Journal of Natural Gas Science and Engineering 17 (2014) 49e57

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Journal of Natural Gas Science and Engineering

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Foaming study combined with physical characterization of aqueous

MDEA gas sweetening solutions
Emad Alhseinat 1, Priyabrata Pal 1, Mohmmad Keewan 1, Fawzi Banat*
Department of Chemical Engineering, The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: This study has been carried out to investigate the foaming behavior of aqueous Methyldiethanolamine
Received 23 November 2013 (MDEA) in presence of different degradation products and other contaminants as additives. This foaming
Accepted 18 December 2013 study was combined with physical characterization of the tested solution to enhance the understanding
Available online 31 January 2014
of the foaming behavior. The foaming tendency of aqueous MDEA solution was reported in terms of foam
volume. Foam stability was reported on the basis of the time required for the last bubble to break. The
Keywords:
effect of degradation products and heavy and light dissolved organics on solution physical properties i.e.
Gas sweetening
density, surface tension and viscosity were studied. The addition of 2.5 wt% of propionic acid decreased
Foaming
Foam break time
the foam volume by about 4% and the foam stability by about 7.14%, while the heaver organic acids (C5eC7)
Parametric studies increased foaming. All organic acids increased the solution viscosity and density and decreased the solution
Foaming model surface tension by various extents. Formaldehyde increased the foaming tendency and enhanced the
stability of the foam on MDEA solution. Iron(II) sulfide increased the foaming tendency by about 39.7%,
although it decreased the foam stability by about 95.6%. The addition of both pentane and heptane
decreased the foaming tendency and stability of the 50 wt% MDEA solution. Finally, a mathematical model
was proposed to understand the parametric effects behind the foaming problem of aqueous MDEA solu-
tions and to facilitate the tracking of the sources of foaming and alleviate them or reduce their impact.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction there are a few studies considering systematic and quantitative

Foaming is one of the main operational problems facing the
alkanolamine-based absorption process. Indeed, foaming generally
leads to serious consequences such as loss of absorption capacity,
reduced mass transfer area and efficiency, and carryover of amine
solution to the downstream plant (Chen et al., 2011). Foaming can
be induced by various chemical contaminants including condensed
liquid hydrocarbon, fine particulates like iron sulfide, additives
containing surface active chemicals, and amine degradation prod-
ucts (AbdiMeisen, 2000; Al-Dhafeeri, 2007; Pauley, 1991; Pauley
et al., 1989; Spooner et al., 2006; Stewart and Lanning, 1994; Phul,
2001). The current operational practices regarding foaming prob-
lems concern more in solving the incidents of foaming rather than
develop a strategy to track the sources of foaming and alleviate
them or reduce their impact. Where in fact, the focus should be on
identifying the sources of foam and eliminate them rather than
trying to suppress the foam (Al-Dhafeeri, 2007). Unfortunately,
* Corresponding author. Tel.: þ971 2 6075099; fax: þ971 2 6075200.
E-mail address: fbanat@pi.ac.ae (F. Banat).
1
Tel.: þ971 2 6075099; fax: þ971 2 6075200.
investigation of foaming in amine solutions that can be found in
literature (Chen et al., 2011). Pauley et al. (Pauley, 1991; Pauley et al.,
1989) investigated the effect of hydrocarbon and organic acids on
the foaming tendency of monoethanolamine (MEA), methyl-
diethanolamine (MDEA), diethanolamine (DEA), and formulated
MDEA; they found that the investigated contaminants increase the
foaming tendency and foam stability of amine solutions to various
extents. McCarthy and Trebble (McCarthy and Trebble, 1996)
studied the foaming tendency of DEA solutions in the presence of
various contaminants such as carboxylic acids. Interestingly, they
found that only those carboxylic acids with more than five carbons
substantially enhanced the foaminess compared to a clean DEA
solution. Thitakamol and Veawab (Thitakamol and Veawab, 2008)
systematically investigated the effects of process parameters on
foaming behavior of MEA, MDEA, and 2-Amino-2-Methyl-Propanol
(AMP) and their mixtures. They identified and used ranges of so-
lution volume and gas flow rates for measuring the foaminess co-
efficient. They emphasize the finding that most clean amine
solutions did not foam, however, the degradation products or
corrosion inhibitors affect the foaming behavior of the solution.
Thitakamol and Veawab (Thitakamol and Veawab, 2009) developed
a foaming model to predict pneumatic steady-state foam heights

