You are on page 1of 6

Multivariate Calibration of CO2 Solubility in

Diethanolamine (DEA) using Raman Spectroscopy


Nuralia Syairah Binti Osman
Chemical Engineering Department, Universiti Teknologi PETRONAS
32610 Bandar Seri Iskandar, Perak
nuraliasyairah.osman@gmail.com
Abstract: Carbon dioxide (CO2) capture process has become essential step in industry due to phenomena of global warming.
Absorption based on alkanolamines like diethanolamine (DEA) have been widely applied in carbon capture plant. Throughout the
process, CO2 solubility is an important parameter that need to measured. In this study, Raman shift and intensity of different DEA
concentration with respect to CO2 loading (mol CO2 / mol amine) are obtained by using Raman spectroscopy. Partial Least Square
(PLS) regression approach will be utilized to develop a calibration model that relate the Raman spectroscopy data to CO2
solubility in different concentration of DEA. From the result obtained, 10%, 20% and 30% model have shown great performance
and demonstrate good prediction of CO2 solubility. In addition, a combined concentration model and combined modified model is
developed to predict CO2 solubility at different DEA concentration . From the study, with the inverse of 900 1100 cm-1 are
added to predicting matrix in combined modified model, the validation R2 have been increased from 0.9004 to 0.9136
Keywords CO2 capture, CO2 loading, Raman Spectroscopy, DEA, partial least square regression, multivariate calibration

I. INTRODUCTION
Phenomenon of global warming and climate change
caused by emission of greenhouse gases like CO2 has been
recognized as a significant environmental problem by the
worldwide scientific community [1]. Besides that, CO2 also is
an unwanted by-products in natural gas processing industries
due to its properties as an acid gas . When CO2 react with
water, it will form carbonic acid that tend to cause corrosion
and give major effects and damage to the oil field equipment
and gas pipelines [2]. Formation of carbonic acid and moisture
will decrease pipeline flow capacities, even resulting in
blockages, and potential harm to valves, filters and
compressors that are being used throughout the process. To
cater this issues, removal CO2 process like absorption by
chemical solvents, physical absorption, cryogenic separation,
membrane separation from industrial flue gas is important [3]
in order to increase heating value of natural gas and optimize
pipeline capacity [2].
Comparison of the technologies available for CO2
capture have been done and conclude that absorption with
aqueous amine solution is the most favoured one because of
lower costsand most efficient [4][5] During the absorption
process, CO2 loading measurement is a vital action for a
proper process control. The earliest method to measure CO2
loading in alkanolamines is by titration. However, this method
is quite tedious as the sample need to be prepared and the
analysis cannot be done during the process [2]
Many studies have been conducted in order to find
most suitable and efficient tools to measure CO2 loading
instantaneously. Infrared, NMR and Raman spectroscopy are
some of the spectroscopic technique that have been used for

instantaneous measurement of gas-liquid concentration.


Raman spectroscopy is chosen because of its properties that is
weak with water molecules, so it suitable for monitoring
aqueous system [6]. It is a non-invasive, non-destructive and
direct measurement method efficient for quantitative analysis
for concentration as low as 0.1 up to 100% [2]
In this project, measurement of CO2 loading in DEA
using Raman spectroscopy is the main focus. To achieve this
focus, Partial Least Square Regression (PLSR) approach will
be utilized to develop a calibration model that relate the
Raman spectroscopy to CO2 loading. PLSR method have been
successfully applied in many areas including multivariate
statistics, analytical chemistry, medicine, face recognition etc.
Combination of analytical instrument and multivariate
calibration tools will aid the process of online monitoring CO2
solubility in DEA.
II. LITERATURE REVIEW
A. CO2 absorption process
Absorption allows acidic gases to be dissolve in a solvent
and will be released by regeneration A typical chemical
absorption process by amine process consists of an absorber
unit, a regenerator unit. In the absorber, flue gas CO2 entered
the bottom of absorber column and the lean amine solution
will absorbed the CO2 counter-currently to produce sweet gas
as a product [5]. Sweetened gas leaving the top of the absorber
passes through an outlet separator and then flows to a
dehydration unit (and compression unit, if necessary) before
being considered ready for sale. Now, the rich amine
solution contains the CO2 gas is further heated in regeneration
column for thermal regeneration. Steam and acid gases
separated from the rich amine are condensed and cooled.

