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Contents lists available at ScienceDirect

**Journal of Natural Gas Science and Engineering
**

journal homepage: www.elsevier.com/locate/jngse

**Prediction of amines capacity for carbon dioxide absorption in gas
**

sweetening processes

Mohammadreza Momeni, Siavash Riahi*

Institute of Petroleum Engineering, Faculty of Chemical Engineering, College of Engineering, University of Tehran, Tehran, Iran

a r t i c l e i n f o

a b s t r a c t

Article history:

Received 23 July 2014

Received in revised form

30 August 2014

Accepted 1 September 2014

Available online 26 September 2014

Almost all gas reservoirs around the world produce sour gas that contains considerable amounts of acid

gases including carbon dioxide and hydrogen sulﬁde. Because carbon dioxide in water tends to cause

corrosion and the presence of CO2 in natural gas reduces its heating value, it must be removed prior to

preparation of natural gas for marketing. Many technologies have offered various solutions to remove

carbon dioxide from natural gas based on regenerable amine-based solvents. In order to make these

technologies more efﬁcient and economical, further research is required in terms of experiment and

modeling to identify the main parameters which inﬂuence the capacity of amines for CO2 absorption.

Numerous studies of amines have shown evidence that some relationships exist between the structure of

amine and its capacity for carbon dioxide absorption. Quantitative Structure Property/Activity Relationship (QSPR/QSAR) provides an effective method for predicting amines capacity for CO2 absorption. In

this paper, ﬁrst, Density functional theory (DFT) method level of B3LYP and 6-311 þ g (d,p) basis set was

employed to complete molecular geometrical optimization. Then, the Quantitative relationship between

the absorption capacities data and calculated descriptors was achieved by the multiple linear regression

(MLR) and model variables were selected by genetic algorithms (GA). The accuracy of the model was

veriﬁed by different statistical methods and the result proved high statistical qualities of the model.

Unlike other QSPR researches, the reported equation in this paper consists of simple and easy-calculated

descriptors which form a robust model for predicting amines capacity of carbon dioxide absorption.

© 2014 Elsevier B.V. All rights reserved.

Keywords:

Gas sweetening

Rich loading

Carbon dioxide

Absorption

Amines

QSPR

1. Introduction

Amines are molecules containing nitrogen atoms attached to a

carbon-based chain structure. They can be applied in various ﬁelds

of engineering and science. One of the most important applications

of amines is using them as an acidic gas absorption liquid for

removing carbon dioxide from natural gas or oxygen containing

systems for instance ﬂue gas (Singh et al., 2007, 2009). The Absorption capacity of amines is an important characteristic. Moreover, Different aspects of the molecules behavior of toxicity and

environmental protection to technical issues can be affected by this

feature. The solubility and absorption rate of carbon dioxide in

amine based CO2 absorbents are not only important due to technical considerations but also are vital for environmental issues.

Since experimental determination of absorption capacity (or rich

loading) is very time-consuming and expensive and the values are

*** Corresponding author. University of Tehran, Tehran 11365-4563, Iran. Tel.: þ98
**

21 61114714.

E-mail address: riahi@ut.ac.ir (S. Riahi).

http://dx.doi.org/10.1016/j.jngse.2014.09.002

1875-5100/© 2014 Elsevier B.V. All rights reserved.

**not always available in literature sources, estimation plays an
**

important role (Pourbasheer et al., 2011). Hence, the development

of capable methods for predicting absorption capacity of different

amines becomes an urgent task.

Gas sweetening or acid gas removal (for instance CO2 and H2S) is

conventionally used in various industries (Bohloul et al., 2014).

Almost all gas reservoirs around the world produce sour gas that

contains considerable amounts of acid gases including carbon dioxide and hydrogen sulﬁde. Owing to the fact that carbon dioxide in

water tends to cause corrosion and the presence of CO2 in natural

gas reduces its heating value, it must be removed prior to the

preparation of natural gas for marketing (Mokhatab and Poe, 2012).

