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international journal of greenhouse gas control 1 (2007) 355359

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Adsorption of carbon dioxide on alkali-modied zeolite 13X adsorbents


Zhonglin Zhao, Xingyu Cui, Jinghong Ma, Ruifeng Li *
Key Laboratory of Coal Science and Technology, MOE, Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, China

article info
Article history: Received 9 August 2006 Received in revised form 25 April 2007 Accepted 25 April 2007

abstract
Shaped zeolite 13X adsorbent with kaolin as binder was hydrothermally modied in sodium hydroxide solution to improve its adsorption performance. The characterization of the product by XRD, N2 adsorptiondesorption and water vapour adsorption displayed that kaolin component in zeolite adsorbent can be converted into zeolite during the alkali treatment, resulting in the modied adsorbent consisting entirely of effectual adsorption composition. Compared with the unmodied adsorbent, the modied adsorbent exhibited higher adsorption capacity and uptake rate for carbon dioxide, because of the increase of

Keywords: Adsorbent Zeolite 13X Kaolin binder Carbon dioxide adsorption

effective adsorption surface and the decrease of diffusion resistance owing to conversion of kaolin binder into zeolite. The model parameters of isotherms and the isosteric heats calculated by the ClausiusClapeyron equation for CO2 adsorption showed the stronger interaction of adsorbateadsorbent and the higher degree of heterogeneity of adsorption centers in modied than unmodied adsorbents. # 2007 Elsevier Ltd. All rights reserved.

1.

Introduction

Carbon dioxide is contained in atmosphere, natural gas, exhaust gas from combustion of fossil fuels and by-products in the industrial processes. Recently, much attention has been paid to the global warming effect caused by the excessive emission of carbon dioxide. The amount of carbon dioxide in atmosphere increases globally about six billion tonnes per year. Nearly, the contribution of 55% to rise in worldwide temperature has come from carbon dioxide emission. Therefore, it is a great challenge to concentrate and recover carbon dioxide. Various strategies have been proposed and investigated; one of the most promising approaches is rst ingathering CO2 by pressure swing adsorption (PSA) or temperature swing adsorption (TSA) process (Gomes and Yee, 2002; Chou and Chen, 2004). The capture and concentration of carbon dioxide by adsorptive technology is mainly based on preferential adsorption of the objective adsorbates

on a porous adsorbent, hence the development of adsorbent with high adsorption capacity, high selectivity and high adsorption rate is critical for a successful adsorptive process. In the industrial process, zeolite 13X, because of its high adsorption capacity, is frequently used as adsorbent of carbon dioxide (Rege et al., 2000; Siriwardane et al., 2001; Lee et al., 2002). Zeolites are hydrated, crystalline aluminosilicates, whose crystal size is commonly in the range of 110 mm. Assynthesized zeolite samples are usually powder and need to be shaped with binders into bodies such as granules, spheres and extrudates with high mechanical strength before their applications as industrial adsorbents. However, because of poor adsorption performance of the binder such as kaolin, decrease of adsorption capacity and increase of diffusion resistance of adsorbates in zeolite adsorbent containing binder is inevitable. It has been known that zeolite A or X can be synthesized from kaolin (Breck, 1974), therefore, to

* Corresponding author. Tel.: +86 351 6010121; fax: +86 351 6010121. E-mail address: ri@tyut.edu.cn (R. Li). 1750-5836/$ see front matter # 2007 Elsevier Ltd. All rights reserved. doi:10.1016/S1750-5836(07)00072-2

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international journal of greenhouse gas control 1 (2007) 355359

convert the kaolin binder in zeolite adsorbent into zeolite is a good way to improve the adsorption performance of shaped zeolite adsorbent. In present work, shaped zeolite 13X adsorbent with kaolin binder was hydrothermally modied in sodium hydroxide solution. The structure of the modied sample was characterized by XRD and N2 adsorption (77 K). The adsorption isotherm and kinetics for carbon dioxide on modied and unmodied zeolite 13X adsorbent were investigated. Compared to previous published works, our research showed a new technology to prepare the advanced industrial zeolite adsorbents with high adsorption capability on CO2 by increasing the effective components and improving the surface properties of the industrial zeolite adsorbents. This technology revealed that the binder used in adsorbents and/or catalysts could be translated into the utilizable active elements.

Fig. 1 XRD spectra of (a) 13X powder, (b) 13X-K, and (c) 13X-N.

