Aerobic biodegradability of methyldiethanolamine

(MDEA) used in natural gas sweetening plants in

batch tests and continuous ow experiments
M. F uurhacker, A. Pressl
*
, R. Allabashi
Department for Sanitary Engineering and Water Pollution Control, Institute for Water Provision, Water Ecology and
Waste Management, University of Agricultural Sciences, Vienna A-1190, Muthgasse 18, Austria
Received 26 August 2002; received in revised form 25 March 2003; accepted 31 March 2003
Abstract
Mixtures of dierent amines including tertiary amines (methyldiethanolamine, MDEA) are commonly used for the
removal of CO
2
from gas mixtures or in gas sweetening processes for the extraction of CO
2
and H
2
S. The absorber
solutions used can be released into the industrial waste water due to continuous substitution of degraded MDEA,
periodically cleaning processes or an accidental spill. In this study, the aerobic biodegradability of MDEA was in-
vestigated in a standardised batch test and a continuous ow experiment (40 l/d). The results of the batch test indicated
that the MDEA-solution was non-biodegradable during the test period of 28 days, whereas the continuous ow ex-
periments showed biodegradation of more than 96% based on TOC-measurements. This was probably due to the
adaptation of the microorganisms to this particular waste water contamination during continuous ow experiment.
2003 Elsevier Ltd. All rights reserved.
Keywords: Methyldiethanolamine (MDEA); Absorber solution; Carbon dioxide; Hydrogen sulphide removal; Gas sweetening; Waste
water treatment
1. Introduction
Blends of activating primary or secondary amines
(diethanolamine, DEA) with tertiary amines, (methyld-
iethanolamine, MDEA) are commonly used for the re-
moval of carbon dioxide (CO
2
) from gas mixtures
(Schubert et al., 2001), from natural gas, as well as from
ue gas. Aqueous amine systems for CO
2
recovery from
ue gas have been studied from dierent authors, with
the main emphasis on MDEA, or amino acid salts and
MDEA promoted with piperazine (Erga et al., 1995;
Hagewiesche et al., 1995; Rinker et al., 1995).
MDEA is also one component used for the absorp-
tion and stripping of hydrogen sulde (H
2
S) and carbon
dioxide (CO
2
), as well as and the removal of carbonyl
sulde (COS) from natural gas in natural gas sweetening
processes (Carey et al., 1991; Lammers et al., 1995). Sour
gas purifying facilities use the process of chemical ab-
sorption by alkanolamines to remove H
2
S and CO
2
from
raw natural gas. Alkanolamines and their aqueous sol-
utions will absorb carbon dioxide and hydrogen sulde
at lower temperatures and release the acid gases at higher
temperatures. This process allows the separation of car-
bon dioxide and hydrogen sulde from natural gases.
To combine dierent chemical properties MDEA is
mixed with other chemicals like piperazine. MDEA se-
lectively removes H
2
S from natural gas streams while
piperazine acts mainly as a corrosion inhibitor and
surfactant. The slower rate of reaction of CO
2
with
Chemosphere 52 (2003) 17431748
www.elsevier.com/locate/chemosphere
*
Corresponding author. Tel.: +43-1-36006-5811; fax: +43-1-
3689-949.
E-mail address: pressl@iwga-sig.boku.ac.at (A. Pressl).
0045-6535/03/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0045-6535(03)00371-0
MDEA is compensated through the addition of small
amounts of rate-promoting agents such as DEA or
piperazine (Kohl and Nielsen, 1997).
During the gas sweetening process of absorption and
desorption, non-reclaimable contaminants (exhausted
amines) tend to accumulate in the system and can cause
both major reductions in eciency and operational prob-
lems due to the closed loop nature of the system. There
are basically four types of remediation action: (i) par-
tially purge the contaminated solution and replace it
with fresh amine; (ii) replace the entire volume of con-
taminated solution; (iii) inject caustic solution to free the
amines bound up as heat stable salts and some CO
2
-
induced degradation products; (iv) reclaim the solutions.
Therefore, waste water from gas sweetening units fre-
quently becomes contaminated with raw amine-solu-
tions, amine degradation products, thermal stable salts,
heavy hydrocarbons and particulates.
The objectives of our study were
to investigate the degradation kinetics of a specic
waste water from a gas sweetening plant, and the
MDEA-solution used in the absorber, in a biodegra-
dability batch test based on (ISO 7827, 1994) as a rst
clue,
to study the degradation of MDEA-contaminated
waste water from a gas sweetening plant in an aero-
bic treatment process.
This results should indicate an passable way for
treating the generated waste water in a nearby waste
water treatment plant.
2. Materials and methods
2.1. Amine solution
The amine-solution used as sorption agent contained
