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problems of counter-current multistage batch solid-liquid

extractors for complex systems: Application to vanilla extract

Rodrı́guez-Jimenes V.J. Robles-Olvera M.A.

Salgado-Cervantes M.A. Garcı́a-Alvarado

PII: S0098-1354(16)30057-6

DOI: http://dx.doi.org/doi:10.1016/j.compchemeng.2016.03.004

Reference: CACE 5388

Revised date: 27-2-2016

Accepted date: 8-3-2016

Please cite this article as: Castillo-Santos, K., Aguirre-Alonso, R. O., Rodríguez-

Jimenes, G. C., Robles-Olvera, V. J., Salgado-Cervantes, M. A., and García-

Alvarado, M. A.,An optimization based algorithm for solving design problems

of counter-current multistage batch solid-liquid extractors for complex systems:

application to vanilla extract, Computers and Chemical Engineering (2016),

http://dx.doi.org/10.1016/j.compchemeng.2016.03.004

This is a PDF file of an unedited manuscript that has been accepted for publication.

As a service to our customers we are providing this early version of the manuscript.

The manuscript will undergo copyediting, typesetting, and review of the resulting proof

before it is published in its final form. Please note that during the production process

errors may be discovered which could affect the content, and all legal disclaimers that

apply to the journal pertain.

1

2 An optimization based algorithm for solving design problems of counter-current

3 multistage batch solid-liquid extractors for complex systems: application to vanilla

4 extract

5

6 Castillo-Santos, K., Aguirre-Alonso, R.O., Rodríguez-Jimenes, G.C., Robles-Olvera, V.J.,

t

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7 Salgado-Cervantes, M.A. and García-Alvarado, M.A.*

8

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9 Unidad de Investigación y Desarrollo en Alimentos. Instituto Tecnológico de Veracruz. Av.

10 Miguel Angel de Quevedo 2779. Veracruz, Ver. 91860 México

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11

12 Abstract

13 Solid-liquid extraction is one of the aged unit operations in chemical engineering. However

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14 the process design models, universally included in textbooks, continue considering infinite

15 dilution of extractable material and single component solvent. Extraction processes of

16 bioactive compounds with composite solvents (ethanol-water) from plants or foods

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17 products require a better understanding of equilibrium between phases of bioactive

18 compounds and their role in the process design. Then, a general mathematical model of

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19 counter-current ideal multi-stages batch solid-liquid extractors was developed. The model

20 considers composite solvents and the two equilibrium relations required for the total

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22 proposed for solving the design problems. Experimental equilibrium relations were

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25 included and experimentally validated.

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26

27 Key words: Multistage solid-liquid batch extractors; equilibrium relation; specific retained

28 solution; optimization based algorithm; vanilla extract.

29

30 Nomenclature

31 D Dried residual kg

32 Ej Extract in stage j kg

33 F Feed kg

Page 1 of 32

2

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38 N

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Number of stages

39 Oj Solid phase in underflow in stage j kg

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40 S Solvent kg

41 Rj Underflow in stage j kg

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42 xEji Extract mass fraction of i compound in stage j

44

45

xOji

xSi an

Solids mass fraction of i compound in stage j

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46 xRji Underflow mass fraction of i compound in stage j

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50 y Vector of variables that define product

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51

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52 Greeks

53 η Extraction yield

54 ρ Density kg ⋅ m -3

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55

56 Subscripts

57 i Indicate the component. 1: inert solids,

58 2: extractable solids; 3: solvent first component (water),

59 4: solvent second component (ethanol).

60

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3

60 1. INTRODUCTION

61

62 Counter-current multistage solid-liquid extraction is one of the first unit operation

63 studied in chemical engineering. Ravenscroft (1936) proposed a graphical method for the

64 process design in terms of ideal stages assuming that equilibrium is reached when the

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65 extract ( E ) concentration is equal to retained solution ( L ) by underflow ( R ). This design

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66 method was applied in the oil extraction from Halibut livers. Later, Grosberg (1950)

67 reported an analytical method for design the process with the same equilibrium

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68 consideration, including underflow variable and non-equilibrium. In case of non-equilibrium,

69 a similar function to distillation plate efficiency was included. Both methods calculated the

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70 solute in underflow by mass balance assuming that the whole extractable material in solid

71 phase was transferred to liquid phase (liquid phase is split in extract and retained solution).

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72 Then, the equilibrium property in both methods (graphical and analytical), was taken as the

73 specific retained solution ( M ) per kg of inert in underflow. This assumption and the

74 graphical method have been preserved in modern chemical engineering text’s books

M

75 (McCabe et al., 2004), including Perry’s Chemical Engineers Handbook 7th Edition (Perry et

76 al., 2009).

