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be potentially hazardous reactions, stand the process. term of heat flow monitoring, i.e. by
especially because the hydroxyl- In order to access the role of mass monitoring the difference between
amine intermediates formed are transfer, experiments with differ- the temperature of the reactor con-
often thermally unstable and can ent stirrer speeds were performed. tents and the temperature of the
disproportionate with a significant Experiments with different pressure jacket (Tr -Tj).
temperature increase causing large were also done. The goal was to
explosions [1]. define the necessary rules to run
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The MultiMax RB04-50 Reac- tion initiation, reaction end point Automatic Gas Uptake Manual Gas Uptake
ity of the temperature control and this work. The Hastelloy reactor Figure 2
measurement allows the user to get vessel is also available without the Overview of one reactor with magentic coupling, sensors and IR
probe on the bottom of the reactor
valuable information such as reac- IR-ATR probe.
5. Results and discussion tor the instantaneous and the total Figure 5
View of the evolution of the monitored signals during
5.1 Hydrogen uptake hydrogen consumption. the experiment.
The reaction was monitored by Using the volumetric method to
measuring the consumption of measure the H2 uptake, the pres-
the hydrogen using a Mass Flow sure and the temperature in the
Meter (see Figure 6 and 12) and by reservoir have to be monitored as
measuring the pressure drop in the shown in Figure 5.
reservoir used to feed hydrogen to
the reactor (volume of 150 mL and Figure 7 instead shows the agree-
maximum pressure of 250 bar, see ment between the heat flow trend-
Figure 1 and 7). ing and the gas consumption.
A comparison is shown in Figure
8. It may be noted that the reac- A comparison between the hydro-
tion was carried out at a constant gen uptake using the Mass Flow
hydrogen pressure. Meter and the volumetric method is Figure 6
Totalizer integrated in the MultiMax™ software
Using the Mass Flow Meter, the shown in Figure 8. The two meth-
software allows the user to moni- ods give the same result [7].
Figure 7
Monitoring of the pressure in the reservoir and the pressure in
the reactor
Hydrogenation of Nitrobenzene
to Aniline
Figure 12
Comparison between the measurements done with the Mass
Flow Meter (gas flow) and the difference of Tr-Tj (heat flow).
Reaction conditions: substrate: nitrobenzene (0.025 mol); cata-
lyst: 5% Pd/C (~0.03 g); solvent: methanol (35 mL); stirrer
speed: 900 rpm; pressure: 2.4 to 6.3 bar; temperature: 50 °C;
ratio catalyst/substrate = 1.25 g • mol-1.
Hydrogenation of Nitrobenzene
to Aniline
5.5 IR measurements
As mentioned previously and to the C-H bending, the peaks at
shown in Figure 1, the MultiMax™ 1605 cm-1 and 1630 cm-1 corre-
system is provided with an FTIR. spond to the NH2 bending absorp-
The spectrophotometer is directly tion of aniline, the peak at 1530
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connected in the MultiMax cm-1 to the NO2 asymmetric stretch
software as shown in Figure 13 absorption, and the peak at 1350
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(MultiMax IR ). cm-1 to the NO2 symmetric stretch
absorption of nitrobenzene. All
The IR spectra were acquired using these peaks were chosen to follow
the ReactIR4000 Spectrophotom- the reaction (see Figure 14) [4, 7].
eter and the ReactIR software. The Figure 13
spectra were measured using an The time-dependent profiles of The MultiMax™ software can communicate with different instru-
attenuated total reflectance (ATR) the initial compound and the final ments, including the ReactIR
Figure 14
Part of the IR spectrum recorded as a function of time during the
hydrogenation of nitrobenzene at 50 °C. The peaks indicated at
1530 and 1350 cm-1 were used to determine the decreasing
concentration of nitrobenzene and the peaks indicated at 1505,
1605 and 1630 cm-1 were used to determine the increasing
concentration of aniline during the hydrogenation reaction.
Hydrogenation of Nitrobenzene
to Aniline
6 Conclusions Three-phase reactions under The hydrogen uptake and the heat
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The MultiMax RB04-50 Reactor pressure such as hydrogenations flow trending (Tr -Tj) have also
Box (four reactors of 50 mL each) of nitrobenzene have been per- been used to characterize the
has been used to investigate the formed in order to demonstrate chemical reaction.
hydrogenation of nitrobenzene. the advantage and the quality of The heat flow trending (Tr -Tj)
The main advantage of these the instrument’s measurement shows as a first qualitative result
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reactors is the small amount of with the MultiMax IR RB04-50 that accumulation of reagent
compounds necessary to investi- system for high pressure com- takes place, i.e. the reaction in not
gate the reaction. In addition, the bined with a real-time FTIR dosing-controlled.
reactors are completely indepen- spectrophotometer.
dent of temperature controlling, Moreover, to improve the infor-
pressure and stirrer speeds. The rate of hydrogenation of mation content of a single
This enables the user to investi- nitrobenzene to aniline over a 5% measurement of a reaction, the
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gate more than one parameter at Pd/C catalyst in a three-phase MultiMax has been combined
the same time and logging all reaction at 50 °C is strongly with an IR-ATR probe per vessel.
the data. influenced by the intraparticle The absorbance spectra for all
It has been shown that even at the mass transfer as well as by the the components of the reaction
50 mL scale the hydrogenation gas-liquid and liquid-solid mass have therefore been acquired and
can be investigated in details. transfer. studied.
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The MultiMax experiment pro- Therefore, the effects of H2 pres-
vides some very good informa- sure and stirrer speed on the ini- The Hastelloy vessels are easily
tion related to kinetics and mass tial rates were discussed to asses exchangeable and available with
transfer. the role of mass transfer. and without the IR-ATR probe.