Article pubs.acs.org/jced
Adsorption Equilibrium of N2, CH4, and CO2 on MIL-101 Yu Zhang,† Wei Su,†,‡ Yan Sun,§ Jia Liu,∥ Xiuwu Liu,⊥ and Xiaojing Wang*,† †
School of Chemical Engineering and Technology, and §Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China ‡ Tianjin Key Laboratory of Membrane and Desalination Technology, Tianjin 300072, China ∥ College of Engineering, Peking University, Beijing 100871, China ⊥ School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China ABSTRACT: MIL-101 is a promising adsorbent because of its large pore volume, high separation selectivity, easy regeneration, and good stability. MIL-101 was synthesized and characterized by X-ray diffraction, scanning electron microscopy, and nitrogen adsorption at 77 K. Adsorption isotherms of pure N2, CH4, and CO2 were measured on MIL-101 from 263 K to 313 K and at pressures up to 0.8 MPa. The Langmuir model was a good fit for the experimental isotherms and the isosteric heats of adsorption decreased in the order: CO2 > CH4 > N2. The CO2/CH4 separation selectivity was sensitive to the adsorption pressure and temperature and it varied from 3.2 to 6.3. In contrast, the CH4/N2 separation selectivity changed from 2.6 to 3.3 with temperature and pressure.
1. INTRODUCTION The recovery of methane from low-quality natural gas not only provides more energy, but also reduces greenhouse gas emissions.1 Methane is a much more powerful greenhouse gas than CO2, and its global warming potential is 20 times higher than that of CO2.2 Poor quality coal-bed methane, biogas, and landfill gas, which are mainly composed of N2, CH4, and CO2, are three common low-quality natural gases.3,4 Adsorption separation technology is an energy efficient and low cost method for the removal of CO2 and N2 from natural gas.5 Generally two steps are required to enrich methane. First the CO2 needs to be removed and then the N2 and CH4 gases are separated. Finding a suitable adsorbent is generally the first step in developing an adsorption process. Many adsorbents have been tested for the separation of CO2/CH4 and CH4/N2.6 However, the separation of N2 from CH4 remains a challenge because of the poor selectivity of the adsorbents.7 Clinoptilolites and their derivatives,8,9 which depend on kinetic separations, seem to be more promising than adsorbents based on equilibrium separation. These materials have higher adsorption capacity for N2 than for CH4, and CH4 can be collected from the tops of clinoptilolite columns. However, further research is needed to improve the selectivity of these materials. For the separation of CO2/CH4, most adsorbents, such as activated carbon,10 amine modified adsorbents,11,12 synthesized zeolites,13 and metal organic frameworks (MOFs) materials are based on adsorption equilibria.14,15 Although the separation selectivity of MOFs is not any better than that of amine modified adsorbents and synthesized zeolites, MOFs have the advantages of high adsorption capacity.16 These are important considerations in choosing a suitable adsorbent. © XXXX American Chemical Society
MIL-101 is a chromium-based MOF with large pore volume and good stability. Since it was synthesized and reported by Férey et al. in 2005,17 a large number of researchers have investigated its adsorption properties. Most work has focused on the adsorption-based capture of CO2,18,19 the storage of CH420 and H2,21 the separation of C2H6/C2H4,22 or the removal of H2S.23 Reports on the recovery of methane from low-quality natural gas with MIL-101 are scarce. Munusamy et al.24 measured the adsorption properties of N2, CH4, CO2, and CO on MIL-101 at 288 to 313 K and at pressures up to 850 mmHg. However, for pressure swing adsorption processes, it is necessary to get adsorption data over a wider temperature range and at higher pressure. In this work, adsorption isotherms of N2, CH4, and CO2 were collected over a temperature range of 263 K to 313 K, and at pressures up to 0.8 MPa. In addition, isosteric heat and separation selectivity are determined and discussed.
