Transient catalyst

Shimizu, K.I., Kawabata, H., Maeshima, H. et al. (2000) Intermediates in the selective reduction of NO by propene over Cu-Al203 catalysts Transient in-Situ FTIR study, J. Phys. Chem. B, 104, 2885. 

Improvement in catalyst transient warm up performance through the use of smaller, high surface area substrates. 

Efstathiou et al. studied the adsorbed species present on Rh/Al203 catalysts. Transient reaction studies indicated once again that CO is present up to one monolayer on the catalyst surface. Two forms of carbon were also present on the catalyst a reactive form, CH, present in small amounts (less than 0.06 monolayer), and alkyl chains C Hy. Formation of methane during reduction of the carbon species on the catalyst surface with H2 was mainly due to the active CH species. In addition, FTIR indicated that formate and carbonate species build up slowly on the alumina support but do not participate in the formation of methane. 

Fish, M.J., and Ollis, D.J. (1977) Characterization of enantioselective hydrogenation catalysts transient electrochemical oxidation of D-(+)-tartaric acid on Nickel, J. Catal. 50, 353-363. 

Arsenic Peroxides. Arsenic peroxides have not been isolated however, elemental arsenic, and a great variety of arsenic compounds, have been found to be effective catalysts ia the epoxidation of olefins by aqueous hydrogen peroxide. Transient peroxoarsenic compounds are beheved to be iavolved ia these systems. Compounds that act as effective epoxidation catalysts iaclude arsenic trioxide, arsenic pentoxide, arsenious acid, arsenic acid, arsenic trichloride, arsenic oxychloride, triphenyl arsiae, phenylarsonic acid, and the arsenates of sodium, ammonium, and bismuth (56). To avoid having to dispose of the toxic residues of these reactions, the arsenic can be immobi1i2ed on a polystyrene resia (57). 

Maintenance of isothermal conditions requires special care. Temperature differences should be minimised and heat-transfer coefficients and surface areas maximized. Electric heaters, steam jackets, or molten salt baths are often used for such purposes. Separate heating or cooling circuits and controls are used with inlet and oudet lines to minimize end effects. Pressure or thermal transients can result in longer Hved transients in the individual catalyst pellets, because concentration and temperature gradients within catalyst pores adjust slowly. 

E. Jobson and co-workers. Deterioration of Three-Way Automotive Catalysts, Parti—Steady State and Transient Emission of Aged Catalyst, SAE 930937, Society of Automotive Engineers, Warrendale, Pa., 1993. 

Heat exchanger-like, multi-tube reactors are used for both exothermic and endothermic reactions. Some have as much as 10,000 tubes in a shell installed between tube sheets on both ends. The tubes are filled with catalyst. The larger reactors are sensitive to transient thermal stresses that can develop during startup, thermal runaways and emergency shut downs. 

The fundamental reason for runaway at transient changes is the large difference in the thermal capacity of the catalyst charge and the flowing fluid, especially if it is a gas-phase reaction. In these cases, if the reaction is running close to the runaway limit but still somewhat below it, sudden changes can start a thermal runaway. 

Kinetic studies involving enzymes can principally be classified into steady and transient state kinetics. In tlie former, tlie enzyme concentration is much lower tlian that of tlie substrate in tlie latter much higher enzyme concentration is used to allow detection of reaction intennediates. In steady state kinetics, the high efficiency of enzymes as a catalyst implies that very low concentrations are adequate to enable reactions to proceed at measurable rates (i.e., reaction times of a few seconds or more). Typical enzyme concentrations are in the range of 10 M to 10 ], while substrate concentrations usually exceed lO M. Consequently, tlie concentrations of enzyme-substrate intermediates are low witli respect to tlie total substrate (reactant) concentrations, even when tlie enzyme is fully saturated. The reaction is considered to be in a steady state after a very short induction period, which greatly simplifies the rate laws. 

It has been proposed that protonation or complex formation at the 2-nitrogen atom of 14 would enhance the polarization of the r,6 -7i system and facilitate the rearrangement leading to new C-C bond formation. The equilibrium between the arylhydrazone and its ene-hydrazine tautomer is continuously promoted to the right by the irreversible rearomatization in stage II of the process. The indolization of arylhydrazones on heating in the presence of (or absence of) solvent under non-catalytic conditions can be rationalized by the formation of the transient intermediate 14 (R = H). Under these thermal conditions, the equilibrium is continuously pushed to the right in favor of indole formation. Some commonly used catalysts in this process are summarized in Table 3.4.1. 

In the major catalytic processes of the petroleum and chemical industries, continuous and steady state conditions are the rule where the temperature, pressure, composition, and flow rate of the feed streams do not vary significantly. Transient operations occur during the start-up of a unit, usually occupying a small fraction of the time of a cycle from start-up to shut-down for maintenance or catalyst regeneration. 

Then let us examine the rate relaxation time constant x, defined as the time required for the rate increase Ar to reach 63% of its steady state value. It is comparable, and this is a general observation, with the parameter 2FNq/I, (Fig. 4.13). This is the time required to form a monolayer of oxygen on a surface with Nq sites when oxygen is supplied in the form of 02 This observation provided the first evidence that NEMCA is due to an electrochemically controlled migration of ionic species from the solid electrolyte onto the catalyst surface,1,4,49 as proven in detail in Chapter 5 (section 5.2), where the same transient is viewed through the use of surface sensitive techniques. 

