Analytical Products Sales Engineering

Supercritical Fluid Chromatography

for Process Control

Kenneth J. Melda
SC7-25-198
 SUPERCRITICAL FLUID CHROMATOGRAPHY
FOR PROCESS CONTROL

KENNETH J. MELDA
ABB Inc. Analytical Products
LEWISBURG, WEST VIRGINIA

KEYWORDS

Chromatography
Supercritical Fluids
Process Control

ABSTRACT

Process Gas Chromatographs have long been used for "on-line" analysis in the
chemical, petrochemical and refining industries. The application range of
Process GC's are somewhat restricted by the limited volatility and thermal
stability of many organic compounds. Mixtures of less volatile compounds have
been analyzed by liquid chromatography or High Temperature Gas
Chromatography (HTGC) but these techniques have not successfully made the
transition from laboratory to process instrumentation.

Another form of chromatography, using supercritical fluids, gained wide

popularity in laboratory during the 1980's. Supercritical Fluid Chromatography
(SFC) combines several features of gas and liquid chromatography, which
makes it an ideal technique for analyzing samples of low volatility and thermal
stability. In addition this technique has been shown to be easily adaptable to "on-
line" process chromatography.

An overview of Supercritical Fluid Chromatography, along with several areas of

applications relevant to the chemical, petrochemical and refining industries will
be discussed.

INTRODUCTION

The separating power of Gas Chromatography (GC) is unparalleled, however the

limited volatility and thermal stability of many organic compounds restrict its
applicability. It is generally estimated that only 20% of known compounds can be
volatilized without sample decomposition. High Performance Liquid
Chromatography (HPLC) is capable of separating non-volatile mixtures since it
takes advantage of the strong solvating properties of a liquid mobile phase. This
chromatographic technique has found limited use in the process industry due to

1
the expense and disposal problems with the solvents required to carry out the
analyses.

With the ever-growing tighter control on product specifications, there is a great

need for the "on-line" measurement of these low to non-volatile samples. One
method that has always shown great promise for the analysis of these samples is
Supercritical Fluid Chromatography (SFC). Hardware requirements for a SFC
analyzer allow it to be easily adapted into a Process Chromatograph. SFC had a
renewed interest in the laboratory during the 1980's (1,2), however lately its use
and advancement has become stagnated. There have been several factors that
have contributed to the slow growth in SFC, the most significant being the
technological advancements in High Temperature Gas Chromatography (HTGC).
This is another technique that has not been adapted to the Process GC. The
high temperatures used present safety problems in the process environment and
also put severe strains on columns and analyzer hardware.

Supercritical Fluid Chromatography is a chromatographic technique that uses

supercritical fluids for the mobile phase. When a gas is heated and compressed
above its critical temperature and pressure, it exhibits properties that are
intermediate between those of gases and liquids. The most important property is
the density, which varies as a function of the temperature and pressure: as the
pressure increases, the density increases, increasing the solvent strength.
Consequently, by varying the pressure, the solvent strength can be adjusted thus
changing the partitioning of the analyte between the stationary phase and the
supercritical fluid (SCF) mobile phase. Other properties related to the density
include diffusion coefficients less than that of a gas but greater than that of a
liquid, and viscosities similar to gases but much lower than that of liquids.

Taken together, these characteristics lead to a number of differences with

respect to GC and HPLC. For example, because the diffusion coefficient is
greater in a supercritical fluid than a liquid, one can achieve higher resolution and
faster analysis times at the same conditions when using SCF mobile phases
rather than a liquid mobile phase. Viscosity also plays a major role in the
transport properties of the SCF through a column. Since the viscosity of a
supercritical fluid is similar to that of a gas, the pressure drop across the column
is low. This allows the use of capillary columns, which helps expand the
analytical capability of this technique.

While there are several commercially available gases which could be used for
supercritical fluid applications; Carbon Dioxide (CO2) is the most commonly used
mobile phase because of its low critical temperature and pressure. Carbon
Dioxide has an intermediate polarity, making it an ideal solvent for a wide variety
of samples. Also, it is ideal because of its non-toxicity and lack of Flame
Ionization Detector (FID) response. Figure 1 shows a phase diagram of CO2 that
depicts its triple point, critical temperature (31.1oC) and critical pressure (73 atm,
1070 psig).

2
INSTRUMENTATION

Figure 2 shows a schematic of a Process Supercritical Chromatograph (PSFC).

There are a few key components that are critical to the operation of the PSFC
and also make it uniquely different from a Process GC. Foremost is the pump,
which delivers the supercritical fluid to the analytical system. The pump is a
pneumatic amplifier, which generates the pressure to make the CO2 mobile
phase supercritical, and also generates a programmed pressure ramp for elution
of components in the sample matrix. The pump is controlled by a
microprocessor and is pneumatically driven by an 80 psig auxiliary air supply to
deliver Supercritical CO2 from 1000 psig to 7000 psig. Pressure ramps can be
generated from 50 to 1500 psig per minute, depending on the program entered
for a given analysis.

