Biphasic systems rates

Recently, the use of ionic liquids instead of organic solvents has been published for the biphasic system. For PaHNL and SbHNL, the reaction rates are increased in comparison to organic solvents without a change of enantioselectivity. ... 

The volumetric ratio of the two liquid phases (j6 = Forg/ Faq) can affect the efficiency of substrate conversion in biphasic media. The biocatalyst stability and the reaction equilibrium shift are dependent on the volume ratio of the two phases [29]. In our previous work [37], we studied the importance of the nonpolar phase in a biphasic system (octane-buffer pH 9) by varying the volume of solvent. The ratio /I = 2/10 has been the most appropriate for an improvement of the yield of the two-enzyme (lipase-lipoxygenase) system. We found that a larger volume of organic phase decreases the total yield of conversion. Nevertheless, Antonini et al. [61] affirmed that changes in the ratios of phases in water-organic two-phase system have little effect upon biotransformation rate. 

FIG. 5 Rate of hydroperoxide production in (a, ) lipoxygenation in pure aqueous medium, (b, ) lipoxygenation in biphasic system, (c, x) two-enzyme (lipase-lipoxygenase) system in two-phase medium, determined experimentally, and (d, ) modeled kinetic of the two enzyme system. (From Ref 63.)... 

One approach that has been successfully used to separate the catalyst from the product aldehyde is to use a biphasic system in which the rhodium catalyst is soluble in water and the product is soluble in an organic phase. This approach is used by Hoechstdlhone-Poulenc to produce more than 600,000 t/year of butyraldehyde (a lower aldehyde) (2). Unfortunately, this process caimot be used to produce higher aldehydes because the water solubihty of the higher olefins that are the feedstock is very low, which dramatically reduces the reaction rate. 

In heterogeneous liquid/liquid reactions, cavitational collapse at or near the interface will cause disruption and mixing, resulting in the formation of very fine emulsions. When very fine emulsions are formed, the surface area available for the reaction between the two phases is significantly increased, thus increasing the rates of reaction. The emulsions formed using cavitation, are usually smaller in size and more stable, than those obtained using conventional techniques and often require little or no surfactant to maintain the stability [8]. This is very beneficial particularly in the case of phase-transfer catalyzed reactions or biphasic systems. 

Typical approaches to this biphasic system have involved the immobilization of catalysts in the aqueous phase as colloids [53] or using water-soluble catalysts based on ligands such as the trisulfonated TPPTS [55, 56]. Particularly high reaction rates have been obtained with surfactant-stabilized microemulsions and emulsions that allow for intimate contact of all reagents with the catalyst during the reaction [57]. The emulsions separate readily into two phases by small pressure changes and the C02-phase is then vented to isolate the products. The catalyst RhCl(tppds)3 (tppds =... 

As outlined in Chapter 5, Section 5.2.3.2 various approaches to overcoming the low rates of the hydroformylation of long chain alkenes in aqueous biphasic systems have been proposed. Some of these, such as the use of microemulsions [24-26] or pH dependent solubility [27], have provided improvements often at the expense of complicating the separation process. Perhaps the most promising new approaches involve the introduction of new reactor designs where improved mixing allows for... 

Other salts of formic acid have been used with good results. For example, sodium and preferably potassium formate salts have been used in a water/organic biphasic system [36, 52], or with the water-soluble catalysts discussed above. The aqueous system makes the pH much easier to control minimal COz is generated during the reaction as it is trapped as bicarbonate, and often better reaction rates are observed. The use of hydrazinium monoformate salts as hydrogen donors with heterogeneous catalysts has also been reported [53]. 

Before discussing the kinetics of reactions in biphasic systems, the basics of kinetics in homogeneous reactions will be briefly revised. In all systems, the rate of a reaction corresponds to the amount of reactant that will be converted to product over a given time. The rate usually refers to the overall or net rate of the reaction, which is a result of the contributions of the forward and reverse reaction considered together. For example, consider the isomerization of -butane to Ao-butane shown in Scheme 2.1. 

In a biphasic system, the same rules as above apply, however, the rate of the reaction and the position of the equilibrium are determined by the concentration of the reactants and products in the phase where the reaction takes place, rather than their overall concentration in the system. Exactly where the reaction actually takes place is still a matter of debate, with two locations proposed, specifically, at the interfacial layer between the two phases (model 1) and in the bulk of the catalyst-containing phase (model 2), as shown in Figure 2.9. 