2.
2.1.

Experimental
Preparation of samples
versus time was measured from initial pressure 0.01 to 0.05 atm at 298 K.

Zeolite adsorbents were formed by thoroughly mixing 20 wt% kaolin clay with commercial zeolite 13X powder with a Si/Al (mole ratio) of 1.3, converting the mixture into pastes by adding water and kneading. The pastes were extruded by an extruder to form cylindrical shaped products with size of 2 mm 4 mm. The products were air-dried for about 24 h, and then calcined in air at 873923 K for 2 h to obtain zeolite adsorbent with binder (denoted as 13X-K), in which kaolin was converted into metakaolin and the structure of zeolite 13X was not changed. The thus-obtained solid products 13X-K was treated in sodium hydroxide solution of 1.01.2 mol/L at 363 K for 68 h to convert the kaolin binder into zeolite. The treated products were isolated, washed, dried and activated at 823 K, and denoted as 13X-N.

3.
3.1.

Results and discussion


Characterization of adsorbent

2.2.

Characterization of samples

Fig. 1 shows XRD diffraction spectra of three samples, i.e., zeolite 13X powder, shaped sample calcined at 923 K (13X-K) from mixture of zeolite 13X powder and kaolin clay, and the alkali-treated 13X-K sample (13X-N). They display the same diffraction pattern, in which no other phase can be observed for 13X-K and 13X-N compared with 13X powder, only strengths of diffraction peaks decrease in the order 13X powder, 13X-N, and 13X-K. N2 adsorptiondesorption isotherms at 77 K on 13X-K and 13X-N, and corresponding pore structure parameters are shown in Fig. 2 and Table 1, respectively. The adsorption isotherm on 13X-K shows a combination of type I and II

The crystallinity of samples was checked by X-ray diffraction diffractometer (Rigaku D/max-2500, 40 kV, 100 mA, Ni ltered, Cu Ka radiation). N2 adsorptiondesorption isotherms were obtained at 77 K using NOVA 1200e analyzer (Quantachrome). The microporous surface area and pore volume were obtained from t-plot analysis of the adsorption branch of isotherms. All measurements were performed after outgassing the samples at 623 K for 4 h under evacuation. Water adsorption capacities of the samples activated at 823 K for 2 h were measured by maintaining the samples over the saturated solution of sodium chloride in a hydrator at 35 8C for 24 h. The mechanical strength of activated samples was measured by particle strength examiner. The adsorption isotherms and kinetics of carbon dioxide were measured using a NOVA 1200e analyzer, a static volumetric type of apparatus. Prior to measurement of adsorption, the samples were activated in a vacuum at 623 K for at least 4 h. Isotherms were obtained at two temperatures (273 K and 298 K) for the purpose of determining isosteric heats of adsorption. The uptake of carbon dioxide

Fig. 2 N2 adsorption isotherms (77 K) of (a) 13X-K and (b) 13X-N.

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Table 1 Physical property of 13X-K and 13X-N Properties


BET surface area (m2 g1) Micropore surface area (m2 g1) Micropore volume (cm3 g1) Average crash strength (kg) Water adsorption capacity (wt%)

