Propylene oxide oxidation— oscillations

Direct Oxidation of Propylene to Propylene Oxide. Comparison of ethylene (qv) and propylene gas-phase oxidation on supported silver and silver—gold catalysts shows propylene oxide formation to be 17 times slower than ethylene oxide (qv) formation and the CO2 formation in the propylene system to be six times faster, accounting for the lower selectivity to propylene oxide than for ethylene oxide. Increasing gold content in the catalyst results in increasing acrolein selectivity (198). In propylene oxidation a polymer forms on the catalyst surface that is oxidized to CO2 (199—201). Studies of propylene oxide oxidation to CO2 on a silver catalyst showed a rate oscillation, presumably owing to polymerization on the catalyst surface upon subsequent oxidation (202). 

The damped torsional oscillator mechanism seems appropriate for this low molecular weight poly (propylene) oxide in this high frequency region. 

Rate Oscillations During Propylene Oxide Oxidation on Silver Films in a Continuous Stirred Reactor... 

The oxidation of propylene oxide on porous polycrystalline Ag films supported on stabilized zirconia was studied in a CSTR at temperatures between 240 and 400°C and atmospheric total pressure. The technique of solid electrolyte potentiometry (SEP) was used to monitor the chemical potential of oxygen adsorbed on the catalyst surface. The steady state kinetic and potentiometric results are consistent with a Langmuir-Hinshelwood mechanism. However over a wide range of temperature and gaseous composition both the reaction rate and the surface oxygen activity were found to exhibit self-sustained isothermal oscillations. The limit cycles can be understood assuming that adsorbed propylene oxide undergoes both oxidation to CO2 and H2O as well as conversion to an adsorbed polymeric residue. A dynamic model based on the above assumption explains qualitatively the experimental observations. 

A simple Langmuir-Hinshelwood model explains quantitatively the steady-state behavior (4) but it fails to explain the oscillatory phenomena that were observed. The origin of the limit cycles is not clear. Rate oscillations have not been reported previously for silver catalyzed oxidations. Oxidation of ethylene, propylene and ethylene oxide on the same silver surface and under the same temperature, space velocity and air-fuel ratio conditions did not give rise to oscillations. It thus appears that the oscillations are related specifically to the nature of chemisorbed propylene oxide. This is also supported by the lack of any correlation between the limits of oscillatory behavior and the surface oxygen activity as opposed to the isothermal oscillations of the platinum catalyzed ethylene oxidation where the SEP measurements showed that periodic phenomena occur only between specific values of the surface oxygen activity (6,9). 

There is evidence for isomerization of chemisorbed propylene oxide to acrolein on silver and for surface polymer formation on metal oxide catalysts (11,12). Formation of a surface polymeric structure has also been observed during propylene oxidation on silver (13). It appears likely that the rate oscillations are related to the ability of chemisorbed propylene oxide to form relatively stable polymeric structures. Thus chemisorbed monomer could account for the steady state kinetics discussed above whereas the superimposed fluctuations on the rate could originate from periodic formation and combustion of surface polymeric residues. 

Figure 4 shows the effect of increasing partial pressure of propylene oxide at constant p02 T an< sPace velocity. The simulation shows the existence of a lower limit for oscillations in qualitative agreement with the experiment but does not predict an upper limit. 

A simple dynamic model is discussed as a first attempt to explain the experimentally observed oscillations in the rate of propylene oxide oxidation on porous silver films in a CSTR. The model assumes that the periodic phenomena originate from formation and fast combustion of surface polymeric structures of propylene oxide. The numerical simulations are generally in qualitative agreement with the experimental results. However, this is a zeroth order model and further experimental and theoretical work is required to improve the understanding of this complex system. The in situ use of IR Spectroscopy could elucidate some of the underlying chemistry on the catalyst surface and provide useful information about surface coverages. This information could then be used to either extract some of the surface kinetic parameters of... 

Figures (E9-4 1) and (E9-4 2) show the reactor Concentration and temperature of propylene oxide as a function of time, respectively for an initial temperature of 75°F and only water in the tank (i e., C,, = 0) One observes, both the teinperature and concentration oscillate around their steady-state values T = 138°F, = 0Q39...

Sheintuch and Luus (1981) studied propylene oxidation and observed horatian oscillations, see Section E.ll. 

HIE) Sheintuch, M., Luss, D. Reaction Rate Oscillations During Propylene Oxidation on 1981 Platinum. J. Catal. 68, 245-248... 

Fig. 5. Chaotic oscillations of the overall heat generated by propylene oxidation on a Pt ribbon in the constant-resistance mode after [43].

Figure 13 shows typical complex impedance spectra of the three types of polymer electrolytes sandwiched between lithium electrodes at an oscillation level of 0.5 V. The profiles of the spectra were two neighboring arcs. The low-frequency arcs (right-hand side arcs) and the high-frequency arcs (left-hand side arcs) corresponded to the loci of the charge transfer impedance and the bulk electrolyte impedance, respectively. The bulk resistance (/ .0 and the charge transfer resistance (R ) are shown in Fig. 13. The ionic conductivities at 50°C for the polymer electrolytes (1), (2), and (3) were approximately 10 to 10 S cm (depending on the LiC104 concentration (see Table 1), 10 S cm, and 10 S cm , respectively. The values, corresponding to the electrode reaction, were about lO" Cl, irrespective of the kinds of polymer electrolytes. These values were similar to those found in the poly(propylene oxide) networks with dissolved lithium salts [93] and to those found in the poly(ethylene succinate) with dissolved lithium salts [88,94], but were considerably higher than those found in poly(p-propiolactone)-LiC104 complexes [95].

In the oxidation of propylene with the same experimental setup, fronts propagating back and forth were obtained [43]. The latter were associated with macroscopic oscillations. The motion of the front could even become irregular (Figure 4) [43], at the same time the integral oscillations became chaotic (Figure 5) [48,49]. 

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