Prediction of Adsorption Equilibrium of VOCs onto Hyper-Cross

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Prediction of Adsorption Equilibrium of VOCs onto Hypercrosslinked Polymeric Resin at Environmentally Relevant Temperatures and Concentrations using Inverse Gas Chromatography Lijuan Jia, Jiakai Ma, Qiuyi Shi, and Chao Long Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b05039 • Publication Date (Web): 12 Dec 2016 Downloaded from http://pubs.acs.org on December 12, 2016

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Environmental Science & Technology

1

Prediction

of

Adsorption

2

Hypercrosslinked Polymeric Resin at Environmentally Relevant

3

Temperatures

4

Chromatography

and

Equilibrium

Concentrations

of

using

VOCs

Inverse

onto

Gas

Lijuan Jiaa, Jiakai Maa, Qiuyi Shia, Chao Longa,b,*

5 6

a

7

Environment, Nanjing University, 163 Xianlin Avenue, Nanjing 210023, China

8

b

9

Engineering Research Institute, 888 Yingbin Road, Yancheng 22400, China

10

*Corresponding author. Phone: +86 25 89680380, E-mail: [email protected]

State Key Laboratory of Pollution Control and Resource Reuse, School of the

Nanjing

University

Yancheng

Environmental

Protection

11 12 13 14 15 16 17 18 19 20 21 22 1

ACS Paragon Plus Environment

Technology

and


23 24

Abstract

25

Hypercrosslinked polymeric resin (HPR) represents a class of predominantly

26

microporous adsorbents and has good adsorption performance towards VOCs.

27

However, adsorption equilibrium of VOCs onto HPR are limited. In this research, a

28

novel method for predicting adsorption capacities of VOCs on HPR at

29

environmentally relevant temperatures and concentrations using inverse gas

30

chromatography data was proposed. Adsorption equilibrium of six VOCs (n-pentane,

31

n-hexane, dichloromethane, acetone, benzene, 1, 2-dichloroethane) onto HPR in the

32

temperature range of 403-443K were measured by inverse gas chromatography (IGC).

33

Adsorption capacities at environmentally relevant temperatures (293-328K) and

34

concentrations (P/Ps = 0.1-0.7) were predicted using Dubinin-Radushkevich (DR)

35

equation based on Polany’s theory. Taking consideration of the swelling properties of

36

HPR, the volume swelling ratio (r) was introduced and r·Vmicro was used instead of

37

Vmicro determined by N2 adsorption data at 77K as the parameter q0 (limiting

38

micropore volume) of the DR equation. The results showed that the adsorption

39

capacities of VOCs at environmentally relevant temperatures and concentrations can

40

be predicted effectively using IGC data, the root-mean-square errors between the

41

predicted and experimental data was below 9.63%. The results are meaningful

42

because they allow accurate prediction of adsorption capacities of adsorbents more

43

quickly and conveniently using IGC data.

44 2


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45 46 47

TOC

48

49

50

51

Introduction

52

The continuous discharge of volatile organic compounds (VOCs) such as

53

halohydrocarbons, alkanes and ketones has caused severe outdoor air pollution. They

54

may undergo photochemical reactions with nitrogen oxides in the presence of sunlight,

55

yielding even more hazardous compounds,1, 2 such as secondary organic aerosol (SOA)

56

particles,3-7 and leading to the formation of photochemical smog and ozone depletion.

57

With the increasing awareness of environmental protection, regulations on VOCs

58

emission have grown more stringent worldwide. Therefore, it is urgently required to

59

develop environmentally friendly technologies to minimize the release of VOCs into

60

the atmosphere. 3



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61

Adsorption has been proven to be an effective approach to remove VOCs from the

62

gas streams with high removal efficiencies and simple process units.8-10 The core of

63

adsorption process technology is to develop suitable adsorbents with high specific

64

surface, stable physical, chemical properties and regenerability on site, etc.

65

Hypercrosslinked polymeric resin (HPR) represents a class of predominantly

66

microporous adsorbents with high surface areas and high micropore volume.11,

67

Adsorption equilibrium of some VOCs onto HPR has been investigated, such as

68

halohydrocarbon,15-17 benzene,16-18 methyl ethyl ketone,18 and alkanes,19-21 indicating

69

that HPR has good adsorption performance towards VOCs.18-22 However, compared

70

with activated carbon, the adsorption equilibrium data of VOCs onto HPR are limited.

