Accepted Manuscript

Green synthesis of zeolite 4A using fly ash fused with synergism of NaOH and
Na2CO3

Liyun Yang, Xiaoming Qian, Peng Yuan, Hao Bai, Takahiro Miki, Fanxu Men, Hong
Li, Tetsuya Nagasaka
PII: S0959-6526(18)33662-X
DOI: https://doi.org/10.1016/j.jclepro.2018.11.259
Reference: JCLP 15018

To appear in: Journal of Cleaner Production

Received Date: 15 June 2018

Revised Date: 17 September 2018
Accepted Date: 27 November 2018

Please cite this article as: Yang L, Qian X, Yuan P, Bai H, Miki T, Men F, Li H, Nagasaka T, Green
synthesis of zeolite 4A using fly ash fused with synergism of NaOH and Na2CO3, Journal of Cleaner
Production (2019), doi: https://doi.org/10.1016/j.jclepro.2018.11.259.

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 ACCEPTED MANUSCRIPT

1 Green synthesis of zeolite 4A using fly ash fused with synergism of

2 NaOH and Na2CO3

3 Liyun Yang1,2 *, Xiaoming Qian1, Peng Yuan1, Hao Bai1, Takahiro Miki2, Fanxu Men1, Hong Li1and
4 Tetsuya Nagasaka2
5 1 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, 100083,
6 P.R. China

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7 2 Department of Metallurgy, Graduate School of Engineering, Tohoku University, 02 Aoba-yama, Sendai
8 980-8579, Japan.

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9 Abstract

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10 A high-purity zeolite 4A was synthesized by the hydrothermal method using fly ash as the

11 raw material. The effects of sodium hydroxide (NaOH) or/and sodium carbonate (Na2CO3) on

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12 the activation of fly ash were studied, and the removal efficiency of Cu2+ in aqueous solution
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13 was also investigated for the synthesized zeolite. The formation process of the zeolite from fly

14 ash was surveyed by ex situ techniques such as X-ray diffraction (XRD), thermogravimetric
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15 analysis and differential scanning calorimetry (TG-DCS), scanning electron microscopy and

16 energy dispersive X-ray spectroscopy (SEM-EDX) and Fourier transform infrared

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17 spectroscopy (FTIR). The important influential factors of energy and water consumption were
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18 analysed by orthogonal tests, and the best conditions for green synthesis were accurately

19 determined through batch tests. The factors affecting the green synthesis of zeolite are the
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20 alkali mixture ratio, alkali melting temperatures, solid-to-liquid ratios, crystallization times

21 and crystallization temperatures. The alkali mixture ratio was indicated to be an important
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22 factor for green synthesis according to the results of the orthogonal test. Compared with the
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23 use of alkali alone, when NaOH and Na2CO3 were mixed at a mass ratio of 1:2.8, the alkali

24 melting temperature (760°C) and solid-to-liquid ratios (1:5) were both lower, the

25 crystallization time (4 h) was shorter in the zeolite synthesis process, and the relative

26 crystallinity was the highest at 75.8%. The removal rate of 100 mg/L Cu2+ solution from pH 3

27 to pH 7 by 0.18 g of zeolite synthesized for 60 min was close to 100%, and the adsorption

28 capacity was 55.5 mg/g. After the zeolite was desorbed and reused 4 times, the removal

29 efficiency of Cu2+ was maintained at 73% at a pH of 3.

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30 Keywords: Coal fly ash; zeolite 4A; NaOH and Na2CO3; the hydrothermal method.

31 1 Introduction

32 Fly ash is a by-product of coal combustion for power generation, and each ton of coal

33 produces approximately 0.15 tons of fly ash depending on its composition (Mei et al., 2016; R,

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34 2016). Coal is one of the world’s most important fossil fuels. With the development of the

world economy and the rapidly increasing energy demand, large amounts of fly ash are

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35

36 produced by power generation or industrial coal combustion. According to statistics,

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37 approximately 500 Mt fly ash is produced by coal-fired power generation in China each year

38 (Xiaotong et al., 2015). Due to the lack of adequate use, approximately 50% of fly ash is

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39 expelled through waste stacks or deposited in landfills (Izidoro et al., 2012), which not only
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40 wastes resources but also causes environmental pollution. It has been found that fly ash

41 contains a large amount of Si and Al, which can be used as raw materials for the synthesis of

42 high-value-added inorganic materials such as zeolites (Aldahri et al., 2016; Fukasawa et al.,
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43 2017).
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44 Fly ash has a half-empty or solid spherical structure composed of a glass substrate with

45 inner and outer shells, where Si and Al exist in the amorphous phase and α-quartz and mullite
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46 comprise the crystal phase (Tanaka et al., 2006). Si and Al are presence in high proportions in

47 the α-quartz and mullite crystals phases and are difficult to dissolve in water, which prevents
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48 the release of active Si and Al in solution (Marion et al., 2010). On the other hand, dissolution

49 of the Si and Al components plays a crucial role in zeolite nucleation and crystallization
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50 (Ojumu et al., 2016). Therefore, the activation of Si and Al in fly ash is one of the important
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51 links in the synthesis of zeolite from fly ash. The melting-hydrothermal synthesis is a

52 traditional and conventional method which has potential for the scale-up production for the

53 development of zeolite from fly ash (Hong et al., 2017). This traditional method mainly uses

54 alkaline activators to convert SiO2 and Al2O3 into zeolite crystalline phases under

55 hydrothermal conditions (high temperature and water saturation pressure) (Holler and

56 Wirsching, 1985). Alkaline activators can weaken the binding between SiO2 and Al2O3 in the

57 α-quartz and mullite crystal phases of fly ash, damage the SiO2 and Al2O3 bond structure,
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58 produce a large number of faults and free ends at the break point, cause particle movement,

59 induce a thermodynamically unstable state, and form soluble amorphous Si, Al and

60 hydroxysodalite (Cheng, 2006; Ke Ming et al., 2007; Wang et al., 2013). It is known that Na+

61 has a good promotion effect on the nucleation and crystallization of the zeolite synthesis

62 process (Murayama et al., 2002). Therefore, researchers generally use molten NaOH or

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63 Na2CO3 to treat fly ash, in which the alkaline component activates Si and Al to produce a

64 high-activity component (And and Shih, 1998) and Na+ participates in nucleation and

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65 crystallization.

66 And and Shih (1998) found that the quartz and mullite crystalline phases of fly ash are

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67 gradually converted to water-soluble sodium silicate and sodium aluminate by melting with

68 NaOH at 550°C. El-Naggar et al. (2008) observed that when fly ash mixed with NaOH at the

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69 mass ratio of 1:1 and melted at 550°C, a rough porosity gradually developed on the originally
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70 smooth spheres. In additional, deeper pores were created with an increase in the alkali fusion

71 time. Their observations indicate that the quartz in the original fly ash gradually transformed
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72 into sodium silicate. In previous studies, it was noted that OH- in NaOH has a high alkalinity.

