers in the transition region. Fig. 4 is a plot of their
in the field. data showing local Nusselt number versus 8 for
three Reynolds numbers. It is apparent from the
Efsects of cataIyst shape Figure that the rate of heat transport is highest near
The shape of a catalyst influences the hydro- the stagnation point where the boundary layer
dynamic flow surrounding it; and the flow, in turn, is thin, and is lowest just downstream from the
influences rates of heat, mass and momentum point of separation where reverse-flow begins. In
transport to the surface. For this discussion, hydro- order to maximize heat transport and, by analogy,
dynamic flow normal to an infinite cylinder will
be taken as representative of the flow past a single
wire of a high porosity screen. The actual flow is,
of course, perturbed by the presence of adjacent
wires, and the magnitude of the perturbation
increases with decreasing porosity. However, the
infinite cylinder is a useful model for visualizing
the effects to be discussed. The flow is laminar at low
Reynolds numbers, but at higher Reynolds num-
bers a slow transition occurs, during which a
turbulent wake develops downstream from the
cylinder. This transition begins at NRe = -0.5
for a circular cylinder, and the wake flow is fully
developed at NRe = N 100. Although the wake is
turbulent, the boundary-layer on the forward
portion of the cylinder remains laminar until
NRe > 5 x 106. Reynolds numbers for most FIG. 3

23
E.J.NowAK

FIG.5

0 20 40 60 60 100 120
Angle from forward stagnation

FIG.4
140 160
point,
160 200
8
Direction
of

0
FIG.6

mass transport, it would appear advantageous to


delay boundary-layer build-up and separation. 2.6
That is, the angle 13should be maximized. 13depends
24
on the shape of the immersed body and on the Rey-
nolds number. For example, boundary-layer
separation on a circular cylinder does not occur
(0 = 180’) when the Reynolds number is less than
-0.5. But with a 3 :l axis-ratio elliptical cylinder
(long axis parallel with flow), the Reynolds number
can be increased to -5 before separation occurs.
Also, in fully-developed wake flow the separation
occurs at 8 = - 120’ for the elliptical cylinder
rather than at 8 = -95” as for the circular cross-
section. Typical flow about an immersed elliptical
06
cylinder is shown in Fig. 5. A streamlined cylinder
cross-section, sketched in Fig. 6, should also have 0.4 -

advantageous flow characteristics. The effect of 0.2

cylinder shape on heat transport is shown in Fig. 7


0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 O-6 0.9 1.0 I.,
using data from the work of DRAKE, SEBAN, x/d ratio
DOUGHTY, and LEVY[32] for a 3 : 1 elliptical cylinder
FIG.7
at high Reynolds number (> 100,000). Even at such
high Reynolds numbers, separation occurs well
near the trailing edge as indicated by the minimum turbulence-promoting wires has been shown in the
in the curve. works of SCHMIDT and WENNER [33], and of DUKE,
SEBAN, DOUGHTY, and LEW [32]. The surface
Eflects of catalyst roughness roughness must, however, exceed a certain height of
Surface roughness of the kind found on activated projection. If the roughness projections are below
ammonia oxidation catalyst screens may influence an admissible height, the body can be considered
transport rates. Enhancement of heat transport by hydraulically smooth. SCHLICHTING [34] has

