Accepted Manuscript

Title: PRODUCTION OF ACTIVATED CARBON AND

FUNGICIDAL OIL FROM PEACH STONE BY
TWO-STAGE PROCESS

Author: Tugce Uysal Gozde Duman Yunus Onal Ihsan Yasa

Jale Yanik

PII: S0165-2370(14)00123-5
DOI: http://dx.doi.org/doi:10.1016/j.jaap.2014.05.017
Reference: JAAP 3209

To appear in: J. Anal. Appl. Pyrolysis

Received date: 8-12-2013

Revised date: 8-4-2014
Accepted date: 7-5-2014

Please cite this article as: T. Uysal, G. Duman, Y. Onal, I. Yasa, J. Yanik, PRODUCTION
OF ACTIVATED CARBON AND FUNGICIDAL OIL FROM PEACH STONE
BY TWO-STAGE PROCESS, Journal of Analytical and Applied Pyrolysis (2014),
http://dx.doi.org/10.1016/j.jaap.2014.05.017

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2 PRODUCTION OF ACTIVATED CARBON AND FUNGICIDAL OIL FROM PEACH

3 STONE BY TWO-STAGE PROCESS

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5 Tugce Uysal a, Gozde Duman a, Yunus Onal b, Ihsan Yasa c and Jale Yanik a†

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a
6 Faculty of Science, Department of Chemistry, Ege University, 35100 Bornova, Izmir,

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7 Turkey,
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8 Faculty of Engineering, Department Of Chemical Engineering, Inonu University, 44280

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9 Malatya, Turkey
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Faculty of Science, Department of Biology, Ege University, 35100 Bornova, Izmir, Turkey

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13 †Corresponding author: jale.yanik@ege.edu.tr

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14 Tel/Fax:+90 232 3888264

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20

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24 ABSTRACT

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25 In this study, the production of activated carbons from peach stone with zinc chloride

26 activation was investigated by means of a two-stage process: precarbonization and chemical

27 activation. Precarbonization was performed at two different temperatures 300 °C and 400 °C

28 in order to obtain the bio-oil. Then the activation of precarbonized chars after impregnation

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29 with zinc chloride was carried out. The activation temperatures varied from 500 °C to 700 °C

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30 to determine the optimal processing conditions. For comparison, traditional chemical

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31 activation was also performed. In two-stage process, the precarbonization temperature had

32 important effect on the surface area of activated carbon as well as activation temperature. The

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33 surface area of activated carbons obtained from the two-stage process was lower than that

34 those from the one-stage process. The bio-oil obtained from precarbonization step showed

35
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fungicidal activity against fungi C. versicolor. The adsorption capacities of activated carbons

for phenol and methylene blue were found to be in the range of 51.6-64.9 mg g-1 and 104.2-
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37 121.9 mg g-1, respectively.

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38
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39 Key words: Precarbonization; Activated carbon; Adsorption; Fungicidal oil

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48 1. INTRODUCTION

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49 Activated carbon has been widely used for the separation of gases, the recovery of

50 solvents, and the removal of pollutants from water/wastewater and as a catalyst support.

51 Adsorption capacity is based on the physical properties of the pores, namely the specific

52 surface area, the pore size and distribution as well as its surface chemistry [1]. These

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53 properties vary depending on the precursor and activation conditions used to produce

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54 activated carbons.

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55 Although commercial activated carbon is mainly produced from coal, wood, and coconut

56 shell, a number of researchers have used many carbonaceous materials which are cheap and

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57 readily available.

58 Because of its low ash content and reasonable good hardness, production of activated

59
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carbon from fruit stones such as peach stone [2], olive stone [3, 4], apricot stone [5], date
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60 stone [ 6, 7], cherry stone [8, 9], plum stone [10], besides other lignocellulosic wastes, such as

61 almond shell [3,5], palm shell [11], tea wastes [12], pine cone [13], tobacco wastes [14] etc.
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62 was studied by a number of researchers,

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63 Activated carbons can be basically produced by two methods: Physical or chemical activation

64 or a combination of both of them. The physical activation method involves carbonization of

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65 the raw material and the subsequent activation at high temperature in a carbon dioxide or
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66 steam atmosphere. The chemical activation method involves the carbonization of the raw

67 material previously impregnated with a chemical agent such as zinc chloride, phosphoric acid,
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68 potassium hydroxide etc. Since a large number of studies have been carried out on activated

69 carbon production, the general mechanism for both the chemical and physical activation is

70 well known.

71 The advantage of chemical activation over physical activation is that chemical

72 activation produces much higher yield and better-developed, more uniformly-sized pores

73 compared to physical activation, and leads to a decrease in the mineral matter content. It also

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74 uses lower temperatures for carbonization. Nevertheless, there are also some disadvantages of

75 the chemical activation process, one of which is the prevention of the utilization of valuable

76 volatiles. For example, the pyrolysis liquids obtained from lignocellulosic materials can be

77 used as sterilizing agent, smoke flavors, environmentally-friendly wood preservative,

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78 antimicrobial and growth promoting agent etc. [15]. Because of this, the physical activation

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79 method compares favorably with the chemical activation process if the bio-oil derived from

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80 carbonization step is used as a chemical feedstock. Our previous study showed that pistachio

81 shell could be used for production of both fungicidal oil and activated carbon. In that study,

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82 the microporous activated carbon having a BET surface 708m2 g−1 with a loss of char mass

83 57.5 wt % was obtained from pistachio shell by CO2 activation at 900 °C [16].

84
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One of the biomass sources in Turkey is food processing wastes. Currently, food-
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85 processing industries, such as the fruit juice industry, are growing fast and, as a result, several

86 by-products are being produced in large quantities. One of the main food processing wastes is
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87 peach stone which is disposed by burning. However, peach stone contains hydrocyanic acid or
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88 cyanide, in the form of cyanogenic glycosides, which may led to environmental problems

89 when burned. Peach stone is a valuable agro industrial by-product that is available not only in
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90 Turkey but also in many countries (especially in the Mediterranean region). The low ash
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91 content and the absence of transportation costs make peach stones an ideal precursor for

92 activated carbon production.

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93 The preparation of activated carbon by chemical activation using H3PO4 [17-23] and

94 K2CO3 [24, 25] and physical activation [2, 26-29] of peach stones have been previously

95 studied. The chemical activation of peach stone using K2CO3 was studied to obtain activated

96 carbons for the removal of dyes [24] and acetaminophen [25]. Molina-Sabio and Rodriguez-

97 Reinoso compared the activating agents on the porosity development in production of

98 activated carbon from peach stone [23]. They observed that KOH only produced a widening

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99 of micropore width, ZnCl2 additionally developed small mesoporosity and H3PO4 led to a

100 more heterogeneous pore size distribution. On the other hand, it was observed that steam

101 activation of peach stone chars led to the development of microporosity accompanied by an

102 increase in the number of oxygen surface groups [26]. Duranoglu et al. prepared microporous

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103 activated carbon from peach stone by steam activation [2]. They determined that activated

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104 carbon had acidic oxygen functionalities, mainly in the form of phenolic groups. Similarly,

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105 Galiatsatou et al produced the activated carbon with microporous structure steam activation

106 [28]. It was found that chemical functionality of the activated carbon surface depend on the

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107 type of the activating agent (steam and carbon dioxide) in physical activation of peach stone

108 [29].