71

Adsorption isotherm and adsorption capacity are the essential part for modeling,

72

simulating, and optimizing the adsorption system in engineering applications. The

73

commonly used methods for measuring VOCs adsorption isotherms include

74

gravimetric and volumetric methods.23 However, both of the methods are time

75

consuming and may be affected by toxicity or the availability of the adsorbate.

76

Recently, it has been proved that inverse gas chromatography (IGC) is a

77

straightforward and very sensitive technique for the characterization of porous

78

adsorbent.24-28 Compared with traditional gravimetric and volumetric methods, the

79

smaller amount of adsorbent and the shorter experimental time were required for IGC

80

measurements at the finite concentration to determine adsorption isotherms. However,

81

it is noted that the adsorbent-packed column temperature of IGC such as

82

343-548K,29-34 is generally higher than the operation temperature of adsorption units 4


12

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83

in practical engineering application. Moreover, the VOCs concentrations measured in

84

IGC are far lower than the emission concentration of VOCs from manufacturing

85

facilities.32-34 For the design of a reliable adsorption system, therefore, it is necessary

86

to predict the adsorption isotherms at environmentally relevant temperatures and

87

concentrations (corresponding to practical environmental systems) according to the

88

adsorption equilibrium

89

Dubinin-Radushkevich (DR) model based on Polanyi potential theory is commonly

90

used for describing physical adsorption of organic vapors onto microporous

91

adsorbents.35-37 According to Polanyi potential theory, the curve of adsorbed volume

92

against adsorption potential, which is called adsorption characteristics curve,37 is

93

independent of temperature,38 allowing the use of DR equation without introducing

94

any additional parameters to predict adsorption isotherms at other temperatures in

95

terms of that at experimental temperature. Therefore, if the adsorption isotherms

96

obtained using IGC can be described well with DR equation, it would be possible to

97

predict the adsorption isotherms at environmentally relevant temperatures and

98

concentrations according to IGC data.

data

obtained using IGC. It is well-known

that

99

The aim of this present study is to predict the adsorption isotherms of VOCs onto

100

HPR at environmentally relevant temperatures and concentrations using a

101

combination of DR model and adsorption equilibrium data determined by IGC. The

102

adsorption isotherms of several VOCs (n-pentane, n-hexane, dichloromethane,

103

acetone, benzene and 1, 2-dichloroethane) at 403K, 423K, and 443K were measured

104

using IGC at the finite concentration, and the traditional gravimetric method was used 5



105

to determine adsorption isotherms at environmentally relevant temperature

106

(293-328K). The accuracy of the prediction was assessed by comparing the predicted

107

adsorption capacities with experimental capacities at environmentally relevant

108

temperatures and concentrations. To the best of our knowledge, this is the first time

109

that the adsorption capacities of polymeric resin for VOCs at environmentally

110

relevant temperatures and concentrations were predicted using IGC.

111

Materials and experiments

112

Materials. N-pentane, n-hexane, dichloromethane, acetone, benzene and 1,

113

2-dichloroethane were supplied by Nanjing Chemical Reagent Company, China

114

(>99.5% purity). The HPR were synthesized by suspension polymerization of

115

4-Vinylbenzyl chloride and divinylbenzene followed by a Friedel-Crafts-type

116

post-cross-linking reaction using 1, 2-dichloroethane as solvent; the synthetic process

117

was provided in detail in our previous study.

118

post-cross-linking reaction, two resins with different pore structure parameters were

119

obtained, and named HPR-1 and HPR-2, respectively.

28

By controlling the degree of

120

Characterization. Nitrogen adsorption-desorption isotherms at 77 K were

121

measured using an ASAP 2010 (Micromeritics Instrument Co., USA). The specific

122

surface area was determined using the N2 isotherms data by the means of BET

123

equation. The micropore pore volume (Vmicro) and mesopore pore volume (Vmeso)

124

were calculated from the N2 isotherms data by Dubinin–Radushkevich (DR) and

125

Barrett–Joyner–Halena (BJH) methods, respectively. The pore size distributions were

126

calculated by applying the density functional theory (DFT) to N2 isotherm data. In 6


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127

addition, the swelling property of HPR was studied by VOCs solvent adsorption in a

128

column. The column was made of glass (ID=5mm) with a porous plate at the bottom.

