Hydrogenation catalyst loadings

Hydrogenation of aromatic nitro compounds is very fast, and the rate is limited often by the rate of hydrogen transfer to the catalyst. It is accordingly easy to use inadvertently more catalyst than is actually necessary. Aliphatic nitro compounds are reduced much more slowly than are aromatic, and higher catalyst loadings (6,11) or relatively lengthy reduction times may be... 

Even in a simple hydrogen fuel cell system, capital cost reduction requires improvements in many diverse areas, such as catalyst loadings, air pressuriza-... 

Johnson et al. (J4) investigated the hydrogenation of a-methylstyrene catalyzed by a palladium-alumina catalyst suspended in a stirred reactor. The experimental data have recently been reinterpreted in a paper by Polejes and Hougen (P4), in which the original treatment is extended to take account of variations in catalyst loading, variations in impeller type, and variations of gas-phase composition. Empirical correlations for liquid-side resistance to gas-liquid and liquid-solid mass transfer are presented. 

The prafoimance of foe catalyst for foe CTA hj hopurification was evaluated in a batch autoclave r ictor under conditions similar to those in the indtistry. 90g of CTA containing about 3000 ppm o f 4-CBA and 240 ml of water were chaigrf to foe reactor with Ig catalyst loaded. Hydropurification of foe CTA was conducted at 280ti in foe reactor under stirring (800 rpm) and 0.7 MPa hydrogen pressure. Samples takra after 0.5 h of reaction were analyzed with HPLC [4]. The catalytic performance of foe Pd/CNF catalyst was characterized by 4-CBA s conversion. 

GL 16] [R 12] [P 15] As excess of cyclohexene was used, the kinetics were zero order for this species concentration and first order with respect to hydrogen [11]. For this pseudo-first-order reaction, a volumetric rate constant of 16 s was determined, considering the catalyst surface area of 0.57 m g and the catalyst loading density of1g cm. ... 

GL 21] [no reactor] [P 22] A constant conversion is approached on increasing the reaction rate constant [73]. This shows that liquid transport of hydrogen to the catalyst has a dominant role. In turn, this means that a higher catalyst loading should have not too much effect. 

Bidentate NHC-Pd complexes have been tested as hydrogenation catalysts of cyclooctene under mild conditions (room temperature, 1 atm, ethanol). The complex 22 (Fig. 2.5), featuring abnormal carbene binding from the O carbon of the imidazole heterocycles, has stronger Pd-C jj, bonds and more nucleophilic metal centre than the bound normal carbene chelate 21. The different ligand properties are reflected in the superior activity of 22 in the hydrogenation of cyclooctene at 1-2 mol% loadings under mild conditions. The exact reasons for the reactivity difference in terms of elementary reaction steps are not clearly understood [19]. 

In the majority of the known examples, the donor of hydrogen equivalents is isopropanol HCOO" or HCOOH/EtjN azeotrope are less successful. Aromatic ketones (mainly acetophenone and benzophenone) were the easiest to reduce even under mild conditions and low catalyst loadings. 

An example for a non-structure-sensitive reaction is provided by Davis et al. [102], who investigated the liquid-phase hydrogenation of glucose over carbon and silica based ruthenium catalysts with particle sizes between 1.1 and 2.4 run. Depending on catalyst loading which was between 0.56 wt.% and 5 wt.%, dispersion decreased from 91% to 43%. At the same time, TOFs varied only insignificantly in a range between 0.21 1/s and 0.32 1/s. 

Process Evaluation and Improvement. As homogeneous asymmetric hydrogenation processes are scaled up, one major concern is cost because the catalyst is usually expensive. Hence, several criteria for a commercially viable process (2), including selectively, conversion, catalyst loading (S/C, the molar ratio of substrate to catalyst), reaction time, and TOF (turnover frequency, the ratio of catalyst loading to reaction time), should be considered to evaluate the process and provide a guide for improvement. 

Addition of a strong acid snch as methanesnlfonic acid (MSA) to the reaction mixture has a positive impact on the reactivity, as shown in Figure 3.8. The induction time is shortened by 10 minutes and the reaction rate almost doubled. Due to the reaction rate increase from the acid addition, the catalyst loading could be lowered. In addition, the hydrogen pressnre conld be donbled to rednce the reaction time by half. However, improvements from addition of acid and pressure increase are not sufficient to make this process commercially viable because the catalyst loading and the TOF are significantly lower than the criteria listed in Table 3.n. Therefore, we initiated a search for catalysts more active than Et-DnPhos-Rh catalyst. 

The deleterious effects of catalyst poisoning when carrying out asymmetric hydrogenations at low catalyst loading caimot be overemphasised. In order to eliminate the possibility that the substrate synthesis introduced inhibitory impurities, an alternative synthetic protocol was examined (Scheme 7.4). The use of a brominating agent and an expensive palladium catalysed step in the initial route could limit the development of this as an economically favourable process and this was further motivation to examine alternative routes to the hydrogenation substrate. 

Low yields and high catalyst loading in the hydrogenation reaction... 

With all other pieces of the synthesis in place our attention now focused on the final piece in the jigsaw-the asymmetric hydrogenation of the amide enamide 42. Screening of hydrogenation conditions rapidly led to identification of a number of conditions which allowed the desired hydrogenation to proceed at low catalyst loadings and in non-chlorinated solvents (Table 9.9). 

Figure 1 Hydrogen uptake curves of 3%Pd/CPS4 and 5%Pd and 10%Pd on CPS1, CPS2 and CPS4. The reaction conditions are 10 g 4-(benzyloxy) phenol in 100 methanol, hydrogen pressure 1.1 bar, agitation rate 200 rpm, temperature 35°C, catalyst loading 3wt%.

---