The most common absorption media for this purpose are aqueous

amine solutions. Amine derivatives including monoethanolamine

(MEA), diethanolamine (DEA) and methyldiethanolamine (MDEA)

are widely being used in commercial and industrial applications

(Kohl and Nielsen, 1997). Due to the importance of amines in acid

gas removal technologies, a descriptive and a novel model has to be

developed from which amine chemical properties can be predicted.

There are evidences in the literature indicating the existence

of relationships between the structure of an amine and its

etc. It seems that the rate of the initial reaction can be reduced by the steric hindrance effects. the number of calculated descriptors was decreased by the accepted procedure below: 1. They performed semi-quantitative study of these effects on the capacity of amines for CO2 absorption (Singh et al. exact polarizability. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 capacity for carbon dioxide absorption (rich loading). 1998). The selected model was validated using statistical tests and validation methods for instance leave-one-out-cross-validation method. All of the results in this paper are based on mathematical calculations and model development. 2007. the number of amine available to react with CO2 grows noticeably (Chakraborty et al. 2. as a result. geometrically optimized structures of each molecule were fed into the Dragon software developed by the Milano Chemometrics and QSAR research group (Todeschini et al. Freire et al. The structural properties of molecules were extracted and calculated by using computer software. 2012): 1. this work is the ﬁrst quantitative research on amines capacity for CO2 absorption based on the simple and robust model. 2000. topological descriptors. 2010. p) basis set was employed to perform geometrical optimization (Cramer. The accuracy of the model was veriﬁed by different statistical methods and the result proved high statistical qualities of that model. These descriptors can be divided into different groups for instance: constitutional descriptors. environmental functions or physico-chemical behaviors. This paper focuses on the development of a descriptive novel model in QSPR analysis by which the prediction of absorption capacity (or rich loading) of various amines used in industrial carbon capturing units can be predicted. The QSPR approach is based on the assumption that differences of molecules behaviors can be correlated with deviation of some molecular features that are technically termed descriptors. Multiple linear regression (MLR). Liang et al. Since nitrogen charge is reduced by this interaction. 2009). Furthermore. (361 excluded) 2. These calculations were performed by Gaussian software (Frisch et al. 3. 2006. The model also demonstrates high statistical qualities by which the predictive power and robustness of the model can be guarantee. The descriptors are numerical values that belong to the shape and structure of the molecule. which results in an accelerated hydrolysis.. consequently. In addition. Quantum chemical descriptors include properties for example dipole moment. the knowledge of molecules chemical structures is quite adequate and there is no necessity to conduct experimental conditions.. LUMO energies (Lowest Unoccupied molecular orbital energy). 1986). QSPR often requires consecutive procedures.. the number of functional groups.. In addition a computational study in the reactions between functionalized amines and CO2 was performed by Lee and Kitchin. 1995). For using QSPR method. The quantitative relationship between the absorption capacities data and calculated descriptors is achieved by the multiple linear regressions (MLR) and model variables were selected by genetic algorithm (GA) (Depczynski et al. 443 4. A data set of molecules was taken from the literature with their corresponding absorption capacities. Next. it was explained by Sartori and Savage that steric hindrance effects produced by asubstituent are responsible for these instabilities (Sartori and Savage. solvent screening experiments and investigation of the effects of some variables for example chain length. Marengo et al. 2000. the equation reported in this paper. 2007). the following steps were taken (Fini et al. consists of descriptors which are simple in terms of both calculation and interpretation. They highlighted the molecular descriptors by which reactivity trends can be obtained. This process calculates a group of precise and applicable descriptors introducing electronic and quantum chemical properties of molecules. position of side chains and functional group. In their work. Genetic algorithm (GA) is one famous method by which this task can be accomplished. 2.M. Riahi et al. 2009. 2009. This technique is used to quantitatively develop a correlation which can predict speciﬁc molecular properties. da Silva and Svendsen. were taken from the literature (Singh et al. An effective method for processing.98) that had better cor- .. Signiﬁcant contribution to analyzing the relationships between the structure and absorption capacity of amines has been made by Chakraborty et al. One of the collinear descriptors (R > 0. S.. Because of the large amount of numerical data that result in imprecise and slow further calculation. 2013. the amount of bicarbonate increases which leads to higher carbon dioxide loading (Chakraborty et al. Quantitative structureeproperty relationship technique relates chemical or physical properties of compounds to their molecular structures. Riahi.. for each molecule more than 1486 theoretical molecular descriptors were calculated. In addition. Jouan-Rimbaud et al. however. Firstly. HOMO energy (highest occupied molecular orbital energy). has been conducted by Singh et al. atomic charges.. The input of Gaussian software was pre-optimized molecule structures using semi-empirical geometry optimization method AM1. 1992). it has been shown that the existence of substituents at a-carbon causes a carbamate instability.. One of the main disadvantages of QSPR technique is that for most of the researches conducted in this area. Consequently. The best model which contains an optimum number of descriptors was selected by the means of several alternative algorithms for example genetic algorithm (GA) and MLR. 1983). To the best of the author's knowledge.. 2012. 1988). principle component regression (PCR) and partial least squares (PLS) are most widely used in QSPR modeling (Katritzky et al. molecular properties. analyzing and predicting the characteristics of different molecules can be provided by Quantitative Structure Property/Activity Relationship (QSPR/QSAR) (Beheshti et al.. etc. 2005. Constant and near constant value descriptors were eliminated. To achieve this goal. sum of the electronic and thermal free energies. Chakraborty studied the electronic effects of substituents and suggested that substitution at carbon atom causes an interaction of the p and p* methyl group orbital with the lone pair of the nitrogen.. In QSPR approaches. functional group counts. it reduces the strength of the NeH bond which results in the raise of the hydrolysis in the aqueous solution. 2008). Materials and methods The absorption capacity (rich loading) of 23 amines-based solvents for carbon dioxide absorption (Table 1). a close observation of the relationship between the chemical structure and the activity of different aminebased solutions is required. density functional theory (DFT) at the level of B3LYP and 6-311 þ G (d. etc. 2012). respectively (Lee and Kitchin. Variable selection for building a well-ﬁtted model is a further step. 2008. 2002). Godavarthy et al. for example. Their work revealed that electron withdrawing and donating groups tend to destabilize and stabilize CO2 reaction products.. Fortunately.. 2004). Momeni.. As a result. selecting the proper method for constructing a robust and precise model is very important. a total number of 31 quantum chemical descriptors were calculated for each molecule. the ﬁnal equation reported as best model contains unfamiliar descriptors which are not only hard to be calculated but also are difﬁcult or impossible to be interpreted..

