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Accepted Manuscript Adsorption kinetics and thermodynamics properties of Supercritical CO2 on activated clay Hedi Jedli, Jihed Brahmi, Hachem Hedfi, Mohamed Mbarek, Souhayel Bouzgarrou, Khalifa Slimi PII:

S0920-4105(18)30250-X

DOI:

10.1016/j.petrol.2018.03.064

Reference:

PETROL 4805

To appear in:

Journal of Petroleum Science and Engineering

Received Date: 28 November 2017 Revised Date:

26 February 2018

Accepted Date: 15 March 2018

Please cite this article as: Jedli, H., Brahmi, J., Hedfi, H., Mbarek, M., Bouzgarrou, S., Slimi, K., Adsorption kinetics and thermodynamics properties of Supercritical CO2 on activated clay, Journal of Petroleum Science and Engineering (2018), doi: 10.1016/j.petrol.2018.03.064. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT

Adsorption kinetics and thermodynamics properties of Supercritical CO2 on Activated Clay (1,*)

Hedi. Jedli, (2)Jihed. Brahmi, (1)Hachem. Hedfi, (3)Mohamed,Mbarek (4)Souhayel. Bouzgarrou and (5)Khalifa. Slimi

National Engineering School of Monastir University, IbnEljazzar Street, 5019, Monastir, Tunisia.

(2)

Laboratoire de Synthèse Hétérocyclique, Produits Naturels et Réactivités, Faculté des Sciences de Monastir,

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(1)

Avenue de l’Environnement, 5000 Monastir, Tunisia.

Unité de Recherche (UR 11ES55), Matériaux Nouveaux et Dispositifs Electroniques Organiques, Faculté des

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(3)

Sciences, Université de Monastir, 5000, Tunisie.

(5)

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(4)National Engineering School of Tunis, Tunis El ManarUniversity, Tunis, Tunisia

Higher Institute for Transport and Logistics, Sousse University, Riadh City, 4023, Sousse, Tunisia.

*Corresponding author:[email protected]

Abstract

A modified clay was used as a retention for gas adsorptions. The structural

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modification caused by activation clay was investigated by XRD, SEM and BET. As results, this modification indicated that the activated clay showed the highest BET surface area (16.29-24.68 m2/g) and pore volume (0.056–0.064 cm3/g). The capacity of

was measured

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at different temperatures 298, 323 and 353 K using a batch reactor. Langmuir and Freundlich

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isotherm models were applied to describe the experimental results for

adsorption.

Thermodynamic parameters suggested the heterogeneous surface, exothermic and physical nature. Adsorption kinetics data on clay samples presented a slightly slower diffusion compared to the activated clay.

Keywords: Adsorption; CO2; Clay; Langmuir; Freundlich, Diffusion.

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Introduction It is known that carbon dioxide is the main greenhouse gas emitted through industrialization [1]. The greenhouse effect caused by carbon dioxide emission has become a threat to the environment, and

emission has increased over recent years [2]. Thus,

capture and storage (CCS) technology has been considered as the best option for reducing from gas

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carbon dioxide emissions from large point sources [3]. In order to separate

mixtures; adsorption is considered as a promising process for the CSS technology. It is very important to elaborate adsorbent materials for retention of such gases. In fact, clay is considered as the most abundant natural materials for the CO2 adsorption. Chen et al. by kaolinite treated with H2SO4. Venaruzzo et al.