77 The equality of concentrations between extract ( E ) and retained solution ( L ) is

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78 practically evident because they form a homogenous liquid phase. However the complete

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79 transfer of extractable solids to solvent assumption implies an infinity solubility which is not

*

80 necessarily true. Klinkenberq (1951) introduced a distribution coefficient ( K eq ) between

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ce

82

83 xE2 = K eq* xR2 (1)

84

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86 (inert) solids, extractable solids non transferred to liquid phase by saturation (the sum of

87 two are declared as O ) and the retained solution ( L ). In this sense, in solid-liquid

*

88 systems, K eq must be declared as an effective distribution coefficient. The rigorous

89 distribution law, result of the chemical potential of extractable material in liquid and solid

90 phases (Kassing et al., 2010; Kassing et al., 2012), must be expressed as,

91

92 ( )

xE2 = f xO2 (2)

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4

93

94 which can be called thermodynamic equilibrium relation because the extract concentration

95 is a function of extractable solids in solid phase instead at the underflow. If equilibrium

96 relation is linear, Eq. (2) may be reduced to Nernst´s distribution law,

97

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98 xE2 = K eq xO2 (2a)

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99

100 It is important to note in Eq. (2), infinite solubility is expressed when K eq → ∞ which

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101 produces that xO2 → 0 and therefore xO1 → 1 . This demonstrates that Eq. (2a) can be

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102 reduced to the classical consideration (Ravenscroft 1936; Grosberg 1950; McCabe et al.,

103 2004; Perry et al., 2009) in which the complete transfer of extractable material from solid to

104 liquid phase (infinite solubility) is assumed.

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105 By the other hand, the solid-liquid extraction operation has recently returned to

106 interest by the extraction of bioactive compounds from natural sources (Garcia-Perez et

107 al., 2010; Kassing et al., 2010; Yu et al., 2012; Pan et al., 2012) and therefore the

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108 mathematical modeling of the process has been revised. Most of the mathematical models

109 reported for solid-liquid extraction commonly deals with extraction kinetics based in mass

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110 transfer theory (Simeonov et al., 1999; Espinoza-Pérez et al., 2007; Garcia-Perez et al.,

111 2010; Kassing et al., 2010; Kassing et al., 2012; Rodríguez-Jimenes et al., 2013).

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112 However, the cited mass transfer models have been applied in solid-liquid extraction

113 kinetic of one single stage, and therefore the specific retained solution ( M ) has not been

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114 considered. Recent modeling of a continuous solid-liquid extraction process has been

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115 reported by Veloso et al. (2005). They modeled a continuous counter-current solid-liquid

116 extractor of seed oil considering the mass transfer in a continuous flow of product and

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117 solvent and with the thermodynamic equilibrium described by Nernst´s distribution law

118 (similar to the Eq. 2a). However, this model is not applicable in the case of multi-stages

119 batch extractors, and at the same of others mass transfer models referred, the specific

120 retained solution ( M ) was not considered. Ideal multistage batch extractors are required

121 when the contact time, required for to reach equilibrium, must be large. As example, vanilla

122 pods solid-liquid extraction requires 25 hours for to reach equilibrium like we reported in a

123 previous work on mass transfer during solid-liquid extraction (Rodríguez-Jimenes et al.,

124 2013).

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125 In the field of bio-active compounds solid-liquid extraction, the recent modeling

126 tendency, including counter-current multistage, has been by statistical methods and

127 surface response methodology (Yu et al., 2012; Pan et al., 2012; Nayak & Rastogi 2013;

128 Prakash-Maran et al., 2014). However, these types of models are valid only in the

129 experimental conditions at which they were fitted, and therefore they are not adequate for

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130 a general chemical engineering modeling. By the other hand, the bio-active compound

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131 extraction is usually performed with a mixture ethanol-water as solvent (Pan et al., 2012;

132 Yu et al., 2012; Rodríguez-Jimenes et al., 2013) and the natural resources normally have a

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133 given amount of water. This situation is not considered in the solid-liquid extraction design

134 methods reported in Chemical Engineering literature (McCabe et al., 2004; Perry et al.,

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135 2009).

136

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137 Therefore in this work a theoretical model for design counter current ideal

138 multistage solid-liquid batch extractors applied to complex systems (composite solvent and

139 natural resources) was conceptualized; a solution algorithm was proposed and

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140 experimental validation was performed. The theoretical model was conceptualized in terms

141 of macroscopic mass balances at the end of bath process, that is, when equilibrium would

142 be reached (ideal stages), and therefore the mass transfer properties must be previously

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143 known. The model takes into account composite solvent, feed with one component of

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144 solvent and two equilibrium properties. The two equilibrium properties considered were:

145 the specific retained solution ( M ) per kg of inert (non-extractable solids) in underflow, and

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146 the thermodynamic equilibrium relation between phases (Eq. 2). The process analysis

147 shows that the design problem of a N stages counter current ideal multistage solid-liquid

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148 batch extractor on the proposed model must solve a system of 13N non-linear equations.

149 Such problem may be difficult to solve even with classical numerical methods like

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151 applied in chemical engineering design problems when mathematical model is particularly

152 complex (Satyanarayana et al., 2009; Gebreslassi and Diwekar, 2015). Then, the solution

153 method proposed is an optimization based algorithm for the design problem solution, and it

154 was applied for different thermodynamic equilibrium mathematic relations in Eq. (2).

155 Experimental evaluation of the two equilibrium properties was described for vanilla-

156 ethanol-water system, and the experimental validation of the vanilla counter-current ideal

157 three stages batch solid-liquid extraction was developed. Moreover, it is a fact that the

*

158 effective distribution coefficient ( K eq ) for a particular solute has been usually evaluated

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6

160 (Simeonov et al., 1999; Espinoza-Pérez et al., 2007; Rodríguez-Jimenes et al., 2013). In

161 order to take into account this knowledge, the use of model for the prediction of a particular

*

162 solute concentration with known K eq in the extracts was shown.