1875-5100/$ e see front matter Ó 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jngse.2013.12.004
50 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57
for the CO2 adsorption process using aqueous monoethanolamine
(MEA) solutions. Their model consists of an empirical correlation
for foam height prediction and a series of subroutine modules for
physical property estimation. Their simulation showed that the
predicted foam height is most sensitive to process parameters (i.e.
solution volume followed by solution temperature) and to physical
properties (i.e. liquid viscosity followed by liquid density and sur-
face tension). They concluded that foam height increases as the gas
flow rate, solution density and viscosity increase, and the surface
tension decrease. Thus, a proper characterization of the physical
properties variations as a result of solvent degradations or the
presence of contaminates is essential for initiate a reliable model
for foam behavior predication. Recently, Chen, Freeman et al. (Chen
et al., 2011) investigated the effect of amine concentration and
various additives, including electrolytes, liquid hydrocarbon, and
degradation products on foaming. In their paper both aqueous
piperazine (PZ) monoethanolamine (MEA) were studied. They
found that formaldehyde substantially increases foaming in PZ. PZ
foamed after 163 h of oxidative degradation, but this effect was
greatly mitigated with an oxidation inhibitor. They also found that
the tendency of PZ to foam was increased by 40% with the addition
of iron (II), but dissolved iron had no significant effect on MEA.
This investigation comes as a part of the ongoing project
studying the deterioration of solvent quality and foaming problems
in Habshan Gas Sweetening Unit (HGSU), GASCO, Abu Dhabi. In
Gasco Habshan approximately 50 wt% methyldiethanolamine
(MDEA) is used to remove H2S/CO2 from the feed gas. The major
degradation products and contaminates concentrations in HGSU
lean amine were determined as discussed before (Pal et al., 2013).
The main objective of this paper is to investigate the effect of each
degradation products and contaminates on the foaming behavior
and solution physical properties. This will enhance the under-
standing of the reasons behind the foaming problem and will
facilitate the tracking of the sources of foaming and alleviate them
or reduce their impact. This will help to reduce the high capital
losses occur annually due to foaming in amine systems.
2. Foaming theory
2.1. Foam mechanism
Foam is a system with cluster of gas bubbles being dispersed in a
liquid. To form foam, gas is purged into liquid through a diffuser or
an orifice. A bubble from the diffuser is lifted up through bulk liquid
by the buoyancy force (Fbuoy), which is a function of density dif-
ference between liquid and gas (r), bubble volume (Vbub), and
gravitational acceleration (g) as expressed below in Eq. (1).
Fbuoy ¼ rVbub g
The buoyancy force must overcome the hydrostatic force and
the surface force (Fsurf), which is produced by surface tension of
liquid solution (g) and capillary perimeter (l) as expressed in Eq. (2),
in order for the bubble to detach from the diffuser.
Fsurf ¼ gl
Once foams are formed in the system, they can undergo the
thinning process caused by drainage, foam coalescence, and foam
rupture. By nature, foams are subject to three main instabilities,
i.e. thinning, coalescence, and rupture. Such instabilities lead to a
decrease in their surface area and consequently surface free energy
(Thiele et al., 2003).
Foam tendency and stability are functions of process parameters
and solution physical properties. Solution viscosity, density, and
surface tension play a major role in foam tendency and stability
through acceleration and deceleration of liquid drainage from the
foam. In order to develop a foaming model for predicting foam
tendency and stability there is need to understand and address the
effect of degradation products and other contaminates on the
physical proprieties of the amine solution.
3. Experiments
3.1. Experimental setup
Foaming experiments were carried out using the pneumatic
method modified by (Thitakamol and Veawab, 2008) from the
standard ASTM D892 for foaming tests of lubricating oils (ASTM,
1999). As illustrated in Fig. 1, the experimental setup was
composed of a 500 ml graduated cylinder cell, a temperature bath, a
flow meter. Compressed and dry air was used as a dispersed gas
bubbles to the tested amine solution.
3.2. Experimental procedures and conditions
Prior to each experiment, a 100 ml of the tested solution was
placed into the test cell without mechanical shaking or stirring and
then left in a water bath with fixed temperature (25  C) for
approximately 20 min to reach thermal equilibrium. A gas diffuser
was inserted into the test cell and left for approximately 5 min to be
saturated with the test solution. Then air was introduced to the cell
at a fixed volumetric flow rate (3 L/minute). A stopwatch was used
to track duration of bubbling and breaking time. The test solution
was vigorously bubbled by air through the gas diffuser with a
blowing time of 20 min  5 s. The blowing time was first counted
when the first air bubble raised from the gas diffuser. The air was
eventually released to the atmosphere from the outlet of the test
cell.
During the blowing time, the foam volume above the gas
dispersion layer was recorded during 20 min. Prior to testing each
specific contaminates, 50 wt% MDEA (without any additive) was
run as a base line. The foaming tendency of MEDA was reported in
terms of foam volume. Foam stability was reported on the basis of
the time required for the last bubble to break after air flow was
discontinued.
The DMA 4500 M density meter manufactured and supplied by
Anton Paar was used to measure the samples density. The accuracy
of DMA 4500 M is up to 0.000005 g/cm3. Solutions viscosity was
measured by AVSÒ 470, viscosity measuring unit, manufactured
and supplied by Schott Instruments. The measuring accuracy of
AVSÒ 470 is 0.01%. The Digital Tensiometer K9 manufactured and
(1)
(2)
Fig. 1. Schematic diagram for foaming experimental setup.
 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57 51