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(2015)[4] studied the adsorption of the

(2002) [5] characterized the effect of acid treatment on bentonitic clay materials and on the

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CO2 adsorption. Giestinga et al. (2012)[6] investigated the structural behavior of

in Na-

exchanged montmorillonite by experiments in high-pressure environmental chambers. Pour et al. (2016)[7] carried out the adsorption of

by synthesized and commercial NaA zeolites at

different temperatures ( 277, 290 and 310 ) for pressures up to 10 bar. Rada et al. (2010) [8] presented the ability of zeolite T for selective adsorption and separation of Quiroz-Estrada, et al. (2016) [9] evaluated the capacity of

from

.

adsorbed on kaolinite. The

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available experimental studies demonstrate that adsorption capacity of samples (ie clay, kaolinite and zeolite..) could be improved after specific modifications. In this context, natural clay was modified with sulphuric acid solution (3M) and used as retention for gas adsorption. The aim of this article’s study is to characterize the adsorption capacity of clay after specific

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modifications with sulphuric acid. In order to determine the best isotherm, experimental data has been modeled using Langmuir and Freundlich models. At last, thermodynamic parameters

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of the adsorption were determined and the enthalpy was studied.

2. Materials and methods Natural clay material powder was used as a raw material. This material was treated

with

solution (3 ). A ratio of 1 g of clay per 10 ml of acid was fixed. The clay was

dissolved to the sulfuric acid solution. Then, the sample was heated in a bath at 90 °C and further stirred at 300 rpm for 15 h. Then, the dispersions were filtered, washed with distilled water and dried overnight at 70 °C.

adsorption capacities of the acid-treated clay were

performed in a sealed reactor (Fig 1) with a 6.5 cm diameter, a 7 cm length and a volume of

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ACCEPTED MANUSCRIPT 232 cm3. The apparatus was also equipped with a manometer (Kpa 1 MPA 422p), electric heating apparatus (VMS-A S40) and connected to a CO2 supply.

3. Characterization X-ray diffraction (XRD) was conducted using Philips PW1710 (X-Ray Diffraction

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Spectrometer). The surface morphology was observed by Scanning Electron Microscope (SEM, JEOL JSM 5600LV). The textural characterization was analyzed with an N2 adsorption isotherm at 77 K using a Micromeritics 3-Flex.

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4. Modelling of adsorption isotherms The

adsorption by the adsorbent was fitted to isotherm models such as

Langmuir, Freundlich and BET. Langmuir isotherm is developed to depict monolayer

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adsorption on homogeneous surface according to the following equation (1)[11]: =

Where P is the partial pressure and

is the equilibrium adsorption capacity,

(1) is the

maximum monolayer capacity and K is the constant Langmuir isotherms. The Freundlich isotherm can be applied to the surface heterogeneity and expressed by the equation (2) [11]:

Where

(2)

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/!

=

and n are the Freundlich model parameters.

As BET model assumes that multiple layers are formed on the surface of an adsorbent; it’s equation is expressed as:

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qm kb p  p (qs − q) 1 + (kb − 1)  p0  

(3)

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q=

Where qm is the maximum loading of

constant and ps is the saturation pressure of

onto the surface of the adsorbent, kb is a .

5. Results and discussion 5.1 Chemical analysis The X-ray fluorescence analysis was used to identify the chemical compositions of the clay and the changes that occurred under the effect of the sulfuric acid. Table 1 illustrates the compositions of the raw material and the acid treated clay. XRF indicated the presence of silica and alumina as major constituents of the clay, along with traces of other oxides such as 3

ACCEPTED MANUSCRIPT magnesium oxide, calcium oxide, potassium oxide. After acid treatment, a change on the composition of the clay was observed. The increase of the acid’s amount was joined by an increase in SiO2 content and a decrease in "#

$,

% and

contents which consequently

caused an increase in the Si/Al ratio. During the acid treatment, the concentration of % , & and

were reduced. However, the concentration of '(

2 remained

almost unchanged

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at a low concentration.

