Hydroformylation industrial plant development

The Rh/PPhs hydroformylation catalyst system was developed approximately simultaneously by Geoffrey Wilkinson (and students),Union Carbide, BASF, and Celanese. This catalyst system has been extensively studied, and the key species is HRh(CO)(PPh3)2. Once again the core mechanism is the same as that discussed previously for the cobalt systems and shown in Figure 12. Rhodium catalysts are approximately 1,000 times faster than ones based on cobalt (Rh is also about 1,000 times more expensive). Thus, rhodium catalysts can be run at considerably milder pressures and temperatures (8-10 bar, 125 °C), which dramatically reduces the capital expenditures for industrial plant construction. The increased activity of Rh over Co mainly derives from the stronger electronic preference of... 

Of course, there is still a large amount of research to be done to develop further the very preliminary character of the above described economic evaluation of an ionic liquid hydroformylation process. Only on the basis of more detailed data it will be possible to decide whether we will see an industrial hydroformylation plant using ionic liquids in the future. 

Hydroformylation of Propene the Ruhrchemie/Rhone-Poulenc (RCH/RP) Process - The industrial process for the hydroformylation of propene in a two phase system was developed by Ruhrchemie AG after a period of successful scale up tests in pilot plants.31 34 35-38-42 48 50 52-57 61 64-6 70-7 74,132-134,224,307.322,323,... 

The history of aqueous industrial two-phase catalysis began in 1984 when the hydroformylation of propene in water was first carried out in the plants of Ruhrchemie AG. The development of the aqueous two-phase process was completely atypical in that the initial research work was done by Rhone-Poulenc but the development work was done by the former Ruhrchemie (today part of Hoechst AG). A rather long time elapsed before further fundamental work was begun in academic laboratories. 

Catalyst performance has of course been a permanent theme in industry. For example, the catalytic activity of oxo catalysts (in hydroformylation) has improved in the past 50 years by a factor of 10 000 change from diadic and triadic process technology to continuous plant operation, replacement of cobalt by rhodium, tailoring of the ligand sphere (phosphines), change of phase application (from mono- to two-phase processes). At the same time, an improvement of selectivity has been achieved, apart from the ease of product/catalyst separation [132]. A similar development seems to occur in the Monsanto acetic acid process [49]. 

This book is restricted essentially to aqueous-phase catalyses and thus to one area of the more comprehensively defined two-phase catalyses. This restriction to the most recent and successful development of homogeneous catalysis takes account of the rapid technical advances in the process concept first described by Manassen et al. in 1973, which was followed in rapid succession in the 1970s by hesitant basic work and in 1984 by the first commercial implementation. This unusual sequence - industrial implementation in a 100000 tonnes per year oxo plant for the hydroformylation of propylene before years of time-consuming basic research to determine mechanistic, kinetic and other data - demonstrates clearly the great leap forward that this process development represented in the field of homogeneous catalysis and in solving the central problem mentioned earlier. Since then... 

Industrial interest in soluble polymer-bound catalysts has been closely linked to the development of ultrafiltration membranes with sufficient long-term stability in organic solvents. Membranes fulfilling these requirements were prepared first in the late 1980s. Today, solvent-stable flat sheet membranes and membrane modules are available from several suppliers. As for the viability of ultrafiltration in organic solvents, rhodium-catalyzed hydroformylation of dicydopentadiene with continuous catalyst recovery and recycling has been demonstrated successfully on a pilot plant scale over an extended period of time [5]. The synthesis of other fine chemicals by asymmetric reduction and other reactions has also been carried out in continuously operated membrane reactors (also cf Section 7.5) [6-9]. The extent of commercial interest in catalysts bound to soluble polymers appears to fluctuate at intervals. Amongst other factors, the price of precious metals can be a driver. 

---