Hydrocarbon Processing - December 2022 - 44

Process Optimization
heavier sulfur compounds should end up
almost entirely in the gasoline stream.
In practice, contrary to the vapor pressure
expectations of very little mercaptan
partitioning into the propane stream,
more than 50%-60% of the R1
SH has
been measured there. COS indeed partitions
between the ethane/propane mix
and the propane stream.
Simulators also attempt to calculate
partitioning based on available property
data (critical properties, eccentric factors,
regressed VLE data, etc.), but even
with these data, simulators are challenged
to match one another in key component
partitioning predictions, perhaps because
not all property data are valid.
Presently, in-plant analysis with sulfurspecific
gas chromatograph testing capabilities
is the best way to understand the
partitioning of sulfur species and, ultimately,
the quantity of each component
in each hydrocarbon stream that must
eventually be removed by the amine soFIELD
TEST DATA
AND TRENDS
Gas compositions used to determine
the figures presented in the following section
come from samples collected on live
plant sites. All samples were collected in
sulfur-inert containersa,b
. Samples were
analyzed on proprietary gas chromatographsc
columnsd
(GCs)
equipped with proprietary
and flame photometric detectors
(FPD). The GCs were transported to
site and calibrated in-situ with a traceable
standard for all reported components.
COS. To render the trends more meaningful,
data points with very little COS
(< 4 ppm) were removed, as these are
more likely to be errors due to sampling
lution. Feed-stream sulfur speciation
and treated-stream sulfur speciation will
characterize the true performance of the
amine solvents in removing the various
extended sulfur species in the plant.
and analysis. Cases where the amine solvent
was significantly contaminated with
another amine were also not considered.
The data presented below come from
five refinery fuel gas absorbers operating
between 3.5 barg and 13 barg with
inlet COS concentrations ranging from
4 ppmv-336 ppmv.
The removal of COS in DEA was
trended against the following: absorber
operating pressure, lean loading, rich
loading, amine strength, amine temperature,
simulated absorber maximum bulge
temperature, inlet COS content and gasto-liquid
ratio. The removal of COS in
DEA appears to have a strong linear correlation
with the gas-to-liquid ratio, with
other parameters having less impact. This
is shown in FIG. 3.
For COS removal in MDEA, a linear
correlation was found between the simulated
temperature bulge in the absorber
column and COS removal (FIG. 4). The
data come from four refinery fuel gas absorbers,
two TGTUs and two natural gas
plant absorbers. The absorbers operated
between atmospheric and 29 barg pressure,
with the inlet COS ranging from
9 ppmv-522 ppmv. Absorber operating
pressure, lean loading, rich loading, amine
strength, lean amine temperature, inlet
COS content and gas-to-liquid ratio did
not show strong correlations (linear or
otherwise) with COS removal.
In TGTU absorbers, there is (generally)
no significant temperature bulge in
the absorber and amine flowrates are minimized
to reduce CO2
FIG. 3. COS removal in DEA vs. absorber V/L ratio for five absorbers.
absorption. Therefore,
other factors may dominate COS absorption
in TGTUs. Generally, not much
COS is removed in TGTU absorbers.
R1SH. For primary and secondary
FIG. 4. COS removal in MDEA vs. simulated absorber bulge temperature for eight absorbers.
44 DECEMBER 2022 | HydrocarbonProcessing.com
amines, there was a very rough correlation
between increased methyl mercaptan
removal efficiency and smaller gas-toliquid
ratios (FIG. 5). Note: These are live
plants and not controlled experimental
environments. This was further investigated
in a test run at Preemraff Lysekil
on the T2904 visbreaker fuel gas absorber-a
much stronger trend was observed,
shown in FIG. 6. The removal of up to 80%
of inlet mercaptan appears to be achievable
with generic primary and secondary
amines when low gas-to-liquid ratios are
used in the column.
This trend has also been observed in
deliterature.
A paper presented by Dow20
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Hydrocarbon Processing - December 2022

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Hydrocarbon Processing - December 2022 - 1
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Hydrocarbon Processing - December 2022 - 10A
Hydrocarbon Processing - December 2022 - 10B
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