5.2 X-ray diffraction (XRD)

The structural changes occurred on the clay due to the acid effect were obtained using

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X-ray diffraction. XRD diffraction of the clay is presented in Figure.2. It’s observed that the clay presents a dominance of illite at 4.45 Å and 3.33 Å . Besides, the reflections at (7.51,3.78, 2.56 and 2.48 Å) are characteristics of kaolinite. The characteristic reflection of

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dolomite were observed at (2.88 Å) and for quartz at (3.33 and 1.87 Å). After the acid treatment, we can notice that the reflection of the sample was found to decreasing, no impurity peaks were observed and the peaks were sharp. This change impacts the structure and the crystalline character of the clay. Furthermore, the effect of the treatment can be observed by the reduction of some minerals such as "#

$

and % contents according to the

5.3 SEM analysis

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results of chemical analysis presented in table 1.

The Scanning Electron Micrographs of the clay are provided in Figure (3). The SEM

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of the clay presents a stratified form containing stacked flakes in the form of agglomerates. The morphology of the activated clay (3M) presents different particle morphology. In

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addition, the acidic dissolution decreases the size of the clay particle which display irregular and angular edges. This decreases the density and increases the intergrannular space and porosity of clays.

5.4 Adsorption–desorption isotherm and BET surface area N2 adsorption–desorption isotherms of the clay and the acid activated clay are showed in Figure 4. According to the IUPAC classification, the isotherm was of type /0, characterizing the mesoporous materials [12]. The hysteresis loop of these samples is attributed to the type H3 loop. After acid activation, we can notice a change in the hysteresis

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ACCEPTED MANUSCRIPT loop indicating a modification in the pore shape. The volume of the adsorbed nitrogen was increased for the acid activation clays compared to the raw clay. The textural characteristics including the specific surface area, pore volumes and pore sizes of the raw and treated clay, are presented in Table 2. The surface area and pore volume of the raw clay sample was 16.29 m /g and 0.056 cm$ /g, respectively, suggesting that the

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original clay showed a low porosity. After the acid treatment, the values increased up to 24.68 m /g and 0.064 cm$ /g , respectively. This indicated that acid activation can improve the textural properties of the clay.

Figure 5 shows the

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5.5 Adsorption isotherms

adsorption isotherms depicted at different temperatures. The 456 .

In addition, an increase in adsorption

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adsorption capacity increases with the increasing

temperature leads to a reduction in the amount of

adsorbed, in agreement with the

exothermic adsorption phenomenon. Figure. 6(a) and 6(b) give the experimental data fitted by Langmuir and Freundlich models. The landmarks points provide the experimental data while the solid lines present the isotherm models used in the present study. The constant of these isotherm models and the coefficient of correlation (R) are reported in table 3.

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Figure 7 depicts that Langmuir model approaches well the experimental adsorption isotherms. In fact, this model displays a better agreement with the experimental results. This isotherm model gives a well-fitting correlation with R values of around 0.99.

This

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demonstrates the heterogeneous nature of the adsorbent surface. With reference to Langmuir fitting presented in table 3, Qm and K values decrease with the temperature rise, this confirms the exothermic adsorption phenomenon. Also,

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Freundlich equation appeared to fit the data better over the entire range of partial pressure indicating the surface heterogeneous nature [13]. The n parameter is larger than 1 indicating the physisorption phenomena of

adsorption on the treated clay. Furthermore, the values

of 1/n were below 1which indicated a good adsorption intensity [13].

The essential features of the Langmuir isotherm can be described in terms of a separation factor (78). This factor is given by the following equation. (4). 79 =

(4)

:4;

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ACCEPTED MANUSCRIPT Where C0 is the initial concentration and b is the Langmuir constant. The 79 value indicates the nature of adsorption to be either favorable (0 < 79 < 1), unfavorable(7# > 0), linear (79 = 1) of irreversible (79 = 0) [13]. The 79 values indicate that adsorption is favorable.