163

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164 2. EXPERIMENTAL PROCEDURE

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165 Experimental determination of equilibrium properties

166 Vanilla extract is traditionally obtained by maceration of a given amount of 1 cm cured

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167 vanilla pieces (Rodríguez-Jimenes et al., 2013) in 100 mL of ethanol-water (60% w/w) at

50oC ( ρ = 880 kg ⋅ m -3 ). The vanilla extract concentration is commonly expressed in

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168

169 “folds”: 1 fold or 1x is extract obtained by solid-liquid extraction at equilibrium of 10 g of

170 vanilla pieces in 100 mL of solvent; 2x is the extract obtained with 20 g of vanilla pieces at

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171 the same conditions; 3x with 30 g and so on.

172

173 Vanilla characterization

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174 A complete characterization of vanilla pods in terms of solid-liquid extraction implies the

175 evaluation of water mass fraction, extractable solids mass fraction, inert solids mass

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176 fraction, vanillin mass fraction (as the most important compound of extractable solids), the

177 specific retained solution ( M ) per kg of inert in underflow and the thermodynamic

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178 equilibrium relation between phases (Eq. 2). The mass transfer properties of this system

179 and vanillin mass fraction in vanilla were previously reported by Rodríguez-Jimenes et al.,

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180 (2013).

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181

182 Vanilla samples

Cured vanilla pods of 2nd quality (the first quality is not used for extraction) were purchased

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183

184 directly to producers from Papantla, Veracruz, Mexico. A random sample of ca 3 kg was

185 taken from three vanilla boxes and the pods were cut into 1 cm pieces.

186

187 Water determination in vanilla pods

188 Three random samples of ca 1 g were taken from the cut pods, in agreement with

189 one treatment completely randomized experimental design, and put in a vacuum oven at

190 60 oC and 6X104 Pa until constant weight. It is possible that some of the volatile

191 compounds were lost during this process, however the principal volatile compound in

Page 6 of 32

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192 vanilla is vanillin and its vapor pressure is 4 magnitude orders lower that water vapor

193 pressure. Then, the lost was considered as neglected. The water content was expressed

194 as water mass fraction in feed ( xF3 ).

195

196 Non-extractable solids in vanilla pods

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197 Three random samples of ca 2.5 g were taken from the cut pods, in agreement with

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198 one treatment completely randomized experimental design, and exhaustively extracted in

199 150 mL of solvent (ethanol–water 60% w/w) at 50oC by 25 hours. This time was previously

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200 reported as the required for to reach the equilibrium concentration in extract (Rodríguez-

201 Jimenes et al., 2013). The extracted vanillas were extracted again two times more at same

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202 conditions. After the third extraction the residue was put in vacuum oven (60oC and 6X104

203 Pa) until constant weight. The remains solids are the non-extractable material in vanilla

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204 pods was expressed in mass fraction ( xF1 ).

205

206 Extractable solids in vanilla pods

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207 The extractable mass fraction was estimated by difference: xF2 = 1 − xF1 − xF3

208

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210 Three random samples of ca 10 g (1x extract) and three random samples of 30 g

211 (3x extract) were taken from the cut pods, in agreement with a 21 factorial completely

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212 randomized experimental design, and each sample was extracted in 100 mL of solvent. In

213 all cases the solvent was ethanol–water (60% w/w) at 50 oC and the process was kept by

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214 the 25 hours required to reach equilibrium. The extract ( E ) and underflow ( R ) were

215 carefully separated and weighted in order to avoid losses by evaporation. The underflow

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216 was placed in a vacuum oven (60oC and 6X104 Pa) until constant weight. The dried

217 residual of underflow ( D ) contains the solids phase ( O ) and the extractable solids that

218 remain in underflow with retained solution assuming that retained solution has the same

219 concentration of extract ( LxE2 ). Its difference with respect to vanilla total solids ( FxF1,2 ) is

221

222 ExE2 = FxF1,2 − D where xF1,2 = xF1 + xF2

223

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224 and like E is known by the extract weight, xE2 can be calculated. The amount of ExE2

225 was verified by extract total evaporation in a rotary evaporator. Then, It was stated that,

226

227 D = O + LxE 2 (3a)

228

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229 the underflow is constituted by solid phase and retained solution,

230

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231 R =O+ L (3b)

232

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233 and the solids phase are the non-extractable solids ( FxF1 ) plus the extractable solids that

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235

236 O = FxF1 + OxO2 (3c)

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237

238 Combining Eqs. (3a) and (3b),

239

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R−D

240 L= (4)

1 − xE2

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241

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242 And O and xO2 can be easily calculated from Eqs. (3). Knowing xE2 and xO2 at different

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243 concentrations (the extraction were developed at two different solvent/vanilla relations) it is

244 possible to estimate the equilibrium distribution indicated in Eq. (2) or (2a).

245 It is important to note that the proposed methodology allows proof if the extractable

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246 material is completely transferred to liquid phase. If the experimental results and Eqs. (3)

247 conduce to O ≈ FxF1 then xO2 ≈ 0 (from Eq. 3c), and K eq → ∞ (from Eq. 2a). In this case,

248 the classical consideration would be validated and the system could be treated with the

249 classical equations (Ravenscroft 1936; Grosberg 1950; McCabe et al., 2004; Perry et al.,

250 2009).

251 Finally the specific retained solution per kg of inert can be calculated from,

L

252 M=

FxF1

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253

254 at different extract concentrations.

255

256 Vanilla extract elaboration

257 Vanilla extract was prepared by multistage solid-liquid extraction with ca 100 g

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258 samples randomly taken from the cut pods. The procedure will be detailed in results

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259 section because depends of model solution results.