73 Thus, it activates the inert Si and Al in fly ash. Na2CO3 is not as basic as NaOH, but, under the
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74 same alkalinity conditions, Na2CO3 provides a high content of Na+. Murayama et al. (2002)
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75 successfully synthesized zeolite P, which has a relatively high crystallinity, from fly ash

76 treated with Na2CO3. For the pretreatment and nucleation of fly ash, Na2CO3 has an optimal

alkalinity and a high content of Na+, which should have beneficial effects on the zeolite
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77

78 nucleation process (Murayama et al., 2002). Comparing NaOH to Na2CO3 at the same

alkalinity, NaOH provides less Na+, while Na2CO3 provides excess Na+. Therefore, NaOH and
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80 Na2CO3 mixed at a certain percentage to treat fly ash can provide the appropriate amount of
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81 OH- and Na+ and may lead to the highest activation of Si and Al in the fly ash to achieve the

82 highest degree of crystallization, as well as low energy and water consumption, which is

83 probably useful in realizing a green synthesis. However, related studies have not been yet

84 conducted in this area.

85 Due to this background, our study activated fly ash using NaOH, Na2CO3, and a

86 combination of NaOH and Na2CO3 to synthesize zeolite 4A with orthogonal and batch tests.

87 The important influential factors of energy and water consumption were analysed by the
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88 orthogonal tests and the optimal conditions for green synthesis were determined by batch

89 experiments. The efficiency and reuse times of synthetic zeolite 4A for the adsorption of Cu2+

90 in aqueous solution were also investigated.

91 2 Materials and methods

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92 2.1 Materials and equipment

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93 The fly ash used in the experiments was obtained from the Datang International

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94 coal-fired power plant of Erdos City in China. To reduce the cost of actual production in the

95 future, diatomite, obtained from Fengsheng mining in Chin, was used as a silicon source

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96 instead of a pure chemical reagent. Analytical-grade NaOH, Na2CO3 and Cu(NO3)2 were

97 obtained from the Beijing chemical plant of China. The purity levels of the analytical grade
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98 NaOH, Na2CO3 and Cu(NO3)2 are 96%, 99.8% and 99.5% respectively. Among them, NaOH

99 and Na2CO3 were used to synthesize zeolite, and Cu(NO3)2 was used for the adsorption
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100 experiment. Deionized water with a conductivity of 1.5 µs/cm and total organic carbon of
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101 0.48 mg/L was used in the experiments. The samples were oven-dried at 105°C for 12 h to

102 remove any adsorbed moisture prior to analysis. The identification and quantification of the
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103 mineral phases present in the raw materials and zeolite products were carried out using

104 qualitative X-ray diffraction (XRD, Japan Science Company). The samples were step-scanned
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105 over a range of 5°< 2θ < 90° at intervals of 0.07° and measured for 0.5 s per step. Crystalline

106 mineral phases present in the samples were identified with the help of Jade 5.0 software by
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107 comparing the spectra with the standard line patterns from the powder diffraction file
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108 database supplied by the International Centre for Diffraction Data. The high-temperature

109 reaction product from the fly ash mixture was examined by means of thermal gravity analysis

110 using a distributed control system (TG-DCS, Japan Electronics Corporation). The

111 morphology and elemental content of both the raw materials and solid products were

112 examined by scanning electron microscopy and energy dispersive X-ray spectroscopy

113 (SEM-EDX, Japan Electronics Corporation). Compositional analysis of both the raw

114 materials and products was carried out using X-ray fluorescence spectrometry (XRF,
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115 Shimadzu Corporation), and the functional groups present in the fly ash and the solid products

116 were identified using Fourier transform infrared spectroscopy (FTIR, Nicolet Company).

117 Physical and chemical adsorption analysis of the products was carried out using the

118 Brunauer-Emmett and Teller equation (BET) and temperature programmed desorption (TPD,

119 Micromeritics Instrument Corporation). The metal ion concentration in the liquid samples was

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120 determined using a flame atomic absorption spectrophotometer (FAAS, Shimadzu

121 Corporation).

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122 2.2 Methods

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123 2.2.1 Synthesis of zeolite 4A

124

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The hydrothermal synthesis experimental procedure of fly ash alkali melted separately
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125 with NaOH, Na2CO3, NaOH and Na2CO3 was performed as follows. The fly ash was ground

126 through a ball mill and passed through a 325-mesh sieve to obtain a particle size of less than
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127 45 µm; then, it was mixed with diatomite and NaOH/Na2CO3/NaOH and Na2CO3. After

128 mixing, the fly ash was packed in the crucible and placed in a box sintering furnace for
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129 high-temperature calcination, and a constant temperature was maintained for a certain period
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130 of time. After cooling in the furnace, the calcined product was removed, stirred with

131 deionized water at room temperature for 2 h and aged for 4 h. Then, the product was
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132 transferred into a PTFE-lined stainless-steel reactor and placed in a drying oven for a certain

133 period of time. Then, after filtration, washing, and drying at 80°C, the zeolite 4A product was
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134 obtained. The detailed experimental process is shown in Fig. 1.

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135
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136 Fig. 1. Process for the synthesis of zeolite 4A by the hydrothermal method. A: Alkali fusion

137 hydrothermal synthesis using only NaOH, B: Alkali fusion hydrothermal synthesis using only
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138 Na2CO3, C: Alkali fusion hydrothermal synthesis using NaOH and Na2CO3.

139 The characteristic diffraction peaks, Im of the zeolite 4A were determined from the X-ray
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140 diffraction pattern of standard commercial 4A molecular sieves with known crystallinity
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141 (Rayalu et al., 2005). The relative crystallinity of the sample is

142 Pi = Ii / Im × Pm
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143 where Pi and Pm are the relative crystallinity of the sample zeolite and the crystallinity of the

144 commercial-grade zeolite, respectively. Ii and Im are the peak intensities of the characteristic
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145 diffraction peaks of the zeolite and the commercial-grade zeolite 4A at 7.2°, respectively.
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146 2.2.2 Orthogonal tests and batch experiments

147 According to the synthetic method described above (2.2.1), the orthogonal test was

148 carried out to determine the important influence factors for green synthesis. In the process of

149 zeolite 4A synthesis, alkali melting temperature, alkali mixture ratio, solid-liquid ratio,

150 crystallization time and crystallization temperature are the main parameters, in which, alkali

151 melting temperature, crystallization time and crystallization temperature determine energy

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152 consumption and solid-liquid ratio influences water consumption. According to the former

153 literature (Cardoso et al., 2015; Hu et al., 2017; K. S. Hui and C. Y. Chao et al., 2005; Hui

154 and Chao, 2006; Ke-Ming and Zhu, 2007; Kim and Lee, 2009), the optimal crystallization

155 temperature is 90°C whether choosing NaOH or Na2CO3 alone as the alkali source, thus the

156 crystallization temperature was preliminarily set at 90°C in these orthogonal tests. Alkali

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157 melting temperature, alkali mixture ratio, solid-liquid ratio and crystallization time were the

158 four main factors and five levels were designed in orthogonal tests (Table 1). A total of groups

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159 of tests were carried out.