129

The solvent was pumped into the column by the peristaltic pump (LongerPump,

130

China) continuously with a flow velocity of 5mL/min. After the height of resins was

131

constant and stable, the volume swelling ratio (r) was determined by comparing the

132

height of dry resins (H0) and swollen resins (Ht) (Equation 1). The experiment was

133

conducted for three times to obtain an average value for all the VOCs.

134

r = (Ht-H0)/H0

(1)

135

Adsorption equilibrium: Inverse gas chromatograph method (IGC). IGC

136

experiments were carried out in a gas chromatograph (Shimadzu GC2014, Japan)

137

equipped with a flame ionization detector. The injector and detector were stabilized in

138

the GC system at 453 K and 523 K, respectively. The adsorption experiments were

139

operated in the column temperature range of 403-443K under a nitrogen flow rate of

140

35 ml/min. The resins (1 g) were dried at 383 K and placed in the chromatographic

141

stainless steel column (50 cm length, 3 mm i.d.). Experiments were carried out at

142

finite dilution region. To satisfy the finite concentration, small amounts (1-10 µL) of

143

pure hydrocarbons (n-pentane, n-hexane, dichloromethane, acetone, benzene and 1,

144

2-dichloroethane) were injected separately with a 10 µL syringe into the GC and were

145

eluted isothermally. For each measurement, at least three repeated injections were

146

taken, obtaining reproducible results.

147

Adsorption isotherms were obtained from the chromatographic peaks using a

148

characteristic-peak elution method.24 When the adsorbate density, molecular weight 7



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149

and the volume injected are accurately known and the corrected carrier gas flow rate,

150

Fc, remains constant, the adsorbate partial pressure, p, is calculated as Equation 2:

p=

151

qhi RT

(2)

Fc Speak

152

In which q is the injection amount (mol), hi is the particular height at corresponding

153

concentration (µV) (shown in Figure S124), Speak is the area of the chromatographic

154

peak (µV·s), R is the ideal gas constant (8.314 m3 Pa/mol K), T is the temperature of

155

the column (K), Fc is the corrected flow rate (Equation 3; cm3/min),

=

156

(3)

157

where Fm is the uncorrected flow rate (cm3/min), Tamb is the ambient temperature

158

(K), j is the James-Martin factor for the correction of gas compressibility when the

159

column inlet (Pi) and outlet (P0) pressures are different and it is given by:

161 162

2

3 pi /p0 -1 2 pi /p0 3 -1

j=

160

(4)

The amount adsorbed at different i values Vi (mol/g) could be calculated from Equation 5:

163

=

(5)

164

where m is the mass of polymer in the column, Si（µV·s）indicates the adsorbent

165

holdup contribution and is the area at a peak height of hi, but it differs from Speak in

166

the respect that it includes the adsorbent holdup time, shown as the shaded area in

167

Figure S1.

168

Adsorption equilibrium: Gravimetric method. The adsorption of VOCs at

169

environmentally relevant concentrations and temperatures was determined by 8


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gravimetric method. The detailed experimental apparatus and adsorption procedure

171

have been described previously.17 Briefly, about 0.1 g of HPR was precisely weighed

172

out and put into the glass adsorption column. The carrier gas containing a scheduled

173

concentration of VOCs vapor was passed through the column until the weight of the

174

column become stable, and the equilibrium amount adsorbed was equal to the weight

175

change of adsorbent before and after the adsorption process. After a series of

176

equilibrium VOCs uptakes at different relative pressures, the VOCs isotherm was

177

obtained at the destined temperature (293-328K). Here, a high precision microbalance

178

(AL104, Mettler Toleod，Switzerland) was adopted as the weighing device. The

179

adsorption of n-pentane, n-hexane and dichloromethane at environmentally relevant

180

temperature were conducted on HPR-1 and acetone, benzene, 1, 2-dichloroethane on

181

HPR-2.

182

Results and discussion

183

Characterization of the hypercrosslinked polymeric resins. The N2 adsorption–

184

desorption isotherms of HPR-1 and HPR-2 at 77 K are demonstrated in Figure 1(a).

185

According to IUPAC classification, both of them were typical of adsorbents with a

186

predominantly microporous structure, since the majority of pore-filling occurred at

187

relative pressures below 0.1. The higher adsorption capacities of nitrogen on HPR-1

188

resulted from the higher degree of post-cross-linking reaction of HPR-1 than HPR-2.

189

The slope of the plateau at medium relative pressures and accelerated uptake at higher

190

relative pressure meant that they contained a proportion of mesopores and macropores.

