Biphasic Catalysis Using Ionic Liquids

Ionic liquids (ILs) are basically salts with poorly coordinated ions, resulting in low melting points. Since low is a relative term (NaCl, for example, is an IL between 801 °C and 1465 °C), chemists use it to refer either to salts which melt below 100 °C, or to salts that are liquid at 25 °C. The latter group is known as room-temperature ionic liquids (RTILs). In most RTILs, one of the ions is organic, with a delocalized charge. Note that ILs are not concentrated salt solutions. They are nonmolecular liquids which contain, in theory, no water (in practice, many ILs contain at least traces of water). 

ILs are also attractive candidates for replacing volatile organic compounds (VOCs) as solvents, because they have practically no vapor pressure [165]. However, the environmental impact of ILs and VOCs should be compared on the basis of life-cycle analysis, and for that we are still missing many data on the toxicity and environmental effects of I Ls [ 166,167]. Another point is that the current prices of I Ls are much higher than those of VOCs. Handy et al. recently demonstrated a handy synthesis of mim-type ILs starting from fructose, which could eventually lead to truly eco-friendly IL solvents [168]. 

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Because of the great importance of liquid-liquid biphasic catalysis for ionic liquids, all of Section 5.3 is dedicated to specific aspects relating to this mode of reaction, with special emphasis on practical, technical, and engineering needs. Finally, Section 5.4 summarizes a very interesting recent development for biphasic catalysis with ionic liquids, in the form of the use of ionic liquid/compressed CO2 biphasic mixtures in transition metal catalysis. 

To estimate costs for the liquid-liquid biphasic hydroformylation using ionic liquids, a process was designed for the production of 100,000 tons per year of nonanal. The use of ionic liquids in hydroformylation catalysis is a fairly new technology and exact kinetic data are scarce, thus the TOFs reported for the Rh-sulfoxantphos system [80] have been used to determine catalyst inventory and reactor dimensions. In a similar way the plant design for the SILP process for a production capacity of 100,000 tons per year of butanal has been derived based on preliminary literature results [68]. The process flow sheets for both process variations are shown in Figures 7.12 and 7.13. 

TABLE 7.6. Process characteristics for optimised nonanal production (using liquid-liquid biphasic catalysis with ionic liquids) and butanal production (using SILP catalysis) on a 100.000 tons/year scale... 

In the previous sections the use of catalysts dissolved in ionic liquids has been documented with a variety of examples from the most recent literature. They were classified are catalytic systems based on the adoption of Strategies A, B and C, when solvent-less conditions were not adopted. In an ideal liquid-liquid biphasic system, the IL must dissolve the catalytic intermediates and, in part, the substrate to avoid that mass transfer limits reaction rates. Moreover, products should have a limited solubility in the IL to allow a facile product removal or extraction, and, possibly, the recycle of the ionic liquid-trapped catalyst. The separation of the catalyst from the products is made easier if solid support-immobilised ILs are used. The preference for a solid catalyst is dictated not only by the easier separation but also, as outlined by Mehnert in an excellent review article, " by (i) the possible use of fixed bed reactors, and (ii) the use of a limited amount of IL, a generally expensive chemical which can limit the economic viability of the process. In this section attention will be focused only on the most recent examples of solid-phase assisted catalysis using ionic liquids, following Strategy D. Examples prior to 2006 are covered in recent reviews and will not be discussed here. " ... 

In Section 5.3 it was demonstrated with many examples that ionic hquids are indeed a very attractive class of solvents for catalysis in liquid-liquid biphasic operation (for some selected reviews see Refs. [16-20]). In this section, we wfll focus on a different way to apply ionic liquids in catalysis, namely the use of an ionic liquid catalyst phase supported on a solid carrier, a technology that has become known as supported ionic liquid phase (SILP) catalysis. In comparison to the conventional liquid-liquid biphasic catalysis in ionic liquid-organic liquid mixtures, the concept of SILP-catalysis combines well-defined catalyst complexes, nonvolatile ionic liquids, and porous solid supports in a manner that offers a very efficient use of the ionic liquid catalyst phase, since it is dispersed as a thin film on the surface of the high-area support. Recently, the initial applications using such supported ionic liquid catalysts have been briefly summarized [21]. In contrast to this report, where the applications were distinguished by the choice of support material, the compilation here will divide the applications using the supported ionic liquid catalysts into sections according to the nature of the interaction between the ionic liquid catalyst phase and the support. 