III.
B. Diethanolamine (DEA) Reaction Mechanism
During the absorption of CO2 in the DEA, carbonate
(CO32-), bicarbonate (HCO3-) and carbamate (
will formed as the final product along the reaction. The
equation of chemical reaction that take place can be written as
below [7], [8] [5]
Water ionization:
(1)
Dissociation of Carbon Dioxide:
(2)
Dissociation of Bicarbonate:
(3)
Carbamate Formation:
(4)
Overall Equation:
(5)
C. Raman Spectroscopy
Raman spectroscopy is a one of the spectroscopic
technique that are available for analysis of material and
chemical. It is commonly used to characterize chemical
components by providing a fingerprint by which the molecule
can be identified. Raman spectroscopy is a non-destructive
analysis, fast, sensitive and flexible [9]. Besides that, Raman
has minimal sensivity with water due to water is weak Raman
scatter [10]. Hence, it is suitable for analysis of aqueous
system.
D. Multivariate Calibration - Partial Least Square (PLS)
Regression
Multivariate calibration is widely applied in chemometrics
field where mathematical and statistical method was used to
analyzed enourmous amount of chemical data. It will construct
mathematical model that relates the multivariate response
(spectrum) to the concentration of analyte to predict the
concentration of new samples. One of the multivariate
calibration tools is PLS regression where it used to analyse the
relationship between two data matrices, X and Y (predictor
variable) by constructing new predictor variable [11]. PLS is
suitable for quantitative modelling and prediction [12]. This
technique actually is an extension of multiple linear regression
(MLR) analysis where the effect of linear combinations of
several predictors on multiple response variable are analysed
[13]

METHODOLOGY

A. Obtaining CO2 loading


CO2 absorption cell is use to obtain CO2 solubility data in
DEA. Distilled water was used for the preparation of solution.
10%, 20%, 30% of DEA aqueous solution was prepared and
feed into the absorption vessel. CO2 from feed tank will
disperse into absorption vessel and was absorbed by DEA.
CO2 loading was measured by using pressure drop method.
B. Raman Spectroscopy
The portable Raman spectrometer was used to project the
laser source to the sample. The laser source had wavelength of
785 nm and power of 500 mW [6]. To capture the spectra, the
software SpectraWiz was used. CO2 absorption cell is
connected with optical fiber probe of Raman spectrometer.
C. Pre-processing Raman Spectrum
After that, pre-processing of Raman spectra need to be
done in order to get a good spectra. In the other typical
measurement techniques, noise can cover the information
hidden in a spectrum. Besides that, the information might
contained in the high intensity and low intensity spectra.
Hence, pre-processing is recommended to remove the noise
effect and maximize the data obtained in spectrum. The
Raman spectra were reduced by using Savitzky-Galoy filter
D. Partial Least Square Regression Modelling
Modelling approaches must be applied in order to convert
the data contained in Raman spectra. The data will be divided
into two types of data set, calibration and validation data.
Calibration data set will be used to develop few models using
PLS regression while validation data set is to test the
performance of calibration model. The calibration and
validation data set comprise Raman Intensities with respective
Raman shift as X variable and CO2 loading as Y variable.
Data matrix of X and Y need to be normalized first before
do PLS regression in order to get accurate result. It will scaled
up and centred the dataset and give mean equal to 0 and
standard deviation equal to 1. For validation data set, X and Y
data matrix will be scaled up using mean and standard
deviation obtained from calibration mode l.
Then, PLS regression is applied to the calibration dataset.
It will generate XL, YL, XS, YS and Beta. XL and YL is a
predictor and response loading respectively. It consist of
coefficient between PLS components and original predictor
and response variable respectively [11]. XS and YS is refer to
score of X and Y. Beta is coefficient which will be used in
predicting CO2 loading.