Table 1
Effect of different additives on foaming behavior and physical properties for 50 wt% MDEA solution.

Sl. No. Name of the chemical (purity and Foam volume change Break time change Viscosity change Surface tension change Density change
concentration ranges) percentage percentage percentage percentage percentage

1. Formic acid, 85% (0.0e3) wt% 5.70% þ13.0% e e e

2. Acetic acid, 99% (0.0e3) wt% þ34.0% þ83.1% e e e
3. Propanoic acid, 99.5% (0.0e2.5) wt% 4.00% 7.14% þ11.4% 3.80% þ0.63%
4. Butanoic acid, 99.5% (0.0e2.5) wt% þ20.0% 7.14% þ12.0% 1.73% þ0.48%
5. Pentanoic acid, 99.5% (0.0e2.5) wt% þ130% þ42.9% þ10.7% 3.90% þ0.32%
6. Hexanoic acid, 99.5% (0.0e2.5) wt% þ340% þ221% þ14.4% 7.30% þ0.35%
7. Heptanoic acid, 99.5% (0.0e2.5) wt% þ300% 25% þ15.3% 10.0% þ0.41%
8. Dodecanoic acid, 99.5% (0.0e0.2) wt% þ50% þ180% e e e
9. Formaldehyde (0.0e2) wt% þ60.0% þ328% 11.8% 0.80% þ0.20%
10. Pentane, 99.49%, (0.0e2) wt% 46.3% 40% þ7.93% 1.04% þ0.14%
11. N-Heptane, 96% (0.0e2) wt% 89.3% 96.0% þ16.9% 1.70% þ0.23%
12. N-Octane, 99% (0.0e1) wt% 30.8% 66.7% e e e
13. Ferrous sulfate as Fe(II), 98% (0e6) wt% þ39.7% þ95.6% e e e
14. Iron sulphide FeS 98%, (0e0.235) wt% þ30% 53.6% þ29.1% 2.23% þ0.39%
15. Ferric chloride (Feþ3), 98% (0e5.6 wt%) 14.3% þ44% e e e

