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Remediation and Control Technologies

Recycling Spent Cr-Adsorbents as Catalyst for Eliminating Methylmercaptan
Dedong He, Liming Zhang, Yutong Zhao, Yi Mei, Dingkai Chen, Sufang He, and Yongming Luo
Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b06357 • Publication Date (Web): 05 Mar 2018
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1 Recycling Spent Cr-Adsorbents as Catalyst for Eliminating Methylmercaptan

2 Dedong He,†,‡ Liming Zhang,† Yutong Zhao,† Yi Mei,‡ Dingkai Chen,† Sufang He,§ and

3 Yongming Luo,*,†

†
4 Faculty of Environmental Science and Engineering, Kunming University of Science and

5 Technology, Kunming 650500, P. R. China.

‡
6 Faculty of Chemical Engineering, Kunming University of Science and Technology,

7 Kunming 650500, P. R. China.

§
8 Research Center for Analysis and Measurement, Kunming University of Science and

9 Technology, Kunming 650093, P. R. China.

10

11

12 * Corresponding author

13 Tel: +86-871-65103845

14 Fax: +86-871-65103845

15 E-mail: environcatalysis222@yahoo.com (Y. Luo)

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16 Table of Contents (TOC)

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18 Abstract

19 Waste adsorbents generated from treating Cr(VI) containing wastewater are hazardous

20 materials and generally landfilled or treated by acid or base desorption, with concomitant

21 high cost and toxic effects. The present work shows that these Cr-adsorbents can be reused

22 as highly efficient catalysts for treating sulfur-containing VOCs (CH3SH), not only

23 avoiding the economic and environmental impact from the conventional approaches, but

24 also achieving the efficient treatment of sulfur-containing waste gas. Importantly, these

25 reused Cr-adsorbents exhibit enhanced activity and stability compared with the catalysts

26 reported elsewhere, indicating a new avenue of green chemistry. The highly toxic adsorbed

27 Cr(VI) species are reduced to a Cr2O3 crystalline phase by calcination and finally

28 immobilized as a Cr2S3 solid phase while converting and eliminating CH3SH. Still, the

29 presence of Cr(VI) species on the reused Cr adsorbent provides enough reactive sites for

30 reaction, but high concentration of Cr(VI) species causes serious accumulation of coke

31 deposit on the catalyst, leading to fast deactivation of the catalyst.

32 Keywords: Waste Cr Adsorbents; Reuse and Recycle; Highly Efficient Catalyst; CH3SH

33 Catalytic Elimination.

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34 1. INTRODUCTION

35 Hexavalent chromium (Cr(VI)) combines high toxicity, potential carcinogenicity and

36 mutagenicity and poses a significant threat to human health.1,2 Various treatment strategies,

37 such as adsorption, have been extensively employed for Cr(VI) removal from wastewater

38 effluents, due to its simplicity and low cost.3,4,5,6,7 One of the most promising adsorbents for

39 Cr(VI) treatment are an organic-inorganic modified silicon material, MCM-41 with good

40 mechanical stability and high adsorption capacity.8,9,10 However, after adsorption, the

41 question of how to dispose of adsorbents after usage cannot be avoided.

42 Present disposal strategies proposed for the adsorbents after usage are either landfilling11,12

43 or desorption by acid and base treatment.6,13,14,15 Landfill is often the preferred option and

44 the most direct and easy method to tackle the problem of the generated adsorbents. Yet,

45 these chromium-loaded adsorbents may generally exhibit toxic effects on human health and

46 environment.16 Complete desorption of chromium from theadsorbents, therefore, is a

47 necessity before these are released. An acid and base treatment is suggested as a feasible

48 method.6,13,14,15 However, the required disposal of the spent acid and base solution, with a

49 high concentration of Cr(VI) is a major disadvantage. It is therefore important to develop

50 an alternative strategy to dispose Cr-adsorbents.

