jem00 | ACSJCA | JCA11.1.4300/W Library-x64 | research.3f (R4.1.i3 HF01:4938 | 2.

1) 2018/08/24 11:08:00 | PROD-WS-120 | rq_1131155 | 3/15/2019 13:38:49 | 13 | JCA-DEFAULT

Article

pubs.acs.org/IECR

1 Amine Modification of Binder-Containing Zeolite 4A Bodies for Post-

2 Combustion CO2 Capture

3 Debashis Panda,† E. Anil Kumar,*,∥ and Sanjay Kumar Singh*,‡,§

†
4 Discipline of Mechanical Engineering, ‡Discipline of Chemistry, §Discipline of Metallurgy Engineering and Materials Science,
5 Indian Institute of Technology Indore, Simrol, Indore 453552, India
∥
6 Department of Mechanical Engineering, Indian Institute of Technology Tirupati, Tirupati 517506, India
7 *
S Supporting Information

8 ABSTRACT: In the current study, a new type of composite

9 adsorbent was synthesized by amine modification of binder-containing
10 zeolite 4A bodies and its potential application in the post-combustion
11 CO2 capture was evaluated. A wide range of aliphatic straight chain
12 amines such as propylamine (PA), butylamine (BA), pentylamine
13 (PEA), and their respective branched chain amines, iso-propylamine
14 (IPA), iso-butylamine (IBA), and iso-pentylamine (IPEA), were used
15 in a smaller fraction to modify binder-containing zeolite 4A bodies.
16 The synthesized materials were characterized by various spectro-
17 analytical techniques to elucidate the effect of amine modification on
18 physicochemical properties of binder-containing zeolite 4A bodies and
19 its reactivity for CO2 capture. Among all of the studied hybrid
20 adsorbents, the iso-butyl amine-modified binder-containing zeolite 4A
21 bodies (IBA-Z4A) exhibited excellent CO2 adsorption performance with a maximum adsorption capacity of 2.56 mmol g−1 at
22 25 °C and 1 bar of pressure. Notably, IBA-Z4A also demonstrated excellent purity (98%) and remarkably high CO2/N2
23 selectivity (335) as compared to the pristine binder-containing zeolite 4A bodies (24). Such enhanced CO2 adsorption capacity
24 and high CO2/N2 selectivity values for IBA-Z4A can be attributed to the symbiotic interactions between CO2 and amines
25 governed by the basicity, electron density at the N atom of amines, and the steric effect of adsorbing molecules (CO2 and N2) at
26 the adsorbent surface. Notably, IBA-Z4A also displayed a marginal isosteric heat of adsorption for CO2 (51 kJ mol−1) along
27 with the encouraging thermochemical cyclic stability over five consecutive CO2 adsorption−desorption cycles at 25 °C and 1
28 bar, believed to be the best suited for post-combustion CO2 capture.

1. INTRODUCTION expected to have a significant impact on the future energy 49

Emission of anthropogenic CO2 due to uncontrolled burning of solution. 50

29
While dealing with flue gas composition (ca. 70−90% N2, 10− 51
30 fossil fuels has become an important environmental problem,
15% CO2, and remaining moisture), the choice of adsorbents 52
31 which contributes up to 60% of the global warming effects.1,2
plays a vital role in efficient CO2 adsorption and separation.3,4,8 53
32 Therefore, different preferential carbon sequestration strategies In addition to adsorption capacity, working capacity under the 54
33 such as absorption, adsorption, membrane separation, wet required pressure window, the selectivity of CO2 over N2, facile 55
34 scrubbing, and cryogenic separation are extensively explored as regenerability, adsorption/desorption kinetics, hydrophobicity, 56
35 frontier processes.2−4 Among these well-established strategies and prolonged thermochemical stability are a few of the essential 57
36 for post-combustion CO2 capture, the adsorption technique has criteria which make the materials suitable for post-combustion 58
37 gained considerable interest due to its minimal energy CO2 capture.8 In recent years, various adsorbent materials, such 59
38 requirements and low capital cost investment.5 In particular, as zeolite,3,4,7 mesoporous silica,3 activated carbon (AC),4 60
39 pressure swing adsorption (PSA), vacuum swing adsorption metal−organic frameworks (MOFs),9 and covalent organic 61
40 (VSA), and thermal swing adsorption (TSA) techniques are frameworks (COFs),10 have been extensively explored for the 62
41 being widely employed for CO2 capture from power plants.5 For selective capture of CO2 from power-plant flue gas. Compared 63
42 post-combustion CO2 capture, VSA and PSA techniques are with the other microporous adsorbents, zeolites offer most of the 64
43 mostly used due to their easy process control and low-cost features mentioned above, especially in the low-pressure regime 65
44 equipment.6 Moreover, considering the importance of CO2,
45 which is no longer regarded as a waste product and is found to be Received: August 17, 2018
46 an essential source for the production of various value-added Revised: February 1, 2019
47 chemicals,7a and fuel (such as methanol),7b the selection of an Accepted: March 12, 2019
48 economically viable carbon capture storage (CCS) technique is Published: March 12, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.8b03958

Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

66 along with superior CO2/N2 selectivity.11,12 Further, zeolites are containing zeolite 4A bodies by the post-synthesis technique 129
67 cost-effective and can be readily synthesized and some of the (dipping in amine solution) and investigate its applicability 130
68 zeolites (such as 4A and 5A) are produced from industrial toward post-combustion CO2 capture. 131
69 waste.13,14 Several zeolites such as zeolite 13X, Y, A, β, chabazite, In this context, herein, the work presents a study on the 132
70 and ZSM are also used for separation of CO2 from N2.11 Due to synthesis of amine-modified binder-containing zeolite 4A bodies 133
71 the high working capacities, zeolite 13X and NaY are widely using a wide range of primary aliphatic amines, with good 134
72 utilized in post-combustion CO2 capture, whereas zeolite NaA adsorption performances for post-combustion CO2 capture. 135
73 offers excellent CO2-over-N2 selectivity compared to FAU due The effects of steric hindrance and the carbon chain length of 136
74 to its narrow pore window.11,15 amines on CO2 adsorption performance in amine-modified 137
75 Further, amine modification of zeolites have also attracted binder-containing zeolite 4A bodies are investigated. The single 138
76 substantial scientific recognition as promising candidates for gas adsorption of CO2 and N2, selectivity of CO2 over N2, and 139
77 CO2 adsorption in the low-pressure regime, presumably due to thermocyclic stability of these amine-modified binder-contain- 140
78 symbiotic interaction of amine-CO2 and CO2-metal sites of ing zeolite 4A bodies are critically explored. Moreover, the 141
79 zeolites. 3,4,16−20 However, pore blockage and diffusion effects of pore size and surface area on CO2 adsorption 142
80 hindrance of amine molecules into the zeolite pores are the properties have also been meticulously scrutinized in this work. 143
81 major hurdles in achieving high CO2 adsorption capaci- Several characterization techniques such as P-XRD, SAXS, BET, 144
82 ty.17b,18,19,20a This effect is more severe for small pores FE-SEM, TGA, XPS, 15N NMR, and FTIR have been used to 145
83 containing zeolites such as zeolite 4A due to the steric hindrance investigate the proposed structural and chemical modification, 146
84 of amines with the pores of the zeolite.21 Therefore, zeolites amine reactivity, and their effect on CO2 adsorption properties 147
85 containing larger pores such as 13X, NaY, and β are widely used for post-combustion applications. 148
86 for the amine modification, as these pores are easily accessible
87 for amine modification.16−19 In this context, the binder- 2. EXPERIMENTAL DETAILS
88 containing commercial zeolite 4A can be a better alternative 2.1. Materials. Commercially available binder-containing 149
89 for enhanced CCS properties due to the presence of a zeolite 4A bodies in the form of cylindrical pellets of 150
90 heterogeneous pore size distribution developed by the binders22 approximately 3.2 mm diameter were purchased from Sigma- 151
91 which can be utilized for amine modification. Notably, the Aldrich (batch no. 334294). Aliphatic amines such as propyl- 152
92 binder (such as kaolin or attapulgite) itself contains a network amine (PA), iso-propylamine (IPA), butylamine (BA), iso- 153
93 (arteries) of mesopores which provides an additional pathway butylamine (IBA), pentylamine (PEA), and iso-pentylamine 154
94 for the diffusion of CO2 into the mouth of zeolite crystal pores.23 (IPEA) were procured from Sigma-Aldrich and used as received 155
95 Since micropores of the crystals present inside the commercial without any further purification. Anhydrous ethanol was used as 156
96 binder-containing zeolite 4A bodies cannot accommodate solvent purchased from analytical CSS. The capacity of gas 157
97 amine molecules within it, the amine modification of the adsorption measurement was conducted using high purity CO2 158
98 additional larger pore created by the binder may advantageously (99.99%) and N2 (99.99%) supplied by Inox Air Products Pvt 159
99 enhance the CO2 adsorption property and the CO2-over-N2 Ltd., India. 160
100 selectivity.24 2.2. Preparation of Amine-Modified Binder-Contain- 161
101 Recent studies have shown the usage of various amines, such ing Zeolite 4A Bodies. Prior to amine incorporation, 300 mg 162
102 as monoethanolamine (MEA), iso-propanolamine (IPPA), of binder-containing zeolite 4A bodies (preheated under a 163
103 tetraethylenepentamine (TEPA), and polyethylenimine (PEI), vacuum at 350 °C for 3 h) was soaked in 30 mL of anhydrous 164
104 to modify zeolites and other porous adsorbents for CO2 capture, ethanol under slight agitation for 20 min. After that, the 165
105 albeit in high loading, ca. 10−40 wt %.3,16−19 Although MEA is respective amines (linear chain amines, PA, BA, PEA, and 166
106 well-known for the CO2 capture process, other aliphatic amines branched chain amines, IPA, IBA, IPEA) in a fixed concentration 167
107 (such as iso-butylamine, butylamine, iso-propylamine, and (0.3 wt %) were added in the above suspension, and the resultant 168
108 propylamine) have also been reported for their high affinity suspension was vigorously stirred for 24 h at room temperature. 169
109 toward CO 2 molecules for the post-combustion CO 2 Finally, the solid adsorbent was filtered, repeatedly washed with 170
110 capture.25,26 Notably, the absorption capacity of iso-butylamine ethanol, and subsequently dried under a vacuum at 120 °C for 3 171
111 (0.78 mol of CO2/mol of amine) for the post-combustion CO2 h. The obtained samples were designated as (x)-Z4A, where x 172
112 capture in amine-based CO2 absorption systems (also known as represents the respective amine. For example, butylamine- 173
113 the amine scrubbing process) is higher than the MEA (0.72 mol modified binder-containing zeolite 4A bodies were represented 174
114 of CO2/mol of amine).25a In particular, primary and secondary as BA-Z4A, whereas pristine binder-containing zeolite 4A bodies 175
115 amines interact favorably with CO2 to form ammonium were represented as Z4A throughout the manuscript. The 176
116 carbamate, where the basicity and electron density at the N quantitative analysis of amine content on amine-modified 177
117 atom play a vital role in the selection of these amines for CO2 binder-containing zeolite bodies was calculated by the back- 178
118 capture.26a In addition to that, a few studies have focused on titration technique.28 About 5 mg of amine-modified binder- 179
119 amine modification of binder-containing solid sorbents containing zeolite 4A bodies was dispersed in 100 mL of 1.0 mM 180
120 (mesoporous silica) for CO2 capture, but they are limited to HCl solution under sonication for 30 min. After centrifugation 181
121 presynthesis only (the aqueous binder solution mixed with the for 10 min, 20 mL of the supernatant was titrated with 182
122 amine-modified sorbent to make a pellet).27 For instance, standardized 1.0 mM NaOH solution, in the presence of 183
123 Klinthong et al.27a used polyallylamine and NaOH for making a phenolphthalein indicator, to estimate the amine content in the 184
124 binder solution to construct a highly durable pellet from synthesized amine-modified binder-containing zeolite 4A 185
125 powdered amine-functionalized mesoporous silica which is able bodies. 186
126 to achieve 90% CO2 recovery over the powder adsorbent. Thus, 2.3. Characterization. Powder X-ray diffraction (P-XRD) 187
127 these findings have helped to explore the above-mentioned patterns of the binder-containing zeolite 4A bodies and amine- 188
128 primary aliphatic amines for modification of commercial binder- modified binder-containing zeolite 4A bodies were recorded on 189

B DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

190 a Rigaku SmartLab advanced diffractometer with monochro- 2.5. Adsorption Isotherm Modeling. To evaluate the 252
191 matic Cu Kα radiation (λ = 0.154 nm) at a step size of 0.03° over adsorption affinity between the adsorbate and the adsorbent in 253
192 a 2θ range from 5 to 80°. The small-angle X-ray scattering the pressure range (0−1 bar), the CO2 and N2 adsorption data 254
193 (SAXS) measurements were performed using Anton Paar were modeled by fitting them to the Toth and Sips equations 255
194 SAXSpoint 2.0 with monochromatic Cu Kα radiation (λ = (eqs 1 and 2), respectively. The Toth isotherm is an empirical 256
195 0.154 nm). The distance between the sample and the detector modification of the Langmuir equation, whereas the Sips 257
196 was fixed at 1076 mm, and the region of the scattering vector (q isotherm is the combined form of the Langmuir and Freundlich 258
197 = 4π sin θ/λ) lay between 0.02 and 3 nm−1 corresponding to a 2θ equations developed to reduce the error between experimental 259
198 range of approximately 0−4.2°. The surface morphology and data and the predicted value of equilibrium data. These models 260
199 pore structure of the synthesized amine-modified binder- are used to describe the heterogeneous adsorption systems, 261
200 containing zeolite 4A bodies were determined by field emission subjected to low and high adsorbate concentration10,30 262
201 scanning electron microscopy (FE-SEM) using a Carl ZEISS qtbtP
202 Supra-55 instrument. Thermogravimetric study (TGA) was q=
203 performed to analyze the thermal stability and dehydration (1 + (btP)t )1/ t (1) 263
204 characteristics of the studied adsorbents using a Mettler-Toledo 1/ s
205 TGA/SDTA851 thermal analyzer. The nitrogen sorption qs(bsP)
q=
206 isotherm and the physicochemical properties (surface area, 1 + (bsP)1/ s (2) 264
207 pore volume, pore size) of the adsorbent materials were
208 measured at −196 °C using a Quantachrome Autosorb iQ2 where P is the equilibrium adsorbate pressure (bar), q is the 265
209 TPX automated gas sorption system. Samples were degassed at adsorption capacity (mmol g−1), and qt and qs are the saturated 266
210 120 °C for 3 h under a high vacuum (10−4−10−5 bar) before CO2 adsorption capacities (mmol g−1) and bt and bs are the 267
211 analysis. The surface area of the adsorbents was calculated using affinity constants for both the Toth and Sips models, 268
212 the Brunauer−Emmett−Teller (BET) equation applied to respectively. The parameters t and s are usually less than unity 269
213 adsorption data in the relative pressure (P/P0) range of 0.05− and characterize the heterogeneity of the adsorption system.30 270

214 0.30. The micropore surface area of binder-containing zeolite 4A The values of the parameters of the Toth and Sips models can be 271

215 bodies was calculated by subtracting the Langmuir surface area evaluated by nonlinear curve fitting of the respective isotherm 272

216 [obtained from the CO2 adsorption isotherm at 0 °C in the data. Henry constant (Kh) calculations were based on the virial 273

217 relative pressure (P/P0) range of 0.0002−0.008] and the BET plots of the CO2 and N2 adsorption isotherms at 1 bar and 25 °C, 274

218 surface area as reported by Akhtar et al.11 The total pore volume respectively, as mentioned in eq 331 275

219 was calculated from the amount of adsorbed N2 at P/P0 = 0.99 q

P= exp(A1q + A 2q2 + ...)
220 using the single point adsorption method and the nonlocal KH (3) 276
221 density functional (NLDFT) algorithm (considering spherical
222 pores kernel), respectively.29 Similarly, the mesopore volume where A1 and A2 are the virial coefficients and q is the adsorption 277

223 (Vmeso) and mesopore diameter (Dp) were calculated from the capacity (mmol g−1). A plot of ln(P/q) versus q should approach 278

224 BJH method using desorption data. The above physicochemical the axis linearly as q → 0 with the intercept −ln(KH). The Henry 279

225 properties are evaluated using Quantachrome ASiQwin data constant depicted the quantitative information about the 280

226 processing software. Fourier transform infrared spectra (FTIR) interaction strength of the adsorbate with the adsorbent at 281

227 of the studied adsorbents were recorded using a spectrometer very low coverage.31 282

228 equipped with an attenuated total reflectance (FTIR/ATR 2.6. Adsorption Thermodynamics. The thermodynamic 283

229 model FTIR-STD-10, PerkinElmer, MA, U.S.A) in the wave- property such as the isosteric heat of adsorption at a given CO2 284

230 number range 4000−500 cm−1. 15N NMR spectra [retrieved adsorption capacity (q) under isothermal conditions was 285

from heteronuclear multiple bond correlation (HMBC) experi- calculated from the isotherm data at two different temperatures 286
231
(0 and 25 °C) by applying the Clausius−Clapeyron equation, as 287
232 ments] were recorded in CDCl3 using a Bruker Avance 400 (400
represented in eq 432

jij ∂(ln P) zyz = qst

288
233 MHz) spectrometer. The detailed experimental procedure of

jj zz
15
N NMR and SAXS is given in the Supporting Information.
k ∂(1/T ) {q
234
235 2.4. Adsorption Measurements. The gas sorption R
236 measurements were carried out in a Quantachrome Autosorb (4) 289
237 iQ2 TPX automated gas sorption system equipped with highly where qst and R are the isosteric heat of adsorption and the 290
238 accurate pressure transducers and a thermostatic bath. The static universal gas constant, respectively. The difference between the 291
239 volumetric mechanism measured the amount of gas adsorbed in activation energy for adsorption and desorption is called the 292
240 the adsorbents. Before adsorption experiments, the samples isosteric heat of adsorption. It depends on the temperature and 293
241 were degassed at 120 °C for 8 h under a turbomolecular vacuum surface coverage signifying the interacting binding strength 294
242 pump using a customized heating program, allowing slow between adsorbate and adsorbent.32 295
243 removal of moisture at low temperature, without structural 2.7. Adsorbent Evaluation Parameters for CO 2 296
244 changes to samples. The CO2 and N2 adsorption capacities of Capture. As flue gas streams emitting from coal-fired power 297
245 binder-containing zeolite 4A bodies and amine-modified binder- plants contain relatively low CO2 and high N2 concentrations, 298
246 containing zeolite 4A bodies were evaluated at 1 bar and 25 °C, the adsorbent must be capable of selectively adsorbing the CO2 299
247 respectively. Further, an additional CO2 adsorption experiment component from the gas mixture. Further, the purity of CO2 is 300
248 was carried out for binder-containing zeolite 4A bodies and the also desired for developing a suitable transport and storage 301
249 best performing amine-modified binder-containing zeolite 4A infrastructure.33 Thus, in this study, adsorbents were evaluated 302
250 bodies at 1 bar and 25 °C with high degassing conditions (350 regarding a few essential parameters, such as selectivity of CO2 303
251 °C for 12 h). over N231 and purity of CO2 captured,33 retrieved from their 304

C DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

305 adsorption data. The evaluation of the adsorption performance Table 1. Physicochemical Properties of the Amine-Modified
306 of an adsorbent from the adsorption isotherm data points for Binder-Containing Zeolite 4A Bodies
307 studied gas is a well-established methodology and has been used
pore volume
308 by various groups. 12,31−33 Pure component adsorption
a
selectivity (KhCO2/KhN2) was estimated as the ratio of the SBET Dpc Vtotald Vmesoe amine content
309 material (m2 g−1) (nm) (cc g−1) (cc g−1) (mmol g−1)
310 Henry constants for respective CO2 and N2 at 25 °C (eq 5),
Z4A 37, 337b 3.4 0.140 0.138
311 whereas the CO2/N2 selectivity and purity of CO2 under
PA-Z4A 36 3.4 0.135 0.132 0.89
312 adsorption conditions were calculated at 25 °C using the IPA-Z4A 33 3.4 0.133 0.130 0.90
313 following equations (eqs 6 and 7)12,31,33 BA-Z4A 35 3.9 0.139 0.136 0.96
K hCO2 IBA-Z4A 32, 255b 3.8 0.125 0.123 0.98
Pure component adsorption selectivity = PEA-Z4A 35 3.4 0.135 0.132 0.94
K hN2 (5) IPEA-Z4A 32 3.4 0.127 0.118 0.91
314
a
BET surface area. bMicropore surface area. cMesopore diameter.
qCO /qN d
Total pore volume. eMesopore volume.
2 2
Selectivity (αCO2 /N2) =
PCO2 /PN2 (6)
315 The P-XRD and FESEM results suggest the intactness of 356

qCO structural and morphological integrity for binder-containing 357

Purity = 2
× 100 (%) Z4A bodies after amine modification (Figure 1 and Figure S1). 358 f1
qCO + qN (7) The effect of amine(s) on the physicochemical properties of 359
316 2 2
binder-containing zeolite 4A bodies is also evaluated and listed 360

317 where qCO2 and qN2 are the amounts of CO2 and N2 adsorbed at in Table 1. 361

318 their respective equilibrium partial pressures (PCO2 and PN2).

