On-stream time

Ca.ta.lysts, Catalyst performance is the most important factor in the economics of an oxidation process. It is measured by activity (conversion of reactant), selectivity (conversion of reactant to desked product), rate of production (production of desked product per unit of reactor volume per unit of time), and catalyst life (effective time on-stream before significant loss of activity or selectivity). 

Eig. 4. Typical TLE outlet temperatures as a function of time on stream for various feedstocks A, HVGO high severity B, naphtha high severity C,... 

The chapter by Bridger and Woodward deals with methanation as a means for removing carbon oxides from ammonia synthesis gas. This technology, together with earlier pioneer work by Dent and co-workers (I), are the forerunners of all modern methanation developments. The chapter deals with catalyst formulation and characterization and with the performance of these catalysts in commercial plants as a function of time on-stream. 

Catalyst° Time on Stream, hrs Inlet S/G Inlet Hot Spot Outlet... 

Figure 2. Study of chloride poisoning hot spot location vs. time on stream...

Fig. 3. Catal5Tst stability with time on stream in the methane leftmnlng with carbon dioxide T=700 C, GHSV=3500 ft ).

The stability of catalyst is one of the most important criteria to evaluate its quality. The influence of time on stream on the conversion of n-heptane at SSO C is shown in Fig. 5. The conversion of n-heptane decreases faster on HYl than on FIYs with time, so the question is Could the formation of coke on the catalyst inhibit diffusion of reactant into the caves and pores of zeolite and decrease the conversion According to Hollander [8], coke was mainly formed at the beginning of the reaction, and the reaction time did not affect the yield of coke. Hence, this decrease might be caused by some impurities introduced during the catalyst synthesis. These impurities could be sintered and cover active sites to make the conversion of n-heptane on HYl decrease faster. 

The catalytic pyrolysis of R22 over metal fluoride catalysts was studied at 923K. The catalytic activities over the prepared catalysts were compared with those of a non-catalytic reaction and the changes of product distribution with time-on-stream (TOS) were investigated. The physical mixture catalysts showed the highest selectivity and yield for TFE. It was found that the specific patterns of selectivity with TOS are probably due to the modification of catalyst surface. Product profiles suggest that the secondary reaction of intermediate CF2 with HF leads to the formation of R23. 

Fig. 3. The effects of time on stream on the conversions of CO2 and CH4 and tire product distribution over Ni-YSZ-Ce02 catalyst. (Reaction temp. = 800 °C, CH4/CO2 = 1, Total flow rate = 40 cc/min)...

Table 3 shows the performance of the promoted-catalysts for the decomposition of methane to hydrogen at 5, 60, 120 and 180 min of time on stream. The results in Table 3 revealed that the activity of the parent catalyst and MnOx-doped catalyst remained almost constant until 120 min of time on stream. The activity of the other promoted-catalysts, on the other hand, decreased with an increase in the time on stream. The data for the CoO-doped catalyst and 20 mol%NiO/Ti02 could not be recorded at 120 min and 180 min, respectively because of the pressure build-up in the reactor. This finding indicates that adding MnOx enhances the stability and the resistibility of the NiO/Ti02 catalyst towards its deactivation. 

Fig. 1(b) represents the selectivity to styrene as a ftmcfion of time fijr the above catal ts. It is observed that the selectivity to styrene is more than 95% over carbon nauofiber supported iron oxide catalyst compared with about 90% for the oxidized carbon nanofiber. It can be observed that there is an increase in selectivity to styrene and a decrease in selectivity to benzene with time on stream until 40 min. In particrdar, when the carbon nanofiber which has been treated in 4M HCl solution for three days is directly us as support to deposit the iron-precursor, the resulting catalyst shows a significantly lows selectivity to styrene, about 70%, in contrast to more than 95% on the similar catalyst using oxidized carbon nanofiber. The doping of the alkali or alkali metal on Fe/CNF did not improve the steady-state selectivity to styrene, but shortened the time to reach the steady-state selectivity. 

Equation (1) consists of various resistance terms. l/Kj a is the gas absorption resistance, while 1/ K,a corresponds to the maleic anhydride diffusion resistance and l/i k represents the chemical reaction resistance. The reaction rate data obtained under the reaction conditions of 250°C and 70 atm were plotted according to equation (1). Although catalytic reaction data with respect to time on stream were not shown here, a linear correlation between reaction rate data and catalyst loading was observed as shown in Fig. 2. The gas absorption resistance (1/ a) was -1.26 h, while the combined reaction-diffusion resistance (lJK,a + 1 T]k) was determined to be 5.57 h. The small negative value of gas absorption resistance indicates that the gas-liquid diffusion resistance was very small and had several orders of magnitude less than the chanical reaction resistance, as similarly observed for the isobutene hydration over Amberlyst-15 in a slurry reactor [6]. This indicates that absorption of malei c anhydride in solvent was a rapid process compared to the reaction rate on the catalyst surface. 

Figure 8.13. Rate of methanol synthesis of a Cu/Zn0/Al203 catalyst in a plug flow reactor as a function of time on stream. The catalyst was operated at 494 K and 63 bar in a gas steam of 5 % CO, 5 % COj, 88% H2, and 2% N2. Note the steady decrease in reactivity, which is ascribed to sintering ofthe copper particles. The CO2 was removed from the reactants for 4 h after 168 h. After reintroduction the catalyst displays a restored...

It should be noted that the catalytic activity falls markedly with an increase in the time-on-stream. Similar falls in catalytic activity were also observed in the cases of the other W-based mixed oxides, such as W-Sn, W-Ti, and W-Mo. It was also found that the deactivated catalysts can easily be regenerated by a heat-treatment at 500°C in air for 1 h. 

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