87 0.63 0.06 0.37 1.79 0. No Name 1 Structure Exp.72 8 4-Amino-1-butanol 0.79 0.81 1.82 16 Monoethanolamine 0.78 0.09 0.88 0.444 M.23 7 3-Amino-1-Propanol 0.20 1. (1) 1. (2) (Model) Eq. Eq.48 1.82 13 Ethylenediamine 1.86 0.21 1.27 19 N-Pentylamine 0.53 1.72 0.4-Diamino butane(T) 1.15 1.72 0.29 1.23 1.79 0. experimental and calculated values of amines capacities for CO2 absorption (rich loading).83 1.30 1.17 18 N.61 17 N-(2-Hydroxyethyl)ethylenediamine 1.08 6 2-Pyridylamine 0.N'-bis(2-hydroxyethyl)ethylenediamine 1.91 0.08 1.3-diamino propane 1.28 0.20 14 Hexamethylenediamine 1.46 15 Isobutylamine(T) 0.80 5 2-Methyl pyridine 0.71 0.23 2 1.29 1.79 0.90 . S.59 0. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 Table 1 The structure.2-diamino propane 1.27 1.87 0.29 4 2-Amino-1-butanol 0.25 3 1.84 0.26 1.83 0.77 12 Ethylamine 0.63 0.88 0. Momeni.76 9 5-Amino-1-pentanol(T) 0.85 10 Butylamine 0.25 1.84 11 Diethylenetriamine 1.