Fig. 2. (a and b): Effect of carboxylic acids (C3eC7) addition on foam volume of 50 wt%
MDEA solution. Fig. 3. (a and b): Effect of carboxylic acids (C3eC7) addition on foam break time of
50 wt% MDEA solution.
52 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57
Fig. 4. Effect of 2.5 wt% carboxylic acids (C3eC7) addition on foam volume and break
time of 50 wt% MDEA solution.
supplied by Kruss was used to measure the surface tensions of the
tested solutions. The resolution of the Digital Tensiometer K9 is
0.1 mN/m. Thus, the main source of error in this study was assumed
to be due to the experimental error in solutions preparation and
foam volume and breaking time measurements.
4. Results and discussion
This work sheds the light on the effect of different degradation
products and contaminates on aqueous 50 wt% methyldiethanol-
amine (MDEA) foaming behavior. To enhance the understanding of
the foaming behavior, physical characterization of the tested solu-
tions were carried out, as well.
Table 1 shows the degradation products and contaminants that
were used in this study and their effects on foam volume, foam
stability, solution viscosity, solution density and surface tension.
These degradation products and contaminants include; formic acid,
acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic
acid, heptanoic acid, dodecanoic acid, n-pentane, n-heptane, n-
octane, formaldehyde ferrous sulfate, ferrous sulfide and ferric
chloride. All results in Table 1 were calculated at the maximum
concentration of the additive that is shown in the same row in the
table at fixed temperature (25  C). In Table 1 the minus sign denotes
a decrease from the original value (for pure 50 wt% MDEA solution)
and the positive sign denotes an increase from the original value.
4.1. Carboxylic acids
The effect of acidic amine degradation products was evaluated
by adding a series of light and heavy organic acids (C3eC7) to 50 wt
Fig. 5. Effect of different organic acids addition on 50 wt% MDEA solution density.
Fig. 6. Effect of different organic acids addition on 50 wt% MDEA solution surface
tension.
% MDEA solutions. It was observed that light organic acids (C3 and
C4) do not appreciably affect the foam while the heaver organic
acids (C5eC7) enhance the foaming behavior by various degrees. As
can be seen in Fig. 2(a and b) for low heavy organic acids (C5eC7)
concentrations, less than 1 wt%, heptanoic acid (C7) increased the
foam volume more than hexanoic acid (C6) and pentanoic acid (C5).
However, once the concentration exceeded 1 wt% the effect of C7
on foam volume decreased. Fig. 3 (a and b) shows that the addition
of light organic acids (C3 and C4) decreased the foam stability while
the addition of heaver organic acids (C5eC7) increased the foam
stability.
Fig. 4 shows the effect of 2.5 wt% carboxylic acids (C3eC7)
addition on foam volume and break time of 50 wt% MDEA solution.
It can be noted from this figure that hexanoic acid (C6) has the
highest effect on solution foaming tendency and stability. While,
propanoic acid acted as a defoarmer by decreasing the foaming
tendency and stability.
Figs. 5e8 show the effect of organic acids addition on 50 wt%
MDEA solution density, surface tension and viscosity. As can be
seen form Fig. 5 all organic acids increase the solution density,
however, interestingly the light organic acids (propanoic acid (C3)
and butanoic acid (C4)) affected the solution density more than the
heaver organic acids. Also it can be noted that propanoic acid (C3)
increased the density more than butanoic acid (C4), while hepta-
noic acid (C7) increased the density more than hexanoic acid (C6)
and pentanoic acid (C5).
Fig. 7. Effect of different organic acids addition on 50 wt% MDEA solution viscosity.
 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57
Fig. 8. Effect of 2.5 wt% carboxylic acids (C3eC7) addition on 50 wt% MDEA solution
viscosity, surface tension and density.
Figs. 6 and 7 also show the different behavior between light
organic acids (C3eC4) and heavy organic acids (C5eC7). In Fig. 6
the addition of light organic acids (C3eC4) and heavy organic
acids (C5eC7) decreased the surface tension of the solution.
However, it can be noted in case of the heavy organic acids (C5eC7)
the surface tension of the solution decreased more as the number of
carbon atoms increase. While in case of light organic acids, the
surface tension of the solution increased more as the number of
carbon atoms increase. As can be seen from Fig. 7 for heavy organic
acids (C5eC7), the surface viscosity of the solution increased more
as the number of carbon atoms increase. While in case of light
organic acids (C3eC4), the viscosity of the solution decreased as the
number of carbon atoms increase. Fig. 8 shows that the effect of
organic acids addition was mainly on solution viscosity (increase)
and surface tension (decrease).
Also the effect of lighter organic acids (C1 and C2) on foaming
behavior of 50 wt% MDEA solution has been examined. Formic acid
(C1) decreased the foam volume by about 5.7% as formic acid wt%
increased to 3 wt%. While acetic acid (C2) increased the foam vol-
ume by about 34% as acetic acid wt% increased to 3 wt%. Both acids
(C1 and C2) were observed to increase the foam stability. Dodeca-
noic acid (C12) was used to study the effect of heaver organic acid
on foaming behavior of 50 wt% MDEA solution. It has been
