Methods of butane hydrogenolysis under hydrogen-lean conditions
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example 1
Hydrogenolysis of Butane-Catalyst Activity-Single Pass Reactor Comparative vs. Invention Mole Ratio at 275° C.
[0061]Using the single pass reactor and catalyst described in the General Procedure section above, the catalyst activity was measured at various H2 / C4H10 ratios at a temperature of 275° C. and a pressure of 100 psig, and WHSVs as shown in Table 1. The results are illustrated in FIG. 6 and tabulated in Table 1. In this figure, steeper slope indicated faster catalyst deactivation (short catalyst lifetime), and vice versa. When the H2 / C4H10 was between 0.34 at 23 h−1 and 0.70 at 32 h−1, catalyst deactivation was the most minimized. After 80 h on stream, the catalyst activity at the H2 / C4H10 molar ratio of 0.59 at 14 h−1 dropped less than 10%, which was significantly less than the activity drop at the H2 / C4H10 ratios of 0.15 and 1.01. Notably, when the H2 / C4H10 ratio was less than 0.34 and greater than 1.01, the catalyst deactivated faster than that at the H2 / C4H10 ratio from 0....
example 2
Hydrogenolysis of Butane-Catalyst Activity-Single Pass Reactor Comparative Vs. Invention Mole Ratios at 310° C.
[0062]Using the single pass reactor and catalyst described in the General Procedure section above, the catalyst activity was measured at various H2 / C4H10 ratios at a temperature of 310° C. and 100 psig. The results are illustrated in FIG. 7 and tabulated in Table 2. The deactivation rates were observed at the H2 / C4H10 molar ratios of the present invention at about 0.3:1 to 0.8:1, with the slowest rates being at 0.5:1 to 0.8:1 molar ratios. In a comparative example, when the H2 / C4H10 molar ratio decreased further below 0.3, the catalyst deactivation become faster than at H2 / C4H10 of about 0.15:1. In other comparative examples, when the H2 / C4H10 ratio increased from greater than 0.8:1 to 2.57:1, under the same conditions, catalyst deactivation rate accelerated.
TABLE 2H2 / C4H10WHSV (h−1, C4H10-based)Initial n-C4H10 conversion2.5749 33%0.9962 22%0.8088 18%0.6574 14%0.581125.6%0....
example 3
Reaction Rate—Single Pass Reactor
[0063]From Examples 1 and 2, the slow-deactivation conditions could overlap with those with fast reaction rates. As shown in FIG. 8, the maximum reaction rate (scaled linearly on the vertical axis) appeared at the region where the H2 / C4H10 was between 0.75 and 1.5. In combination of the slow-deactivation conditions presented in Examples 1 and 2 (shaded areas in FIG. 8), the catalyst offered relatively high activity and slow deactivation at H2 / C4H10 molar ratio of 0.75:1 to 0.8:1.
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