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ABSTRACT
The formation of organic acid and inorganic acids in CO2 and H2S removal process are common phenomenon.
Amines are basic in nature, which react easily with the acidic components to form heat stable salts and other
degradation products. Heat stable salt and degradation products are problematic in the operation of CO2, H2S
removal unit, as they reduce the solvent capacity to absorb CO2 and H2S, cause corrosion, foaming and solvent
losses. This paper gives an insight on the degradation of amine solvent due to these acidic components and
highlights the latest findings and research work carried out in this area of study.
Keywords: acid; degradation; amine; alkanolamine; absorption; heat stable salt
1. INTRODUCTION
Amines and alkanolamines are widely used in the
natural gas refining for the sweetening of sour gas by
absorbing the CO2 and H2S acidic gases. During the
absorption process amine are highly degraded by this
acidic oxide as a result amine loses its capacity to
absorb these acidic gases. All acidic gases of natural
gas composition play an important role to form amine
to aldehyde and acids. Oxygen directly oxidized the
amine and converted into carbonyl compounds like
aldehyde or ketone or acid compound. Aldehydes
react with water; in aqueous solution of formaldehyde
is hydrated [1]. Aldehydes also react readily with
primary amines. These reactions would not be
significant with tertiary amines. In aqueous solution
of monoethanolamine, formaldehyde will be present
as an equilibrium mixture primarily in the form of
imine with some hydrated aldehyde, carbinolamine,
and aminal. Similar reactions can occur with other
aldehydes such as hydroxyacetaldehyde. The imine
formed from primary or secondary amines such as
MEA may be subject to similar attack by radical
oxidants. The presence of formaldehyde may also
facilitate the oxidation of the amine molecule. Other
less compounds easily hydrated to aldehydes, such as
acetaldehyde and hydroxyacetaldehyde, react at room
temperature with oxygen to produce the
corresponding organic acid [2, 3]. The oxidation
ususally takes place by a free radical chain
mechanism. An initiator extracts a H from the
carbon to produce a free radical. The radical reacts
with O2 to produce a peroxyacid radical. The
peroxyacid radical reacts with aldehyde to propagate
the reaction with the production of the aldehyde
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H+ + OH
H2O
H+ + HS
H2S
HCO
O3 + H+
CO2 + H2O
RNH
H3+
RNH2 + H+
RNH2 + CO2
RN
NHCOO + H+
Sww
wet Gas
H+ + HS
H H2S
COS + H2O
CS2 + H2O
CO
OS + H2O
CO2 + H2S
H+ + HCO-3
H2O + CO2
Figure. 1: Typical CO
O2 absorption and
a desorptioon
prrocess [4]
Sour gas components
c
reeact with aminne solvent durring
absorption-desorption cy
ycles graduallly at higher and
a
lower tempperature and some
s
of these reactions (A.11 to
A.11) are given in the following
f
to shhow how DGP
P is
formed [5].
HO-C2H4NH
H2 + HCl
DEA
HO-C2H4NH
H 2 + H 2S
DEA
R-NH2 + O2
MEA + CO22
MEA + COSS
DEA + CO2
DEA + COS
O2
MDEA + CO
DGA + CO2
DGA + COS
DIPA + CO2
HO-C
H 2H4NH3+Cl
HSS
HO-C
H 2H4NH3+HS
HSS
CnH2n+1COOH / Imidazolidonne
OZD, HEI,, HEED
DEA Urea
HEOD, BH
HEEP, THEED
MEA, HEI, BHEED
EG, HMP, DEA, TEA, BHEP
BHEEU
BHEETU
HMPO
B.1
B.2
B.3
B.4
B.5
A.11
A.2
A.33
A.44
A.55
A.66
A.77
A.88
A.99
A.110
A.111
B.6
B
B
B.7
B
B.8
B
B.9
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mentioned below.
D dithiocarbamate
DEA+CS2 DEA
DEA dithiocarbaamate + DEA DEA dithiocarbamate
d
salt
B.10
DEA + H+
B.12
B.13
DEA + CO2
DEAH+ + CO2
DEAH+
DEACOO-H+
MEA + C2H4OH + CO2
B.11
B.14
B.15
B.16
- +
THEED + CO2
DEACOO-H+
HEOD + H2O
B.17
B.18
Nitritee
NO2
Inorgganic
Formaate
CHO2
Orgaanic
5000
Oxalatte
C2O4
Orgaanic
2500
Acetatte
C2H2O2
Orgaanic
10000
Sulfatee
SO4
Inorgganic
5000
4. ACID FORMATION
F
N REACTION IN AMINE
SYSTEM
Sulfitee
SO3
Inorgganic
5000
Phosphate
PO4
Inorgganic
Thiosuulfate
S2O3
Inorgganic
10,000
Thiocyyanate
CNS
Inorgganic
10,000
Glycolate
C2H3O3
Orgaanic
5000
Malonnate
C3H3O3
Orgaanic
5000
Succinnate
C4H5O4
Orgaanic
10000
Chloriide
Cl
Inorgganic
5000
- +
MEACOO H + MEA
BHEED + CO2
HEI + H2O
BHEI + H2O
B.19
B.20
6. SPEC
CIFIC DEGRA
ADATION PRO
ODUCTS BY ACID
A
Whiile Heat Stable Salts (HSS) are common to all
amine solvents, deggradation prooducts are soolventA descriiption of com
mmon
specificc [6, 15-17]..
