Improve amine unit efficiency by

optimizing operating conditions

10/1/2014
How can the efficiency of an amine gas sweetening unit be improved without additional
capital investment? Operation at optimum conditions is the first key to enhance the
performance of the unit, as revealed by a case study performed on a commercial gas
plant using a kinetics-based simulation analysis.

Lower amine temperature provides a significant reduction in solvent circulation rate,

steam consumption rate, pumping duty and dehydration unit load while posing no risk of
hydrocarbon condensation or hydrate formation. Also, higher amine strength is best
suited for the unit under study, as it results in potential savings of operating costs
without increasing the risks of corrosion and fouling.

In recent years, there has been emphasis on improving amine gas sweetening plant
efficiency due to the increased exploitation of highly sour gas fields. This triggers the
development of several optimization techniques to maintain the profitability of gas
plants. Schemes involving operational changes alone are most preferred, due to the
simplicity and flexibility in restoring plant operations and for the low retrofitting costs
attached to them.

To this end, a case study was performed for a commercial gas sweetening unit to
analyze the effect of various operating conditions on the plant efficiency. Operating data
for this unit was used to quantify the impact of tuning various process conditions and to
provide guidelines to achieve optimum operation of the amine sweetening unit.

Process simulation model

To investigate the effect of various process conditions, a process simulation model is

developed for a commercial amine sweetening unit. Table 1 provides the plant
operating data used to develop the simulation model.
The process simulation model developed using a commercial process simulator follows
an “ideal-stage” approach, coupled with kinetic modeling for CO2. With an ideal-stage
model, each stage is assumed to reach thermodynamic equilibrium, and a real column
is modeled by determining the number of ideal stages that yields the same performance
as the real column.

The kinetics model accounts for varying absorption rates of the relatively slow
absorption of CO2, which is kinetically limited. Residence time for this calculation is
computed based on column hardware and total number of trays. A customized Peng-
Robinson model is used as the thermodynamic method in this study. The simulation
model predictions are validated against plant operating data, as shown in Table 2.

Result and analysis

Optimum performance of the amine sweetening unit depends on proper tuning of the
operating conditions. These generally include feed gas pressure and temperature, lean
amine temperature and amine concentration. However, for the plant in this study, raw
natural gas is directly fed to an absorption column without being compressed or heated
within the battery limits of the amine sweetening unit. Therefore, the operator cannot
manipulate the feed gas pressure and temperature, as they are governed by the
upstream sections. The scope of this study focuses on the analysis of the effects of lean
amine temperature and amine concentration on the amine sweetening unit
performance.

Lean amine temperature. Lean solvent temperature has always been a point of
interest, as it is the only parameter available for controlling the absorber temperature.
Low operating temperatures are generally preferred for better performance of the
absorption column due to the increased acid gas absorption governed by vapor-liquid
equilibrium. However, there are also detrimental effects on the absorber operation
associated with low lean amine temperatures.

The optimum choice of lean amine temperature entering the absorber is not a
straightforward exercise, and it should be handled carefully to ensure the right balance
between maximum performance possible in terms of acid gas removal, and smooth
operation. To this end, a thorough quantitative investigation of the impact of varying
lean amine temperature on several operational parameters of the amine sweetening
unit is required. These operational conditions are:

 Sweet gas H2S content

 Sweet gas CO2 content
 Foaming due to hydrocarbon condensation
 Hydrate formation
 Lean solvent pumping duty
 Sweet gas water vapor content.

Analysis is performed using the process simulation model that is developed based on
the operating data of a commercially operating amine sweetening unit, as shown
in Table 1.
The table shows that the operating temperature of the lean amine is 63.3°C. The
sensitivity analysis was carried out by varying the lean amine temperature in the range
of 63.3°C to 47.3°C. The lower bound of this range is dictated by the gas feed
temperature, which is 42.3°C, as stated in Table 1.

The 5°C value is a difference that is widely recommended as a general rule for the gas
feed and lean amine temperatures.1 The impact of varying the lean amine temperature
in the range of 63.3°C to 47.3°C is detailed below for the abovementioned operation
parameters.

Effect on H2S and CO2 absorption. Low lean solvent temperature is generally sought in
gas sweetening plants due to its positive impact on H2S absorption driven by
equilibrium. However, MDEA solvents are known to react kinetically with CO 2, and any
lowering of the lean amine temperature should reduce the reaction rate constant,
thereby increasing the CO2 slip. For this reason, lowering the lean amine temperature
may be ruled out due to its undesirable effect on sweet gas CO2 content. Therefore, for
any change in lean amine temperature, the resulting additional CO2 slippage must not
cause the sweet gas CO2 content to exceed the plant’s product specifications. If this
cannot be ensured, it may cause significant reduction in the gas calorific value and/or
dry ice formation in the downstream units.

