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The most commonly used technique to detect sulfur in
petroleum samples utilizes a Dry Colorimetric Detector ("tape"
technology) . The organically bound sulfur is first converted to H2S.
The H2S formed reacts with the moist paper tape
impregnated with lead acetate. An "electronic eye" detects the
change in color of the tape as H2S passes by the tape and
forms black lead acetate. The chemical reaction on the tape surface
is:
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H2O
Pb(OAc)2 + H2S
→ PbS +2HOAc
(colorless)
(colored)
* Pb(OAc)2
-------- Lead Acetate, a white salt
* H2S--------------- Hydrogen Sulfide, a gas
* PbS -------------- Lead Sulfide, a black precipitate |
The lead acetate detection method is the only
detection system that can determine H2S without any
interference. This fact is clearly stipulated in ASTM method. This
is an important feature in a detector when one is detecting very low
levels of sulfur in a complex hydrocarbon matrix.
There are two ways to convert organically bound sulfur to H2S.
The first technique is to use reductive pyrolysis. The organically
bound sulfur is mixed with excess of hydrogen and passed through a
high temperature ceramic tube held at 1200șC. The sulfur combines
with hydrogen to form H2S while the hydrocarbons are
reduced to methane gas. The lead acetate tape detects the H2S.
The second technique for this conversion requires, first, oxidative
pyrolysis, and then, reductive pyrolysis. This technique is used to
solve the coking problem. A sample containing sulfur compounds and
hydrocarbons is blended with air at 1200șC. The sulfur compounds are
oxidized to SO2 and SO3 and the hydrocarbons
to CO2 and H2O. In the second zone, a flow
stream of hydrogen then reduces the oxides of sulfur to H2S.
The water and carbon dioxide formed as by-products interfere with
the tape detector and must be removed.
Dry Colorimetric Detection technique's strength is that it is based
on simple chemistry, and there are no known interferences. Both
Chemiluminescence and Pulsed uV Fluorescence suffer interference
from hydrocarbons, requiring GC separations and/or an extremely
efficient high temperature reactor to make clean combustion. |