Except for transitions from heterogeneous to homogeneous catalysis, there is also common groimd for the various methodologies described here the application of SCCO2 is described in the presence of ionic liquids [32a] or of fluorous solvents [32b,c] as well in aqueous operation [33a-d] and aerobic epoxidations have been attained in fluorous biphasic systems using ionic liquids [33e]. On the other hand, ionic liquids [34] or fluorous solvents [35a,c] have been used together with aqueous operations and water-soluble polymers are the focal point of the application of... 

Note that all the weak points related to liquid-liquid biphasic catalysis with ionic liquids are effectively addressed by continuous gas-phase catalysis with SILP materials. The amount of ionic liquid used in SILP materials is much smaller than in liquid-liquid biphasic systems (referenced by the productivity of the catalyst system). This is due to the much better IL utilization in the SILP system, which is a direct consequence of the very short diffusion lengths... 

In comparison with traditional biphasic catalysis using water, fluorous phases, or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way to combine the specific advantages of homogeneous and heterogeneous catalysis. In many applications, the use of a defined transition metal complex immobilized on a ionic liquid support has already shown its unique potential. Many more successful examples - mainly in fine chemical synthesis - can be expected in the future as our loiowledge of ionic liquids and their interactions with transition metal complexes increases. 

In contrast, we intend to demonstrate the principle aspects of catalyst recycling and regeneration using the ionic liquid methodology. These aspects will be explored in more detail for the example of Rh-catalysed hydroformylation (see Section 7.2). First, however, we will briefly introduce important general facts concerning transition metal catalysis in ionic liquids (see Section 7.1.2). This will be followed by a consideration of liquid-liquid biphasic reactions in these media from an engineering point of view (see Section 7.1.3). 

In comparison to traditional biphasic catalysis using water, fluorous phases or polar organic solvents, transition metal catalysis in ionic liquids represents a new and advanced way of combining the specific advantages of homogeneous and heterogeneous catalysis. 

Catalysis in ionic liquids is not limited to biphasic reaction systems. When the reaction mixture is homogeneous, an extraction solvent that is immiscible with the ionic liquid can be used to remove the product. A number of organic solvents display little or only limited miscibility with these liquids. However, this advantage is of limited value in practice, because one major incentive for using ionic liquids is to avoid volatile organic compounds. 

Most studies of catalysis in ionic liquids have focused on issues of increased selectivity and particularly the easy separation of product from the catalyst and catalyst recycling via use of a biphase. In some cases, the reaction may occur in a biphase in others, the biphase is only used for product separation. In some special cases, the second phase is exclusively product, due to insolubility of the organic products in the ionic liquid, and is easily separated by decantation, allowing the recovered ionic catalytic solution to be reused. Of course, use of an organic solvent for extraction does reduce some of the potential green benefits of the ionic liquid approach. More recently, SCCO2 has been used to extract the products. Alternatively, volatile products can be separated from the ionic liquid and catalyst by distillation. 

Examples of applying biphasic system to catalyzed reactions, such as phase-transfer catalysis, show the efficiency over stoichiometric reactions. In a typical catalytic biphasic system, one phase contains the catalyst while the substrate is in the second phase. In some systems, the catalyst and substrates are in the same phase while the product produced is transferred to the second phase. In a typical reaction, the two phases are mixed during the reaction and after completion, the catalyst remains in one phase ready for recycling while the product can be isolated from the second phase. The most common solvent combination consists of an organic solvent combined with another immiscible solvent, which, in most applications, is water. However, there are few examples of suitable water-soluble and stable catalysts, therefore various applications are limited to some extent [4]. Immiscible solvents other than water are recently becoming more applicable in biphasic catalysis due to the better solubility and stability of various catalysts in such solvents. For example, ionic liquids and fluorous solvents have many successful applications in liquid-liquid biphasic syntheses such as Heck reactions and hydroformylations using ionic liquid media, or Baeyer-Villiger reactions... 

Since no special ligand design is usually required to dissolve transition metal complexes in ionic liquids, the application of ionic ligands can be an extremely useful tool with which to immobilize the catalyst in the ionic medium. In applications in which the ionic catalyst layer is intensively extracted with a non-miscible solvent (i.e., under the conditions of biphasic catalysis or during product recovery by extraction) it is important to ensure that the amount of catalyst washed from the ionic liquid is extremely low. Full immobilization of the (often quite expensive) transition metal catalyst, combined with the possibility of recycling it, is usually a crucial criterion for the large-scale use of homogeneous catalysis (for more details see Section 5.3.5). 

From all this, it becomes understandable why the use of traditional solvents (such as water or butanediol) for biphasic catalysis has only been able to fulfil this potential in a few specific examples [23], whereas this type of highly specialized liquid-liquid biphasic operation is an ideal field for the application of ionic liquids, mainly due to their exactly tunable physicochemical properties (see Chapter 3 for more details). 

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