260

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261 Extractable solids and vanillin in vanilla extract,

262 The extractable solids in multistage vanilla extract were evaluated by direct

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263 evaporation in a rotatory evaporator. Vanillin was evaluated by the procedure 966.12

264 (AOAC, 2003). 1 mL of extract was diluted to 10 mL with distillated water. Two samples of

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265 1 mL of resulting solution were diluted to 50 mL with distillated water, one of them was

266 added with 1 mL of 0.1 N NaOH. The absorbance of the two resulting solutions was

267 measurement at 348 nm in a Biorad Smart Spect 300 spectrophotometer. The vanillin

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268 concentration was calculated with the absorbance difference between the alkaline solution

269 with respect to neutral solution and with a standard curve previously developed.

270

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272 Three random samples of ca 2 g were taken from the cut pods in agreement with one

273 treatment completely randomized experimental design, and extracted in 150 mL of solvent

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274 (ethanol–water 60% w/w) at 50 ºC by 25 h. The obtained extract was analyzed for vanillin

275 with the same procedure described in above section.

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276

277 3. MODELING AND EXPERIMENTAL RESULTS

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279 In the elected system as example of complex system (vanilla-ethanol-water), the

280 solvent is a mixture of two miscible components and the feed (vanilla pods) contains one

281 of these components (water). Therefore the proposed model in this paper must consider

282 the components: 1) inert, 2) extractable, 3) water and 4) ethanol and the two equilibrium

283 relations referred in section 1. It is evident that a system with one component solvent may

284 be described similarly without the ethanol equations. The mathematical description of one

285 single ideal stage was obtained from the macroscopic mass balances at the end of the

286 batch extraction, that is, when solid-liquid equilibrium has been reached,

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287

288 Overall balance: F + S − R1 − E1 = 0 (5)

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291 Water balance (8)

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292 Ethanol balance SxS4 − R1 xR14 − E1 xE14 = 0 (9)

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293

294 In order to take into account the two equilibrium properties it is necessary the

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295 macroscopic mass balances of underflow when solid-liquid equilibrium has been reached,

296

297 Overall balance: R1 − L1 − O1 = 0 (10)

298

299

Inert balance

Extractable balance

R1 xR11 − O1 xO11 = 0

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R1 xR12 − L1 xE12 − O1 xO12 = 0

(11)

(12)

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300 Water balance R1 xR13 − L1 xE13 = 0 (13)

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302

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303 Like the equilibrium has been reached the model is a system of 10 mass balance

304 equations in steady state. In order to calculate the equilibrium time required for the batch,

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305 the system mass transfer properties must be previously known. As example, mass transfer

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307 could be found in Espinoza-Perez et al., (2007), Rodríguez-Jimenes et al., (2013) and

308 García-Pérez et al., (2010). Eqs. (10) to (14) assume that the concentration of retained

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309 solution is the same that extract because the two phases are in equilibrium. The first

310 equilibrium property, the specific retained solution ( M ) per kg of inert in underflow (which

311 may a function of extract concentration), was introduced in the calculation of retained

312 solution,

313

314 ( )

L1 = M xE12 R1 xR11 (15)

315

316 Or, as consequence of Eq. (6),

317

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318 ( )

L1 = M xE12 FxF1 (15a)

319

320 The second equilibrium property, the distribution of extractable between phases (solids-

321 solvent) is defined by Eq. (2) or (2a).

322 Finally, as it was considered in Eq. (5), the solid phase of underflow is constituted

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323 by the inert and the extractable solids that cannot be transferred to extract by the

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324 distribution between phases,

325

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326 O1 − FxF1 − O1 xO12 = 0 (16)

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327

328 Although Eq. (5) is the sum of Eqs. (6) to (9), and Eq. (10) is the sum of Eq. (11) to

329 (14), the Eqs. (2), (15) and (16) introduce enough information for allow that the 13

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330 equations were lineally independent, as it was demonstrated in the following analysis.

331

332 Process analysis

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333

334 Defining,

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336 u ∈R 3 = {S , x , x } the set of 3 real variables that define the service variables (solvent)

S3 S4

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339 {

y ⊂ x ∈R 4 = E1 , xE12 , xE13 , xE14 } the set of 4 real variables that define the product (vanilla

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340 extract)

341

342 In agreement with above scheme one single stage of solid-liquid extraction of vanilla pods

343 with a mixture of ethanol-water as solvent, is a system with 20 variables. Since 13

344 equations were stated (Eqs. 2, 5-16), there are 20-13=7 degrees of freedom. The 7

345 degrees of freedom represent 7 variables that must be defined by the engineer: the four

346 variables of feed, the two variables of solvent composition and one more variable

347 depending of problem type: design or simulation.

348

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350 In a design problem an element of product variables ( y ) must be defined, in this case, the

351 extractable concentration in extract ( xE12 ). Then, the design problem can be analytically

352 solved by following sequence. xE12 defines the specific retained solution per kg of inert

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353 ( M 1 is a known function of xE12 ). xE12 defines xO12 with equilibrium concentration (Eq. 2 or

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354 2a) and L1 with the specific retained solution function (Eqs. 15 or 15a). xO12 defines O1

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355 with Eq. (16). L1 and O1 define R1 with Eq. (10). R1 defines xR11 with Eq. (6) and xR12 with

356 Eq. (12). E1 can be calculated with Eq. (7), S with Eq. (5) and xO11 with Eq. (11). xR13 ,

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357 xR14 , xE13 , and xE14 can be calculated with Eqs. (8), (9), (13) and (14) as a linear system of

358 four equations.