approx. 426 g/l MDEA and approx. 22.3 g/l piperazine
(as shown in Fig. 1). MDEA (C
5
H
13
NO
2
; [CAS 105-59-
9] mole wt. 119.16, density 1.04 g/ml) is a clear, co-
lourless, hygroscopic liquid with an ammoniacal odour.
Piperazine (diethylenediamine; C
4
H
10
N
2
; [CAS 110-85-
0] mole wt. 86.14, density 1.1 g/ml) consist of o-white
crystals which are hygroscopic/light sensitive. MDEA is
used as an absorbent in the form of a 40% aqueous
solution and was supplied from a gas sweetening plant.
The 40% aqueous MDEA-solution used contained con-
centrations of 87.7 g/l TKN, 237 mg/l NH
4
Nand 245 g/l
TOC.
2.2. Experimental methods
The nitrogen species analysed during this work are
total-Kjeldahl-nitrogen (TKN, according to EN 25663,
1993) and ammonium nitrogen (NH
4
N, according to
DIN 38406-5, 1983). The organic carbon is determined
as total organic carbon (TOC), and dissolved organic
carbon (DOC according to EN 1484, 1997). The method
used for this determination was based on the non-
dispersive infrared detection of the produced CO
2
after
a total combustion of the sample (instrument used:
Shimadzu TOC 5000).
MDEA was determined by gas-chromatography t-
ted with a ame ionisation detector). One microlitre of
the water sample is injected into a Hewlett Packard
Instrument 5890 Series II equipped with a chromato-
graphic column HP Ultra 1 (25 m0.2 mm0.33 lm).
The oven temperature is held isotherm at 120 C. The
ow rate of the carrier gas (He) was 0.67 ml/min and
detection temperature 290 C. The detection limit under
the above measuring conditions was 0.2 g/l MDEA.
2.3. Batch test
The batch tests were carried out according to the
international standard (ISO 7827, 1994) which is adap-
ted as Austrian standard (OENORM EN ISO 7827,
1996). This method investigates the ultimate biodegra-
dability of water soluble, non-volatile organic com-
pounds in an aerobic, aqueous medium at a starting test
concentration corresponding to 540 mg/l DOC (con-
centrations of >40 mg/l DOC could be applied if nec-
essary) using optimum conditions. The calculation of
degradation is based on loss of DOC within 28 days.
A pre-determined amount of the dierent samples
were added to the test medium, an inorganic nutrient
solution inoculated with microorganisms. The rst in-
vestigated sample was the euent of a gas sweetening
unit; initial concentration 342 mg/l TOC (sample 1). The
inoculum used was activated sludge from a municipal
waste water treatment plant (1920 mg/l TOC, dry matter
9.4 g/l TS). The sludge volume was kept at 1% of the
total volume. In the same way as the test solution, a
control (blank solution) was prepared only with puried
water (RO-water), nutrients and inoculum. To monitor
other potential losses of DOC (e.g. through adsorp-
tion or volatilisation) sample 1 was mixed with mer-
cury(II)chloride HgCl
2
as an inhibitor (test solution
inhibited). To check the activity of the inoculum a ref-
erence solution was prepared consisting of sodium ace-
tate CH
3
COONa as a carbon source, nutrients and
Methyldiethanolamine (MDEA)
HO
OH
N
CH3
Diethylenediamine (Piperazine)
HN
Fig. 1. Molecular model of MDEA and piperazine.
1744 M. Fuurhacker et al. / Chemosphere 52 (2003) 17431748
inoculum to create an ultimate biodegradable solution.
To verify possible inhibiting eects of the sample the
reference solution and sample 1 were mixed in equal ra-
tios (sample 1 +reference solution). In addition to the
waste water sample the biodegradability of the amine
solution as used in the absorber of the gas sweetening
plant was investigated. To simulate technical conditions,
the amine concentration was raised to achieve 1600 mg/l
TOC which reects average TOC-concentrations of the
industrial waste water (ww+MDEA solution) 5 ml
MDEA-solution (40%) per litre was added to the test
medium.
In the waste water, concentrations of several g/l
MDEA could be observed due to accidental spills. In
order to check the degradability at these concentrations,
4 g/l MDEA (10 ml MDEA-solution 40%) was added to
the test medium (nutrients and inoculum) and incubated
(P11 and P12). The incubation time and conditions for
the dierent preparations were 28 days in a dark place at
a temperature of about 20 C. The concentration of
DOC was determined according to the international
standard at the beginning (start), at the end (after 28
days) and additionally at three equal time intervals (7, 14
and 21 days). Additionally to this sampling interval the
samples P11 and P12 were investigated on days 3, 10, 17
and 24.
2.4. Continuous ow experiment
The degradation test was conduced in an activated
sludge treatment system. The design and size of this
facility is shown in Fig. 2. The storage tank was stirred
with a paddle mixer. The waste water originated from
the gas sweetening plant.
The continuous biological treatment system with its
activated sludge tank and settlement tank was charged