Alkali

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Alkali mixture ratio Solid-liquid Crystallization
Factors melting
ratio time
Levels temperature
(B) (C) (D)

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(A)
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1 700°C(A1) 18g Na2CO3 (B1) 1:3(C1) 2h(D1)

2 760°C(A2) 13.5g Na2CO3, 3.75g NaOH (B2) 1:5(C2) 4h(D2)

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3 800°C(A3) 9g Na2CO3, 7.5g NaOH (B3) 1:6(C3) 5h(D3)

4 840°C(A4) 4.5g Na2CO3, 11.25g NaOH (B4) 1:8(C4) 6h(D4)

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5 900°C(A5) 15g NaOH (B5) 1:10(C5) 8h(D5)

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160 Table 1 Orthogonal tests for the importance influential factors of green synthesis of zeolite

161 4A
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162 After the orthogonal tests, the values Kjm, kjm and Rj need to be calculated to determine

163 the important influential factors (Gao et al., 2016a). Kjm is the sum of the test index valus
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164 corresponding to the m (1, 2, 3, 4, 5) level of the j (A, B, C, D) factor. For example, KA1
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165 means the sum of the test index values of relative crystallinity while using the alkali melting

166 temperature of 700°C. kjm is the mean value of Kjm. Rj is the range of the j factor. For example,

167 RA corresponds the difference of the maximum and minimum of kAm. In the results of the

168 orthogonal tests, the larger the Rj, the greater the impact of this factor on the experimental

169 index (Jiaqiang et al., 2018). According to Rj, the order of the primary and secondary factors

170 can be judged as the important influential factors (E et al., 2018). These parameters are shown

171 in Table 4.

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172 After the orthogonal tests, the batch experiments were carried out in accordance with the

173 above processes (2.2.1 and Fig. 1).

174 2.2.3 Cu2+ adsorption

175 To confirm the removal efficiency and reuse times of the synthesized 4A zeolite for

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176 heavy metal ions, the Cu2+ adsorption experiment was carried out using the single-factor

177 method. The Cu2+ solution was prepared by dissolving copper nitrate in deionized water to

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178 reach a concentration of 100 mg/L. Then, a 150 mL Erlenmeyer flask was filled with 100 mL

179 of Cu2+. 180 mg of the synthesized 4A zeolite was added to the flask and shaken in a

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180 temperature-controlled shaker at 150 rpm and at 25°C constant temperature. After the reaction,

181 10 mL of the solution was collected by centrifugation at 4000 rpm for 10 minutes. The filtrate

182
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was collected in a polyethylene tube and the concentration of Cu2+ was determined by FAAS
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183 after dilution. All experiments were performed in duplicate.

184 The effect of the initial solution pH on the synthesized 4A zeolite was determined by the
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185 process described above for pH gradients at 1, 2, 3, 4, 5, 6, and 7. The reaction time was 60

186 min. The pH was adjusted with 0.1 M HNO3 and 0.1 M NaOH to prepare acidic and neutral
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187 solutions, respectively.

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188 The adsorbent efficiency (ŋ, %) and the adsorption amount at time t (qt, mg/g) of Cu2+

189 per unit of 4A zeolite synthesized were calculated by the following equations.
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(  )
190 ŋ= × 100% (1)


(  )
 = (2)
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191


where C0, Ce and Ct represent the initial Cu2+ concentration, the equilibrium Cu2+
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192

193 concentration and the Cu2+ concentration (mg/L) at time t (min), V is the solution volume (L),

194 and m is the mass of the 4A zeolite synthesized (g).

195 An adsorption kinetic study of the synthesized 4A zeolite was carried out at the time

196 gradients for 5 min, 10 min, 30 min, 60 min and 120 min and the initial solution pH was 4.

197 The pseudo-first-order (Vernadakis, 1907) and the pseudo-second-order kinetic models (Ho

198 and Mckay, 1998) were applied to analyse the adsorption of the synthesized 4A zeolite. The

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199 pseudo-first order equation is as follows:

200 ln( −  ) = ln  −   (3)

201 where qe (mg/g) is the adsorption capacity at the reaction equilibrium and k1 (g/mg·min–1) is

202 the rate constant of the pseudo-first-order process. The pseudo-second order kinetics model is

203 based on the adsorption capacity of a solid surface, which depends on the number of surface

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204 reaction sites. Compared with other models, this model assumes that the chemical adsorption

205 is the predominant mechanism (Ho, 2006). Its linear equation is

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206 =  + (4)
   

207 where k2 is the pseudo-second order rate constant (g/mg·min-1).

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208 For determining the reuse possibility of the synthesized zeolite, 180mg of the

209 synthesized 4A zeolite was used to treat 100 mg/L Cu2+ solution at pH 3 by the process

210

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described above. After testing the Cu2+ adsorption, desorption of zeolite 4A was carried out
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211 with 5 mol/L NaCl for 60 min, followed by filtering and drying at 105°C for 24 h. The dried

212 and recovered zeolite 4A was used to adsorb 100 mg/L Cu2+4 times under the same conditions
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213 as the previous adsorption experiments.

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214 3 Results and discussion

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215 3.1 Physicochemical properties of raw materials

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216 The chemical composition of fly ash is shown in Table 2. The fly ash used in this work is

a type of high-alumina fly ash in which the contents of SiO2, Al2O3 and Fe2O3 are over 80%.
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217

218 Aluminium and silicon in fly ash are the main raw materials for the zeolite synthesis. The
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219 main components in diatomite are shown in Table 3. The SiO2 content in diatomite is

220 approximately 90%, which can provide silicon for zeolite synthesis.

Component Al2O3 CaO Fe2O3 SiO2 LOI Other

Content (%，ω) 45.66 4.00 2.22 43.80 0.10 4.22
221 Table 2 Chemical compositions of coal fly ash by XRF (%, ω)
222 LOI: loss on ignition
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Component Al2O3 CaO Fe2O3 SiO2 LOI Other

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Content（%，ω） 2.49 0.28 1.15 89.16 2.76 4.16
224 Table 3 Chemical compositions of diatomite by XRF (%, ω)
225 LOI: loss on ignition
226 Fig. 2 (a) shows the XRD pattern of fly ash, which indicates that the mineral phase of fly

227 ash mainly consists of mullite (JCPDS card 15-0776) and quartz (JCPDS card 46-1045), and

228 the main crystal phase is mullite. The surface of the fly ash is smooth and clean, and the

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229 contents of Al and Si were high (Fig. 2 (b)). According to the XRD pattern of diatomite in Fig.

230 2(c), the mineral phase of diatomite mainly consists quartz. Diatomite forms strips and the

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231 surface is rough and concave. The content of silica was particularly high (Fig. 2 (d)).