51 In recent decades, the use of Cr-MCM-41 has attracted interest as a catalyst.17,18,19,20

52 Generally, the presence of Cr(VI) species introduces favorable redox properties through the

53 system of Cr(VI)/Cr(III).19 Meanwhile, the Cr(VI) species are related to the development of

54 Brönsted centers, while the Cr(III) centers contribute to Lewis acidity.21 Our recent

55 work22,23,24,25 and other reports26,27 have shown that redox and acidity properties may play

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56 an important role in any methyl mercaptan (CH3SH) catalytic elimination system. This

57 compound is representative for sulfur-containing volatile organic compounds (SVOCs),

58 which is harmful to human health and causing serious smell problems.28 The treatment of

59 VOCs has gained considerable attention in environmental protection areas.29

60 Based on this background, an alternative way of disposing and reusing of Cr-adsorbents is

61 proposed in this paper. A Cr-MCM-41 sample with high catalytic performance for CH3SH

62 elimination can be obtained directly by calcinating Cr-adsorbents in air. Hence, the

63 environmental impact of landfilling or desorption by using acid and base treatment are

64 avoided, and a high value catalyst and reactant is created. To the best of our knowledge,

65 such recycling of Cr-adsorbents as high performance catalyst has not been reported in

66 previous studies. Actually, also so far there has been no report proposing Cr-MCM-41

67 catalysts for CH3SH elimination. To our surprise, the Cr-MCM-41 samples obtained from

68 Cr-adsorbents exhibit enhanced activity and stability, compared with all other

69 catalysts22,23,24,25,26,27,30,31 reported for CH3SH treatment. Therefore, we analyze the physical

70 and chemical properties of the obtained Cr-MCM-41 catalyst and appreciate the reason

71 why this reused Cr-adsorbent demonstrates such high catalytic performances for CH3SH

72 elimination, on the basis of characterization results.

73 2. MATERIALS AND METHODS

74 2.1 Chemicals and Materials

75 Potassium dichromate, ammonium chromate, cetyltrimethylammonium bromide,

76 tetraethylorthosilicate, sodium hydroxide, and other chemical reagents were purchased

77 from Shanghai Chemical Reagent Company of China. All chemicals were of at least

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78 analytical grade and used without further treatment. Methyl mercaptan (1 vol. % CH3SH in

79 N2) was obtained from Dalian Special Gases Co. Ltd., China.

80 2.2 Reusing Cr-Adsorbents

81 Details on the synthesis of adsorbents and the chromium column adsorption experiment are

82 recorded in the Supporting Information. The Cr-adsorbents were directly calcined in air at

83 550 oC for 6 h to obtain the Cr/MCM-41 catalyst ready for use. A schematic pathway for

84 preparing and reusing the Cr-adsorbents is suggested in Scheme 1.

85 For comparison purposes, the fresh adsorbents (without any chromium species) were

86 calcined at 550 oC for 6 h as blank catalyst supports (MCM-41). Then, K2Cr2O7 and

87 (NH4)2CrO4 were loaded on the calcined fresh adsorbent by the conventional incipient

88 wetness impregnation method. Details are recorded in Supporting Information.

89 2.3 Characterization

90 Details on catalyst characterization are shown in Supporting Information.

91 2.4 CH3SH Catalytic Elimination Experiment

92 The CH3SH catalytic elimination experiment was carried out in a fixed-bed micro-reactor

93 at atmospheric pressure. An amount of 0.2 g of catalyst was loaded into a quartz tube

94 reactor. Then 1 vol. % CH3SH in N2 was introduced into the reaction system with flow rate

95 of 30 mL/min. The reaction temperature was increased from 350 to 600 oC in 25 oC

96 increments (from 350 to 400 oC) and 50 oC increments (from 400 to 600 oC), and held for

97 0.5 h for stabilization. The stability test was carried out at 500 oC with 0.2 g of CeO2 or

98 reused Cr adsorbent and 0.4 g of HZSM-5. The reactants and products were analyzed by

99 online GC (gas chromatograph) equipped with FID, TCD and FPD detectors. CH3SH

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100 conversion was calculated by the following equation:

C[ CH 3SH ]in − C[ CH 3SH ]out

101 CH3SH Conversion = × 100%
C[ CH 3SH ]in

102 C[CH3SH]in represents the initial concentration of CH3SH before the reaction, while C[CH3SH]out

103 is the remaining ones after the reaction.