observed that dodecanoic acid increased the foam volume by about
50% and the foam stability by about 1800%.
Fig. 9. Effect of formaldehyde addition on foam volume and break time.
53
Fig. 10. Effect of formaldehyde addition on 50 wt% MDEA solution surface tension and
density.
4.2. Oxidation products
Formaldehyde is believed to be one of the important products of
oxidation, and its effect on foaming needs to be studied more (Chen
et al., 2011). Formaldehyde was added to 50 wt% MDEA solution to
study its effect on foaming behavior and physical properties of the
solution.
As shown in Fig. 9 the foam volume increased with formalde-
hyde addition. With 2.5 wt% formaldehyde, the volume of the foam
reached 80 ml that is 30 ml increase from the initial (neat solution)
volume. Also the break time increase with the addition of formal-
dehyde, break time reached 120 s with the addition of 2.5 wt% of
formaldehyde; this is 4 times greater than the original neat solu-
tion. Thus, formaldehyde increased the foaming tendency and
enhanced the stability of the 50 wt% MDEA solution. As can be seen
from Figs. 10 and 11 the addition of formaldehyde affects the so-
lution density, viscosity and surface tension. Formaldehyde
increased the solution density and decreased the solution viscosity
and surface tension. Therefore, it is believed that increasing solu-
tion density and decreasing the surface tension by adding formal-
dehyde play a major role in increasing the foaming tendency and
stability of the solution, even though there was a decrease in so-
lution viscosity.
4.3. Iron sulfide
Iron sulfide is produced by the reaction of H2S in the feed gas
with iron found in the plant’s material of construction or iron ox-
ides brought in with the feed gas. Iron sulfide produced in this
Fig. 11. Effect of formaldehyde addition on 50 wt% MDEA solution viscosity.
54 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57
Fig. 12. Effect of FeS addition on foam volume and break time.
manner is extremely fine (Pauley et al., 1988). So it is necessary to
study the effect of FeS on Foaming. FeS was added to 50 wt% MDEA
solution. The amount of FeS was varied from 0 to 0.235 wt%. As can
be seen from Fig. 12, FeS increased the foaming tendency, although
it decreased the foam stability. Figs. 13 and 14 show that the
addition of FeS increased the solution viscosity and density but
decrease the solution surface tension. Thus, the increase of foaming
tendency of the 50 wt% MDEA solution can be related to the in-
crease of solution viscosity and density as a result of FeS addition.
Also the effect of dissolved ferrous or ferric ions on foaming
behavior of 50 wt% of MDEA solution has been examined. A solu-
tion of 0.1 M FeSO4 with 0.05 M H2SO4 was added to 50 wt% MDEA
solution. The amount of Fe2þ in the MDEA solution was varied from
0 to 2 mM. As shown in Table 1. Fe2þ, increased the foam volume by
about 39.7% as Fe2þ was increased to 2 mM. It was observed that
the 50 wt% MDEA solution turned from light yellow to dark yellow
as Feþ2 was gradually increased. It has been suggested by (Du et al.,
2003) and (Gonzenbach et al., 2006) that if particles have the cor-
rect range of surface energy, they could be favorably absorbed to
the interface and form closely packed layer, thus preventing or
reducing disproportionation and coalescence of bubbles (Chen
et al., 2011). It was thus suggested that the fine particles
composed of ferrous oxides or ferrous hydroxide in the 50 wt%
MDEA solution might contribute to the increase of foaming ten-
dency. Ferric chloride was also added to pure 50 wt% MDEA
Fig. 13. Effect of FeS addition on 50 wt% MDEA solution surface tension and density.
Fig. 14. Effect of FeS addition on 50 wt% MDEA solution viscosity.
solution to study the effect of ferric ion (Fe3þ) on foaming behavior
of the solution. It has been observed that the foam volume
decreased by about 14.2% once the added Fe3þ was 1 mM. The ferric
ion did not contribute to foam behavior like the ferrous ion did, that
is may be because the ferric ion has higher solubility in amine so-
lutions than ferrous ion and thus it did not form fine particles to
stabilize the foam.
4.4. Liquid hydrocarbon
Liquids hydrocarbon are important cause of foaming observed
in some plants (Al-Dhafeeri, 2007; Pauley et al., 1989; Abdi, 2001).
Pentane and N-Heptane were used in this study to examine the
effect of liquid hydrocarbon on foaming behavior and physical
properties of 50 wt% MDEA solution. As can be observed from
Fig. 15, the addition of both pentane and heptane decreased the
foaming tendency and stability of the 50 wt% MDEA solution. N-
Heptane seems to have more influence in team of defoaming than
Pentane; as the addition of 2 wt% of heptane almost eliminate the
foam. The reason behind this defoaming behavior is believed to be
due to the hydrocarbon droplets that were dispersed in the solu-
tion. The hydrocarbon droplets may enter liquid thin film, spread
on the gas-aqueous liquid interface and act as foam breaker as was
suggested by (Wasan et al., 1994). Even though, Figs. 16e19 show
that n-heptane and n-pentane has increased the solution viscosity
and density and reduced the solution surface tension which should
Fig. 15. Effect of liquid hydrocarbon addition on foam volume and break time of 50 wt
% MDEA.
 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57 55