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Fig. 2. (a) XRD pattern of coal fly ash, (b) SEM image and EDX analysis of coal fly ash, (c)
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XRD pattern of diatomite, (d) SEM image and EDX analysis of diatomite
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232 3.2 Theoretical basis for the synthesis of zeolite 4A

233 Accurate control of zeolite synthesis requires many factors, mainly the type and ratio of

234 reactants, liquid-to-solid ratio, alkalinity, and crystallization temperature and time. Synthetic

235 4A molecular sieves usually require a raw material ratio in the range of n(SiO2)/n(Al2O3) =

236 1.3~2.4,n(Na2O)/n(SiO2) = 0.8~3.0, and n(H2O)/n(Na2O) = 35~100. The ratio

237 n(SiO2)/n(Al2O3) = 2:1 is the most suitable for the formation of pure 4A-type molecular
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238 sieves (Xue and Zhu, 2001). Fly ash in the raw material has less silicon and more aluminium,

239 but a silicon source (diatomite) can be added. According to the Si-Al ratio of pure 4A-type

240 molecular sieves and the contents of Si and Al in fly ash and diatomite (Table 2 and Table 3),

241 fly ash and diatomite are mixed in an 8.5:1.5 ratio. The main reaction equation for the

242 synthesis of zeolite 4A is as follows (Yao, 2010):

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243 96Na2SiO3 +96NaAlO2 +312H2O → Na96Al96Si96O384·216H2O +192NaOH

3.3 The important influential factors

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244

Alkali melting Alkali mixture Solid-liquid Crystallization Relative

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Tests temperature ratio ratio time crystallinity
(A) (B) (C) (D)
1 1(A1) 1(B1) 1(C1) 1(D1) 1.7%

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2 1 2(B2) 2(C2) 2(D2) 2.5%
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3 1 3(B3) 3(C3) 3(D3) 38.7%
4 1 4(B4) 4(C4) 4(D4) 34.5%
5 1 5(B5) 5(C5) 5(D5) 55.2%
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6 2(A2) 1 2 3 4.0%
7 2 2 3 4 2.2%
8 2 3 4 5 47.8%
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9 2 4 5 1 3.4%
10 2 5 1 2 3.4%
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11 3(A3) 1 3 5 1.0%
12 3 2 4 1 1.7%
13 3 3 5 2 30.8%
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14 3 4 1 3 46.9%
15 3 5 2 4 52.1%
16 4(A4) 1 4 2 37.3%
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17 4 2 5 3 36.5%
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18 4 3 1 4 36.2%
19 4 4 2 5 49.6%
20 4 5 3 1 8.6%
21 5(A5) 1 5 4 11.1%
22 5 2 1 5 0.7%
23 5 3 2 1 3.7%
24 5 4 3 2 16.1%
25 5 5 4 3 31.7%
K1 132.6% 55.1% 88.9% 19.1%
K2 60.8% 43.6% 111.9% 90.1%

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K3 132.5% 157.2% 66.6% 157.8%
K4 168.2% 150.5% 153.0% 136.1%
K5 63.3% 151.0% 137.0% 154.3%
k1 26.5% 11.0% 17.8% 3.8%
k2 12.2% 8.7% 22.4% 18.0%
k3 26.5% 31.4% 13.3% 31.6%
k4 33.6% 30.1% 30.6% 27.2%
k5 12.7% 30.2% 27.4% 30.9%

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Range R 21.4% 22.7% 17.3% 27.8%
245 Table 4 The results of orthogonal tests

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246 By comparing the R values in Table 4 (Gao et al., 2016b), the sequence of the important

247 factors that affect the test index is DBAC. Thus, the crystallization time has the greatest

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248 influence, followed by the alkali mixture ratio. The alkali mixture ratio is the second key

249 factor, which indicates this parameter has an important effect on the synthesis of zeolite 4A,

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250 especially for energy and water consumption. Therefore, it is indicated that the alkali mixture
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251 ratio does have an important effect on the green synthesis according to the results of

252 orthogonal test.

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253 3.4 Determination of the green synthetic parameters

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254 3.4.1 Crystallization time

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255 The crystallization time has an important effect on the crystal morphology, size, crystal
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256 number and crystallinity during zeolite crystallization. The crystallization period involves the

257 dissolution of the silicon aluminium source and the growth of the zeolite crystal (Xu, 2004).
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258 Fig. 3(a) shows that the product was crystallized with Na2CO3 for 4 h to obtain the zeolite 4A
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259 (JCPDS card 43-0142) with a relative crystallinity of 44.5%. As the crystallization time was

260 extended, the characteristic diffraction peak at 7.2° gradually increased and reached a

261 maximum at 6 h, and the maximum relative crystallinity was 72.4%. Fig. 3(b) shows that the

262 optimum crystallinity was 68.2% for 4 h when NaOH was chosen to treat fly ash; above 4 h,

263 the sodalite crystal phase appears.

264 The above analysis shows that suitable crystallization times of Na2CO3 or NaOH-treated

265 fly ash were 6 or 4 h, respectively. The crystallization time of the zeolite 4A synthesized by

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266 NaOH-treated fly ash was short compared with Na2CO3-treated fly ash, thus, saving energy,

267 but the relative crystallinity decreased by 4.2%.

(a) (b)







-Zeolite 4A



-Zeolite 4A 1600

1200










6h 1200 6h

Intensity
800
Intensity

800

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400

400

4h 4h

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0
0
0 10 20 30 40 50 60 0 5 10 15 20 25 30 35 40 45
2-Theta(°) 2-Theta(°)

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Fig. 3. XRD patterns of the hydrothermal crystallization products of Na2CO3 (a) and NaOH

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268 3.4.2 Alkali melting temperature
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269 Fig. 4 shows the TG-DCS curve of fly ash treated with by NaOH or Na2CO3. The weight

270 of the Na2CO3-treated fly ash sample decreased from 82°C to 150°C due to the loss of
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271 unbound water on the surface of the sample. An exothermic peak occurs at 300°C to 400°C
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272 due to the exothermic reaction of fly ash and diatomite mixed with Na2CO3. At approximately

273 850°C, a violent exothermic reaction occurs due to mullite and quartz in the fly ash and
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274 diatomite reacting with Na2CO3 to produce sodium aluminosilicate and sodium silicate. This

275 outcome released a large amount of carbon dioxide, resulting in a sharp decrease in the weight
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276 of the sample (Li and Ma, 2004). Compared with the Na2CO3 alkali melting calcination, the

NaOH alkali melting reaction temperature decreased by approximately 90°C. The highest
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277

278 exothermic reaction occurred at approximately 760°C, indicating that the most insoluble

279 mullite phase began to react.

280 Compared to the Na2CO3 alkali flux, the NaOH alkali melting temperature is low, and the

281 heat flow in the reaction is rapid and intense, which can save energy. However, the reaction

282 product easily bonds with the crucible during the experiment, making scraping necessary.

283 Although the Na2CO3 alkali melting temperature is high, the CO2 produced during the

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284 reaction causes agitation, preventing the alkali melting product from caking on the crucible.

285 Therefore, according to the TG-DCS curve analysis, when NaOH and Na2CO3 were used to

286 treat fly ash, 760°C and 850°C, respectively, were selected as the ideal temperatures.

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287
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288 Fig. 4. TG-DCS curves of fly ash, diatomite and Na2CO3/NaOH

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289 3.4.3 Alkalinity ratio

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290 Na2CO3 calcination can cause glassy silica and aluminium oxide to dissolve to produce

291 soluble sodium aluminosilicate salt, which is a precursor for synthetic zeolite; however,
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292 different alkalinity ratios during zeolite synthesis will create different synthetic zeolite species

293 (Liu et al., 2008; Ming-Yan et al., 2006; Molina and Poole, 2004). Fig. 5(a) shows that when
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294 the Na2CO3 alkalinity ratio is 0.8, compared with the target product zeolite 4A (JCPDS card
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295 43-0142), the crystallization product is nepheline (NaAlSiO4) (JCPDS card 35-0424), in

296 which the proportion of each element is the same, except for the number of water molecules.