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359

360 Simulation Problem

361 In a simulation problem, must be defined the four variables of input ( w ) and the three

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362 variables of solvent ( u ). The 13 variables that must be calculated are the 13 state

363 variables x . Due the possible non-linear nature of Eq. (2) and the specific retained

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364 solution as function of extract concentration, the simulation problem is a system of 13 non-

365 linear equations with 13 variables. Even with the current compute power this problem may

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366 be difficult to solve due that convergence problem or multiplicity of solution. However, like

367 it was demonstrated for a design problem: if xE12 is known, the system has analytical

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368 solution (described in above section). Therefore, the simulation problem can be solved as

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370

( )

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373

374 where S is the defined solvent amount in simulation problem and S * the calculated

375 solvent amount at the xE12 value in the function by the procedure described in “design

problem”. It is evident that f xE12

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378 If M are constant and the system can be described with Nernst´s distribution law

379 (Eq. 2a), it is possible to solve the simulation problem analytically by the following

380 procedure. Defining constant terms as, ϕ1 = FxF1 , ϕ 2 = FxF2 , φ3 = F + S and combing

382

t

383 R1 − L1 − ϕ1 − ( R1 − L1 ) xO12 = 0 (17)

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384

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385 Eq. (5) and (2a) with (3),

386

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387 ϕ 2 − R1 xR1 − (ϕ 3 − R1 ) K eq xO1 = 0

2 2

(18)

388

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389 And finally Eq. (12) with (10) and (2),

390

391 R1 xR12 − L1 K eq xO12 − ( R1 − L1 ) xO12 = 0 (19)

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392

393 These last three Eqs. can be combined in the unique one,

d

394

ϕ + 2 L1 + ϕ 2

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1

395 − 1 R12 + 2 L1 + ϕ1 + ϕ 3 − 1 R1

K eq K eq

p

ϕ 2 L1 + L12 + ϕ1 L1

396 + − L1 ( L1 + ϕ1 ) − ϕ 3 ( L1 + ϕ1 ) = 0 (20)

K eq

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397

398 Eq. (20) is a second order polynomial that can be easily solved for R1 . There will be two

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399 solutions, one feasible and one unfeasible. The feasible solution can be used in Eq. (5)

400 and (10) to solve E1 and O1 . L1 can be calculated from Eq. (15a), xO12 from Eq. (17) and

401 xE12 from Eq. (2a) and the rest of sequence is equal to design problem. It is important to

402 note that Eq. (20) has solution even when K eq → ∞ . Therefore, if the solid-liquid system

403 accepts the classical consideration (Ravenscroft 1936; Grosberg 1950; McCabe et al.,

404 2004; Perry et al., 2009) in which the complete transfer of extractable material from solid to

Page 13 of 32

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405 liquid phase is assumed, the proposed sequence and Eq. (20) with K eq → ∞ can solve the

407

408 3.2. Modeling counter-current multistage

409 Process analysis

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410 Generalizing Eqs. (2), (5)-(16) in agreement with Fig. 1 representation, the ideal multistage

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411 counter-current solid-liquid batch extractors with two equilibrium properties and a solvent

412 with two miscible liquids are described by the following macroscopic mass balances at the

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413 end of the each stage batch extraction, that is, when solid-liquid equilibrium has been

414 reached,

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415

416 R j −1 + E j +1 − R j − E j = 0 (21)

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417 R j −1xRj −11 − R j xRj1 = 0 (22)

M

419 R j −1xRj −13 + E j +1xEj +13 − R j xRj3 − E j xEj3 = 0 (24)

d

421 Rj − Lj − Oj = 0 (26)

te

p

ce

Ac

427 ( )

L j = M xEj2 FxF1 (32)

428 xEj2 = f (x )

Oj2 (33)

429

430 Where F = R0 and S = E N +1 .

431

432 The design problem may be proposed as follows,

Page 14 of 32

15

433 Defining,

434 w ∈R 4 = {F , xF1, xF 2 , xF 3 }

435 u = u1 ∪ u 2

436 {

u1 ∈R 3 = S , xS3 , xS4 }

t

437 u 2 ∈ N = {N }

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438 {

x ∈R 13 N = E j : ∀j = 1,..., N , R j : ∀j = 1,..., N , L j : ∀j = 1,..., N , O j : ∀j = 1,..., N ,

cr

439 xEji : ∀j = 1,..., N ∧ ∀i = 2,.., 4, xRji : ∀j = 1,..., N ∧ ∀i = 1,.., 4,

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440 xOji : ∀j = 1,..., N ∧ ∀i = 1, 2

441 {

y ⊂ x ∈R 4 = E1 , xE12 , xE13 , xE14 }

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442

443 Then the total number of variables is 13 N + 8 and the model (Eqs. 21 to 33) provides 13N

equations lineally independent (as a whole). Therefore the system has 13 N + 8 - 13N =8

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444

445 degrees of freedom. These 8 degrees of freedom are used to define w , N , xS3 , xS4 and

446 xE12 . The rest of variables can be calculated with the 13N Eq. (21) to (33) system. The

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447 solution of 13N non-linear equations is an enormous problem with multiplicity of solutions

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448 by the non-linear nature of Eqs. (22) to (25), (27) to (31), like it was demonstrated in Eqs.

