Академический Документы
Профессиональный Документы
Культура Документы
405
Ammonia synthesis:
the bellwether reaction in heterogeneous catalysis
M. Boudart
Department of Chemical Engineering, Stanford University, Stanford,
CA 94305-5025, USA
1. Introduction
where y / x is close to 1.5. In 1940, Temkin and Pyzhev derived an equation consistent with both of these observations. It has formed the basis for most of the kinetic
J.C. Baltzer AG, Science Publishers
406
407
Orderwithrespect
toNI-I3
Metal
RDS
Ref.
H
M
L
LL
L
M
H
HH
fractional
zero
fractional
one
Fe
Ru
Mo
Pt
desorptionofN2
same
none
adsorptionofNH3
[2]
[I0]
[II]
[I2]
M. Boudart/ Thebellwetherreaction
408
kdO2(K [N2][H213
[NH312
l)
409
ered as the best example of Taylor's activated adsorption. Early work reviewed in
this volume [15] deals with single crystal surfaces of iron at very low pressures of
N2. The work did not reveal the expected activation barrier for chemisorption of
N2, as only surface temperature was varied. But more recent work with seeded
molecular beams of N2 shows that the sticking coefficient of N2 on iron increases
with increasing kinetic energy of the incident molecules [16]. This is due to "hot"
molecules of N2 surmounting an activation barrier for adsorption. Taylor's concept of activated adsorption first introduced in 1932 [17] has been vindicated 55
years later in connection with the rate determining step for ammonia synthesis.
This most important theoretical and experimental result was discussed in this Conference by Ertl [15] and Bowker [18], as well as by Stoltze and Norskov [19].
Thus we must retain both indirect activation, mediated through a molecular
adsorbed precursor and direct dissociation by surmounting an activation barrier,
as discussed by Butler and Hayden in the case of H2 on W(100) [20]. Both modes of
activation have been discussed in the case of N2 on Fe(111) [15,19]. As a noteworthy result of the Havreholm Conference, it was agreed upon that the direct
mode of dissociation by activated adsorption is the one of importance under the
conditions of ammonia synthesis [18].
410
When a commercial iron catalyst is examined under ammonia synthesis conditions by temperature programmed reaction, first at increasing temperatures, then
at decreasing temperatures, the yield of ammonia versus temperature exhibits an
interesting hysteresis loop first reported by Richard and Vanderspurt [28]. This
hysteresis was interpreted in terms of a beneficial reconstruction of the surface
under increasing amounts of NH3 followed by a return to the original surface structure at lower yields of ammonia. Similar, more extensive observations were
reported at the Havreholm Conference by Waugh et al. [29].
Two related questions remain to be answered. What is the role of the alumina
and potassium oxide promoters in the commercial catalysts? First, do they contribute to the restructuring of the iron surface? Second, does the iron surface of the
commercial catalyst behave in synthesis like the best face of crystalline iron, i.e.,
the (111) face? Let us address these two questions in turn.
411
412
ment in the paper of Waugh et al. in this Volume [29]: "The surface restructuring
of the industrial catalysts does not produce dominantly the (111) surface, the
observed turnover numbers being 103 times lower than that of the (111) surface."
Unfortunately, what the authors call turnover number is actually an areal yield:
NH3 molecules cm -2 s -1. Until a TOF value is available, the nature and magnitude
of the discrepancy noted by Waugh et al. remains unclear.
In the meantime, it is useful to note that Dumesic et al. [33] used successfully a
microkinetic analysis to calculate values of site time yield for commercial Fe catalysts over a wide range of temperatures and pressures. They note that the same
microkinetic models were successful "within a factor of about 3" to describe both
the results of Spencer et al. [23] on Fe(111) and those ofTopsoe et al. [31] on a commercial catalyst. Again, it appears that the active sites on the commercial catalyst
are (111) facets, but this conclusion remains tentative.
At this moment what is clear from the work of Topsoe et al. [31] is that most of
the surface of a commercial Fe catalyst seems to be covered with the most active
sites capable of chemisorbing nitrogen at high temperature. This, together with the
high surface coverage by nitrogen at high values of nitrogen fugacity, helps in
understanding why the Langrnuir model is so successful, though not perfect, in
describing the kinetics of ammonia synthesis under commercial conditions.
The problems of identifying and counting the active sites on a catalytic surface
have just been discussed. A way to bypass this difficult task is to measure directly
the turnover frequency. As of now, the best technique to approach this elusive goal
is the steady state isotope technique for kinetic analysis, or SSITKA, which consists of perturbing a catalytic reaction taking place at the steady state in a stirred
tank reactor by an isotope jump. The method is similar to the isotope jump technique of Horiuti, reviewed above, except that the Horiuti method perturbs the equilibrium and SSITKA perturbs the steady state. In the case of ammonia synthesis,
the perturbation is effected by replacing suddenly 14N14N in the feed by 15N tagged
nitrogen and measuring the relaxation time r of the decay of the 14N containing
ammonia. The technique is described by Nwalor and Goodwin [5] and applied by
them to ammonia synthesis on a silica supported ruthenium without and with
potassium promoter. As the authors note, the turnover frequency TOF is given by
TOF --- O/r,
where 0 is the fraction of the active sites covered with adsorbed N atoms which
are the most abundant surface intermediates passing through the rate determining
step. If we assume that 0 is equal to unity, we obtain an upper bound value for
TOF:
413
TOFmax = 1 / r .
On the other hand, we may obtain a lower bound value for the T O F by referring
the rate to the total number of sites, active or not, as counted by a chemisorption
technique such as hydrogen chemisorption on supported metal clusters. This value
of T O F will be called TOFmin.