5.6 Thermodynamics of adsorption

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Figure 8 illustrates Vant’ Hoff plot in the range temperature of 298 − 353 . The plot of #@ (A) versus inverse temperature (1/') was depicted by the equation (5). ∆F

ln(A) = D H − ( G

∆I° GK

)

(5)

The ∆ ° value for the adsorbent was −4.504 L/MN#. This value indicates that the

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adsorption process was exothermic in nature. The ∆ ° of the adsorbent compared with other samples presented in the literature (Table 4) indicates the physisorption process. OP was

estimated from the Clausius-Clapeyron equation

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Isosteric heat of adsorption ∆

(6). The ∆HRS value was calculated from the slope (∆HRS /R) of the plot of ln(p) Vs (1/') at a specific concentration. ∆

OP =

−7' (V ln(W)/V')

Figure 8 presents the heat of adsorption for

(6)

at different temperatures. This result OP

of the clay treated

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may be attributed to the heterogeneous nature of the clay surface. The X

is compared with other available adsorbents in the literature [13] [14] [15] indicated the physical adsorption.

5.7 Adsorption Kinetics

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on the treated clay were measured at 298, 323, and 353 . The

Adsorption kinetics of

diffusion time constant was obtained by fitting the fractional uptake curve with the diffusion

YZ

Y[\

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model. The fractional uptake is defined by (7) [15] ]

= 1 − ^ 6 ∑f !b `aW D

Where

P

and

gh

bcd !6 ^ 6 P e6

H

(7)

are respectively the gas uptake at time t and at equilibrium, with

cd e6

being

Y

the diffusion constant. The plot of ln (1 − Y Z ) versus t was used to determine the diffusion [\

time constants for

gas on the sample at 298 , 323 and 353 . Both of the fractional

uptakes of the untreated clay and the treated one are presented in Figure 9 (a), 9(b) respectively. The untreated clay presented slightly slower diffusion at 298K and 323 K than at

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ACCEPTED MANUSCRIPT 353 K, compared to the treated clay. We can see that

reached the equilibrium in a time

around 40i at 298 . As presented in table 4, the treated clay depicted a significant increase in the surface area and pore structure compared to the untreated clay. In addition, after the reaction, the adsorption rates of the treated clay were nearly same in the order of magnitude, implying a very slow uptake of

compared to the untreated clay.

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6. Conclusion

The conducted study in this article aimed to improve enhances the structural properties of raw clay by a sulfuric acid (3M) treatment. As a matter of fact, the surface area and pore volume

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of the treated clay were much higher than the untreated which proved the effect of the acid. Moreover, the CO adsorption capacity of the clay was also improved by the acid activation. experimental isotherm data of

was measured at 298, 323 and 353K. To fit the adsorption, Langmuir and Freundlich model were

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The adsorption equilibrium of the

investigated. The results showed a good agreement with the experimental adsorption isotherms. In addition, thermodynamic parameters indicated that CO adsorption process on activated clay was exothermic and physisorption in nature. At last, adsorption kinetics data on the clay sample measured at different temperatures (298, 323 and 353 K) presented a

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slightly slower diffusion compared to the activated clay.

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ACCEPTED MANUSCRIPT 7. References [1] Bachu S. Sequestration of

in geological media: criteria and approach for site selection

in response to climate change. Energy Convers Manage 2000;41:953–70 [2] Tarkowski, R., 2005. Industrial sources of

emissions in Poland in the light of

underground storage possibilities. C. R. Geosci. 337, 799–805.

the reservoir and cap rocks of the Chabowo Anticline caused by International Journal of Coal Geology 130 (2014) 79–88 [4] Yen-Hua Chen, De-Long Lu.

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[3] MagdalenaWdowin, Radosław Tarkowski,Wojciech Franus. Determination of changes in –brine–rock interactions.

capture by kaolinite and its adsorption mechanism.

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Applied Clay Science 104 (2015) 221–228.

[5] J.L. Venaruzzo, C. Volzone M.L. Rueda J. Ortiga. Modified bentonitic clay minerals as adsorbents of

,

and

gases. Microporous and Mesoporous Materials 56 (2002)

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73-80.