Models Descriptors R2 Q2 F s Eq. the following model was selected: AC ¼ 0:19 þ 0:04 nH þ 0:54 nRNH2 þ 0:40 nRNHR (2) Table 2 shows some statistical factors. Bold names with (T) superscripts are test set molecules. (1) Propylamine(T) 0. nRNH2. due to the chemical reaction of amines with carbon dioxide. the calculation of two descriptors in the above model is difﬁcult because these calculations should be performed by computer. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 445 Table 1 (continued ) No Name 20 Structure Exp. 18 molecules (about 80% of molecules) were selected to construct a training set and 5 molecules built test set (about 20%).12 22 sec-Butylamine 0. To take this into account. the three descriptors appeared in the model are easily calculated and thus there is no need for computational calculation. the calculated descriptors formed a (23 545) data matrix. Mor09v is one of the 3D-MoRSE descriptors and it is deﬁned as signal 09 weighted by van der Waals volume.082 0. in order to provide a better comparison between the two models. The following linear equation was built based on molecules with the training set: AC ¼ 0:36 þ 1:57 Mor09v 0:32 RDF035m þ 0:43 nN (1) AC is used instead of absorption capacity.65. to the best of our knowledge. The correlation matrix of descriptors is also shown in Table 4. this model demonstrates high statistical qualities. So it was decided to investigate some new models with new simple descriptors. from the total 23 amine-based carbon dioxide absorbents. S. RDF035m nH.84 0.01 0. Model development After descriptors calculation. The test set was used for external cross-validation of Table 2 Some basic statistical values for two models. (2). 4. The information on the chemistry of carbon dioxide reactions with amine-based solvents will be presented in the discussion section. based on the training set. interpretation of the model and descriptors is a necessary and important step. either in the calculation or interpretation of results are more important. (2) nN. Therefore.87 23 Triethylenetetramine 2. Descriptor Type nH nRNH2 nRNHR Deﬁnition Constitutional indices Number of Hydrogen atoms Functional group counts Number of primary amines (aliphatic) Functional group counts Number of secondary amines (aliphatic) .54 0.05 0. The linear correlation value for each of the two descriptors is less than 0. Eq. including discussion and conclusion section will focus on this model.51 2. After developing numerous simple equations and evaluating them with different statistical methods. mor09V. As can be observed.127 All statistic parameters in this table calculated before training and test procedure. nRNHR 0.71 0. Finally. the above model is the simplest equation that can ever predict the capacity of amines for carbon dioxide absorption under speciﬁc conditions. GA-MLR was applied as a variable selection and model development procedure for obtaining the best model with the highest predictive power. RDF035m belongs to the group of RDF descriptors and it describes the radial distribution function-035 weighted by mass and nN represent the number of Nitrogen atoms. 3. a total of 514 descriptors were selected for each molecule as an output of this stage. where. it is concluded that the number of amino groups may affect amines capacity of carbon dioxide absorption. The GA-MLR analysis led to the development of one model with three variables. After the above constraints. As can be noticed. Results One of the most critical factors that inﬂuence the quality of regression model is how to select and construct training and test set in order to warrant the molecular diversity on both of them. 23 represents the number of compounds and 545 were the number of descriptors. The procedure of constructing training and test sets will be discussed in the results section.M. (611 excluded).971 0. In QSPR studies. Indeed. relation with absorption capacity was saved and other descriptors were eliminated. But the simpler descriptors of the second model. The ﬁrst equation demonstrates higher statistical parameters.47 All the absorption capacities (rich loading) numerical values are in the basis of (mol CO2/mol amine). Moreover.979 0. (2) (Model) Eq.79 0. Molecular descriptors and their deﬁnitions are given in Table 3. In addition.80 21 Pyridine(T) 0. we introduce the second equation as a preferred model to predict absorption capacity of amines and the rest of this paper.77 0.41 2.96 121. which demonstrates these descriptors are independent of each other and can be used to develop a QSPR model. It also seems it is not easy to describe the relationship between these two descriptors and absorption capacity of amines.945 300. (1) Eq. Table 3 The three molecular descriptors used in Eq.950 0. Momeni.

