The catalytic hydrogenation of an aromatic sulfonyl chloride was investigated in
continuous and semi-batch mode processes using a Robinson-Mahoney stationary basket
reactor. A complete experimental unit was designed and built. The operating and
analytical procedures have been developed and the methodologies to gather the kinetic
data have been described. Hydrogenation reactions were conducted at a reaction pressure
of 364.7 psia, at three different reaction temperatures: 85 °C, 97 °C and 110 °C, at five
different residence times: 0.6 (only at 110 °C), 1.0, 1.5, 2.0, 3.1 hr, with the hydrogen to
the aromatic sulfonyl chloride molar ratio: 8.0 mol/mol and hydrogen to argon molar
ratio: 3.0 mol/mol. Intrinsic reaction rates of the reacting species were obtained on the
surface of a commercial 1 wt% palladium on charcoal catalyst.
The conversion and molar yield profiles of the reacting species with respect to
process time suggest a deactivation of the 1 wt % palladium on charcoal catalyst. Kinetic
data collected in a continuous process mode show that the catalyst is deactivated during
an experiment when the process time equal to two to three times the residence time of
the liquid within the reactor. XRD analysis shows that the active sites are blocked and an
amorphous layer was formed on the surface of the palladium catalyst. Semi-Batch mode
experimental data were obtained at 110 °C after 8 hours of reaction time for several
aromatic sulfonyl chlorides. A kinetic model has been developed, which includes adsorption of individual
components and surface reactions as well as rate equations of the Hougen-Watson type.
A hyperbolic deactivation function expressed in term of process time is implemented in
the Hougen-Watson equation rates. The mathematical model consists of non-linear and
simultaneous differential equations with multiple variables. The kinetic parameters were
estimated from the minimization of a multi-response objective function by means of a
sequential quadratic program, which includes a quasi-Newton algorithm. The statistical
analysis was based on the t- and F-tests and the simulated results were compared to the
experimental data.
Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2686 |
Date | 15 May 2009 |
Creators | Rouckout, Nicolas Julien |
Contributors | Anthony, Rayford G., Froment, Gilbert F. |
Source Sets | Texas A and M University |
Language | en_US |
Detected Language | English |
Type | Book, Thesis, Electronic Dissertation, text |
Format | electronic, application/pdf, born digital |
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