191

The pore size distributions of two resins are shown in Figure 1(b). It is clearly 9



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observed from Figure 1(b) that the two adsorbents showed a similar pore size

193

distribution because of the similar synthesis method. The salient pore structure

194

parameters are shown in Table 1.

195

Adsorption isotherms by IGC and DR modeling. Adsorption isotherms of six

196

VOCs

(n-hexane,

n-pentane,

dichloromethane,

acetone,

benzene,

and

1,

197

2-dichloroethane) onto HPR-1 at the temperature of 403, 423, and 443 K are

198

presented in Figure 2. The isotherms were calculated from chromatographic peaks

199

according to the method described above. At lowering temperature, the increasing of

200

the maximum amount adsorbed (qv) was observed; very small pressure values

201

indicated that the surface coverage is low.

202

Dubinin–Radushkevich (DR) model, which is based on Polanyi adsorption

203

potential theory, is a commonly used isotherm model for physical adsorption of

204

organic vapors onto microporous adsorbent and can be defined as the following

205

equations:

206

qv =q0 exp(-(ε/E)2 )

(6)

207

ε=RTln(Ps /P)

(7)

208

Where qv is the volume adsorbed capacity (mL/g), E is the characteristic adsorption

209

energy (KJ/mol), q0 is the limiting micropore volume (mL/g), ε is the adsorption

210

potential (KJ/mol), calculated by Equation 7.

211

For a given adsorbent，the parameter q0 of DR equation has been shown to relate to

212

the microporous structure of the adsorbent and is generally assumed to be a constant

213

regardless of which adsorbates are used. Since the swelling of HPR is negligible for 10


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the adsorption of VOCs on HPR-1 at lower relative pressure measured by IGC, q0 was

215

assumed to be equal to Vmicro calculated by N2 adsorption isotherms at 77 K. The

216

fitting results of adsorption isotherms using DR equation for every temperature are

217

listed in Table S1. Clearly, the experimental data were well fitted by the DR equation

218

with the correlation coefficient R2 larger than 0.845. In addition, according to the

219

Polanyi adsorption potential theory, plots of adsorbed volume qv against ε will form

220

an adsorption characteristic curve, and can be employed to examine whether the

221

Polanyi adsorption potential theory mechanistically captures the adsorption process of

222

compounds by adsorbent.39, 40 The Figure 3 presents plots of qv against the adsorption

223

potential (ε) of six VOCs on HPR-1. It is shown clearly that the data at three

224

temperatures fell essentially onto a single curve for each adsorbate. The characteristic

225

adsorption curves of six VOCs on the HPR-1 were fitted with DR equation. It is

226

learned from Figure 3 that the fitting curves were in good agreement with the

227

experimental data. The fitting parameters were listed in Table S2. The above results

228

suggested the mechanistic usefulness of Polanyi adsorption potential theory to VOCs

229

adsorption on HPR-1 and the feasibility of using DR equation to describe the

230

adsorption isotherms of VOCs. Moreover, it is pivotal because it allowed to predict

231

adsorption isotherms at environmentally relevant temperature without introducing any

232

additional parameters according to adsorption equilibrium data obtained by IGC

233

method.

234

Prediction of the adsorption capacities on HPR-1 at environmentally relevant

235

temperatures and concentrations. It is known that the characteristic adsorption 11



236

curves (qv vs. ε) are independent of temperatures. Therefore, the adsorption capacities

237

at environmentally relevant temperatures (293-328 K) and concentrations (p/p0=

238

0.1-0.7) on HPR-1 would be predicted using the adsorption equilibrium data obtained

239

by IGC at higher temperature (403, 423, and 443 K). The parameters of q0 and E of

240

DR equation were set to the microporous volume of HPR-1 (Vmicro=0.53) and the

241

fitting E values of adsorption equilibrium data at the high temperatures (listed in

242

Table S2), respectively. The predicted adsorption capacities of n-pentane, n-hexane,

243

and 1, 2-dichloromethane on HPR-1 at environmentally relevant temperatures and

244

concentrations are shown in Figure 4. A big discrepancy was observed between the

245

experimental and predicted adsorption capacities. Figure 4(d) clearly shows that the

246

predicted adsorption capacities were lower than the experimental results. For VOCs

247

adsorption on HPR, the previous studies have found that the fitting parameter q0 by

248

experimental data was greater than the microporous volume of resins determined by

249

N2 adsorption isotherms at 77 K when the higher relative pressure of VOCs was

250

adsorbed.15-17, 19, 21 The possible reason is that HPR can swell strongly after adsorbing

251

organic solvents,41, 42 resulting in that the actual microporous volume is larger than the

252

measured value based on N2 adsorption data. Davankov et al.43 and Urban et al.44

253

proposed that the swelling property of HPR in solvent is due to the strong inner stress.