In the current work. There are some statistical tests and parameters that need to be considered. Moreover.344 1.344 0. it can be concluded that the compounds in the training and test sets were representatives of the whole data. The principal component analysis of the molecules in training and test sets. 2009.000 0. 2008). The predicted result of all molecules either in training or test set with statistical parameters are given in Table 5. the intercepts of the model should be close to zero.642 0.446 M. leave-one-out cross-validation (LOO-CV) method was applied to assess the performances of different resulting models. the slopes of regression lines forced through zero (k.000 0. Furthermore. 2002): 1 Q 2 > 0:5 (9) 2 R2 > 0:6 (10) 3 R2 R20 R2 < 0:1 and 0:85 k 1:15 (11) where R20 is the coefﬁcient of determination characterizing linear regression with Y-intercept set at zero. root mean square error (RMSE) and standard error of the estimate (s) are the most important ones. Also the following criteria described by Golbaraikh and Tropsha were applied to check the predictability of the QSPR model (Golbraikh and Tropsha.005 1. Descriptor nH nRNH2 nRNHR nH nRNH2 nRNHR 1. S. All statistical parameters formulas used in this paper are mentioned below: 2 Pn exp yi ycalc i¼1 i R2 ¼ 1 2 Pn exp y i¼1 yi (3) RMSE ¼ vﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ uP 2 u n exp t i¼1 yi ycalc i n 2 df M F¼ 2 Pn exp df E ycalc i¼1 yi i Pn i¼1 P P 0 k ¼ s¼ yexp ycalc i (5) exp yi ycalc i P calc 2 yi k¼ (4) (6) exp yi ycalc i P exp 2 yi vﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ uP u n yexp ycalc 2 t i¼1 i i df E (7) (8) where dfM and dfE refer to the degrees of freedom of the model and error. (2). Fig.000 the model. k0 ). The training set was used to build the model while the test set was used to validate the predicting power. Coefﬁcient of leave-one-out cross validation (Q2). PCA was employed to classify data set of molecules into training and test sets. Riahi et al. Coefﬁcient of determination (R2).5% and 33. For this purpose PC1 and PC2 were calculated based on descriptors in the model.. Momeni. The result showed that these two principal components made 57. During the model development procedure. . One of the common techniques in QSPR approach for constructing training and test set with the constraint of structural diversity is a PCA (principal component analysis) method (Hu et al. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 Table 4 Correlation matrix of three descriptors used in Eq. and then the best model was selected based on the high value of this parameter. High values of the F-ratio test indicate reliable models. Fig.5% of the variation in data respectively and played the main roles. respectively.005 0. Some points belong to more than one molecule.642 0. 1. adjusted R2. The ﬁrst ﬁve parameters should be near to unity while RMSE and s should be low enough near to zero.. 1 shows the distribution of the data for PC1 and PC2 and by observing this ﬁgure. The Q2LOO was calculated for each obtained equation. the Fisher function (F) is another vital statistical test.