319 KhCO2 and KhN2 are the corresponding Henry constants for CO2
320 and N2 at 25 °C. It was assumed that the flue gas was generated
321 at a total pressure of approximately 1 bar having a CO2
322 concentration of 15% and a N2 concentration of 75%. Therefore,
323 under these conditions, the corresponding partial pressure was
324 found to be 0.15 bar for CO2 and 0.75 bar for N2.33
325 2.8. CO2 Adsorption Capacity over Prolonged Cyclic
326 Testing. For the post-combustion CO2 capture, adsorbents
327 should not only possess a high adsorption capacity but also
328 display a stable cyclic adsorption performance to avoid their
329 frequent replacement during long-term cyclic operation. There-
330 fore, cyclic CO2 adsorption and desorption experiments were
331 conducted for the best performing adsorbent at 25 °C. After
332 attaining the adsorption equilibrium, the sample was degassed
333 under two different conditions: (i) via vacuum desorption at
334 different pressures (0.01 and 0.1 bar) and combination of
335 vacuum and thermal desorption (0.01 bar at 120 °C) for 30
336 min.34 The results were illustrated in the form of the adsorption
337 index (abbreviated as AI, %), which is defined as a percentage
338 ratio of the adsorption capacity of the regenerated samples to Figure 1. (a−c) FE-SEM images and (d) P-XRD patterns of Z4A, BA-
339 fresh samples.34 Thus, 100% AI implies that the adsorbent has Z4A, and IBA-Z4A.
340 not deteriorated at all during these cyclic adsorption−
341 desorption studies. It has been well established that, for the binder-containing 362
zeolite bodies, the BET surface area represents the total surface 363
3. RESULTS AND DISCUSSION area including the internal surface (pore) and the external 364
342 3.1. Synthesis and Characterization of Amine-Modi- surface (crystal, binder).35 On the other hand, for binder-free 365
343 fied Binder-Containing Zeolite 4A Bodies. Amine- microporous zeolites such as 4A, the surface area represents the 366
344 modified binder-containing zeolite 4A bodies are synthesized external surface area only, which is accessible for the N2 367
345 by treating a suspension of binder-containing zeolite 4A bodies molecule.35 In this context, the studied binder-containing 368
346 in ethanol with a fixed concentration of 0.3 wt % of respective zeolite 4A bodies exhibit quite a different physicochemical 369
347 amines (linear chain amines, PA, BA, PEA, and branched chain behavior than the conventional binder-free microporous zeolite 370
348 amines, IPA, IBA, IPEA), as elaborated in the Experimental 4A due to the presence of the binder. As shown in Figure 2a and 371 f2
349 Details. The schematic diagram of amine modification and the Figure S2, all of the individual isotherms of binder-containing 372
350 molecular structure of the amines used are illustrated in Schemes zeolite 4A bodies before and after amine modification are 373
351 S1 and S2, respectively. The amine content in the synthesized classified as type IV having a well-defined plateau with modest 374
t1 352 amine-modified binder-containing zeolite 4A bodies (Table 1) hysteresis, whereas binder-free microporous LTA type zeolite 375
353 is estimated by the titration technique, and it is inferred that the (4A, 5A) generally displays a type I isotherm.36 Moreover, it has 376
354 amine loading is equivalent in all cases (using a different been observed that the binder-containing zeolite 4A bodies 377
355 concentration of HCl), as listed in Table 1. display a higher BET surface area (37 m2 g−1) and DFT total 378

D DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

Figure 2. (a) N2 adsorption−desorption isotherm, (b) BJH pore size distribution curves, (c) small-angle X-ray scattering patterns, and (d) pore-size
distribution curve obtained from small-angle X-ray scattering of Z4A, BA-Z4A, and IBA-Z4A (solid and open symbols represent adsorption and
desorption isotherms, respectively).

379 pore volume (0.074 cc g−1) as compared to the other binder-free interparticle mesopores present in the binder or zeolite pore 416
380 microporous zeolite 4A (typically ∼5−32 m2 g−1 11,37a−d and space.20a It is anticipated that, in zeolite systems, the amine will 417
381 DFT total pore volume ∼0.029 cc g−1),37a reported in the first clog onto pore walls rather than filling the pores, as 418
382 literature. The binder also increases the total pore volume of the suggested by Cogswell et al.20a and Holewinski et al.39 Since 419
383 system.37e Since the kinetic diameter of the nitrogen molecule most of the amine molecules can be preferentially accom- 420
384 (0.36 nm) is comparable to the effective pore opening of zeolite modated into the large mesopore network available in the binder 421
385 4A (about 0.4 nm), it is unable to enter into a pore (as of the zeolite bodies, the mesopore volume is proportionately 422
386 shrinkages of eight-membered ring (8-MR) pore window) at a decreased (Figure 2b). 423
387 temperature of −196 °C, and consequently, it exhibits a low It is evident that the pores which are smaller than the size of 424
388 BET surface area and pore volume.37a−d Therefore, the obtained N2 will not be detected and therefore a conventional micropore 425
389 surface area of the binder-containing zeolite 4A bodies is not the model such as the Horvath−Kawazoe (HK) model may 426
390 true surface area of microporous zeolite 4A powder (crystal); underestimate the size accuracy of the micropores smaller 427
391 rather, it is the surface area of the binder itself. Alternatively, than 0.36 nm.37d Consequently, the Kelvin equation is not 428
392 CO2, having a kinetic diameter (0.33 nm) less than N2, will more appropriately applicable for small pores less than 1 nm.40a In this 429
393 easily enter into the pore opening of zeolite 4A; thus, the context, a small-angle X-ray scattering (SAXS) is quite fruitful in 430
394 Langmuir surface area is calculated for the binder-containing overlapping the range of 1−2 nm and can provide a reasonable 431
395 zeolite 4A bodies from the CO2 adsorption isotherm at 0 °C and estimate of the pore size distribution of binder-containing 432
396 found to be 374 m2/g. In addition to that, the micropore surface zeolite 4A bodies after amine modification (bearing both micro- 433
397 area is calculated as 337 m2 g−1, which is comparable to the and mesopores).40b In the SAXS technique, Guinier’s law is used 434
398 findings of other research groups on microporous zeolite 4A to calculate the mean pore radius (referred to as structural sizes) 435
399 powder.11 It is further noted that all of the samples that display a of the particle by applying the method of tangents (Figure 436
400 closed hysteresis loop (Figure 2a) in the relative pressure region S3a).37c The Guinier equation describes the mean intensity of 437
401 of 0.45−1.0 could be related to the capillary condensation in the radiation scattered by a particle of any shape, averaged 438
402 mesopores.38 The presence of mesopores is probably due to the through all of its possible orientations in space. As shown in 439
403 binder (existence of nonrigid aggregates of plate-like particles), Table S1, the values of surface fractal dimension (pore diameter) 440
404 which is in accordance with some existing reports.22a,23 It is clear of binder-containing zeolite 4A bodies expressed as the radius of 441
405 from Table 1 that the textural properties of binder-containing gyration are in the mesoporous or slightly macroporous range 442
406 zeolite 4A bodies seemed to be heterogeneous and decreased (51 nm), which indicates the primary particle of the sample has a 443
407 after incorporation of amines. The reduction of surface area and rough pore−solid interface, presumably due to the presence of 444
408 pore volume (for IBA-Z4A: total pore volume from 0.140 to binder.37c It means that the binder circumscribed the micro- 445
409 0.125 cc g−1 and mesopore volume from 0.138 to 0.123 cc g−1 in porous particles within it. The observed and calculated SAXS 446
410 comparison to Z4A bodies) is supposed to fill the external pores patterns (I(q) vs q) and the resultant broad pore size 447
411 (as generated by the binder) during the amine modification distributions are shown in Figure 2c,d. The broad pore size 448
412 process. Due to the difference in critical diameters between the distribution obtained by SAXS indicates the region between 449
413 amine and the window aperture, it is assumed that amine micro and meso and includes a contribution from every pore size 450
414 molecules fail to insert themselves into the small micropores of within the entire range.41 The observation is in good agreement 451
415 the zeolite 4A units inside the binder and thus fill or clog the with the finding of commercial zeolite 4A reported by Du et 452

E DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

Figure 3. (a, b) CO2 and N2 adsorption isotherms for binder-containing zeolite 4A bodies and amine-modified binder-containing zeolite 4A bodies at
25 °C in the pressure range: (a) CO2 adsorption isotherms in 0−1 bar; (b) N2 adsorption isotherms in 0−1 bar.

Table 2. CO2 and N2 Adsorption Capacities of Amine-Modified Binder-Containing Zeolite 4A Bodies at 25 °C

CO2 adsorption capacity N2 adsorption capacity
0.15 bar 1 bar 0.75 bar 1 bar chemical shift
−1 −1 −1 −1
adsorbent (mmol g ) (mmol g ) wt % (mmol g ) (mmol g ) 15
N δ (ppm)
Z4A 0.97 2.20 9.69 0.20 0.25
PA-Z4A 0.89 2.33 10.27 0.04 0.05 21.58
IPA-Z4A 0.96 2.43 10.68 0.07 0.09 43.74
BA-Z4A 1.14 2.48 10.89 0.04 0.06 21.95
IBA-Z4A 1.34 2.56 11.26 0.02 0.02 17.14
PEA-Z4A 0.37 1.90 8.38 0.10 0.13 20.97
IPEA-Z4A 0.68 1.91 8.39 0.09 0.12 22.06