449 (17) to (19) for one single step. Actually, MatLab solves systems of K non-linear equation

p

450 as a minimization problem of K variable in order to close zero K equations with Gauss-

ce

451 Newton algorithm. However, like xE12 is known, and by mass balance 0 ≤ xE 32 ≤ xE 22 ,…,

452 0 ≤ xEN2 ≤ xEN −12 , an algorithm based in the optimization of N − 1 variable (instead of the

Ac

453 13N variables of the whole model) can be proposed. The optimization problem is,

454

455 (

min f xE 22 , xE 32 ,..., xEN 2 ) (34)

457 0 ≤ xE 32 ≤ xE 22

458 .

459 .

460 .

Page 15 of 32

16

462

463 Where the objective function is the positive difference,

464

465 ( )

f xE 22 , xE 32 ,..., xEN2 = xE 22 − x *E 22 + xE 32 − x *E 32 + ⋅⋅⋅

t

ip

466 + xEN 2 − x *EN 2 (35)

cr

467

468 And the proposed algorithm is the following,

469

us

470 Step 1. Knowing xE1 and the initial valid guess for xE 22 , xE 32 , …, xEN2 applied in Eq.

2

an

2 2 2

472 Step 2. L1, L2 , ⋅⋅⋅, LN are calculated with Eq. (32) taking into account that R j xRj = FxF

1 1

M

474 Step 3. O1, O2 , ⋅⋅⋅, ON are calculated with Eq. (31).

d

476 Step 5. xR1 , xR 2 , ⋅⋅⋅, xRN are calculated with R j xRj = FxF (Eq. 22).

1 1 1 1 1

te

477 Step 6. xO1 , xO 2 , ⋅⋅⋅, xON are calculated with Eq. (27).

1 1 1

p

478 Step 7. xR1 , xR 2 , ⋅⋅⋅, xRN are calculated with Eq. (28).

2 2 2

ce

480 Step 9. E1, E2 , ⋅⋅⋅, E N −1 are calculated with Eq. (21) beginning with j = N − 1 .

Ac

482 Step 11. x *E 22 , x *E 32 , …, x *EN 2 are calculated with Eq. (23) for with j = 1, ⋅⋅, N − 1 . The

483 results are applied in the objective function (35). It is evident that the minimum for

484 ( )

f xE 22 , xE 32 ,..., xEN 2 is zero and represents a part of the system solution.

485 When a convergence would be reached, the other part is the solution for

486 xE13 , xE 23 , ⋅⋅⋅, xEN3 , xR13 , xR 23 , ⋅⋅⋅, xRN3 , xE14 , xE 24 , ⋅⋅⋅, xEN 4 and xR14 , xR 24 , ⋅⋅⋅, xRN 4

487 with the 4N linear equations that can be built with Eqs. (24), (25), (29) and (30). The

Page 16 of 32

17

489 al., 2006), which does not require derivatives evaluation like Gauss-Newton algorithm.

490

491 3.3. Experimental equilibrium results

492 Experimental characterization of vanilla pods used for extraction with ethanol-water

t

493 (60% w/w) at 50 oC is listed in Table 1. The two equilibrium properties were calculated

ip

494 from solid-liquid extraction until equilibrium at two solid/product relations as it was

495 described in experimental procedure section. The results are plotted in Figs. 2 and 3. Fig.

cr

496 2 indicates that specific retained solution is constant, at least in the extract concentrations

497 under study, in a value of M = 2.8 (kg retained solution)/(kg inert) ± 0.215 (95%

us

498 confidence interval). Linear line of Fig. 3 shows the fitted Nernst´s distribution law (Eq. 2a)

499 on experimental results, giving K eq = 0.25 ± 0.127 (95% confidence interval). This last

an

500 confidence interval was calculated with the parameter variance like is detailed in Garcia-

501 Perez et al. (2010) or in Rodríguez-Jimenes et al., (2013). The observed dispersion in Fig.

502 3 is due that mass fractions in extract and underflow were calculated by mass balances,

M

503 assuming that the initial solute concentration in different vanilla samples are equal to those

504 reported in Table 1. This assumption is necessary because the determination of each

d

505 component is destructive and therefore the samples for exhaustive extraction are different

506 of those used for obtaining the equilibrium state. However, the 95% confidence interval for

te

507 K eq indicates that the linear behavior is statistically significant (p<0.05) even the

508

p

dispersion. Additionally, it is important to note that any paper that report an analytical

509 solution of mass transfer equation of solid-liquid extraction process (Crank, 1975;

ce

510 Mikhailov, 1977; Kassing et al., 2010; Chilev et al., 2014), assume implicitly or explicitly a

511 constant distribution between phases, which has been statistically demonstrated for the

Ac

513 ethanol-water system cannot be modeled with classical consideration (Ravenscroft 1936;

514 Grosberg 1950; McCabe et al., 2004; Perry et al., 2009), because exist statistic evidence

515 (the significant value of K eq = 0.25 ) that O ≠ FxF1 .

516 The proposed model is a macroscopic mass balance when equilibrium has been

517 reached. Therefore, the critical points with respect to model capacity to predict a real

518 process are the equilibrium properties. Then, in order to show the proposed model

519 capacity for handle other equilibrium properties, three equilibrium relations were introduced

520 for model simulations: the experimentally validated Nernst´s law (Eq. 36a), a Langmuir

Page 17 of 32

18

521 type distribution law (non-linear continuous line in Fig. 3 and Eq. 36b) and a hypothetic law

522 in which infinite distribution between phases occurs until saturation (Eq. 36c).

