Acidic and basic contaminants in

amine treating
Ralph H Weiland and Nathan A Hatcher Optimized Gas Treating, Inc.

S
ources of heat stable salt (HSS) contami- contains only water, amines, and acid gases. In
nants in amine treating solutions are some cases, the solubility of light hydrocarbons
discussed and their effect on reaction equi- and inert gases may be taken into account. Until
libria in acid gas-amine systems is analysed. The recently, however, the process effect of organic
requirement of solution electro-neutrality is used and inorganic acids that enter amine solutions
to validate solution analyses. Case studies when tail gas from Claus sulphur plants is
demonstrate the important role of HSSs in treated, or which are almost universally encoun-
determining amine plant performance, that tered in oil refining operations, has been
simulations must incorporate ionic contami- ignored. These components are called heat stable
nants into their calculations, and the need to salts (HSS) or heat stable amine salts (HSAS). A
simulate the whole plant rather than isolated few are acids, both organic and inorganic, that
units. occur in treating solvents at a total concentra-
tion that does not typically exceed ten to fifteen
Introduction thousand parts per million by weight, and is
A common and proven way to remove the acidic often very much lower than this. Apart from
components CO2 and H2S from gas streams is by being blamed for corrosion problems, HSSs can
absorption into aqueous solutions containing have a profound effect on process performance.
one or more amines. Use of alkanolamines dates Ignoring them or misunderstanding their chem-
from the patent awarded to Bottoms in 1930. istry can lead to very bad processing decisions,
However, despite nearly 80 years of commercial to recommendations to make expensive equip-
use, further developments in amine treating ment changes that, in fact, make the process
continue to appear each year. Triethanolamine worse than ever, and to continuing to surround a
(TEA) was the first alkanolamine applied number of modern proprietary solvents with an
commercially but today it has been completely undeserved mystique. Indeed, HSSs are some-
supplanted by a large number of other amines times purposely added to an amine solvent to
used singly or in mixtures with other amines, boost the level of treating performance well
as well as with non-amine additives. Along beyond that attainable in a “clean” system. They
with these changes, our ability to simulate and can be both friend and foe — how to view them
predict the performance of amine treating and deal with them in a given circumstance
processes has increased enormously in recent depends on understanding the chemistry, vapour
years. liquid equilibrium constraints, and the mass
Commercial software packages for amine plant transfer rate processes taking place in absorp-
simulation use column models that range from tion and regeneration columns. Outside the
simple equilibrium stages, equilibrium stages laboratory, clean solvents exist in many plants
modified for reaction kinetics, equilibrium stages for only a short time immediately following
with computed stage efficiencies, right through initial system charging and startup. In real
to true mass and heat transfer rate models. processes, solutions are always contaminated to
However, regardless of the underlying principles some degree. The work reported here attempts
on which each one is based, simulations of to provide a scientific understanding of HSS
amine plants have traditionally assumed the chemistry and the effect of these components on
solvent to be perfectly clean, meaning that it the process.

