International Journal of the Physical Sciences Vol. 6(25), pp.

5877-5890, 23 October, 2011

Available online at http://www.academicjournals.org/IJPS
DOI: 10.5897/IJPS11.237
ISSN 1992 - 1950 ©2011 Academic Journals

Review

Degradation studies of amines and alkanolamines

during sour gas treatment process
M. S. Islam1, R. Yusoff1, B. S. Ali1*, M. N. Islam2 and M. H. Chakrabarti1
1
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia.
2
Department of Chemistry, Faculty of Engineering, Bangladesh University of Engineering and Technology (BUET),
Dhaka-1000, Bangladesh.

Accepted 5 August, 2011

Aqueous solutions of alkanolamines are widely used for the removal of acidic gases such as H2S, CO2,
COS and CS2 in the sour gas treatment process. In spite of the resistance of alkanolamines to chemical
breakdown, plant and laboratory reports indicate that, on prolonged use, alkanolamines may be
transformed into undesirable products from which the amines are not easily recovered. This
phenomenon, commonly referred to as ‘amine degradation’, not only leads to amine losses, but may
also contribute to operational problems such as foaming, corrosion, high solution viscosity and fouling
as a result of decreasing the plant life. Amine based gas purification plants having absorption and
stripping system, solvents are degraded at these two units mainly by oxidative degradation at absorber
condition and thermal degradation at stripper condition. Identification of amine degradation routes,
remediation of degradation, types of degradation products and studies on degradation reaction
mechanism becomes essential for successful plant operation. Gas chromatography-mass spectrometry
(GC-MS), ion chromatograph (IC), high performance liquid chromatography (HPLC), nuclear magnetic
resonance spectroscopy (NMR) and Fourier transform infrared absorption spectrometry (FT-IR) are
extensively used to identify the various degradation products. A comprehensive review of the latest
research activities on alkanolamines degradation, best method for identification, various properties of
degradation products and their classification is presented in this paper. This study would help to
develop better understanding of amine degradation.

Key words: Degradation, alkanolamines, absorption, stripping, sour gas.

INTRODUCTION

Natural and refinery gases typically contain acid gases in The toxicity of H2S, and the lack of heating value of
concentrations ranging from a few parts per million to CO2, NG or LPG must be purified prior to liquification and
tens of volume percent. The major acid gases are use, because of the corrosivity of acidic gases in the
hydrogen sulfide (H2S) and carbon dioxide (CO2). presence of water. Amines and alkanolamines are widely
used in natural gas refining for the sweetening of sour
gas by removing CO2 and H2S. In the amine based
purification plant alkanolamines of primary significance
*Corresponding author. E-mail: [email protected]. include monoethanolamine (MEA), diethanolamine
[email protected]. Tel: +603-79676896. Fax: +603-7967 (DEA), methyldiethanolamine (MDEA), di-2-
5319. propanolamine (DIPA) and diglycolamine (DGA). For the
5878 Int. J. Phys. Sci.