297 The molecular weight of nepheline is very small, which may be due to the lower amount of

298 Na2CO3 transforming mullite and quartz minerals into small molecular weight aluminosilicate.

299 When the alkalinity is increased to 1.8, the characteristic peak intensity at 7.2° was the

300 highest, and the relative crystallinity was 48.8%, indicating that Na+ could promote the

301 product morphology and crystallization reaction (Murayama et al., 2002). However, when the
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302 alkalinity ratio is higher than 1.8, the 4A molecular sieve is still present in the product, but the

303 relative crystallinity is greatly reduced. A proper amount of Na2CO3 can dissolve the inert

304 silica aluminium in fly ash and diatomite into the initial silicon aluminium gel. Fig. 5(b)

305 shows that the crystallinity of the zeolite 4A is the best when NaOH-treated fly ash is used

306 with an alkalinity ratio of 1.5.

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307 Compared with the amount of Na2CO3, the amount of NaOH used was lower, but the

308 relative crystallinity was only 42.6%. It is clear that the use of Na2CO3 alone produces zeolite

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309 4A with a slightly higher relative degree of crystallinity, but the amount of alkali required is

310 higher.

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（ b）
（ a） -Zeolite 4A 3000 -Zeolite 4A
  ■-Nepheline ■-Nepheline
        
   2.2
    1.8
    
2000
Intensity

   2000    

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Intensity

1.8 
 
 1.5
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1000 ■ ■ ■ ■
■■ 0.8 1000

■ ■ ■ ■■ ■
0.8
0 0
10 20 30 40 10 20 30 40
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2-Theta(°) 2-Theta (°)

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Fig. 5. XRD patterns of the hydrothermal crystallization products of Na2CO3 (a) and NaOH
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(b) with different basicity ratios

311 3.4.4 Solid-to-liquid ratio

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312 At a solid-to-liquid ratio of 1:5, the synthetized zeolite 4A (JCPDS card 43-0142) had the
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2-
313 highest purity and a relative crystallinity of 72.4% (Fig. 6(a)), with a CO 3 concentration of
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314 1.2 mol/L. Compared with Na2CO3 alkali melting, it can be concluded that, for NaOH alkali

315 melting, the solid-to-liquid ratio of 1:8 produces the most crystalline products (Fig. 6(b)),

316 with a relative crystallinity of 64.8%. When the solid-to-liquid ratio is 1:3, 5 mol/L OH- is

317 present in solution, and the sodalite phase is completely synthesized. The ring skeleton of the

318 zeolite 4A beta cage has a metastable structure, and the structural energy is higher than that of

319 sodalite (Xiaoqiang et al., 2016). Thus, a high-alkalinity environment will cause the zeolite

320 4A skeleton to crack, accompanied by sodalite formation.

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321 Therefore, the best soild-to-liquid ratios of Na2CO3-treated or NaOH-treated fly ash were

322 1:5 or 1:8, respectively. When Na2CO3-treated fly ash is used, the water consumption is low,

323 resulting in a corresponding decrease in the waste liquid, and the relative crystallinity of the

324 product is 72.4%.

325

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（ a） （ b）
■-Zeolite 4A ■-Zeolite 4A
●-Sodalite 1500 ▲ ▲-Sodalite
1200 ▲ ▲ ▲ ▲








▲

1:8 ▲
▲
Intensity

▲ 1:8

Intensity

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800

1000 ▲


▲


▲ ▲
▲ ▲ ▲
1:5 ▲ ▲
400

1:5





500

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1:3
●
1:3
0



0
10 20 30 40
10 20 30 40
2-Theta (°) 2-Theta (°)

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Fig. 6. XRD patterns of the hydrothermal crystallization products of Na2CO3 (a) and NaOH
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(b) with different solid-to-liquid ratios

326 3.4.5 Crystallization temperature

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327 Crystallization temperature can affect the reactor pressure, crystallization rate, crystal
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328 type and size (Ke-Ming and Zhu, 2007). At the crystallization temperature of 40°C, the degree
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329 of crystallization is minimal, and the product is mainly amorphous aluminosilicate (Fig. 7(a)).

330 When the temperature is increased to 60°C, a small amount of nepheline phase appears.
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331 Because the hydrothermal reaction is carried out in a closed autoclave, when the temperature

332 increases, the gas expands and increases the pressure on the PTFE liner, increasing thermal
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333 motion and effective collisions and improving the dissolution and crystallization rates of the
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334 hydrothermal reaction. Thus, when the crystallization temperature reaches 90°C, zeolite 4A

335 (JCPDS card 43-0142) with a relative crystallinity of 72.4% is synthesized. The optimum

336 crystallization temperature of zeolite 4A synthesized by alkali fusion with NaOH is also 90°C

337 (Fig. 7(b)).

338 Therefore, the crystallization temperature has a large influence on the synthesized zeolite,

339 and the optimum crystallization temperature of the two alkalis is 90°C.

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（ a）
-Zeolite 4A （ b） ▲-Zeolite 4A

-Nepheline ▲ ▲ ▲
2100
▲ ▲ ■-Nepheline



▲

▲ ▲




800 ▲

90℃
Intensity

Intensity
1400 90℃


60℃









80℃ 400 ■
700
60℃ ■

40℃

■


40℃


0 0

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10 20 30 40 10 20 30 40
2-Theta(°) 2-Theta (°)

Fig. 7. XRD patterns of the hydrothermal crystallization products of Na2CO3 (a) and NaOH

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(b) at different crystallization temperatures

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340 3.4.6 Green synthetic parameters

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341 The advantages and disadvantages of the synthetic parameters are shown in Table 5 for
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342 the synthesized zeolite 4A from fly ash treated by NaOH or Na2CO3. To achieve the green

343 synthesis of zeolite 4A, the advantages of two kinds of alkali fusion were combined, and the
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344 synthetic parameters of low energy and water consumption (alkali melting temperature of

345 760°C, solid-to-liquid ratio of 1:5, and crystallization time of 4 h) were selected as the green
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346 synthetic condition when the mixture of NaOH and Na2CO3 is used to treat fly ash. The
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347 selection of these parameters effectively reduced the energy and water consumption in the

348 synthesis process and realized a green synthesis.

