Journal of Natural Gas Science and Engineering 24 (2015) 124e131

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Journal of Natural Gas Science and Engineering

journal homepage: www.elsevier.com/locate/jngse

Role of aqueous methyldiethanolamine (MDEA) as solvent in natural

gas sweetening unit and process contaminants with probable reaction
pathway
Priyabrata Pal a, *, Ahmad AbuKashabeh a, b, Sameer Al-Asheh b, Fawzi Banat a
a
Department of Chemical Engineering, The Petroleum Institute, Abu Dhabi, United Arab Emirates
b
Department of Chemical Engineering, Jordan University of Science and Technology, Jordan

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

Article history: Aqueous methyldiethanolamine (MDEA) is used as a solvent in natural gas sweetening unit, whose
Received 16 December 2014 quality deteriorates while absorbing H2S/CO2 causing corrosion and foaming in the process. Total process
Received in revised form contaminants of lean MDEA obtained from GASCO Company (Habshan, Abu Dhabi) were determined
2 March 2015
using different instruments. The major hydrocarbons found in inlet natural gas was analyzed using gas
Accepted 5 March 2015
Available online 23 March 2015
chromatography mass spectrometry (GC-MS). Heat stable salt (HSS) anions and metal ions were detected
using ion chromatograph (IC) and inductively coupled plasma optical emission spectrometry (ICP-OES).
Liquid chromatography mass spectrometry (LC-MS) and direct sample analysis time of flight (AxION
Keywords:
Methyldiethanolamine
2TOF) analysis were carried out to determine and major organic degraded products present in lean
Natural gas sweetening MDEA solvent. The UVeVIS spectrophotometer also justified the presence of total organic acid anions.
Process contaminants Acetate and propionate were found to be present in higher amounts of 2806 and 1614 ppm, respectively.
Heat stable salts Substantial amount of metal ions were also detected using ICP-OES with maximum level of heavy metal
ions of lead and iron of 1.009 and 0.967 ppm, respectively. Large numbers of organic degraded products
such as diethanolamine followed by methylethanolamine, N,N-bis(2-hydroxyethyl) glycine (bicine) etc.
were identified using LC-MS and AxION 2TOF analyses; which are considered to be major organic
thermally degraded products. Thermal degradation experiment was compared with H2S and in presence
of both H2S/CO2 to obtain same compounds with varying concentration. On the basis of MDEA degra-
dation as reported by previous researchers and from the analyzed lean MDEA samples, probable reaction
pathways have been proposed.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction than CO2, as it does not form carbamate (Lepaumier et al.,

Methyldiethanolamine (MDEA) is a tertiary alkanolamine widely
used as absorbent in natural gas sweetening process for removal of
hydrogen sulfide (H2S) and carbon dioxide (CO2). Aqueous MDEA
solutions considered as a selective and efficient absorber for H2S
2009a,b,c,d; Blauwhoff et al., 1984; Klare et al., 2000; Shahi et al.,
1994; Saleem and Essa, 2010; Mazari et al., 2015).
Hydrogen sulfide (H2S) reacts directly with the MDEA to give an
amine salt (methyldiethanolamine sulphide) as per the following
reversible exothermic reaction:

This is a direct proton transfer instantaneous reaction in an

ionized medium. Its rate is very fast or infinite for all amines. To
* Corresponding author. achieve selective desulphurization of acid gas streams using MDEA,
E-mail address: ppriyabrata@pi.ac.ae (P. Pal). the gaseliquid contact time in the absorber should be such long

http://dx.doi.org/10.1016/j.jngse.2015.03.007
1875-5100/© 2015 Elsevier B.V. All rights reserved.
 P. Pal et al. / Journal of Natural Gas Science and Engineering 24 (2015) 124e131 125