Fig. 16. Effect of n-heptane addition on 50 wt% MDEA solution surface tension and
density. Fig. 18. Effect of pentane addition on 50 wt% MDEA solution surface tension and
density.

enhance the foaming behavior of the solution. Pentane and n-

heptane are expected to have very low solubility in the 50 wt% each layer of fluid i.e. viscosity of the solution and surface tension
MDEA solution. It is difficult to add a small quantity of pentane and force relates the surface tension of the solution. The ratio of two
n-heptane below their solubility limit which is still under our forces explains the dimensional numbers as:
investigation, so the starting wt% of both pentane and n-heptane
was 0.5 wt% and gradually increased to 2 wt% for n-heptane and
4.5 wt% for pentane, until the foam was almost eliminated.
Reynolds numberðReÞ gravitational force
Also the effect of longer liquids hydrocarbon (n-octane) on ¼ (3)
foaming behavior of 50 wt% MDEA solutions has been examined. n- Froude numberðFrÞ viscous force
Octane decreased the foam volume by about 30.8% and the foam
stability by about 66.7% as its wt% increased to 1.
viscous force
5. Foaming model ¼ Capilary numberðCaÞ (4)
Surface tension force
Several parameters (solution density, viscosity and surface Considering the above three forces a correlation was established
tension) have been recommended in the literature as having an (Pilon et al., 2001) to explain the foam height as follows:
influence on the foam thickness. The other parameters are: the
dimensions of the container, the initial liquid height or volume, the


n
type of gas injected and the solid particles may present in the so- H Re
lution. To explain the steady state foaming behavior three forces are Ca ¼ K (5)
r Fr
most importantly considered as: gravitational force, viscous force
and surface tension force. The gravitational force relates the density where K (109.85) and n (1.8) are constant parameters determined
of the solution mixture, viscous force is coming from the flowing of from experimental data (Thitakamol and Veawab, 2009). Eq. (5) can
be expressed in dimensional form as:

Fig. 17. Effect of n-heptane addition on 50 wt% MDEA solution viscosity. Fig. 19. Effect of pentane addition on 50 wt% MDEA solution viscosity.
56 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57

Table 2
Equivalent foam height and bubble radius of 50 wt% MDEA solution with different
additives.

Weight% Height, Height, Bubble radius,

mm (exp.) mm (theo.) mm

50% MDEA 0.0000 27.500 27.514 3.4800

Propanoic acid 0.5000 27.500 27.731 3.4800
1.5000 26.400 26.468 3.5600
2.5000 26.400 26.437 3.5400
Butanoic acid 0.5000 30.250 30.440 3.2600
1.5000 33.00 33.016 3.1300
2.5000 33.000 33.009 3.1200
Pentanoic acid 0.5000 31.350 31.448 3.2200
1.5000 35.750 35.861 2.9500
2.5000 60.500 60.604 2.1200
Hexanoic acid 0.5000 46.750 47.797 2.5200
1.5000 93.500 94.935 1.600
2.5000 121.00 122.57 1.3500
Heptanoic acid 0.5000 55.000 54.898 0.5460
1.5000 71.500 71.488 0.4450
2.5000 77.000 76.193 0.4250
Formaldehyde 1.5000 38.500 38.288 0.6580
2.5000 44.000 43.655 0.6000 Fig. 20. Comparison between experimental and predicted steady state foam thickness.
Pentane 2.0000 16.500 16.545 4.8000
4.5000 2.7500 2.7560 14.800 state foam thickness shows excellent agreement as can be observed
Heptane 1.0000 9.9000 9.9790 6.5500
2.0000 1.1000 1.1100 26.400
from Fig. 20.

