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Asha Masohan1, Mamshad Ahmed1, Sushil Kumar Nirmal1, Ajay Kumar2 and Madhukar Onkarnath Garg1
1
amasohan@iip.res.in, masohan_asha@hotmail.com
Abstract: CO2 is recognized as a major contributor of
Typically primary and secondary amines form acidic
global warming. We report a facile, sensitive and anion species like bicarbonate, carbonate and carbamate
accurate method for estimating CO2 content in the with CO2 (equations 1 to 5).
alkanolamine solvents. It can be applied to a host of R2NH + H2O R2NH2+ + OH (1)
alkanolamine solvents as well as solvent mixtures for CO2 + 2 H2O HCO3- + H3O+
(2)
screening for prospective absorbent for CO2 capture. In HCO3- + H2O CO3-- + H3O+
(3)
this method, pH of the CO2-loaded absorbent sample is CO + R NH R NH+COO- (zwitterions) (4)
2
2
2
measured and referred to a reference pH graph of R NH+COO- + R NH
2
2
corresponding amine with sulphuric acid that is R NCOO- + R NH +
(5)
2
2
2
constructed under specific conditions. The authenticity of (carbamate) (protonated amine)
the method was validated from known amounts of CO2
Tertiary amines cannot form carbamate species,
added in the form of CO2-saturated water to three because they do not have hydrogen attached to the
different types of alkanolamines i.e. the primary nitrogen atom. Typically tertiary amines react according
(monoethanolamine, MEA), secondary (diethanolamine, to equation 6.
DEA) and tertiary (triethanolamine, TEA) alkanolamines.
CO2 + R3N + H2O HCO3- + R3NH+
(6)
The method was compared with known methods and
One of the main criteria for selection of suitable
found to be better in terms of accuracy.
solvent requires estimation of CO2 in both the gas and
Keywords: CO2 estimation, pH, pKa, Alkanolamines, Gas
liquid phases for ascertaining the mechanism and
absorption.
material balance for rate and capacity estimation of the
Introduction
solvent. Accurate amounts of CO2 in liquid solvents are
Carbon dioxide (CO2) has been proven to be
also required to remove discrepancies in parameter
responsible for 80% of green house gases, contributing to
estimation in simulation and modeling by mathematical
the increase of earths temperature. Half of the CO2
model for plant design and feasibility studies.
emission is produced by industries and power plants
There are many methods available for estimation of
using fossil fuel (Desideri et al., 1999). Consequently,
carbon dioxide in absorbing liquids specifically the
modern research geared towards developing new CO2
alkanolamines. The UOP method 826-81 (UOP Method,
capture technologies worldwide.
1981) uses phosphoric acid to liberate the dissolved CO2
Traditionally, absorption/stripping via circulated
in amine solutions. The method involves quite a few steps
aqueous alkanolamines have been the most favored
like use of mercury for determining the volume of
technology for removing CO2 from process and waste gas
calibrated tube, introducing sample of CO2-containing
streams. The existing commercial processes based on
amine, adding phosphoric acid to liberate CO2 from
alkanolamines are highly energy- and cost- intensive. As
sample and use of mercury leveling bulb to force the
much as 80% of the total energy consumption in an
liberated gas into the measuring burette repeatedly till no
alkanolamine absorption process occurs during solvent
further CO2 remains dissolved in the amine and washing
regeneration (White. et al., 2003). Therefore, search is on
of carbonimeter. Regarding precision of the method no
for new improved solvents with higher rates and
estimated standard deviation is reported due to lack of
capacities for absorption of CO2, high degradation
sufficient data to permit this calculation with at least 4
resistance, low corrosiveness and low energy use for
degrees of freedom. Also the elapsed time for one
regeneration. Such a solvent will decrease both capital
analysis is 1.0 hour.
and operating costs of the process thereby reducing the
Currently the most popular analytical method for
cost of electricity at thermal power plant when CO2
determining the acid gas concentration in aqueous amine
removal is integrated in the plant. Many new solvents are
solutions employs a wet chemistry titration. In the
being researched for potential commercial use to remove
method for CO2, the amine sample is mixed with an
CO2 from flue gas streams.
