Accepted Manuscript

Regeneration and reuse of highly polluting textile dyeing effluents through catalytic
ozonation with carbon aerogel catalysts

Enling Hu, Songmin Shang, Xiao-ming Tao, Shouxiang Jiang, Ka-lok Chiu

PII: S0959-6526(16)31100-3
DOI: 10.1016/j.jclepro.2016.07.194
Reference: JCLP 7766

To appear in: Journal of Cleaner Production

Received Date: 9 January 2016

Revised Date: 23 June 2016
Accepted Date: 27 July 2016

Please cite this article as: Hu E, Shang S, Tao X-m, Jiang S, Chiu K-l, Regeneration and reuse of highly
polluting textile dyeing effluents through catalytic ozonation with carbon aerogel catalysts, Journal of
Cleaner Production (2016), doi: 10.1016/j.jclepro.2016.07.194.

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Graphical Abstract

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3 Regeneration and reuse of highly polluting textile dyeing effluents through catalytic

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4 ozonation with carbon aerogel catalysts

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6 Enling Hu, Songmin Shang*, Xiao-ming Tao, Shouxiang Jiang, Ka-lok Chiu

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7 Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong

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9 *Corresponding author:
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10 Dr. Songmin Shang

11 Institute of Textiles and Clothing

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12 The Hong Kong Polytechnic University

13 Hong Kong
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14 Tel.: +852-34003085
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15 Fax: +852-27731432
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16 E-mail: shang.songmin@polyu.edu.hk

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18 The manuscript submitted to Journal of Cleaner Production

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20 Abstract

21 Reactive dyeing of cotton generates a great deal of coloring wastewater containing

22 residual dyes, electrolyte, alkali, and other auxiliaries. Especially for the effluent from

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23 the first/initial spent dyeing bath, it may be comprised of as high as 60% of the initial

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24 dye dosed, 30-90 g/L of sodium chloride or sodium sulphate, and plenty of sodium

25 carbonate, making it to be the most contaminative effluent among the entire reactive

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26 dyeing process. This paper presents a new alternative to regenerate the waste effluent

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27 from the first spent dyeing bath through catalytic ozonation with novel catalysts for

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reuse of the effluent in successive dyeing. Two novel ozonation catalysts, mesoporous
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29 carbon aerogel and its supported cobalt oxide nanoparticles, were successfully

30 prepared and used in catalytic degradation of residual dyes in waste effluents with
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31 ozone. Degradation efficiency was determined by both decolorization and chemical

32 oxygen demand removal. The result showed novel catalysts could improve both of
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33 these two targets. For chemical oxygen demand removal, carbon aerogel supported
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34 cobalt oxide strikingly enhanced the efficiency by 30% on the whole comparing to
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35 ozonation alone (approximately 50%) without the catalyst. Waste effluents after

36 catalytic ozonation were thereafter reused in successive dyeing in the same process. It

37 has been validated that the waste effluent was successfully regenerated and can be

38 additionally reused twice without sacrificing fabric quality, which cannot be realized
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39 in ozonation alone. Color difference of the fabric dyed with the regenerated effluent

40 was within the acceptable tolerance, and excellent levelness and equal colorfastness

41 had also been achieved. This is probably the first study to investigate the feasibility of

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42 regenerating highly polluting dyeing effluents for reuse by catalytic ozonation with

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43 carbon aerogel materials. With novel catalysts, it could be speculated that catalytic

44 ozonation is a promising technology for in-situ regeneration of waste effluents in

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45 textile dyeing plant for reuse.

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Keywords: Textile dyeing wastewater; Effluent reuse; Catalytic ozonation; Carbon
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48 aerogel; Color quality; In-situ regeneration

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50 1 Introduction

51 Wastewater treatment is a crucial issue in textile industry, which generates a great

52 deal of polluting effluents containing significant residual dyes and dyeing auxiliaries.

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53 Considering both the great volume and effluent composition, textile dyeing plant is

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54 thought to be the most polluting one in all industry sectors (Alkaya and Demirer, 2014).

55 Among all dyeing processes, cotton is the most commonly used materials (Rosa et al.,

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56 2015). As the most critical dye class for cotton, reactive dyes are developed

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57 dramatically to fulfill all around requirements, such as easy application, wide color

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range and good colorfastness. However, one of the biggest issues to tackle is the
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59 relative low fixation rate. It is estimated that dyes lost during dyeing could be as high as

60 60% of the initial dosage (Rosa et al., 2015) and in addition dyeing of 1 kg of cotton
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61 would consume around 70-150 L of fresh water totally to form the dyeing bath

62 (Allegre et al., 2006). Consequently, at the end of dyeing procedure, significant

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63 reactive dyes that are not fixed onto the fabric are disposed with the substantial spent
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64 dyeing bath, generating enormous volume of extremely contaminative effluents.. If the

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65 effluent is discharged without appropriate treatments, adverse influence would be given

66 not only on the environment but also human health (Ozturk et al., 2015). As a

67 consequence, removal of dyes, as well as other organic or inorganic contaminants, in

68 textile dyeing effluent has been rated as the most important task in sustainable
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69 production of textile products (Wang et al., 2013b).

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71 However significant challenges still exist in removal of dyes in dyeing effluents over

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72 the past years (Tian et al., 2013). Due to low biodegradability of synthetic dyes,

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73 conventional biological method, such as activated sludge, is ineffective to degrade dyes

74 satisfactorily. It was underlined in many studies that removal of dyes by adsorption

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75 was efficient and economic (Abidi et al., 2015), but the heavy burden in replacement of

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76 adsorbents should not be ignored. Chemical oxidation, which involves dosing active

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oxidants onto wastewater, has been approved to be an effective approach. The
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78 reported oxidants or oxidation techniques include Fenton reagent (Yaman and Gunduz,

79 2015), Ultra Violet (UV) photolysis (Xing et al., 2015), ozone (Qu et al., 2015), and
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80 some combined techniques. Wherein, ozonation is thought to be a promising approach

81 due to merits of ozone, such as high oxidation capacity, no by-products from

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82 self-decomposition and easy application without additional thermal or light energy.

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83
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84 Currently the environmental policy is increasingly more restricted than ever, thus more

85 sustainable approaches are needed for cleaner production of textiles. Recent studies

86 have been extended to carry out advanced treatments of dyeing effluents for reuse by

87 suitable technologies, which demonstrate more significant and direct towards

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88 sustainability development. Previous research on applications of adsorption (Li and He,

89 2014), membrane filtration (Allegre et al., 2006), H2O2 oxidation (Li et al., 2013), UV

90 photolysis (Kusic et al., 2013), radiation (Bhuiyan et al., 2016), and combining

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91 method of persulfate oxidation and lime-soda softening (Zheng et al., 2015) showed

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92 high feasibility in regeneration of dyeing effluents for successive reuse in coloration.

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94 As growing investigations were made to utilize ozone in wastewater treatment, two

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95 pioneer studies have attempted to perform decolorization of spent effluents from

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bench-scale dyeing bath (Senthilkumar and Muthukumar, 2007) and industrial dyeing
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97 bath (Sundrarajan et al., 2007) by ozonation alone for reuse. However, since then few

98 related studies are reported focusing on ozonation for reuse, especially on catalytic
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99 ozonation with catalysts. There is little available information on catalytic ozonation for

100 regeneration of waste effluents for reuse. Comparing to ozonation alone, catalytic
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101 ozonation has great advantages. It has been long recognized during ozonation
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102 catalysts are capable to promote oxidative degradation of organic contaminants and
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103 thereby improve degradation efficiency. More important, they could yield

104 mineralization, during which organics converts into inorganics completely.

105 Consequently over the past decades numerous attentions are paid to develop efficient

106 catalysts to improve degradation efficiency and strengthen mineralization during

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107 ozonation. Materials which have been prepared as ozonation catalysts are mainly

108 transition metaloxides (Zhao et al., 2014) or its hybrids (Li et al., 2015) in different

109 forms, shapes or sizes. Unfortunately these significant outcomes have rarely been

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110 adopted in wastewater regeneration for reuse, almost all the attempts have overlooked

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111 the significance of catalytic ozonation in wastewater regeneration and reuse.

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113 Recently a novel material, carbon aerogel (CA), has been developed for several

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114 applications due to its unique properties originating from excellent three-dimensional

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continuous porous structure (Yin et al., 2014). It has been used mostly for super
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116 capacitors (Liu et al., 2015) and biosensors (Peng et al., 2015), and also has also been

117 adopted in wastewater treatment, such as catalysts for dye degradation via catalytic
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118 ozonation (Park et al., 2013) and photocatalysis (Lin and Chang, 2014), electrodes for

119 dye electrolysis (Wu et al., 2008b), and absorbents for color removal (Wu et al., 2012).
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120 These attempts by other researchers encourage authors to pursue exploration of CA

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121 materials in wastewater regeneration by catalytic ozonation. With this in mind, the
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122 primary purpose of the present study is to evaluate the reusability of textile dyeing

123 effluents which treated by catalytic ozonation in the presence of CA based catalysts.

124 The catalysts used were mesoporous carbon aerogel (MCA) and MCA supported

125 cobalt oxide nanoparticles (Co3O4/MCA) prepared in laboratory. Their catalytic

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126 performance was evaluated by decolorization and COD removal during catalytic

127 ozonation. C.I. Reactive Blue 19 was selected as the target dye for degradation due to

128 its frequent application in reactive dyeing. Dyeing effluents for catalytic ozonation

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129 were collected from the first/initial spent dyeing bath (known as the exhaustion &

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130 fixation bath), which is highly contaminated and full of residual hydrolyzed dyes, alkali

131 and electrolyte. Fabrics from the dyeing with fresh water (fresh dyeing) and the

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132 treated/regenerated effluent (reuse dyeing) were compared, in terms of color

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133 difference, color fastness and color levelness, to assess the reusability of treated

134 effluents.
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136 On the basis of literature surveys, this is probably the first attempt to regenerate waste
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137 dyeing effluents by catalytic ozonation with MCA materials for effluents reuse. With

138 the present study, it is expected to provide the feasibility assessment of reusing highly
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139 polluting dyeing effluents in successive dyeing, and simultaneously strengthen the
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140 understanding on MCA catalysts in catalytic ozonation for regeneration of waste

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141 effluents.

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143 2. Experimental

144 2.1 Reagents and Materials

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145 Cotton fabrics for dyeing (190 g/m2) were purchased from Seven Seas Knitting &

146 Dyeing Woks Ltd, China. Prior to dyeing, fabrics were firstly treated in a bath,

147 containing 0.5 g/L sodium dodecyl sulfate (SDS) and 2.0 g/L Na2CO3, at 95 oC for

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148 30 min, and then rinsed with cold water thoroughly. After naturally dried at ambient

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149 temperature, fabrics are ready for dyeing. C.I. Reactive Blue 19 (RB19) was purchased

150 from Zhejiang Longsheng Group Co., Ltd., China, and used without further

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151 purification. Its molecular structure and UV-vis adsorption spectra are illustrated in Fig.

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152 1.

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154
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155 Fig. 1 Basic information of C.I. Reactive Blue 19

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157 Other chemicals, such as formaldehyde, resorcinol, hexadecyl trimethyl ammonium

158 bromide, cobalt (II) nitrate hexahydrate, are of analytical grades and commercially

159 available.
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160

161 2.2 Preparation of catalysts

162 The entire fabrication procedure has been described in our previous work (Hu et al.,

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163 2016). Specifically, MCA was synthesized via the sol-gel method and MCA supported

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164 cobalt oxide nanoparticles (Co3O4/MCA) was prepared by the impregnation approach.

165 During impregnation, MCA granules was immersed into 0.2 mol/L Co(NO3)2 aqueous

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166 solution for loading with Co3O4 precursor. The loading percentage of Co3O4 was

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167 around 4.1% which was simply determined by thermal gravity analysis (TGA).

168
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169 2.3 Experimental set-up and procedure

170 2.3.1 Dyeing procedure

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171 Bench-scale dyeing was performed on a laboratory dyeing machine (Datacolor AHIBA

172 IR™). At the beginning, at room temperature the fabric was gently immersed into the
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173 dyeing bath (fresh water) containing reactive dyes (2%, on the weight of fabric) and
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174 Na2SO4 (40 g/L) with a liquor ratio of 50:1. Subsequently temperature of the dyeing
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175 bath was gradually raised and later maintained at 60 oC for 30 min to fulfill dye

176 exhaustion. The fabric was later on taken from the dyeing vessel which carefully added

177 with Na2CO3 (10 g/L) soon (Shang, 2013). Afterwards, the fabric was re-immersed into

178 the dyeing bath which was maintained at 60 oC for another 30 min for dye fixation.
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179 Towards the end, the fabric was gently transferred from the dyeing vessel and the

180 fixation bath was carefully collected to form the highly contaminative dyeing effluent

181 for eventually catalytic ozonation. The fate of dyeing effluents is illustrated in Fig. 2.

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182

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183
184 Fig. 2 Flow chart for treatment and reuse of dyeing effluents
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186 The fabric from fixation bath was then rinsed for one warm bath (50 oC), followed by

187 soaping with 0.5 g/L SDS at 95 oC for 15 min. One additional warm rinsing was

188 conducted for thorough removal of the loose color on the fabric. All rinsing and

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189 soaping baths were prepared with a liquid ratio of 50:1. The fabric was finally air dried

190 for later on evaluation of color quality. The entire dyeing process can be observed in

191 Fig. 3.

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192

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193
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194 Fig. 3 Process curve for cotton dyeing with fresh water

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196 2.3.2 Catalytic ozonation of dyeing effluents

197 Prior to ozonation, the effluent filtered through filtration paper (0.45 µm) to remove
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198 fiber tows for better utilization of ozone. Catalytic ozonation was performed in a
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199 1000 mL glass reactor (Hu et al., 2016), in which the 750 mL dyeing effluent was
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200 continuously bubbled by an ozone and oxygen gas mixture through a gas diffuser

201 which allocates at the reactor bottom. Ozone gas in the gas mixture is produced by a

202 medical ozone generator (Medozons BM-02, Russia) which was fed with industrial

203 oxygen with a purity of 99.9%. The off-gas containing residual ozone is washed by KI
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204 solution. After each predetermined time intervals in ozonation, 3 mL of effluent sample

205 was carefully transferred out and slowly filtered through membrane filter (Millipore,

206 0.45 µm) to remove the trace catalyst from the liquid thoroughly. The filtrated liquid

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207 was then used for color and COD determination. To reduce experimental error, each

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208 independent measurement is performed triply, and the average value is adopted. At the

209 end, the treated effluent in the reactor was completely transferred out and carefully

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210 filtrated again before reuse in dyeing afterwards.

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2.3.3 Reuse of dyeing effluents in successive dyeing
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213 Prior to carrying out successive dyeing, the effluent was first neutralized with 1 mol/L

214 H2SO4 solution to avoid dye hydrolysis during reuse dyeing. The reuse dyeing
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215 procedure was principally in accordance with that in fresh dyeing as descript in

216 section 2.3.1, except the dyeing medium was changed to treated effluents and the
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217 amount of Na2SO4 was re-calculated separately. Na2SO4 concentration in reuse dyeing
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218 was determined by effluent conductivity (Rosa et al., 2015), which should be
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219 equivalent to 40 g/L of Na2SO4 in fresh dyeing. The Na2SO4 concentration as a

220 function of conductivity of its solution is shown in Fig. 4. According to the calibration

221 equation from Fig. 4, the conductivity of treated effluents was therefore corrected to

222 around 36.0 mS/cm to maintain the electrolyte effect in reuse dyeing.
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223

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225 Fig. 4 Calibration curve of Na2SO4 solution (23.3 oC)

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227 2.4 Analytical methods

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228 The structure and morphology of catalysts are investigated by SEM (Leica Stereoscan

229 440), TEM (JEOL Model JEM-2100F) and XRD (Rigaku, SmartLab) using Cu Kα
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230 radiation.

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232 The efficiency of dye degradation was measured by both decolonization and COD
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233 removal. Decolonization is determined on a UV-vis spectrophotometer (Perkin-Elmer,

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234 Lambda 18) by evaluating the decrease of absorbance at the wavelength of 595 nm.

235 The decolorization percentage is calculated by using Eq. (1):

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237 Decolorization (%) = (A0-At)/A0 x 100 (1)

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238 Where A0 is the initial absorbance of the dyeing effluent; and

239 At is the absorbance of the dyeing effluent after a specific time of ozonation.

240

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241 COD is determined in accordance with the Hach Method 8000: Oxygen Demand,

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242 Chemical (Zhao et al., 2015). COD removal is calculated by using Eq. (2).

243

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244 COD removal (%) = (COD0-CODt)/COD0 x 100 (2)

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245 Where COD0 is the initial COD of the dyeing effluent; and

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CODt is COD of the dyeing effluent after a specific time of ozonation.
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248 Color quality of fabrics dyed from reuse dyeing is compared with those from fresh
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249 dyeing. The CIELab color system (Gundogan and Eren, 2014) is adopted to evaluate

250 lightness (L*), chromaticity (a* and b*) and color difference (∆Ecmc(2:1)) on a
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251 spectrophotometer (Macbeth Color-Eye 7000A) in accordance with a testing standard

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252 (AATCC, 2009). AATCC Test Method 61 and AATCC Test Method 8 are used to
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253 determine colorfastness to laundering and crocking.

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255 3 Results and Discussion

256 3.1 Characteristic of catalyst

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257 XRD patterns of MCA and Co3O4/MCA are presented in Fig. 5. For both of curves,

258 broad peaks at around 2θ=23° could be associated to the (0 0 2) plane of amorphous

259 carbon materials (Han et al., 2015), which are similar to that of carbon nanofiber (Wang

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260 et al., 2013a). By comparing Co3O4/MCA to pure MCA, some new peaks were clearly

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261 observed. According to the JCPDS card no. 80-1541, characteristic peaks at 19.1°,

262 31.1°, 36.8°, 59.2° and 64.6° well matched up to the (1 1 1), (2 2 0), (3 1 1), (5 1 1) and

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263 (4 4 0) planes of Co3O4 in sequence (Guo et al., 2008), suggesting Co3O4 having a

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264 crystalline cubic structure (Lai et al., 2008).

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266
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267 Fig. 5 XRD pattern of MCA and Co3O4/MCA

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269 Fig. 6 shows TEM illustration of Co3O4/MCA. According to Fig. 6a and Fig. 6b, grey

270 flakes and black spots were assigned to carbon particles and Co3O4 particles, which

271 were main components of the composite. Carbon particles, ranging from 20 to 30 nm,
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272 interconnected to each other to form the three dimensional structure, and meanwhile

273 numerous mesopores were generated among the agglomerated carbon nanoparticles

274 (Wu et al., 2012). In addition, the even distribution of nano-size black spots on grey

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275 flakes demonstrates that Co3O4 nanoparticles were well-dispersed and embedded in the

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276 amorphous MCA. According to high resolution images in Fig. 6c and Fig. 6d, evident

277 spinel patterns were observed within the dark tone, suggesting Co3O4 existed as

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278 excellent nanocrystals, which was in a good agreement with the evidence from Fig. 5.

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279
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280 Fig. 6 TEM images of Co3O4/MCA

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282 On the basis of Fig. 6a, the diameter distribution of total 323 Co3O4 nanoparticles was

283 statically analyzed and the result can be found in Fig. 7. It is apparently nanoparticle

284 diameter, which was 4.86 nm averagely, was mainly from 2 to 8 nm. The particle sizes
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285 of almost 50% of all nanoparticles were rather close to 4 nm, implying that the size

286 distribution was of excellent monodispersity.

287

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289 Fig. 7 Size
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distribution of Co3O4 over MCA
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291 Fig. 8a and Fig. 8b show the SEM images of MCA in different scales. The rough
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292 surface was evidently observed, which predominantly stemmed from agglomerated

293 carbon particles. This evidence was parallel to TEM patterns in Fig. 6a and Fig. 6b.
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294 The surface morphology of Co3O4/MCA is illustrated in Fig. 8c. It is hardly to observe
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295 clearly Co3O4 nanoparticles. This could be explained that the sizes of the nanoparticles
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296 were too small to be noticed in the current SEM resolution. This is thought to be an

297 additional evidence to prove the particles were of nanoscale (Han et al., 2015). On the

298 basis of characterization results mentioned above, the schematic representation of

299 Co3O4/MCA surface/interface is inferred in Fig. 8d. Cubic Co3O4 nanoparticles are
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300 speculated to grow evenly on the surface/interface of MCA, which is consisted of

301 agglomerated carbon particles.

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304 Fig. 8 SEM images of MCA (a & b) & Co3O4/MCA (c),

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305 and schematic representation of Co3O4/MCA (d)

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307 3.2 Catalytic ozonation of dyeing effluents

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308 In order to evaluate the potential of MCA materials in promoting ozonation of dyeing

309 effluents, three ozonation essays, single ozonation and catalytic ozonation in the

310 presence of MCA and Co3O4/MCA, were performed and compared with respect to

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311 decolorization, COD removal, pH and conductivity. Unless further stated, essays were

312 performed under following conditions: T= 24 oC; ozone dosage= 2.5 mg/min; catalyst

313 amount= 3 g.

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315 3.2.1 Decolorization of dyeing effluents

316 Decolorization is critical in reuse dyeing, as color quality could not be guaranteed if

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317 color removal was not implemented. Residual color in reused dyeing bath probably

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318 influences the followed dyeing, in terms of color tones, color depth and color fastness.

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In the current study the intention was to determine decolorization behavior of effluents
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320 by ozonation with or without catalysts, towards evaluation of catalytic performance in

321 color removal. It is evident from the results that in cases involving ozonation,
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322 decolorization percentage was rapidly enhanced with time (see Fig. 9) on the whole. In

323 addition, there was a sudden rise at the first beginning regardless of the presence of
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324 catalysts or not. Afterwards the increasing tendency leveled off at 5 min and no
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325 substantial improvements were observed.

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326

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327
328 Fig. 9 Decolorization of dyeing effluent by catalytic ozonation

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329

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330 However, exact situations in these cases were not fairly the same. For example, in two

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catalytic ozonation, before reaching to completed decolorization, color removal rates
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332 were substantially larger than that in ozonation alone. This could be inferred that the

333 presence of catalysts, either MCA or Co3O4/MCA, could increase decolorization

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334 comparing to ozonation alone. Previously, it has been reported that in some

335 circumstances the strengthened color removal stemmed from physical adoption of dyes
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336 by catalysts (Lin and Chang, 2014). Nevertheless, when considering the reference
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337 process which was only provided with oxygen, marginal decolorization percentage (as
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338 low as 3%, see Fig. 9) was observed. This goes against the evidence reported in a study

339 (Wu et al., 2012), in which MCA displayed undeniable adsorption capacity to C.I. Basic

340 Yellow 87. The contradictory could be interpreted as the target dye used in the previous

341 study was much smaller (molecular weight: 337.4 g/mol) than RB19 (molecular weight:
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342 626.5 g/mol). Thus in the present study dye adsorption was not as noticeable as that for

343 C.I. Basic Yellow 87. This implies that in this study color removal by physical

344 adsorption was almost negligible according to Fig. 9. The improved efficiency

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345 presumably arised from chemical oxidation induced by catalytic ozonation.

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346

347 It has been suggested that porous carbon materials could play important roles, besides

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348 adsorption, in catalytic ozonation in improving degradation efficiency (Wu et al.,

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349 2015). The most acceptable mechanism is porous carbon could enhance mass transfer

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of ozone into aqueous phase, and simultaneously promote decomposition of ozone to
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351 generate reactive species which may have even higher oxidation capacity than ozone

352 itself (Liu et al., 2012). Because decolorization of dye is the consequence of oxidative
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353 cleavage of chromophoric group (mono azo group, –N=N–, in this case) within dye

354 molecules (Wu et al., 2008a), the generated reactive species are likely to accelerate
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355 cleavage of –N=N– group and the relevant decolorization percentage is therefore
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356 higher. As total decolorization was almost achieved after the beginning 5 min, the
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357 advantage of catalysts in decolorization was believed to be fully shown only at the very

358 short start.

359

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360
361 Fig. 10 Dyeing effluents after catalytic ozonation

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362

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363 As discussed previously decolorization almost reached 99% after the first 5 min, in the

364 case of ozonation with MCA. Further supplying of ozone in the reactor was unlikely to

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account for additional color removal. Nevertheless, when carefully inspect the

366 appearance of effluents during catalytic ozonation visually, shades of these treated
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367 effluents were considerably distinct. Fig. 10 corresponds to the visible image of waste
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368 effluents after catalytic ozonation with MCA for varied time. As can be observed in
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369 Fig. 10, the shade of color for the effluent without ozonation (0 min) was dark navy to
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370 black, being the deepest among four samples. After 5 min catalytic ozonation, the

371 effluent was strikingly converted into transparent but with dark yellowish color.
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372 Continuously aeration of the effluent with ozone contributed to further reduction of
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373 color depth. After total 30-min catalytic ozonation, the yellowish color was appreciably

374 lightened and was close to fresh water in appearance. These contradict evidences of

375 color removal mainly originated from the instrumental method used in the color

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376 detection. In decolorization determination, the absorbance of the effluent obtained from

377 the UV-vis spectrophotometer is accompanied with the concentration of dyes. In this

378 case, absorbance used for calculation of decolorization is exclusively recorded at the

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379 wave length of 595 nm, where RB19 has the maximum absorbance (see Fig. 1). Thus

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380 99% decolorization only suggests that almost all dyes having complete chromophoric

381 group(s) were decomposed, rather than all coloring matters. For example, by-products

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382 from dye degradation may have no or little absorbance at the wave length,

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383 λmax= 595 nm, but they possibly have absorbance elsewhere and may display certain

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color. It could be speculated by-products yielded the yellowish shade of the effluent
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385 which has been almost 100% decolorized according to UV-vis absorbance. The fact

386 that increasingly paler shade of the effluent with ozonation time points to the likelihood
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387 that by-products were gradually degraded by catalytic ozonation as reaction proceeded.

388 The inconsistent between observed yellowish shade and 100% decolorization of the
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389 effluent may imply that 5-min ozonation seemed not adequate to guarantee the treated
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390 effluent could be regenerated for reused.

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391

392 3.2.2 COD removal in catalytic ozonation

393 Decolorization is only one of the objectives in catalytic ozonation for wastewater

394 treatment. The more important aspect is to understand the capability of catalytic
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395 ozonation in degradation of organic pollutes towards total mineralization. For the sake

396 of evaluation of catalysts in promoting mineralization, chemical oxygen demand (COD)

397 was assessed to quantitatively describe the organic contaminants remaining in the

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398 solution, probably including residual dyes, dye intermediates from dye decomposition,

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399 and other by-products from advanced oxidation of dye/intermediates. This is because

400 COD measures the overall organic substances that can be oxidized chemically in

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401 solution (Vittenet et al., 2015).

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402
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403
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404 Fig. 11 COD removal of dyeing effluents by catalytic ozonation

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405
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406 As shown in Fig. 11, unlike color removal, COD removal rose steadily rather than

407 suddenly on each occasion, suggesting COD removal is much harder than

408 decolorization. This could be attributed to the fact that decolorization only involves

409 primary oxidation stage, corresponding to cleavage of azo group –N=N– in this study,
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410 which is much easier to implemented. 100% decolorization may only yield slight

411 COD reduction especially when the dye molecule is large. Considerable COD

412 reduction may require more complicated multistage oxidative reactions. Fig. 11 also

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413 demonstrates that the catalyst MCA strikingly enhanced the COD reduction efficiency

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414 by 20% on the whole, comparing to ozonation alone (approx. 50%). Besides the

415 contribution from adsorption (approx. 2.6%), MCA could reasonably improve COD

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416 reduction, implying dye degradation was promoted via chemical oxidation by ozone

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417 in the aid of MCA. The most widely known reason for such improvement is the

418
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presence of carbon material imitates the decomposition of ozone into hydroxyl
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419 radicals (HO•) (Oulton et al., 2015), of which the oxidation capacity is even greater

420 than ozone. It is also worth noting that process involving catalyst Co3O4/MCA could
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421 be ranked as the most efficient treatment, in which 30-min ozonation enabled around

422 80% of COD to be removed. This could be explained that both multivalence oxidation
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423 states of Co3O4 strengthened interfacial transfer of electrons, which plays critical roles
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424 in oxidation (Hu et al., 2008), resulting in improved catalytic activity of the catalyst.
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425

426 3.2.3 pH and conductivity changes

427 pH control is important in textile dyeing, especially in reactive dyeing. Alkalinity

428 should be maintained appropriately to certain extent to assist dye fixation onto fabric
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429 (Shang, 2013). Thus at the end of reactive dyeing, the first dyeing bath is generally

430 alkaline. As it has been found that catalytic activity of MCA materials were greater in

431 alkaline condition (Hu et al., 2016), the waste effluent was not neutralized or acidized

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432 before ozonation. It has been reported ozonation of organic compounds led to the

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433 generation of acidic by-products (Ikhlaq et al., 2014), causing pH fall in the solution.

434 However, pH hardly varied through the entire treatment and little differences were

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435 noticed among the three essays according to Fig. 12.

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436
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437
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438 Fig. 12 pH evolution during catalytic ozonation

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439
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440 In a similar study (Colindres et al., 2010), in which C.I. Reactive Black 5 was adopted

441 as the target degradation dye by ozonation, pH declined radically to acidic range after

442 ozonation. This dissimilar evolution trend of pH may attribute to the significantly

443 excess amount of Na2CO3 (initial concentration was 10 g/L) presented in the effluent,
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444 which likely depleted newly generated acidic by-products and sustained the effluent

445 being alkaline. To proof this conjecture, a parallel experiment, in which the effluents

446 for ozonation were neutralized first, the results are shown in Fig. 13.

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447

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448
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449 Fig. 13 pH evolution during catalytic ozonation (effluent after neutralization)

450
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451 According to Fig. 13, pH declined with treatment time before the first 20 min, which

452 could be attributed to the accumulation of acidic byproducts as mentioned earlier.

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453 However, the acidity of the effluent treated by ozonation alone was moderately lower
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454 than the two catalytic processes. This could be explained that in ozonation alone,
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455 molecular ozone which was oxidatively selective could not mineralize refractory

456 acidic byproducts, such as oxalic acid and oxamic acid (Faria et al., 2008), to

457 inorganics. In addition, although the hydroxyl radicals, which could be generated from

458 spontaneous decomposition of molecular ozone, were oxidatively non-selective and

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459 therefore were capable to mineralize the refractory acids, acid removal in the effluent

460 still hardly happened. This was because in the acidic condition, the spontaneous

461 decomposition of molecular ozone was extraordinarily weak. Thus, these acids

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462 accumulated in the effluents gradually causing pH decline. While in catalytic

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463 ozonation, hydroxyl radicals could be produced from catalytic decomposition of

464 molecular ozone in the presence of catalysts, in addition to spontaneous

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465 decomposition. Consequently the accumulation of refractory acids in the effluents

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466 subjected to catalytic ozonation was less severe than that in ozonation alone. As a

467
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result, the pH of effluents reclaimed by catalytic ozonation was higher than that of the
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468 effluent from ozonation alone.

469
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470 After 30-min ozonation, the final pH was perceived to rise slightly comparing to the

471 pH at 20 min in the two catalytic ozonation. This may be explained that when
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472 approaching the final mineralization of dye in catalytic ozonation. The degradation of
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473 refectory acids was strengthened, which led to the decreased solution acidity. By
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474 contrast in ozonation without catalyst, the degradation of refractory acid only depended

475 on the hydroxyl radicals generated from the spontaneous decomposition of molecular

476 ozone. Thus the final pH did not rise up as that in catalytic ozonation.

477
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478 After the 30-min treatment for comparison, 100 mL of effluents from the three

479 different ozonation processes were added with 1 g of Na2CO3, which was equivalent

480 to the dosage in real dyeing process. It was observed the pH raised to around 10.7 no

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481 matter which process applied, suggesting the amount of Na2CO3 was substantially

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482 excess to acidic byproducts in effluents. Therefore regardless of the fact the amount of

483 acidic byproducts generated during ozonation processes was slightly different, the

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484 overall pH of effluents was almost identical.

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485

486
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Conductivity is another essential target to monitor in addition to pH. As stated before,
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487 conductivity has been adopted to measure the electrolyte effect, which can be ranked

488 as one of the most critical parameters in process control of reactive dyeing, of the
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489 effluent in this study. This is because the salt is usually added into reactive dyeing bath

490 to overcome repulsive forces between the fabric and ionized dye molecules, so as to
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491 improve the substantivity of the fabric to dyes and eventually improve the dye uptake
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492 (Shang, 2013). In the fresh dyeing, electrolyte strength is generally sustained by
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493 dosing fixed amount of Na2SO4 or NaCl into dyeing bath. Nevertheless, in a reuse

494 dyeing simple dosing of fixed salt amount is not ideal to process control, because the

495 existence of significant amount of residual salt in the effluent has to be considered

496 particularly. In modem wastewater reuse, electrolytes in aqueous solution are

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497 generally removed by reverse osmosis (Bunani et al., 2015). But in textile dyeing with

498 reactive dye, salt presents in effluent can be recycled and the removal by reverse

499 osmosis tends to be not extremely necessary. In a recently published research (Rosa et

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500 al., 2015), treated effluent was not desalinated but supplemented with additional salt

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501 to the required degree which was equivalent to that in fresh dyeing, on account of the

502 dyeing effluent to be reused in that case had been diluted.

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503

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504
505 Fig. 14 Conductivity evolution during catalytic ozonation
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506 The objective on monitoring the conductivity was to add understanding on catalytic
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507 ozonation, and determine the concentration of salt in effluents as well. As displayed in
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508 Fig. 14, there were almost no differences observed from the beginning to the end for

509 each process or among the distinct processes. This is not in agreement with the

510 expectation that conductivity was likely to rise after ozonation (Colindres et al., 2010),

511 due to the generation and accumulation of sulfate and nitrate ions from dye denitration
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512 and desulfuration (Tehrani-Bagha et al., 2010). The unexpected evidence may

513 probably attribute to that the plenty Na2SO4 and Na2CO3 presented in the effluent.

514 Under the same treatment conditions, the conductivity of the simulated waste

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515 effluents, which were in the absence of Na2SO4 and Na2CO3 but possessed equivalent

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516 dye amount, was increased from 193 µS/cm to 308 µS/cm, 395 µS/cm, 446 µS/cm, for

517 ozonation alone, ozonation with MCA and ozonation with Co3O4/MCA. Despite the

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518 fact that the simulated effluents were not exactly as same as the real waste effluents

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519 from dyeing bath, it pointed to that the ions from dyes (completed dye molecules and

520
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byproducts from dye degradation) hardly contributed to the overall conductivity of
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521 effluents. Consequently, conductivity differences, which were no larger than 0.5

522 mS/cm, between the processes could be neglected if considering the overall
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523 conductivity of the effluents was as high as 41 mS/cm.

524
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525 3.3 Color quality evaluation

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526 3.3.1 Color reproducibility

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527 As mentioned earlier, recent objective on chemical oxidation is not only limited to

528 wastewater treatment. Attempts have been made towards reuse of the treated

529 wastewater for certain purposes. Thus understanding removal of color and COD, as

530 well as the evolution of pH and conductivity, are not the only intensions in the current
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531 study. More importantly it is necessary to ascertain the feasibility of catalytic

532 ozonation in regeneration of waste dyeing effluents for reuse. therefore, effluents after

533 30-min treatments were collected for dyeing of cotton to exam the reuse possibility.

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534 The other samples treated less than 30 min were not selected, as they still displayed

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535 substantial visible yellowish color (see Fig. 10) though 100% decolorization (see Fig.

536 9) has been achieved according to instrumental assessment by UV-vis

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537 spectrophotometer. CIELAB system is used to evaluate the color quality of fabrics

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538 dyed with treated effluents, including lightness value L*, chromaticity a* and b*, and

539
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most importantly color difference ∆Ecmc(2:1).
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540

541 Table 1 Color quality of fabrics dyed with fresh water and treated effluents
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L* a* b*
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∆Ecmc(2:1)

Reference 46.305 -2.254 -36.674 /

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O3 47.921 -3.382 -34.785 1.54

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O3 + MCA 46.681 -2.879 -35.824 0.68

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O3 + Co3O4/MCA 46.509 -2.399 -36.423 0.19

542

543 As summarized in Table 1, lightness of fabrics from reuse dyeing (fabric-R) was

544 relatively greater than the control fabric from fresh dyeing (fabric-F), indicating that
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545 fabric-R was slightly lighter in shade than fabric-F. The chromaticity a* and b*

546 represent green-red axis value and yellow-blue axis value of the specific color located

547 in the three-dimensional CIELAB color system (Rosa et al., 2014). The greater

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548 positive a* of fabric-F listed in Table 1 implies that fabric-R was greener comparing to

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549 the reference fabric; by contrast the weaker positive b* indicates that fabric-R was not

550 as blue as fabric-F. These variations of color parameters mentioned above were mainly

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551 affected by the accumulation of by-products from dye degradation, which tended to

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552 influence the dyeing procedure, in either exhaustion or fixation stages.

553
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554 The color difference ∆Ecmc(2:1), which correlates well with visual assessment by human

555 naked eyes (AATCC, 2009), is the most significant indicator to objectively evaluate
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556 color reproducibility in general. It can be seen in Table 1, the effluent treated with

557 pure ozonation caused the fabric with the largest ∆Ecmc(2:1) corresponding to 1.54
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558 against the control fabric-F, conversely the effluent treated by catalytic ozonation with
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559 Co3O4/MCA showed the lowest ∆Ecmc(2:1), which was only 0.19. It has long been
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560 known that larger ∆Ecmc(2:1) means the color difference between two fabrics is easier to

561 perceive by human naked eyes. Thereby the evidence from Table 1 points to the

562 probability that effluents after catalytic ozonation could re-produce more similar color

563 quality. Furthermore, by comparing effluents from catalytic ozonation processes with
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564 MCA and Co3O4/MCA, the later process could better regenerate effluents to obtain

565 closer color performance than the former one. This could be associated with the result

566 illustrated in Fig. 11, from which catalytic ozonation with Co3O4/MCA displayed the

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567 highest efficiency in contaminant removal. To sum up, it could be inferred that, in the

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568 aid of high efficient catalysts based on MCA, catalytic ozonation extensively

569 eliminated by-products in effluent, which may affect dyeing procedure, by appreciable

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570 mineralization effect.

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571

572
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In general ∆Ecmc(2:1) no more than 1.0 is thought to be acceptable in evaluation of
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573 color reproducibility (Li and He, 2014), as human naked eyes could rarely detect the

574 color variation within this limit. On this ground, it is conceivable that pure ozonation
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575 in the present conditions was not adequate to effectively regenerate the effluent to

576 fulfill color reproduction in reuse dyeing. However, it can be validated that catalytic
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577 ozonation in same conditions offered waste effluents with reusability, without
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578 sacrificing color performance beyond acceptable level. Furthermore, colorfastness

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579 evaluation (see Table 2) also indicated that the fastness of fabric-R was almost

580 identical to the control one fabric-F.

581

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582 Table 2 Colorfastness of fabric-R and fabric-F

Laundering Crocking

Staining on cotton Color change Dry Wet

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Reference 4.5 5 5 4.5

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O3 4.5 5 5 4

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O3 + MCA 4.5 5 5 4.5

O3 + Co3O4/MCA 4.5 5 5 4.5

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583

584
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This practically valuable innovation demonstrates the feasibility of regeneration of
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585 highly contaminant effluent by simple catalytic ozonation for subsequent reuse in

586 dyeing. Although some studies have been conducted on decolorization by ozonation
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587 alone (Colindres et al., 2010), or mineralization of textile dyeing effluents for reuse by

588 Fenton reaction (Li et al., 2013) or H2O2 promoted photocatalysis (Rosa et al., 2015),
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589 the target effluents, which have been diluted by other colorless effluents, were of very
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590 low concentration of residual hydrolyzed dyes, electrolyte, and/or alkali, comparing to
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591 the effluent from the first spent dyeing bath. However, in this study the high

592 contaminative effluent from the first spent dyeing bath was selected, rather than those

593 diluted by rinsing or soaping bath from wastewater treatment plants. This is because

594 regeneration of highly polluting effluents is much more significant. Firstly, there is no
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595 need to induce effluents to wastewater treatment plant for treatment and pump back for

596 reuse after treatment. The effluents can be in-situ regenerated and renovated by

597 ozonation devices in dyeing plant, which shortens recycling time and meanwhile

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598 downsize the scale of recycling system. In addition, the treatment of initial waste

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599 effluents could lead to saving of electrolyte. As stated earlier, reactive dyeing consumes

600 a large quantity of salt to assist dyeing exhaustion. The effluent with high concentration

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601 of salt makes it unnecessary to add extra salt in successive reuse dyeing, provided that it

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602 has been successful regenerated. The salt can be recycled along with the reuse of

603
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regenerated effluents, until the effluent cannot be further used for the consideration of
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604 quality control. By contrast, once the initial dyeing effluent was induced to wastewater

605 treatment plants, it is inevitably diluted by other effluents. Thus additional quantity of
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606 salt must be dosed into the regenerated dyeing effluents to compensate the decrease of

607 electrolyte strength. It is believed that catalytic ozonation with MCA based catalysts
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608 could save both freshwater and salt by reuse of highly polluted waste effluents, so as
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609 to relief some burdens in wastewater treatment. Simultaneously the valuable

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610 innovation offers a new sight in in-situ regeneration of waste effluents to simplify the

611 reuse process.

612

613 3.3.2 Effect of reuse cycles on color reproducibility

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614 Though catalytic ozonation in the current study has demonstrated surprising potential

615 in regeneration of waste effluents being of high pollution, the reused effluent has to be

616 discharged and disposed eventually for consideration of quality control. Because

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617 persist by-products from catalytic degradation of dye would gradually accumulate in

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618 the effluent and may affect dyeing quality. For the purpose of knowing the repetitive

619 utilization potential of effluents after catalytic ozonation, color differences ∆Ecmc(2:1)

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620 of fabric-R against the number of reuse was examined. The result in Fig. 15 shows that

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621 ∆Ecmc(2:1) rose with the recycle number for both of the two catalytic ozonation and the

622
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increasing tendency accelerated as recycling proceeded forward. This phenomenon is
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623 parallel to findings from previous studies (Colindres et al., 2010; Li et al., 2013).

624
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625
626 Fig. 15 CIELAB Color differences of fabric-R

627

628 In addition, color similarity obtained from the effluent treated by catalytic ozonation
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629 with Co3O4/MCA was somewhat higher than that with pure MCA. The probably

630 reason has been mentioned earlier, it corresponded to the likelihood that strengthened

631 transfer of electrons on Co3O4 interface brought about improved mineralization of

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632 by-products. On account of the tolerance of color difference is 1.0, it can be

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633 speculated from Fig. 15 that the effluent could be reused twice after catalytic

634 ozonation with Co3O4/MCA; however it could be only used one more time by

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635 catalytic ozonation with pure MCA. The reusability of effluents presented in the

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636 current study was relatively not as appreciable as those from similar studies regarding

637
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dyeing effluents reuse. There are several probabilities accounting for the difference.
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638 To begin with, effluents selected in the present study was highly contaminated from

639 the first spent dyeing bath but others are not (Colindres et al., 2010; Li et al., 2013;
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640 Rosa et al., 2015), which makes effluents much more difficult to be regenerated

641 through catalytic ozonation. In addition, the contaminant RB19 in effluent is a persist
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642 dye containing anthraquinone group (Tehrani-Bagha et al., 2010), leading to

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643 substantial difficulty in mineralization. Furthermore, one study employed extra means
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644 in reclamation of effluents such as adsorption (Li and He, 2014), producing effluents

645 being of better quality.

646

647 3.3.3 Dyeing levelness of fabric-R

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648 Dyeing levelness of fabrics dyed in exhaustion process is generally seldom concerned

649 in conventional reactive dyeing. Because the electronic repulsion between ionized

650 fabric (Cell-O-) and soluble dye (Dye-SO32-) in dyeing bath is significant, dye

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651 absorption and de-absorption by fabrics dynamically occur in the dyeing bath at the

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652 same time, leading to good evenness of dye adsorption by fabrics. However, in reuse

653 dyeing, the ingredients from dyeing bath were more complicated. Uncertain

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654 by-products from dye decomposition may influence the absorption and de-absorption

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655 procedures, contributing to affected distribution of dyes on fabric and inferior dyeing

656
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levelness in turn. Thus leveling property is essential to be considered in reuse of
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657 regenerated waste effluents.

658
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659
660 Fig. 16 Evolution of RUI during excessive reuse of dyeing effluents

661

662 Relative unlevelness index (RUI), which has been proposed and used previously
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663 (Chong et al., 1992), was adopted as an objective method to quantify the evenness

664 degree of colored fabrics. RUI of fabric dyed with the effluent treated by catalytic

665 ozonation with Co3O4/MCA is illustrated in Fig. 16. The increasing number of reuse

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666 time gave rise to enlarged RUI, suggesting inferior evenness was achieved on the

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667 dyed fabric. This observed phenomenon may ascribe to gradual accumulation of

668 retardant by-products in repeatedly reused effluents. The grades of RUI have also

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669 been illustrated in Fig. 16, from which RUI no more than 0.2 is associated with

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670 ‘excellent’ grade and by contrast RUI ranging from 0.2 to 0.5 is recognized as ‘good’

671
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grade. Therefore, it is clear that the levelness of fabrics dyed from the first two cycles
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672 of reuse dyeing was both ‘excellent’ but it declined to ‘good’ in the followed third

673 circle. This result could be related to the evolution of color difference ∆Ecmc(2:1) in
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674 successive reuse dyeing, which probably owning to the increasing accumulation of

675 degradation by-products, from little to substantial, in regenerated effluents.

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676
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677 3. Conclusions
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678 Reuse of wastewater is a new tide for environmental protection and sustainability

679 development in textile industry. Very little research has been conducted concentrating

680 on catalytic ozonation of highly polluting dyeing effluent towards reuse. Published

681 reports predominantly focused on regeneration and reuse of dyeing effluent of much
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682 lower contaminative degree by photocatalysis, Fenton reaction or ozonation alone. In

683 the present study, carbon aerogel materials were prepared and used as catalysts in

684 regeneration of effluents pursuing successive reuse through catalytic ozonation. The

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685 results suggest that catalyst materials were well prepared and played important roles

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686 in promoting catalytic degradation of residual dyes in effluents. The addition of novel

687 catalysts in catalytic ozonation enabled the waste effluent to be successfully

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688 regenerated and reused in successive dyeing without sacrificing color quality of the

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689 dyed fabrics, which could not be realized in ozonation alone without catalysts at same

690
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treatment conditions. This study is analogous to wastewater treatment & reuse, and
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691 textile coloration technology as well. It innovatively concentrates on regeneration of

692 waste effluents from the first dyeing bath and extends treatment methods to catalytic
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693 ozonation with carbon aerogel materials. To the best of the authors’ knowledge, this is

694 the first attempt to apply MCA catalysts in waste effluents regeneration and reuse.
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695 The finding could offer an essential recognition of catalytic ozonation in reuse of
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696 waste effluents, and meanwhile provide a new insight into in-situ regeneration of
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697 waste dyeing effluents in textile dyeing plant rather than remote treatment in

698 wastewater treatment plant. The research may help to develop a new alternative

699 approach for both cleaner production of textile dyeing and sustainable development of

700 textile industry, which benefits the whole industry and environment protections.
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701

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704 173 (2009), The American Association of Textile Chemists and Colorists, USA

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705 Abidi, N., Errais, E., Duplay, J., Berez, A., Jrad, A., Schaefer, G., Ghazi, M., Semhi, K.,

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707 (2015). DOI 10.1016/j.jclepro.2014.08.043.

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708 Alkaya, E., Demirer, G.N., Sustainable textile production: a case study from a woven

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710 10.1016/j.jclepro.2013.07.008.

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712 dyeing effluents, J Membrane Sci (2006). DOI 10.1016/j.memsci.2005.06.014.

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720 Levelness of Dyed Materials, J Soc Dyers Colour (1992). DOI

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726 oxamic and oxalic acids, Appl Catal B (2008). 10.1016/j.apcatb.2007.10.021.

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735 Hu, C., Xing, S.T., Qu, J.H., He, H., Catalytic ozonation of herbicide 2,4-d over cobalt

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738 Hu, E., Wu, X., Shang, S., Tao, X.-m., Jiang, S.-x., Gan, L., Catalytic ozonation of
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739 simulated textile dyeing wastewater using mesoporous carbon aerogel supported

740 copper oxide catalyst, J Clean Prod (2016). DOI 10.1016/j.jclepro.2015.06.127.

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742 organic contaminants in water on ZSM-5 zeolites, Appl Catal B (2014). DOI

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743 10.1016/j.apcatb.2014.02.010.

744 Kusic, H., Koprivanac, N., Bozic, A.L., Environmental aspects on the

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745 photodegradation of reactive triazine dyes in aqueous media, J Photoch Photobio A

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746 (2013). DOI 10.1016/j.jphotochem.2012.11.018.

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748 fabrication of Co3O4 nanorods and application to the degradation of phenol, Catal

749 Today (2008). DOI 10.1016/j.cattod.2007.10.039.

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750 Li, B., Dong, Y.C., Ding, Z.Z., Xu, Y.M., Zou, C., Renovation and Reuse of Reactive

751 Dyeing Effluent by a Novel Heterogeneous Fenton System Based on Metal Modified
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777 Park, H.W., Kim, J.K., Hong, U.G., Lee, Y.J., Song, J.H., Song, I.K., Catalytic

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809 Effective Photo-Fenton-like Catalyst for the Degradation of Anionic and Cationic Dyes
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843 Zhao, H., Dong, Y.M., Jiang, P.P., Wang, G.L., Zhang, J.J., Li, K., Feng, C.Y., An

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Highlights

Meroporous carbon aerogel catalysts have been prepared for catalytic ozonation.

Dye degradation efficiency was strikingly improved by ozonation with the

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catalyst.

Regeneration of highly polluting effluents was realized by catalytic ozonation.

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The regenerated effluent can be reused in textile dyeing without quality defection.

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