When a process model is used for the prediction of


process variables, the quality of that prediction must be
judged. The prediction of calibration and validation has been
evaluated by using coefficient of determination (R2) and mean
square error (MSE). R2 will be used to see how well the
regression line approximated the data.
IV. RESULT AND DISCUSSION
A. Qualitative Analysis of Raman

Figure 1 shows the Raman spectrum of DEA at 10%, 20%


and 30% concentration. It can be seen that the intensity of
30% concentration is higher at spectral region 1200cm -1 to
1500cm-1. It might be because of formation carbamate when
there is higher concentration of amine. The formation of
carbonate and bicarbonate is identified between spectral
regions of 1000 cm-1 to 1080 cm-1. It has been observed that
peak intensities at that range is increasing during CO2
absorption. Then, the peaks declined due to the consumption
of amine during absorption process.
B. Partial Least Square Regression
1) Calibration model for 10%, 20% and 30% DEA
concentration

(a)

Calibration model of 10%, 20% and 30% of DEA


concentration have been developed named D10, D20 and D30.
The data set used to load in MATLAB will be divided into
calibration set and validation set. All the model were
developed using PLS approach with 10 numbers of
component.

Figure 1: Raman Spectrum of DEA

(a)

(d)

(b)

(c)

(e)

(f)

Figure 2 (a-f): Graph of Actual & Predicted CO2 loading. (a) Calibration in D10 (b) Validation in D10 (c) Calibration in D20
(d) Validation in D20 (e) Calibration in D30 (f) Validation in D30
As we can see in Figure 2 (a) (c) (d), calibration set in D10, D20 and D30 give good prediction of CO 2 loading with
excellent linearity while in validation set, the linearity of prediction CO2 loading is quite low as expected. The performance of the
3 models will be evaluated by their R2 and MSE value in the table below

Models
D10
D20
D30

Table 1: Calibration and Validation Results in D10, D20, D30


Coefficient of Determination (R2)
Mean Square Error (MSE)
Calibration
Validation
Calibration
Validation
0.9995
0.9346
0.00048943
0.0802
1.0000
0.9375
0.0000064189
0.0680
0.9999
0.9644
0.000096595
0.0329

The evaluation of the fit of D10, D20 and D30 was done
by correlate the actual values of CO2 loading and predicted
CO2 loading values calculated by PLS. The calibration R2
values for all 3 models are greater than 0.9. Calibration model
of D20 shows the best performance with the highest R2 value
which is 1.0. Meanwhile, in validation set R2 values is slightly
low compared to calibration model as expected. However, the
value is remain to be considered good. D30 model showed the
highest R2 value (0.9644).
2)

(a)

Calibration model for Combined Concentration

To develop a model that able to predict CO2 solubility at


different concentration of aqueous DEA, combined
concentration modified model (DC1) is introduced in next
phase. DC1 consist of combination dataset CO2 loading and
Raman intensities from D10, D20 and D30.

(b)

(a)

Figure 4: Actual and Predicted CO2 loading (a)Calibration in


DC2 (b)Validation in DC2
Table 2: Calibration and Validation Result in DC1 And DC2
Coeffiecient of
Determination (R2)
(b)

Figure 3: Actual and Predicted CO2 loading (a)Calibration in


DC1 (b)Validation in DC1
DC2 model was developed to investigate the effect of
concentration column in the prediction performances. In this
case, additional column consists of the amine concentration is
added to the X data matrix (observed variable).

Mean Square Error


(MSE)

Calibration

Validation

Calibration

Validation

DC1

0.9780

0.9004

0.0218

0.1143

DC2

0.9775

0.9035

0.0224

0.1107

By combining CO2 loading and Raman intensities of


10%, 20% and 30% of DEA into 1 dataset, DC1 still give
quite good prediction of CO2 loading with good linearity in
calibration model. However, in validation model, the linearity
is not so good compared to calibration model. The result of R2
after add additional column consists of amine concentration is
still not satisfying enough especially in the validation model.
The error obtained in DC2 does not have much difference
from DC1 model. Further study need to be done in order to
improve validation model of DC1 and DC2.

Another model, DC3 model is introduced to see the


effect of formation carbonate, bicarbonate and carbamate in
the DEA reaction with CO2 in the range of Raman shifts 900
1100 cm-1. The subsequent study is to investigate how this
range can be further exploited. There are 3 sub models of DC3
which are DC3-A, DC3-B and DC3-C in developed to further
improve the R2 value.
Models

Details

DC3-A

To see the influence of this range, we are


duplicating by add additional column in
X data matrix.