with waste water from a gas sweetening unit for two
months before the experiment started. At the beginning,
the facility was inoculated with activated sludge from a
municipal waste water treatment plant. Two fresh waste
water samples of 6 m
3
each from a gas sweetening plant
were stored and used for the following experiment. To
ensure the adaptation of microorganisms to the new
waste water (day 0), the experiment started without any
addition of MDEA-solution. To investigate the specic
biodegradability of the MDEA-solution it was added
after a start-up time directly into the aeration tank. At
the beginning, the dosage of MDEA was 80 ml MDEA-
solution (40%) per day, resulting in a concentration of
0.8 g/l MDEA. This amount was afterwards reduced
to 40 ml MDEA-solution (40%) per day.
Additional features of the treatment system were
a sludge loading ratio of 0.11 kg BOD
5
/(kg TS*d),
equivalent to a volume charge of 0.50 kg BOD
5
/(m
3
d).
The waste water inuent was 40 l/d with a return-sludge
quantity of about 63 l/d, corresponding to a recircula-
tion ratio of 1.58. The hydraulic retention time was
about 2 days and the sludge age >100 days due to
marginal surplus sludge withdrawal by the euent.
The parameters TKN and TOC were used for de-
termination of degradation during the continuous ow
experiment. GC/FID analysis showed that, MDEA
could be characterised by carbon and nitrogen para-
meters as used in our experiments. Therefore the degra-
dation of MDEA-solution was described by the nitrogen
parameter TKN as well as TOC and DOC.
3. Results and discussion
3.1. Batch test
The percentage of aerobic biodegradation was cal-
culated as the dierence between DOC concentration at
the start and DOC concentration at a specic sampling
time. The results are given in Fig. 3. Due to constant
degradation, the batch test was stopped after 21 days
with exception of ww+MDEA solution.
The lag-time, which represents the period of time
between inoculation and a biodegradation of 10%, was
calculated as <1 day for the reference solution and as
about 2 days for the investigated waste water (sample 1),
while no lag time could be determined for the mixture of
ww+MDEA solution.
The initial and endpoint DOC concentrations of
sample 1 (waste water from a gas sweetening unit) were
229 and 6.9 mg/l DOC, respectively, indicating a bio-
degradation of 97%. After 14 days the reference solution
with a starting concentration of 30.9 mg/l DOC and the
sample 1 +reference solution with an initial concentration
Fig. 2. Schematic diagram of the continuous aerobic treatment
facility.
M. Fuurhacker et al. / Chemosphere 52 (2003) 17431748 1745
of 132 mg/l DOC also reached a biodegradation of 95%
and 97% respectively, showing a fast degradation for the
reference solution as expected. The inhibited test solution
indicated losses during the rst two weeks, but only a
negligible removal rate could be detected by the end of
the investigations.
No degradation could be observed in the mixture
ww+MDEA solution after 28 days in the batch test by
either using the parameter DOC (graphically demon-
stration in Fig. 3) or by GC/FID analysis. In the highly
concentrated samples P11 and P12, a small increase in
degradation could be noticed on day 7 and after 21 days
(Fig. 4). The early increase could be due to autolysis
processes of the inoculum. The rise in the later stage
might be the beginning of biodegradation after a long
adaptation period. The test was stopped after 28 days
according to the standardised method.
The batch test (ISO 7827, 1994) is designed to assess
whether chemicals have any potential for biodegrada-
tion. A result for biodegradability of <20% after 28 days
means that non-biodegradability should be assumed. A
gure of more than 20% biodegradation may be re-
garded as evidence for inherent biodegradation. A gure
of more than 70% mineralisation may be regarded as
evidence for ultimate biodegradation. This indicates that
the investigated compound will not persist indenitely in
the environment. Under the specications of the batch
tests, sample 1 is considered to be ultimately biode-
gradable and MDEA is regarded as a non-biodegrad-
able substance.
3.2. Continuous ow experiment
The results for the TOC removal in the continuous
ow experiments are shown in Fig. 5. It can be seen, that
the start up period required to reach stable conditions
was about two weeks for TOC and three weeks for TKN
(Fig. 6). After these adaptation phases the degradation
was constant at a level of more than 95% for TOC
inf
and
up to 70% for TKN
inf
.
To investigate the biodegradability of the MDEA-
solution under commonly used waste water treatment
conditions, dosage of MDEA start with 80 ml MDEA-
solution (40%) per day after nine weeks continuous
0
10
20
30
40
50
60
70
80
90
100
0 4 8 12 16 20 24 28
days [d]
M
D
E
A