Fig. 1 shows the evolution of sweet gas H2S and CO2 contents as functions of lean
amine temperature. As expected, H2S absorption is favored with lower lean amine
temperature, while CO2 concentration in the sweet gas increases from 1.2% to 2%. The
sweet gas profile for the lowest lean amine temperature (47.4°C) considered in this
analysis is found to be compliant with the abovementioned plant requirements in terms
of acid gas contents, despite the additional CO2 slippage.

Fig. 1. Effect of lean solvent temperature on sweet gas H2S and CO2 contents.
Therefore, reducing the lean amine temperature does not make objectionable changes
in the sweet gas CO2. It is worth noting that a decrease in lean amine temperature
results in a decrease in sweet gas H2S content from 4.2 ppm to 2.8 ppm. However, this
decrease is not needed since the sweet gas H2S content is already below the plant
specification.

In the following analysis, while decreasing the amine lean temperature, the sweet gas
H2S content will be kept at 4.2 ppm by decreasing the energy requirement for stripping
and decreasing the amine circulation rate.

Effect on foaming and hydrate formation. Low column temperatures promote

undesired condensation of hydrocarbons. Indeed, accumulation of hydrocarbons in
amine solvent often results in foaming that leads to poor column operation and to total
shutdown, in some cases. Therefore, gas temperature must be sufficiently higher than
the hydrocarbon dewpoint to prevent the occurrence of foaming.
Another ill effect associated with column temperature, but less frequently encountered,
is hydrate formation, which can lead to catastrophic failure. Generally, hydrate formation
temperature is far below the operating temperature. However, for columns operating at
high pressures and low temperatures, hydrate formation temperature should be
monitored.

Hydrocarbon condensation temperature, hydrate formation temperature and gas

operating temperature are plotted against lean amine temperature for the amine unit
under study (Fig. 2). For the lowest lean amine temperature that can be considered, the
sweet gas temperature is 25°C higher than the hydrocarbon dewpoint, which eliminates
any possibility for the absorber to foam due to hydrocarbon condensation. Likewise,
hydrate formation is obviously not a possibility, since the hydrate formation temperature
is much lower than the hydrocarbon dewpoint.

Fig. 2. Effect of lean solvent temperature on foaming and hydrate formation.

Effect on lean solvent pumping duty. As the solvent viscosity increases with
decreasing temperature, pumping loads are expected to be higher at lower lean amine
temperatures. Therefore, pumping power must always be less than the available
pumping power in the plant.

Fig. 3 shows the total electric load for pumping the lean solvent from the regenerator to
the absorber. The pumping load is at its minima at the lowest lean amine temperature
(47.4°C), which seems counter-intuitive. This is, in fact, due to the reduction in solvent
circulation rate at a lower lean amine temperature, which is needed to meet the same
acid gas removal level (4.2 ppm of H2S).
 Fig. 3. Effect of lean solvent temperature on solvent pumping energy.
The reduction in amine circulation rate is more pronounced than the increase in solvent
viscosity, thereby reducing the net pumping duty. It can be concluded that lowering the
lean amine temperature will reduce the pumping cost, if the same sweet gas
specifications are to be achieved.

Effect on sweet gas water vapor content. It is well known that lower column
temperature causes higher water vapor condensation in the absorber. This can have a
potential benefit due to the reduced load on the dehydration unit downstream of the
sweetening unit. Fig. 4 shows that sweet gas water vapor content decreases
monotonically with lean amine temperature. As the lean amine temperature is
decreased from 63.3°C to 47.4°C, half of the water vapor that should be carried by the
sweet gas to the dehydration unit will condense and remain in the absorber. This results
in a significant reduction in the operating cost of the dehydration unit.

Fig. 4. Effect of lean solvent temperature on sweet gas water vapor.

Summary of potential savings. Analysis of the effect of lowering the lean amine
temperature on various operational parameters of the absorber results in potential
benefits without disturbing the smooth operation of the absorber. Therefore, lower lean
amine temperatures with a minimum of 47.3°C are recommended for the operation of
the amine sweetening unit being studied.

For this case, simulations have been performed and process optimization has been
carried out while maintaining the sweet gas H2S concentration at the same level as that
in the operating case. Also, simulations have been performed for the plant’s average
lean amine operating temperature to quantify the savings resulting from the proposed
case.