2. EXPERIMENTAL SECTION 2.1. Materials. MIL-101 was synthesized in our lab using Cr(NO3)3·9H2O (Tianjin Damao Chemical Co., Ltd., ⩾ 99 %), terephthalic acid (Aladdin, China, ⩾ 99 %) and natrium aceticum (Tianjin Jiangtian Co., Ltd., ⩾99 %). The gases, helium (⩾99.999 %), nitrogen (⩾99.999 %), methane (⩾99.99 %), and carbon dioxide (⩾99.99 %), were all purchased from Tianjin Liufang Industrial Gases Co., Ltd. 2.2. Synthesis of MIL-101. MIL-101 was synthesized via a hydrothermal method reported in the literature.25 Briefly, Received: April 8, 2015 Accepted: August 25, 2015
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2.0 g of Cr(NO3)3·9H2O and 0.82 g of terephthalic acid were dissolved in 25 mL of 0.05 mol·L−1 sodium acetate solution. After being stirred for 30 min at ambient temperature, the mixture was transferred to an autoclave. Then, the mixture was heated at 473 K for 12 h. A fine powder was obtained. The powder was washed with deionized water and dried overnight at 423 K. 2.3. Characterization. An ASAP 2020 apparatus was used to measure the nitrogen adsorption−desorption isotherms on the MIL-101 at 77 K. Pore size distribution (PSD) was determined using nonlocal density functional theory (NLDFT).26 The scanning electron microscope (SEM) images, acquired from a Hitachi S-4800 field emission scanning electron microscope, were used to observe the specific microstructures of the samples. X-ray diffraction (XRD) analysis was carried out on Rigaku D/MAX-2500 X-ray diffractometer using Cu Kα (λ = 1.5406 Å) radiation with a scan rate of 2°/min in the 2θ range of 2° to 20°. 2.4. Adsorption Isotherm Measurements. Adsorption equilibrium isotherms of N2, CH4, and CO2 on MIL-101 were collected using the volumetric experimental apparatus. The measurements are based on volumetric principles, and the device had been described in our previous study.27 To improve the measurement precision, in this work, the high pressure transmitter (M3 in the previous study: 0 MPa to 20 MPa) was replaced by a low pressure transmitter (0 MPa to 1.6 MPa), with an accuracy of 0.1 %. Gas adsorption isotherms were measured at 263 K to 313 K, and the highest pressure was about 0.8 MPa.
Figure 1. N2 adsorption−desorption isotherm of MIL-101 at 77 K.
3. RESULTS AND DISCUSSION 3.1. Characterization of MIL-101. Figure 1 shows the adsorption isotherm of N2 on MIL-101 at 77 K. The isotherm is type-I. The specific BET surface area is about 2560 m2/g, and the pore volume, calculated from the nitrogen adsorption
Figure 2. Pore size distribution of MIL101.
Figure 3. SEM images of MIL-101. B
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capacity at a pressure of P/P0 = 0.98, is 1.29 cm3/g. The pore size distribution determined by NLDFT is plotted in Figure 2. The two peaks indicate that there are two sizes of pores. One is in the range of 0.5 nm to 1.2 nm and the other is in the range of 1.8 nm to 3.5 nm, which agrees with a previous report.28 The SEM images of MIL-101 (Figure 3) indicate that the material possesses a regular polyhedral cone structure. The X-ray diffraction pattern (Figure 4) is consistent with previous research.29
Figure 4. Powder XRD pattern of MIL-101.
3.2. Adsorption of Gases. The N2, CH4, and CO2 adsorption isotherms on MIL-101 at different temperatures are shown in Figure 5. Experimental values shown in Figure 5 are listed in Tables 1 to 3. At all temperatures, the isotherms for CO2 are type-I and those for N2 are almost linear. The isotherms for CH4 at low temperatures (263 K and 273 K), are type-I, and at 313 K the isotherm is nearly linear. The curves at 283 K, 293 K, and 303 K are between type-I and linear. It is shown that the adsorption capacity on MIL-101 in this work is lower than that of previous research.24 In this work, the unreacted terephthalic acid was removed by washing with deionized water other than solvent extraction. It was possible that there was still some terephthalic acid in the pores, which may cause the difference of adsorption capacity. In a commercial adsorptive process, activated carbon and zeolite have been widely applied. The adsorption capacity of CO2 on MIL-101 at 0.7 MPa, is almost the same as that of activated carbon and zeolite.30 However, the adsorption of N2 and CH4 is much lower than that of activated carbon and zeolite. It implies that MIL-101 has higher separation selectivity on the separation of CO2/CH4 and CO2/N2. Compared with MIL-101 and activated carbon, zeolite has a poor separation selectivity on CH4/N2. The Langmuir equation31 has been widely applied to adsorption and is given by ⎛q ⎞ bp θ = ⎜⎜ ⎟⎟ = ⎝ qm ⎠ 1 + bp
Figure 5. Adsorption isotherms of a, N2; b, CH4; and c, CO2. Adsorption on MIL-101 of this work: ○, 263 K; ●, 273 K; ▽, 283 K;▼, 293 K; □, 303 K; ■, 313 K. Adsorption on MIL-101:24 ★, 313 K. Adsorption on activated carbon:30 △, 293 K. Adsorption on zeolite:30 ▲, 293 K. Solid lines, Langmuir model.