excess of standard base and heated to boiling. Since the
Three classes of alkanolamines, primary (MEA),
amine-acid gas complex is thermally unstable, the acid
secondary (DEA) and tertiary (TEA and methyl
gas is converted into an ionic species and is precipitated
diethanolamine, MDEA) or their mixtures, are generally
by an appropriate metal salt like BaCl2. The filtrate is
used as absorbing liquids. The different categories of
titrated with a standard acid to determine the
amines differ in the type of mechanisms with which they
concentration of uncarbonated amine in the sample (here
react with CO2 as well as the reaction products and the
onwards termed as BaCl2 method). Indicators like
heats of reaction.
bromocresol green, cresol red and phenolphthalein etc.
Research article
Indian Society for Education and Environment (iSee)
60
Indian Journal of Science and Technology
pH
pH
pH
are commonly used to indicate the end points (Coldrey & verified daily before use. Blank runs should also be made
Harris, 1976; Ellis et al., 1963; Hikita et al., 1977; Jensen to properly execute the titration. The solution analysis by
et al., 1954; Gas Conditioning Fact Book, 1962; Jou et al., titration is often complicated by the presence of impurities
1982; Weiland &Trass,1969). The CO2 content of the and degradation products (Arnold & Pearce, 1960). Most
solution is calculated as the difference between the total chemical methods of ethanolamine analysis depend on
amine and uncarbonated amine. However, the amine functionality and are nonspecific and inaccurate
calculations require assumption of 1:1 stoicheometry (Brydia & Pearce, 1967).
A method based on GC has been reported by
between amine and CO2 (Weiland et al., 1969) which is
not true. Another titrimetric method for determination of Robbins and Bullin (Robbins & Bullin, 1984) which is fast,
CO2 in ethanolamine is the
accurate and analyses the amine
solution for acid gases like H2S and
UOP method 829-82 [here
Fig. 1. pH graph of 2.6M AMP vs H 2 SO 4
CO2, hydrocarbons, water and
onwards termed as MeONa
13
amine content.
However, the
method]
(UOP
Method,
12
example cited is with MDEA only
1982). The method involves
11
10
and the structural characteristics of
dissolution of CO2-absorbed
9
other alkanolamines are bound to
sample
in
anhydrous
8
affect the retention time of the
methanol.
The
7
constituent components and lot of
amine/methanol solution is
6
work needs to be done on their
titrated
with
standard
5
separation using the prospective
methanolic sodium hydroxide
4
solvents used in CO2 separation for
solution
using
3
thymolphthalein
as
the
this method to become a standard
2
indicator and calculating the
method. Moreover the effects of
1
CO2 content.
amine salts, that result when the
0
alkanolamine reacts with CO2, on
The
wet
chemistry
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
methods
involving
retention time is not known.
moles of H2SO4 mole -1 amine
precipitations and titrations
Thus, the analytical methods
Fig. 2. pH graph of MEA, DEA, TEA and MDEA
have serious disadvantages.
reported above can provide only
vs H 2 SO 4
The total time required for an
the directional values for total
13
experienced technician to
amount of CO2 in the lean and rich
MEA- H2SO4
12
analyze
one
carbonated
amines but are not suited for
DEAH2SO4
11
TEA- H2SO4
amine solution could be as
studies involving small changes in
10
MDEA- H2SO4
long as 1-2 hours. During
CO2 content as is required in
9
part of this time, the CO2studies
like kinetics of absorption in
8
the
stirred
contactor/wetted-wall
amine solution is open to the
7
column. The number of data points
atmosphere so both flashing
6
in these studies is large and the
of CO2 and degradation of the
5
CO2 build up that starts from just a
amine can occur. Also
4
stoicheometry for different
few mg is very gradual. Present
3
types
of
alkanolamines
studies were, therefore, aimed to
2
(primary,
secondary
and
0.0 0.1 0.2 0.3
0.4 0.5 0.6 0.7 0.8 develop a sensitive and fast
-1
tertiary) for CO2 is usually
method for estimation of CO2 for
moles of acid mole of amine
assumed as one which is not
analyzing sequential build up of
Fig. 3. pH graph of 2.6M AMP vs acetic acid
true and leads to erratic
CO2 in the alkanolamine solvents
13
results for CO2 content. This
ranging from ppm to percent level
12
for absorption-based studies. The
has serious bearing on results
11
method was applied to CO2-loaded
for the weight of CO2
10
estimated
because
the
alkanolamines which were obtained
species formed upon reaction
after absorption of CO2 in the
9
of alkanolamine with CO2 may
alkanolamines of different chemical
8
structures (MEA, DEA, TEA etc.).
