Supercritical restrictor

J. T. B. Strode and L. T. Taylor, Supercritical fluid exti action employing a vai iable restrictor coupled to gas chi omatography via a sample pre-concentration cap , ]. High Resolut. Chromatogr. 19 651-654 (1996). 

An on-line supercritical fluid chromatography-capillary gas chromatography (SFC-GC) technique has been demonstrated for the direct transfer of SFC fractions from a packed column SFC system to a GC system. This technique has been applied in the analysis of industrial samples such as aviation fuel (24). This type of coupled technique is sometimes more advantageous than the traditional LC-GC coupled technique since SFC is compatible with GC, because most supercritical fluids decompress into gases at GC conditions and are not detected by flame-ionization detection. The use of solvent evaporation techniques are not necessary. SFC, in the same way as LC, can be used to preseparate a sample into classes of compounds where the individual components can then be analyzed and quantified by GC. The supercritical fluid sample effluent is decompressed through a restrictor directly into a capillary GC injection port. In addition, this technique allows selective or multi-step heart-cutting of various sample peaks as they elute from the supercritical fluid... 

SEE is an instrumental approach not unlike PLE except that a supercritical fluid rather than a liquid is used as the extraction solvent. SFE and PLE employ the same procedures for preparing samples and loading extraction vessels, and the same concepts of static and dynamic extractions are also pertinent. SFE typically requires higher pressure than PLE to maintain supercritical conditions and, for this reason, SFE usually requires a restrictor to control better the flow and pressure of the extraction fluid. CO2 is by far the most common solvent used in SFE owing to its relatively low critical point (78 atm and 31 °C), extraction properties, availability, gaseous natural state, and safety. 

The instrumental requirements for supercritical fluid extraction are quite simple. A pump is essential to generate the extraction pressure in a themostated extraction vessel. The soluble sample components are then swept from the vessel through a flow restrictor into a collection device that is normally at ambient pressure. The fluid used for supercritical fluid... 

To date most of the work which has been done with supercritical fluid extraction has concentrated on the extraction of analytes from solid matrices or liquids supported on an inert solid carrier matrix. The extraction of aqueous matrices presents particular problems [276-278]. The co-extraction of water causes problems with restrictor plugging, column deterioration, and phase separation if a nonpolar solvent is used for sample collection. Also, carbon dioxide isay have limited extraction efficiency for many water soluble compounds. 

The solvent elimination appro2K h is quite straightforward for supercritical fluids lAich are often gases at atmospheric pressure. Each chromatographic peedc is deposited fron the end of a restrictor, connected to the end of the column by a heated transfer line, onto a small area of infrared-transparent support [110,128,129,134]. The support can be moved manually to collect each peak at a n osition or stetq>ed continuously to record the... 

Off-line SFE is conceptually a simple experiment to perform and requires only relatively basic instrumentation. The instrumental components necessary include a source of fluid, most often CO2 or CO2 with an organic modifier, a means of pressurizing the fluid, an extraction cell, a method of controlling the extraction cell temperature, a device to depressurize the supercritical fluid (flow restrictor), and a device for collecting the extracted analytes. 

Application of SFE necessitates a CO2 source, a pump to pressurize the fluid, an oven containing the extraction vessel, a restrictor to maintain a high pressure in the extraction line, an analyte collection vessel, and an overall system controller. CO2 is drawn from the bottom of the tank with a dip tube because the liquid is the more dense of the two phases. The substantial vapor pressure of the CO2 at ambient temperature helps to displace the liquid into the pump. CO2 remains a liquid throughout the pumping or compression zones and passes through small-diameter metal tubing as it approaches the extraction vessel. A preheating zone in front of the extraction vessel allows supercritical temperature, pressure, and density conditions to be applied immediately to the analyte matrix in the vessel. 

Extractions can be carried out in dynamic, static, or combination modes. In the dynamic mode, the supercritical fluid continuously flows through the sample in the extraction vessel and out the restrictor to the trapping vessel. In the static mode, the supercritical fluid circulates in a loop containing the extraction vessel for some period of time before being released through the restrictor to the trapping vessel. In the combination mode, a static extraction is performed for some period of time, followed by a dynamic extraction. 

In SFC, the mobile phase is initially pumped as a liquid and is brought into the supercritical region by heating it above its supercritical temperature before it enters the analytical column. It passes through an injection valve where the sample is introduced into the supercritical stream and then into the analytical column. It is maintained supercritical as it passes through the column and into the detector by a pressure restrictor placed either after the detector or at the end of the column. The restrictor is a vital component it keeps the mobile phase supercritical throughout the separation and often must be heated to prevent clogging both variable- and fixed-restrictors are available. 