13X-K
443 410 0.21 3.2 25.1

13X-N
482 458 0.24 3.6 28.5

Table 2 Values of LF model parameters fit to experimental isotherm data Sample


13X-K

Temperature (K)
298.2 273.2 298.2 273.2

qs (ml g1)
116.6 119.9 142.8 162.3

b (atm1)
7.1 16.7 8.3 20.0

n
1.06 1.04 1.39 1.43

13X-N

isotherm (micropore and macropore adsorption), though the character of isotherm is dominated by type I, implying the formation of interparticle voids (so-called second pore) created by mixing of zeolite and binder. The adsorption isotherm on 13X-N is type I, with adsorption increasing fairly rapidly at low relative pressure, followed by a slow uptake. This indicates that 13X-N is essentially microporous, in which only a very small portion of mesopore is present. From the data listed in Table 1, it is also seen that the total surface area of 13X-N increases with increase of micropore surface area, compared with 13X-K. Kaolin with a Si/Al ratio of 1.0 is conveniently used as an ideal raw material for synthesis of low silica zeolite. Usually, the synthesis of low silica zeolite from kaolin essentially consists of two steps: calcination of kaolin to get an amorphous product called metakaolin, and then hydrothermally crystallization in alkali solution. Kaolin is a layer silicate composed of sheets of SiO4 tetrahedra and AlO6 octahedra. During heatedly converting kaolin to metakaolin at 873 1073 K, complexing of aluminium changes from 6- into 4- and 5-coordination, the latter has much higher reactivity than the former for the formation of zeolite (Breck, 1974). For the shaped mixture of zeolite 13X and kaolin in this study, during calcined at 873973 K, kaolin can be transformed into metakaolin, zeolite structure did not changed because of its high thermal stability. When 13X-K was hydrothermally treated in NaOH solution, kaolin was easily converted into zeolite under the inducement of a large amount of zeolite X seeds. Hence, X-ray diffraction strengths of 13X-N, corresponding micropore surface area and pore volume, increases compared with of 13X-K. In addition, water adsorption capacity in 13X-N, which is also an indication of zeolite crystallinity, is higher than in 13X-K, reecting the formation of zeolite from kaolin. The modication of alkali treatment on zeolite adsorbents improves their mechanical strength. As listed in Table 1,

average crush strength of adsorbents increases from 3.2 kg of 13X-K to 3.6 kg of 13X-N.

3.2.

Adsorption isotherm of carbon dioxide

Fig. 3 presents adsorption isotherms of carbon dioxide on zeolites 13X-K and 13X-N at 298 K and 273 K, respectively. Obviously, the equilibrium adsorption amount of carbon dioxide on 13X-N in the range of pressure 01.0 atm is higher than on 13X-K, because of the higher adsorption surface of 13X-N, in which kaolin binder in adsorbent was converted to zeolite, resulting in increase of adsorption capacity of carbon dioxide on the adsorbent. All adsorption isotherms can be well tted by Langmuir Freudlich isotherm model (Ahn et al., 2004):  q qs b p1=n 1 b p1=n 

where q is the adsorbed amount at equilibrium pressure p, qs the saturated adsorbed amount, b and n are the isotherm parameters. b is the strength of the interaction between adsorbate and adsorbent (Newalkar et al., 2003), and n can be regarded as the parameter characterizing the system heterogenity (Do, 1998). The values of LF parameters obtained by tting are listed in Table 2. Higher b values of 13X-N at both temperatures suggest strong adsorption of carbon dioxide on the 13X-N surface, and higher n values of 13X-N indicate that its surface is more heterogeneous. The magnitude of the adsorption heats and its variation with adsorbed amount can provide some useful information concerning nature of the surface and the adsorbed phase. To calculate isosteric heats of CO2 adsorption on 13X-K and 13XN, ClausiusClapeyron equation was applied to process these isotherm data at 298 K and 273 K. Isosteric heats of adsorpion

Fig. 3 Adsorption isotherms of CO2 on 13X-K and 13X-N.

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international journal of greenhouse gas control 1 (2007) 355359

Fig. 4 Adsorption heats of CO2 adsorption on 13X-K and 13X-N.

are plotted in Fig. 4 as a function of adsorbed amount. On 13XK, the heat increases with adsorbed amount below 1.5 mmol/ g, and reaches a relative plateau at higher adsorbed amount. While the heat on 13X-N decreases gradually and then increases with adsorbed amount, there is the extremum in the bottom of line. In general, the decrease of heats reveals the strong interaction between adsorbate and zeolite and higher degree of heterogeneity of adsorption centers, whereas, the heats increase indicates the dominance of adsorbateadsorbate interaction and a relatively homogeneous environment for gassolid interaction, and a at heat prole with adsorbed amount indicates a balance between the strength of energetic heterogeneity of adsorbatezeolite interaction and adsorbent adsorbate interaction. Moreover, the heterogeneity of the adsorption centers depends on the distribution of exchangeable cations over various sites in the zeolite lattice, and for quadrupolar molecule CO2, the effect of ion type on heats of adsorption is dramatic, with Na+ ions providing the strongest electric eld within the pore (Dunne et al., 1996; Khelifa et al., 2004). It has been reported that the isosteric heats of CO2 on binderless NaX presents a continuous decrease with adsorbed amount, which could be attributed to interactions of Na+ ions located in sites II and III with the quadrupole moment of carbon dioxide (Dunne et al., 1999; Khelifa et al., 2004). But for 13X-K, it is possible that the surface property of zeolite is changed upon shaping, owing to solid-state migration of cations present in kaolin binder to zeolite extraframework sites during shaping, resulting in the change of adsorption heats (Jasra et al., 2003). During the modication of adsorbent in NaOH solution, the metakaolin in 13X-K is transformed into NaX zeolite, in which re-exchange of the adsorbent with Na+ occurs simultaneously. Therefore, the decrease of initial adsorption heats with adsorbed amount on 13X-N due to the existence of more Na+ ions located in sites II and III as active adsorption centers, are accessible to carbon dioxide. As Na+ ions located in sites II and III are responsible for the adsorption heterogeneous characteristics (Khelifa et al., 2004), the higher amount of Na+ ions located in sites II and III in 13XN, the more heterogeneous surfaces are certain, which is