109
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In comparison with those studies, this study covered pyrolysis at low temperatures
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110 (precarbonization) and then chemical activation using ZnCl2. To our knowledge, this is the

111 first time that the production of both activated carbon with high yields and fungicidal oil are
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112 provided by two-stage process at low temperatures. The effects of temperatures of

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113 precarbonization and activation steps on the yield and textural properties of activated carbons

114 from peach stone were investigated. In addition, phenol and methylene blue adsorption
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115 capacities of the produced activated carbons were studied. In order to compare two methods,
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116 one-stage chemical activation was also performed.

117
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118 2. MATERIAL and METHODS

119 2.1. Materials

120 Peach Stone (kernel+ shell) was supplied by a juice company (Dimes Food Company,

121 Turkey) and used as received. The stones consisted of approximately 6 % kernel and 94 %

122 shell. The proximate, ultimate and component analyses of stones are shown in Table 1.

123 2.2. Experimental setup

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124 2.2.1 TG Analysis

125 Thermo gravimetric analysis of raw stone, precarbonized stone, and ZnCl2-

126 impregnated raw- or precarbonized stone at ratio of ZnCl2 to biomass 1:1 by weight was

127 performed in a thermogravimetric (TG) analyzer (Perkin-Elmer Diamond TG/DTA) under N2

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128 atmosphere. The impregnated samples were prepared as follows. The raw stones or

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129 precarbonized stones were impregnated with ZnCl2 solution by the wet method. After

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130 impregnation, the samples were dried overnight at 105 °C. The sample (particle size <100

131 μm) was about 10 mg for each TG run. The flow rate of purge gas (N2, 99.99%) was kept at

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132 200 mL min-1. The sample was heated from the ambient temperature up to 700 °C at a heating

133 rate of 10 °C min-1. The repeatability of the experimental data was within ± 2.5 %.

134 2.2.2. One-stage process

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135 40 g of grounded raw stones (< 2mm) was mixed in a beaker with 150 mL of ZnCl2

136 solution (1.96 M) which corresponded to an impregnation ratio of 1:1 (weight of

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137 impregnation reagent/weight of stone). The slurry was then dried overnight in a moisture oven
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138 at 105 °C. The impregnated samples were pyrolyzed in a fixed bed design and stainless steel

139 reactor (L, 210 mm; Ø, 60 mm). The reactor was heated under nitrogen gas stream at a
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140 heating rate of 5 °C min-1 to the desired activation temperature (500, 600 and 700 °C) and
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141 held at this temperature for 1 h. After pyrolysis, the furnace was cooled to room temperature

142 in a nitrogen gas stream overnight. The char was boiled with 200 mL of 10% HCl solution for
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143 60 min, filtered in a vacuum flask, washed with hot water and finally washed with cold water

144 to remove the chloride ions and other inorganics. After washing, the activated carbon samples

145 were dried at 110 °C for 24 h and weighed.

146 The yield of activated carbon was calculated by

147 Yield, % = (m /M) x 100 (1)

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148 where M is the initial mass of raw stone, g; m is the mass of resultant activated carbon, g. The

149 experiments were performed in duplicate. The repeatability of the experimental data was

150 within ± 2.8 %.

151 2.2.3. Two-stage process

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152 In a typical run, 100 g of stones (whole stone as received) was filled in a reactor and

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153 then the reactor temperature was increased by a heating rate of 5 °C min-1 up to pyrolysis

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154 temperature (300, 400 and 500 °C) and held for 1 h at this temperature. The reactor was

155 continuously purged with nitrogen at a flow rate of 25 mL min-1. The nitrogen gas swept the

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156 volatile products from the reactor into the ice-cooled traps. All the liquid products were

157 condensed in the traps. The non-condensable volatiles (gases) were vented to the atmosphere.

158
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After pyrolysis, the furnace was cooled to the room temperature in a nitrogen gas stream. All
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159 traps were weighted before and after each run. The total liquid amount was calculated by

160 difference. The yields of liquid product and char were determined by weighting. The amount
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161 of gas was determined by difference. The liquid product consisted of two phases: aqueous
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162 phase and oil phase. The aqueous phase was separated from oil phase by funnel and weighted.

163 The chars obtained at 300 °C, 400 °C and 500 °C were denoted as RC300, RC400 and
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164 RC500, respectively.

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165 The chars obtained from pyrolysis (precarbonized stones) were ground below 0.5 mm and

166 mixed with ZnCl2 solution at an impregnation ratio of 1:1. The impregnated samples were
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167 then pyrolyzed in a nitrogen gas stream at different temperatures (500 °C, 600 °C and 700 °C)

168 for 1 h. The char was washed and dried as in the one-stage process. The yield of activated

169 carbon was calculated based on initial mass of raw stone (as in Eq 1). The experiments were

170 performed in duplicate. The repeatability of the experimental data was within ± 2.6 %.

171 2.2.4 Characterization of activated carbons

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172 The BET surface area was calculated from the adsorption isotherms by using

173 Brunauer-Emmett-Teller equation. The BET (Brunauer–Emmett–Teller) surface area

174 measurements were obtained from nitrogen adsorption isotherms at 77 K using a

175 Micrometrics FlowSorb II-2300 Surface Area Analyzer. Automatic equipment (TriStar 3000)

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176 was used to obtain the nitrogen adsorption isotherms. To determine the micropore volumes

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177 (Vo) and the external area, the t-plot approach was applied. Mesopore volumes (Vm) and areas

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178 were determined by subtracting micropore volumes and areas from total pore volumes (V) and

179 areas. Attenuated total reflectance infrared (ATR/IR) spectrometry of activated carbons was

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180 performed by using a spectrophotometer (Spectrum 100, Perkin-Elmer). The amount of the

181 surface oxygen groups on the activated carbons was determined by Boehm titration method

182 [30].
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183 2.2.5. Analysis of liquid products

184 The condensable pyrolysis products were separated into aqueous fractions and oils.
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185 The oils were extracted with ethyl acetate that allows qualitative analysis of contained organic
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186 compounds. The ethyl acetate extracts were analyzed by gas chromatography coupled with

187 mass selective detector (GC–MSD), performed on an Agilent 6890N GC–5975 inert XL
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188 Agilent MSD working at 70 eV. The column used was an HP5 - MS column with a 30 m 0.25
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189 mm i.d. cross-linked methyl siloxane with 0.25 μm film thickness. The following parameters

190 were used: injector temperature of 225 °C, split ratio of 50:1, volume of injected sample of
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191 0.2 μl; temperature program – initial temperature of 35 °C that was held for 1 min, followed

192 by heating up to 50 °C by a heating rate of 5 °C min-1 then up to 240 °C by a heating rate of

193 10 °C min-1 and finally held at 240 °C for 7 min; flow rate program– initial flow rate of 0.5 ml

194 min-1 that was held for 4 min, then increased to 1 ml min-1 that was maintained until the end

195 of analysis. Identification of compounds was performed according to library data.

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196 The amount of the total phenols in aqueous fractions and oils was determined by

197 colorimetry (reaction of phenols with 4-nitroaniline to a yellow complex) with the photometer

198 by Hach Lange-DR2800. The amount of water in oils and aqueous fractions were determined

199 by coulometric or volumetric Karl Fischer Titrator (Mettler Toledo DL 31).

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200 2.2.6 Fungal cultures and inhibition test

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201 In this study, the anti fungal activity of bio-oil obtained from pyrolysis at 300 ºC was

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202 tested for two types of fungal cultures, namely Aspergillus niger TEM (a saphrophytic

203 fungus) and Coriolus versicolor ATCC 200801, (a white rot fungus). The inhibition test was

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204 carried out in a similar way described by Mourant et al. [31]. Since the commercial anti-

205 fungal substance used at the concentrations smaller than 50 mg/ml, the concentration range

206 tested was 2-50 mg/ml.