523 Mathematical description for these equilibrium relations are,

524

525 xE2 = 0.25 xO2 (36a)

t

526

ip

0.12 xO2

527 xE2 = (36b)

0.1 + xO2

cr

528

lim K eq xO2 if xE 2 < 0.12

us

K eq →∞

529 xE2 = (36c)

0.12 otherwise

530

an

531 It is important to remark that experimental results only validated Eqs. (36a). Eq.

532 (36b) plotted as non-linear continuous line in Fig. 3 and Eq. (36c) are introduced only as

533 examples of the proposed model and solver algorithm capacity for to solve solid-liquid

M

534 extraction problems with different distribution laws. Problems with Eq. (36c) were

535 discussed (not solved) in McCabe et al., (2004) Chemical Engineering´s text book.

536

d

te

538 Taking the specific retained solution M = 2.8 (kg retained solution)/(kg inert) and

539 the equilibrium distribution of Eqs. (36), simulations of 1 stage vanilla pods (100 kg) solid-

p

540 liquid extraction were developed for 1x (1000 mL extract), 2x (500 mL) and 4x (250 mL)

ce

541 extracts.

542

543

Ac

544

545 Nernst´s distribution equilibrium results

546 The results are listed in Table 2a. These results were obtained with analytical procedure

547 based in Eq. (20). It is evident that rising the fold increase the extract concentration but

548 lose extraction yield, defined like the ratio of total extractable solids recovered in extract on

549 total extractable material in feed: η = E1 xE12 FxF2 .

550

551 Langmuir type distribution law equilibrium results

Page 18 of 32

19

552 The results are listed in Table 2b. In this case the results were obtained with optimization

553 problem planted in “Simulation problem” section. The optimization was solved with Excel

554 solver routine. The yields are greater than the above case because the grater extract

555 concentration predicted by Eq. (36b).

556

t

557 Saturation and infinite distribution equilibrium results

ip

558 The results are listed in Table 2c. These results were obtained with analytical procedure

559 based in Eq. (20) with K eq = 100000 following Eq (36c). However, the 4x case, Eq. (20)

cr

560 produced a value of xE2 = 0.128 , which is impossible by the saturation limit imposed (Eq.

us

561 36c). This case is a simulation problem in which the solvent amount is lower than the

562 required for to obtain a saturated extract. Only for such case, another analytical procedure

563 must be introduced. This simulation problem must be solved with xE2 known (the

564

565

an

saturation value) and neglecting the equilibrium relation (Eq. 36c) because after the

saturation value there is not information on xO2 . Combining Eq. (5) and (10),

M

566

567 E = ϕ3 − L − O (37)

d

568

569 And combining Eqs. (7), (12) and (16),

te

570

571 ϕ 2 − ExE − LxE − O + ϕ1 = 0 (38)

p

2 2

572

ce

573 Where ϕ1 , ϕ 2 and ϕ 3 are the defined for Eqs. (17) to (20). Like xE2 is known (the

574 saturation value), L can be calculated with Eq. (15a), and therefore Eqs. (37) and (38) are

Ac

575 two linear equations for E and O variables. The rest of problem is solved by the design

576 sequence. The result is listed in Table 1c for 4x extract.

577

578 3.5. Counter-current ideal multi-stages problem

579 Taking the extract concentration obtaining with 1 stage at 4x ( xE12 = 0.08 for Eq.

580 36a; xE12 = 0.09 for Eq. 36b; xE12 = 0.119 for Eq. 36c with K eq = 100000 ) as target output

581 variable, the counter-current ideal multi-stages solid-liquid batch extractors for 100 kg

582 vanilla pods were defined with Eqs. (21)-(33) and solved with the proposed algorithm

Page 19 of 32

20

583 (section 3.2) for N = 2,3, 4 . The extreme stages ( j = 1 and j = N ) results are

584 summarized in Tables 2a, 2b and 2c. Obviously, the process scale-up is implicit in Eqs.

585 (21)-(33): if 100 Mg vanilla were used instead of 100 kg as calculus basis, the values of

586 tables results would be the same but in Mg.

587 Until 3 stages the problem was solvable with excel solver. However for >3 stages

t

588 the problem is impractical (the 4N linear system is laborious) and the solver algorithm do

ip

589 not find the solution. The general model for any stages was programed in FORTRAN,

590 solving the optimization problem with the Box-Ruiz-Rodríguez-García algorithm (Ruiz-

cr

591 López et al., 2006). The results until 3 stages are practically the same in both programs

592 (excel and FORTRAN).

us

593 The results of Tables 3b and 3c are examples of the model versatility. The unique

594 results with experimental support are listed in Table 3a. However it is interesting to note

an

595 that in the Table 3c results, the underflow is constant. This was because the process was

596 calculated just below saturation with the classical consideration (Ravenscroft 1936;

597 Grosberg 1950; McCabe et al., 2004; Perry et al., 2009) by using K eq → ∞ and M

M

598 constant, but the proposed model and solving methods can easily deals with variable

599 underflow, like it was shown in Tables 3a and 3b. The evident increasing in extraction

d

600 yield is the result of multi-stage approach. This extraction yield with such extract

601 concentration cannot be greater in any other solid-liquid extraction scheme. Single 1 stage,

te

602 co-current or multistage with new solvent in each stage may reach the same yield but the

603 extract concentration will be much lower.

p

604

ce

606 In order to validate the vanilla counter–current solid-liquid extraction process

607 simulation presented in last section the following experiments was developed.