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 Heat Stable Salt Process Chemistry tion by steam in the regenerator and it
Over time, solvents accumulate contaminants accumulates in the overhead condensing system.
primarily from the gases being treated or This leaves the protonated amine/HSS anion
through the use of makeup agents (water and pair in the amine solution. The reactions are:
amine) that are not completely pure.
Contaminants of interest here are frequently the RCN + 2 H2O →→ NH4+ + RCOO- (R=H, alkyl group) (1a)
anions of organic and inorganic acids, also called
heat stable salts (HSSs). Anions commonly NH4+ + R1R2R3N↔↔ R1R2R3NH+ + NH3 (1b)
found in amine solutions include thiosulphate,
2 HCN + O2 + 2 H2S + 2 R1R2R3N →→ 2 R1R2R3NH+ + 2 SCN- + 2 H2O (1c)
oxalate, sulphite, sulphate, glycolate, propionate,
acetate, thiocyanate, formate, and chloride,
which usually enter the solution as a result of Hydrogen from gasoline reformers can also
absorption from the gases or liquids being contain HCl which will react directly via acid-
treated. Contaminants may also be cationic such base neutralisation with the amine. Thus, for a
as alkali metal ions (sodium, potassium, calcium, strong acid HnX where X is an n-valent anion
and magnesium) that accumulate from makeup (Cl –, SO4=, etc.) the reaction with amine is
water hardness or through deliberate addition in
the form of hydroxides or carbonates to deproto- HnX + n R1R2R3N → n R1R2R3NH+ + X–n (2)
nate amine associated with HSAS anions. As
contaminants, all of these ions can have a Thiosulphates generally result from the reac-
profound effect, sometimes positive, frequently tion of dissolved oxygen with H2S or from SO2
negative, on amine treating unit performance. reaction with H2S in Claus tail gas units when no
Other HSS anions such as sulphate or phosphate HCN is present. Sulphates can either be formed
are purposely added to enhance H2S removal in from absorption of sulphuric acid or from
tail gas treating units (TGTUs), a practice that, further oxidation of thiosulphates. The reactions
with greater understanding of the basic science, are
is becoming increasingly common.
2 H2S + 2 O2 + 2 R1R2R3N →→ 2 R1R2R3NH+ + S2O3= + H2O (3a)
Sources of Heat Stable Salts
2 H2S + 4 SO2 + H2O + 6 R1R2R3N → 6 R1R2R3NH+ + 3 S2O3= (3b)
There are three major sources of acidic and basic
contaminants in most amine systems: cracking
S2O3= + 5/2 O2→ 2 SO4= (3c)
unit operations (refinery FCCs and Cokers for
example), oxidation products from Claus sulphur The third source of contaminants comes from
plants, and certain amine reclaiming practices deliberate or inadvertent introduction through
(see Hatcher et al., 2006). solvent reclaiming practices. With increasing
After a period of use, especially in treating time-on-stream, acidic contaminants continue to
sour gases generated from refinery cracking build until a point is reached where something
operations (Cokers, FCCs), trace amounts of acid must be done to recover the permanently
anion contaminants can build to significant neutralised, bound amine to restore free amine
levels in the solvent. The most commonly found circulation capacity or to prevent the amine unit
acid anions are formate and thiocyanate, which from self dissolving through corrosion. Some
result from the absorption of hydrogen cyanide. operators employ addition of a stronger base
Formate is formed by the hydrolysis of the (typically NaOH or KOH) to “neutralise” the
cyanide ion to ammonium formate, while thiocy- amine heat stable salt, that is, remove the proton
anate forms from dissolved oxygen reacting with from the protonated amine and “attach” the
H2S, followed by reaction of the oxysulphur anion to the alkali metal ion. This forms the
anion with cyanide ion. Higher molecular weight sodium or potassium salt of the HSS, i.e., NaX
organic acid anions come from the hydrolysis of or KX, and releases R1R2R3NH+ or R1R2NH2+
higher molecular weight nitrile compounds. back into the free amine forms R1R2R3N or
Ammonium ion produced by the hydrolysis reac- R1R2NH. Using NaOH as an example,
tion will yield an H+ to the amine; the resulting
ammonia molecule is then stripped from solu- NaOH + R1R2R3NHX → R1R2R3N + NaX + H2O (4a)