104 2.5 Catalyst Regeneration

105 Regeneration of the spent catalyst (after reaction) was carried out at 500 oC for 2 h, by

106 introducing 30 mL/min air flow, and then catalytic reactivity of the regenerated

107 Cr-adsorbent was measured.

108 3. RESULTS AND DISCUSSION

109 3.1 Catalyst Performance

110 The evaluation of catalytic activity and stability on the elimination of CH3SH is shown in

111 Figure 1(A) and (B), respectively. Figure 1(A) shows that the reused Cr adsorbent is more

112 active than reported for CeO222,23,30,31 and HZSM-524,25,27,28 catalysts. At 400 oC, reused Cr

113 adsorbent exhibits the highest activity and its CH3SH conversion is almost 100%, while

114 about 93% and 64% are obtained over CeO2 and HZSM-5 catalysts.

115 Moreover, a remarkable stability of the reused Cr adsorbent is also observed. Figure 1(B)

116 shows that the reused Cr adsorbent maintains nearly 100% of its initial activity for 90 h

117 when the reaction is carried out at 500 oC, while the corresponding time for the reported

118 CeO2 and HZSM-5 catalysts is only 10 and 15 h, respectively. Thus, the reused Cr

119 adsorbent demonstrates higher stability than both CeO2 and HZSM-5 that are reported

120 previously22,23,24,25,27,28,30,31. The above findings indicate that for the same reaction

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121 conditions, our reused Cr adsorbent presents an enhanced activity and stability for CH3SH

122 catalytic elimination.

123 The reason for the reused Cr adsorbent shows much higher stability in comparison with

124 CeO2 and HZSM-5 is stated as follows: on the one hand, active Cr sites can be well

125 dispersed on the MCM-41 support with high surface area. On the other hand, due to

126 weak/no acidity of MCM-41, small amount of coke deposit can be formed and accumulated

127 on catalyst (Figure S13 in Supporting Information). All these should be responsible for

128 high stability of the reused Cr adsorbent.

129 3.2 Catalyst Characterization

130 The low-angle XRD pattern of the reused Cr adsorbent displays three diffraction peaks in

131 the 2θ range of 1-5o (Figure S1 in Supporting Information), which can be indexed to the

132 (100), (110) and (200) reflexes and are characteristic of hexagonal mesostructures.32

133 Therefore, XRD results suggest that the ordered structure of MCM-41 is retained after the

134 reuse. To some extent, however, Cr-incorporation may destroy the ordered arrangement of

135 the MCM-41 structure,33 as confirmed by the TEM image in Figure S2 (Supporting

136 Information). The above results illustrate that the reused Cr adsorbent basically preserves

137 its original structural features.

138 The Cr 2p XPS spectra for the reused Cr adsorbent and the calcined fresh adsorbents

139 (MCM-41) are shown in Figure 2(A). The Cr 2p signals at binding energy (BE) values of

140 577 and 586 eV are assigned to trivalent chromium Cr(III) species, whereas those at BE

141 values of 579 and 588 eV are attributed to hexavalent chromium Cr(VI) species.34,35

142 Considering the oxidation state of the introduced chromium (K2Cr2O7, see Supporting

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143 Information) from the adsorption process is Cr(VI), the presence of both Cr(VI) and Cr(III)

144 herein obviously indicates the reduction of Cr(VI) to Cr(III) occurs. To analyze this

145 reduction process, a comparative FT-IR and XPS (N 1s) study of the reused Cr adsorbent

146 before and after calcination is presented (note that the adsorbents are not calcined before

147 conducting Cr adsorption experiments, which is different from the calcined fresh

148 adsorbents, see Scheme S1 in Supporting Information). Figure S3A (Supporting

149 Information) displays the FT-IR spectra. It is found that three peaks at about 2923, 2854

150 and 1473 cm-1, respectively corresponding to the stretching and bending vibrations of -CH3,

151 -CH2 and N-C, are observed in the spectrum of the Cr adsorbent before calcination, but not

152 in the spectrum of the calcined Cr adsorbent. Furthermore, as demonstrated from the N1s

153 spectra (Figure S3B in Supporting Information), the total nitrogen amount is substantially

154 reduced after calcination, suggesting interaction of the positively charged ammonium group

155 with the electron-withdrawing Cr(VI) species (e.g. HCrO4-, Cr2O72-) due to the electrostatic

156 interaction.36,37 After that, when a proton of the ammonium group is released, the reduction

157 of Cr(VI) to Cr(III) occurs.38 This assumption is consistent with the result exhibited in

158 Figure S3B (Supporting Information), where the peak intensity for the group of (-NH3)+

159 decreases while it for the group of (-NH2) increases. This conclusion is well in accordance

160 with the reported results.38 Therefore, the above results can generally be applied to explain

161 the existence of Cr(III) species on the reused Cr adsorbent, although the introduced

162 chromium source is Cr(VI) from K2Cr2O7 (See Scheme S2 in Supporting Information).

163 In order to verify the above conclusions and also for purposes of comparison, K2Cr2O7 and

164 (NH4)2Cr2O7 were directly impregnated on the calcined fresh adsorbents (MCM-41). An

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165 examination of Cr 2p spectra (Figure S4A in Supporting Information) reveals that the major

166 oxidation state of the chromium species formed on the K2Cr2O7 impregnated sample is

167 Cr(VI). This is probably due to the absence of -CH3 and -NH3 etc. species on the calcined

168 fresh adsorbents, which cannot provide the proton for Cr(VI) reduction. In contrast, as for

169 the (NH4)2Cr2O7 impregnated sample, the peaks at 577 and 586 eV, which signify the

170 presence of Cr(III), suggesting that the ammonium group causes Cr(VI) to be reduced,

171 which is in conformity with the foregoing analysis. Besides, XRD measurements (Figure

172 S4B in Supporting Information) confirm that both (NH4)2Cr2O7 impregnated sample and

173 the reused Cr adsorbent show the development of Cr2O3 crystalline phase,32 whereas in the

174 pattern corresponding to the K2Cr2O7 impregnated sample, one sharp diffraction peak

175 centered around 2θ = 26o indicates the presence of the CrO3 phase.21 These XRD

176 observations are consistent with the XPS results and also verified by the UV-vis DR

177 analysis. Figure S4C (Supporting Information) shows the (NH4)2Cr2O7 impregnated sample

178 as well as the reused Cr adsorbent displays absorption above 550 nm due mainly to Cr(III)

179 species in Cr2O3 particles,38 which is not detected in the K2Cr2O7 impregnated sample.

180 Hence, the above XPS, XRD and UV-vis DR investigations evidence the reduction process

181 of Cr(VI) to Cr(III) towards the reused Cr adsorbent.

182 Figure 2(B) illustrates the O 1s spectra of the reused Cr adsorbent and the calcined fresh

183 adsorbents (MCM-41). For the MCM-41 sample, symmetric O 1s peak is seen at a BE

184 value of 533 eV, likely resulting from the contribution of oxygen from the silica

185 support.34,39 Over the reused Cr adsorbent sample, there is additional signal with BE value

186 of 530 eV attributable to the surface lattice oxygen of Cr2O3.34,39 Thus O 1s measurement

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187 confirms the presence of agglomerated metal chromium oxides on the reused Cr adsorbent.

188 Figure 2(C) shows the high-angle XRD patterns obtained for the reused Cr adsorbent and

189 the fresh MCM-41sample. From Figure 2(C), a broad band located at 2θ ≈ 25o is

190 characteristic of amorphous silica.21 Furthermore, for the sample of reused Cr adsorbent,

191 XRD exhibits nine sharp diffraction peaks, which are ascribed to the presence of Cr2O3

192 crystalline phase.32 These XRD investigations concur with the results of XPS. Figure 2(D)

193 exhibits the UV-vis DR spectra of the reused Cr adsorbent and the fresh MCM-41sample.

194 One can observe three broad absorption peaks for the reused Cr adsorbent sample. In

195 general, the regions at 200-400 and 400-550 nm are attributed to the Cr(VI) ions in the

196 monochromate and di/polychromates species, respectively.32,38 Meanwhile, the region at

197 higher wavelengths (above 550 nm) could be assigned to the formation of crystalline

198 Cr2O3.32,38 Therefore, the UV-vis DR results indicate the existence of crystalline Cr2O3 on

199 the reused Cr adsorbent sample, again in agreement with the mentioned XPS and XRD

200 investigations.

201 H2-TPR profiles of the reused Cr adsorbent and the fresh MCM-41 catalyst samples in the

202 temperature range of 100-800 oC are given in Figure 2(E). In the case of the reused Cr

203 adsorbent sample, two reduction peaks appear at about 320 and 460 oC as a result of the

204 reduction of Cr(VI) species (2CrO3 + 3H2 = Cr2O3 + 3H2O) interacting differently with the

205 support.19,32,38 The first peak could correspond to the reduction of di/polychromates Cr(VI)

206 species, and the second one could be due to the reduction of monochromates Cr(VI)

207 species.32,40 As shown in Figure S4D (Supporting Information), the K2Cr2O7 impregnated

208 sample shows an obvious reduction peak since the Cr species present on this sample is

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209 mainly Cr(VI), as proved by the mentioned characterization results of XRD, XPS and

210 UV-vis. Moreover, from Figure S4D (Supporting Information), it is noted that (NH4)2Cr2O7

211 impregnated sample demonstrates increased intensity for the first reduction peak than that

212 of the reused Cr adsorbent, suggesting that more monochromates Cr(VI) species are formed

213 on the reused Cr adsorbent. In fact, it is accepted that the distribution of the adsorbed Cr

214 species from the column adsorption experiment would be more uniform than that from the

215 traditional impregnation process, thus contributing to the more monochromates Cr(VI)

216 species on the adsorbents.

217 The acidic properties of the fresh MCM-41 and the reused Cr adsorbent samples were

218 investigated by using the NH3-TPD method, and the corresponding results are collected in

219 Figure 2(F). The NH3-TPD profile for the reused Cr adsorbent exhibits a low-temperature

220 peak at about 220 oC attributed to weak Lewis type acid sites, and a high-temperature peak

221 above 600 oC, ascribed to the presence of Brönsted acid sites.41,42 This location in acidity is

222 in good agreement with the reported results,43 whereas the K2Cr2O7 impregnated sample

223 (mainly containing Cr(VI) species) shows the presence of the high-temperature peak only

224 (Figure S4E in Supporting Information). Previous reports have revealed that the

225 development of Lewis acidic centers is directly related to Cr(III) species, while the

226 presence of Cr(VI) induces the appearance of Brönsted acidic centers.21,44 Hence, our

227 NH3-TPD results confirm this conclusion.

228 Meanwhile, catalytic stability tests over the synthesized catalysts (K2Cr2O7/(NH4)2Cr2O7

229 impregnated MCM-41 samples and the reused Cr adsorbent) are shown in Figure S5

230 (Supporting Information). Clearly, the K2Cr2O7 impregnated MCM-41 sample exhibits

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231 lower catalytic stability, since CH3SH conversion after 30 h time on stream decreases to

232 less than 50%. Conversely, a (NH4)2Cr2O7 impregnated MCM-41 sample reveals enhanced

233 catalytic stability, and CH3SH conversion can maintain 100% after 50 h of exposure time,

234 though still lower than that of our reused Cr adsorbent. As discussed before, the distribution

235 of adsorbed Cr(VI) species on reused Cr adsorbent is more uniform than that of the

236 traditional impregnation samples. As expected, our reused Cr adsorbent exhibits better

237 catalytic performance than the impregnated one. However, K2Cr2O7 impregnated MCM-41

238 sample with high concentration of Cr(VI) species (Table S1 and Figure S4A in Supporting

239 Information) shows very poor catalytic performance. As known, this sample contains high

240 amount of Brönsted acidic centers contributed by the Cr(VI) species (as proved by the XPS,

241 H2-TPR and NH3-TPD investigations). As a matter of fact, Brönsted acid sites may result in

242 the formation of coke and catalyst deactivation during the dehydrogenation and/or cracking

243 of hydrocarbons.45,46 Therefore, it is deduced that the poor catalytic stability of the K2Cr2O7

244 impregnated MCM-41 sample is to be attributed to the severe accumulation of coke

245 deposits during the reaction. As exhibited in Figure S6 (Supporting Information), the band

246 intensity corresponding to the presence of coke deposit46,47 over the spent K2Cr2O7

247 impregnated MCM-41 sample is higher than that on other spent samples after the same

248 exposure time (30 h), providing evidence for the deactivation of K2Cr2O7 impregnated

249 MCM-41 catalyst and verify the above conclusions.

250 On the whole, the results from the aforementioned analysis indicate that the presence of

251 Cr(VI) on reused Cr adsorbent can provide enough reactive sites for CH3SH catalytic

252 elimination (as indicated and analyzed in Figure S7 and Figure S8 in Supporting

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253 Information). Nevertheless, a high concentration of Cr(VI) species may cause fast

254 deactivation of the catalyst (e.g. K2Cr2O7 impregnated MCM-41 sample), and as a result,

255 serious accumulation of coke deposit is observed on this catalyst.

256 3.3 Analysis of the Spent Catalyst and Catalyst Regeneration

257 The XRD patterns and Cr 2p XPS spectra of the fresh (the reused Cr adsorbent) and the

258 spent (the reused Cr adsorbent after reaction) catalyst samples are presented in Figure 3A

259 and Figure 3B, respectively. From Figure 3A, several new diffraction peaks assigned as the

260 formation of Cr2S3 phase (JCPDS 82-1545) are found in the XRD patterns over the spent

261 catalyst. Furthermore, as obtained from Figure 3B, the relative percent content of Cr(III) on

262 the spent catalyst sample is increased to 89.33% compared to the fresh one (62.27%). To

263 our surprise, the formation of Cr2S3 phase on the spent catalyst illustrates that the present

264 reaction system can achieve the goal for the immobilization of both chromium and sulfur

265 species, which reflects important environmental significance. Moreover, to analyze how did

266 CH3SH interact with active Cr species on adsorbent surface, in situ FTIR technique was

267 used to study adsorption and transformation behaviors of CH3SH over the reused Cr

268 adsorbent, and FTIR spectra is shown in Figure S9 (as analyzed in Supporting Information).

269 Besides, the mechanism involving immobilization of Cr2O3 by thiol groups onto Cr2S3 is

270 suggested in Figure S10 (Supporting Information).

271 Furthermore, this spent catalyst is regenerated and the catalytic reactivity of the regenerated

272 Cr-adsorbent is displayed in Figure S11. It indicates that the regenerated sample can be

273 recovered to its original reactivity. Meanwhile, from Figure 3C and 3D, it is seen that the

274 regenerated Cr-adsorbent shows characteristic diffraction peaks of Cr2O3, and the relative

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275 percent content of Cr(VI) on the regenerated sample is increased to 48.12%. Besides, no

276 accumulation of coke deposit and sulfur species is observed on regenerated Cr-adsorbent.

277 Therefore, it is deduced that spent reused adsorbent is to be regenerated for the case that

278 they are intended for recycle.

279 3.4 Effects of Other Chemical Species in Wastewaters

280 In order that the results might be applicable for real spent Cr-adsorbents, different initial

281 concentrations (20, 50, 100, 200 and 300 mg/L) of Cr(VI) have been applied for the

282 synthesis of Cr-adsorbents, and the influences of various chemical species (coexisted

283 anion/cation ions) present in real wastewaters are considered. From Figure 4A, the reused

284 Cr-adsorbents synthesized from different concentrations of Cr(VI) show similar reactivity

285 for CH3SH elimination, revealing that initial concentration of Cr(VI) has no significant

286 influence on catalytic activity of the reused Cr-adsorbents. From Figure 4B, it is seen that

287 coexisted cation ions has no influence on activity while sample synthesized from coexisted

288 anion ions exhibits slightly decreased reactivity, but it still higher than the reported

289 HZSM-5 catalyst. Hence, the above investigations indicate that it can be applicable for real

290 spent Cr-adsorbents, which highlights its application. Besides, the effects of these other

291 chemical species on physicochemical properties of the reused Cr-adsorbent are also

292 investigated, and results are shown in Figure S12 (as analyzed in Supporting Information).

293 3.5 Environmental Implications

294 Large amounts of waste Cr adsorbents are generated during the removal of Cr(VI) from

295 wastewater. Disposal options include landfilling and acid and base desorption treatment

296 generally show toxic effects on environment. Therefore, the exploration of the reuse of the

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297 spent Cr-adsorbents as a highly efficient catalyst for sulfur-containing VOCs (CH3SH)

298 catalytic elimination has important environmental implications. Our results suggest that the

299 highly toxic Cr(VI) contamination could finally be immobilized as Cr2S3 solid phase (as

300 reported4, Cr(III) is 100 times less toxic than Cr(VI)). Furthermore, CH3SH can be

301 selectively transformed into value added hydrocarbons (including CH4, olefins and BTX),

302 hydrogen sulfide (the produced H2S can be commercially converted to elemental sulfur

303 from Claus technique) and CS2 (the produced CS2 can be used for the production of

304 sulfuric acid and applied as a raw material for fine petrochemicals48) over the reused Cr

305 adsorbents (as shown in Figure S14 in Supporting Information). More importantly, the

306 obtained catalysts from the spent Cr-adsorbents show better performance than the reported

307 catalysts. Meanwhile, the study of effects of other chemical species indicates that it can be

308 applicable for real spent Cr-adsorbents. Besides, the spent reused adsorbent can be

309 regenerated for the case of recycle. All these indicated that the recycle of the Cr-adsorbents

310 as a highly efficient catalyst for CH3SH catalytic elimination has great potential in treating

311 waste Cr adsorbents and is therefore of great environmental importance. Furthermore, the

312 reused Cr adsorbents of the present work can also be applied to other reactive systems (e.g.

313 catalytic dehydrogenation of propane to propene).

314 Acknowledgements

315 The National Natural Science Foundation of China (U1402233, 21667016 and 21367015)

316 is gratefully acknowledged for financial support to this research work.

317 Supporting Information Available

318 Details about synthesis of materials (adsorbents, K2Cr2O7/MCM-41 and (NH4)2CrO4

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319 impregnated MCM-41), and chromium column adsorption experiment are available as

320 Supporting Information. Characterization results of the fresh and spent samples and

321 catalytic stability tests are shown. The schematic mechanism of CH3SH removal by spent

322 Cr-adsorbents is illustrated.

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476 2007, 163, 645-652.

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500 Scheme 1. Schematic pathway for preparing and recycling the Cr-adsorbents.
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512

513

514 Figure 1. The evaluation of (A) activity and (B) stability on the catalytic elimination of
515 CH3SH.
516

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517

518

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519

520

521 Figure 2. (A) and (B) Cr 2p and O 1s XPS spectra, (C) high-angle XRD patterns, (D)
522 UV-vis DR spectra, (E) H2-TPR profiles and (F) NH3-TPD profiles of the reused Cr
523 adsorbents and the fresh MCM-41sample.
524

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531

532
533 Figure 3. (A) The XRD patterns, (B) Cr 2p XPS spectra of the fresh (the reused Cr
534 adsorbent) and the spent (the reused Cr adsorbent after reaction) catalyst samples; (C)
535 The XRD patterns, (D) Raman spectra, S 2p and Cr 2p XPS spectra of the spent and
536 regenerated catalyst samples.

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537
538

539
540 Figure 4. Effect of (A) initial concentrations of Cr(VI), (B) coexisted ions (initial
541 concentrations of Cr(VI) is 20 mg/L) on the catalytic activity of the reused Cr
542 adsorbents.

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