vary from monoionic HCO37
Experimental
and carbamate to di-ionic
6
CO3-- ions (equations. 2, 3 and
1. Reagents and equipments: All
5
5) in different proportions.
the chemicals used in the present
4
Freshly prepared solutions of
study were 97-99% pure. H2SO4
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7 (98%), DEA (98%), TEA (97%) and
standardized acid and base
moles of acetic acid mole -1 amine
must also be available and
NaOH (97%) were purchased from
Research article
pH-based CO2 estimation
Asha Masohan et al.
Indian Society for Education and Environment (iSee)
http://www.indjst.org
Indian J.Sci.Technol.
61
Indian Journal of Science and Technology
pH
SD Fine Chem. Ltd., India. HCl, MEA (98%), oxalic acid addition of acid (0.5 ml) the pH was noted. Addition of
ampules (volumetric solution N/10) and BaCl2 (99%) were acid increased the temperature of mixture and was
purchased from Qualigens, India while MDEA (99+%) allowed to cool to 25oC before taking the pH reading.
was purchased from Aldrich Organics, New Jersy, USA. Initial pH of amine was nearly 12. Readings were taken
Methanol (>99%) from Merck Limited, India; Acetic acid till the pH fell to nearly 3 (pH range of acid). Weight of
(99.8%) from Rankem Fine
acid added was calculated from
Chemicals Ltd., India and
its normality and the volume
Fig. 4. pH graph of MEA, DEA and TEA vs
oxalic acids
Na2CO3 from BDH, E. Merck,
added. The weight thus obtained
13
was converted to moles of acid
India and 2-amino-2-methyl-112
by dividing with 98 and
propanol (AMP) from Merck
MEA- Oxalic acid
11
DEA- Oxalic acid
subsequently to moles acid moleSchuchardt OHG, Germany
TEA- Oxalic acid
10
1
were purchased. All solutions
amine by dividing the moles of
9
were prepared in double distilled
acid by moles of amine. A graph
8
water. Thymolphthalein indicator
was plotted for moles acid mole-1
7
solution taken was from Loba
amine vs. corresponding pH for
6
Chemie Pvt. Ltd., India.
the whole pH range. This was the
5
pH meter used was of
reference pH graph (Fig. 1).
4
Thermo Orion, Model 420,
3
Similarly
reference
pH
2
Beverly, MA 01915, USA. All
graphs were obtained for MEA,
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
titrations were carried out at
DEA, TEA and MDEA with
-1
moles of oxalic acid mole of amine
25oC.
H2SO4 (Fig. 2). Graphs were
also plotted for 2.6M AMP (Fig.
2. Preparation of solutions
3) with acetic acid and MEA,
100 ml of desired strengths
DEA and TEA with oxalic acid
(1M or 2.6M) of MEA, DEA, TEA,
(Fig. 4) to study the effect of
MDEA, and AMP absorbents were
structure of acid on pH curve and
prepared.
Methanolic NaOH
stoicheometry.
(0.05M)
was
prepared
by
dissolving 2.1 g NaOH in 100 ml
4. Preparation of CO2-loaded
water and making up the solution
alkanolamine samples
to 1L by adding methanol as given
4.1. Absorption of CO2 in
in reference (UOP Method, 1982).
alkanolamine: 50 ml of 1M
BaCl2 used was 0.68 M while
solution of MEA was taken in a
100 ml three-neck round bottom
H2SO4, acetic acid and oxalic
flask. CO2 absorption in amine
acids used for pH titration were
0.1N.
was started by passing CO2 gas
250 ml each of 0.05N NaOH,
at a flow rate of 5.5 sec for 10 ml
0.06M BaCl2 and 0.02N HCl were
of CO2 gas. Absorption was
prepared for use for estimation of
continued for 1h. This resulted in
CO2 in CO2-saturated water.
the CO2-loaded amine sample.