Now, if I combine the last columns of tables 2 and 3 in the paper of Nwalor
and Goodwin, I obtain with the above symbols the following results. For unpromoted ruthenium:
TOFmin = 0.6 x 10 -4 s -1
and
TOFmax = 5.6 x 10 -4 s -1 .
and
TOFraax -- 88 x 10 -4 s -I .
What I note is that for the u n p r o m o t e d catalyst, the lower bound and upper bound
values of T O F differ by a factor of 10. But for the promoted catalyst, they differ
by a factor of only 1.4. Thus, as noted by Nwalor and Goodwin [5], the role of the
promoter is to create sites of superior activity that actually cover most of the metal
surface [5]. I believe that this notion of m i n i m u m and m a x i m u m values of T O F
can be of general use whenever SSITKA is applicable: i.e., it gives an upper bound
value for T O F and kinetic guidance in the search for more active catalysts. In conclusion, it must be noted that the first application of SSITKA was for the study of
a commercial iron catalyst for ammonia synthesis, the trustworthy bellwether of
heterogeneous catalysis [34].
9. C o n c l u s i o n
Twenty years ago, a Battelle Colloquium took place in Gstaad, Switzerland, on
"The Physical Basis of Heterogeneous Catalysis" [2]. As noted in the Introduction,
it was dedicated to Paul H. Emmett "for his contributions to heterogeneous catalysis over fifty years". The prefatory chapter by Emmett in the Battelle Colloquium
Volume was a summary of "Fifty Years of Progress in the Study of the Catalytic
Synthesis of A m m o n i a " . This chapter is well worth reading today. Twenty years
later, the Havreholm Conference has looked again at ammonia synthesis with an
emphasis on current developments, especially as they impact on the future of heterogeneous catalysis. The Havreholm Conference was dedicated to Haldor Topsoe
and Anders Nielsen for their fifty years of leadership in heterogeneous catalysis
and a m m o n i a synthesis. After reviewing the proceedings of the Conference, I have
every reason to believe that they will be eminently worth reading twenty years
from now.
414
References
[I] M.I. Temkin andV. Pyzhev, Acta Physicochim. URSS 12 (1940) 327.
[2] P.H. Emmett, in: The Physical Basis for Heterogeneous Catalysis, eds. E. Grauglis and
R.I. Jaffee (Plenum Press, New York, 1975).
[3] M. Boudart and G. Dj~ga-Mariadassou, Kinetics of Heterogeneous Catalytic Reactions
(Princeton University Press, Princeton, 1984).
[4] M. Boudart, Kinetics of Chemical Processes (Butterworth-Heinemann, Stoneham, 1991).
[5] J.U. Nwalor and J.G. Goodwin Jr., this volume.
[6] K. Tamaru, communication at the conference.
[7] M. Boudart and K. Tamaru, Catal. Lett. 9 (I 991) 15.
[8] C.T. Campbell, this volume.
[9] M. Boudart, Ind. & Eng. Chem. Res., submitted.
[10] W. Tsai and W.H. Weinberg, J. Phys. Chem. 91 (1987) 5302.
[11] M. Boudart, C. Egawa, S.T. Oyama and K. Tamaru, J. Chim. Phys. 78 (1981) 987.
[12] D.G. L6ffler and L.D. Schmidt, I. Catal. 41 (1976) 440.
[13] L.M. Aparicio and J.A. Dumesic, this volume.
[14] B. Fastrup, this volume.
[15] G. Ertl, this volume.
[16] C.T. Rettner and H. Stein, Phys. Rev. Lett. 59 (1987) 2768.
[17] H.S. Taylor, Trans. Faraday Soc. 28 (I 932) 137.
[18] M. Bowker, this volume.
[19] P. Stoltze and J.K. N~rskov, this volume.
[20] D.A. Butler and B.E. Hayden, this volume.
[21] R. Westrik and P. Zwietering, Proc. Koninkl. Ned. Akad. Wetenschap. B56 (1953) 492.
[22] J. Schfitze, W. Mahdi, B. Herzog and R. Schl6gl, this volume.
[23] N.D. Spencer, R.C. Schooumaker and G.A. Somorjai, J. Catal. 74 (1982) 129.
[24] G.A. Somorjai and N. Materer, this volume.
[25] J.A. Dumesic, H. Topsee and M. Boudart, Proc. Natl. Acad. Sci. US 74 (1977) 806.
[26] J.A. Dumesic, H. Topsoe and M. Boudart, J. Catal. 37 (1975) 513.
[27] R. Brill, E.L. Richter and E. Ruth, Angew. Chem. 6 (1967) 882.
[28] M.A. Richard and R.H. Vanderspurt, J. Catal. 94 (1985) 563.
[29] K.C. Waugh, D.A. Butler and B.E. Hayden, this volume.
[30] D.C. Silverman and M. Boudart, J. Catal. 77 (1982) 208.
[31] H. Tops~e, N. Topsee, H. Bohlbro and J.A. Dumesic in: Proc. 7th Int. Congr. on Catalysis,
Part A, eds. T. Seiyama and K. Tanabe (Kodansha, Tokyo, 1981) p. 247.
[32] M. Boudart and D.G. L6ffler, J. Phys. Chem. 88 (1984) 5763.
[33] J.A. Dumesic, D.F. Rudd, L.M. Aparicio, J.E. Rekoske and A.A. Trevifio, The Microkinetics
of Heterogeneous Catalysis (American Chemical Society, Washington, 1993) p. 155.
[34] J.U. Nwalor, J.G. Goodwin Jr. and P. Biloen, J. Catal. 117 (1989) 121.