950 0. At the last part of this section it should be noticed that the present work focuses exclusively on developing a simple model by which amines capacities for carbon dioxide absorption can be predicted. In this data set the warning value of leverage is around 0.984 1.M. For this reason. 2003). where X is the descriptor matrix. .67. 2 (OECD. Williams plot is used to identify both the response outlier and the structurally inﬂuential chemicals in the model. the standardized residuals (R) versus the leverage (hat diagonal) values (h) were plotted. 4 shows the standardized coefﬁcients (also called beta coefﬁcients) (XLSTAT. Furthermore. Fig. The overall reaction mechanism for chemical absorption of CO2 in amine solvent systems is still under debate. In Y-scrambling test. The experimental absorption capacity (rich loading) values of amines are plotted in Fig.999 0. A termolecular single step mechanism suggested by Crooks and Donnellan (1989): B þ CO2 þ R1R2NH 4 R1R2NCOO þ BHþ (3) Table 6 R2 train values after several Y-scrambling tests. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 Table 5 Validation parameters and statistical result of GA-MLR model. the more important the weight of the corresponding variable in the model.962 0. It also shows that there is no outlier in training or test sets and all compounds lie between the two horizontal lines. It led to the assumption of the single-step mechanism of these reactions (reaction (3)). QSPR should provide powerful insight for the mechanism of carbon dioxide solubility in amine based solvent. It is expected that newly developed QSPR models should have low enough R2 and Q2 values.116 76. 2007).060 0.119 0. mean effect (MF) is another term that helps to interpret the result and shows the effect of each descriptor Although high statistical parameters are signiﬁcant in demonstrating the capability of the model.976 0. Furthermore.. By observing this ﬁgure. 2005): 1 hi ¼ xTi X T X xi individually or relative to other descriptors. Momeni. But more recent studies showed zwitterion seemed to be short-lived and may be an entirely transient state (da Silva and Svendsen.942 0.144 0. but it does not consider as an outlier as its corresponding standardized residual might be small.135 0. The bonding between amine and carbon dioxide also takes place simultaneously.074 0.004 0. The ﬁgure is used to compare the relative weights of the descriptors.035 0. compounds with standardized residual rather than three standard residual unit (>3s) is considered as an outlier compound. In this mechanism.060 0. In Williams plot.096 0.102 0. Y-scrambling test was applied in order to examine the robustness of the model (Tropsha et al. Leverage demonstrates the distance of a compound from the centroid of the X.50 17. If it happens differently.904 0. the predominant difference between this study and the previous ones is that this work concentrates ﬁrstly on quantitative and then on qualitative representation of structural effects on the capacity of amines for CO2 absorption. The leverage of a compound is calculated by the following equation (Netzeva et al. It is common in the literature to use 3 as an accepted cut-off value for evaluating prediction results of the model. 2013). Iteration R2 train 1 2 3 4 5 6 7 8 9 10 0. . The higher the standardized coefﬁcients value of a descriptor. the dependent variable (Absorption Capacity) is randomly dedicated to different amines and new QPSR modeling is performed based on the previous matrix of independent variables. B is a base molecule which can be a water molecule.930 0. In fact.990 0..31 123. 5. Fig.119 0.127 0. 2003): h* ¼ 447 3ðp þ 1Þ n (13) n is the number of training objects and p is the number of descriptors in the model.67. an acceptable interpretation of descriptors in the QSPR model should be provided. it can be concluded that the number of primary amines (nRNH2) and secondary amines (nRNHR) descriptors play the main role in the amines capacity for carbon dioxide absorption respectively and the number of hydrogen (nH) has the least effect.039 where B is again the base molecule. NH group is attacked by base molecule and deprotonation of amine occurs. Discussion (12) where xi is the descriptor vector of the relevant compound.79 1. The applicability domain of the model was studied by Williams plot in Fig. The warning leverage (h*) is deﬁned as (Eriksson et al. A mechanism for this reaction which supports the formation of zwitterion intermediate theory and by proton-remover base B through reactions (1) and (2) below suggested by Caplow (1968): CO2 þ R1R2NH 4 R1R2NHþ COO (1) R1R2NHþ COO þ B 4 R1R2COO þ BHþ (2) R1 and R2 demonstrate substituted group attached to amine group. A compound with hi > h* inﬂuence the regression line.027 0.188 0. 2 demonstrates that there is no chemical with leverage higher than the warning h* value of 0. This ﬁgure shows. 3 against corresponding calculated values for QSPR model.942 0. 2004). It is better to diagnose which parameters affect the amines capacity and which descriptors could appear in the model due to principal chemical reactions between carbon dioxide and an amine-based solvent. S.128 In Table 6.209 0. This ﬁgure demonstrates the mean effect of the descriptors in the model.. the reported model is not accurate for the particular data set and method of modeling. The intermediate in the reaction is zwitterion. all descriptors in the model have positive effects and the amines capacity for CO2 absorption is directly related to each of these descriptors. Train Test Overall n R2 R2adj RMSE F k k0 s 18 5 23 0.