Packed or capillary columns can be used in the PSFC. To obtain the separation
efficiencies similar to those achieved in Gas Chromatography smaller bore
columns are required. With packed columns, 1 mm i.d. columns are typically
used and with capillary columns, 0.1 mm i.d. or smaller are used. Because the
sample capacities of these columns are extremely small, direct injection of
stream samples onto them is not recommended due to overloading of the
column. Typically in GC sample splitters are used to avoid overloading of
capillary columns. However, for splitters to be applicable in SFC, split ratios of
greater than a 1000 to 1 must be employed. These split ratios are impractical
since they are very unreliable and non-reproducible.

To avoid samples splitters, the PSFC contains a sample diluter, wherein a small
amount of stream sample (1 to 4 µl) is injected into a chamber filled with
Supercritical CO2. The sample is dissolved and mixed in the chamber and a
fixed volume of the diluted sample can then be injected onto the column without
the use of a splitter.

The final critical component of the PSFC is the column-detector interface. The
Flame Ionization Detector requires the chromatographic effluent to be de-
pressurized before detection. This is generally achieved by using some form of
capillary restrictor. This restrictor must not only provide for a complete transfer of
the non-volatile solute to the detector without formation of analyte particles and
plugging of the restrictor, but also provide a pulse free flow throughout the
column. The PSFC utilizes a porous ceramic frit restrictor (Dionex, Salt Lake
City, UT). This restrictor has been shown to be both rugged and not easily
plugged by particles in the CO2 and sample matrix.

APPLICATIONS

One of the major application areas for SFC is in the petroleum industry.
Simulated distillation by GC has long been used in the laboratory and process

3
industry for the characterization of gasoline and light distillate samples.
Typically, simulated distillation analysis by Process Gas Chromatography has
been limited to those petroleum fractions which have final boiling points (FBP)
lower than 430oC. High Temperature Gas Chromatographic techniques have
been used in the laboratory to analyze samples with final boiling points above
430oC but, because of the strains it puts on the chromatographic hardware, this
technique has not been adapted to the process chromatograph.

The mild conditions of SFC make it an ideal method for the analysis of these
higher boiling point fractions. Figure 3 shows a chromatogram and distillation
report of a vacuum gas oil sample with a final boiling point of approximately
600oC.

Over the past several years the fuel formulations for various grades of diesel and
gasoline have been changing as a result of improvements in refining processes,
environmental restrictions and engine performance. Most of the emphasis on
reducing emissions has been directed toward reducing aromatic content in fuels.
Environmental regulations control the amount of particulate emissions generated
by gasoline and diesel combustion. Because aromatics present in these fuels
promote particulate emissions, refineries require "on-line" methods to monitor
aromatic content during blending processes. Various GC and spectroscopic
methods have been developed to measure aromatics in gasoline. However, the
most common industry method for measuring aromatics content in fuels, such as
diesel, has been fluorescent indicator adsorption (FIA) - ASTM D 1319. This
method is limited by the precision provided and the boiling point range of fuels
that can be analyzed, which is a particular problem with diesel fuels. A SFC
method, ASTM D 5186, also determines aromatic content in jet and diesel fuels.
Many regulatory bodies are now replacing ASTM D1319 with ASTM D 5186 as
the method of choice to determine aromatic content in diesel fuel. Figure 4
shows a chromatogram of the analysis of the aromatic content in diesel fuel by
the SFC method.

Figure 5 shows a chromatogram for the analysis of 1-butene in an alpha olefin

stream. This application is unique because even though the chromatogram only
shows a component analysis from C4 to C22, the actual stream composition
contained alpha olefin components well above carbon number 60. The unique
selectivity of supercritical fluids was utilized for this application. The stream
sample was injected into the diluter, which was filled with Supercritical CO2 at
1100 psig. At this pressure the density of the CO2 is low, allowing only the light
alpha olefins to dissolve into the CO2 and be injected on the column. By
analyzing only part of the stream the cycle time is greatly reduced.

Shown in Figure 6 is a chromatogram of a dimethyl silcone sample. The

chromatogram shows the ability of the PSFC to analyze samples of wide
molecular weight distribution.

4
CONCLUSION

Supercritical Fluid Chromatography has been shown to have good potential for
analyzing compounds that are very difficult, if not impossible, to measure by
conventional gas chromatographic methods. Process SFC is still a young and
growing technique. New applications are continuing to be developed. SFC is a
robust and easy to use form of chromatography that is ideally suited for Process
Analytical Chemistry, making it an ideal compliment to the Process GC.

REFERENCES

1. C.M. White, R.K. Houk, HRC &CC, Vol. 9, 1986, pp. 4-17.

2. P.A. Peaden, J.C.Fjeldsted, M.L. Lee, S.R. Springston, M. Novotny, Anal.

Chem. Vol. 54, 1982, pp. 1040-1093.

5
Figure 1. Phase Diagram for Carbon Dioxide

Figure 2. Schematic Diagram for a PSFC

6
Figure 3. Simulated Distillation Chromatogram of a Vacuum Gas Oil

7
Figure 4. Chromatogram of the analysis of Total Aromatics in Diesel Fuel

8
Figure 5. Chromatogram of the analysis of 1-butene in an alpha olefin stream

9
Figure 6. Chromatogram of a Dimethyl Silicone Sample

10