453 al.37c From Figure 2c, it is quite clear that IBA-Z4A displays a The CO2 and N2 adsorption capacity of Z4A bodies is found 488
454 higher scattering intensity compared to Z4A, which is attributed to be comparably lesser than the reported binder-free micro- 489
455 to its high porosity.40a,42 The development of new and smaller porous zeolite 4A (100% active material), presumably due to 490
456 pores (<2 nm) after amine modification can be observed in the lower volumetric efficiency.11 Analogously, a lower CO2 491
457 pore size distribution (Figure 2d). The new pore space adsorption capacity was also observed by other researchers, 492
458 generation is apparently due to the decrease in pore number while dealing with the binder-containing zeolite bodies.44 In 493
459 density observed for the same pore sizes by the filling of amine,41 general, the zeolite 4A based adsorbents are being degassed at a 494
460 which is in line with the reported results.20 higher temperature (300−350 °C) to get rid of the moisture.12 495
461 Further, to verify the prejudicial impact of amine modification However, enduring such high degassing temperature after each 496
462 on textural properties, FTIR and TGA analyses are also adsorption cycle is highly energy intensive. On the other hand, 497
463 performed for these amine-modified Z4A bodies (Figures S4 the low-temperature exhaust gases (70−230 °C) exiting from 498
464 and S5, respectively). As compared to Z4A, FTIR spectra of BA- recovery devices in gas-fired boilers and ethylene furnaces 499
465 Z4A and IBA-Z4A display increasing intensity and broadness of remain largely unutilized for electricity generation due to their 500
466 bands ranging from 3600 to 2800 cm−1, which could be due to low Carnot efficiency.45 Hence, these unused low-temperature 501
467 the overlapping of several bands including 3270 cm−1 (N−H exhaust gases can be utilized to regenerate the adsorbents. In this 502
468 stretching) and 1470 cm−1 (NH2 bending) in the single region context, a lower degassing temperature (120 °C) for binder- 503
469 (Figure S4b).19,43 Z4A, BA-Z4A, and IBA-Z4A exhibit containing zeolite 4A bodies is selected for investigating the CO2 504
470 analogous thermograms with a significant weight loss (∼17%) adsorption performance to utilize the waste heat generated from 505
471 in the temperature range 100−160 °C, which is attributed to the recovery devices. 506
472 removal of moisture17a,24 and the elimination of amine. With a On the other hand, it is observed that the studied amine- 507
473 further increase in temperature, the weight loss becomes modified Z4A bodies display enhanced CO2 adsorption 508
474 insignificant, and no weight loss is observed for the remaining properties at 0.15 and 1 bar, respectively, at 25 °C. From Figure 509
475 weight of 83% up to 650 °C, indicating the high thermal stability 3 and Table 2, it is evident that, among several amines utilized 510
476 of Z4A/amine-modified binder-containing zeolites bodies for modification of binder-containing zeolite 4A bodies, the 511
477 (Figure S5). branched chain amines display superior CO2 adsorption 512
478 3.2. CO2 and N2 Adsorption Studies of Amine- capacities as compared to the straight chain amine-modified 513
479 Modified Binder-Containing Zeolite 4A Bodies. The binder-containing zeolite 4A bodies. Notably, among a wide 514
480 efficacy of the amine-modified zeolite bodies for post- range of utilized branched chain amines, the iso-butylamine- 515
481 combustion CO2 capture applications is extensively investigated modified binder-containing zeolite 4A bodies (IBA-Z4A) 516
482 through quantifying the CO2 and N2 adsorption capacities at the display the steepest increase in CO2 adsorption capacity at 517
483 low-pressure regime (up to 1 bar), pertaining to flue-gas-like 0.15 bar (1.34 mmol g−1, 5.89 wt %), which further increases to 518
f3 484 conditions (Figure 3). The results related to CO2 and N2 2.56 mmol g−1 (11.26 wt %) at 1 bar. Notably, IBA-Z4A also 519
485 adsorption capacities of amine-modified binder-containing exhibits the lowest N2 adsorption capacity (0.02 mmol g−1) 520
486 zeolite 4A bodies along with the parent binder-containing among all of the studied absorbents at 1 bar. In contrast to IBA- 521
t2 487 zeolite 4A bodies are listed in Table 2. Z4A, pentylamine- and iso-pentylamine-modified binder-con- 522

F DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

Figure 4. (a) CO2 adsorption isotherms for Z4A and IBA-Z4A at 0 and 25 °C. (b) Isosteric heat of adsorption of CO2 for Z4A and IBA-Z4A. (c)
Comparative chart for the isosteric heat of adsorption of CO2 of other amine-modified adsorbents.

523 taining Z4A bodies display a lower CO2 adsorption capacity, partial coverage of the nitrogen atom by long organic chains, 554
524 presumably due to the bulky nature of pentylamine and iso- owing to the lower accessibility of the lone pair of electrons, 555
525 pentylamine25a and/or narrower adsorption energy distribution, resulting in decreased interaction with CO2.16a,46b,c On the basis 556
526 which means amines are not able to modify the binder- of these findings, 0.3 wt % amine loading in binder-containing 557
527 containing zeolite 4A bodies properly.46a With this under- zeolite 4A bodies is believed to be optimal to achieve high CO2 558
528 standing, the loading of iso-butylamine in binder-containing adsorption capacity in binder-containing zeolite 4A bodies. 559
529 zeolite 4A bodies is further varied (0.1, 0.3, and 1 wt %) to study In order to further investigate the adsorbate−adsorbent 560
530 the effect of amine loading on CO2 adsorption capacity at 25 °C interaction, the measured pure component adsorption isotherm 561
531 and 1 bar (Figure S6a). Results showed that at minimal loading data for CO2 and N2 on the studied adsorbents are fitted with the 562
532 (0.1 and 0.3 wt %) the CO2 adsorption capacity is better in Toth and Sips models, respectively (Figure 3 and Figure S7). All 563
533 comparison to the higher amine loading of 1 wt %. These of the fitted parameters with the normalized standard deviation 564
534 findings are consistent with the earlier report of Bezerra et al.17a (NSD) are summarized in Table S2. The goodness-of-fit value 565
535 At optimal minimum loading (0.3 wt %), the CO2 adsorption (R2 ∼ 0.99) for the Toth model over the entire pressure and 566
536 capacity is found to be high in comparison to the loading of 0.1 temperature range in amine-modified binder-containing zeolite 567
537 and 1 wt % in IBA-Z4A. Further study revealed the effect of 4A bodies indicates that CO2 molecules are efficiently adsorbed 568
538 loading (0.1, 0.3, and 1 wt %) of another amine, iso-pentylamine on amine-modified Z4A bodies in multimolecular layers due to a 569
539 (IPEA), which is closest to iso-butylamine (IBA) in terms of its high degree of adsorbent surface heterogeneity.32a,33 Partic- 570
540 basicity, on the CO2 adsorption properties. Contrary to IBA- ularly, CO2 interacts with the lattice oxygen present inside the 571
541 Z4A, results infer no significant enhancement in CO2 adsorption zeolite framework (Lewis basic site) which acts as an adsorption 572
542 capacity for IPEA-Z4A with varying amine loading. Even with a center. Since the framework of the zeolite 4A crystal lies inside 573
543 higher loading of 1 wt % IPEA, the CO2 adsorption is analogous the binder, these broad ranges of pores present inside the binder 574
544 to that of 0.3 wt % IPEA (Figure S6b). These results are act as microreactors for the capture of CO2. Therefore, when the 575
545 consistent with the assumption that, due to the sterically bulky amine modifies these pores, they exhibit superior CO 2 576
546 nature of IPEA and its narrow adsorption energy distribution, adsorption performance, due to the symbiotic interaction 577
547 the pores of the binder-containing zeolite 4A bodies may be between CO2 and amines. 578
548 unable to be properly modified by the amine.25a,46a It is believed After amine modification, the basicity of binder-containing 579
549 that the basicity of straight chain amines increases with the zeolite 4A bodies increases due to the formation of extra 580
550 increase in chain length (to a certain limit) due to the increase in adsorption centers by the presence of free −NH2 groups (Table 581
551 electron donating alkyl groups and decreases due to the steric 2). The mechanism of CO2 adsorption on amine-modified 582
552 hindrance effect, which adversely affects the interaction of the adsorbents has been described in recent literature report- 583
553 amines with CO2 molecules. This complexity occurs due to s.16a,26,47 Recently, Yaghi et al.47b investigated the interaction 584

G DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

585 between CO2 and the −NH2 group using solid-state NMR and Table 3. Adsorbent Evaluation Parameters for CO2 Capture
586 identified the formation of ammonium carbamate and carbamic
Henry constant
587 acid as an important species. Perinu et al.26 also established a Kh
588 relationship between the reactivity of a series of primary straight (mmol g−1 bar-
−1
589 chain alkyl amines (propylamine, butylamine) and branched ) selectivity
590 chain alkyl amines (iso-propylamine, iso-butylamine) using 15N adsorbents CO2 N2 (KhCO2/KhN2)a αCO2/N2b purity (%)
591 NMR spectroscopy for CO2, where the formation of carbamate
Z4A 11 0.30 37 24 83
592 at equilibrium depends upon the basicity of the interacting PA-Z4A 12 0.07 171 111 96
593 amine. Therefore, the higher CO2 adsorption capacity observed IPA-Z4A 17 0.17 100 69 93
594 for IBA-Z4A bodies is in accordance with the lowest 15N NMR BA-Z4A 18 0.04 450 143 97
595 chemical shift of IBA (Table 2 and Figure S8) which may IBA-Z4A 18 0.03 600 335 98
596 facilitate the efficient amine interaction with CO2. PEA-Z4A 3 0.12 25 19 79
597 3.3. Adsorption Thermodynamics and Evaluation IPEA-Z4A 6 0.15 40 38 88
598 Parameter of Amine-Modified Binder-Containing Zeo- a
Pure component adsorption selectivity. bSelectivity based on the
599 lite 4A Bodies for CO2 Capture. Further, to study the energy
adsorption conditions (qCO2 at 0.15 bar, qN2 at 0.75 bar).
600 penalty associated with the regeneration of the studied
601 adsorbents, the isosteric heat of adsorption (Qst) is estimated
adsorbent (Figure 5a). As a result, IBA-Z4A displays excellent 646 f5
f4 602 for Z4A and IBA-Z4A. Figure 4a shows that there is a 10.2%
pure component adsorption selectivity of CO2/N2 measured 647
603 increase in CO2 adsorption capacity, when the temperature rises from the value of the Henry constant ratio at 25 °C (Table 3). 648
604 from 0 to 25 °C for IBA-Z4A, due to the effect of chemisorption The observed higher CO2/N2 selectivity in IBA-Z4A could be a 649
605 (forming covalent C−N bonds), which is often seen in amine- consequence of the exceptionally larger polarizability and 650
606 modified adsorbents.16b,18a,19 Concurrently, the CO2 adsorption quadrupole moment of CO2 (29.11 × 10−25 cm−3 and 4.30 × 651
607 capacity decreases in Z4A with an increase in temperature 10−26 esu−1 cm−1, respectively) than those of N2 (17.40 × 10−25 652
608 because of the exothermic nature of physisorption (Figure 4a). cm−3 and 1.52 × 10−26 esu−1 cm−1, respectively) and the steric 653
609 Notably, the derived Qst value of Z4A bodies (38 kJ mol−1) is in effect of adsorbing molecules (CO2, N2) at the adsorbent 654
610 line with the zeolite 4A series (ca. 35−50 kJ mol−1) reported in surface.11,33 Furthermore, IBA-Z4A exhibits excellent flue gas 655
611 the literature.32b,c Furthermore, upon amine modification, IBA- normalized selectivity (αCO2/N2 = 335) along with the high VCO2/
612 Z4A displays a significantly higher value of Qst (51 kJ mol−1). 656