2 June 2014 www.digitalrefining.com/article/1000953

 However, unless carried out very precisely, R1R2R3N, CO2 and H2S dissociate and react with
neutralisation with strong bases can have disas- each other to form seven ions (eight when the
trous, unforeseen consequences. The danger lies amine is primary or secondary). For this
in the possibility of over neutralisation. If the perfectly clean amine solvent, reaction equilibria
solvent becomes over neutralised, the excess (5) through (10) are shifted towards reactants
caustic permanently binds H2S and CO2: (i.e., to the left) by increasing the temperature.
This thermal reversibility of the reactions is what
NaOH + H2S → Na+ HS– + H2O (4b) makes treating with amines economically feasi-
ble. But things can go awry when the gas
NaOH + CO2 → Na+HCO3– (4c) contains certain types of components, even in
trace amounts. This is especially the case when
The resulting elevated concentrations of HS– the amine is tertiary (typically methyldiethanola-
and HCO3– remain chemically bound in solution mine, MDEA) and selective treating is being
no matter how hard the solvent is stripped in the done to remove H2S from the gas but to leave as
regenerator, i.e. there is a permanent high lean much CO2 behind as possible.
loading. In some cases, an order-of-magnitude H2S absorption takes place primarily via reac-
increase in lean loading has been observed. As a tion (7), with reaction (8) being of little
result, the regenerated solvent has a much high- consequence in the operating pH range of most
er-than-expected residual acid gas loading which alkanolamine solutions. With tertiary amines,
cannot be reduced by the application of further CO2 absorption relies mostly on reaction (9).
heat, and it may become impossible to meet With primary and secondary amines at normal
treating requirements. loadings, however, reaction (11) dominates. The
Effect of HSSs on Chemical Reaction Equilibria important observation is that each reaction even
Clean solvents consist of water solutions of in uncontaminated solutions has protonated
one or more amines together with the acid gases amine, R1R2R3NH+, on its right hand side:
CO2 and H2S. A number of reaction equilibria
are set up, all involving ionic species, and all H2S + R1R2R3N ↔ R1R2R3NH+ + HS– (7)
depending on the presence of water. For a
system containing a single amine together with CO2 + R1R2R3N + H2O ↔ R1R2R3NH+ + HCO3– (9)
H2S and CO2 in aqueous solution, six equilib-
CO2 + 2 R1R2NH ↔ R1R2NH2+ + R1R2NCOO– (11)
rium ionic reactions occur:

H2O ↔ H+ + OH– (5) For a lean tertiary amine at regenerator

temperatures (i.e., towards the bottom of the
R1R2R3N + H2O ↔ R1R2R3NH+ + OH– (6) column and in the reboiler) the acid gas loadings
are intended to be quite low so the concentra-
H2S + R1R2R3N ↔ R1R2R3NH+ + HS– (7)
tions of HS–, HCO3– and R1R2NCOO– are small.
In a clean solvent, the concentration of
HS– + R1R2R3N ↔ R1R2R3NH+ + S= (8)
R1R2R3NH+ or R1R2NH2+ will be quite small, too.
However, when the solvent becomes increasingly
CO2 + R1R2R3N + H2O ↔ R1R2R3NH+ + HCO3– (9) contaminated with acid anions that are stronger
than HS- and HCO3–, the concentration of proto-
HCO3– + R1R2R3N ↔ R1R2R3NH+ +CO3= (10) nated amine (R1R2R3NH+ or R1R2NH2+) at the
regenerator’s lean end becomes greatly influ-
If the amine is primary (R2, R3 = H) or second- enced by the extent of contamination, as set by
ary (R3 = H), it is also capable of reaction with reactions (1), (2) and (3). Unlike the acid
CO2 to form the carbamate of the amine, with gas-amine reactions (5–11), reactions (1), (2) and
the overall reaction: (3) are not thermally reversible (thus the term
heat stable salt), so the HSSs permanently tie up
CO2 + 2 R1R2NH ↔ R1R2NCOO– + R1R2NH2+ (11) part of the amine as R1R2R3NH+ ion. The amine
is gradually converted to HSAS and becomes
Thus, the four molecular species H2O, inactivated. Of potentially greater concern than a