are listed in Table 4. R2 is given by n
2
R =1− (1)
y̅ =
where θ is the fraction of surface coverage, q represents the absolute amount adsorbed, qm is the monolayer adsorption saturation capacity, b is an equilibrium constant, and p is the equilibrium pressure. The two parameters, qm and b, can be obtained from a nonlinear fit of the Langmuir equation. These two parameters and the coefficients of determination, R2, at different temperatures
1 n
∑i = 1 (yi − yi ̂ )2 n
∑i = 1 (yi − y ̅ )2
(2)
n
∑ yi i=1
(3)
where n is the number of experiment points in each isotherm, yi is the experimental adsorption capacity data and ŷi is the adsorption capacity calculated by fitting the curve. From eq 2, it is clear that the value of R2 must be less than one. The closer the value of R2 is to one, the better the fit is. C
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Table 1. Adsorption Data of N2 on MIL-101 263 Ka p
a
b
273 Ka n
c
p
b
283 Ka n
c
p
b
293 Ka c
b
n
p
303 Ka n
c
p
b
313 Ka n
c
p
b
nc
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
0.0769 0.1794 0.3024 0.4259 0.5733 0.7030 0.7748
0.126 0.295 0.485 0.664 0.863 1.028 1.125
0.0865 0.2167 0.3613 0.5083 0.6633 0.7726
0.119 0.304 0.496 0.677 0.859 0.985
0.0825 0.2053 0.3464 0.4922 0.6412 0.7778
0.094 0.245 0.412 0.572 0.732 0.875
0.0828 0.2016 0.3356 0.4276 0.5408 0.7215 0.7897
0.078 0.200 0.328 0.419 0.525 0.691 0.750
0.0836 0.2056 0.345 0.4853 0.6331 0.7718
0.062 0.167 0.287 0.398 0.519 0.638
0.0838 0.2106 0.3552 0.5056 0.6569 0.7781
0.055 0.149 0.256 0.360 0.464 0.543
Measured with 0.1 K uncertainty. bMeasured with 0.4 kPa uncertainty. cCalculated with 6.1·10−3 mmol·g−1 uncertainty.
Table 2. Adsorption Data of CH4 on MIL-101 263 Ka pb
a
273 Ka nc
MPa
mmol·g
0.0612 0.1700 0.2891 0.4202 0.5624 0.6960 0.7700
0.377 0.864 1.359 1.883 2.373 2.812 3.044
pb −1
283 Ka nc
MPa
mmol·g
0.0712 0.1734 0.3142 0.4571 0.5942 0.757
0.319 0.715 1.195 1.637 2.043 2.469
pb −1
293 Ka nc
MPa
mmol·g
0.0648 0.162 0.2809 0.4044 0.5244 0.6442 0.782
0.218 0.527 0.854 1.169 1.451 1.715 2.006
pb −1
303 Ka nc
pb
MPa
mmol·g
0.0691 0.1773 0.2917 0.4158 0.5451 0.6761 0.7978
0.183 0.454 0.723 0.997 1.265 1.517 1.727
−1
313 Ka nc −1
pb
nc
MPa
mmol·g
MPa
mmol·g−1
0.0728 0.1746 0.2978 0.4227 0.556 0.6912 0.7908
0.155 0.379 0.621 0.851 1.087 1.312 1.473
0.0741 0.1777 0.2942 0.4169 0.5428 0.7065 0.7988
0.139 0.335 0.536 0.745 0.946 1.170 1.294
Measured with 0.1 K uncertainty. bMeasured with 0.4 kPa uncertainty. cCalculated with 6.1·10−3 mmol·g−1 uncertainty.