that it removes H2S. However, CO2 reacts with water to produce the reaction pathway has been proposed.
carbonic acid which finally reacts with MDEA. Since the reaction of
MDEA with CO2 is slow, it hinders the absorption process. Thus,
2. Process contaminants
allowing H2S to be readily absorbed by MDEA solution and making
it selective for H2S removal (Younas and Banat, 2014). In the real gas
MDEA contaminants such as condensed hydrocarbons, organic
sweetening MDEA plant, natural gas containing hydrogen sulfide/
acid anions (in higher ppm level) as major degraded products,
carbon dioxide is dispersed in aqueous alkanolamine solution
metal ions (mostly ppb level) from process corrosion and erosion,
(45e50 weight % MDEA in GASCO Company, Habshan, Abu Dhabi)
water contaminants from make-up water such as inorganic anions
in tray tower to absorb the acid gases. In this process, stable bubbles
(in lower ppm level) and well-treating chemicals can be considered
are formed that build to a foam. The gas carries the foam overhead
as foaming constituents. Table 1 lists some typical foaming agents
due to high surface area to weight ratio for these stable bubbles.
and their sources.
Huge foaming occurs when this stable foam builds on one tray and
The acid reacts with amine to form an amine salts which cannot
move to the bottom of the next tray. This moves up the tower and
be regenerated in normal conditions. These are the heat-stable-
carries over into the downstream equipment. In this foam forma-
salts (HSS); which are considered as another major constituent of
tion, two parameters play major roles for its stability: a) a
foaming agents. Some of the HSS anionic species that can be found
contaminant as a foam initiator, and b) solids stabilizing the foam.
in amine systems (Verma and Verma, 2009) are nitrate (NO
3 ), ni-
Foaming in amine solutions occur principally because of certain
trite (NO
2
2
3

2 ), sulfate (SO4 ), sulfite (SO3 ), phosphate (PO4 ), thio-
contaminants such as amine degradation products including heat


sulfate (S2O2
3 ), thiocyanate (SCN ), formate (HCOO ), acetate
stable salts (HSS), corrosion inhibitors added to the solution, iron
(CH3COO
), oxalate (C2O2
4 ) etc. All inorganic anions mostly come
sulfide particles that get dislodged from the corroded pipe/vessel
from make-up water, corrosion inhibitors, sulfur species oxidation
surface, carboxylic acids, alcohols and hydrocarbons (Pauley, 1991;
product from sour gas and degradation products. Several factors
McCarty and Trebble, 1996; Yanicki and Trebble, 2006). It is well
need to be considered on studying formation of primary degrada-
known that foaming are the most severe operating problems in the
tion compounds like alcohols, aldehydes acids, ammonia and pri-
gas sweetening operation. Thus it can be interrelated in the sense
mary amines. Vevelstad et al. (2014) explained about different
that some of the MDEA degraded products are important contrib-
factors like oxygen availability, volatility of the degradation prod-
utors to the foaming problem (besides corrosion products, traces of
uct, the mechanisms of formation of the studied degradation
hydrocarbons, etc.) (Thitakmol and Veawab, 2008; Alhseinat et al.,
compound and their intermediates and volatility of intermediates
2014). Foaming studies were carried out by Alhseinat et al. (2014) to
which play a major role for the formation of primary degradation
understand the effect of foaming behavior (foam height and foam
products. Kadner and Rieder (1995) also studied the anions in ‘rich’,
break time) for different degradation products (organic acids
‘semi-lean’ and ‘lean’ MDEA solutions and reported similar ions as
(C3eC7), formaldehyde, ferrous sulfide and hydrocarbons)
mentioned by Verma and Verma (2009).
including solution physical properties (density, viscosity and sur-