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Single experiment Synthesis of zeolite 4A by Synthesis of zeolite 4A by

Na2CO3 NaOH
Alkali melting 850 760
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temperature (°C)
Solid-to-liquid ratio 1:5 1:8
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(g/mL)
Crystallization time (h) 6 4
Crystallization 90 90
temperature (°C)
Advantages Relatively high degree of Low energy consumption, short
crystallinity (72.4%), less synthesis cycle
waste
Disadvantages High energy consumption, Relative crystallinity is low
long synthesis cycle (68.6%), more wastewater
349 Table 5 Parameters for the synthesis of zeolite 4A using NaOH or Na2CO3
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350 3.5 Synthesis of zeolite 4A from a mixture of Na2CO3 and NaOH

351 Group Fly ash (g) Na2CO3 (g) NaOH (g)

352 1 10 16.2 1.5
2 10 12.6 4.5
353
3 10 9 7.5

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4 10 5.4 10.5

354 Table 6 The mixing amount of Na2CO3 and NaOH

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355

-Zeolite 4A
-Sodalite

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3000      
   4
Intensity

    
   
2000  3

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 2
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1000
    
   
 1
0
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5 10 15 20 25 30 35 40
356 2-Theta (°)
357 Fig. 8. XRD patterns of the hydrothermal crystallization products produced from mixing
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358 NaOH with Na2CO3

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359
Component SiO2 Al2O3 Na2O CaO MgO Other
Content (%,ω) 39.36 30.43 22.78 3.04 0.19 4.2
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360 Table 7. XRF patterns of the hydrothermal crystallization products produced from
361 mixing NaOH with Na2CO3
362 Under the conditions of the green synthetic parameters, the mixing amount of Na2CO3
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363 and NaOH is shown in Table 6. Hydrothermal crystallization using Na2CO3 mixed with
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364 NaOH at a mass ratio of 2.8:1 produced zeolite 4A (JCPDS card 43-0142) with the highest

365 relative crystallinity of 75.8% in group 2, and the product had almost no sodalite (JCPDS card

366 37-0476) (Fig. 8). When the two bases exist together, the equations concerning water

2- 2- 2-
367 solubility are Na2CO3⇌2Na+ + CO 3 , CO 3 + H2O⇌HCO 3 + OH- and NaOH⇌Na++OH-.

368 Comparing the same mass of Na2CO3 with NaOH, Na2CO3 provides an appropriate amount of

2-
369 Na+ but little OH-. Upon OH- consumption, CO 3 is continuously hydrolysed to produce OH-.

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370 In addition, OH- can only be stably kept in solution at a relatively low concentration, which is

371 not beneficial to activation and crystallization. The NaOH hydrothermal synthesis is

372 characterized by the ability to provide enough OH- for the hydrothermal reaction but little Na+.

373 OH- and Na+ are indispensable in the process of hydrothermal crystallization, and the contents

374 of the two ions need appropriate proportions. Mixing Na2CO3 with NaOH at a mass ratio of

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375 2.8 to 1 gives the best crystallinity, which may be because the most appropriate OH- and Na+

376 concentrations are obtained and the OH- concentration is relatively stable during the reaction.

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377 According to the XRF component analysis (Table 7), the silica alumina ratio (the mole

378 ratio of SiO2 and Al2O3) in the synthesized 4A zeolite was 1, which was consistent with the

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379 silica alumina ratio in the chemical formula of 4A zeolite. However, when XRF was used to

380 analyse chemical compositions, the atomic number of the detected elements was higher, with

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381 higher accuracy. Because the atomic numbers of Si and Al are in the front, this may cause
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382 some errors in the analysis results. Therefore, FTIR and SEM-EDX were used to further

383 investigate the synthesized 4A zeolite.

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384 Fig. 9 shows the FTIR characterization of the fly ash and synthesized 4A zeolite under

385 the green synthetic conditions. The main infrared absorption peaks are located near 459, 873,
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386 1103 and 3413 cm-1 in Fig. 9 (a), which belong to the symmetrical stretching vibration peaks
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387 of Si-O, Si-O-Si, Si-O-Si and Al-O-Si bonds, and the bending vibration peaks of H2O,

388 respectively. These functional groups were in conformity with mullite and silica’s, and the
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389 FTIR results were consistent with Table 1 and Fig. 1(a). Fig. 9 (b) is the FTIR of the

390 synthesized zeolite 4A. The peak at approximately 3467 cm-1 is associated with the OH-

hydrogen-bond stretching vibration. The peak at 1640 cm-1 is associated with the OH-
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391

392 hydrogen-bond bending vibration of zeolite 4A, indicating that zeolite 4A is bound to water.
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393 The peak at 993 cm-1 corresponds to the characteristic peak of the T-O-T (where T is Al or Si)

394 tetragonal stretching vibration, and the peak at 558 cm-1 is the characteristic peak for the

395 bicyclic vibrations in a tetrahedron. The peak at 465 cm-1 corresponds to T-O (where T is Al

396 or Si) flexural stretching vibrations (Purnomo et al., 2012). These results are consistent with

397 the FTIR spectrum of the synthesized zeolite 4A by Tanaka et al. (2008). The functional

398 groups of FTIR are shown in Table 8.

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3413

Transmittance
Trasmittance

465
558
1640

873

459 993

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1103 3467

0 500 1000 1500 2000 2500 3000 3500 4000 0 500 1000 1500 2000 2500 3000 3500 4000
Wave number/cm-1 Wave number/cm-1

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(a) (b)

Fig. 9. FTIR characterization of the (a) fly ash and (b) synthesized zeolite 4A

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399
Wave number/cm-1 Functional groups

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459, 465 Si-O
558 bicyclic vibrations in a tetrahedron
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873,993,1103 Si-O-Si and Si-O-Al
1640,3413,3467 OH- hydrogen-bond
400 Table 8 The functional groups of samples by FTIR
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401 Fig. 10(a)-(c) shows SEM images of the zeolite 4A produced under the optimum
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402 conditions from fused fly ash via hydrothermal crystallization. From Fig. 10(a), it can be seen

403 that the baked surface of fused fly ash has irregular holes with different sizes, and is rough
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404 and wrinkled. The crystalline products in Fig. 10(b) are well dispersed and exhibit a regular

405 cubic structure. Fig. 10(c) represents a low-power microscope image of the synthesized
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406 zeolite 4A under the optimum conditions, which mostly comprise of regular cubic grains, and

407 Si, Al and Na are the main components of the zeolite by EDX analysis.
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AC

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Fig. 10. SEM image of baked fly ash (a), high-magnification (b) and low-magnification of the

synthesized zeolite 4A and the element content analysis by EDX (c), image and the element

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content of the synthesized zeolite 4A after being reused 4 times (d).
408

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409 XRD, XRF, FTIR and SEM-EDX analyses showed that the synthesized product
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410 conformed to the characteristics of 4A zeolite in term of the crystal phase, composition,

411 functional groups present and morphology. In addition, the zeolite and reached the highest
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412 relative crystallinity of 75.8%. Therefore, when Na2CO3 and NaOH are synergistic, the 4A

413 zeolite with high crystallinity can be successfully synthesized under low energy and water
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414 consumption conditions.

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415 3.6 Removal efficiency by the synthesized zeolite 4A

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416 The removal rate of the zeolite 4A was only approximately 22% when the initial solution

417 pH was 1 or 2. However, when the initial solution pH ≥ 3, the Cu2+ removal rate by the zeolite
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418 4A was close to 100%, and the highest Cu2+ removal amount was 55.5 mg/g (Fig. 11(a)).
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419 Under strong acid conditions (pH was 1 or 2), the H+ ions concentration was high, because the

420 zeolite was highly selective for H+ ions (Hui et al., 2005), the Cu2+ removal efficiency by

421 zeolite was relatively lower. At an initial solution pH≥3, because the surface hydroxyl groups

422 generated by the zeolite surface with water would neutralize the H+ (Hui et al., 2005) and the

423 final solution pH reached neutral (Fig. 11(b)), the Cu2+ removal efficiency by the zeolite 4A

424 was increased and approached 100%. The TPD of zeolite 4A showed that there was a weak

425 acid site centre near 159°C and a strong acid site centre near 338°C (Fig. 12), which indicated

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426 that the zeolites synthesized had good adsorption properties. The pseudo-second order

427 kinetics model well described the Cu2+ adsorption by the zeolite (Table 9), which indicates

428 that chemical adsorption is the predominant mechanism. This result is consistent with other

429 research findings in which the removal of Cu2+ by zeolite 4A mainly occurred through

430 adsorption and ion exchange between Na+ and Cu2+ (Hui et al., 2005; Jha et al., 2008).