613 The large Qst value of IBA-Z4A indicates the heterogeneity and VN2 selectivity (128 at 1 bar), suggesting that high purity CO2 657
614 higher affinity of IBA-Z4A for CO2 adsorption (Figure 4b). In (98%) could be recovered from the dry flue gas (Figure 5b). It is 658
615 fact, it has been observed that there is a reasonable increment in quite obvious that generating pure CO2 would support the 659
616 Qst (13 kJ mol−1) with a little rise in CO2 adsorption capacity in reduction of high capital investment for compression, trans- 660
617 IBA-Z4A as compared to Z4A bodies, which is presumably due portation, and storage/utilization of CO2 in power plants.33 661
618 to the high carbamate formation tendency of iso-butylamine For further investigations, additional CO2 and N2 adsorption 662
619 during the chemical reaction with CO2.26b experiments were conducted for the studied binder-containing 663
620 Figure 4b displays an initial decreasing and then almost zeolite 4A bodies and IBA-Z4A at 1 bar and 25 °C with higher 664
621 stabilizing trend in Qst value with CO2 loading (indicating the degassing conditions (350 °C for 12 h). The effect of degassing 665
622 preferential occupancy of high energy sites) followed by a temperature on CO2 adsorption performance (Figure S10 and 666
623 plateau (saturation level). The Qst value (51 kJ mol−1) obtained Tables S3) is estimated. From the results, an obvious 667

624 for IBA-Z4A is lying in the very narrow range of weak enhancement in the CO2 and N2 adsorption capacity for both 668

625 chemisorption, which is at par with or even smaller than the Z4A and IBA-Z4A is observed, due to the elimination of amine 669

626 established amine-modified adsorbents as reported in the and water molecules from these adsorbents at the higher 670

627 literature (Figure 4c).48 The obtained lower Qst value of IBA- degassing temperature.12 Additionally, the higher degassing 671

628 Z4A suggests that regeneration of the adsorbents will consume temperature for adsorbents may also adversely affect the CO2/ 672

629 less energy.48c N2 selectivity, due to the unhindered mobility of the adsorbing 673

630 The above results are encouraging enough to calculate the gases (CO2 and N2) in the pores of the binder-containing zeolite 674

631 Henry constant (Kh), CO2-over-N2 selectivity, and purity of the bodies. Results infer that the CO2/N2 selectivity of IBA-Z4A 675

632 amine-modified binder-containing zeolite 4A bodies to study decreases significantly to 58 under degassing at 350 °C for 12 h, 676

633 their further applicability in selective CO2 capture under flue gas in comparison to the higher CO2/N2 selectivity of 335 observed 677

634 conditions (Figure S9 as an example). under degassing at 120 °C for 8 h. Hence, the preferential 678

t3 635 As listed in Table 3, it is found that the pure component adsorption of CO2 over N2 on IBA-Z4A makes it a suitable 679
candidate for selective CO2 capture from flue gas with low 680
636 adsorption selectivity of Z4A bodies (KhCO2/KhN2 = 37) is higher
energy penalty. 681
637 than the reported microporous powder zeolite 4A (ca. KhCO2/ Besides high CO2/N2 selectivity, IBA-Z4A also exhibits a 682

638 KhN2 = 19) at 25 °C (gas composition: 94.9% N2, 5.1% CO2).32b better adsorption performance during the cyclic CO 2 683

639 The reason may be due to the selection of different gas phase adsorption−desorption experiment at 25 °C and 1 bar (Figure 684

640 compositions while calculating the pure component selectivity 5c,d). While operating the experiment at moderate desorption 685

at low pressure. The calculated Henry constant (KhCO2) of Z4A pressure (0.1 bar), the respective CO2 adsorption capacity and 686
641
adsorption index of the spent IBA-Z4A are significantly reduced 687
642 is in accordance with the reported literature.44c It is worth to 0.62 mmol g−1 (AI = 24%) after 10 cycles of CO2 adsorption− 688
643 noticing that the observed higher KhCO2 for IBA-ZA as compared desorption (Figure S11). However, when the experiment was 689
644 to the other amine-modified Z4A and parent Z4A bodies is conducted at low desorption pressure (0.01 bar), after the initial 690
f5 645 presumably due to the strong interaction of CO2 with the drop, the respective CO2 adsorption capacity and adsorption 691

H DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

Figure 5. (a) Semi-log plot of CO2 adsorption isotherm on amine-modified adsorbents at 25 °C. (b) CO2 over N2 selectivity (αCO2/N2) of studied
adsorbents. (c, d) Cyclic CO2 adsorption−desorption experiment for IBA-Z4A under different desorption conditions: (c) vacuum desorption at 0.01
bar and (d) combined vacuum and thermal desorption at 0.01 bar and 120 °C. (e) P-XRD patterns of spent IBA-Z4A before (i) and after five
consecutive CO2 adsorption−desorption cycles under desorption conditions (ii) 0.01 bar and and (iii) 0.01 bar at 120 °C.

692 index show better values and remain stable after the 5th cycle modification of the binder-containing zeolite 4A bodies, it is 718
693 (1.4 mmol g−1 and 55%) with only a marginal loss in CO2 possible to achieve superior CO2/N2 selectivity under the flue 719
694 adsorption capacity even up to the 10th cycle (Figure S11). The gas conditions. Further, the low utilization of amine is able to 720
695 decrease in CO2 adsorption capacity and adsorption index in address the conventional limitations like corrosion and high 721
696 both prior cases could be attributed to the chemical interaction regeneration cost for solid amine-based adsorption systems. The 722
697 of CO2 and IBA-Z4A, where the adsorbed CO2 is unable to upgradation of CO2/N2 selectivity and purity of adsorbents 723
698 desorb completely from IBA-Z4A only by decreasing the upon amine modifications are in line with the previous literature 724
699 desorption pressure. Hence, a fresh cyclic experiment (five reports (Table S4).24,46b,50 Several studies have been conducted 725
700 cycles) was conducted at 0.01 bar desorption pressure with by various researchers on amine-modified adsorbents to increase 726
701 thermal treatment (120 °C). It is worth noticing that, at the CO2/N2 selectivity. For instance, Xu et al.24 reported the 727
702 combined vacuum and thermal desorption, the cyclic CO2 enhancement of CO2/N2 selectivity from 12.19 (parent zeolite 728
703 adsorption capacity is found to be almost unchanged (2.4 β) to 25.67 upon 40 wt % MEA loading in zeolite β, 729
704 mmol g−1) with 96% adsorption index (Figure 5d). The stable predominantly due to the steric effect of adsorbate by reduction 730
705 adsorption capacity during the following five cycles is of the adsorbent’s pore diameter and chemical adsorbate− 731
706 comparable with the other well-established amine-modified adsorbent interaction. Especially in the flue gas, due to 732
707 adsorbents.49 Notably, P-XRD analysis of the spent IBA-Z4A competitive adsorption, CO2 is preferentially adsorbed on 733
708 after cyclic adsorption−desorption displays no significant amine-modified adsorbents by displacing the preadsorbed N2 734
709 change in the characteristic diffraction patterns, confirming the over time, which increases the CO2/N2 selectivity. This is in 735
710 excellent physico- and thermochemical stability of IBA-Z4A agreement with the results obtained by Jadhav et al.50a and 736
711 (Figure 5e). Hence, the study suggests that the combined Demessence et al.50b They evaluated the CO2/N2 selectivity for 737
712 vacuum and thermal treatment (0.01 bar at 120 °C) is the most triazolate-bridged MOF (Cu-BTTri) before and after ethyl- 738
713 suitable desorption condition to regenerate the spent IBA-Z4A enediamine modification (Cu-BTTri-en) under post-combus- 739
714 during CO2 adsorption experiments. tion CO2 capture conditions and observed an enhancement in 740
715 3.4. Comparison of Adsorption Performance of IBA- CO2/N2 selectivity of 21−25 after amine impregnation. Unlike 741
716 Z4A and Other Amine-Modified Adsorbents. In the amine impregnation, grafting of amine onto the surface of silica 742
717 current study, it has been observed that, after successful amine also helps in increasing CO2/N2 selectivity. Wang et al.50c 743

I DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

Table 4. Comparison of Adsorption Capacities of Various Amine-Modified Adsorbentsa

equilibrium CO2 adsorption
operating conditions capacity

support amine loading (vol/wt %) PCO2 (bar) T (°C) (mmol g−1) (wt %) ref
zeolite β MEA 40 (w) 1 30 0.77 3.38 24
zeolite Y MEA 20 (w) 1 25 1.15 5.06 18b
zeolite Y TEPA 20 (w) 1 25 1.90 7.08 18b
zeolite Y MEA 40 (w) 1 25 1.97 8.66 18b
zeolite Y IPPA 40 (w) 1 25 1.61 8.36 18b
zeolite 13X MEA 0.2 (v) 0.1 25 1.68 7.39 17a
zeolite 13X MEA 0.5 (w) 1 30 1.25 5.50 50a
zeolite 13X MEA 10 (v) 1 25 0.56 2.46 50a
zeolite 13X MEA 25 (w) 1 30 0.78 3.43 50a
AC PEHA 40 (w) 1 25 1.10 4.80 51a
Si-MCM-41 PEI 50 (w) 1 25 0.74 3.29 51b
Z4A bodies BA 0.3 (w) 1 25 2.47 10.89 this work
Z4A bodies IBA 0.3 (w) 1 25 2.56 11.26 this work
a
MEA, monoethanol amine; TEPA, tetraethylenepentamine; IPPA, iso-propanol amine; PEHA, pentaethylenehexamine; PEI, polyethylenimine;
BA, butylamine; IBA, iso-butylamine; Z4A bodies, binder-containing zeolite 4A bodies.