result in an increase in amine capacity for CO2 absorption (Singh et al. the accuracy of the model is good for linear amine compounds. Number of primary (nRNH2) and secondary (nRNHR) amines is two main descriptors appearing in the model. All these results demonstrate that the chemical reaction mechanism coordinates with the proposed model. Momeni. 2. predicted rich loading values (mol CO2/mol amine) e regression line. They showed that an increase in the chain length between amines and other functional groups in the amine structure. or in other words. 3. it is not better for unsaturated cyclic amines. these two descriptors have a positive effect and a higher mean effect. the reaction between CO2 and amine based solvent takes place because of the existence of NH bond. 2007). NH group is an active site of the amine molecule where base molecule (water) undergoes a chemical termolecular reaction. .. the amount of NH bonds. According to Fig. The reason of nH descriptor presence in the model can be explained by the result of experimental work performed by Singh et al.448 M. At last. Although. The model also contains number of Hydrogen atoms (nH) as another descriptor. S. it should be noted that the simplicity of the model is interesting and the results are quite acceptable for predicting amines capacity for carbon dioxide absorption. Experimental vs. Fig. As can be noticed. the number of primary and secondary amine groups in the amine molecule plays an important role in the capacity of amines for CO2 absorption. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 Fig. so apparently it seems it should have a positive effect due to the experimental work. 4 shows nH descriptor has a positive effect which is considerably less than two other descriptors. Consequently. So. 4. Williams plot of GA-MLR model development. Increasing with chain length results in increasing numbers of hydrogen atoms. This can be explained by two Fig.