DC3-B

In DC3-B, the additional column will be


squared.
In DC3-C, the additional column from
DC3-B will be inversed. It will be

Figure 5: Actual and Predicted CO2 loading (a)Calibration in


DC3 (b)Validation in DC3
V. CONCLUSION

0.9802

0.8943

0.0204

0.1188

Based on the result obtained, it can conclude that individual


models have shown good performance and great ability to
predict CO2 solubility at 10%, 20% and 30% concentration of
DEA. This can be shown by the calibration R2 values of this 3
models is nearly to unity and the validation R2 values are more
than 0.9. Besides that, another model also have been
developed in order to predict CO2 solubility at different
concentration DEA. This model also demonstrate great ability
to predict CO2 solubility. In conclusion, multivariate PLS
regression has been successfully used to predict CO2 solubility
in different concentration of aqueous amine using Raman
spectroscopy.

0.9756

0.8994

0.0242

0.1153

REFERENCES

0.9751

0.9136

0.0247

0.0991

DC3-C

Table 3: Calibration and Validation Result in DC3


Coefficient of
Mean Square Error
Determination (R2)
(MSE)
Calibration
DC3 A
DC3 B
DC3 C

(b)

Validation

Calibration

Validation

The table below shows the result obtained after do


PLS regression. We can see that calibration R2 values is kept
decreasing but still in the good range while validation R2
values is kept increasing. DC3-C shows the highest validation
R2 values compared to DC1, DC2, DC3-A and DC3-B which
is 0.9136.

[1]

Y. E. Kim, J. A. Lim, S. K. Jeong, Y. Il Yoon, S. T. Bae, and S. C.


Nam, Comparison of carbon dioxide absorption in aqueous MEA,
DEA, TEA, and AMP solutions, Bull. Korean Chem. Soc., vol. 34,
no. 3, pp. 783787, 2013.

[2]

M. K. Wong, M. A. Bustam, and A. M. Shariff, International


Journal of Greenhouse Gas Control Chemical speciation of CO 2
absorption in aqueous monoethanolamine investigated by in situ
Raman spectroscopy, Int. J. Greenh. Gas Control, vol. 39, pp.
139147, 2015.

[3]

S. Park, B. Min, J. Lee, and S. Nam, Absorption Characteristic of


Continuous Co 2 Absorption Process, Fuel, vol. 49, no. 1, pp. 249
250, 2004.

[4]

L. S. Tan, a. M. Shariff, K. K. Lau, and M. a. Bustam, Factors


affecting CO2 absorption efficiency in packed column: A review,
J. Ind. Eng. Chem., vol. 18, no. 6, pp. 18741883, 2012.

[5]

C.-H. Yu, A Review of CO2 Capture by Absorption and


Adsorption, Aerosol Air Qual. Res., pp. 745769, 2012.

[6]

M. A. B. MZ Shahid, Abdulhalim Shah Maulud, Prediction of the


Concentration of Diethanolamine (DEA) and Methydiethanolamine
(MDEA) Aqueous Solutions by using Raman Spectroscopy, J.
Appl. Sci., vol. 14, no. 11, pp. 11981203, 2014.

[7]

J. Gabrielsen, M. L. Michelsen, E. H. Stenby, and G. M.


Kontogeorgis, A Model for Estimating CO 2 Solubility in Aqueous
Alkanolamines, Ind. Eng. Chem. Res., vol. 44, no. 9, pp. 3348
3354, 2005.

(a)

[8]

[9]

[10]

T. Neveux, Y. Le Moullec, J. P. Corriou, and E. Favre, Modeling


CO2 capture in amine solvents: Prediction of performance and
insights on limiting phenomena, Ind. Eng. Chem. Res., vol. 52, no.
11, pp. 42664279, 2013.
A. Koistinen, Introduction to Infrared and Raman spectroscopy
Types of Spectroscopy molecular vibrations, pp. 128, 2012.
T. Vankeirsbilck, a. Vercauteren, W. Baeyens, G. Van der Weken,
F. Verpoort, G. Vergote, and J. P. Remon, Applications of Raman
spectroscopy in pharmaceutical analysis, TrAC - Trends Anal.
Chem., vol. 21, no. 12, pp. 869877, 2002.

[11]

Statistics Toolbox TM User s Guide R 2014 a, 2014.

[12]

M. Mortsell and M. Gulliksson, An overview of some non-linear


techniques in Chemometrics, Fibre Sci. Commun. Netw. Rep. Ser.,
2001.

[13]

L. M. Carrascal, I. Galvn, and O. Gordo, Partial least squares


regression as an alternative to current regression methods used in
ecology, Oikos, vol. 118, no. 5, pp. 681690, 2009.