Table 3. Adsorption Data of CO2 on MIL-101 263 Ka p
a
b
273 Ka n
c
p
b
283 Ka n
c
p
b
293 Ka c
b
n
p
303 Ka n
c
p
b
313 Ka n
c
p
b
nc
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
MPa
mmol·g−1
0.0349 0.103 0.2058 0.3420 0.5068 0.6438 0.7361
0.998 2.602 4.481 6.497 8.468 9.874 10.640
0.043 0.1164 0.2127 0.3365 0.4815 0.6333 0.7182 0.7600
0.836 2.117 3.545 5.089 6.628 8.007 8.710 9.048
0.0546 0.1306 0.2256 0.3296 0.449 0.5829 0.7114 0.7786
0.732 1.699 2.760 3.794 4.852 5.899 6.810 7.244
0.056 0.1333 0.237 0.3551 0.483 0.6128 0.7244
0.534 1.295 2.204 3.153 4.080 4.951 5.616
0.0548 0.1402 0.2393 0.3576 0.4773 0.6 0.7025 0.7676
0.389 1.034 1.742 2.584 3.287 3.976 4.508 4.825
0.0623 0.15 0.2515 0.3707 0.493 0.612 0.725 0.7852
0.347 0.881 1.460 2.099 2.722 3.276 3.752 4.018
Measured with 0.1 K uncertainty. bMeasured with 0.4 kPa uncertainty. cCalculated with 6.1·10−3 mmol·g−1 uncertainty.
As shown in Table 1, all the coefficients of determination are above 0.999 indicating that experimental data agrees very well with the Langmuir equation. 3.3. Isosteric Heat of Adsorption. The heat effect is an important factor in packed bed pressure swing adsorption systems. For industrial processes, the isosteric heat of adsorption is more useful than the limit heat which is defined as the isosteric heat at near-zero surface loading. Generally, surface heterogeneity effects and sorbate−sorbate interactions affect the process of adsorption. As a result, the heat of adsorption varies with coverage, which can provide useful information concerning the nature of the surface and the adsorbed phase.24 The isosteric heats of adsorption can be calculated using the Gibbs−Helmholtz equation,31 which is given by ⎛ ∂ ln f ⎞ ΔH ⎜ ⎟ = ⎝ ∂T ⎠n RT 2
Equation 4 can be integrated to give ln f = a −
ΔH RT
(5)
where f is fugacity of the pure gas, ΔH is the isosteric enthalpy of adsorption, n is the amount adsorbed and a is a constant. f is determined through f = pΦ and ln Φ =
∫0
p
z−1 dp p
(6)
The accuracy of the isosteric heat of adsorption can be improved when it is obtained from many numbers of isotherms. In this work, it was calculated with the data from six different temperatures. The adsorption pressure p at certain adsorption capacity was determined through Figure 4 and the corresponding f is determined through f = pΦ and eq 6. According to eq 5, a plot of ln( f) versus 1/T should be linear. These plots are
(4) D
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Table 4. Langmuir Parameters for CH4, CO2, and N2 at Different Temperatures adsorbate N2
CH4
CO2
parameter
263 K
273 K
283 K
293 K
303 K
313 K
qm/(mmol·g−1) b/(MPa−1) R2 qm/(mmol·g−1) b/(MPa−1) R2 qm/(mmol·g−1) b/(MPa−1) R2
7.246 0.236 0.99995 11.027 0.492 0.99948 22.547 1.204 0.99964
7.836 0.186 0.99996 9.705 0.449 0.99979 22.858 0.856 0.9999
10.264 0.120 0.99991 8.090 0.419 0.99989 21.592 0.647 0.99998
14.092 0.071 0.99992 8.616 0.315 0.99998 22.991 0.447 0.99997
12.248 0.069 0.99996 8.708 0.257 0.99996 22.908 0.349 0.99974
14.610 0.050 0.99973 6.941 0.288 0.99989 22.789 0.273 0.99986
Figure 7. Variation of isosteric heat of adsorption with adsorption capacity on MIL-101: ▲, CO2; □, CH4; ■, N2.