As for a single phase system, the rate of the reaction is still dependent on the probability of reactants meeting and therefore on the concentration of the reagents. However, in the biphasic system, the critical concentration of these components is no longer their total concentration in the whole system but the concentration where the reaction takes place. This concentration will be dependent on a number of factors, and the most influential are the rate of diffusion of the reactants to the catalyst and the relative solubility of the reagents in each phase. These two factors are interdependent, and will be considered in turn. 

For diffusion in a biphasic system, there is the additional complication of the phase boundary. Therefore, diffusion in each phase will be described by Equation 2.11, but in the region of the phase boundary different rules apply to take into account the mass transfer of the reactant from one phase to the other. Where the solubility of the solute is the same in both phases, the rate of diffusion across the phase boundary J for a solute moving from the higher concentration [A]i to the lower concentration [A]2 through a film of thickness l is given by Equation 2.12, which also describes an exponential decrease in concentration, but... 

In most biphasic systems, the solubility of the solute differs between the two phases. In this case, it is not the absolute concentration of the reagent that affects the rate of diffusion, but the concentration relative to the saturation of the solution. In the extreme example shown in Figure 2.12, although the actual concentration of solute A is higher in phase 1 than in phase 2, diffusion will proceed in the direction of phase 1 from phase 2, because phase 1 is less saturated by solute A than phase 2. The saturation is determined by the solubility of the solute in... 

As for the rate of diffusion, the equilibrium constant for a reaction in a biphasic system is not determined by the overall concentration of each reagent, but by their concentrations in the reaction phase. In some cases this can drive the forward reaction to completion, and in other cases it can be inhibitory, depending on the relative concentrations of the reactants and products. In model 1, where the reaction takes place at the phase boundary, the effective concentration of the reactants and products will be that in phase 1, and assuming each has an equivalent solubility, the equilibrium position will approach that of a homogeneous system. Where the reaction takes place in the bulk solvent, as in model 2, the equilibrium position is very much dependent on the solubility of the reagents in phase 2. For example, if the product is less soluble in phase 2 than the reactant, as the product is formed it will diffuse back into phase 1, reducing its concentration in phase 2 where the reaction is occurring and therefore the reaction will... 

In a homogeneous system, the rate of diffusion in the system can be directly related to the rate of the reaction as it governs the number of times the catalyst will interact with the reactants over a set time. In a biphasic system, diffusion still affects the rate of reaction, as this is dependent on the catalyst and reactants meeting. However, the rate of diffusion also affects the time it takes for the reactants to reach the place where the reaction takes place. How diffusion affects rate depends on the catalytic turnover. 

As the measured rate of the reaction in a biphasic system can be dramatically affected by diffusion, the measured rate of reaction is termed the observed rate of... 

It should be pointed out that many biphasic systems have found their way into the chemical industry, starting from PTC and continuous flow (CF) processes. The reasons are that efficiency can be increased (rates, selectivity, energy requirements, reaction intensification), making them more economic and often more environmentally compatible, in short, more sustainable. 

For the rhodium-catalyzed hydroformylation of propylene in an aqueous biphasic system. Cents et al. have shown that the accurate knowledge of the mass transfer parameters in the gas-liquid-liquid system is necessary to predict and optimize the production rate [180]. Choudhari et al. enhanced the reaction rate by a factor of 10-50 by using promoter Ugands for the hydroformylation of 1-octene in a biphasic aqueous system [175]. 

Fig. 13 Mean bubble sizes and specific surface areas of the dispersed gas phase in the biphasic system H2/H2O as a function of the hydrogen volume rate...

The only other olefin feedstock which is hydroformylated in an aqueous/organic biphasic system is a mixture of butenes and butanes called raffinate-II [8,61,62]. This low-pressure hydroformylation is very much like the RCH-RP process for the production of butyraldehyde and uses the same catalyst. Since butenes have lower solubility in water than propene, satisfactory reaction rates are obtained only with increased catalyst concentrations. Otherwise the process parameters are similar (Scheme 4.3), so much that hydroformylation of raffinate-11 or propene can even be carried out in the same unit by slight adjustment of operating parameters. 

---