An MDEA absorption plant aims to remove mostly H2S from sour
face tension) containing 50 wt% MDEA. It was observed that lighter
gas. The inlet sour gas composition mostly contains C1 and higher
organic acids (C3 and C4) acted as a defoamer while the heavier
hydrocarbons with acid gases. Thus, higher hydrocarbons soluble in
organic acids (C5eC7) enhance the foaming behavior. All organic
MDEA solvent are another class of contaminants.
acids increased the solution density; however, the light organic
Different degradation compounds from MDEA solvents were
acids (C3 and C4) affected the solution density more than the
detected by different researchers. The primary degradation prod-
heavier organic acids. Formaldehyde increased the foaming ten-
ucts in aqueous 7 molal methyldiethanolamine (MDEA) loaded to
dency and enhanced the stability of the 50 wt% MDEA solution. It
0.1 mol CO2/mol alkalinity and degraded in the integrated solvent
also increased the solution density and decreased the solution
degradation apparatus (ISDA) were diethanolamine (DEA), bicine
viscosity and surface tension. Ferrous sulfide increased the foaming
and formate (Closmann and Rochelle, 2011; Mazari et al., 2014).
tendency, although it decreased the foam stability. Finally, addition
Closmann (2011) reported thermal degraded products using 7
of hydrocarbons (pentane and heptane) decreased the foaming
molal MDEA solution as shown in Table 2.
tendency and increased foam stability. Thus, foaming studies could
The degradation of MDEA during carbon dioxide and carbonyl
correlate the foaming in absorption column as it creates flooding as
sulfide absorption was proposed by Islam et al. (2011). The pro-
well as loss of separation efficiency of acid gases. Corrosion by the
posed degraded organic compounds are ethylene glycol (C2H6O2),
dissolved acid gases at the high operating pressure in the absorp-
diethanolamine (C4H11NO2), triethanolamine (C6H15NO3) and
tion column and the moderately high temperature of the regener-
bis(hydroxyethyl) piperazine (C8H18N2O2). Further, diethanolamine
ation column contributes substantially to the foaming problem.
reacts with carbon dioxide to produce hydroxyethyloxazolidone
Addition of antifoam, generally silicone-based compound is the
(C5H9NO3), bis(hydroxyethyl) piperazine and tris(hydroxyethyl)
most common technique for solving such problem, although it is
ethylendiamine (C8H20N2O3). Again, Diethanolamine on reacting
expensive and keeps on accumulating in the liquid as correct
with carbonyl sulfide produces monoethanolamine (C2H7NO),
dosing is difficult to the system.
hydroxyethylimidazolidone (C5H10N2O2) and bis(hydroxyethyl)
The present study is an attempt to estimate the possible total
process contaminants present in industrial lean MDEA solvent and
compare the results with previous research work to understand Table 1
novelty of this work. The inlet gas was analyzed using gas chro- Typical source for foaming agents.
matography mass spectrometry (GC-MS) to determine the major
Contaminants Source
hydrocarbons present in natural gas. Ion chromatograph (IC),
Condensed hydrocarbons Rich natural gas
inductively coupled plasma optical emission spectrometry (ICP-
Organic acid anions Cracked hydrocarbon inlet gas
OES), liquid chromatography mass spectrometry (LC-MS) and Metal ions Process equipment corrosion and erosion
direct sample analysis time of flight (AxION 2TOF) analysis of lean Water contaminants Process water
MDEA solvents were carried out to determine heat stable salt (HSS) Iron sulfide solids Inlet gas from sour well formation
anions, metal ions and organic degraded products present in the Amine degradation products High reboiler temperature/oxygen
contamination
solvent, respectively. Finally, on the basis of degradation products
126 P. Pal et al. / Journal of Natural Gas Science and Engineering 24 (2015) 124e131