Table 3 presents a detailed quantitative summary of the major operational parameters

for both cases. Besides the benefits discussed in the preceding sections, a significant
reduction in steam consumption rate and solvent circulation rate can be observed for
the proposed case. This is attributed to the increased acid gas holding capacity, which
is due to the vapor-liquid equilibrium shift at low solvent temperatures. Also, the lean
solvent cooler load is expected to be higher in the proposed case, as the outlet lean
amine temperature is lower. However, this is outweighed by the lower solvent circulation
rate, resulting in a lower solvent cooler duty, as shown in Table 3.

Therefore, this study concludes that lower amine temperature (47.3°C) provides
significant reductions in solvent circulation rate, steam consumption rate, pumping duty
and dehydration unit load while posing no risk of hydrocarbon condensation or hydrate
formation.

Amine concentration. Amine concentration is of significant importance, primarily due

to its impact on the sweet gas profile, since the former dictates the number of amine
molecules that must be in contact with gas in the absorber. Industrial literature2, 3 has
documented that poor choice of amine concentration leads to corrosion and fouling.
Therefore, it is essential to maintain optimum amine strength to achieve a fine balance
of the aforementioned associated effects.

Lower amine concentrations are generally considered to be an industrial precaution

against corrosion. However, low amine concentrations, in combination with under-
circulation of amine, lead to higher rich acid gas loading, thereby causing severe
corrosion in the rich amine line.1 Also, low amine concentrations require a higher amine
circulation rate and/or a higher reboiler steam rate to achieve sweet gas specifications
in terms of acid gas removal.

On the other hand, higher amine concentrations often significantly minimize the
operating cost as an implication of lower amine circulation rate and steam rate.
However, higher amine concentrations promote corrosion rates on lean amine lines with
time, due to acid gas flashing and the formation of layers of FeS and FeCO 3.4 However,
this risk can be mitigated with proper selection of solvent circulation rate and steam
rate.

To summarize, the optimum choice of amine concentration can be made only through
an investigation of its effect on several parameters:

 Sweet gas H2S and CO2 concentrations

 Steam consumption rate
 Amine circulation rate
 Rich amine loading (corrosion on rich amine lines)
 Lean amine loading (corrosion on lean amine lines).

To this end, the impact of amine strength on the preceding parameters has been
analyzed through process simulations using different amine solvent concentrations:

 42% (present operating condition)

 45% (average lean amine strength in the plant)
 47.5%
 50% (plant design limit).

Simulations for the four cases were optimized to meet the operating value of sweet gas
H2S concentration (4.2 ppm) to provide a candid comparison of the remaining
parameters. Table 4 shows that sweet gas CO2 content is compliant with the
requirements of the plant’s downstream section in all three cases. Rich and lean amine
loadings are always less than the allowable limits (0.5 and 0.01, respectively1), which
guarantees corrosion-free operations. Also, it can be concluded from the results that
steam consumption and amine circulation rates significantly decrease as the amine
strength increases, with the lowest values for steam use and amine circulation rate
occurring at the highest amine strength (50%).
In summary, amine strength of 50% is best suited for the plant’s operating conditions,
as it results in potential savings of operating costs without increasing the risk of
corrosion and fouling.

Recommendations. Optimization of amine sweetening plants through operational

changes has been a point of discussion due to the easy adoptability of changes without
additional capital expense. This article investigated the impact on the plant performance
of tuning the lean amine temperature and amine strength. Process simulations of an
industrial gas sweetening unit are performed to analyze the possible benefits and
detrimental effects that prevail as the two operating conditions are adjusted.

Lean amine temperature lower than the present operating condition is proposed as an
optimum value based on simulation analysis. The proposed condition promotes H 2S
absorption with additional CO2 slippage, but within acceptable levels. This results in a
reduction in steam consumption rate and solvent circulation rate to achieve the same
sweet gas H2S specification.

Moreover, both the lean solvent pumping energy and the load on the dehydration unit
decrease due to the reduction in the solvent flowrate and the higher degree of water
vapor condensation in the absorber, respectively. The study also shows that the
proposed operating conditions do not increase foaming tendency and hydrate formation.

The design limit for amine strength is recommended as the optimum value for the amine
plant in this study. The process simulation model is optimized for this amine strength
while meeting the desired levels of acid gas absorption. The results show that
significant reductions in the steam consumption rate and the solvent circulation rate are
achieved without increasing the risk of corrosion for the rich and lean amine streams.