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Emulsions containing 2, 10, 20, 30, 40 and 50 mg extract ml-1 were prepared by serial
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208 dilutions in 1% dimethylsulfoxide. An aliquot of 50 µl of the extracts was added to peripheral

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209 holes and a 6 mm in diameter cylindrical plug of mycelium cut from the edge of actively
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210 growing colony was also added to central hole. Petri dishes were incubated at 27 °C for 10

211 days. The distance between the peripheral holes and the rim of the fungal colony was
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212 measured after 10 days. All experiments were done triplicate. Then, the inhibition was
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213 calculated by the following formula:

214 Inhibition % = (1-[ dt – di ]) / dt) x 100 (2)

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215 where dt is total distance between the central hole and the peripheral hole and di is the

216 distance between mycelial edge of fungal growth and the peripheral hole.

217 2.2.7 Adsorption from solution

218 To determine the adsorption capacity of activated carbons from the aqueous solution,

219 we selected methylene blue, representing colored pollutants, and phenol representative of the

220 phenolic pollutants. The adsorption isotherms were obtained by adding 0.1 g activated carbon

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221 sample into 100 ml test solutions of various concentrations (ranging between 225 and 325 mg

222 L-1 for methylene blue and 10-100 mg L-1 for phenol,) in flasks. The suspensions were shaken

223 for an equilibrium time determined in preliminary studies (24 and 2 h for methylene blue and

224 phenol, respectively). The filtrates were analyzed for residual methylene blue and phenol

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225 concentrations, using the UV-vis spectrophotometer (UV-160A, Shimadzu) at 665 and 269

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226 nm, respectively. The each test was carried out in duplicate and standard deviations were

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227 found to be ± 2.4 %.

228 3. Results and discussion

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229 3.1. Thermogravimetric Analysis Results

230 Thermal analysis is used to have a better understanding about the activation process.

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The volatile evolution during carbonization of the impregnated samples was monitored by
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232 TGA, and the results were compared to those of the untreated material.

233 Generally, the occurrence of the main two weight-loss steps has been reported in
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234 literature on the pyrolysis of different lignocellulosic materials [3]. The first weight-loss step
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235 is associated with the decomposition of hemicellulose, and the second with cellulose

236 decomposition whereas lignin degradation occurs over a broad temperature interval (150–480
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237 °C or higher). The decomposition temperatures of these fractions depend on the

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238 lignocellulosic material. In the present study, following the weight loss corresponding to loss

239 of moisture (below 100 °C), the DTG curve for peach stone exhibits two weight-loss steps ( at
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240 295 °C and 355 °C ) between 200 and 470 °C (Fig 1). As expected, in the degradation of the

241 precarbonized stones, one major peak at higher temperatures was observed corresponding to

242 degradation of char. In the case of precarbonized stone at 300 °C, the decomposition of the

243 lignin took place besides degradation of char. It is clear that the presence of ZnCl2 has a

244 significant effect on the pyrolysis behavior of peach stone. When the peach stone was

245 impregnated with ZnCl2, the degradation started at a relatively low temperature, accompanied

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246 by dehydration, degradation and condensation reactions. The first maximum weight-loss

247 observed around 200 °C (attributed to hemicellulose and cellulose degradation) and the

248 sample continued gradually losing weight up to 400 °C. The second maximum weight-loss

249 was observed around 550 °C (attributed to both lignin degradation and the release of ZnCl2).

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250 Concerning the thermal volatilization of ZnCl2, it was observed that in the temperature range

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251 of 400–590 °C, the weight loss of ZnCl2 was significant, particularly at temperatures around

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252 570 °C [32]. We can suggest that the weight loss between 400 °C and 700 °C may be

253 attributed to the release of ZnCl2 accompanied by the volatiles from the degradation of lignin.

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254 The overall weight loss was lower than that of obtained by raw stone. The stone with ZnCl2

255 impregnation yielded 66 % of residue, which was higher than that of raw stone (ca. 24 %).

256
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The yield was calculated on the basis of 50% stone in the sample and by assuming that all
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257 ZnCl2 was evaporated. It is well known that ZnCl2 works as a dehydration reagent but it also

258 limits the formation of tar during the carbonization treatment, increasing the yield of the
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259 remaining solid product. This observation is in agreement with the results of studies on other
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260 lignocellulosic materials [13, 23].

261 In the case of precarbonized stones, the residue yields of impregnated samples were
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262 lower than that of non-impregnated samples. Thus, the residue yields were about 80%, 82 %
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263 and 95 % for the impregnated-RC300, -RC400 and -RC500, respectively, whereas the yields

264 were 70%, 76% and 88% for the non-impregnated-RC300, -RC400 and -RC500, respectively.
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265 3.2. Pyrolysis Yields

266 The product yields for the pyrolysis of peach stone at different temperatures are given

267 in Table 2. As seen from Table 2, the product distribution did not significantly change when

268 the temperature was below 500 °C. But the char yield decreased as the temperature rose from

269 400 °C to 500 °C while gas yields increased. The results revealed that char decomposed to

270 mainly gaseous product when the temperature increased from 400 °C to 500 °C. On the other

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271 hand, the temperature significantly affected the composition of the liquid product. The liquid

272 product obtained from pyrolysis at 300 °C was in one phase. Although the yield of total liquid

273 (oil and aqueous phase) was slightly increased by the rise in pyrolysis temperature from 400

274 °C to 500 °C, the amount of oil in total liquid product considerably decreased. All these

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275 results showed that the compounds in oil phase were degraded into water and water soluble

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276 compounds by the secondary cracking reactions, besides char degradation.

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277 The effect of temperature on pyrolysis of lignocellulosic material was studied by many

278 researchers. Some differences were observed due to the difference in the biomass species. In

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279 our previous study on the slow pyrolysis of cherry seed, the product distribution has not

280 significantly changed when the pyrolysis temperature was above 300 ºC [33]. There was a

281
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slight increase in gas and liquid products, and a decrease in char product yields as temperature
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282 rose from 400 to 600 ºC. However, in some studies related to slow pyrolysis of lignocellulosic

283 materials oil yield reached a maximum value at 500-550 ºC, and above these temperatures oil
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284 yields decreased while gas yield increased [34,35]. Meanwhile, the char yield continuously
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285 decreased with increasing temperature.

286 3.3. Composition of Pyrolysis Liquids

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287 Biomass pyrolysis liquids are either homogenous one phase oil containing large
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288 amount of water or a heterogeneous liquid separated into an aqueous and oil phase. In this

289 study, the pyrolysis liquids obtained from the pyrolysis at 400 °C and 500 °C consisted of two
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290 phases: aqueous phase and oil phase. The aqueous phase contained mainly water (≥ 92 %).

291 Bio-oils contained huge amount of water (Table 2), although oil phase was separately

292 collected from the aqueous phase. This showed that some compounds in bio-oil acted as

293 emulsifier. In other words, the bio-oil can be considered a microemulsion in which the

294 continuous phase is an aqueous solution of holocellulose and lignin decomposition products

295 [36]. Because of high water content, bio-oils had poor fuel quality, but they contained some

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296 valuable chemicals, such as phenolic compounds (Table 2). As known, biomass derived

297 phenols can be used as smoke flavor, anti-fungal materials, and raw material for phenolic

298 resins. As can be seen in Table 2, bio-oils contained high amount water (free water in biomass

299 + reaction water). By considering the liquid product yields and water contents, it can be

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300 concluded that the increase in the pyrolysis temperature also leads to an increase in water

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301 formation.

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302 The bio-oils were characterized by using GC-MSD. The GC-MSD chromatograms of

303 bio-oils obtained at different temperatures are presented in Fig 2. The phenols were found to

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304 be the dominant species in all bio-oils.