d
e
g
r
a
d
a
t
i
o
n

[
%
]

sample P11
sample P12
degradation mean
Fig. 4. Degradation of MDEA after 28 days by using a GC/
FID sampler.
0
500
1000
1500
2000
2500
3000
07
1
4
2
1
2
8
3
5
4
2
4
9
5
6
6
3
7
0
7
7
8
4
9
1
9
8
1
0
5
1
1
2
1
1
9
1
2
6
1
3
3
1
4
0
days [d]
T
O
C

[
m
g
/
l
]
0
10
20
30
40
50
60
70
80
90
100
d
e
g
r
a
d
a
t
i
o
n

[
%
]
TOC
inf total
[mg/l] TOC
eff
[mg/l] degradation [%]
dosage of 80 ml
MDEA-sol. per
day (after 64 days)
dosage of 40 ml
MDEA-sol. per
day (after 78 days)
new waste
water (after
113 days)
Fig. 5. TOC concentrations of the treatment system during operation and dosage with MDEA-solution.
0
10
20
30
40
50
60
70
80
90
100
0 4 8 12 16 20 24 28
days [d]
b
i
o
d
e
g
r
a
d
a
b
i
l
i
t
y

[
%
]

sample 1
reference solution
sample 1 + reference sol.
test solution inhibited
ww + MDEA solution
Fig. 3. Biodegradability of the investigated solutions in [%]
during the batch test.
1746 M. Fuurhacker et al. / Chemosphere 52 (2003) 17431748
operation. As batch tests predicted a low degradability
of MDEA-solution, these quite high concentrations
were added to the inuent. An noticeable rise of
TOC
inf; total
and TKN
inf; total
concentration in the inuent
was the result of this addition, where inf, total repre-
sents the total TOC/TKN concentration resulting from
the waste water itself and the additional of MDEA-
solution (see Fig. 7). After two weeks both parameters
showed a major increase in the euent concentration
due to the overloading of the system combined with
deteriorating settling performance of the sludge. After
reduction of the added volume of MDEA-solution by
50% (40 ml/d) and a sludge removal of 247 g TS, the
system recovered and stabilised within one week. The
degradation thereafter increased again and reached
more than 95% and 80% for TOC and TKN respec-
tively. As apparent in Figs. 5 and 6, these degrada-
tion levels were not changed when a new load of fresh
waste water was introduced about 16 weeks after the
start and 7 weeks after the rst addition of MDEA-
solution.
The worst case scenario e.g. a possible accidental spill
should be represented by addition of high amounts of
MDEA-solution according to the batch tests (P11 and
P12). In contrast to the ndings in the batch tests, the
continuous experiments showed a TOC removal in the
treatment plant of up to 96% TOC. That means that
the MDEA-solution added to the waste water of the gas
sweetening plant was readily biodegradable. These
ndings were also conrmed by the total hydrolysation
of the TKN resulting in the release of ammonium in the
euent. Nevertheless, the results from the dierent tests
did not corroborate one another.
For an interpretation of the dierences between
batch and continuous ow tests it should be considered
that activated sludge from a municipal waste water