Table 2
Identified compounds from aqueous MDEA degradation (Closmann, 2011).

Name Formula Molecular structure

Formate HeCOOe

Acetate CH3eCOOe

Glycolate HOeCH2eCOOe

Oxalate OOCeCOOe

Monoethanolamine NH2eCH2eCH2eOH

N-Methylaminoethanol CH3eNHeCH2eCH2eOH

Diethanolamine NH(CH2eCH2eOH)2

Glycine H2NeCH2eCOOH

N,N-bis(2-hydroxyethyl) glycine (bicine) (CH2eCH2eOH)2NeCH2eCOOH

ethylenediamine (C6H16N2O2). Monoethanolamine is also absorbed
carbon dioxide to produce oxazolidone (C3H5NO2), hydrox-
yethylimidazolidone and bis(hydroxyethyl) ethylenediamine.
Chakma and Meisen (1988, 1997) used GC-MS to explain the
degraded products of 4.28 M MDEA solutions reacting with carbon
dioxide at a partial pressure of 2.59 MPa and operating temperature
of 180  C for 144 h. According to the authors, the degraded com-
pounds are as follows: methanol (MeOH), ethylene oxide (EO),
trimethylamine (TMA), N,N-dimethylethanamine (DMA), ethylene
glycol (EG), 2-(dimethylamino)ethanol (DMAE), 4-
methylmorpholine (MM), 1,4-dimethylpiperazine (DMP), N,N-bis-
(2-hydroxyethyl)piperazine (BHEP), 3-(hydroxyethyl)-2-
oxazolidone (HEOD), N,N,N-tris-(hydroxyethyl)ethylenediamine
(THEED) and few unknown degraded products.
Reza and Trejo (2006) studied the degradation of aqueous
alkanolamine blends and it was found that MDEA degraded more
slowly than both diethanolamine (DEA) and 1-amino-1-propanol
(AMP).
Bedell et al. (2011) reported disproportionation reactions of
quaternary amine in the thermal degradation (at 140  C) of meth-
yldiethanolamine, MDEA. They suggested the role of a quaternary
or a protonated amine intermediate as reactant. Proposed mecha-
nisms are presented (Fig. 1) to show the observed products.
It has been reported (Reza and Trejo, 2006) that thermal
degradation of MDEA occurs faster when partly loaded with the
acid gases. In lean MDEA solutions, small amounts of protonated
MDEA are always present. If the protonated MDEA can convert to a
quaternary (Fig. 1), larger amounts of quaternary could form in the
solution. This is consistent with the detection of mostly DMEA and
TEA along with DEA. Rochelle (2012) explained that tertiary amines
degrade by transalkylation and elimination. The transalkylation
takes place in presence of secondary N's in the parent molecule or
from other degradation mechanisms. Thus major thermal degra-
dation products of MDEA were found to be DEA, dimethylmonoe-
thanolamine (DMMEA), MEA and other related molecules. Voice
et al. (2013) used integrated solvent degradation apparatus (ISDA)
to determine the rate of degradation products and observed MDEA
did not oxidize in the absorber but oxidized in the stripper due to
reaction of dissolved oxygen and homolytic decomposition of
peroxides at high temperature.
In our previous research work (Pal et al., 2014) carried out
thermal degradation of 3.781 M fresh MDEA loaded with sour gas
(H2S 38 ppm and RSH 40 ppm) at different temperatures at high
pressure laboratory reactor and multiwave digester. Organic
degraded products like methylethanolamine, bicine, bis(hydrox-
yethyl) piperazine, N,N dimethylacetamide were detected using
GC-MS and DSA-TOF instruments. The formation of different frag-
mented organic degraded products (e.g., mass (m)/charge (z): 102,
88) were also observed. Heat stable salts such as formate, acetate
and glycolate were also found with considerable amounts in
degraded MDEA samples.
Other sources of process contaminates may represent corrosion
inhibitors added to the solution, iron sulfide particles that get
dislodged from the corroded pipe/vessel surface.
Metal ions are also one of the contaminants accumulated in
aqueous MDEA solvent (Pal and Banat, 2014). Due to the presence
of certain metal ions, absorption efficiency of aqueous MDEA so-
lution decreases. Most of the metal ions are accumulated due to
corrosion and erosion of the process equipment and some might be
accumulated from the addition of make-up water to maintain
 P. Pal et al. / Journal of Natural Gas Science and Engineering 24 (2015) 124e131 127

Fig. 1. Proposed mechanism for thermal disproportionation of protonated MDEA (Bedell et al., 2011).

MDEA concentration. spectrophotometer (Test kit 365). The other major inorganic
anionic contaminant present was sulfates. Barium chloride in
3. Materials and methods aqueous solution is a major reagent to detect sulfate ions as barium
sulfate which is sparingly soluble in water. The turbid solution was
3.1. Materials measured using Test kit 153. The minor contaminant, nitrate was
detected using Test Kit 339. 2, 6-dimethylphenol reacts with nitrate
Lean MDEA solvents were obtained from the GASCO Company ions containing sulfuric acid and phosphoric acid in solutions to
(Habshan, Abu Dhabi) containing 45 wt% methyldiethanolamine produce 4-nitro-2, 6-dimethylphenol which was detected by
(MDEA). ICP standard solutions were obtained from Perkin, Elmer. UVeVIS Spectrophotometer (Pal et al., 2013).