degradaation productss found in various
v
gas trreating
solventss follows.
5. TYPICA
AL HSS IN AM
MINE SYSTE
EM
Heat sttable salt (HSS
S) formation iss another form
m of
active amiine loss. The amine
a
and an acid form a salt
s
that cannoot be regeneraated in the stripper [12, 13].
1
Strong acidd anions such as formate, accetate, thiosulfaate,
thiocyanatee, and chloridee can tie up ann amine moleccule
mides
Formam
N-foormyl aminess (formamides) are degraadation
productts generally foound in gas treeating solutionns that
are baseed on primary and secondaryy amines [18]. Under
certain conditions all primary andd secondary amines
a
react with
w the formic acid in solutioon (via dehydrration)
to form
m n-formyl amines.
a
The data from process
p
solutionns containing formate
f
as a HSS
H anion show
w that
the following equilibbrium relationnship exists in
i the
solutionn between thee formate HSS
S and the n-fformyl
MEA (M
MEA-F) [19].
Form
mic Acid + ME
EA MEA-F + Water
Since thhe above equaation represennts equilibrium
m, it is
also possible to hydroolyze MEA-F back into ME
EA and
243
MEA
In the presence of certain chemical compounds
(oxygen) or intermediates, it is possible to degrade or
break down the DEA molecule to simpler amines.
Monoethanolamine (MEA) is one of the simpler amines
that may be formed from DEA degradation. It is
important to monitor the level of MEA in the circulating
DEA system due to Amine Stress Corrosion Cracking
(ASSC) concerns associated with MEA. MEA will also
generally further degrade in the system.
Bicine
Bis-(hydroxyethyl) glycine (Bicine) is a degradation
product formed in the presence of DEA and unstable
chemical intermediates, and is considered corrosive [23,
24].
DIPA-OX
Hydroxypropylmethyloxazolidone (HPMO or DIPAOX) is a well-known degradation product of DIPA from
reactions with CO2. There is a wealth of literature on the
reaction mechanism of DIPA-OX [20, 21, 25]. The
literature also states that DIPA-OX is the endpoint of
DIPA degradation in CO2 service (due to steric
hindrance), so polymers of DIPA are not supposed to be
formed like they are with MEA and DEA.
MDEA Fragments
MDEA in Tail Gas Treating units (TGTU), Acid Gas
Enrichment units (AGE), and in some main amine
systems should be monitored for MDEA fragments.
These include MMEA, DEA, Bicine and C2+ HSS
anions [26]. It is also important to note that as
ethanolamines (from MDEA degradation) accumulate in
the solvent, they will generally undergo further
degradation to compounds listed in the above sections.
The presence of these primary and secondary amines
may affect the gas treating selectivity of the amine
solution.
Dimers
The literature states that steric hindrance prevents
further degradation of DIPA-OX to diamines
(dimers). However, we generally do find dimers in
Sulfinol-D systems treating H2S and CO2. These
dimers are similar to the diamines found in MEA and
DEA systems, and are likely formed via the same
pathway.
TIPA
TIPA may be found in systems treating H2S and CO2
utilizing Sulfinol-D, when evidence of oxygen
degradation is present. Literature shows that when
amines degrade they generally form simpler amines, but
sometimes these simpler amines react with the base
amine molecule (or others) to form a more complex
amine [27].
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Proceeedings of MARTE
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7. COMMO
ON DEGRADAT
TION PRODUCTS AND EFFEC
CT
All alkkanolamine deg
gradation produucts are not saame
in behavior, some of these are acidic and
a some of thhese
are alkalinne based. Dep
pending on thhe nature of the
degradationn products thesse are classifieed as follows.
7.1 Acidic degradation product
p
Acidic degradation prroducts are higghly corrosive for
plant unit, thus metallic unit
u of the gas sweetening pllant
is highly interactive by
y this product. So the aciidic
degradationn products are
a
very harm
mful among all
degradationn products. Heeat stable saltss are the comm
mon
degradationn products off amine strippping system and
a
these are potentially co
orrosive. All of these aminnes
degraded and
a formed caarboxylic acidss. These acids are
capable of
o causing fu
urther chemicaal reaction with
w
miscellaneeous degradatio
on products. Byy this reaction the
concentratiion of contam
minants increaases continuouusly
during abssorption-desorp
ption cycles and finally shoows
operational problems.
d
product
p
7.2 Basic degradation
The alkkaline degradaation products are
a less corrossive
than acidicc or some of these
t
are noncoorrosive but both
still have a bad impact on plant operaation or even the
neutral DG
GP has the sam
me effect too.. It increases the
viscosity and
a as a resultt it highly inhhibits the soluttion
flow rate. This lower flow rate shhould affect the
efficiency of the plant [28]. To accelerate the pllant
lower flow
w rate to satisfactory flow rate,
r
high enerrgy
consumptioon is required. For this reasoon no degradattion
products arre expected.
d
prroduct
7.3 Ionic degradation
The deegradation product which coontains chargee at
the chain end
e and it may
y be positive or negative thhese
are definedd as ionic degrradation produccts. The literatture
is citied itss effect on thee plant perform
mance [8, 29, 30].
3
Ionic degrradation produccts are more porn
p
to affect the
plant perfoormance becau
use it is easilly react with the
componentts and form miiscellaneous reaction productts.
7.4 Polymeric degradatiion product
Many articles refleect a lot of information on
polymeric degradation products but there is no speciific
polymer formation deegradation reeaction [31-333].
Polymeric degradation products
p
identtified by GC-M
MS
detection may be neutrral or living. Living polym
mer
means it coontains a functtional group at the chain endss of
the moleccule which arre capable off causing furtther
chemical reaction with accidic oxide or any reactive unnit.
The literaature cited very inadequuate informattion
regarding the polymerization reacttion mechaniism
though it has a satisfaactory detectioon report. Wide
W
ranges off research on
n polymerizatiion reaction are
Capital/MaterialofConstructionIsssues
Corrosioneffectofdegradation
products
Environmentaleffectof
degradationproducts.
Foulingeffecto
ofdegradation
products
NCLUSION
8. CON
Durring the sour gas sweeteninng process a lot of
solvent are losses by amine degradation. The
245
THEED
The literature mostly cited the heat stable salt and its
minimization. HSAS are basically the reaction products
of acid and amine. Amine is the main solvent; on the
other hand an acid is the by product, if we control the
acid formation in amine system then automatically
reduces the HSAS formation. Acids can also be
converted to acid amides by adding some additives.
Because amides contain CONH2 functional group this is
capable to capture more acid gases. So we need further
research on it to recover the research gap. The author
suggested the acid remediation by converting into
amides compound. Author also would like to put
emphasis for the minimization of the acidic content
inside the solution. The above mentioned contents of
this review paper highlighted very important and recent
information regarding alkanolamines degradation by
acid. Knowledge of the reaction mechanism aids the
development of procedures to minimize degradation or
purify partially degraded solutions. Therefore, the
overall representation would help to understand the role
of both inorganic and organic acid on amine
degradation.
HPLC
BHEI
BHEEU
NMR
GC-MS
IC
FTIR
HPLC-RID
REFERENCES
[1]
[2]
[3]
ACKNOWLEDGEMENT
The authors would like to acknowledge Ministry of
Science, Technology and Innovation (MOSTI),
Malaysia, for the project: RG003/09AET and the
University of Malaya for the financial support and for
providing us with an excellent research environment.
[4]
[5]
[6]
ABBREVIATIONS
NG
DIPA
DEA
MDEA
MEA
DGP
DGA
HSS
HSAS
AMP
HEP
BHEED
BHEP
HEOD
Natural gas
Di-isopropanolamine
Diethanolamine
Methyldiethanolamine
Monoethanolamine
Degradation product
Diglycolamine
Heat stable salts
Heat stable amine salts
Aminomethyl propanol
Hydroxyethyl piperazine
N,N-Bis(hydroxyethyl) ethylnediamine
N,N-Bis(hydroxyethyl)-piperazine
Hydroxyethyl-oxazolidone
N,N,N-Tris(hydroxyethyl)ethylenediamine
N,N Bis (hydroxyethyl)imidazolidone
N,N-Bis(hydroxyethoxy-ethyl)urea
Nuclear magnetic resonance
Gas chromatography mass
spectrometer
High performance liquid
chromatography
Ion chromatography
Fourier transforms infrared resonance
spectrometer
High performance liquid
chromatography-refractive index
detector
[7]
[8]
[9]
246
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
247