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431
60 12
100 100

adsorption capacity(mg/g)

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50 10
Removal rate (%)
Removal rate (%)

Removal rate (%)

80 adsorption capacity

pH after reaction
80
40 8
Removal rate (%)

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60 60 pH after reaction 6
30

40 4
20 40

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20 10 20
1 2 3 4 5 6 7 0
1 2 3 4 5 6 7
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pH pH

(a) (b)
432 Fig. 11. (a) Ability of the synthesized zeolite 4A to remove Cu2+ in solution at different initial
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433 pH values and (b) Cu2+ removal rate and the final pH of solution (180 mg of zeolite, C0 = 100

434 mg/L for Cu2+, 60 min)

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435
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0.375

0.370
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TCD Signal (a.u.)

0.365
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0.360
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0.355

0.350

0.345
159 338
0.340
100 200 300 400 500
436 Temperature(℃ )
437 Fig. 12. TPD of the synthesized zeolite 4A
438

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Pseudo first order Pseudo two order

Metal
kinetic equation kinetic equation
ion
qc(mg/g) k1 × 10-2 R2 qc(mg/g) k2 × 10-2 R2
Cu2+ 19.70 4.80 0.9116 57.14 0.035 0.9982

439 Table 9 Parameters and regression coefficients (R2) of the adsorption kinetic models

The removal efficiency of Cu2+ by the synthesized zeolite 4A is superior to that of natural

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440

441 zeolite or modified natural zeolite (Table 10). The average pore size of the synthesized

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442 zeolites is smaller than natural zeolites, which may increase the pore per unit volume and

443 enhance the removal ability for Cu2 +. However, due to the difference in removal conditions,

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444 the removal efficiency of Cu2+ by the zeolite will be greatly affected (Sprynskyy et al., 2006;

445 Hui et al., 2005).

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Maximum BET specific Average Removal conditions
Adsorbent adsorption surface area pore size Reference
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capacity (mg/g) (m2/g) (nm)
Cu2+ 100 mg/L, 0.18 g
of zeolite, the initial pH
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Zeolite 4A 55.5 18.33 11.34 This work

3, contact time 1 h and
temperature 298 K
Cu2+ 115 mg/L, 1.0 g of
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zeolite, the initial pH

Chabazite (Egashira et al.,
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11.5 159 - 2.5-5, contact time 0-24

zeolite 2012)
h and temperature 300
K
25.8 Cu2+ 800 mg/L, 0.5 g of
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Clinoptilolite (Sprynskyy et
(Theoretical 13.2 95.62 zeolite
zeolite al., 2006)
value)
Cu2+ 200 mL/L, 4 g/L
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Zeolite 28.6 adsorbent, the initial

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composite (Theoretical 16.88 24.6 pH 5.5, contact time 48 (Ji et al., 2012)
fibre value) h and temperature 298
K
446 Table 10 Adsorption capacities of Cu2+ with various adsorbents.

447 After Cu2+ was absorbed, it was desorbed from zeolite 4A in 5 mol/L NaCl and then

448 filtered, and the zeolite 4A after for 4 recycling processes was able to remove Cu2+ in an

449 acidic aqueous solution with a pH of 3. The adsorption rate was stable at approximately 73%

450 (Fig. 13), which was lower than the adsorption the first time (close to 100%). Ji et al. (2012)

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451 measured the desorption and reuse of the composite fibre with zeolite and showed that

452 desorption ratio gradually decreased after being used 5 times. However, the synthesized

453 materials still maintain a certain removal efficiency for Cu2+. SEM images showed the regular

454 cubic structure of the reused zeolite 4A remained, but Cu was found in the zeolite by EDX

455 after the fourth desorption (Fig. 10 (d)). Complete desorption was not possible because

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456 electrostatic and complexation reactions occurred between the sorbent and the metal ion

457 (Mishra and Sharma, 2011) and some of the adsorption sites were irreversibly occupied by

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458 Cu2+ (Zhang et al., 2017).
80

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Removal rate(%)

70

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60 AN
50

40
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1 2 3 4

459 Repeated times of zeolite 4A

460 Fig. 13. Recycling of the synthesized zeolite 4A to absorb Cu2+ (pH 3, 180 mg of zeolite, 100
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461 mg/L Cu2+, 60 min)

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462 4 Conclusion
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463 When zeolite 4A was synthesized by the hydrothermal method using coal fly ash as the
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464 raw material, the important factors influencing energy and water consumption were the alkali

mixture ratio, alkali melting temperatures, solid-to-liquid ratios, crystallization times and
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465

466 crystallization temperatures. According to the results of the orthogonal tests, the ratio of the

467 NaOH and Na2CO3 mixture was proven to be an important influential factor for the green

468 synthesis. Through batch experiments, green synthetic parameters were determined: an alkali

469 melting temperature of 760°C, a solid-to-liquid ratio of 1:5, a crystallization time of 4 h and a

470 crystallization temperature of 90°C. Because the synergism of Na2CO3 and NaOH provided

471 an appropriate amount of OH- and Na+ as well as a stable OH- concentration during the

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472 reaction process, the mixture of these two bases can lead to the highest activation of Si and Al

473 in fly ash to achieve the highest degree of crystallization as well as low energy and water

474 consumption. Therefore, when Na2CO3 and NaOH were mixed in a mass ratio of 2.8 to 1, the

475 synthesized zeolite 4A by fly ash had the highest crystallinity and reached 75.8% under low

476 energy and water consumption conditions.

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477 The synthesized zeolite 4A can effectively remove Cu2+ from acidic aqueous solution

478 (3≤pH<7), with a removal rate close to 100% and a removal capacity of 55.5 mg/g. When

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479 Cu2+ was desorbed from zeolite 4A and when the zeolite was reused 4 times, the Cu2+ removal

480 efficiency by the reused zeolite 4A was stable at 73% in an aqueous solution with a pH of 3.

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481 Acknowledgments

482
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Support from the program of China Scholarships Council is gratefully acknowledged. We are
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483 very grateful to the referees and the editors for their helpful suggestions.