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3.4. Fungicidal value of bio-oil

306 As mentioned before, bio-oil can be used as antioxidant [15] and fungicide [37] since
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307 it contains phenol and derivatives from thermal degradation of lignin. One of the aims of this

308 paper was to investigate the fungicidal properties of bio-oil obtained from peach stone. The
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309 bio-oil obtained from pyrolysis of peach stone at 300 °C and 500 °C were selected for
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310 antifungal activity test. These temperatures were selected as based on lignin decomposition

311 resulting in formation of phenolic compounds. Although lignin decomposition occurs over a
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312 broad temperature interval (150– 500 °C), the maximum degradation rate was around 500 oC
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313 (Fig 1). Because of this reason, 300 °C and 500 °C were selected as minimum and maximum

314 temperature tested for lignin decomposition.

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315 As seen in Table 2, about 1.5 wt % of bio-oils consisted of phenolic compounds which

316 were mainly monomeric phenols (Fig 2).

317 Although the wood decaying properties of fungi were mostly evaluated in the

318 literature about the antifungal activity of bio-oil, fungi used in this study were selected

319 according to wood decaying and saprophiting properties. Aspergillus niger is a fungus which

320 causes a disease called black mold on certain fruits and vegetables such as grapes, onions, and

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321 peanuts, and is a common contaminant of food. Coriolus versicolor- also known as Trametes

322 versicolor- is an extremely common polypore mushroom which can be found throughout the

323 whole world. C. versicolo is commonly called Turkey Tail because of its resemblance to the

324 tail of the wild turkey. The bio-oil produced from peach stone showed fungicidal activity

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325 against C. versicolor fungi at the concentration of 40-50 mg ml-1 whereas it showed no

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326 considerable activity against A. niger fungi even at the concentration 40-50 mg ml-1 (Table 3).

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327 The fact that the bio-oil showed fungicidal activity against C. versicolor fungi is due to its

328 phenolic contents. Mohan et al. reported that 4-Propyl-2-methoxyphenol could contribute to

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329 decay resistance [37]. Another significant result was that the color around the fungal colony

330 changed from white to brown during the test with C. versicolor. This may be due to

331
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metabolizing of the lignin and phenolic compounds in bio-oil by C. versicolor having
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332 lignolytic activity.

333 3.5. Yield and characterization of the activated carbons

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334 In this study, activated carbons were obtained by two ways, namely (one-stage) and
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335 (two-stage) (Fig 3). The yield percentages obtained for the activated carbon produced by both

336 two processes are shown in Table 4. The activated carbons obtained from one-stage process at
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337 500, 600 and 700 °C were denoted as AC-500, AC-600 and AC-700, respectively. For the
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338 activated carbons obtained from two-stage process, the pyrolysis temperature (first-step) was

339 shown as symbols of AC3 and AC4 which represent 300 and 400 °C, respectively. The
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340 temperatures of the second step (activation steps at 500, 600 and 700 °C) were given after

341 dash in symbol. For example, the activated carbon prepared by two-stage process at 700 °C

342 by using the char obtained from pyrolysis at 300 °C was denoted as AC3-700.

343 In the case of one-stage activation, the activation temperature had remarkable effects

344 on the surface area. The surface area decreased gradually with the increasing temperature

345 from 500 °C to 700 °C, probably due to the shrinkage of the carbon structure [9]. This result

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346 is in agreement with the results obtained from chemical activation of other fruit stones [9, 38].

347 It should be noted that in most of the studies, the temperatures of 400-500 °C were chosen as

348 optimum for lignocellulosic precursors in activation using ZnCl2 [5, 11, 17, 38]. The high

349 activation temperature also affected the nature of porosity of activated carbons. The Vo/V did

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350 not change considerably over the temperature 500-600 oC, but significantly increased above

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351 600 oC. This shows that higher temperatures caused some of the mesopores to collapse.

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352 In this study, our aim was not investigate the production of activated carbon with one-

353 stage process. Based on the results from one-stage process, we selected the activation

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354 temperatures which were used in two-stage process. In the case of two-stage activation, the

355 surface area was substantially influenced by the carbonization temperature used in the first

356
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stage. As a comparison between AC3-500 and AC4-500 or AC3-600 and AC4-600, the
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357 activation of AC3 yielded the activated carbon with higher surface area and more mesoporous

358 nature compared to AC4. During carbonization of the lignocellulosic material, degree of
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359 aromaticity and the content of fixed carbon increased in the residual carbonized product with
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360 increasing temperature [8]. As seen in Fig 1, some part of lignin still exists in AC3 char, so

361 AC3 contained reactive groups that easily reacted with ZnCl2. As in one-stage activation, the
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362 activation temperature also exhibited a significant influence on both surface area and the
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363 nature of porosity. The surface area sharply decreased when the activation temperature was

364 increased from 600 °C to 700 °C for AC3 and from 500 °C to 600 °C for AC4. But, Vo/V
Ac

365 significantly increased while surface areas decreased, as in the case of one-stage process.

366 When two-stage process was compared with one-stage process it was clear that activation

367 temperature had a similar effect on the surface area and V0/V of the obtained activated

368 carbons. The surface area of activated carbons obtained from the two-stage activation was

369 found to be lower than those obtained from the one-stage activation, although the former had

370 a higher microporous nature compared to the latter. Previous studies carried out with grain

Page 15 of 39
 16

371 sorghum have shown that the combination of a precarbonization at 300 °C followed by a a

372 chemical activation treatment with H3PO4 produced activated carbon with higher surface area

373 and microporosity than one-stage activation [39]. The differences can be explained by a

374 different reactivity of the surface functional groups presented on the surface of the carbon

t
375 precursors against the activating agent used (ZnCl2).

ip
376 It is generally claimed that ZnCl2 works as a dehydration reagent and it is deduced that

cr
377 the dehydration induces the charring and aromatization of the carbon and restricts the

378 formation of tar in this temperature range. However, in two-stage activation, no dehydration

us
379 effect from ZnCl2 is expected since carbon percursors were already carbonized. As expected,

380 the interaction between the lignocellulosic materials and ZnCl2 is better than the interaction

381
an
between charry material and ZnCl2. Although AC3 and AC4 had very low surface area (< 10

m2 g-1), the activated carbons derived from them had considerably high surface areas. This
M
382

383 result shows the presence of interaction between carbonized material and ZnCl2.
d

384 The surface characteristics of the activated carbons in the present study can be
te

385 compared with other reported values for the peach stone based precursor. The activated

386 carbons obtained from peach stone using H3PO4 had surface area ranging from
p

387 1054 to 1404 m2 g-1 [18, 20, 22], while activated carbon obtained using physical activation
ce

388 had surface area ranging from 608 to 1274 m2 g-1 [2, 12, 26, 27, 29, 40]. The activation of

389 peach stone with H3PO4 at 500 °C produced the highly microporous (Vo/V ≥ 80%) activated
Ac

390 carbons [18, 20]. A previous report related to ZnCl2- and H3PO4-activation of peach stone at

391 a activation temperature of 500 °C indicated that the development of microporosity depended

392 on the concentration of activating agent [2, 26, 40]. Although microporosity was dominant at

393 low concentration (an impregnation ratios of 0.3:1 and 0.23 for H3PO4 and ZnCl2,

394 respectively), the mesoporosity started to develop for higher concentrations. Moreover, steam

395 activation of peach stone produced a highly microporous carbon. On the other hand, the

Page 16 of 39
 17

396 mesoporous activated carbons were prepared from peach stones using a combination of the

397 traditional chemical (with ZnCl2) and physical activation (using CO2) yielded [41].

398 The FT-IR spectrum (Fig. 4) showed similar peaks for all activated carbons (from both

399 one- and two stage). Moreover, the intensity of the absorption bands was very weak, which

t
400 indicates that the preparation of activated carbon from peach stone by different methods is not

ip
401 an effective way of modifying the surface functional groups and structures in the resultant

cr
402 products. There were four bands of interest; the first one at 1738 cm-1, associated with C=O

403 stretching in lactones and carboxylic anhydrides, the second one at 1600 cm-1 associated with

us
404 quinone and keto-enol groups, the third one at 1365 cm-1 associated with C-H alkanes, and the

405 last one at 1230-1210 cm-1 associated with C-O stretching in ethers, lactones, phenols and

406 carboxylic anhydrides.

an
M
407 As known, the chemical nature of activated carbons significantly influences its

408 adsorptive properties as well as its surface area and porosity. The oxygen functional groups
d

409 are very important characteristics of the activated carbons because they determine the surface
te

410 properties of the carbons and hence their quality as adsorbents. In this study, the oxygen-

411 containing functional groups on activated carbon surfaces were evaluated by Boehm titration.
p

412 The greatest amount of oxygen groups (1.09 mmol g-1) was determined in the samples
ce

413 obtained by one-stage activation at 600 °C. The results revealed that the predominant

414 functions at the surface of the activated carbons were basic (Table 5).
Ac

415 3.6. Adsorption from Solution

416 Aqueous adsorption tests were conducted on selected activated carbons (AC-500, AC-

417 600, AC3-500 and AC3-600) with the aim of assessing potential applications in the water-

418 treatment process. The tested adsorbates (methylene blue and phenol) cover a range of

419 molecular sizes, which makes them useful for the investigation of adsorption in pores of

Page 17 of 39
 18

420 different dimensions. Phenol is preferentially adsorbed in small- and medium-sized

421 micropores, while methylene blue is mainly adsorbed in medium- and large sized micropores.

422 In adsorption experiments, optimum equilibrium time and pH was determined as 24 h for

423 methylene blue and 2 h for phenol and natural pH of the solution according to the preliminary

t
424 studies, respectively. The isothermal equilibrium data obtained were processed by employing

ip
425 Langmuir and Freundlich isotherm equations.

cr
426 The former is used to describe the adsorption characteristics in a heterogeneous

427 system; the latter assumes the adsorbate uptake occurs on a homogenous surface by a

us
428 monolayer adsorption.

429 The Freundlich model is given as

430 Qe = KF Ce1/n
an (3)
M
431 Where, KF is freundlich constant and roughly an indicator of adsorption capacity. 1/n gives an

432 indication of the favorability of adsorption. High value of n indicates a strong bond between
d

433 the adsorbent and the adsorbate. Heterogeneity becomes more prevalent as 1/n gets closer to
te

434 zero.

435 The Langmuir model is expressed as

p

436 Ce/qe = 1/KLSM + Ce/SM (4)

ce

437 Where, SM is the monolayer capacity (mg g-1), KL is the Langmuir constant (L mg-1), Ce and

438 qe are the amounts of adsorbate in solution and on solid (mg L-1).
Ac

439 Parameters of the Langmuir and Freundlich adsorption models of methylene blue and

440 phenol are given in Table 6. For phenol adsorption, both equations were found to fit the data

441 well for all tested activated carbons. All carbons (except AC-500) showed similar phenol

442 adsorption capacities. The differences or similarities observed on the adsorption capacities of

443 these carbons could not be indicated their BET surface areas and micropore volumes. The fact

444 that the AC-500 sample with the highest surface area yielded a somewhat lower capacity than

Page 18 of 39
 19

445 the others could not be explained by the surface areas only. In addition, the micropore volume

446 alone does not appear sufficient for the understanding of trends observed on the phenol

447 adsorption capacities of different carbons. Although the AC-500 had a similar micropore

448 volume with AC-600, it showed a lower adsorption capacity than AC-600. The reason might

t
449 be that the phenol adsorption is highly related to the oxygen containing surface functional

ip
450 groups. Since phenol is a weak acid, its adsorption is dependent on the presence of surface

cr
451 groups besides porosity [42]. The influence of basic surface oxygen groups on the adsorption

452 of phenol by activated carbons was already observed by some researchers [13, 43]. It may be

us
453 concluded that due to the lower basic functional groups, AC-500 showed lowest phenol

454 adsorption.

455
an
The phenol adsorption capacities was higher than the adsorption capacity of the
M
456 activated carbon produced from tobacco residues, coffee husks, coconut shell, olive stone and

457 commercial activated carbon [4, 42, 44, 45, 46]. But, it was lower than the derived from date
d

458 stones, piassava fibers, macadamia nut shells [47, 48, 49] For methylene blue adsorption,
te

459 isotherm data fit well to both Langmuir and Freundlich models (except AC3-600). However,

460 higher R2 values were obtained from the Langmuir model. The AC-600 showed the highest
p

461 adsorption capacity for methylene blue, probably due to its highest amount of acidic surface
ce

462 groups. Since methylene blue has a cationic character, surface acid groups presented in

463 activated carbons are good anchoring sites for it. However, two adsorption mechanisms
Ac

464 should take into account; which are electrostatic interactions between cationic dye and

465 negatively charged carbon and dispersive interactions between the delocalized p electron of

466 the carbon surface and the free electrons of the dye molecule). The hereby-derived carbons

467 exhibit lower adsorption capacity for methylene blue in comparison to several reported

468 investigations of 263-738 mg/g [18, 20, 47, 50].

469

Page 19 of 39
 20

470 As known, the nature and the molecular dimension of the organic compound, the

471 porous and the chemical structure of the activated carbon surface, and the pH of the aqueous

472 solution are the most important parameters to determine the adsorptive removal of organic

473 compounds, such as dyes, surfactants, phenols, pesticides, aromatic hydrocarbons, nitro

t
474 compounds, etc, from water. Because of this, it is difficult to make discussion on the potential

ip
475 of activated carbons obtained for each pollutant. But, it can be said that activated carbons

cr
476 obtained in this study may show a reasonable adsorption capacity for small size of nitro

477 compounds, halogenated organic compounds, anionic dyes, as well as phenol, due to the

us
478 their basic surface groups.

an
479 4. Conclusion

480 In this study, the production of activated carbons from peach stone with zinc chloride
M
481 by means of two-stage process was examined. The first step of this process was designed for

482 recovering bio-oil, which can be directly used as fungicidal oil. Another alternative can be the
d

483 separation of phenolic compounds in bio-oil which show fungicidal activity. In the second
te

484 step of the process, activated carbon was produced by activation of chars from the first step.

485 For comparison purpose, activated carbon from peach stone by conventional chemical
p

486 activation was also carried out. Generally speaking, the two-stage process produced activated
ce

487 carbons with moderate surface areas (388-1178 m2g-1), whereas the conventional one-stage

488 pyrolysis yielded activated carbons with large surface areas (1344-1776 m2g-1). Nevertheless,
Ac

489 the activated carbons from the two-stage activation had higher microporous nature. The main

490 advantage of the two-stage process was that the bio-oil produced in the first step showed

491 fungicidal activity.

492 The adsorption capacity of the prepared activated carbons for phenols was mainly

493 proportional to the basic surface oxygen groups, irrespective of the activation process. On the

Page 20 of 39
 21

494 other hand, the adsorption of methylene blue on the activated carbons depended on both the

495 BET surface area and the amount of acidic surface groups.

496 Although energy consumption in two-stage process seems higher than that in one-

497 stage, the fact that utilization of by-product is the main advantage of this process. In addition,

t
ip
498 the char obtained from first-stage has good grindability compared to raw material, resulting in

499 lower grinding energy requirements. From the obtained results in this study, we concluded

cr
500 that further research, for instance the selection of other chemical activators (H2SO4, KOH,

us
501 etc.), is necessary for the induction of a large surface area and the optimization of the surface

502 chemistry of the activated carbon from two-stage process that can be used as adsorbent in

an
503 water-treatment process.

504 In addition, for a better understanding of the properties of these activated carbons, it is
M
505 necessary to expand this work by including the adsorption of other potentially polluting

506 molecules.
d

507 References
te

508 [1] R.C. Bansal, M. Goyal Activated Carbon Adsorption Taylor and Francis Group, CRC

509 Press, Boca Raton, USA (2005)

p

510 [2] D. Duranoglu, A. W. Trochimczuk, U. Beker, A comparison study of peach stone and
ce

511 acrylonitrile-divinylbenzene copolymer based activated carbons as chromium(VI)

Ac

512 sorbents, Chemical Engineering Journal 165 (2010) 56–63.

513 [3] J.F. Gonzalez, S. Roman, J.M. Encinar, G. Martinez, Pyrolysis of various biomass

514 residues and char utilization for the production of activated carbons, Journal of

515 Analytical and Applied Pyrolysis 85 (2009) 134–141.

516 [4] T. Bohli, N. Fiol, I. Villaescusa and A. Ouederni, Adsorption on activated carbon from

517 olive stones: kinetics and equilibrium of phenol removal from aqueous solution,

518 Journal of Chemical Engineering & Process Technology 4(6) (2013) 1-5.

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519 [5] M. Soleimani, T. Kaghazchi, Agricultural waste conversion to activated carbon by

520 chemical activation with phosphoric acid, Chemical Engineering & Technology 30(5)

521 (2007) 649–654.

522 [6] M. L. Sekirifa, M. Hadj-Mahammed, S. Pallier, L. Baameur, D. Richard, A. H. Al-

t
523 Dujaili, Preparation and characterization of an activated carbon from a date stones

ip
524 variety by physical activation with carbon dioxide, Journal of Analytical and Applied

cr
525 Pyrolysis 99 (2013) 155–160.

526 [7] C. Bouchelta, M. S. Medjram, O. Bertrand, J.P. Bellat, Preparation and

us
527 characterization of activated carbon from date stones by physical activation with

528 steam, Journal of Analytical and Applied Pyrolysis 82 (2008) 70–77.

529
an
[8] C.J. Duran-Valle, M. Gomez-Corzo, J. Pastor-Villegas, V. Gomez-Serrano, Study of
M
530 cherry stones as raw material in preparation of carbonaceous adsorbents, Journal of

531 Analytical and Applied Pyrolysis 73 (2005) 59–67.

d

532 [9] D. Angin, Production and characterization of activated carbon from sour cherry stones
te

533 by zinc chloride, Fuel 115 (2014) 804–811.

534 [10] P. Nowicki, H. Wachowska, R. Pietrzak, Active carbons prepared by chemical

p

535 activation of plum stones and their application in removal of NO2, Journal of
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536 Hazardous Materials 181 (2010) 1088–1094.

537 [11] R.H. Hesas, A. Arami-Niya, W. M. A. W. Daud, J.N. Sahu, Comparison of oil palm
Ac

538 shell-based activated carbons producedby microwave and conventional heating

539 methods using zincchloride activation, Journal of Analytical and Applied Pyrolysis 104

540 (2013) 176–184.

541 [12] A. Gundogdu, C. Duran, H. B. Senturk, M. Soylak, M. Imamoglu, Y.Onal,

542 Physicochemical characteristics of a novel activated carbon producedfrom tea industry

543 waste, Journal of Analytical and Applied Pyrolysis 104 (2013) 249–259.

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 23

544 [13] G. Duman, Y. Onal, C. Okutucu, S. Onenc, J. Yanik, Production of activated carbon

545 from pine cone and evaluation of its physical, chemical, and adsorption properties,

546 Energy&Fuels 23 (2009) 2197–2204.

547 [14] M. Kilic, E. Apaydin-Varol, A. E. Pütün, Adsorptive removal of phenol from aqueous

t
548 solutions on activated carbon prepared from tobacco residues: equilibrium, kinetics and

ip
549 thermodynamics, Journal of Hazardous Materials 189 (2011) 397–403.

cr
550 [15] A.Y. Loo, K. Jain, I. Darah, Antioxidant activity of compounds isolated from the

551 pyroligneous acid, Rhizophora apiculata, Food Chemistry 107 (2008) 1151-1160.

us
552 [16] C. Okutucu, G. Duman, S. Ucar, I. Yasa, J. Yanik, Production of fungicidal oil and

553 activated carbon from pistachio shell, Journal of Analytical and Applied Pyrolysis 91

554 (2011) 140–146.

an
M
555 [17] D. Kim, Activated carbon from peach stones using phosphoric acid activation at

556 medium temperatures, Journal of Environmental Science and Health Part A-

d

557 Toxic/Hazardous Substances&Environmental Engineering 39 (5) (2004) 1301-1318.

te

558 [18] B. S. Girgis, A. A. Attia, N.A. Fathy, Modification in adsorption characteristics of

559 activated carbon produced by H3PO4 under flowing gases, Colloids and Surfaces A:
p

560 Physicochemical and Engineering Aspects 299 (2007) 79–87.

ce

561 [19] Y. Munoz-Gonzalez, R. Arriagada-Acuna, G. Soto-Garrido and R. Garcia-Lovera,

562 Activated carbons from peach stones and pine sawdust by phosphoric acid activation
Ac

563 used in clarification and decolorization processes, Journal of Chemical Technology

564 and Biotechnology 84 (2009) 39–47.

565 [20] A. A. Attia, B. S. Girgis, N. A. Fathy, Removal of methylene blue by carbons derived

566 from peach stones by H3PO4 activation: batch and column studies, Dyes and Pigments

567 76 (2008) 282-289.

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568 [21] D.A. S. Maia, K. Sapag, J. P. Toso, R. H. López, D. C.S. Azevedo, C. L. Cavalcante

569 Jr., G. Zgrablich, Characterization of activated carbons from peach stones through the

570 mixed geometry model, Microporous and Mesoporous Materials 134 (2010) 181–188.

571 [22] D. A. S. Maia, J.C. Alexandre de Oliveira, J. P. Toso, K. Sapag, R. H. López, D. C.S.

t
572 Azevedo, C. L. Cavalcante Jr., G. Zgrablich, Characterization of the PSD of activated

ip
573 carbons from peach stones for separation of combustion gas mixtures, Adsorption 17

cr
574 (2011) 853–861.

575 [23] M. Molina-Sabio, F. Rodriguez-Reinoso, Role of chemical activation in the

us
576 development of carbon porosity, Colloids and Surfaces A: Physicochemical and

577 Engineering Aspects 241 (2004) 15–25.

578
an
[24] Ö. Gerçel, A. Özcan, A. S. Özcan, and H. F. Gerçel, Capacity of activated carbon
M
579 derived from peach stones by K2CO3 in the removal of acid, reactive, and direct dyes

580 from aqueous solution, Journal of Environmental Engineering 135 (2009) 333-340.
d

581 [25] I. Cabritaa, B. Ruiz, A.S. Mestre, I.M. Fonseca, A.P. Carvalho, C.O. Ania, Removal
te

582 of an analgesic using activated carbons prepared from urban and industrial residues,

583 Chemical Engineering Journal 163 (2010) 249–255.

p

584 [26] R. Arriagada, R. Garcia, M. Molina-Sabio, F. Rodriguez-Reinoso, Effect of steam

ce

585 activation on the porosity and chemical nature of activated carbons from Eucalyptus

586 globulus and peach stones, Microporous Materials 8 (1997) 123-130.

Ac

587 [27] M. Yalcin, A. I. Arol, Gold cyanide adsorption characteristics of activated carbon of

588 non-coconut shell origin, Hydrometallurgy 63 (2002) 201– 206.

589 [28] P. Galiatsatou, M. Metaxas, and V. Kasselouri-Rigopoulou, Mesoporous activated

590 carbon from agricultural byproducts, Microchimica Acta 136 (2001) 147-152.

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591 [29] G. Bello, R. Cid, R. Garcia and R. Arriagada, Retention of Cr(VI) and Hg(II) in

592 Eucalyptus globulus- and peach stone-activated carbons, Journal of Chemical

593 Technology and Biotechnology 74 (1999) 904-910.

594 [30] H.P. Boehm, E. Diehl, W. Heck, R.Sappok, Surface Oxide of Carbon, Angewandte

t
595 Chemie International Edition 3 (1964) 669-677.

ip
596 [31] D. Mourant, D.Q. Yang, X. Lu, C. Roy, Anti-fungal properties of the pyroligneous

cr
597 liquor from the pyrolysis of softwood bark, Wood and Fiber Science 73 (2005) 542–

598 548.

us
599 [32] V. Boonamnuayvitaya, S. Sae-ung, W.Tanthapanichakoon, Preparation of activated

600 carbons from coffee residue for the adsorption of formaldehyde, Separation and

601
an
Purification Technology 42( 2005) 159-168.
M
602 [33]G. Duman, C. Okutucu, R. Stahl, S. Ucar, J. Yanik, The slow and fast pyrolysis of

603 cherry seed, Bioresource Technology 102 (2011) 1869-1878.

d

604 [34] F. Ates, M.A. Isıkdag, Influence of temperature and alumina catalyst on pyrolysis of
te

605 corncob, Fuel 88 (2009) 1991-1997.

606 [35] J.F. Gonzalez, A. Ramiro, C.M. Gonzalez-Garcia, J. Ganan, J.M. Encinar, E. Sabio,
p

607 Pyrolysis of almond shells. Energy applications of fractions, Industrial & Engineering
ce

608 Chemistry Research 44 (2005) 3003-3012.

609 [36] D. Mohan, C.U. Pittman Jr., P.H. Steele, Pyrolysis of Wood/Biomass for Bio-oil: A
Ac

610 Critical Review, Energy&Fuels 20 (2006) 848-889.

611 [37] D.Mohan, J. Shi, D.D. Nicholas, C.U. Pittman Jr., P.H. Steele, J. E. Cooper,

612 Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark

613 fast pyrolysis, Chemosphere 71 (2008) 456-465.

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 26

614 [38] M. Olivares-Marin, C. Fernandez-Gonzalez, A. Macias-Garcia, V. Gomez-Serrano,

615 Preparation of activated carbon from cherry stones by chemical activation with ZnCl2,

616 Applied Surface Science 252 (2006) 5967–5971.

617 [39] Y.Diao, W.P.Walawender, L.T.Fan, Activated carbons prepared from phosphoric acid

t
618 activation of grain sorghum, Bioresource Technology 81 (2002) 45-52.

ip
619 [40] D. Duranoglu, U. Beker, Steam and KOH activated carbons from peach stones,

cr
620 Energy sources part a-recovery utılızatıon and envıronmental effects 34(11) (2012)

621 1004-1015.

us
622 [41] A. Silvestre-Albero, M. Goncalves, T. Itoh, K. Kaneko, M. Endo, M. Thommes, F.

623 Rodriguez-Reinoso, J. Silvestre-Albero, Well-defined mesoporosity on lignocellulosic-

624
an
derived activated carbons, Carbon 50 (2012) 66 –72.
M
625 [42] G.G. Stavropoulos, P. Samaras, G.P. Sakellaropoulos, Effect of activated carbons

626 modification on porosity,surface structure and phenol adsorption, Journal of Hazardous

d

627 Materials 151 (2008) 414–421.

te

628 [43] E. Gonzalez-Serranoa, T. Corderoa, J. Rodriguez-Mirasola, L. Cotorueloa, J.J.

629 Rodriguez, Removal of water pollutants with activated carbons prepared from H3PO4
p

630 activation of lignin from kraft black liquors, Water Research 38 (2004) 3043–3050.
ce

631 [44] M. Kilic, E. Apaydin-Varol, A.E. Pütün, Adsorptive removal of phenol from aqueous

632 solutions on activated carbón prepared from tobacco residues: equilibrium, kinetics and
Ac

633 thermodynamics, Journal of Hazardous Materials 189 (2011) 397–403.

634 [45] C.A. L. Oliveira, E. Pereira, I. R. Guimaraes, A. Vallone, M. Pereira, J. P. Mesquita,

635 K. Sapag, Preparation of activated carbons from coffee husks utilizing FeCl3 and ZnCl2

636 as activating agents, Journal of Hazardous Materials 165 (2009) 87–94.

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637 [46] K.P. Singh, A. Malik, S. Sinha, P. Ojha, Liquid-phase adsorption of phenols using

638 activated carbons derived from agricultural waste material, Journal of Hazardous

639 Materials 150 (2008) 626–641.

640 [47] M. J. Ahmed, S.K. Theydan, Physical and chemical characteristics of activated carbon

t
641 prepared by pyrolysis of chemically treated date stones and its ability to adsorb

ip
642 organics, Powder Technology 229 (2012) 237–245.

cr
643 [48] K.R. Hall, L.C. Eagleton, A. Acrivos, T. Vermeulen, Pore- and solid-diffusion

644 kinetics in fixed-bed adsorption under constant-pattern conditions, Industrial and

us
645 Engineering Chemistry Fundamentals 5 (1966) 212–223.

646 [49] L. A. Rodrigues, L. A. S. Ribeiro, G. P. Thim, R. R. Ferreira, M. O. Alvarez-Mendez,

647
an
A. R. Coutinho, Activated carbon derived from macadamia nut shells: an effective
M
648 adsorbent for phenol removal, Journal of Porous Materials 20 (2013) 619–627.

649 [50] M. Stals, J. Vandewijngaarden, I. Wróbel-Iwaniec, G. Gryglewicz, R. Carleer, S.

d

650 Schreurs, J. Yperman, Characterization of activated carbons derived from short rotation
te

651 hardwood pyrolysis char, Journal of Analytical and Applied Pyrolysis 101 (2013) 199–

652 208.
p

653
ce
Ac

Page 27 of 39
 28

653

654
655  Production of both activated carbon (AC) and bio-oil by two-stage process.
656  Production of bio-oil having antifungal property.
657  ACs had higher microporous nature than ACs obtained from conventional process.