24
Catalytic oxidation of ammonia on platinum

recommended the following relation to estimate the that the rearrangement of platinum surface atoms
admissible height on immersed bodies : during ammonia oxidation on platinum is due
either to local surface heating nearly to the melting
k ad,,, 5 L&y (11) point or to the catalytic effect of an unknown
lVRe
reaction intermediate.
where kadm is the admissible height, and L is the The activated catalyst loses weight steadily during
length of the immersed body in the direction of flow. ammonia oxidation under the usual commercial
For 0.003 in. diameter wire at the highest Reynolds conditions. Rates of catalyst loss were measured
numbers of commercial importance (iVRe= lo’), by HANDFORTHand TILLEY[27], using a single 80
kadmis of the order of L. PARSONS[5] has published mesh screen of 0.003 in. dia. platinum wire
photographs of unused and activated platinum with a rectangular exposed area measuring 4 in.
wire catalyst screens which show smooth and rough- x 5.5 in. A feed of -9-12 volume per cent
ened surfaces. Comparison of the photographs ammonia in air was passed over the gauze at rates of
reveals that the “whiskers” formed during activation 40-250 lb of ammonia per troy ounce of catalyst
cause the wire to appear about twice its original per day. The resulting catalyst losses, measured by
diameter. Therefore the average height of the weight difference, were reported as troy ounces of
whiskers must be of the order of the original wire catalyst lost per 100,000 pounds of ammonia fed.
diameter, L. Catalyst surface roughness, then, may HANDFORTHand TILLEY observed that the total
have a measurable effect on transport rates during catalyst loss at a given temperature and with a given
ammonia oxidation. alloy was proportional to the total weight of oxygen
in the gas mixture that had passed over the catalyst.
SURFACEALTERATIONAND EROSION Some of their data for pure platinum and for a plat-
OF PLATINUM-BASE
CATALYSTS inum-rhodium alloy at various temperatures are
Platinum-base ammonia oxidation catalysts presented as an Arrhenius plot in Fig. 8. Since
undergo surface alteration and erosion during use. feed rates varied over a wide range and may affect
The smooth, unused catalyst is only weakly active, loss rates, only those data in the range 93 to 125 lb
but soon after reaction commences, whiskers of NH3 fed/troy ounce catalyst/day were chosen
platinum begin to grow on the surface, the surface for plotting. The resulting straight lines (dashed
becomes very rough, and the catalyst reaches peak lines in Fig. 8) correspond to an activation energy
activity. This initial erosion-activation process of -40 kcal/g mole, if the single point for 100 % Pt
causes the apparent catalyst thickness to increase at 810” is disregarded.
by a factor of two or more. However, the thickness The kinetics of oxidative volatilization of plati-
of the structurally sound catalyst material under- num as determined by FRYBURGand PETRUS [36]
neath the whiskers decreases. Therefore catalyst corresponds well with the plotted platinum loss
structures must be designed thick enough to main- rate data. The solid straight line in Fig. 8 was com-
tain sufficient physical strength after activation. puted using the following rate equation from
PARSONS [5] has described the activation pro- FRYJWRGand PETRUS,which correlates measured
cedure and published pictures of activated catalysts. rates of evaporation of PtO, from electrically heated
Platinum catalysts can be activated by heating for platinum ribbons in oxygen and in air:
a few hours at -800°C in an ammonia-air mixture
R = 1.09 x 10’“(To,)-*(Po,) Peexp (-42,50O/RT)
rich in ammonia. GARTON and TURKE~ICH [35]
(12)
studied the erosion-activation process under various
conditions. They found that heating platinum To, and PO, are the absolute temperature and partial
ribbons to 1000°C in mcuo (lo-’ Torr) or in oxygen pressure of oxygen gas over the platinum. To, is
for 12-24 hr would not produce changes in struc- taken here to be equal to T, the temperature of the
ture equivalent to those found during ammonia platinum. The factor Pe is the escape probability
oxidation. Pure ammonia, nitric oxide, and nitro- of evaporated PtOz molecules. Its value depends
gen peroxide were also ineffective. They conclude on the geometry of the platinum specimen and on

25
E. J. NOWAK

erosion is the responsible mechanism. Any such


postulated mechanism, however, must be verified
experimentally before it can be accepted as fact.

Acknowledgement-The author wishes to thank Professor


MICHELBOUDARTwho suggested the topic for this paper and
whose encouragement and constructive criticism are appreci-
ated.