254

The inner stress could form an additional strong driving force for the polymer

255

networks to be swollen. Therefore, the solvent uptake by HPR could arise from both

256

micropore filling and swelling of the polymer network.43 That is to say, the predicted

257

adsorption capacities based on the micropore volume (Vmicro) may be lower than the 12


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experimental adsorption capacities. Therefore, the volume swelling ratio (r) of HPR

259

was introduced and r·Vmicro was used instead of the Vmicro for predicting the adsorption

260

capacities of HPR-1 for VOCs at environmentally relevant temperatures and

261

concentrations using the DR equation.

262

The swelling ratio of HPR-1 and HPR-2 after adsorbing different VOCs is listed in

263

Table S3. After the parameters q0 of DR equation was set to r·Vmicro, the predicted

264

adsorption capacities of n-pentane, n-hexane and dichloromethane at environmentally

265

relevant temperatures and concentration are shown in Figure 5. It is clear that the

266

predicted adsorption capacities were consistent with the experimental results. The

267

root-mean-square error (RMS %), determined via Equation 8, was 5.36% and much

268

lower than that (21.41%) when the parameters q0 of DR equation was set to Vmicro. The

269

results demonstrate the effectiveness of predicting the adsorption capacities at

270

environmentally relevant temperatures and concentrations by IGC data using DR

271

equation, assuming that the parameters q0 of DR equation was equal to r·Vmicro.

272

RMS %=100 k ∑ k 1 "

# exp -# cal

1

# cal

2

+

(8)

273

Prediction of adsorption capacities on HPR-2 at environmentally relevant

274

temperatures and concentrations. Because the pore structure of HPR are affected

275

by many factors, such as reaction temperature, reaction time, and the dose of

276

pore-forming,45, 46 the pore size distribution and salient properties parameters of HPR

277

may be different even if the same monomer and crosslinking agent are used during the

278

synthesis. Therefore, it would be very valuable if the adsorption capacities of one

279

resin for VOCs can be predicted by the IGC data on another resin. It is learned from 13



280

Figure 1 that the pore size distributions of HPR-1 was similar with that of HPR-2,

281

however, their pore diameters were different. We can find that the average pore

282

diameter of HPR-1 was larger than HPR-2. It is known that the characteristic

283

adsorption energy, E of DR equation, is a function of pore size distribution of

284

adsorbent.47 For the adsorption of a given adsorbate on the different adsorbents, it is

285

suggested that the characteristic adsorption energy, E, is inversely related to the

286

average width of the pores (W), i.e, W·E=C (C is constant).48 In this study, therefore,

287

for the adsorption of a given adsorbate on HPR-2, the fitting parameter E of DR

288

equation can be obtained from the relation of WHPR-2·EHPR-2= WHPR-1·EHPR-1. So, the

289

adsorption capacities of acetone, benzene, and 1, 2-dichloroethane on HPR-2 at

290

environmentally relevant temperatures and concentrations were also predicted by IGC

291

data on HPR-1 at 403K, 423K and 443K using DR equation, where q0=r·Vmicro and E

292

HPR-2=

293

of acetone, benzene and 1, 2-dichloroethane on HPR-2 were in agreement with the

294

experimental data with RMS lower than 9.63 %, conforming the feasibility of the

295

predicted method by IGC data combined with DR equation. As a comparison, the

296

parameters q0=Vmicro and E HPR-2= WHPR-1·E HPR-1/ WHPR-2 were also used to predict the

297

adsorption capacities of acetone, benzene and 1, 2-dichloroethane on HPR-2. From

298

the Figure S3, it is found that there was an obvious discrepancy predicted between the

299

predicted and experimental adsorption capacities with large RMS of 27.80%.