t
658

ip
659
660

cr
us
an
M
d
p te
ce
Ac

Page 28 of 39
 29

660 Figure Captions

661 Figure 1. TG and DTG curves of (a) peach stone, (b) coke obtained from pyrolysis at 300°C,
662 (c) coke obtained from pyrolysis at 400°C, (d) coke obtained from pyrolysis at 500°C (blue
663 lines: impregnated Sample; red lines: non-impregnated sample).
664 Figure 2. The GC-MSD chromatograms of bio-oils obtained from pyrolysis at (a) 300°C (b)
665 °C 400 (c) 500°C. 1: Solvent, 2: Acetic acid, 3: 1-hydroxy-2-propanone, 4: Propanoic acid, 5:
666 1-hydroxy-2-butanone, 6: Butanoic acid, 7: Furfural, 8: 2-Butenoic acid (crotonic), 9:
667 Acetylfuran, 10: Pentenoic acid;Benzaldehyde, 11: Methylfurfural;Methylfuroate, 12: Phenol,

t
668 13: 2-methylphenol, 14: 4-methylphenol, 15: Guaiacol, 16: 2,6-dimethylphenol, 17: 2-

ip
669 ethylphenol 18: 2,4-dimethylphenol, 19: Dihydroxybenzaldehyde, 20: Methylguaiacol, 21:
670 vinylguaiacol 22: Pyrocatechol, 23: Methylpyrocatechol, 24: Methoxypyrocatechol, 25:
671 Ethylguaiacol, 26: Homocatechol, 27: Syringol, 28: Propylguaiacol, 29: Ethylguaiacol, 30:

cr
672 Vanillin 31: Methylsyringol, 32: Acetovanillone, 33: Methoxyeugenol, 34: Homovanillic acid
673 35: Syringaldehyde, 36: Acetosyringone, 37: Homosyringic acid.
674 Figure 3. The experimental set-up.

us
675 Figure 4. FTIR spectrum of activated carbons.
676
677

an
M
d
p te
ce
Ac

Page 29 of 39
Figure(s)

Figure 1

100 7 100 4.5

a 6 4
80 80 b 3.5
5 3

Weight, %
Weight, %

60 60

dw/dT
dw/dT
4 2.5
3 40 2
40
1.5
2
20 20 1
1 0.5

t
0 0 0 0

ip
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature,°C Temperature, °C

cr
100 5 100 5

us
80 c 4 80 d 4
non-impregnated
Weight, %

60 3 Weight, % 60 3
dw/dT

dw/dT
sample

40

20
impregnated
sample
2

1
an 40

20
2

1
M
0 0 0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature,°C Temperature,°C
ed
pt
ce
Ac

Page 30 of 39
Non-impregnated materials
Figure(s)

Figure 2

1
16 21 27 (a)
2 25
7 22 31
24 26
15 33

t
12 23 30

ip
29
20 32
3 14 28
11 13 18 36
17 19 34 35

cr
5 9 10
4 6 8 37

us
16 21
2
7 25
an 27
31
(b)

33
12
M
15 24 26
11 19 23 30
13 28 32
4 9 10 14 17
6 29
ed

7 16 21
2 (c)
pt

25 27

31
ce

11 33
12
13 15 30
4 23 26 28 32
6 9 10 14 17 19
Ac

Page 31 of 39
Figure(s)

Figure 3

One- stage
Impregnation
Activation Activated
with ZnCl2 Carbon

Peach
stone

t
ip
Impregnation Activation Activated

cr
Carbonization
with ZnCl2 Carbon
Two- stage

us
Bio-oil
an
M
ed
pt
ce
Ac

Page 32 of 39
Figure(s)

Figure 4

751

t
1610
1230

ip
1738
1365

cr
us
an
M
ed
pt
ce
Ac

Page 33 of 39
Table(s)

Table 1. Proximate, ultimate and component analyses of Peach Stone.

Proximate Analysis (as received, wt %)

moisture 9.3
volatile matter 71.7
fixed carbon 17.9
ash 1.1

t
Ultimate Analysis (dry, %wt)

ip
C 45.92

cr
H 6.09
N 0.58
S 0.03

us
Oa 47.38

HHVb, MJ kg-1 19.33

Component Analysis (dry, %wt)

an
Cellulose 46
M
Hemicellulose 14
Lignin 33
Extractives c
ed

a
calculated from difference
b
pt

high heating value

c
toluene/alcohol (2/1) (v/v)
ce
Ac

Page 34 of 39
Table(s)

Table 2. Product distribution of pyrolysis of peach stone at different temperature and the
content of total phenols and water in bio-oil.

Temperature;°C 300 400 500

Pyrolysis Yields

t
Gas* 17 18 24

ip
Liquid
bio-oil 35 23
43**
aqueous

cr
10 24
Char 40 37 29
Bio-oil composition

us
Phenol, ppm 14440 21550 18550
Water, % 57.5 55.0 42.5
*by difference
** bio-oil+aqueous
an
M
ed
pt
ce
Ac

Page 35 of 39
Table(s)

t
ip
cr
us
an
Table 3. Antifungal activity of bio-oil obtained from pyrolysis of peach stone.

A. niger C. versicolor

M
Pyrolysis
300 500 300 500
Temperature, ºC
Concentration Inhibition, Inhibition, Inhibition, Inhibition,
dt di dt di dt di dt di
(mg ml-1)

d
% % % %
50 23 10 43.5 23 12 52.2 23 15 65.2 23 20 86.9
40
30
23
23
4
2
te 17.4
8.7
23
23
10
8
43.5
34.8
23
23
12
8
52.2
34.8
23
23
17
14
73.9
60.9
ep
20 23 0 0 23 4 17.4 23 4 17.4 23 10 43.5
10 23 0 0 23 0 0 23 0 0 23 6 26.1
c

2 23 0 0 23 0 0 23 0 0 23 0 0
Ac

Page 36 of 39
Table(s)

Table 4. Yield percentages and textural characterization parameters of activated carbons from
peach stone

Activated Yield, SBET Smic Sext V Vo Vm

Vo/V
carbon % (m2g -1) (m2 g -1) (m2 g -1) (cm3 g -1) (cm3 g -1) (cm3 g -1)
AC-500 43 1776 237 1538 0.96 0.14 0.82 0.15
AC-600 41 1535 243 1292 0.84 0.14 0.70 0.17
AC-700 41 1344 393 951 0.76 0.21 0.55 0.28

t
ip
AC3-500 31 1178 458 720 0.75 0.24 0.51 0.32
AC3-600 31 1169 431 738 0.71 0.23 0.48 0.32

cr
AC3-700 28 842 441 401 0.48 0.23 0.25 0.48
AC4-500 30 749 628 121 0.42 0.33 0.09 0.79

us
AC4-600 33 388 345 43 0.20 0.18 0.02 0.90

an
M
ed
pt
ce
Ac

Page 37 of 39
Table(s)

Table 5 Total amounts of surface acidic and basic sites of activated carbons.

Total acidic sites, Total basic sites,

Activated carbon
mmol H+/g AC mmol OH−/g AC
AC-500 0.19 0.71
AC-600 0.35 0.74
AC3-500 0.03 0.76
AC3-600 0.14 0.80

t
ip
cr
us
an
M
ed
pt
ce
Ac

Page 38 of 39
Table(s)

Table 6 . The Freundlich and the Langmuir isotherm constants for phenol and methylene blue
adsorption.

Activated Langmuir constants Freundlich constants

Adsorbates -1 -1 2
carbon SM(mg/g ) KL(Lmg ) R 1/n KF R2

Phenol AC-500 51.6 0.19 0.99 0.36 11.50 0.99

AC-600 60.9 1.43 0.99 0.18 31.89 0.99

t
AC3-500 63.7 1.82 0.99 0.44 11.19 0.99

ip
AC3-600 64.9 0.15 0.99 0.38 14.25 0.97
Methylene AC-500 121.9 1.47 0.99 0.10 98.11 0.97

cr
blue AC-600 191.3 2.86 0.96 0.28 161.59 0.96
AC3-500 104.2 1.20 0.99 0.08 83.29 0.98

us
an
M
ed
pt
ce
Ac

Page 39 of 39