If the adsorbent surface is uniform and there are no sorbate− sorbate interactions, the isosteric heat of adsorption should be independent of coverage. However, as shown in Figure 7, at low coverage, the isosteric heat of adsorption decreases significantly with adsorption capacity, especially for CO2. At higher coverage there is little variation with coverage. For example, the isosteric heat of adsorption decreased from 25.4 kJ/mol to about 20 kJ/mol, as the adsorption capacity of CO2 increased from 0.5 mmol·g−1 to 1.5 mmol·g−1. The isosteric heat remained constant at about 20 kJ/mol for coverages of 1.5 mmol·g−1 to 5 mmol·g−1. The isosteric heat of CH4 was about 14.8 kJ/mol for coverages of 0.4 mmol·g−1 to 1.4 mmol·g−1 and that of N2 was about 11.5 kJ/mol for coverages of 0.1 mmol·g−1 to 0.7 mmol·g−1. The isosteric heats of adsorption for CO2 are higher than those for CH4 and N2, which is consistent with the polarizabilities of the gases. 3.4. Separation Selectivity. The separation selectivity of an adsorbent is very important for adsorption-based separation processes. The separation selectivity S1,231 can be calculated according to S1,2 =
(x1/y1) (x 2/y2 )
(7)
where x1 and y1 are the mole fractions of component 1 in the adsorbed and fluid phases at equilibrium, respectively, and x2 and y2 are those same mole fractions for component 2. Multicomponent adsorption equilibrium data are necessary to calculate the separation selectivity using eq 7. The ideal adsorbed solution theory (IAST)15,22 has been successfully used to evaluate multicomponent adsorption equilibria. In this work, the separation selectivity was estimated based on IAST. For the separation of N2 from CH4, the effect of the adsorption pressure and temperature on the separation selectivity
Figure 6. Isosters of the adsorption of (a) N2, (b) CH4, and (c) CO2 on MIL-101.
shown in Figure 6 and all the plots are linear as expected. The isosteric heats of adsorption at different coverages were evaluated from these plots, and the variation of the isosteric heat with coverage is presented in Figure 7. E
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Funding
Financial support from the National Natural Science Foundation of China (No 21206108; 21406004) and the Tianjin Municipal Science and Technology Commission (No 14JCYBJC21200) is greatly appreciated. Notes
The authors declare no competing financial interest.
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Figure 8. Variation of selection factors with pressure for (a) CH4/N2 and (b) CO2/CH4 mixtures on MIL-101: ○, 263 K; ●, 273 K; △, 283 K; ▲, 293 K; □, 303 K; ■, 313 K.
was very small, which is shown in Figure 8a. The value of the separation selectivity for CH4/N2 only varied from 2.6 to 3.3. In contrast, the separation selectivity for CO2/CH4 mixtures was very sensitive to the adsorption pressure and temperature as shown in Figure 8b. For a given temperature, the separation selectivity increased linearly with pressure. The separation selectivity increased more at lower temperatures. For example, the separation selectivity of CO2/CH4 at 263 K increased from 5.2 to 6.3, as the pressure increased from 0.1 to 0.7 MPa, whereas at 313 K the selection factor only increased from 3.2 to 3.6 for the same pressures.
4. CONCLUSIONS MIL-101 was synthesized and then characterized with XRD, SEM, and nitrogen adsorption at 77 K. The material had a double-peaked PSD, which agrees well with the crystallographic dimensions of the MIL-101 channels. The adsorption isotherms for N2, CH4, and CO2 on MIL-101 fit well with the Langmuir model. The adsorption capacities for the gases decreased in the order CO2 > CH4 > N2, and the isosteric heat of adsorption followed the same trend. The CO2/CH4 separation selectivity was more sensitive to adsorption pressure and temperature than that of CH4/N2. The largest CO2/CH4 separation selectivity was 6.3, and that for CH4/N2 was 3.3. This means that MIL-101 should be an effective adsorbent for removing CO2 from lowquality natural gas.
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DOI: 10.1021/acs.jced.5b00327 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.jced.5b00327 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