744 reported a CO2/N2 selectivity enhancement from 46 (parent Interestingly, the CO2 uptake behavior of amine-modified 784
745 SBA-15) to 131 for (3-aminopropyl) trimethoxysilane grafted binder-containing zeolite 4A bodies is found to be substantially 785
746 SBA-15 under flue gas conditions (0.15 bar of CO2 and 0.85 bar affected by the carbon chain length, straight/branched nature, 786
747 of N2). Besides, adsorbents with high N-donor molecules are and electronic behavior of the aliphatic amines. The findings 787
748 also useful to achieve high CO2/N2 selectivity. Recently, Tekin have inferred that amine-modified binder-containing zeolite 4A 788
749 et al.50d found an enriched CO2/N2 selectivity of 473 at 23 °C in
bodies, with iso-butylamine (IBA-Z4A), demonstrate superior 789
750 the microporous metal dicyanamide cluster [Co(hmt)(dca)2
751 (hmt, hexamethylenetetramine; dca, dicyanamide)] because of CO2 adsorption capacity (2.56 mmol g−1), high purity (98), and 790

752 diffusion hindrance of N2 to the small pore cavity of the excellent CO2/N2 selectivity (335) as compared to various other 791
753 adsorbent. amine-modified Z4A bodies. The high CO2/N2 selectivity 792
754 Notably, apart from excellent CO2/N2 selectivity, we also values can be attributed to the steric effect and strong chemical 793
755 observe a much higher CO2 adsorption capacity of 2.56 mmol adsorbate−adsorbent interaction. Notably, IBA-Z4A exhibits a 794
756 g−1 (11.26 wt %) even with ∼10 times less amine loading (0.3 wt marginal isosteric heat of adsorption (51 kJ mol−1) at 1 bar, 795
757 %) in binder-containing zeolite 4A bodies as compared to suggesting the facile regenerability of IBA-Z4A and prolonged 796
t4 758 previously reported results (Table 4).17a,18b,24,48a,51 Earlier thermocyclic stability over five consecutive cycles of CO2 797
759 reports revealed that amine-modified zeolite Y exhibited adsorption−desorption. To the best of our knowledge, the 798
760 enhanced CO2 adsorption capacities with high amine loading
obtained pure component CO2/N2 selectivity (600) and the 799
761 (20−40 wt %) of MEA, IPA, or TEPA.18b Further, with other
762 adsorbents such as activated carbon or ordered MCM-41, at 25 CO2/N2 selectivity (335) derived from the adsorption condition 800

763 °C, even with the high surface area and with high amine loading, for IBA-Z4A is comparable with the best values reported for 801
764 the observed CO2 adsorption capacities are much lower than other microporous materials. Thus, the study of amine 802
765 those obtained with IBA-Z4A in the present work (Table S5). modification of binder-containing zeolite 4A bodies to achieve 803
766 Moreover, the adsorbent binder-containing zeolite 4A bodies superior CO2 adsorption capacity has demonstrated a better way 804
767 and the respective modifying agent iso-butylamine (code to utilize the cost-effective material binder-containing zeolite 4A 805
768 I14150) are of lower cost than the commonly used microporous bodies as a promising adsorbent for the carbon capture storage 806
769 zeolite 13 X powder (or bodies) and MEA (code 398136). (CCS) process. 807

■
770 Hence, IBA-modified binder-containing zeolite 4A bodies (IBA-
771 Z4A) can be considered as a promising adsorbent for efficient
772 CO2 capture. ASSOCIATED CONTENT 808

* Supporting Information
S 809
4. CONCLUSIONS The Supporting Information is available free of charge on the 810
773 Efficient CO2 adsorption capacity over binder-containing zeolite ACS Publications website at DOI: 10.1021/acs.iecr.8b03958. 811
774 4A bodies is achieved by modification of a wide range of aliphatic
775 amines (straight and branched chain amines) in binder- The physicochemical characterization (P-XRD, BET, 812

776 containing zeolite 4A bodies. In this study, various character- FTIR, TGA, 15 N NMR, and SAXS) for studied 813

777 ization techniques such as BET, SAXS, and FESEM have adsorbents, fitting parameters for CO2 and N2 adsorption 814

778 confirmed the presence of a heterogeneous pore size distribution isotherms from respective Toth and Sips models, effect of 815

779 in binder-containing zeolite 4A bodies, which are utilized for amine loading on CO2 adsorption properties, CO2 and N2 816

780 amine modification. It is anticipated that amines are located in adsorption properties for Z4A and IBA-Z4A at high 817

781 the bigger pore of zeolite bodies created by the binder or filler of degassing temperature, and comparison of pure gas 818

782 zeolite crystals owing to a decrease in mesopore volume, and adsorption selectivity of CO2/N2 and adsorption capacity 819

783 therefore, it facilitates enhanced interaction with CO2. for IBA-Z4A with other porous materials (PDF) 820

J DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

821

822
■ AUTHOR INFORMATION
Corresponding Authors
(10) (a) Zeng, Y.; Zou, R.; Zhao, Y. Covalent Organic Frameworks for
CO2 Capture. Adv. Mater. 2016, 28, 2855−2873.
(11) Akhtar, F.; Liu, Q.; Hedin, N.; Bergström, L. Strong and binder
884
885
886
823 *E-mail: anil@iittp.ac.in. free structured zeolite sorbents with very high CO2-over-N2 selectivities 887
824 *E-mail: sksingh@iiti.ac.in. and high capacities to adsorb CO2 rapidly. Energy Environ. Sci. 2012, 5, 888
825 ORCID 7664−7673. 889

826 Sanjay Kumar Singh: 0000-0002-8070-7350 (12) Liu, Q.; Pham, T.; Porosoff, M. D.; Lobo, R. F. ZK-5: A CO2- 890
Selective Zeolite with High Working Capacity at Ambient Temperature 891
827 Notes and Pressure. ChemSusChem 2012, 5, 2237−2242. 892
828 The authors declare no competing financial interest. (13) (a) Padhi, P.; Rout, S. K.; Panda, D. Effect of modification of

■
893
zeolite A using sodium carboxymethylcellulose (CMC). Bulg. Chem. 894
829 ACKNOWLEDGMENTS Commun. 2014, 46, 777−783. (b) Rout, S. K.; Padhi, P.; Panda, D. 895
Effect of modification of Zeolite A using Poly Vinyl Alcohol (PVA). 896
830 The authors thank IIT Indore, CSIR-HRDG, New Delhi, and Bulg. Chem. Commun. 2016, 48, 779−786. 897
831 SERB-DST, New Delhi, for the financial support. SIC National (14) Querol, X.; Moreno, N.; Umaña, J. C.; Alastuey, A.; Hernández, 898
832 facility of IIT Indore is acknowledged for instrumentation E.; López-Soler, A.; Plana, F. Synthesis of zeolites from coal fly ash: an 899
833 facilities. The authors thank Ms. Navjot Saini and Mr Shyama overview. Int. J. Coal Geol. 2002, 50, 413−423. 900
834 Prasad Pal (Anton Paar Gurgaon, Delhi) for their valuable (15) Liu, Q.; Mace, A.; Bacsik, Z.; Sun, J. L.; Laaksonen, A.; Hedin, N. 901
835 support in SAXS and BET characterization. The authors would NaKA sorbents with high CO2-over-N2 selectivity and high capacity to 902
836 also like to thank Dr. Pratibha Sharma from DAVV Indore and adsorb CO2. Chem. Commun. 2010, 46, 4502−4504. 903
837 ACMS, IIT Kanpur, for providing the FTIR and XPS facility, (16) (a) Hiyoshi, N.; Yogo, K.; Yashima, T. Adsorption characteristics 904
838 respectively. D.P. thanks IIT Indore for the fellowship. Dr. Rohit of carbon dioxide on organically functionalized SBA-15. Microporous 905
839 Kumar Rai, Dr. Kavita Gupta, and Ms. Chinky Binnani (IIT Mesoporous Mater. 2005, 84, 357−365. (b) Chang, A. C.; Chuang, S. S. 906
C.; Gray, M.; Soong, Y. In-Situ Infrared Study of CO2 Adsorption on 907
840 Indore) are acknowledged for their valuable suggestions to
SBA-15 Grafted with γ-(Aminopropyl)triethoxysilane. Energy Fuels 908
841 understand the chemical reaction mechanism. Dr. Lakshmi 2003, 17, 468−473. (c) Ü nveren, E. E.; Monkul, B. ö.; Sarıoğlan, Ş .; 909
842 Iyengar (former visiting faculty, School of Humanities and Karademir, N.; Alper, E. Solid amine sorbents for CO2 capture by 910
843 Social Science, IIT Indore) is highly acknowledged for her chemical adsorption: A review. Petroleum 2017, 3, 37−50. 911
844 valuable support in proof correction.