3.2. Instrumentation 3.3.3. Metal ions

The inlet and outlet gas compositions were measured using GC-
MS (GC-6890, Agilent U.S.A.). Organic acid anions and major inor-
ganic anions were detected using Dionex IC 5000 (Thermo Scien-
tific, U.S.A.) chromatographic systems. Heavy metal analysis was
carried out using inductively coupled plasma optical emission
spectrometry (ICP-OES, Optima 8000; Perkin Elmer). Total organic
acid anions, sulfates and nitrates were detected in UVeVIS spec-
trophotometer (DR5000, Hach Lange). The degraded products from
MDEA were detected using liquid chromatography mass spec-
trometry by QExactive mass spectrometer (Thermo Fischer Scien-
tific, Europe) and direct sample analysis time of flight (AxION 2TOF,
Perkin Elmer) instrument.
Metal ions were detected using ICP-OES. The argon and air flow
rates were adjusted to 12 L/min and 1.2 L/min, respectively. Two
multielement-ICP standard solutions were used for the calibration
curves. Yttrium solution of 1.0 ppm as an internal standard was
added to correct the physical interferences of organic solvent
(MDEA) and aqueous mixture of 2% nitric acid solution as blank,
standards and lean MDEA solvents (Pal and Banat, 2014).
3.3.4. Thermally degraded organic compounds
The degraded products of lean MDEA samples were detected
Table 3
Specific conditions for detection of organic acid and inorganic anions.

3.3. Methodology Parameter Organic acid Inorganic

Analytical column ICE AS1 AS11-HC

3.3.1. Organic acid anions and inorganic ions Guard column e AG11-HC
The specific conditions for detection of organic acid and major Eluent (mmol/l) Heptafluorobutyric acid Potassium hydroxide
Eluent flow rate (ml/min) 0.8 0.38
inorganic anions using the ion chromatography are given in Table 3.
Background signal (mS/cm) <115 <1.0
System pressure (psi) 940 <2400
3.3.2. Organic acid anions, sulfates and nitrates Detection Suppressed conductivity Suppressed
Organic acids react with di-hydroxyl compound in acidic con- conductivity
dition producing fatty acid esters. The esters are reduced by Fe3þ Suppressor AMMS ICE300 micro ASRS300 anion
membrane self-regenerating
salts to form a red colored complex which was detected by UVeVIS
128 P. Pal et al. / Journal of Natural Gas Science and Engineering 24 (2015) 124e131

Table 4 Table 6
HPLC and Mass Spectrometer conditions. Anions and metal ions detected using IC and ICP-OES.

HPLC conditions Mass spectrometer conditions Anions Concentration (ppm) Metal ions Concentration (ppm)