484 References:
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489 Cardoso, A. M., Horn, M. B., Ferret, L. S., Azevedo, C. M., & Pires, M., 2015. Integrated synthesis of
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520 zeolite 4A and residual products from recycled coal fly ash. J. Hazard Mater 127(1), 89-101.
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524 fly ashes and their synthesized zeolites. Fuel Process Technol 97(3), 38-44.
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525 Jha, V. K., Matsuda, M., & Miyake, M., 2008. Sorption properties of the activated carbon-zeolite
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529 composite fiber and its adsorption behavior for heavy metal ions in aqueous solution. Chem Eng J.
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531 Jiaqiang, E., Han, D., Qiu, A., Zhu, H., Deng, Y., & Chen, J., et al., 2018. Orthogonal experimental
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541 from coal fly ash. Journal of Industrial & Engineering Chemistry 15(5), 736-742.
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559 Murayama, N., Yamamoto, H., & Shibata, J., 2002. Mechanism of zeolite synthesis from coal fly ash
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568 Crystallinity in Flyash-Based Zeolite-A Using XRD and IR Spectroscopy. Curr Sci India 89(12),
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Alkali
Alkali mixture ratio Solid-liquid Crystallization
Factors melting
ratio time
Levels temperature
(B) (C) (D)
(A)

1 700°C(A1) 18g Na2CO3 (B1) 1:3(C1) 2h(D1)

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2 760°C(A2) 13.5g Na2CO3, 3.75g NaOH (B2) 1:5(C2) 4h(D2)

3 800°C(A3) 9g Na2CO3, 7.5g NaOH (B3) 1:6(C3) 5h(D3)

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4 840°C(A4) 4.5g Na2CO3, 11.25g NaOH (B4) 1:8(C4) 6h(D4)

5 900°C(A5) 15g NaOH (B5) 1:10(C5) 8h(D5)

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Table 1 Orthogonal tests for the importance influential factors of green synthesis of zeolite

4A

U
Component Al2O3 CaO Fe2O3 SiO2 LOI Other
Content (%，ω)
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45.66 4.00 2.22 43.80 0.10 4.22
Table 2 Chemical compositions of coal fly ash by XRF (%, ω)
LOI: loss on ignition
M

Component Al2O3 CaO Fe2O3 SiO2 LOI Other

Content（%，ω） 2.49 0.28 1.15 89.16 2.76 4.16
D

Table 3 Chemical compositions of diatomite by XRF (%, ω)

LOI: loss on ignition
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C EP
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Alkali melting Alkali mixture Solid-liquid Crystallization Relative

Tests temperature ratio ratio time crystallinity
(A) (B) (C) (D)
1 1(A1) 1(B1) 1(C1) 1(D1) 1.7%
2 1 2(B2) 2(C2) 2(D2) 2.5%
3 1 3(B3) 3(C3) 3(D3) 38.7%
4 1 4(B4) 4(C4) 4(D4) 34.5%

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5 1 5(B5) 5(C5) 5(D5) 55.2%
6 2(A2) 1 2 3 4.0%

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7 2 2 3 4 2.2%
8 2 3 4 5 47.8%
9 2 4 5 1 3.4%

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10 2 5 1 2 3.4%
11 3(A3) 1 3 5 1.0%
12 3 2 4 1 1.7%

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13 3 3 5 2 30.8%
14 3 4 1 3 46.9%
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15 3 5 2 4 52.1%
16 4(A4) 1 4 2 37.3%
17 4 2 5 3 36.5%
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18 4 3 1 4 36.2%
19 4 4 2 5 49.6%
D

20 4 5 3 1 8.6%
21 5(A5) 1 5 4 11.1%
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22 5 2 1 5 0.7%
23 5 3 2 1 3.7%
24 5 4 3 2 16.1%
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25 5 5 4 3 31.7%
K1 132.6% 55.1% 88.9% 19.1%
K2 60.8% 43.6% 111.9% 90.1%
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K3 132.5% 157.2% 66.6% 157.8%

K4 168.2% 150.5% 153.0% 136.1%
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K5 63.3% 151.0% 137.0% 154.3%

k1 26.5% 11.0% 17.8% 3.8%
k2 12.2% 8.7% 22.4% 18.0%
k3 26.5% 31.4% 13.3% 31.6%
k4 33.6% 30.1% 30.6% 27.2%
k5 12.7% 30.2% 27.4% 30.9%
Range R 21.4% 22.7% 17.3% 27.8%
Table 4 The results of orthogonal tests
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Single experiment Synthesis of zeolite 4A by Synthesis of zeolite 4A by

Na2CO3 NaOH
Alkali melting 850 760
temperature (°C)
Solid-to-liquid ratio 1:5 1:8
(g/mL)

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Crystallization time (h) 6 4
Crystallization 90 90
temperature (°C)

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Advantages Relatively high degree of Low energy consumption, short
crystallinity (72.4%), less synthesis cycle
waste

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Disadvantages High energy consumption, Relative crystallinity is low
long synthesis cycle (68.6%), more wastewater
Table 5 Parameters for the synthesis of zeolite 4A using NaOH or Na2CO3

Group
U
Fly ash (g) Na2CO3 (g) NaOH (g)
AN
1 10 16.2 1.5
2 10 12.6 4.5
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3 10 9 7.5
4 10 5.4 10.5

Table 6 The mixing amount of Na2CO3 and NaOH

D

Component SiO2 Al2O3 Na2O CaO MgO Other

Content (%,ω)
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39.36 30.43 22.78 3.04 0.19 4.2

Table 7. XRF patterns of the hydrothermal crystallization products produced from
mixing NaOH with Na2CO3
Wave number/cm-1
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Functional groups
459, 465 Si-O
558 bicyclic vibrations in a tetrahedron
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873,993,1103 Si-O-Si and Si-O-Al

1640,3413,3467 OH- hydrogen-bond
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Table 8 The functional groups of samples by FTIR

Pseudo first order Pseudo two order

Metal
kinetic equation kinetic equation
ion
qc(mg/g) k1 × 10-2 R2 qc(mg/g) k2 × 10-2 R2
Cu2+ 19.70 4.80 0.9116 57.14 0.035 0.9982

Table 9 Parameters and regression coefficients (R2) of the adsorption kinetic models
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Maximum BET specific Average Removal conditions
Adsorbent adsorption surface area pore size Reference
capacity (mg/g) (m2/g) (nm)
Cu2+ 100 mg/L, 0.18 g
of zeolite, the initial pH
Zeolite 4A 55.5 18.33 11.34 This work
3, contact time 1 h and
temperature 298 K
Cu2+ 115 mg/L, 1.0 g of

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zeolite, the initial pH
Chabazite (Egashira et al.,
11.5 159 - 2.5-5, contact time 0-24
zeolite 2012)
h and temperature 300

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K
25.8 Cu2+ 800 mg/L, 0.5 g of
Clinoptilolite (Sprynskyy et

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(Theoretical 13.2 95.62 zeolite
zeolite al., 2006)
value)
Cu2+ 200 mL/L, 4 g/L

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Zeolite 28.6 adsorbent, the initial
composite (Theoretical 16.88 24.6 pH 5.5, contact time 48 (Ji et al., 2012)
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fibre value) h and temperature 298
K
Table 10 Adsorption capacities of Cu2+ with various adsorbents.
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 The synergistic reaction of NaOH and Na2CO3 has an important effect on the

zeolite green synthesis.

 The optimal parameters gained by batch test are as green synthesis condition of

two alkali mixture.

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 The synthetic zeolite can efficiently adsorb Cu2+ from acid solution and be

reused.

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D
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