Reaction #2195470

Reaction equation

N2

H2S H2

H2S H2

CHB

N2

→

Dibenzothiophene

Conditions

Workup

1. 1
   Otherinserted into a horizontal quartz tube
2. 2
   workup.WAITheld there for 2 hours
3. 3
   Temperaturethe catalyst cooled
4. 4
   Otherto 70° C.
5. 5
   OtherAt room temperature, the quartz tube was removed
6. 6
   Otherthe material transferred into a N2 purged glove box
7. 7
   workup.ADDITION100 cc of liquid feed, containing 5 wt % dibenzothiophene in decalin
8. 8
   workup.ADDITIONwas added to the autoclave
9. 9
   Temperaturethe pressure was maintained at 3150 kPa
10. 10
    TemperatureThe temperature was raised to 350° C. at 5-6 deg/min
11. 11
    workup.WAITwas converted or until 7 hours
12. 12
    OtherA small aliquot of product was removed every 30 minutes
13. 13
    OtherAs described in that article, high selectivities to cyclohexylbenzene relative to BP during the desulfurization reaction

Procedure

1.5-2 g of the catalysts of Examples 1-4 were placed in a quartz boat which was in turn inserted into a horizontal quartz tube and placed into a Lindberg furnace. The temperature was raised to 370° C. in about one hour with N2 flowing at 50 cc/m, and the flow continued for 1.5 h at 370° C. No was switched off and 10% H2S/H2 then added to the reactor at 20 cc/m, the temperature increased to 400° C., and held there for 2 hours. The heat was then shut off and the catalyst cooled in flowing H2S/H2 to 70° C., at which point this flow was discontinued and N2 was added. At room temperature, the quartz tube was removed and the material transferred into a N2 purged glove box. Catalysts were evaluated in a 300 cc modified Carberry batch reactor designed for constant hydrogen flow. The catalyst was pilled and sized to 20/40 mesh and one gram was loaded into a stainless steel basket, sandwiched between a layer of mullite beads. 100 cc of liquid feed, containing 5 wt % dibenzothiophene in decalin was added to the autoclave. A hydrogen flow of 100 cc/min was passed through the reactor and the pressure was maintained at 3150 kPa using a back pressure regulator. The temperature was raised to 350° C. at 5-6 deg/min and run until either 50% DBT was converted or until 7 hours was reached. A small aliquot of product was removed every 30 minutes and analyzed by GC. Rate constants for the overall conversion as well as the conversion to the reaction products biphenyl (BP) and cyclohexylbenzene (CHB) were calculated as described by M. Daage and R. R. Chianelli [J. Cat. 149, 414-27 (1994)] and are shown in Table 1. As described in that article, high selectivities to cyclohexylbenzene relative to BP during the desulfurization reaction are a good indication of a catalyst with high hydrodenitrogenation activity, whereas high selectivities of BP relative to CHB indicates a catalyst with high hydrodesulfurization activity.

Source