Solvent A: 5 mM ammonium Instrument: QExactive Formate 233.7 Chromium 0.479

formate and 0.1% formic Scan range 50e500 u Acetate 2806 Iron 0.967
acid in water Resolution: 70,000 FWHM Propionate 1614 Lead 1.009
Solvent B: acetonitrile Tune method e parameters: Butyrate 833.4 Arsenic 0.57
Column: Accucore HILIC, Electrospray positive and negative ion Valerate 262.9 Zinc 0.287
100  2.1 mm 2.6 mm Capillary temperature: 250  C Glycolate 315.5 Manganese 0.111
particle size Vaporizer temperature: 350  C Chloride 9.088 Molybdenum 0.133
Temperature: 40  C Sheath gas pressure: 50 psi Nitrate 0.358 Magnesium 0.075
Injection volume: 10 mL Auxiliary gas flow: 10 ml/min. Sulfate 97.87 Nickel 0.096
Spray voltage: 3750 V Bromide 6.293 Cadmium 0.048
Phosphate 9.32
Thiosulphate 65.92
Thiocyanate 0.944
using LC-MS analysis by QExactive mass spectrometer. The in-
strument is equipped with an accela 1250 UPLC pump and an accela
auto sampler. The QExactive is operated at 70,000 resolutions
GC-MS are shown in Table 5. It is evident from the inlet gas
(FWHM) in full scan mode. An HPLC separation using HILIC mode
composition that C4eC6 hydrocarbons are present in the inlet sour
was employed to separate the components. The sample was
gas and the outlet sweet gas contains lower amounts of higher
analyzed by electrospray ionization in both positive and negative
hydrocarbon. Some of the hydrocarbons may dissolve on MDEA
ion modes. The sample was diluted to 1000 folds and the final so-
solvent to get the following result.
lution was prepared in acetonitrile. The HPLC and mass spec-
trometer conditions are given in Table 4.
The degraded products were also analyzed using AxION 2TOF 4.2. Anions and metal ions in the lean MDEA
instrument (Pal et al., 2014). TOF connects with the AxION DSA
(direct sample analysis) for directly analyzing samples without Concentrations of organic acid anions were measured by Ion
sample preparation. In comparison with mass spectrometry de- chromatograph. Among all organic acid anions present in the lean
tector which analysis samples within 40e50 min DSA-TOF analyses MDEA solution, acetate was present in the highest amount fol-
samples within few seconds for thirteen samples directly. The DSA lowed by propionate, butyrate, glycolate, valerate and formate. This
ion generator is configured with a nebulizer, gas heater and was in accordance with the results obtained by Pal et al. (2013).
vaporizer, thermocouple and a corona discharge needle positioned High concentrations of organic acid anions can be clearly attributed
inside the ion gun exit aperture. Automated sample introduction to ‘oxidative degradation’ of MDEA due to presence of some
system was used for up to thirteen liquid samples and collections of amounts of oxygen in the process. Spectrophotometric measure-
mass spectral data were analyzed. Depending on the molecular ment of total organic acid content using Test kit 365 resulted in a
response, the following experimental conditions were confirmed value of 6065.3 ppm while that by using chromatographic tech-
for the DSA analysis: i) all the MDEA samples provided were diluted niques was found to be 6065.5 ppm. Hence total amount of organic
to 50 folds with methanol, ii) 10 ml pipetted onto a stainless mesh. acid content measured by UVeVIS spectrophotometer gave almost
DSA parameters: auxiliary gas; 70 psi, DSA heater temperature; the same results as measured using Ion-chromatograph technique.
350  C, drying gas flow rate; 3.0 L/min, corona needle voltage; Similarly, inorganic anions (i.e. chloride, nitrate, sulfate, bromide,
2800 V, drying gas temperature; 25  C. phosphate, thiosulfate and thiocyanate) were also detected in the
TOF parameters: pulse mode; positive, mass range; 50e500 m/z, lean MDEA samples. Species containing sulfur bearing components
capillary exit; 100 V, detector voltage; 5000 V. were present in the highest amounts, such as sulfate and thiosul-
fate; whereas other anions, such as chloride, phosphate, bromide,
4. Results and discussions thiocyanate and nitrate were present in smaller amounts. This is an
expected result due to the presence of H2S in the natural gas. The
4.1. Natural gas contaminants inorganic anions such as sulfates (97.70 ppm) and nitrates
(0.361 ppm) also gave almost same results as detected with the
The inlet and outlet gas compositions from GASCO Company spectrophotometer test kit.
(Habshan, Abu Dhabi) for different sampling days (D1 and D2) using Analysis of metal ions in the lean samples of MDEA was

Table 5
Inlet and outlet natural gas compositions of GASCO Company.

Components D1 D2

Inlet (mole %) Outlet (mole %) Inlet (mole %) Outlet (mole %)

CH4 83.5897 94.9249 72.3940 90.4093

C2H6 2.0596 2.0047 7.9472 6.5538
C3H8 0.9793 1.0164 5.1232 0.5283
Iso-C4H10 0.2334 0.2139 0.8206 0.0000
n-C4H10 0.4584 0.38 1.5229 0.0000
Iso-C5H12 0.1808 0.0991 0.3352 0.0000
n-C5H12 0.2081 0.0902 0.3376 0.0000
C6þ 0.4199 0.0456 0.2968 0.0000
CO2 6.3043 0.8057 5.2884 2.1444
N2 0.1303 0.1195 0.2845 0.2643
H2S 5.4363 e 5.6496 e
 P. Pal et al. / Journal of Natural Gas Science and Engineering 24 (2015) 124e131 129