[6] Paul Giestinga, Stephen Guggenheima, August F. Koster van Groos , Andreas Busch. Interaction of carbon dioxide with Na-exchanged montmorillonite at pressures to 640 bars: Implications for

sequestration. International Journal of Greenhouse Gas Control 8 (2012)

73–81

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[7] A. Arefi Pour, S. Sharifnia, R. Neishabori Salehi, M. Ghodrati. Adsorption separation of /CH4 on the synthesized NaA zeolite shaped with montmorillonite clay in natural gas purification process. Journal of Natural Gas Science and Engineering 36 (2016) 630-643 [8] Mina Doroudian Rada, Shohreh Fatemi, S. Mojtaba Mirfendereski. Development of T from CH4 in adsorption processes. chemical engineering

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type zeolite for separation of

research and design 9 0 ( 2 0 1 2 ) 1687–1695

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[9] Karla Quiroz-Estrada, Miguel Ángel Hernández-Espinosa, Fernando Rojas, Roberto Portillo, Efraín Rubio, Lucía López. N2 and

Adsorption by Soils with High Kaolinite

Content from San Juan Amecac, Puebla, México. Minerals 2016, 6(3), 73 [10] H. Jedli, A. Jbara, H. Hedfi, S. Bouzgarrou, K. Slimi. Carbon dioxide adsorption isotherm study on various cap rocks in a batch reactor for

sequestration processes.

Applied Clay Science 136 (2017) 199–207 [11]

Muhammad Anas, Abdullah Göktuğ Gönel, Selmi Erim Bozbag, Can Erkey.

Thermodynamics of Adsorption of Carbon Dioxide on Various Aerogels. Journal of CO2 Utilization. 21(2017) 82-88

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ACCEPTED MANUSCRIPT [12] Mastalerz, M., Hampton, L., Drobniak, A., Loope, H. 2017. Significance of analytical particle size in low-pressure N2 and

adsorption of coal and shale. International Journal of

Coal Geology. 178 ,122–131 [13] P. Ammendola, F. Raganati, R. Chirone.

adsorption on a fine activated carbon in a

sound assisted fluidized bed: Thermodynamics and kinetics. Chemical Engineering Journal

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322, (2017), 302–313 [14] Vinod Kumar Singh, E. Anil Kumar, Measurement and analysis of adsorption isotherms of CO2 on activated carbon. Applied Thermal Engineering 97 (2016) 77–86

[15] Bin Yuan, Xiaofei Wu, Yingxi Chen, Jianhan Huang, Hongmei Luo, Shuguang Deng, , CH4, and N2 on Ordered Mesoporous Carbon: Approach for Greenhouse

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Adsorption of

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Gases Capture and Biogas Upgrading. Environ. Sci. Technol. 2013, 47, 5474−5480

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ACCEPTED MANUSCRIPT Tables Element, wt. % #%q

SiO2

Al2O3 CaO Fe2O3 Na2O K2O MgO TiO2

52.18 11.96

Clay 3 M

I.Lo

8.91

5.09

0.20

2.82

6.89

0.03

9.40

69.87 08.23 6.72

1.84

0.14

2.48

4.02

0.10

7.78

Concentration of |} ~•€

BET surface area

Pore volume

Pore size

(M)

(v} /w)

(uv• /w)

(‚°)

0 (ƒ@„…`%„`† ‡#%q)

16.29

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Table 1: Chemical analysis of clay.

0.056

78.30

0.064

65.71

24.68

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3

Table 2: Textural properties of clay. Temperature

Langmuir

Freundlich

(t)

Qm (uv3/w)

x

t

y

z/y

{

Activated Clay

298

4.6083

0.9971

0.056810

1.139

0.8779

0.9989

4.3478

0.9962

0.055202

1.120

0.892

0.9994

3.8673

0.9953

0.05425

1.079

0.926

0.9951

323 353

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Adsorbent

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Table 3: Equilibrium adsorption parameters according to Langmuir and Freundlich models

Samples

P (bar)

T (K)

−∆|°(ˆ‰/Š‹Œ)

Reference

Activated carbon

45

298

5.92

[13]

Maxsorb

45.86

298

16.2

[14]

Norit R1 Extra

30.30

298

22.0

[15]

Activated Clay

80

298

4.5

Present study

Table 4: comparison of adsorption equilibrium of CO2 on different samples.