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 small loss of amine strength, is its effect on the dissociated state and cause the solution to have
ability to regenerate the rich solvent to satisfac- potentially high concentration of both ions. The
tory acid gas lean loadings (moles of acid gases net result can be failure to meet treated gas
per mole of total amine) and to use the regener- specifications by a wide margin which cannot be
ated solvent effectively in the absorber . overcome using more reboiler energy or
The higher protonated amine concentration increased solvent circulation rate because the
drives reactions (7), (9) and to a small extent bisulphide and bicarbonate ions are tightly tied
(11) more strongly to the left which is beneficial up with and stabilised by the sodium. Thus, the
to regeneration because it produces greater driv- excess sodium remains associated with HS– and
ing force for the reverse or decomposition HCO3– and the situation must remain that way
reaction. Thus, all other conditions being the until HSSs again build up to a level sufficient to
same, from a mass transfer and phase equilib- displace these ions fully and consume all the
rium viewpoint, solvent contaminated with excess caustic.
relatively strong-acid is always easier to regener- To understand and quantitatively simulate the
ate than a clean one simply because the chemical effect of HSSs and alkali metal ions on treating
equilibria are favourably shifted. From the performance, one must be able to model the
chemist’s viewpoint, there is a common ion regenerator with just as much confidence and
effect at work, in which seemingly small accuracy as the absorber — the regenerator sets
amounts of contamination drive the main lean solution quality, the main controlling factor
decomposition reactions further towards at the lean end of the absorber where treat itself
completion and result in a solvent that is is determined. It is equally crucial to account for
stripped to far lower residual concentrations of ionic contaminants and to use a comprehensive
the acid gases CO2 and H2S than could ever be solvent analysis in any accurate process assess-
achieved through using large numbers of contact ment. Before looking at specific examples of HSS
stages or very high energy inputs. contamination, it is worth pointing out the heat
There is a catch, however. The common ion stable salts are not always contaminants —
R1R2R3NH+ also displaces the reactions (7, 9, sometimes they are added on purpose.
and 11) towards the left under absorption condi- Dibble (1985), in a now expired U.S. patent,
tions. Again, all other conditions being the same proposed the use of certain mineral acids to
(same temperature, total amine concentration, promote the stripping of acid gases from amine
and acid gas loadings), a contaminated lean solutions. Included was phosphoric acid which is
solvent entering an absorber will always exert used as an additive to MDEA in some proprie-
greater acid gas partial pressures over it than a tary solvents for deeper removal of H2S,
clean one. Taken by itself, this means that acid especially from Claus sulphur plant tail gas.
contamination is always detrimental to absorp- Because of the low total gas pressure, the
tion. The outcome for the overall process, normally high CO2 to H2S ratios, and the desire
however, depends very much on the exact condi- to remove H2S to levels of a few parts per
tions of operation as to whether the benefit million, this is a difficult application for amine
provided to regeneration by the contaminant treating. Phosphate ions and sulphate ions as
outweighs its penalty to absorption. An assess- either the acids or their ammonium salts act in
ment of the potential benefit or penalty of HSSs the very same way as the HSSs already
to the process requires one to evaluate the entire discussed. If added as an ammonium salt, the
plant, not just an isolated contactor or regenera- proton of the ammonium ion transfers to the
tor. To do this assessment rigorously, a mass amine, and the released ammonia, being volatile,
transfer rate-based amine simulation tool is is removed from the amine unit via overhead
required, and the simulator must be capable of condenser reflux water blow down. The proto-
accounting correctly for ionic contaminants. nated amine acts to drive reactions (7) and (9)
Turning now to sodium contamination, the strongly to the left at low acid gas loadings just
equilibrium of reactions (3), (6), and (7) is as it does when HSSs are present accidentally as
driven to the left at conditions in the absorber contaminants.
despite the fact that HS– and HCO3– appear to be
bound with sodium. In fact, they are in the free, Validating Solution Analyses

