GC

Single Channel Analysis

of Refinery Gas:
Refinery Gas System A
Varian Application Note
Number 34

Mary Schumacher and Brian Thompson

Varian Chromatography Systems

Key Words: Refinery Gas, Unsaturated Hydrocarbons, Methanizer, PLOT Alumina Column

Introduction concentrations of hydrogen in helium carrier gas.

Refinery gas, sometimes called plant gas, is a
collection of various gas streams that are produced in
refinery processes. Refinery gas typically contains
significant amounts of unsaturated hydrocarbons, in
addition to saturated hydrocarbons, elemental and
inorganic gases.
This system for refinery gas analysis involves a
packed column configuration for the separation of H2,
O2, N2, CO2, CH4, and CO and a capillary PLOT
alumina column for the separation of hydrocarbons C1
to about C8. Hydrogen, oxygen, and nitrogen are
detected by thermal conductivity using argon as
carrier. Argon provides the best detectivity of
hydrogen, and its use avoids the complication of peak
reversal, observed when determining higher
Flame ionization detection is used for quantitation of
hydrocarbons and catalyzed carbon oxides (CO and
CO2; converted to methane by means of a nickel
catalyst or “methanizer”).
Experimental
The refinery gas analysis consists of two independent
separations, precisely timed by the use of a delay
column such that a single resultant chromatogram is
obtained. As illustrated in Figure 1, the 10 port valve
(V1) provides simultaneous sample injection into two
places: (1) the porous polymer column, in series with
the molecular sieve, and (2) the PLOT column via a
capillary injector.

Figure 1.
 Concurrently, sample is introduced into the capillary
PLOT column and with temperature programming, the
hydrocarbons C1-C6 are separated within 30 minutes.
Valves V2 and V3 are set up in a series/bypass
The elution of methane from the PLOT column is
configuration to achieve separation of the light gases.
delayed so that it does not interfere with the packed
Initially, the molecular sieve column is positioned in
column separation. The resultant single channel
series such that H2, O2, N2, CH4, and CO pass into it
chromatogram is shown in Figure 2.
and are separated, while CO 2 and heavier
hydrocarbons remain in the porous polymer.
Detector signal switching from the TCD to the FID is
programmed to occur after the elution of N2.
After the elution of H2, O2, and N2, V3 is switched to
bypass the molecular sieve, thus trapping the CH4
and CO. While these components are briefly held, Detector sensitivities down to sub-ppm levels can be
CO2 elutes from the porous polymer, bypassing the achieved for carbon gases, although minimum
molecular sieve. Finally, the molecular sieve is re- detectable quantities sometimes depend on the
positioned in series to allow CH4 and CO to elute, relative concentrations of other sample components.
while at the same time, V2 is switched to backflush
the porous polymer to vent. This backflush removes
For removing heavy material from the PLOT column
heavier hydrocarbons and sulfur compounds,
that may be present in the sample, an optional 4 port
preventing poisoning of the catalyst.
backflush valve may be ordered and configured into
the system.

Peak #TimeName 10.889Hydrogen

21.267Oxygen 31.702Nitrogen 42.532CO 2
53.482CH4 64.452CO 75.045Methane
85.663Ethane
96.326Ethene108.462Propane1111.965Cyclo
propane1214.773i-Butane1315.797n-
Butane1419.914t-Butene-21520.197Butene-
11620.981i-Butene1721.813c-Butene-
21824.551i-Pentane1925.435n-
Pentane2025.6271,3-Butadiene

Figure 2. Synthetic Mixture of Typical Refinery Gas Components

These data represent typical results.

For further information, contact your local Varian Sales Office.
GC34:0191