6. Conclusion

In this study the effect of different degradation products and

! contaminates on the foaming behavior and physical properties of
g 3
H ¼ 109:85 ,6 ðm*jÞ0 , ,3
r1 ðDr*gÞ1
where, g is surface tension of the solution (N/m), m is viscosity of
the MDEA solution with additives (Kg/m sec), j is superficial gas
velocity (m/sec), r is bubble radius and g is acceleration due to
gravity (m/sec2). From the experimental studies it has been
observed that a wide range of density, viscosity and surface tension
was obtained.
The density difference between gas and liquid in this study is
mainly referred to liquid density due to smaller values of gas
density as compared to solution density. It has been observed from
Eq (6) that bubble radius is proportional to surface tension. It
suggests that if the surface tension decreases, the bubble radius
decreases and thus the ratio of surface tension to bubble radius
increases causing increase in foam thickness. The surface tension of
the contaminated MDEA decreases most of the time causes
reduction of interfacial energy and increases the foam stability and
foam thickness. However, as the viscosity of the contaminated
MDEA solution increases, the drainage of liquid in foam films and
the subsequent coalescence is retarded and stable lamellae and
allows foam to propagate to a greater extent (Ivanov and Dimitrov,
1988). Increase in ionic species with amine concentration might
also contribute to the stabilization of foam through electrostatic
repulsive forces (Exerowa and Kruglyakov, 1997). It was observed
from Table 2 that for some additives as the concentration of addi-
tives increases bubble radius decreases and thus the equivalent
amount of foam height increases. For the production of maximum
foam height, stable bubble is required with reasonable size and
thus hexanoic acid produces maximum foam height with inter-
mediate bubble radius. The straight chain hydrocarbons (n-pentane
and n-heptane) acts as a defoaming agent for 50 wt% MDEA solu-
tion and the results are in good agreement with the steady state
bubble radius. It was observed that as the concentration of the
hydrocarbon increases the bubble radius will increase causing
coalescence of the bubble. The experimental and calculated steady-
50 wt% MDEA solution have been examined. The light organic acids
(6)
(C3 and C4) found to act as a defoamer while the heaver organic
acids (C5eC7) enhance the foaming behavior. All organic acids in-
crease the solution density; however, interestingly the light organic
acids (propanoic acid (C3) and butanoic acid (C4)) affected the so-
lution density more than the heaver organic acids. Also it has been
noted that propanoic acid (C3) increased the density more than
butanoic acid (C4), while heptanoic acid (C7) increased the density
more than hexanoic acid (C6) and pentanoic acid (C5). Formalde-
hyde increased the foaming tendency and enhanced the stability of
the 50 wt% MDEA solution. With 2.5 wt% formaldehyde, the volume
of the foam reached 80 ml that is 30 ml increase from the initial
volume. Also the break time increase with the addition of formal-
dehyde, foam break time reached 120 s with the addition of 2.5 wt%
formaldehyde; this is 4 times greater than the original solution.
Formaldehyde also increased the solution density and decreased
the solution viscosity and surface tension. Ferrous sulfide increased
the foaming tendency, although it decreased the foam stability. It
increased the solution viscosity and density but decrease the so-
lution surface tension. It has been observed that the ferric ion did
not contribute to foam behavior like the ferrous ion and this may be
because the ferric ion has higher solubility in amine solutions than
ferrous ion and thus it did not form fine particles to stabilize the
foam. The addition of pentane and heptane decreased the foaming
tendency and stability of the 50 wt% MDEA solution. Finally, a
mathematical model was proposed to understand the parametric
effects behind the foaming problem of aqueous MDEA solutions
and predicted foaming and defoaming behavior of the contami-
nants in terms of bubble radius.
Acknowledgments
The authors are grateful to Gas Research Centre, The Petroleum
Institute, Abu Dhabi for funding the projects. Sincere thanks to The
Gasco, Habshan unit for their co-operation and support.
 E. Alhseinat et al. / Journal of Natural Gas Science and Engineering 17 (2014) 49e57 57

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