NOTATION

A Heat transfer area of matrix *


Matrix average flow area, pAfront. *
A,
A iront81 Matrix frontal area *
Ao Constant of proportionality g”K*/cm2 hr Ton:
G Average mass velocity in matrix,
based on Af *
h Heat transfer coefficient for thermal
convection *
h ew Average heat transfer coefficient for
one or more consecutive screens *
! , j I I I
’ ’ 9,2
ha Average heat transfer coefficient for
so 8.2 8.4 8.6 m 90
an infinite number of consecutive
Reciprocal temperature, OK-x IO4
screens *
i0 Colburn j-factor for convective mass
FIG. 8 transport dimensionless
itf Colburn j-factor for convective
the rate of transport of PtO, molecules in the sur- heat transfer dimensionless
rounding gas. Pe decreases with increasing ambient k adm Admissible height of roughness
for hydraulic smoothness cm
pressure to a lower limiting value of 2 x 10e3 for a 1 Length of screen matrix in direction
stagnant gas at atmospheric pressure. This limiting of flow *
value was used in equation (12). L Length of roughened immersed object
in direction of flow cm
Although this favorable kinetic comparison Viscosity *
CL
suggests the hypothesis that volatilization of plat- NNU Nusselt number dimensionless
inum by oxidation contributes significantly to NP~ Prandtl number dimensionless
NRL? Reynolds number, 2rG/p dimensionless
catalyst losses during ammonia oxidation, addition-
N(RC Modified Reynolds number, 4rHG/p
al data are necessary to reach a firm conclusion. dimensionless
New catalyst loss data at constant gas flow rate P Porosity of a matrix, VW/V, + Vu
dimensionless
over a wider range of temperature can serve to es- Partial pressure of oxygen Torr
PO2
tablish an activation energy. However, the actual Pe Escape probability of PtO2 from
effective surface area of the roughened gauze is the surface dimensionless
r Radius of a wire in a screen *
ill-defined. Therefore a more nearly complete Hydraulic radius for a screen, I Af/A *
rff
verification of the hypothesis involves measuring ox- Ideal gas law constant cal/“K g-mole
idation rates of a heated platinum catalyst that has ii Rate of formation and
evaporation of PtO2 g/cm2 set
been previously activated (roughened) by ammonia T Absolute temperature of catalyst “K
oxidation. In such an experiment, gas flow velocities To2 Absolute temperature of oxygen
and oxygen concentrations comparable to those of over catalyst “K
fl The angle determined by the point of
commercial ammonia oxidation would be used. separation, the center of a cylin-
A catalyst loss mechanism involving erosion of drical cross section, and the stagna-
the platinum by a species other than oxygen alone tion point degrees
VM Volume of a matrix occupied by
is also possible. One may postulate volatilization wires or rods *
of the platinum by a reaction intermediate, such as VV Void volume of a matrix *
PtONH,. Or perhaps rearrangement of the surface *Consistent with units of other quantities in dimensionless
by such an intermediate followed by mechanical group.

26
Catalytic oxidation of ammonia on platinum

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[32] DRAKE, Jr. R. M., SEBANR. A., DOUGHTYD. L. and LEVYS., Trans. Am. Sot. Mech. Engng. 1953 75 1291.
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[361 FRYBURGG. C. and PETRUSH. M., J. electrochem. Sot. 1961 108 496.
R&atm&--L’auteur de cet article, apr&s un retour historique sur les donnees fournies par la litterature,
traite de la Cinetique et du mecanisme d’oxydation catalytique de l’ammoniac sur des tamis et toiles de
platine.
De nouvelles don&es sent exposees sur le transport de chaleur et de masse lors de reactions se
faisant sur supports metalliques; l’auteur les compare et etablit un rapport avec celles relatives a un
simple cylindre circulaire, inf?ni; il nous montre que les vitesses de transport, prevues par la compa-
raison theorique Ctablie entre ces supports metalliques et un cylindre sont relativement faibles: resultat
qui tend a prouver l’existence reelle dun transport de masse pour un mecanisme de reaction a catalyse
exclusivement heterogene.
Les effets catalytiques dus a la forme et la rugosite de la surface sont Bgalement trait& par l’auteur
qui apres analyse des don&es anterieures, avance l’hypothese suivante:
La diminution de l’effect catalytique lors de l’oxydation industrielle est due a la volatilisation du
platine par voie oxydante.
Zusammenfassung-Die historische Entwicklung der Salpeterslure-Herstellung sowie die Kinetik und
der Mechanismus der NHa-Oxidation an Platinnetzen werden diskutiert. Einige neue MeBergebnisse
tiber den W&me- und Stofftransport an ein Netz werden mit einer Korrelation verglichen, die in
einem einzelnen unbegrenzten Zylinder gilt. Die mit Hilfe der Korrelation berechneten Transport-
geschwindigkeiten sind niedrig und bestltigen, da8 der Stofftransport nach einem rein heterogenen
Mechanismus ablluft. Der EinfluR von Katalysator-Gestalt und -Rauigkeit wird ebenfalls unter-
sucht. Die Auswertung frtiherer Messungen stiitzt eine Hypothese, wonach die Katalysator-Verluste
in technischen Anlagen auf einer oxidierenden Verdampfung des Platins beruhen.

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