last two decades the sterically hindered amine such as degradation products and methodology of DGP
AMP (2-amino-2-methyl-1-propanol) has been suggested identification is very important for a better understanding
as an attractive solvent for the removal of acid gases. of amine and alkanolamine based absorption and
The advantages of AMP include high equilibrium loading stripping systems.
capacity (Davis and Gary Rochelle, 2009). Aqueous The main objectives of this review work are to
MDEA solution is used as a solvent for selectively represent the basic degradation study of MEA, DEA,
absorbing H2S (Lepaumiera et al., 2009; Blauwhoff et al., MDEA and PZ with possible degradation pathways.
1984; Closmann, 2009; Klare et al., 2000; Shahi et al., Additionally this work also explains the major cause and
1994; Lepaumier et al., 2009a; Saleem and Essa, 2010). effect of degradation products.
However, in removing acid gases with alkanolamines and
regenerating them, undesirable compounds are likely to
be produced by the irreversible transformation of AMINE BASED ABSORPTION AND STRIPPING
alkanolamines, which is called degradation. SYSTEM
Degradation causes a loss of alkanolamine, and it may
also contribute to operational problems such as foaming, For over seventy years, the alkanolamine process has
corrosion and fouling. While some loss is expected in all been considered the best approach in removing H2S and
operations, extreme losses can negatively impact CO2 for the purpose of purification and separation. It is
economics of operating any amine unit. Degraded DEA based on the reaction between weak acid (H2S and/or
solutions usually contain hydroxyethyl oxazolidone CO2) and weak base (alkanolamines) to give a water
(HEOD) bis (hydroxyethy) piperazine (BHEP) and tris- soluble amine acid gas salt. An amine based natural gas
(hydroxyethyl) ethtlendiamine (THEED), together with low sweetening plant was configured with absorber and
concentrations of various higher boiling compounds regenerator. The temperature range is 40 to 60°C and
(Dawodu and Meisen, 1996, 1993; Shahi et al., 1994; 100 to 120°C at the absorber and the stripper,
Choy and Meisen, 1980; Dawodu and Meisen, 1991; respectively. The sweet gas obtained from the absorber
Dawodu and Axel Meisen, 1994). The degraded solution alternatively exhausts sour gas components at the
of MDEA or MDEA/PZ contains EG, DEA, TEA, DMAE, stripper. Figure 1 represents a sweetening process of
HMP, BHEP, MP and DMP (Lepaumier et al., 2009a; sour gas.
Lepaumier et al., 2009c, b; Oh et al., 2003; Amiri et al., Mainly, amine solvents are used as absorbents in the
2007; Carlson et al., 2001; Haws and Jenkins, 2000). absorber for sweetening natural gas and for prolong use
Literature cited sufficient information on MEA degradation of this solvent that is transferred to the stripper by means
products including volatile and solid substances. It of regenerating absorbed gases. Absorption and
contains more than 15 different degradation products desorption are the common process in these two units
identified by many researchers (Strazisar et al., 2003; occurring continuously during the circulation of amine
Supap et al., 2006; Lepaumier et al., 2009c, b; Sexton solvent. Natural gas containing several acidic oxides is
and Rochelle, 2009; Davis, 2009; Sexton and Rochelle, very harmful for environment and plant operation and for
2010; Strazisar et al., 2010; Haws, 2010). Haws (2010) this reason, these are removed prior to use. Sour gases
noted that the degraded solution of DGA contains react with amine solvent during absorption-desorption
BHEEU and BHEETU, DIPA contains HMPO. In addition cycles gradually at higher and lower temperature and
to these impurities, resulting from acid gas induced amine some of these reactions are given on how the DGP is
degradation, industrial amine solutions frequently contain formed as follows (Haws, 2010):
other contaminants such as suspended solids, dissolved
hydrocarbons, sodium and chloride ions, iron sulfide,
HO-C2H4NH2 + HCl HO-C2H4NH3+Cl− ......................................1
foam suppressants, corrosion inhibitors and heat stable
salts. The accumulation of contaminants in amine DEA HSS
solutions creates major operational problems including
degradation (Lepaumier et al., 2009a), foaming HO-C2H4NH2 + H2S HO-C2H4NH3+HS− .....................................2
(Thitakamol et al., 2009; Pauley and Reza Hashemi, HSS
DEA
1998; Amiri et al., 2007), fouling (Axel Meisen and Abdi,
2010), corrosion (Dawodu and Meisen, 1996), a
reduction in active amine content also causes an The degradation reactions 3 to 11 showed formation of
increase in solution viscosity. The chemical and physical various degradation products of most common industri-
nature of the contaminants makes the development of ally used alkanolamine with acid gas components. The
purification schemes inherently difficult. In this regards, degradation reaction 7 also showed that DEA degraded
an overview of the degradation process of amines into MEA and on the other hand MDEA was degraded to
solvents, degradation reaction mechanism, impact of EG, DEA and TEA (reaction 8). Low molecular weight
 Islam et al. 5879

Sweet Gas C1-C 4 Acidic Gases

H2S, CO2

Lean Amine

Regenerator
Absorber
Sour Gas Components
CH4, C2H6,C3H8,C 4H10
C5H12, H2O,H2S,C0,C02
N2,H2,O2 Cooler
∑
∑ Heat Exchenger
Rich Amine

Amines/Alkanolamines + Sour Gas Swwet Gas

Natural Gas Components: Absorber Chemicals:

CH4, C2H6, C3H8, C4H10, CO Amines/Alkanolamines, Water Sweet Gas + DGP
C5H12, CO2, N2, H2, H2S, O2, ∆
H2O
DGP= Degradation Products; ∆= Absorber/ Stripper Temperature
Figure 1. Sour gas sweetening process.

amine MEA is not degraded into amine but it directly articles have been published in the field of degradation in
forms DGP like OZD, HEI and HEED (Reaction 4). So, the last three decades. The prevention of amine loss,
the higher molecular weight amines are degraded into amine degradation is one of the conditions for successful
low molecular weight amines but low molecular weight plant operation and also the key to economic benefits.
amines are not. This phenomenon of producing amines Hence, it is very important to identify the route of amine
most probably accelerates the absorption process. For degradation.
this reason, recently, many researchers (Lepaumier et
al., 2009c, b) recommended higher molar mass amines
like MDEA, DIPA and AMP in sour gas sweetening CHEMISTRY OF AMINE DEGRADATION
process for its high resistance to degradation and good
absorption capacity. The basic chemistry of degradation of alkanolamine is
explained in the open literature (Wenten, 2010) and these
R-NH2 + O2 CnH2n+1−COOH / Imidazolidone ...... are given as follows. In the following chemical reaction, it
.3
OZD, HEI, HEED ...............................4 is clear that amines occur due to the protonation and
MEA + CO2
DEA Urea .............................................5 carbamate formation reaction brought about by the
MEA + COS
hydrolysis of water and acids.
DEA + CO2 HEOD, BHEEP, THEED ......................6
DEA + COS MEA, HEI, BHEED .............................7
H2 O H+ + OH− ..........................................................12
MDEA + CO2 EG, HMP, DEA, TEA, BHEP ...............8 H+ + HS− ........................................................13
BHEEU .................................................9
H2 S
DGA + CO2
DGA + COS BHEETU ..............................................10 CO2 + H2O HCO3− + H+ .........................................14
DIPA + CO2 HMPO ..................................................11 RNH2 + H+ RNH3+ .................................................15
RNH2 + CO2 RNHCOO− + H+ .................................
.16
This absorption reactions cause a lot of solvent
degradation with various difficulties and as a result, the The same reaction is also explained in the literature
remediation of this problem has become a major focus of (Dawodu and Meisen, 1996; Choy and Meisen, 1980;
interest for the last few decades. Large numbers of Dawodu and Meisen, 1994) for DEA degradation.
5880 Int. J. Phys. Sci.

Amine degradation products

Suspended solids

Nonvolatile contaminants

Lower and higher molecular weight Hydrocarbon

Additives and antifoaming agents

Corrossion inhibitor

Make-up water and water impurities

High temperature of plantoperation

Carbon steel composition

Natural gas impurities

Inorganic and organic acids

Figure 2. Causes of amine degradation.

Hydrogen sulfide emitted hydrogen ion (Reaction 17) in DEA+CS2 DEA dithiocarbamate ............................................................ 3.10 21
water and carbon dioxide as well as carbonyl sulfide and DEA dithiocarbamate + DEA DEA dithiocarbamate salt .......................... 3.11 22
produces COS and H2S, respectively (Reaction 18). This + + .................................................................................. 3.12
DEA + H DEAH 23
reaction causes additional reactions with DEA molecule.
DEA + CO2 DEACOO H ....................................................................... 3.13
- +
These reactions are as follows: 24
DEAH+ + CO2 MEA + C2H4OH + CO2 ...................................................3.14 25
.16 DEACOO-H+ + MEA BHEED + CO2 + H2O .......................................... 3.15 26
+ -
H2 S H + HS ...............................................17 DEACOO-H+ +DEA THEED + CO2 + H2O .......................................... 3.16 27
CS2 + H2O COS + H2O ...............................18 THEED + CO2 BHEP + CO2 + H2O ......................................................3.17 28
DEACOO-H+ HEOD + H2O .................................................................. 3.18 29
COS + H2O CO2 + H2S ................................19 MEACOO-H+ + MEA HEI + H2O .......................................................... 3.19 30
H2O + CO2 H+ + HCO-3 ..............................20 BHEED + CO2 BHEI + H2O .................................................................. 3.20
31

DEA molecule directly reacts with CS2 and successively CAUSES OF AMINE DEGRADATION
produces DEA thiocarbamate salt (Reactions 21 and 22).
On the other hand, it produces carbamate with CO2 Amines and alkanolamines can be degraded in many
(Reaction 23). DEA carbamate reacts with MEA and DEA ways. During the absorption process, amines and
and forms BHEED and THEED, respectively. These two alkanolamine are used for removing acidic oxide for as
DGP further forms BHEI and BHEP with CO2, example CO, CS2, CO2, COS and H2S. Water is the most
respectively. HEOD is one of the familiar DGP of DEA widely used solvent for making amine solution, as this
and this is also from DEA carbamate. Protonated DEA water is one of the causes of amine degradation. Based
molecule reacts with CO2 and converts into MEA, ethanol on the existing studies, the causes of amine degradation
and water. The formation of MEA is better for DEA are shown in Figure 2. This extracted information would
system. However, there is insufficient information in this help to develop our research knowledge.
connection in the open literature. Ethanol can easily
degrade to aldehyde and then an acid. This acid forms
various acetate and ester compounds in amine system. EFFECT OF DEGRADATION PRODUCTS
An overview of the reaction pathways of DEA are
mentioned as follows: Degradation is the undesirable phenomenon in the
 Islam et al. 5881

Reduction solution capacity and plant performance

Foaming effect of degradation products

Capital/Material of construction Issues

Corrosion effect of degradation products

Environmental effect of degradation products

Fouling effect of degradation products

Figure 3. Problems irreversible degradation reaction.

Figure 4. Foam formations in the interior of the stripper by degradation products (CRC,
2010).

replacement of acidic oxides absorption. It is considered Most of the degradation products and corrosion
that degradation products are major problems during the inhibitors in aqueous MEA solutions enhance foaminess
plant operation (Figure 3). The foaming behavior of coefficient. At the same time, the physical properties,
degradation products was conducted (Thitakamol et al., namely surface tension, density and viscosity of solution,
2009; Thitakamol and Veawab, 2008; Goff and Rochelle, play a significant role in foaming tendency through foam
2006). Corrosion behavior of degradation products were formation and foam stability. Among physical properties,
conducted by Dawodu and Meisen (1996) and also the foam height is the most sensitive to liquid viscosity
conducted by the following researchers (Franco et al., followed by liquid density and surface tension, but not
2009; Bedella, 2009; Eide-Haugmo et al., 2009). The sensitive to gas density. A typical view of the foam
recent paper (Bedella, 2009) pointed out several formation is shown in the Figures 4 and 5.
problems which occurred due to irreversible degradation Depending on the type of impurities, two major
reaction. problems may arise, that is:
5882 Int. J. Phys. Sci.

Figure 5. Foam formations by degradation products (Pauley and Reza Hashemi, 1998).

Figure 6. Crevice corrosion in the junction of pipelines (CTL, 2010).

1. The replacement cost of amine for an MEA system including economical and environmental impact during
was shown by Saxena to be about 4% of the total cost of this process. Acidic degradation products may also occur
CO2 sequestration. It should also be realized that in this industry and as a result may also corrode
solvents which are more expensive than MEA may have pipelines. A typical view of crevice and pitting corrosion in
lower degradation rates or may reduce other cost factors industry is shown in Figures 6 and 7.
such as energy or capital. All amines and alkanolamines, and also their
2. Increased viscosity caused by degradation could degradation products are not environmentally friendly.
increase the costs associated with solvent pumping. On Eide-Haugmo conducted researches on the
the other hand, acidic degradation products may be more biodegradability and environmental effect of more than
corrosive and some diamines produced may act as forty amines including alkanolammines like MEA, DEA,
chelants to remove protective films from metal surfaces. MDEA, AMP, etc., (Eide-Haugmo et al., 2009). Effect of
Such corrosivity, could necessitate more expensive degradation products on membrane gas absorption
construction materials. In the amine based NG gas process conducted by Franco, noted that the presence of
purification industry, many operational problems occurred oxalic acid reduced the mass transfer rate of CO2 in MEA
 Islam et al. 5883

Figure 7. Pitting corrosion occuring at the end of the pipe junction (Internet, 2010b).

Figure 8. Fouling effect in the pipe line of gas sweetening plant (ARIANA, 2010;
Internet, 2010a, 2009).

and most significantly followed by formic acid as well as that may be present.
acetic acid (Franco et al., 2009). Amine based purification
plant emitted a lot of toxic volatile products which are
very harmful for living organisms. Hence, considering all AN OVERVIEW OF THE DEGRADATION OF
sides we should think about the environmental effect of ALKANOLAMINES
degradation products and also further research in this
area. Most of the articles highlighted the greenhouse Amine based absorption and stripping system with
effect of sour gases but not on all volatile degradation aqueous amine solution offers a competitive approach for
products. Formation of solid products and solid heat capturing CO2 from raw natural gas and coal-fired power
stable salts may create fouling deposits in piping, heat plant flue gas. Carbon dioxide removal from flue gas is
exchangers and reboilers (Figure 8). As a result, important to reduce greenhouse effect. CO2 absorption
pressure drops will rise and the heat-transfer coefficient with reversible chemical reaction using aqueous
will fall, leading to increased overall energy costs for the alkanolamines solution is currently the most appropriate
plants. Cleaning of piping, heat exchangers and other method for low pressure CO2 sources. In the last
infected areas are also expensive. It is therefore advis- decades, alkanolamines have acquired a well established
able to provide effective filtration to remove any solids position in gas-treating for the removal of the acidic
5884 Int. J. Phys. Sci.

CO2 MEA
HO-CH2-CH 2-NH2 HN O HO-CH2-CH2-NH-CO−NH-CH2-CH2-OH
O MEA MEA/MEA urea orMEA/Other amine urea
Oxazolidone
H H
HN O
MEA N MEA N NH2 MEA
OH NH2 HO N
K1 K2 H Polymer
HEEDA MEA Trimer
O
K3
H K4 CO2
N
OH NH2 HO−H2C−H2C−N NH
HEEDA K−4
O
HEIA
H K5 CO2
N NH2
HO N HN N-CH2-CH2-NH-CH2-CH2OH
H
MEA Trimer K−5
Cyclic urea of trimer

Figure 9. CO2 induced degradation of MEA.

components H2S and CO2. Industrially, important generating environmental impacts. This reaction
alkanolamines are MEA, DEA, DIPA and MDEA. Among produces high molecular weight degradation products
all known solvents, MEA is the benchmark molecule and is expected to occur at the higher temperature region
because of its properties towards CO2 capture (low price, of the stripper. This reaction mechanism is different from
high water solubility, high absorption capacity and fast Lepaumiers et al. (2009a, b, c) studies; there is a
kinetic). However, a major problem associated with difference in their results with reference to polymeric and
chemical absorption using alkanolamines is degradation oligomer degradation product. Oligomer is formed from
through irreversible side reactions with CO2, H2S and O2 O2/CO2 induced degradation of MEA which was shown
which leads to numerous problems with the process: (Lepaumier et al., 2009a, b, c). On the other hand,
solvent loss, foaming, fouling, increased viscosity and Closmann (2009) talked about the formation of polymeric
corrosion. So, the degradation studies of alkanolamines products. From this point, it has created divergent views
are becoming very important for successful plant on the formation of either polymer or oligomer. The
operation. degradation pathways of MEA are explained in the
literature (Strazisar et al., 2003; Goff and Rochelle, 2004;
Lepaumier et al., 2009a; Lepaumier et al., 2009c, b; Abdi,
Degradation study of MEA and MEA blends 1997; Lawal et al., 2005a; Strazisar et al., 2010) for
protonation, polymerization and isomerization reaction
Amine based absorption and stripping system with and miscellaneous route regarding reactions. The CO2
aqueous amine solution offers a competitive approach for induced degradation of MEA is shown in Figure 9.
capturing CO2 from raw natural gas and coal-fired power Effectively to prevent MEA degradation, a degradation
plant flue gas. Among these amine solutions, MEA is prevention strategy needs to be formulated, and this
considered the base line solvent for this application requires knowledge of the degradation products,
(Hilliard 2008; Aron and Tsouris, 2005). For this stoichiometry, mechanism and kinetics of the degradation
consideration, aqueous monoethanolamine (MEA) is process as a function of the various operating variables
used extensively to remove CO2 from flue gas. (Bello and Idem, 2006).

Degradation route of MEA Degradation products of MEA

In power plant flue gas stream, that contains 5 to 10% O2, MEA is a very reactive solvent for gas absorption
10% CO2; three types of degradation can occur. MEA process; as a result, it shows high reaction rate with any
degrades in the presence of O2 and CO2, resulting in components and form much DGP. The major problem is
extensive amine loss and equipment corrosion as well as that the regeneration energy of MEA degradation products
 Islam et al. 5885

Table 1. Degradation products of MEA induced by CO2 (Strazisar et al., 2003).

No. Name Formula

1 N-formylethanolamine (C3H7NO2)
2 N-acetylethanolamine (C4H9NO2)
3 2-oxazolidone (C3H5NO2)
4 N-(hydroxyethyl)-succinimide (C6H9NO3)
5 N-(2-hydroxyethyl)-lanthamide (C5H11NO3)
6 1-hydroxyethyl-3-homopiperazine (C7H14N2O2)
7 1-(2-hydroxyethyl)-2-imidazolidinone (C5H10N2O2)
8 1-hydroxyethyl-2-piperazinone (C6H12N2O2)
9 4-hydroxyethyl-2-piperizinone (C6H12N2O2)
10 3-hydroxyethylamino-N-hydroxy-ethylpropanamide (C7H16N2O3)
11 2-hydroxyethylamino-N-hydroxyethylacetamide (C6H14N2O3)
12 Ammonia (NH3)
13 Acetic acid (C2H4O2)
14 Propionic acid (C3H6O2)
15 n-butyric acid (C4H8O2)
16 Monoethanolamine (C2H7NO)
17 2,6-dimethyl-4-pyridinamine (C7H10N2)
18 2-imidazolecarboxaldehyde (C4H4N2O)
19 1-methyl-2-imidazolecarboxaldehyde (C5H6N2O)

Table 2. Degradation products of MEA induced by CO2 and O2 (Supap et al., 2006).

Major DGP of MEA induced by CO2 and O2

1-methylazetidine; D,L-homoserine lactone; Imidazole; N-(2 hydroxyethyl) -acetamide; N-methyl formamide; 1,3-dioxane; 2-ethyl-1H-
imidazole; 5-hydrazinocarbonyl-1H-imidazole; Uracil; N-(2hydroxyethyl)succinimide; 1-amino-4 methyl piperazine; 2-pyrolidinone; 1-
methyl-4-imidazole-5-carboxylic acid; N-methylene ethanamine; 5-aminovaleric acid; D,L-aspartic acid; 2-[(2-aminoethyl)amino]
ethanol; ethylamine; 4,5dimethyloxazole; 18-crown-6; ethylurea; N-glycylglycine dimethylhydrazone-2-propanone; 1-(2-
hydroxyethyl)-2-imidazolidinone

Additional DGP of MEA induced by CO2 and O2

Ammonia; formic acid; acetic acid; pyrimidine; acetamide; 2-methylaminoethanol; acetaldehyde; ethanol.

Other Products of MEA induced by CO2 and O2

Oxalic acid; glycolic acid; bicine

is high. The miscellaneous degradation products and There is a lot of information of DEA and its blends which
their chemical formula are given in Tables 1 and 2. are also reported in the literature (Lepaumier et al.,
2009a; Blauwhoff et al., 1984; Klare et al., 2000; Dawodu
and Meisen, 1996; Shahi et al., 1994; Choy and Meisen,
Degradation of DEA and its blends 1980; Dawodu and Meisen, 1991, 1992; Kennard and
Axel Meisen, 1983; Lepaumier et al., 2009c, b).
Diethanolamine (DEA) is an important alkanolamine DEA/MDEA and DEA/AMP also have an experience of
successfully used within the 25 to 35 wt% range in sour gas absorption. The first blends MDEA/DEA have
natural gas sweetening plant for sour gas absorption. been used successfully in a wide variety of natural gas
Degradation study of DEA with CO2 to form various sweetening applications for 20 years. Poldermann and
byproducts has been demonstrated as early as 1956. Steele (1956) discovered the following reaction mechanism
5886 Int. J. Phys. Sci.

HOH2CH2C
CO2 O N-CH2-CH2-OH DEA
(HO-CH2-CH2 )2NH NCH2CH2NH
DEA HOH2CH2C THEED CH2CH2OH
HEOD
- H2O

HOH2CH2C N N CH2CH2OH

BHEP

Figure 10. Reaction responsible for the degradation of DEA by C02.

during DEA/CO2 degradation (Dupart et al., 1999). degradation of DEA produced relatively low corrosive
products than O2. DEA is not reclaimable under
regenerator conditions (Meisen and Abdi, 2010); it
Degradation reaction of DEA and DEA blend decomposes below its boiling point at atmospheric
pressure. Vacuum reclaimers, however, have been
A model was developed by Kennard (1983) to explain the successfully used to reclaim DEA solutions (Meisen,
formation of the main degradation products. The following 1996).
reaction shows the major reactions which are believed to
be responsible for the degradation of DEA by C02 (Figure
10). Certain reaction steps cannot be fully confirmed Degradation of MDEA and its blends
since they are based on the existence of DEA carbamate.
Unfortunately, it was impossible to isolate and identify the Among the all alkanolamines, MDEA as an absorption
carbamate, and certain aspects of the reaction solvent of acid gases is widely used today because it
mechanism therefore they remain conjectural. In general, possesses the characteristics such as higher H2S
the DEA degrades via three routes: the fast “molecular selectivity, bigger absorption capacity, lower regeneration
route”, the slower “ionic route” and the very slow “thermal energy, smaller hot-degradation and low corrosion
route”. The molecular route involves CO2 reacting directly (Weiland et al., 2003). Many articles (Closmann et al.,
with DEA to produce the carbamate, whereas the ionic 2009; Klare et al., 2000; Shahi et al., 1994; Lepaumier et
route produces the carbamate from the amine salt al., 2009c; Lawal et al., 2005b) were reported on the
R2NH2+- HC03-. The carbamate then degrades slowly to MDEA degradation induced by CO2/O2, CO2/H2S and
produce THEED, which in turn loses water to form BHEP. CO2, respectively. MDEA is a tertiary amine and
HEOD is a side product, produced by internal commonly used in the 20 to 50 wt% range.
dehydration of the carbamate and it is believed that the
formation of HEOD does not contribute to the overall
degradation of DEA. C02 appears to catalyze the Degradation reaction of MDEA and MDEA blend
degradation of DEA to THEED and of THEED to BHEP
via the formation of carbamate complexes (Dupart et al., MDEA does not have a hydrogen atom attached to the
1999). nitrogen and cannot react directly with CO2 to form
carbamate. The CO2 reaction can only occur after the
CO2 dissolves in water to form a bicarbonate radical,
Degradation products of DEA and DEA blend which then undergoes an acid-base reaction with the
amine. At least six mechanisms for the CO2-MDEA
Since DEA is a secondary alkanolamine, it has a reduced reaction have been proposed (Cornelissen, 1982; Barth
affinity to reaction with H2S and CO2. There are many et al., 1981; Danckwerts, 1979). MDEA can, however,
degradation products which are formed and induced by react with H2S by the same proton transfer mechanism of
several gases which are mentioned in Table 3. The primary and secondary amines (Jou et al., 1982). There
degradation products of DEA are relatively low corrosive is a one CO2 induced degradation of PZ and MDEA
than those of MEA. Exposure to oxygen forms corrosive explained by Closmann (2009) and are presented
acids and on the other hand, COS and CS2 induced reaction mechanism as shown in Figure 11.
 Islam et al. 5887

Table 3. Degradation products of DEA induced by CS2 (Dawodu and Meisen, 1996).

Symbol Name Formula

MEA Monoethanolamine C2H7NO
AMP Aminomethyl propanol C4H11NO
DGA Diglycolamine C4H11NO2
HEP Hydroxyethyl piperazine C6H14N2O
BHEED N,N’-Bis(hydroxyethyl)-ethylenediamine C6H16N2O2
DIPA Di isopropanolamine C6H15NO2
DEA Diethanolamine C4H11NO2
BHEP N,N’-Bis(hydroxyethyl)-piperazine C8H18N2O2
BHEED N,N-Bis(hydroxyethyl)-ethylenediamine C6H16N2O2
HEOD Hydroxyethyl-oxazolidone C5H9NO3
HEI Hydroxyethyl-imidazolidone C6H11NO2
THEED N,N,N’-Tris(hydroxyethyl)-ethylenediamine C8H20N2O3
BHEI N,N’-Bis(hydroxyethyl)-imidazolidone C7H14N2O3
DEAC Diethanolamine carbamat C5H12NO4
MEAC Monoethanolamine carbamat C3H8NO3
DEADTC Diethanolamine dithiocarbamate C5H11NS2
DEADTCS Diethanolamine dithiocarbamate salt C9H22N2O4S2
AEEA Aminoethylethanolamine C4H12N2O

CH3 CH3

+H+ +
HO-CH2-CH2-N-CH2-CH2-OH HO-CH2-CH2-N-CH2-CH2-OH
HN NH
MDEA
H
PZ
−
MDEAH+
COO
H
N CO2 N
H2O + OH MDEA
OH OH DEA
OH + HN N−CH3

HO−H2C−H2C−N O

Figure 11. CO2 induced degradation of PZ and MDEA.

Degradation products of MDEA and MDEA blend distillation. It has been shown that ion exchange is not
very effective in removing this compound since it is either
While MDEA was initially thought of as non degradable, dipolar or a zwitterions (essentially meaning it may
recently it has been shown in many articles that it will behave as an anion or a cation depending on the pH of
often degrade in TGTU services, and efforts are being the solution). Monomethylethanolamine (MMEA) is one of
reflected on improved reclaiming options for solvent the simpler amines that may be formed from MDEA
quality control. MDEA molecule degraded into HSS, DEA, degradation, since MMEA is a secondary amine; it will
MMEA and bicine. Bis-(hydroxyethyl) glycine (Bicine) is a react directly with CO2 and will begin to affect the
degradation product formed in the presence of DEA and performance of the MDEA solvent. Diethanolamine (DEA)
unstable chemical intermediates. It is considered as a is also one of the simpler secondary amines that may be
corrosive DGP and may be removed by vacuum formed from MDEA. Since DEA is a secondary amine, it
5888 Int. J. Phys. Sci.

will react directly with CO2 and will begin to affect the absorption can be considered as a great invention of sour
performance of the MDEA solvent. gas sweetening process. A large amount of experimental
work (Dawodu and Meisen, 1996; Dawodu and Meisen,
1994; Lawal and Idem, 2006; Davis, 2009; Sexton and
Degradation of miscellaneous amines Rochelle, 2010; Lawal et al., 2005a; Oh et al., 2003) has
been done over the past few years to characterize new
In the revolution of engineering science, piperazine (PZ) solvents with respect to different properties such as
has become the most familiar chemical in purification and solubility, absorption, capacity, amine volatility, etc.
in the separation process. Hence, aqueous PZ has been Amines and alkanolamines are among several solvents
investigated as a novel amine solvent for carbon dioxide that have been investigated and current research is
absorption (Freeman et al., 2010). PZ is a cyclic aliphatic focused on designing a chemically stable, less corrosive
diamine containing two substituted hydrogen atoms in its solvent with fast reaction rates and low heats of
molecular structure specifically in the first and fourth absorption to minimize energy requirements for the
positions. This H-atom is capable of reacting with other regeneration of the solvent. Recently, most of the
components and as a result is degraded by scientists have shown an increased interest in the use of
contaminants. The absorption reaction of MDEA/PZ is mixed amine solvents in gas‐treating processes. Blends
explained by Lensen (2004) which is given as follows: comprising of primary, secondary, or tertiary amines have
been suggested for the industrial gas sweetening
MDEA + H+ MDEAH+ 32
6.1 processes (Abdi et al., 2005). Some new amine blends
MDEA + CO2 MDEACO2 33
6.2 (TBEE, APM, DIPATBG and TBE) have been focused
MEACO2 + H2O MDEAH+ + HCO3¯ 34 upon as having no sufficient reports. Hence we should
6.3
continue to get information on it about degradation,
PZ + CO2 PZCO2 35
6.4 modeling, design, absorption, adsorption, kinetics,
PZCO2 + H2O PZH+ + HCO3¯ 36
6.5 mechanism and various comparative sweetening capa-
PZCO2 + H2O PZCOO¯ H3O + 37
6.6 cities. It was also mentioned that there are no aromatic
PZ + H+ PZH+ 6.7
38 amines or unsaturated aliphatic or aromatic amines in
39
6.8
open literature for degradation study including CO2
PZCO2 + MDEA MDEACO2 + PZ
2− +
capture technology. These amines have better absorption
HCO3¯ CO3 + H 40
6.9
capacity with better resistance to degradation.
H2O H+ + OH− 6.10
41
PZCOO¯ + H2O + CO2 PZ (COO¯ )2 +H3O+ 6.11
42
MDEA + PZOO¯ + CO2 PZ (COO¯ )2 + MDEAH+ 6.12
43 CONCLUSION

Amine degradation is an ongoing research area till date,

as there are many unknown areas to be discovered.
SOLVENT BLENDS
Recovery techniques are still being developed to improve
recovery efficiencies, reduce environmental impacts and
Since the mid-1980’s, in order to further improve operating problems of the reclaiming units. The
absorption performance of MDEA solvent, blended aforementioned contents of this review paper highlighted
alkanolamine solvents have been developed by adding very important and recent information regarding
another alkanolamine into MDEA. These blended alkanolamines degradation, degradation path ways,
solvents include MDEA-MEA, MDEA-DEA, MDEA-DIPA, degradation products and effect of degradation.
MDEA-DGA and MDEA-AMP (Pacheco et al., 2000;
Mandal et al., 2001; Xia et al., 2003; Rinker, 1997). The
blended solvents have the compatibility of advantages of RECOMMENDATION
single solvent in blended solvents (Aroonwilas and
Veawab, 2004). Example, a blended solvent, which The author would like to recommend working with three
consists of a mixture of primary or secondary amine with component amine (aliphatic and aromatic) blends for
MDEA, combines the higher CO2 reaction rates of the decreasing degradation, amine losses, corrosion and
primary or secondary amine with the higher CO2 loading miscellaneous side reaction. Many researches and
capacity of the MDEA. Thus, the blended solvent experiments were conducted on degradation but there is
providing both higher CO2 reaction rate and higher CO2 no paper on heterocyclic aliphatic and heterocyclic
equilibrium capacity may result in substantial lower aromatic amines. The author also predicted that this
solvent circulation rates compared to a single solvent. So amine also has the best thermal stability and resistance
the development of a new solvent for maximum CO2 to degradation properties. Therefore, we have to take this
 Islam et al. 5889

information into consideration and implement accordingly. Amiri AP, Haghighi AA, Ehsani MR (2007). Alkanolamines foaming
PZ has become an ideal solvent because, it has two tendency: effect of amine mixing, amine degradation and gas flow
rate. Farayandno, 8: 1-6.
amine functional groups in its structure. So, the author ARIANA (2010). Fouling effect of degradation products, website
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