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ACCEPTED MANUSCRIPT Figure captions Figure 1. The experimental set-up: (1) gas cylinder; (2) pressure regulator; (3) pressure indicator;(4) needle valves; (5) batch reactor.

Figure 3. SEM morphologies: (a) pure clay; (b) acid treated clay.

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Figure 2. XRD of raw and treated clay.

Figure 4. • adsorption-desorption isotherm of raw and treated clay. Figure 5. Adsorption isotherms of

on activated clay.

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Figure 6. Separation factor 79 .

z

Figure 8. ln(P) versus D•H.

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z

Figure 7. ln(b) versus D•H.

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Figure 9. Fractional uptake of CO2 (a) untreated clay (b) treated clay.

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Lin(counts)

10 20

4.46541[A°] 4.26365[A°] 3.95093[A°] 3.78721[A°] 3.22297[A°]

2.58271[A°] 2.45760[A°] 2.40586[A°]

1.7898[A°]

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1.62996[A°]

1.82130[A°]

Clay Clay 3M

40

2.149[A°]

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30

2.82441[A°] 2.67557[A°]

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2.88881[A°]

Fig 1

2.99661[A°]

2θ(Degree)

Figure 2

12

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2600

2400

2200

2000

1800

1600

1400

1200

1000

800

600

400

200

0

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50

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(a)

(b) Figure 3

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ACCEPTED MANUSCRIPT 45

Raw Clay

Clay 3M

40

30 25

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3

Qunatiy adsorbed(cm /g)

35

20 15 10

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5 0 0,2

0,4

0,6

0,8

1,0

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0,0

Relative pressure (P/P0)

Figure 4

25°C 50°C 80°C Langumir model

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12

6

EP

8

AC C

qe (mg CO2/g)

10

4

2

20

40

60

80

100

120

Pression (Kpa)

(a)

14

140

160

180

200

ACCEPTED MANUSCRIPT 25°C 50°C 80°C Freundlich model

12

8

6

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qe (mg CO2/g)

10

4

0 20

40

60

80

100

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0

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2

120

140

Pression (Kpa)

(b)

Figure 5

Clay 3M

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1,0

RL

0,6

AC C

0,4

EP

0,8

0,2

0,0

0

5

10

C0(mg)

Figure. 6

15

15

20

ACCEPTED MANUSCRIPT -4,10

-4,15

-4,25

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ln(b)

-4,20

ln(b)=554.73/T-5.93 -4,30

-4,40 0,0028

0,0029

0,0030

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-4,35

0,0031

0,0033

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1/T(K-1)

0,0032

Figure 7

4,40

4,20

EP

4,25

AC C

ln(P)(bar)

4,30

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4,35

4,15

4,10

0,0028

0,0029

0,0030

0,0031 -1

1/T(K )

Figure 8

16

0,0032

0,0033

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298 K 323 K 353 K

0,6

0,4

0,2

0,0 0

20

40

60

(a)

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1,0

0,6

0,4

0,2

0,0

AC C

EP

0

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Fractional uptake

0,8

20

40

Time (s)

(b) Figure 9

17

80

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Time(s)

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Fractional uptake

0,8

60

298 K 323 K 353 K

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ACCEPTED MANUSCRIPT Highlights

* Sample of clay was subjected to acid treatments to improve their textural properties.

* CO2 adsorption by clay is mainly related to physical adsorption.

on the treated clay were measured at different temperatures

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* Adsorption kinetics data of

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* Adsorption capacity were determined by Langmuir and Freundlich isotherm equations