WHPR-1·E HPR-1/ WHPR-2. Figure 6 shows that the predicted adsorption capacities

300 301 14


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Supporting Information

309

Table S1 and S2: Fitting parameters of DR equation. Table S3: Swelling ratio of

310

two adsorbents. Figure S1: Principles of the characteristic-point elution method used

311

to calculate adsorption isotherms. Figure S2: Adsorption isotherms of six VOCs

312

measured by gravimetric method at 293-328K. Figure S3: The predicted adsorption

313

capacities of acetone, benzene, 1, 2-dichloroethane when the parameters q0 of DR

314

equation was set to Vmicro.

315 316 317 318

Acknowledgments

319

This research was financially funded by National Natural Science Foundation of

320

China (No. 51578281).

321 322 323 15



324

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Polymerization

for

Novel

Hypercrosslinked

468 469 470 471 472 473 474 475 476 477 478 22


Resin

Bead

by

Page 23 of 30


479 480 481 482 483 484 485

Table 1. Pore structure parameters of hypercrosslinked polymeric resins Pore parameters

HPR-1

HPR-2

SBET (m2/g)

1113.2

944.4

Vmicro(cm3/g)

0.53

0.43

Vmeso(cm3/g)

0.31

0.29

average pore diameter(W, nm)

2.56

2.48

486 487 488 489 490 491 492 493 494 495 496 23



497 498 499 500 501 502 503

Figure Captions

504

Figure 1. Pore structure of two hypercrosslinked polymeric resins (HPR-1 and

505

HPR-2)

506

Figure 2. Adsorption isotherms of six VOCs on HPR-1 at 403K, 423K and 443K by

507

IGC: (a) n-pentane, (b) n-hexane, (c) dichloromethane, (d) acetone, (e) benzene and (f)

508

1, 2-dichloroethane

509

Figure 3. Adsorption characteristic curves of six VOCs on HPR-1: (a) n-pentane, (b)

510

n-hexane, (c) dichloromethane, (d) acetone, (e) benzene and (f) 1, 2-dichloroethane

511

Figure 4. The predicted adsorption capacities of (a) n-pentane, (b) n-hexane, (c)

512

dichloromethane and (d) comparison of the experimental and predicted adsorption

513

capacities when the parameters q0 of DR equation was set to Vmicro

514

Figure 5. The predicted adsorption capacities of (a) n-pentane, (b) n-hexane, and (c)

515


516

capacities when the parameters q0 of DR equation was set to r·Vmicro

517

Figure 6. The predicted adsorption capacities of (a) acetone, (b) benzene, (c) 1,

518

2-dichloroethane, and (d) comparison of the experimental and predicted adsorption 24


Page 24 of 30

Page 25 of 30


519

capacities when the parameters q0 of DR equation was set to r·Vmicro, and the

520

characteristic adsorption energy E HPR-2= WHPR-1·E HPR-1/ WHPR-2

521 522

523 524

Figure 1. Pore structure of two hypercrosslinked polymeric resins (HPR-1 and

525

HPR-2)

526

25



527 528

Figure 2. Adsorption isotherms of six VOCs on HPR-1 at 403K, 423K and 443K by

529

IGC: (a) n-pentane, (b) n-hexane, (c) dichloromethane, (d) acetone, (e) benzene and (f)

530

1, 2-dichloroethane

531 532 533 534 535 536 537 26


Page 26 of 30

Page 27 of 30


538

539 540

Figure 3. Adsorption characteristic curves of six VOCs on HPR-1: (a) n-pentane, (b)

541

n-hexane, (c) dichloromethane, (d) acetone, (e) benzene and (f) 1, 2-dichloroethane

542 543

27



544 545

Figure 4. The predicted adsorption capacities of (a) n-pentane, (b) n-hexane, (c)

546


547

capacities when the parameters q0 of DR equation was set to Vmicro

548 549 550 551 552 553 554

28


Page 28 of 30

Page 29 of 30


555 556

Figure 5. The predicted adsorption capacities of (a) n-pentane, (b) n-hexane, and (c)

557


558

capacities when the parameters q0 of DR equation was set to r·Vmicro

29



559 560

Figure 6. The predicted adsorption capacities of (a) acetone, (b) benzene, (c) 1,

561

2-dichloroethane, and (d) comparison of the experimental and predicted adsorption

562

capacities when the parameters q0 of DR equation was set to r·Vmicro, and the

563

characteristic adsorption energy E HPR-2= WHPR-1·E HPR-1/ WHPR-2

564 565 566 567

30


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Prediction of Adsorption Equilibrium of VOCs onto Hyper-Cross

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