4 June 2014 www.digitalrefining.com/article/1000953

In many cases, it has been our experience that of the lean H2S loading can disappear, only to
amine treating solutions are rigorously analysed reappear as thiosulphate. When common prac-
only when the treating unit itself has difficulty tice is to sample directly into an empty
meeting treating specifications, exhibits severe (air-filled) bottle, leave an air space for expan-
foaming, or begins to experience serious corro- sion at the top, then ship the sample (often with
sion. In the present context, the concern is vigorous agitation) for several days and analyse
solution degradation, typified by the need, for it in an air environment, the validity of most, if
example, to determine the appropriateness and not all, lean amine H2S loading analyses must be
likely outcome of solution reclaiming, i.e., of viewed with considerable scepticism.
removing the HSSs either by distillation or ion To analyse the data of Table 1, the raw analysis
exchange, or negating their effect through caus- in terms of weight percents is converted into
tic neutralisation. Accurate simulation is an mole fractions of each ionic species, then into
outstanding tool for answering reclaiming and mole fractions of actual charge. The total charge
contamination questions in terms of process is forced to zero by adjusting the charge concen-
performance, but unless the simulation is based tration of HS– ion shown in the last column to
on accurate solution analysis, its results can be the value 0.00407 mole fraction (the sign is
quite misleading. The accuracy of such an analy- associated with the charge). This indicates that
sis can be validated by checking whether it for electro neutrality the H2S mole fraction must
corresponds to an electrically neutral solution. be 0.00407 and the loading must actually be
Since electro neutrality involves all the ions, 0.0326 mol/mol (0.00407/0.12476) as opposed
including bisulphide, it can be used to assess the to the range 0.005 to 0.006 mol/mol reported
accuracy of lean solution acid gas loadings. The by the laboratory. An Excel spreadsheet for
following example is drawn from a refinery doing this type of calculation is freely available
treating operation in which the amine solution (Optimized Gas Treating, Inc., 2008).
was found contaminated not just with HSSs but
also with caustic soda that had accidentally Refinery Fuel Gas Treater with HSS
entered the amine circuit. Contaminated Solvent
An actual laboratory analysis is shown in the Refinery amine systems are notorious for solvent
first two columns of Table 1. The question is contamination by a variety of heat stable salts
whether the reported data are self consistent. and amine degradation products. If HSSs are not
Ions were measured directly by ion chromatog- properly considered during the design phase,
raphy so one has no option but to assume that and if they are not taken into account when
sodium and the HSS anions are correctly troubleshooting and analysing column and plant
reported. However, H2S is deter-
mined via potentiometric titration A Typical Solution Analysis
with silver nitrate or via starch
iodine titration. Since H2S is a vola- Amine wt% Weight Mole Mole
tile component in the sample, it Fraction Fraction Fraction
Species Species Charge
cannot be taken as a given that the Free 47.4 0.47400 0.12346
sample being analysed is unchanged Bound (MDEAH+) 0.5 0.00500 0.00130 0.00130
from the time of sampling. It does Total 47.9 0.47900 0.12476
not seem to be generally appreci- Ions ppmw
Sodium (Na+) 7717 0.00772 0.01042 0.01042
ated, for example, that great care Formate (HCOO–) 3812 0.00381 0.00263 –0.00263
must be taken in sampling, sample Acetate (CH3COO–) 3322 0.00332 0.00175 –0.00175
transportation to the laboratory, Chloride (Cl–) 27 0.00003 0.00002 –0.00002
and the analysis itself if reliable H2S Sulfate (SO 4
=
) 160 0.00016 0.00005 –0.00010
Thiosulphate (S2O3=) 5658 0.00566 0.00157 –0.00313
content in liquid amine samples is Thiocyanate (SCN–) 36 0.00004 0.00002 –0.00002
to be assured. Unless every precau- Other Components
tion is taken to exclude the samples Acid gas as HS– 0.005–0.006 loading 0.00433 0.00407 –0.00407
from contact with air during each Water 0.49593 0.85471
Total 1.00000 1.00000 0.00000
step along the way from sampling to
final analysis, as much as 80 to 90% Table 1

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 performance, quite erroneous conclusions can be 26 ppmv H2S, in very close agreement with
drawn and expensive changes to plant equip- simulation. The increased equilibrium acid gas
ment will be made with absolutely no benefit. partial pressures over the contaminated solution
The following example demonstrates the conse- are completely in line with expectations from
quences of ignoring the effect of HSSs on amine process chemistry and the common ion effect.
plant performance. After a solvent change from Failure to perform was the result of shifted
MEA to generic MDEA, a packed column that phase equilibrium caused by HSSs — it had
had been sweetening a 0.5% H2S fuel gas failed nothing to do with the column internals.
to achieve satisfactory treat. The solvent vendor However, it must be pointed out that for a real-
expected the column to be capable of reaching 2 istic analysis of the effect of HSSs on the
ppmv H2S in the treated gas but H2S leaks in the performance of this plant it is absolutely neces-
range from 20 to 30 ppmv were being measured sary to include the regenerator in the
regularly, with excursions as high as 80 ppmv. simulation.
A conventional commercial simulation tool Suffice it to say that if proper account of the
predicted that a treated gas containing 1 to 2 HSS effects had been taken in the first place, a
ppmv H2S should have been produced, in agree- costly and ineffective column internals change
ment with the solvent vendor’s expectations. The out would have been avoided, and action would
simulation basis was a clean solvent and simula- have focused instead on providing HSS removal
tions used measured acid gas loadings in the from the solvent. But to take the right steps, it is
lean solvent. The presence of HSSs was not necessary first to understand the chemistry of
considered, however, nor could this factor be the process. In the present case, the HSSs in the
accounted for by the simulators that were used. solvent were undesirable and their presence
Thinking that perhaps the residence time of meant the difference between meeting sulphur
liquid on the packing was too short to allow emissions standards and missing them by a wide
sufficient H2S absorption (despite the fact that margin. The ability to predict their effect
H2S reacts essentially instantaneously upon through truly rigorous simulation helps to avoid
absorption into alkaline solutions and that only design errors, indicates when reclaiming equip-
CO2 absorption with its slow reaction could ment should be included in the design, and helps
possibly be affected by contact time), a change of to make periodic reclaiming decisions as to
tower internals to trays was recommended and when, and how vigorously, to reclaim. As shown
the tower was revamped accordingly. The results in the next example, however, reclaiming can
were extremely disappointing performance was sometimes be done too aggressively, and it may
no better than with packing. result in the plant’s failure to meet treating spec-
If a complete change in the type of tower inter- ifications. In this case, the HSSs are actually
nals resulted in no significant change in overall beneficial to treating and removing them too
performance, obviously the problem was not one vigorously will significantly reduce treating
of mass transfer. The answer had to lie with the ability.
solvent. A detailed solvent analysis by the vendor
showed the solvent contained five different Effect of Reclaiming on a Tail Gas Treating Unit
HSSs, with the total salt level exceeding 2 wt% The refinery tail gas treating unit (TGTU) shown
on a total solution basis. The packed and trayed in Figure 1 is a conventional scheme using 34
versions of the contactor were simulated using wt% MDEA to treat tail gas from a Claus sulphur
the ProTreat simulator, with its mass and heat recovery unit (SRU). The tail gas is 1.7% H2S and
transfer rate-based column model, and its ability 3.4% CO2 and the contactor has 20-ft of
to account for the contaminated solvent analysis. FLEXIPAK 2Y structured packing to minimise
Using the measured solution lean loadings but pressure drop and maximise tower capacity.
without HSSs the simulations indicated 0.6 TGTUs are typically run on a separate solvent
ppmv H2S and 0.7 ppmv H2S for packing and circuit; however, this one was being run as part
trays, respectively. However, the corresponding of the refinery MDEA system. An analysis
simulations with HSSs gave 25 ppmv and 30 performed by the solvent vendor showed several
ppmv, respectively. A performance test on the heat stable salts (HSSs) present at the concen-
trayed column itself showed a treating level of trations shown in the figure, with total HSSs at

6 June 2014 www.digitalrefining.com/article/1000953

Figure 1 Tail Gas Treating Unit

0.8115 wt%. Perhaps surprisingly, the unit treat. This suggests that a serious additional
nevertheless was producing a vent gas with only contribution to the refinery’s allowable sulphur
3 ppmv H2S, a very low concentration for a emissions might result from reclaiming, even if
TGTU where 100 ppmv is much more the norm. done only moderately. Because of this, and the
The solvent is obviously quite contaminated and facts that treating performance was quite good,
plant operations personnel were considering the solution’s treating capacity (amine strength)
reclaiming. The question was asked: If we was also high, and corrosion was not an issue,
reclaim the solvent by removing HSSs, what will the decision was made not to reclaim.
be the impact, if any, on treating performance? CO2 slip is hardly affected by reclaiming, but
The right place to start answering this kind of reclaiming has a tremendous effect on the unit’s
question is a good, reliable simulation capable of H2S leak. Notice also that when the solvent
modelling the real equipment and the real, contains its full compliment of HSSs, lean load-
contaminated solvent. ings are reduced by a factor of 10 for CO2 and a
ProTreat was used to model the complete factor of 100 for H2S compared with the virgin
plant, including the regenerator with a known solvent. Apart from benchmarking the reliability
tray count, the detailed solution analysis (HSS of the simulator, a clean solvent, in a TGTU at
profile), and reboiler duty. The predicted treat of least, may not treat to nearly as low a residual
2.3 ppmv H2S was in good agreement with the H2S level as a contaminated solvent. Of course,
measured level of 3 ppmv H2S. this must be balanced in a practical sense with
If a model that did not account for HSSs had the corrosive effects of excessive levels of HSSs.
been used, the predicted treat would have been Perhaps it would be better in this case to avoid
over 44 ppmv, more than 10 times the observed HSS-induced corrosion by employing a dedi-
value. This change is in the completely opposite
direction to the first example where HSSs caused Effect of HSS Removal on TGTU Performance
a serious loss in performance. It should be
noted, however, that unlike the first example % HSS Lean CO2 Load Lean H2S Load H2S Leak CO2 Slip
where the lean solvent acid gas loadings were Removed (mol/mol) (mol/mol) (ppmv) (%)
0 0.000205 0.000071 2.3 66.05
taken as the measured values, here the entire 25 0.000320 0.000251 6.5 65.79
amine circuit, including the regenerator, is being 50 0.000544 0.000934 17.5 65.55
analysed so the lean solution loadings are also 75 0.001018 0.002790 34.5 65.33
being predicted. Table 2 shows the simulated 100 0.002044 0.006177 44.3 65.17
effect of various levels of HSS removal (degrees
of reclaiming) on lean solution quality and H2S Table 2

www.digitalrefining.com/article/1000953 June 2014 7

 cated amine circuit and using a few 1000s ppmw concentration in the solution), and not by lean
phosphate ion to improve solvent regeneration. loading. Thus, the effect on CO2 slip of even a
The processing effect of HSSs is really felt in the factor of 10 reduction in lean solvent CO2 load is
regenerator where much lower loadings can be negligible.
achieved when the solvent contains HSSs. With One factor that does not generally seem to be
an understanding of the effect of process chem- appreciated, is that using stripping promoters
istry on reaction equilibria, perhaps this is not such as phosphoric acid to reduce H2S leak is
so surprising. effective only if the contactor is lean-end pinched
At high acid gas loadings the impact of a small with respect to H2S. Whether a given column is
amount of additional protonation is completely or is not lean end pinched is unmistakably
negligible because the protonated amine concen- shown by mass transfer rate based simulation of
tration is already very high (small change to a the column. If the column is lean end pinched,
high concentration). But in the reboiler, for the concentration of H2S will remain small and
example, the H2S loading will be very small (if constant over several metres of packing or
low H2S leak is to be achieved from the TGTU), several trays at the top (lean end) of the column.
so even a small amount of additional protona- Reclaiming decisions should start with a good
tion is highly significant relative to the very low set of simulations generated using a process
concentration of protonated amine normally simulator that has high accuracy and reliability.
present. In fact, the additional protonation can Mass and heat transfer rate based simulations
be 10 to 100 times higher than what would meet this criterion. The simulator must also be
normally be found in a well-regenerated virgin able to model the actual system under study,
MDEA solution. The additional amine protona- especially the detailed solution chemistry and
tion caused by HSSs and purposefully added the mass transfer behaviour of the real column
acids displaces reaction equilibria strongly internals being used. Accurate regenerator
towards the formation of free, molecular H2S modelling is just as important as simulating the
capable of desorbing from the solution. absorber simply because the regenerator sets the
Additional (perhaps even artificially introduced) acid gas lean loadings and regeneration is where
protonation enhances solvent regeneration. HSSs and stripping promoters have their real
The higher H2S back-pressure caused by the effect.
increased protonation arising from HSSs,
however, affects absorption negatively. But, it Conclusions and Summary
turns out that in this particular case its benefi- Troubleshooting amine treating unit problems
cial effect on reducing the lean loading in the can often involve much more than simply plug-
regenerator far outweighs its negative effect on ging plant data into an amine plant simulation
back-pressures in the absorber. The result can model. In the first place, amine treating chemis-
easily be a factor of 10 or 20 lower H2S leak try is a rather complex system of ionic reactions,
when HSSs are present in small amounts. Of some thermally reversible, others not, with
course, caution is needed not to let HSSs build common ion effects and great potential for
up too high because they are corrosive. But inconsistencies in plant data. In addition, treat-
caution is also needed not to reclaim too aggres- ing is often done selectively and this requires the
sively or treat may be lost. Even if the corrosion treating operation to be analysed as a mass-
resulting from high HSS concentrations is unac- transfer-rate process—solely basing it on phase
ceptable and they must be removed, their equilibrium is completely inadequate to under-
beneficial effect can still be had by replacing standing the process and the problem. What is
them with a small amount of phosphoric acid. more, all too often an attempt is made to analyse
Simulation will reveal how much phosphoric only the operation of the absorber without
acid is enough, how much to reclaim (from a recognising that its performance hinges heavily
process standpoint) and what the outcome on on the quality of the lean amine being produced
treating unit process performance will be. by the regenerator. Thus, a first rate regenerator
The outlet CO2 concentration is controlled by model is just as important as a good absorber
the extreme slowness of the reaction between simulation.
CO2 and the amine (actually the low OH– ion Careful analysis of plant and laboratory meas-

8 June 2014 www.digitalrefining.com/article/1000953

urements can be complemented very effectively ses — without such a true mass-transfer-rate
by a simulation model capable of accounting for basis, the simulations would have been of little
all the details and applied to the solution of or no help. Furthermore, accurately simulating
treating plant operating problems. In both regeneration was critical to the successful simu-
examples, it is evident that the complete solution lation and analysis.
ion chemistry must be taken into account to
model treating accurately down to low H2S levels
at low lean loadings. Any solvent contaminants Literature Cited
must be included in simulations if these are to 1 Bottoms, R. R., U.S. Patent 1,783,901 (1930).
predict successfully and accurately the operation 2 Dibble, J. H., European Patent Publication Number 0134948,
Application Number 8417586.4, March 27, 1985.
of amine plants.
3 Hatcher, N. A., Keller, A. E., Weiland, R. H., Sivasubramanian,
Understanding the process chemistry is an
M. S., Proceedings of the 56th Laurence Reid Gas Conditioning
essential part of analysing and troubleshooting
Conference, Norman, Oklahoma, February, 2006.
amine plants, and using an amine simulator
capable of accounting for the effects of all the
factors, including detailed solution chemistry,
formed an integral part of the analyses. In the
final analysis, simulations that do not account LINKS
correctly for all the ionic species may give erro-
neous results that can lead to unnecessary and More articles from: Optimized Gas Treating
expensive changes to plant equipment and
solvents. Because the cases studied involved More articles from the following categories:
selective treating, the fact that the simulator was Gas Processing/Treatment
Mass Transfer & Separation
based on sound mass-transfer-rate principles
Process Modelling & Simulation
enabled the modelling to compliment the analy-

www.digitalrefining.com/article/1000953 June 2014 9