performed using ICP-OES. All the ions with concentration in ppm
are shown in Table 6.
4.3. Organic degraded products
Approximately thirty seven compounds were detected upon
thermal degradation of lean MDEA using LC-MS analysis. Based
upon their accurate mass values and isotope pattern, empirical
formulae for some of these major compounds were represented in
Table 7.
The formation of ethyldiethanolamine, diethanolamine, trie-
thanolamine and methyltriethanolamine can be well explained
from the disproportionation reaction of protonated MDEA (Bedell
et al., 2011). Secondary degradation compounds like BHEP, HEMP,
THEED etc. are also formed from the primary degradation com-
pounds and the formation are dependent on both the reaction
chemistry of the secondary reactions and the formation of in-
termediates as explained by previous researcher (Chakma and
Miesen, 1997). Different organic compounds such as methyl-
ethanolamine, 1-amino-1,3-propandiol, ethoxy(2-hydroxy) ethane,
N-2-hyrdoxyethyl acetamide, ethyl amine, 2-hydroxy ethyl
formate, N,N-Bis(2-hydroxyethyl) glycine (bicine), N,N-dimethyl
ethanolamine, diglycolamine, NMEA formamide and DEA form-
amide were identified in lean MDEA samples. The chemistry of
oxidative degradation of MDEA is complex. Several degradation
compounds are possible and unknown degradation compounds
can still be present. Similar compounds like, diethanolamine
(C4H11NO2), methylethanolamine (C3H9NO), dimethylethanamide
(C4H9NO) etc. also detected using DSA-TOF instrument. From
degradation studies, following reaction pathway for MDEA
degradation (Fig. 2) for some of the products are proposed as:
4.4. Thermal degradation in presence of H2S/CO2
To compare the thermal degradation studies with H2S (Pal et al.,
2014) and in presence of H2S/CO2, MDEA solvents were thermally
degraded at a CO2 partial pressure of 0.0675 bars, H2S partial
pressure of 2.025 bars and a temperature of 120  C. In this thermal
degradation studies, formation rate of HSS for organic acids anions
was ranked as formate > acetate > glycolate and lactate mixture
whereas in presence of H2S, rate of formation was
glycolate > formate > acetate. Thus, HSS produced in presence or in
absence of CO2 were same with varying concentration. It was also
observed that similar organic degraded products like methyl-
ethanolamine, diethanolamine, bishydroxyethyl piperazine and
dimethylacetamide were obtained with increasing intensity.
5. Conclusions
In the present study, the composition of natural gas in natural
gas sweetening unit was determined by GC-MS. The quality of
aqueous MDEA used as solvent in this natural gas sweetening unit,
deteriorates while absorbing H2S/CO2 causing corrosion and
foaming in the process. Different types of organic and inorganic
species were found as contaminants in lean MDEA solvent. In
comparison to inorganic anion contaminants, organic heat stable
salts such as acetate (2806 ppm) and propionate (1614 ppm) were
present in much higher concentrations. The UVeVis spectropho-
tometer also confirmed the presence of these anions in almost the
same concentrations in lean MDEA solvent. Heavy metal ions such

Table 7
Organic degradation products as determined using LCMS.

Name; abbreviation Formula m/z Actual R.T. % Peak area

Methyldiethanolamine; MDEA 120.1019 6.28 84.094

Ethyldiethanolamine; EDEA 134.1174 6.86 2.614

Triethanolamine; TEA 150.1122 6.1 1.481

Diethanolamine; DEA 106.0864 6.22 0.892

Methylethanolamine; MMEA 76.0763 6.15 0.579

Methyltriethanolamine; MTEA 164.1279 7.21 1.566

N,N0 -bis(hydroxyethyl)piperazine; BHEP 175.1439 9.53 0.564

N(hydroxyethyl)methylpiperazine; HEMP 145.1333 10.3 0.573

Tris(hydroxyethyl)ethylenediamine; THEED 193.1543 12.04 0.301

130 P. Pal et al. / Journal of Natural Gas Science and Engineering 24 (2015) 124e131

Fig. 2. Predicted degradation reaction pathways of MDEA.

as lead (1.009 ppm) and iron (0.967 ppm) determined by ICP-OES
analysis were also found in substantial amounts in the lean
MDEA solvents of natural gas sweetening units obtained from
GASCO Company (Habshan, Abu Dhabi). Further, large numbers of
organic thermally degraded products such as diethanolamine fol-
lowed by methylethanolamine were identified using LC-MS and
AxION TOF analysis. These organic thermally degraded products
generated in lean MDEA samples of gas sweetening unit are
considered to be another of its major contaminants. Thermal
degradation experiment was compared with H2S and in presence of
both H2S/CO2 to obtain similar compounds with varying concen-
tration. Hence on the basis of all the above studies, especially the
generated degradation products and extensive literature survey,
probable reaction pathways have been proposed.
Acknowledgment
The authors are grateful to the Petroleum Institute Gas Pro-
cessing and Materials Science Research Center, Abu Dhabi for
Funding the Project (GRC 006). Sincere thanks to GASCO Company
(Habshan, Abu Dhabi) for their co-operation and support. Special
thanks to Eirik F. da Silva (SINTEF Materials and Chemistry, N-7465
Trondheim, Norway) for his valuable comments during manuscript
preparation.
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