treatment plant was used as inoculum for the batch test,
whereas in the continuous ow experiment the activated
0
10
20
30
40
50
60
70
80
90
100
07
1
4
2
1
2
8
3
5
4
2
4
9
5
6
6
3
7
0
7
7
8
4
9
1
9
8
1
0
5
1
1
2
1
1
9
1
2
6
1
3
3
1
4
0
days [d]

p
a
r
t

o
f

M
D
E
A

[
%
]
% part of TOC (in
MDEA) in added
TOC
inf tot
% part of TKN (in
MDEA) in added
TKN
inf tot
dosage of 40 ml
MDEA-sol. per day
(after 78 days)
dosage of 80 ml
MDEA-sol. per day
(after 64 days)
Fig. 7. Percentages of TOC and TKN in the total inow concentration originating from MDEA.
0
50
100
150
200
250
300
350
400
450
500
07
1
4
2
1
2
8
3
5
4
2
4
9
5
6
6
3
7
0
7
7
8
4
9
1
9
8
1
0
5
1
1
2
1
1
9
1
2
6
1
3
3
1
4
0
days [d]
T
K
N

[
m
g
/
l
]
n
0
10
20
30
40
50
60
70
80
90
100
d
e
g
r
a
d
a
t
i
o
n

[
%
]
TKN
inf total
[mg/l] TKN
eff
[mg/l] degradation [%]
new waste
water (after
113 days)
dosage of 80 ml
MDEA-sol. per
day (after 64 days)
dosage of 40 ml
MDEA-sol. per
day (after 78 days)
Fig. 6. TKN concentrations of the treatment system during operation and dosage with MDEA-solution.
M. Fuurhacker et al. / Chemosphere 52 (2003) 17431748 1747
sludge could adapt very well due to the operation with
waste water from the gas sweetening plant. The new
international standard Water qualityevaluation of
aerobic biodegradability of organic compounds in an
aqueous mediumStatic test (ZahnWellens method)
(ISO 9888, 1999) in the form of the national standard
(OENORM EN ISO 9888, 1999) consider this charac-
teristic feature in an annotation. The ISO 9888 suggests
the use of a pre-adapted inoculum which is already pre-
exposed to the chemicals used, e.g. from a suitable
sewage treatment plant or from batch tests with equal
pre-tested samples.
4. Conclusions
The applied standardised ISO-batch test Water
quality; evaluation in an aqueous medium of the ulti-
mate aerobic biodegradability of organic compounds;
method by analysis of dissolved organic carbon (DOC)
(ISO 7827, 1994) was not suitable to detect any biode-
gradability of MDEA-solution after 28 days, the MDEA
contaminated waste water (sample 1) was ultimately
degraded. The continuous ow experiment showed a
very good biodegradability of the waste water including
for high concentrations of MDEA-solution with a TOC-
removal of 96%.
The reason for this behaviour was probably due to
the adaptation of the microorganisms to this particular
waste water contamination during continuous ow ex-
periment. So, it was helpful to have the possibility to
investigate the biodegradability under commonly used
waste water treatment plant conditions. However, the
results derived from the applied standardised batch test
could easily mislead designers or decision makers in
waste water treatment planning.
Acknowledgements
The authors are grateful to the sta of the IWGA-
SIG laboratory.
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