ptq&a
Q Our tail gas unit is performing below spec. We are
experiencing high levels of heat stable salts in the solvent. How
do we deal with this?
A Eric Roisin, Claus & TGT Catalysts Business Line Manager,
Axens, eric.roisin@axens.net
The presence of heat stable salts does affect the per-
formance of the amine solvent,1 consequently H2 S slip
from the absorber may increase dramatically. To bring
the H2 S slip back to acceptable levels, the amine sol-
vent needs to be restored back to pristine conditions,
either by a reclaiming process or by partial or full
replacement.
Reviewing the results of the amine analysis and
focusing on the main identified heat stable salts should
help in understanding the root cause of the problem.
Let us assume that the involved amine is used exclu-
sively to treat the outlet gas of the quench column
downstream the Claus tail gas hydrogenation reactor,
and that heat stable salts are mainly thiosulphates (but
may be also sulphites or sulphates). Such species are
likely formed because of the abnormal presence of SO2
in the feed gas to the absorber, assuming that there is no
possibility for oxygen to contaminate the amine.
SO2 should have reacted with hydrogen on the CoMo
catalyst. A breakthrough of SO2 from the reactor can
only result from three potential causes:
Hydrogen deficiency: each mole of SO2 feeding the
reactor requires 3 moles of H2 to be transformed into
H2S on the catalyst. Since the amount of SO2 in the
Claus tail gas does vary over time, so does the hydro-
gen requirement. In case hydrogen is missing, SO2
breaks through. In case no SO2 analyser is installed to
detect it, SO2 does have consequences for the opera-
tion of the quench column: drop of pH, higher caustic
consumption, corrosion of internals, filtration of solid
deposits.
As a safe operating guideline, Axens recommends
maintaining the hydrogen concentration measured at
the outlet of the quench column above 2.5 mol%. If the
measured hydrogen partial pressure is too low, some
designs include a trim line of hydrogen to adjust it.
Another possibility to mitigate the risk of lacking
hydrogen at the hydrogenation section is to operate the
Claus furnace slightly deficient in air (meaning less SO2
feeding the TGTU) by targeting an H2 S/SO2 ratio out
of the Claus section higher than 2 (typical target 4 to 6).
Refer to Figure 1.
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8 4.0
7 3.5
Excess hydrogen after
requirement, kmol/h
96.7%
Total reducing gas
6 3.0
quench, % wet
5 96.9%
2.5
4
97.0%
2.0
3 1.5
96.9%
2 1.0
96.6%
1 Gas requirement 0.5
Excess hydrogen 96.0%
0 0
3 2 1 0 1
Excess air at SRU tail gas, %
2 3
Figure 1 Effect of air demand on the reducing gas requirement
in a two-stage SRU tail gas, 70% H2S acid gas at SOR conditions,
97% recovery efficiency2
Poorly performing catalyst: the first indicator would
be the temperature profile across the bed since most
of the temperature rise should occur on the top sec-
tion of the fresh catalyst bed, moving down as the cat-
alyst ages or gets contaminated (usually by soot or
oxygen coming from the upstream reheater). There are
two types of hydrogenation catalysts: older genera-
tion which need to be operated at an inlet temperature
higher than 270C (520F), while some more recent
products can be operated colder, down to 200-240C
(390-460F) inlet.
In case the performances of the catalyst are suspected
to be insufficient, increasing the inlet temperature by
10-20C (20-35F) may solve the problem, if allowed by
the installed reheating equipment.
Catalyst bypass: a leaking feed effluent heat exchanger,
or a channel across the catalyst bed (rupture of cata-
lyst supporting grid, movement of catalyst in the reac-
tor due to inhomogeneous gas distribution, equipment
left inside the reactor during loading) would also result
in a fraction of the Claus tail gas feeding the quench
column.
References
1 Sivasubramanian R H, Weiland M S, Effect of Heat-Stable Salts on
Amine Absorber and Regenerator Performance, AIChE Meeting, Austin,
TX, USA, 7 Nov 2004.
2 Crevier P P, Roisin E, Klint B, Cundall M, An Assessment of Reducing
Gas Production and Demand in the SRU/RTGU - How much is enough
and what does the RGG contribute?, Laurance Reid Gas Conditioning
Conference, Norman, OK, USA, 21-24 Feb 2010.
PTQ Q4 2017 5