Figure 4.14 shows a similar galvanostatic transient obtained during C2H4 oxidation on Rh deposited on YSZ.50 Upon application of a positive current 1=400 pA with a concomitant rate of O2 supply to the catalyst I/2F=2.M0 9 mol O/s the catalytic rate increases from its open-circuit value r0=1.8 10 8 mol O/s to a new value r= 1.62-1 O 6 mol O/s which is 88 times larger than the initial unpromoted rate value. The rate increase Ar is 770 times larger than the rate of supply of O2 ions to the Rh catalyst surface. 

The complex transient r vs t, or equivalently r vs 0Na or r vs Uwr behaviour of Fig. 4.15 parallels the steady-state rvs UWr behaviour shown in Fig. 4.16, where for each point UWr has been imposed potentiostatically, until the current I has vanished and the corresponding rate value, r, has been measured. This shows that the catalyst surface readjusts fairly fast to the galvanostatically imposed transient 0Na values (Fig. 4.15). The dashed and dotted line transients on the same figure were obtained with the same gaseous composition but with initial Uwr values of 0 and -0.3 V respectively. It is noteworthy that the three transients are practically identical which shows the reversibility of the system. 

Figure 4.17. NO reduction by H2 on Pt/p"-AI203.52 Transient effect of applied constant negative current (Na supply to the catalyst) on catalyst potential (a) under reaction conditions (solid line) and in a He atmosphere (dashed line) and on the rates of formation of N2 and N20 (b). Potentiostatic restoration of the initial rates see text for discussion. Reprinted with permission from Academic Press.

This is easy to understand In the former case the backspillover species (O2 ) is also a reactant in the catalytic reaction. Thus as its coverage on the catalyst surface increases during a galvanostatic transient its rate of consumption with C2H4 also increases and at steady state its rate of consumption equals its rate of creation, I/2F. This means that the backspillover O2 species reacts with the fuel (e.g. C2H4) at a rate which is A times slower than the rate of reaction of more weakly bonded chemisorbed oxygen formed via gaseous chemisorption. 

One of the most important, but not too surprising experimental observations after the discovery of electrochemical promotion is that the work function, O, of the gas exposed catalyst-electrode surfaces changes significantly (up to 2 eV) during galvanostatic transients such as the ones shown in Figures 4.13, 4.14, 4.15 and 4.17 as well as at steady-state and in fact that, over wide experimental conditions, it is (Fig. 4.21)54 ... 

Figure 4.26. Transient response of the rate of CO2 formation and of the catalyst potential during NO reduction by CO on Pt/p"-Al2C>396 upon imposition of fixed current (galvanostatic operation) showing the corresponding (Eq. 4.24) Na coverage on the Pt surface and the maximum measured (Eq. 4.34) promotion index PINa value. T=348°C, inlet composition Pno = Pco = 0.75 kPa. Reprinted with permission from Academic Press.

Figure 4.49. Transient effect of constant applied current (I=+10 pA) on the rate (r) of C2H4 oxidation on Ir02/YSZ, on catalyst work function (AO) and on catalyst potential (Uwr)-Conditions T=380°C, pc>2 = f 5 kPa and PC2H4 =0.05 kPa.88 Reprinted with permission of The Electrochemical Society.

Figure 4.50. Transient effect of constant applied current (I=+300 pA) on the rate of C2H4 oxidation on Ir02 and on 75mol% Ir02 - 25%Ti02 and 25% Ir02 - 75%Ti02 composite catalysts deposited on YSZ. Note the decrease in p upon increasing the Ti02 content and the appearance of permanent NEMCA in all cases.124...

Figure 4.51. Transient effect of a constant applied current on the rates of C02, N2 and N20 production, on NO conversion (XN0) and on catalyst potential (Uwr) during NO reduction by propene in presence of gaseous 02 on Rh/YSZ.70 Reprinted with permission from Elsevier Science.

Figure 5.2. NEMCA and its origin on Pt/YSZ catalyst electrodes. Transient effect of the application of a constant current (a, b) or constant potential UWR (c) on (a) the rate, r, of C2H4 oxidation on Pt/YSZ (also showing the corresponding UWR transient)3 (b) the 02 TPD spectrum on Pt/YSZ4,7 after current (1=15 pA) application for various times t. (c) the cyclic voltammogram of Pt/YSZ4,7 after holding the potential at UWR = 0.8 V for various times t.

The first indication that NEMCA is due to electrochemically induced ion backspillover from solid electrolytes to catalyst surfaces came together with the very first reports of NEMCA Upon constant current application, i.e. during a galvanostatic transient, e.g. Fig. 5.2, the catalytic rate does not reach instantaneously its new electrochemically promoted value, but increases slowly and approaches asymptotically this new value over a time period which can vary from many seconds to a few hours, but is typically on the order of several minutes (Figure 5.2, galvanostatic transients of Chapters 4 and 8.)... 

Figure 5.10. Transient response of catalyst work function O and potential Uwr upon imposition of constant currents I between the Pt catalyst (labeled26 C2) and the Pt counter electrode p"-A1203 solid electrolyte T = 240°C, p02 = 21 kPa Na ions are pumped to (I<0) or from (I>0) the catalyst surface at a rate I/F.26 Reprinted with permission from Elsevier Science.

Figure 5.12. Time evolution of catalyst potential and work function for Pt/p"-Al203 during potentiostatic transients, T = 200°C, po2 = 10 10 Pa.25...

As already shown in Figures 5.10 and 5.11 the equality Aconstant current is applied at t = 0 between the catalyst and the counter electrode and one follows the time evolution of UWr by a voltmeter and of

[Pg.223]

---