Binary high-pressure mixing systems

Figure 3.3 A schematic of the core of a high-pressure mixing (two-pump) system. The pumps are called binary, ternary or quaternary depending upon the number of solvents that can be mixed together (here binary). The mixing chamber, which controls the mobile phase composition, is at the output of the two high-pressure pumps on the downstream side of the pumps.

Pure zirconium tetrachloride is obtained by the fractional distillation of the anhydrous tetrachlorides in a high pressure system (58). Commercial operation of the fractional distillation process in a batch mode was proposed by Ishizuka Research Institute (59). The mixed tetrachlorides are heated above 437°C, the triple point of zirconium tetrachloride. AH of the hafnium tetrachloride and some of the zirconium tetrachloride are distiUed, leaving pure zirconium tetrachloride. The innovative aspect of this operation is the use of a double-sheU reactor. The autogenous pressure of 3—4.5 MPa (30—45 atm) inside the heated reactor is balanced by the nitrogen pressure contained in the cold outer reactor (60). However, previous evaluation in the former USSR of the binary distiUation process (61) has cast doubt on the feasibHity of also producing zirconium-free hafnium tetrachloride by this method because of the limited range of operating temperature imposed by the smaH difference in temperature between the triple point, 433°C, and critical temperature, 453°C, a hafnium tetrachloride. 

The equation of Krichevsky and Ilinskaya can readily be extended to high-pressure solutions of a gas in a mixed solvent, as shown by O Connell (01) and discussed briefly by Orentlicher (03). This extension makes it possible to predict the behavior of simple multicomponent systems using binary data only. 

Experimental results are presented for high pressure phase equilibria in the binary systems carbon dioxide - acetone and carbon dioxide - ethanol and the ternary system carbon dioxide - acetone - water at 313 and 333 K and pressures between 20 and 150 bar. A high pressure optical cell with external recirculation and sampling of all phases was used for the experimental measurements. The ternary system exhibits an extensive three-phase equilibrium region with an upper and lower critical solution pressure at both temperatures. A modified cubic equation of a state with a non-quadratic mixing rule was successfully used to model the experimental data. The phase equilibrium behavior of the system is favorable for extraction of acetone from dilute aqueous solutions using supercritical carbon dioxide. 

It is more common with multicomponent mobile phases to utilise the mixing facility within the quaternary pump. The quaternary pump operates by means of a proportioning valve and a single pump that draws the individual components from the solvent bottles into an inlet valve. The piston pushes the mobile phase into a damper, through a purge valve, and onto the column. This is an example of a low-pressure quaternary system. A high-pressure system would operate using four individual pump heads to draw the components into the system, rather like the binary system described previously. Most manufacturers supply low-pressure quaternary systems, most likely due to cost implications, ease of maintenance, and size. 

In addition to the experimental data, the partitioning behavior of MMA between water and CO2 has been modeled. The Peng-Robinson equation of state combined with various mixing rules as described in Section 14.4.1 has been assessed on the ability to correlate phase equilibrium data from literature of the binary subsystems CO2-H2O, MMA-CO2 and MMA-H2O. Subsequently, the model has been used to predict the phase equilibrium behavior of the ternary system CO2-H2O-MMA. Partition coefficients were calculated at four different temperatures at pressures ranging from 5 to 10 MPa. In order to provide a means for comparison, the experimentally determined partition coefficients obtained in the high-pressure extraction unit were used to evaluate the results of the predictive model for phase equilibrium behavior. 

Due to the high pressures, Langmuir is used with fugacities determined from the virial equation of state. It was found that the predictions with the multi-component Langmuir model were better than with lAST for two binary gas mixtures (H2-CO and CO-CH4) at various temperatures, but lAST proved to be superior when modelling the systems CO-CO2 and CH4-CO2 and for aU the ternary and quaternary systems. However, overall both models proved to adequately predict the mixed gas data and the predictions from the two models were very similar. From a mathematical and computational point of view, the explicit Langmuir model is simpler, while lAST needs an iterative solution method ... 

Carbon dioxide solubility was also investigated in binary and ternary mixtures of esters, at high pressure. The goal of the study was to identify an appropriate system for CO2 capture. Solubility of CO2 was determined by the constant-volume method in mixtures of dimethyl carbonate (DMC) + diethyl carbonate, (DMC + propyl acetate, (DMC + propylene carbonate and DMC + ethylene carbonate, in the temperature range from 282.0 to 303.0 K. It is found that the solubility of CO2 in four mixed solvents follows the Henry s law, and the linear compound has a greater ability to dissolve CO2 than the cyclic compound at the same temperature [73]. 

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