Figure 6.4—Schematic of a supercriticalfluid chromatograph. Carbon dioxide reaches a supercritical state between the pump and the injector. A pressure regulator (restrictor) is located after the column and either before or after the detector, depending on its type. It allows the mobile phase to be kept under supercritical conditions until its exit from the column.

In addition, our design has eliminated the use of a restrictor. Restrictors are the most common means of controlling the pressure or density of a supercritical process. With no restriction, flow is dead-ended (i.e. restricted) via a switching valve in our invention. Supercritical fluid extractions are then conducted in a static mode (no flow). 

The use of a restrictor to control pressure and density in supercritical fluid extraction has also been eliminated. Prior to this, restriction and restriction devices have been the Achilles heel of SFE. With this system, this will no longer be a problem. 

Supercritical fluid extraction system - Hewlett Packard Model 7680A totally automated system with unlimited-capacity reciprocating pump, specially designed extraction chamber with safety interlocks, a variable restrictor nozzle and analyte collection trap. The operation of the extractor is controlled by a personal computer which is a Microsoft Windows-based system. An animated status screen provides real-time monitoring of the extraction process. Table II gives the SFE conditions for the HP extractor. 

We have demonstrated in this paper that two and four samples can be extracted in parallel with supercritical carbon dioxide without significant impact on data quality. Modifications made to an off-line extractor involved addition of a multiport manifold for the distribution of supercritical fluid to four extraction vessels and of a 12-port, two-way switching valve that allowed collection of two fractions per sample in unattended operation. The only limitation that we have experienced with the four-vessel extraction system was in the duration of the extraction. When working with 2-mL extraction vessels and 50-/zm restrictors, and using the pressure/temperature conditions mentioned above, the 250-mL syringe pump allows us a maximum extraction time of 60 min. During this time, two 30-min fractions can be collected with the present arrangement. 

In addition, solute focusing is possible by maintaining a low initial temperature (e.g. 40 °C) for a long period of time (8-12 min ) to allow the mixture of decompressed carbon dioxide, helium gas and the solutes to focus on the GC column. The optimization of the GC inlet temperature can also lead to increased solute focusing. After supercritical fluid analysis, the SF fluid effluent is decompressed through a heated capillary restrictor from a packed column (4.6 mm i.d.) directly into a hot GC split vaporization injector. 

SFC has received attention as an alternative separation technique to liquid and gas chromatography. The coupling of SFC to plasma detectors has been studied because plasma source spectrometry meets a number of requirements for suitable detection. There have been two main approaches in designing interfaces. The first is the use of a restrictor tube in a heated cross-flow nebuliser. This was designed for packed columns. For a capillary system, a restrictor was introduced into the central channel of the ICP torch. The restrictor was heated to overcome the eluent freezing upon decompression as it left the restrictor. The interface and transfer lines were also heated to maintain supercritical conditions. Several speciation applications have been reported in which SFC-ICP-MS was used. These include alkyl tin compounds (Oudsema and Poole, 1992), chromium (Carey et al., 1994), lead and mercury (Carey et al., 1992), and arsenic (Kumar et al., 1995). Detection limits for trimethylarsine, triphenylarsine and triphenyl arsenic oxide were in the range of 0.4-5 pg. 

MS)]. The mobile phase is kept as a supercritical fluid by means of a restrictor until either on-line detection has been performed or just before the expansion into a gas phase detector. Figure 7.1 shows a line diagram for a typical SFC apparatus. 

Sample introduction is a major hardware problem for SFC. The sample solvent composition and the injection pressure and temperature can all affect sample introduction. The high solute diffusion and lower viscosity which favor supercritical fluids over liquid mobile phases can cause problems in injection. Back-diffusion can occur, causing broad solvent peaks and poor solute peak shape. There can also be a complex phase behavior as well as a solubility phenomenon taking place due to the fact that one may have combinations of supercritical fluid (neat or mixed with sample solvent), a subcritical liquified gas, sample solvents, and solute present simultaneously in the injector and column head [2]. All of these can contribute individually to reproducibility problems in SFC. Both dynamic and timed split modes are used for sample introduction in capillary SFC. Dynamic split injectors have a microvalve and splitter assembly. The amount of injection is based on the size of a fused silica restrictor. In the timed split mode, the SFC column is directly connected to the injection valve. Highspeed pneumatics and electronics are used along with a standard injection valve and actuator. Rapid actuation of the valve from the load to the inject position and back occurs in milliseconds. In this mode, one can program the time of injection on a computer and thus control the amount of injection. In packed-column SFC, an injector similar to HPLC is used and whole loop is injected on the column. The valve is switched either manually or automatically through a remote injector port. The injection is done under pressure. 

---