■
(17) (a) Bezerra, D. P.; Oliveira, R. S.; Vieira, R. S.; Cavalcante, C. L., 912
Jr.; Azevedo, D. S. Adsorption of CO2 on nitrogen-enriched activated 913
845 REFERENCES carbon and zeolite 13X. Adsorption 2011, 17, 235−246. (b) Bezerra, D. 914
846 (1) Saha, D.; Bao, Z. B.; Jia, F.; Deng, S. Adsorption of CO2, CH4, P.; Silvaa, F. W. M.; Moura, P. A. S.; Sousa, A. G. S.; Vieira, R. S.; 915
847 N2O, and N2 on MOF-5, MOF-177, and zeolite 5A. Environ. Sci. Rodriguez-Castellon, E.; Azevedo, D. C. S. CO2 Adsorption in Amine- 916
848 Technol. 2010, 44, 1820−1826. Grafted Zeolite 13X. Appl. Surf. Sci. 2014, 314, 314−321. 917
849 (2) Seabra, R.; Ribeiro, A. M.; Gleichmann, K.; Ferreira, A. F. P.; (18) (a) Chatti, R.; Bansiwal, A. K.; Thote, J. A.; Kumar, V.; Jadhav, P.; 918
850 Rodrigues, A. E. Adsorption equilibrium and kinetics of carbon dioxide, Lokhande, S. K.; Biniwale, R. B.; Labhsetwar, N. K.; Rayalu, S. S. Amine 919
851 methane and nitrogen on binderless zeolite 4A adsorbents. Microporous loaded Zeolite for Cabon Dioxide Capture. Microporous Mesoporous 920
852 Mesoporous Mater. 2019, 277, 105−114. Mater. 2009, 121, 84−89. (b) Lee, S. C.; Hsieh, C. C.; Chen, C. H.; 921
853 (3) Choi, S.; Drese, J. H.; Jones, C. W. Adsorbent Materials for Carbon Chen, Y. S. CO2 Adsorption by Y-Type Zeolite Impregnated with 922
854 Dioxide Capture from Large Anthropogenic Point Sources. Chem- Amines in Indoor Air. Aerosol Air Qual. Res. 2013, 13, 360−366. 923
855 SusChem 2009, 2, 796−854. (19) Su, F.; Lu, C.; Kuo, S. C.; Zeng, W. Adsorption of CO2 on Amine- 924
856 (4) Yu, C. H.; Huang, C. H.; Tan, C. S. A Review of CO2 Capture by Functionalized Y-Type Zeolites. Energy Fuels 2010, 24, 1441−1448. 925
857 Absorption and Adsorption. Aerosol Air Qual. Res. 2012, 12, 745−769. (20) (a) Cogswell, C. F.; Xie, Z.; Wolek, A.; Wang, Y.; Stavola, A.; 926
858 (5) Wilcox, J. Carbon Capture; Springer: New York, 2012. Finkenaur, M.; Gilmore, E.; Lanzillottia, M.; Choi, S. Pore structure- 927
859 (6) Zhang, J.; Webley, P. A.; Xiao, P. Effect of process parameters on CO2 adsorption property relations of supported amine materials with 928
860 power requirements of vacuum swing adsorption technology for CO2 multi-pore networks. J. Mater. Chem. A 2017, 5, 8526−8536. (b) Lu, C.; 929
861 capture from flue gas. Energy Convers. Manage. 2008, 49, 346−356. Bai, H.; Wu, B.; Su, F.; Hwang, J. F. Comparative Study of CO2 Capture 930
862 (7) (a) Eliasson, B.; Kogelschatz, U.; Xue, B.; Zhou, L.-M. by Carbon Nanotubes, Activated Carbons, and Zeolites. Energy Fuels 931
863 Hydrogenation of Carbon Dioxide to Methanol with a Discharge- 2008, 22, 3050−3056. 932
864 Activated Catalyst. Ind. Eng. Chem. Res. 1998, 37, 3350−3357. (21) (a) Da Silva, F. A.; Rodrigues, A. E. Adsorption Equilibria and 933
865 (b) Tomasko, D. L.; Li, H.; Liu, D.; Han, X.; Wingert, M. J.; Lee, L. Kinetics for Propylene and Propane over 13X and 4A Zeolite Pellets. 934
866 J.; Koelling, K. W. A Review of CO2 Applications in the Processing of Ind. Eng. Chem. Res. 1999, 38, 2051−2057. (b) Ghosh, A.; Curthoys, G. 935
867 Polymers. Ind. Eng. Chem. Res. 2003, 42, 6431−6456. Characterization of Zeolite Acidity, A Gas-chromatographic Study 936
868 (8) (a) Hedin, N.; Chen, L.; Laaksonen, A. Sorbents for CO2 capture using n-Butylamine and Ammonia. J. Chem. Soc., Faraday Trans. 1 1983, 937
869 from flue gas-aspects from materials and theoretical chemistry. 79, 2569−2572. 938
870 Nanoscale 2010, 2, 1819−1841. (b) Wang, Q.; Luo, J.; Zhong, Z.; (22) (a) Mitchell, S.; Michels, N.-L.; Kunze, K.; Pérez-Ramírez, J. 939
871 Borgna, A. CO2 capture by solid adsorbents and their applications: Visualization of hierarchically structured zeolite bodies from macro to 940
872 current status and new trends. Energy Environ. Sci. 2011, 4, 42−55. nano length scales. Nat. Chem. 2012, 4, 825−831. (b) Whiting, G. T.; 941
873 (c) Oschatz, M.; Antonietti, M. A search for selectivity to enable CO2 Meirer, F.; Mertens, M. M.; Bons, A. J.; Weiss, B. M.; Stevens, P. A.; 942
874 capture with porous adsorbents. Energy Environ. Sci. 2018, 11, 57−70. Smit, E.; Weckhuysen, B. M. Binder Effects in SiO2 - and Al2O3 -Bound 943
875 (9) (a) Millward, A. R.; Yaghi, O. M. Metal−Organic Frameworks Zeolite ZSM-5-Based Extrudates as Studied by Microspectroscopy. 944
876 with Exceptionally High Capacity for Storage of Carbon Dioxide at ChemCatChem 2015, 7, 1312−1321. (c) Mehlhorn, D.; Valiullin, R.; 945
877 Room Temperature. J. Am. Chem. Soc. 2005, 127, 17998−17999. Kärger, J.; Schumann, K.; Brandt, A.; Unger, B. Transport enhancement 946
878 (b) Pachfule, P.; Balan, B. K.; Kurungot, S.; Banerjee, R. One- in binderless zeolite X- and A-type molecular sieves revealed by PFG 947
879 dimensional confinement of a nanosized metal organic framework in NMR diffusometry. Microporous Mesoporous Mater. 2014, 188, 126− 948
880 carbon nanofibers for improved gas adsorption. Chem. Commun. 2012, 132. 949
881 48, 2009−2011. (c) Pachfule, P.; Chen, Y.; Jiang, J.; Banerjee, R. (23) (a) Sircar, S.; Myers, A. L. Gas Separation by Zeolites. In 950
882 Fluorinated Metal−Organic Frameworks: Advantageous for Higher H2 Handbook of Zeolites Science and Technology; Aurbach, S. M., Carrado, 951
883 and CO2 Adsorption or Not? Chem. - Eur. J. 2012, 18, 688−694. K. A., Dutta, P. K., Eds.; Dekker: New York, 2003. 952

K DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

953 (24) Xu, X.; Zhao, X.; Sun, L.; Liu, X. Adsorption separation of carbon microporous zeolites A, X and ZSM-5 studied by small angle X-ray 1022
954 dioxide, methane and nitrogen on monoethanol amine modified β scattering and nitrogen adsorption. J. Phys. Chem. Solids 2007, 68, 1023
955 zeolite. J. Nat. Gas Chem. 2009, 18, 167−172. 1692−1699. (d) Delange, R. S.; Keizer, K.; Burggraaf, A. J. 1024
956 (25) (a) Singh, P.; Niederer, J. P. M.; Versteeg, G. F. Structure and Characterization of Microporous Non-supported Membrane Top- 1025
957 activity relationships for amine based CO2 absorbents-I. Int. J. layers Using Physisorption Techniques. J. Porous Mater. 1995, 1, 139− 1026
958 Greenhouse Gas Control 2007, 1, 5−10. (b) Singh, P.; Niederer, J. P. 153. (e) Whiting, G. T.; Chowdhury, A. D.; Oord, R.; Paalanen, P.; 1027
959 M.; Versteeg, G. F. Structure and activity relationships for amine based Weckhuysen, B. M. The curious case of zeolite−clay/binder 1028
960 CO2 absorbentsII. Chem. Eng. Res. Des. 2009, 87, 135−144. interactions and their consequences for catalyst preparation. Faraday 1029
961 (26) (a) Perinu, C.; Arstad, B.; Bouzga, A. M.; Jens, K. J. 13C and 15N Discuss. 2016, 188, 369−386. 1030
962 NMR characterization of amine reactivity and Solvent Effects in CO2 (38) (a) Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; 1031
963 Capture. J. Phys. Chem. B 2014, 118, 10167−10174. (b) Perinu, C.; Pierotti, R. A.; Rouquér ol, J.; Siemieniewska, T. Reporting 1032
964 Arstad, B.; Bouzga, A. M.; Jens, K. J. Application of 15N NMR Physisorption Data for Gas Solid Systems-With Special Reference to 1033
965 spectroscopy to analysis of amine based CO2 capture solvents. Energy the Determination of Surface-Area and Porosity. Pure Appl. Chem. 1034
966 Procedia 2014, 63, 1144−1150. 1985, 54, 2201−2218. (b) Thommes, M. Physical adsorption 1035
967 (27) (a) Klinthong, W.; Huang, C. H.; Tan, C. S. Polyallylamine and characterization of nanoporous materials. Chem. Ing. Tech. 2010, 82, 1036
968 NaOH as a novel binder to pelletize amine-functionalized mesoporous 1059−1073. 1037
969 silicas for CO2 capture. Microporous Mesoporous Mater. 2014, 197, (39) Holewinski, A.; Sakwa-Novak, M. A.; Jones, C. W. Linking CO2 1038
970 278−287. (b) Klinthong, W.; Huang, C. H.; Tan, C. S. One-Pot Sorption Performance to Polymer Morphology in Aminopolymer/ 1039
971 Synthesis and Pelletizing of Polyethylenimine-Containing Mesoporous Silica Composites through Neutron Scattering. J. Am. Chem. Soc. 2015, 1040
972 Silica Powders for CO2 Capture. Ind. Eng. Chem. Res. 2016, 55, 6481− 137, 11749−11759. 1041
973 6491. (40) (a) Omote, K.; Ito, Y.; Kawamura, S. Small angle x-ray scattering 1042
974 (28) Jung, H.-S.; Moon, D.-S.; Lee, J.-K. Quantitative Analysis and for measuring pore-size distributions in porous low-κ films. Appl. Phys. 1043
975 Efficient Surface Modification of Silica Nanoparticles. J. Nanomater. Lett. 2003, 82, 544−546. (b) Steriotis, Th. A.; Stefanopoulos, K. L.; 1044
976 2012, 2012, No. 593471. Mitropoulos, A. Ch; Kanellopoulos, N. K. Membrane Characterisation 1045
977 (29) (a) Rege, S. U.; Yang, R. T. Corrected Horváth-Kawazoe by Combination of Static and Dynamic Techniques. Membr. Sci. 1046
978 equations for pore-size distribution. AIChE J. 2000, 46, 734−750. Technol. Ser. 2000, 6, 1−34. 1047
979 (b) Harper, R. J.; Stifel, G. R.; Anderson, R. B. Adsorption of gases on (41) Radlinski, A. P.; Mastalerz, M.; Hinde, A. L.; Hainbuchner, M.; 1048
980 4A synthetic zeolite. Can. J. Chem. 1969, 47, 4661−4670. (c) Huang, Y.; Rauch, H.; Maron, M.; Lin, J.-S.; Fan, L.; Thiyagarajan, P. Application 1049
981 Ma, Z.; Yao, H. Characterization of smallpore zeolites with CO2 of SAXS and SANS in evaluation of porosity, pore size distribution and 1050
982 adsorption. Lizi Jiaohuan Yu Xifu 2009, 25, 62−69. surface area of coal. Int. J. Coal Geol. 2004, 59, 245−271. 1051
983 (30) (a) Ayawei, N.; Ebelegi, A. N.; Wankasi, D. Modelling and (42) Ślusarczyk, C.; Fryczkowska, B.; Sieradzka, M.; Janicki, J. Small- 1052
984 Interpretation of Adsorption Isotherms. J. Chem. 2017, 2017, Angle X-Ray Scattering Studies of Pore Structure in Cellulose 1053
985 No. 3039817. (b) Foo, K. Y.; Hameed, B. H. Insights into the Membranes. Acta Phys. Pol., A 2016, 129, 229−232. 1054
986 modelling of adsorption isotherm systems. Chem. Eng. J. 2010, 156, 2− (43) (a) Junaidi, M. U. M.; Khoo, C. P.; Leo, C. P.; Ahmad, A. L. The 1055
987 10. effects of solvents on the modification of SAPO-34 zeolite using 3- 1056
988 (31) Pham, T. D.; Liu, Q.; Lobo, R. F. Carbon Dioxide and Nitrogen aminopropyl trimethoxy silane for the preparation of asymmetric 1057
989 Adsorption on Cation-Exchanged SSZ-13 zeolites. Langmuir 2013, 29, polysulfone mixed matrix membrane in the application of CO2 1058
990 832−839. separation. Microporous Mesoporous Mater. 2014, 192, 52−59. 1059
991 (32) (a) Singh, V. K.; Kumar, E. A. Measurement and analysis of (b) Pechar, T. W.; Kim, S.; Vaughan, B.; Marand, E.; Tsapatsis, M.; 1060
992 adsorption isotherms of CO2 on activated carbon. Appl. Therm. Eng. Jeong, H. K.; Cornelius, C. J. Fabrication and characterization of 1061
993 2016, 97, 77−86. (b) Akten, E. D.; Siriwardane, R.; Sholl, D. S. Monte polyimide−zeolite L mixed matrix membranes for gas separations. J. 1062
994 Carlo Simulation of Single- and Binary-Component Adsorption of Membr. Sci. 2006, 277, 195−202. 1063
995 CO2, N2, and H2 in Zeolite Na-4A. Energy Fuels 2003, 17, 977−983. (44) (a) Li, Y.; Yi, H.; Tang, X.; Li, F.; Yuan, Q. Adsorption separation 1064
996 (c) Palomino, M.; Corma, A.; Rey, F.; Valencia, S. New insights on of CO2/CH4 gas mixture of the commercial zeolites at atmospheric 1065
997 CO2-methane separation using LTA zeolites with different Si/Al ratios pressure. Chem. Eng. J. 2013, 229, 50−56. (b) Garcıá, L.; Poveda, Y. A.; 1066
998 and a first comparison with MOFs. Langmuir 2010, 26, 1910−1917. Khadivi, M.; Rodríguez, G.; Görke, O.; Esche, E.; Godini, H. R.; Wozny, 1067
999 (33) Chowdhury, S.; Balasubramanian, R. Holey grapheme frame- G.; Orjuela, A. Synthesis and Granulation of a 5A zeolite Based 1068
1000 work for highly selective post-combustion carbon capture. Sci. Rep. Molecular Sieve and Adsorption Equilibrium of the Oxidative Coupling 1069
1001 2016, 6, 21537. of Methane Gases. J. Chem. Eng. Data 2017, 62 (4), 1550−1557. 1070
1002 (34) (a) Su, F.; Lu, C.; Chung, A.-J.; Liao, C.-H. CO2 capture with (c) Wilson, S. M. Adsorption Separation of CO2 from CO in Syngas: 1071
1003 amine-loaded carbon nanotubes via a dual-column temperature/ Improving the Conversion of the Reverse Water Gas Shift Reaction. 1072
1004 vacuum swing adsorption. Appl. Energy 2014, 113, 706−712. M.A.Sc. Thesis [online], University of Ottawa, Canada, 2015, https:// 1073
1005 (b) Hsu, S.-C.; Lu, C.; Su, F.; Zeng, W.; Chen, W. Thermodynamics ruor.uottawa.ca/bitstream/10393/33169/1/Wilson_Sean_Michael_ 1074
1006 and regeneration studies of CO2 adsorption on multiwalled carbon Wynn_2015_Thesis.pdf (accessed Feb 28, 2019). 1075
1007 nanotubes. Chem. Eng. Sci. 2010, 65, 1354−1361. (45) Kishore, R. A.; Priya, S. A Review on Low-Grade Thermal Energy 1076
1008 (35) Borgschulte, A.; Callini, E.; Stadie, N.; Arroyo, Y.; Rossell, M. D.; Harvesting: Materials, Methods and Devices. Materials 2018, 11, 1077
1009 Erni, R.; Geerlings, H.; Züttel, A.; Ferri, D. Manipulating the reaction 1433−1478. 1078
1010 path of the CO2 hydrogenation reaction in molecular sieves. Catal. Sci. (46) (a) Tamilarasan, P.; Ramaprabhu, S. Integration of polymerized 1079
1011 Technol. 2015, 5, 4613−4621. ionic liquid with graphene for enhanced CO2 adsorption. J. Mater. 1080
1012 (36) (a) Storck, S.; Bretinger, H.; Maier, W. F. Characterization of Chem. A 2015, 3, 101−108. (b) Choi, H.-S.; Suh, M. P. Highly selective 1081
1013 micro- and mesoporous solids by physisorption methods and pore-size CO2 capture in flexible 3D coordination polymer networks. Angew. 1082
1014 analysis. Appl. Catal., A 1998, 174, 137−146. (b) Tao, Y.; Kanoh, H.; Chem., Int. Ed. 2009, 48, 6865−6869. (c) Zelenak, V.; Halamova, D.; 1083
1015 Kaneko, K. Synthesis of Mesoporous Zeolite A by Resorcinol- Gaberova, L.; Bloch, E.; Llewellyn, P. Amine- modified SBA-12 1084
1016 Formaldehyde Aerogel Templating. Langmuir 2005, 21, 504−507. mesoporous silica for carbon dioxide capture: Effect of amine basicity 1085
1017 (37) (a) Siriwardane, R. V.; Shen, M. S.; Fisher, E. P. Adsorption of on sorption properties. Microporous Mesoporous Mater. 2008, 116, 1086
1018 CO2, N2, and O2 on Natural Zeolites. Energy Fuels 2003, 17, 571−576. 358−364. 1087
1019 (b) Liu, L.; Singh, R.; Xiao, P.; Webley, P. A.; Zhai, Y. Zeolite synthesis (47) (a) Caplow, M. Kinetics of Carbamate Formation and 1088
1020 from waste fly ash and its application in CO2 capture from flue gas Breakdown. J. Am. Chem. Soc. 1968, 90, 6795−6803. (b) Flaig, R. 1089
1021 streams. Adsorption 2011, 17, 795−800. (c) Du, X.; Wu, E. Porosity of W.; Osborn Popp, T. M.; Fracaroli, A. M.; Kapustin, E. A.; Kalmutzki, 1090

L DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
 Industrial & Engineering Chemistry Research Article

1091 M. J.; Altamimi, R. M.; Fathieh, F.; Reimer, J. A.; Yaghi, O. M. The
1092 Chemistry of CO2 Capture in an Amine-Functionalized Metal−
1093 Organic Framework under Dry and Humid Conditions. J. Am. Chem.
1094 Soc. 2017, 139, 12125−12128.
1095 (48) (a) Qi, G.; Fu, L.; Choi, B. H.; Giannelis, E. P. Efficient CO2
1096 Sorbents Based on Silica Foam with Ultra-large Mesopores. Energy
1097 Environ. Sci. 2012, 5, 7368−7375. (b) Kishor, R.; Ghoshal, A. K.
1098 Polyethylenimine Functionalized As-Synthesized KIT-6 Adsorbent for
1099 Highly CO2/N2 Selective Separation. Energy Fuels 2016, 30, 9635−
1100 9644. (c) Saleh, M.; Lee, H. M.; Kemp, K. C.; Kim, K. S. Highly Stable
1101 CO2/N2 and CO2/CH4 Selectivity in Hyper-Cross-Linked Hetero-
1102 cyclic Porous Polymers. ACS Appl. Mater. Interfaces 2014, 6, 7325−
1103 7333.
1104 (49) Choi, S.; Gray, M. L.; Jones, C. W. Amine-Tethered Solid
1105 Adsorbents Coupling High Adsorption Capacity and Regenerability for
1106 CO2 Capture from Ambient Air. ChemSusChem 2011, 4, 628−635.
1107 (50) (a) Jadhav, P. D.; Chatti, R. V.; Biniwale, R. B.; Labhsetwar, N.
1108 K.; Devotta, S.; Rayalu, S. S. Monoethanol Amine modified Zeolite 13X
1109 for CO2 Adsorption at Different Temperatures. Energy Fuels 2007, 21,
1110 3555−3559. (b) Demessence, A.; D’Alessandro, D. M.; Foo, M. L.;
1111 Long, J. R. Strong CO2 binding in a water-stable, triazolate-bridged
1112 metal−organic framework functionalized with ethylenediamine. J. Am.
1113 Chem. Soc. 2009, 131, 8784−8786. (c) Wang, L.; Yang, R. T. Increasing
1114 Selective CO2 Adsorption on Amine-Grafted SBA-15 by Increasing
1115 Silanol Density. J. Phys. Chem. C 2011, 115, 21264−21272. (d) Tekin,
1116 A.; Karalti, O.; Karadas, F. A metal dicyanamide cluster with high CO2/
1117 N2 selectivity. Microporous Mesoporous Mater. 2016, 228, 153−157.
1118 (e) Aroua, M. K.; Daud, W. M. A. W.; Yin, C. Y.; Adinata, D. Adsorption
1119 capacities of carbon dioxide, oxygen, nitrogen and methane on carbon
1120 molecular basket derived from polyethyleneimine impregnation on
1121 microporous palm shell activated carbon. Sep. Purif. Technol. 2008, 62,
1122 609−613. (f) Li, B.; Zhang, Z.; Li, Y.; Yao, K.; Zhu, Y.; Deng, Z.; Yang,
1123 F.; Zhou, X.; Li, G.; Wu, H.; Nijem, N.; Chabal, Y. J.; Lai, Z.; Han, Y.;
1124 Shi, Z.; Feng, S.; Li, J. Enhanced binding affinity, remarkable selectivity,
1125 and high capacity of CO2 by dual functionalization of a rht-type metal−
1126 organic framework. Angew. Chem., Int. Ed. 2012, 51, 1412−1415.
1127 (g) Banerjee, R.; Furukawa, H.; Britt, D.; Knobler, C.; Keeffe, M. O.;
1128 Yaghi, O. M. Control of Pore Size and Functionality in Isoreticular
1129 Zeolitic Imidazolate Frameworks and their Carbon Dioxide Selective
1130 Capture Properties. J. Am. Chem. Soc. 2009, 131, 3875−3877.
1131 (51) (a) Plaza, M. G.; Pevida, C.; Arenillas, A.; Rubiera, F.; Pis, J. J.
1132 CO2 capture by adsorption with nitrogen enriched carbons. Fuel 2007,
1133 86, 2204−2212. (b) Xu, X.; Song, C.; Andresen, J. M.; Miller, B. G.;
1134 Scaroni, A. W. Preparation and characterization of novel CO2
1135 ‘‘molecular basket’’ adsorbents based on polymer-modified mesopo-
1136 rous molecular sieve MCM-41. Microporous Mesoporous Mater. 2003,
1137 62, 29−45.

M DOI: 10.1021/acs.iecr.8b03958
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX