Industrial Applications of Alternative Solvent Systems

1 The Development of the First Aqueous-Organic Diphasic Hydroformylation Plant 

1 Development of a heterogeneously catalysed processes based on cobalt. 

2 Introduction of a high pressure process employing homogeneous cobalt catalysts. 

What is particularly remarkable about the development of the biphasic process is the speed in which it was developed following the initial discovery. Over the next few pages some of the key steps in this process will be described [11]. 

A few years later, Ruhrchemie joined forces with Rhfine-Poulenc to develop a continuous biphasic hydroformylation process since Rhone-Poulenc had no 

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The use of nonclassical reaction conditions in Mizoroki-Heck reactions (e.g. ultrasound, microwaves, alternative solvent systems, or combinations of these methods) is known and has been reviewed excellently by Beletskaya and colleagues [9,12]. Here, we suimnarize the activities in the field of Mizorold-Heckreactionsfromapractical point of view, focusing on preparatively useful laboratory procedures and their possible application to industrial (large-scale) synthetic chenustry. 

There are many important industrial applications of azeotropic separations, which employ a variety of methods. In this book we discuss several of these chemical systems and demonstrate the application of alternative methods of separation. The methods presented include pressure-swing distillation, azeotropic distillation with a light entrainer, extractive distillation with a heavy entrainer (solvent), and pervaporation. The chemical systems used in the numerical case studies included ethanol-water tetrahydrofuran (THF)-water, isopropanol-water, acetone-methanol, isopentane-methanol, n-butanol-water, acetone-chloroform, and acetic acid-water. Economic and dynamic comparisons between alternative methods are presented for some of the chemical systems, for example azeotropic distillation versus extractive distillation for the isopropanol-water system. 

Interests in the phase transfer catalysis (PTC) have grown steadily for the past several years [68-70]. The use of PTC has recently received industrial importance in cases where the alternative use of polar aprotic solvents would be prohibitively expensive [71-74]. Thus, the potential application of the phase transfer catalyzed aromatic nucleophilic displacement reactions between phenoxide or thiophenoxide and activated systems has... 

Figure 1 shows how acid-gas-bearing process gases can be generally treated in industrial processes. The sulfur compounds and CO2 may be absorbed in a liquid medium, such as amines, alkali salts (NaOH, K2CO3), physical solvents (methanol, propylene carbonate), or water (3). The absorbed acid gases are released by reduction of pressure and/or by application of heat. Alternatively, the H2S and CO2 may chemically combine with the absorbent (as in NaOH scrubbing) to form salts which are removed in a liquid treatment unit. This requires continual and expensive makeup of sodium to the system. 

Not surprisingly, the most well developed biphasic system is that using water and organic solvents, despite the first industrial biphasic process involving only organic solvents. Obviously, water is the solvent of choice as it is abundant, cheap, non-flammable, non-toxic and has many other desirable properties such as being polar (and therefore relatively easy to separate from apolar compounds), high thermal conductivity, heat capacity and heat of evaporation. Nevertheless, alternative solvents to water for applications in biphasic catalysis are needed for several reasons ... 

Dense carbon dioxide represents an excellent alternative reaction medium for a variety of polymerization processes. Numerous studies have confirmed that CO2 is a potential solvent for many chain growth polymerization methods, including free-radical, cationic, and ring-opening metathesis polymerizations. Carbon dioxide has also been demonstrated to be an effective solvent for step-growth polymerization techniques. Advances in the design and synthesis of surfactants for use in CO2 will allow compressed CO2 to be utilized for a wide variety of polymerization systems. These advances may enable carbon dioxide to replace hazardous VOCs and CFCs in many industrial applications, making CO2 an enviromentally responsible solvent of choice for the polymer industry. 

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