a good amine solvent for carbon dioxide absorption should have a linear structure with a high number of primary and secondary amine groups as side chains. V. 6. Therefore. Eirik F. Soc. J. Essentials of Computational Chemistry: Theories and Models. 4. Sci. A. 6 and 21). Joanna. University of Tehran.K. da Silva. K. 43 (13). M. The most important descriptors appearing in the model due to the weight of the corresponding variable are number of primary aliphatic amines (nRNH2). Paola. P. Acta 420 (2). Abolghasem. number of secondary aliphatic amines (nRNHR) and number of hydrogen atoms (nH). Paul. 2 (4). 1989. First. J. 1986. 7. Vatani. Electrochim.K. J. Therefore. Quantitative structureeproperty relationship study on ﬁrst reduction and oxidation potentials of donor-substituted phenylquinolinylethynes and phenylisoquinolinylethynes: quantum chemical investigation. Am. respectively. the results of the ﬁrst equation (Eq. Astarita.R.J. Am. Peyghambarzadeh. M. Int.. Riahi / Journal of Natural Gas Science and Engineering 21 (2014) 442e450 449 predictive performance of the model validated with various statistical tests and examined with the test set of ﬁve molecules. Norouzi. Wiley... Eng. Anal. The RDF code provides valuable information. In other words. Molt. energy efﬁciency and operability point of view. Robert M. 3413e3418. Svendsen. Bischoff. 6795e6803. Perkin Trans. Fig. Michael. 2012. As a result two linear equations were developed. electrophilicity index effect. (1)) for predicting amines capacity of CO2 absorption are largely accepted either for linear or aromatic ring type amines (items labeled 5. Molecular orbital approach to substituent effects in amine-CO2 interactions. about bond distances. main reasons. 2005. Res. QSPR approach has been chosen as a modeling technique and model has been developed based on linear method for its simplicity.. A. Chakraborty.. 1988. Crooks.. Christopher J. Jaworska. Lennart. K. according to the industrial point of view. 2000. The accuracy and List of symbols CO2 carbon dioxide QSPR/QSAR quantitative structure property/activity relationship DFT Density Functional Theory MLR Multiple Linear Regression GA Genetic Algorithms PCR principle component regression PLS partial least square HOMO Highest Occupied Molecular Orbital LUMO Lowest Unoccupied Molecular Orbital AC absorption capacity PCA principal component analysis LOO-CV Leave-one-out cross-validation RMSE root mean square error dfM degrees of freedom of the model dfE degrees of freedom of the error References Beheshti. Andrew P.. New improved solvents should also be compared to more conventional ones from corrosively. ring types. it is preferable to use linear amine for CO2 absorption and it is more important for the model to predict CO2 absorption capacity for linear amines rather than unsaturated cyclic amines. J. 90 (24). G.. Fortunately. Chem. J.com.M. it could be argued that. Eriksson. Uwe. 365. 2014. Consequently. Hallvard F. Riahi. RDF descriptors are based on the distance distribution in the geometrical representation of a molecule. 217e227.. Kinetics of carbamate formation and breakdown. Mark TD. 4811e4821.. second equation introduced as a preferred model of this study. Worth. increasing the number of primary and secondary amine groups. Bohloul. McDowell. 2004. et al. Ganjali. Soc.. Momeni. This function is independent of the number of atoms and is invariant against translation and rotation of the entire molecule.. This is because of the presence of RDF descriptor in this model. Chem. Beheshti.. results in increasing the number of NH bonds active sites.B. Soc.g.. Kinetics and mechanism of the reaction between carbon dioxide and amines in aqueous solution. S. Depczynski. Acta 54 (23). The promising results of this study might aid other researchers in the ﬁeld of chemistry and natural gas engineering to design and synthesis new potential amine-based solvents and investigate the feasibility of using them in gas removal processes. CO2absorption in aqueous solutions of hindered amines. 331e333. Indust. Cronin. 2008).. Fluid Phase Equilibr. unsaturated cyclic amines show poor absorption rate and capacity and they are not potential absorbents for CO2 absorption (2). 41 (4). the three descriptors in model are not sensitive to ring type functional group and just count the number of hydrogen atoms. John E. Eng. 6947e6954. First model demonstrate high prediction power while second one is notably simpler and powerfully interpretable due to the chemistry of amines reaction with carbon dioxide. Sci. Methods for reliability and .R. Acknowledgment The authors would like to gratefully acknowledge the support from Institute of Petroleum Engineering (IPE).. Chem. Mean effects of model descriptors (standardized coefﬁcient values). which causes the amine reaction with CO2 to happen. Cramer. 110 (21). 2003.. According to the results. primary and secondary amines. Caplow. Genetic algorithms applied to the selection of factors in principal component regression. S. 2009. Frost. Siavash. Mohammad Reza. Ab initio study of the reaction of carbamate formation from CO2 and alkanolamines. A. Donnellan.M.. A.. Gramatica. Ganjali.. 5368e5375. 1968. Conclusions One of the main concerns of the natural gas industry is to have a robust and accurate model which can predict the chemical behavior of amines for gas treatment process. permits using this model to estimate other amines rich loading under speciﬁc conditions. Experimental and theoretical study of CO2 solubility in N-methyl-2-pyrrolidone (NMP). Electrochem. Chakraborty. planar and nonplanar systems and atom types so it is sensitive to aromatic rings (Todeschini and Consonni. Chim. 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