Fig. 5 Uptake curves of CO2 on 13X-K and 13X-N at different pressures: (a) 0.01 atm, (b) 0.02 atm, (c) 0.03 atm, (d) 0.04 atm, and (e) 0.05 atm.

consistent with the results of LF model tting mentioned above.

3.3.

Adsorption kinetics of carbon dioxide

The uptake curves of carbon dioxide on 13X-K and 13X-N measured at 298 K and pressures from initial of 0.01 to 0.05 atm at intervals of 0.01 atm, are presented in Fig. 5. The adsorption equlibrium of carbon dioxide on 13X-N can be reached more quickly than on 13X-K under each measured pressure. In order to determine kinetic constants of adsorption process and to compare the uptake rate of carbon dioxide on two adsorbents, the relation of uptake versus time is tted. It is found that the relation can match the followed equation well: q q0 A ek1 t B ek2 t In this equation, q is the adsorbed amount at time t; q0, A and B are the coefcients; k1 and k2 are the uptake rate constants that can reect uptake rates during the initial and nal stage of adsorption process, respectively. The correlation coefcients of experimental data with the equation and rate constants are listed in Table 3. It is showed that under each investigated pressure, the values of k1 and k2 of carbon dioxide adsorption on 13X-N are higher than on 13X-K. The results indicate that not only the adsorbed amount, but also adsorption rate of carbon dioxide on zeolite 13X can be improved by alkali modication. The uptake rate of adsorbates on zeolite adsorbent is not only affected by diffusions in micropore of zeolite crystal, but also in macropore formed in shaping. The diffusion of adsorbates in macropores is generally much faster than in micropores, however, the different diffusion lengths between crystal and granule may be comparable to their different

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Table 3 Correlation coefficients of experimental data with the equation and uptake rate constant of CO2 on 13X-K and 13X-N Pressure (atm) R2
0.01 0.02 0.03 0.04 0.05 0.9974 0.9953 0.9943 0.9931 0.9929

13X-K k1 (min1)
14.7 15.5 17.6 17.8 17.0

13X-N k2 (min1)
0.8 0.8 1.0 0.9 0.8

R2
0.9991 0.9981 0.9973 0.9966 0.9957

k1 (min1)
15.1 17.6 20.0 22.1 22.5

k2 (min1)
1.8 1.6 1.5 1.4 1.2

diffusivity, since the radius of the crystal is very short compared with that of the zeolite granules (Ahn et al., 2004). Therefore, the inuence of macropore diffusion on overall diffusion rate of carbon dioxide cannot be neglected. The slower uptake rate on 13X-K can be attributed to the existence of the macropore in adsorbent. When the metakaolin between the crystals of zeolite is converted into zeolite, the macropore decreases dramatically because of the distance decrease between crystals of zeolite, resulting in increase of overall diffusion rate of carbon dioxide signicantly. On the other hand, amorphous metakaolin in shaped adsorbent has blocking effect on the diffusion of carbon dioxide (Klint and Bovion, 1999). Converting metakaolin in 13X-K into zeolite can eliminate such blocking effect and shorten the diffusion distance of adsorbats in between crystal particles. Thus, the favorable diffusion system can further promote the uptake rate of carbon dioxide on 13X-N.

references

4.

Conclusion

Zeolite 13X adsorbents with kaolin binder can be modied by hydrothermal treatment with sodium hydroxide solution, in which kaolin is converted into zeolite 13X. The modied adsorbent has higher adsorption capacity and uptake rate for carbon dioxide, due to the increase of effective adsorption surface area and the decrease of diffusion resistance. Compared with unmodied 13X adsorbents, the modied samples present the stronger adsorbateadsorbent interactions and the more heterogeneous surfaces.

Acknowledgements
This work is nancially supported by SXRSF (2006-22).

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