3. Titration for
reference graphs
plotting
of
10 Drops of thymolphthalein
indicator were added to 20 ml of
methanol in a 100 ml beaker.
This solution was titrated against
methanolic NaOH (termed as
MeONa) till light blue color
appeared. 3 ml of (2.6M) solution
of AMP was added to this
mixture. Moles of amine taken
were calculated by dividing
weight of amine in 3 ml solution
by its molecular weight. pH of this
solution was noted. The resulting
methanolic solution of amine was
then titrated against H2SO4 with
constant stirring by magnetic stirrer. After every small from the graph.
Research article
pH-based CO2 estimation
Indian Society for Education and Environment (iSee)
http://www.indjst.org
62
Indian Journal of Science and Technology
Weight of amine *
Mol. Wt. of amine
44 ..(10)
5. Validation of results
5.1. Reparation of saturated solution of CO2 in water:
Based on the accuracy of the results, the present pHbased method was then used in estimating CO2 content
in the CO2-loaded amine samples prepared as described
under 4.1.
Completely loaded samples of alkanolamines: 3 ml of the
5.2. Adding known volume of CO2-saturated water to CO -absorbed amine sample was added to 20 ml of
2
amine and estimating by the method developed: 3 ml of alkaline
methanol as under 3. pH of the sample is noted
alcoholic amine solution of 2.6M MEA was prepared in
and moles acid mole-1 amine obtained from the MEAsimilar way as mentioned under 2. A 5 ml sample of CO2H2SO4. Weight of CO2 absorbed in amine is then
saturated water prepared as above was added to this
calculated from the value of moles acid mole-1 amine.
amine solution. pH of this mixture was noted. It is to be
Results were compared with those obtained by the
MeONa and BaCl2 methods. Similar
Table 1. Estimation of saturated amount of CO2 in water as such and after
estimations were made for CO2
addition in different amines
absorbed in DEA and TEA. The
Wt. of CO2 in 5 mL of CO2-saturated water (mg)
results are shown in Table 2.
Strength CO2 estimated
Partially
loaded
samples
of
of
alkanolamines containing variable
In water In amine
Amin
amine
amounts of CO2: That the method is
from pH
Methanolic
e
solution, Alkaline BaCl2
suitable for any content of CO2 in
NaOH Method reference graph
BaCl2
Method
(M)
alkanolamines was tested by
(UOP method, of amine with
(Literature)
Method
conducting kinetic experiments in
H2SO4
1982)
stirred cell. CO2 was passed at the
MEA
2.67M
5.701
5.5
6.1813
5.984
interphase of the alkanolamine with
DEA
2.67M
8.11297
2.816
stiiring of the liquid phase and
( 1.9=5.35)
collecting CO2-absorbed samples at
TEA
2.67M
11.44
8.11297
5.104
an interval of few seconds (30
seconds) to minutes till the end of
MEA
2.67M
5.632
6.41
4.699
5.55
experiment. The results are shown in
DEA
2.67M
8.223
3.168
Fig. 5. Similar estimations were
( 1.9=6.02)
made for CO2 in DEA and TEA also.
TEA
2.67M
7.32
9.3985
5.346
In case of secondary amine like DEA
MEA
2.67M
5.700
6.64
5.9
it was observed that the results
neede to be multiplied by a factor of
DEA
2.67M
6.18
2.99
1.9 for exact amounts (perhaps
( 1.9=5.68)
because
of
stoicheometric
TEA
2.67M
7.78
5.34
requirements).
Research article
pH-based CO2 estimation
Asha Masohan et al.
Indian Society for Education and Environment (iSee)
http://www.indjst.org
Indian J.Sci.Technol.
63
Indian Journal of Science and Technology
http://www.indjst.org
Indian J.Sci.Technol.
64
Indian Journal of Science and Technology
http://www.indjst.org
Indian J.Sci.Technol.