Ac

608

609 Vanilla extract elaboration

610 Vanilla extract was prepared by multistage solid-liquid extraction with ca 100 g

611 samples randomly taken from the cut pods. 100 g of 1 cm pieces of vanilla pods were

612 extracted with 220 g (Table 1a for 4x) of ethanol-water (60% w/w) at 50 ºC by 25 hours.

613 The obtained extract was called E01 and the exhausted vanilla pods were called R01 . R01

614 was re-extracted with 373 g (Table 2a for N =2) of the same solvent and same time

615 obtaining R02 (exhausted vanilla) and E02 (extract). R02 was again extracted with 438 g

Page 20 of 32

21

616 (Table 2a for N =3) of the same solvent and same time obtaining R03 and E03 . E01 was

617 considered final product. E02 was used as solvent for a second batch of 100g fresh vanilla

618 pods obtaining R11 and E11 . E11 is final product and mixed with E01 . E03 was used as

619 solvent for extract R11 obtaining R12 and E12 . R12 was extracted with 438 g of fresh solvent

t

620 obtaining R13 and E13 . E12 was used as solvent of 100 g of fresh vanilla pods obtained

ip

621 R21 and E31 (final product mixed with E01 and E11 ), and so on. In 5 sequences a steady-

cr

622 state of vanilla counter-current solid-liquid extraction process was obtained. This

623 procedure is difficult to follow but is the only way to obtain final extract at desired

us

624 concentration since the first sequence. Fig. 1 can help to understand the sequence. The

625 first stage extracts (output extracts) of 5th, 6th and 7th sequence were evaporated in a

626 rotatory evaporator obtaining the results listed in Table 4. The experimental concentrations

an

627 represent deviations of 2.7%, 22% and 5.6% with respect to the value predicted by

628 simulation ( xE12 = 0.08 Table 3a).

M

629

630

631 3.7. Particular solute calculation

d

632 In section 2 it was stated that vanillin concentration in extract can be predicted if the

te

*

634 material and the effective equilibrium constant ( K eq ) and feed mass fraction for vanillin are

p

635 known. The complete characterization of referred system is detailed in section 3.3 and the

ce

636 effective equilibrium constant and vanilla mass fraction of vanillin (called 21 because

637 *

vanillin is part of extractable solids) are K eq = 0.297 (Rodriguez-Jimenes et al., 2014) and

Ac

638 xF21 = 0.023 (Table 1) respectively. The particular solute calculation in each equilibrium

639 stage of a counter-current multistage batch solid-liquid extractor is performed by the

640 following procedure.

641 The particular solute mass balance in a stage j when equilibrium would be

642 reached,

643

644 R j −1 xRj −121 + E j +1 xEj +121 − R j xRj21 − E j xEj21 = 0 (39)

645

Page 21 of 32

22

647

648 xEj21 = K eq* xRj21 (40)

649

650 Like the particular component is part of extractable material, xEj2 = xEj21 + xEj22 holds, and

t

ip

651 the whole of extracts and underflows in equations (39) are completely defined by the

652 original problem solution (section 3.5). Therefore, Eqs. (39) and (40) represent a linear

cr

653 system of 2N equations which can be easily solved for the 2N interest component mass

654 fractions ( xE121 , xR121 , xE 221 , xR 221 ,…, xEN21 , xRN21 ). It must be noted that R0 = F , xR 021 = xF21 ,

us

655 E N +1 = S and xEN +121 = xS21 = 0 . The vanillin concentration prediction for the 3 stages

656 extraction resumed in Table 3a was xE121 = 0.004 . The vanillin experimental determination

657

658

an

in the extracts obtained in 5th, 6th and 7th sequences (section 3.6.), evaluated by the

procedure detailed in Section 2, is listed in Table 4, which represents deviations of 4, 1.75

M

659 and 6% respectively of the predicted value.

660 It is important remark that the particular solute concentration in each stage from

661 effective equilibrium relation can be only performed if the solid-liquid system is completely

d

te

663

664 Conclusions

p

665 The conceptualized model in this paper and the proposed optimization based solver

666 algorithm were successfully applied in the design of ideal multistage counter-current solid-

ce

667 liquid batch extraction process of vanilla. In order to demonstrate the general application of

668 design method, three types of equilibrium distributions were used as examples: Nernst´s

Ac

669 law, Langmuir type law and infinite distribution with saturation. It was shown that the

670 proposed model with Nernst´s law and K eq → ∞ , is reduced to the classical consideration

671 of solute infinite solubility (Ravenscroft 1936; Grosberg 1950; McCabe et al., 2004; Perry

672 et al., 2009). The use of model for a particular solute concentration prediction was

673 deduced and experimentally validated. The conceptualized model and solver algorithm can

674 be applied in process design and optimization of natural resources multistage solid-liquid

675 extraction with composite solvent (as example ethanol-water) and with specific retained

676 solution and thermodynamic equilibrium relations known. The process optimization is

677 understood as the calculation of number of stages and solvent amount that produces the

Page 22 of 32

23

678 maximal extraction yield with maximal extract concentration with the proposed model

679 instead of surface response models. Finally, the model can be easily solved in other

680 cases. As example, a solid-liquid extraction with a single solvent (hexane), which is no part

681 of resource: in this case the proposed model can be used with the same software by

682 making xS 3 → 0 and xF 3 → 0 ( xS 3 = 1 × 10−6 and xF 3 = 1 × 10 −6 ).

t

683

ip

684 Acknowledgments

685 The authors express their acknowledgments to Tecnológico Nacional de México by

cr

686 the financial support through the project 5177.13-P, and Consejo Nacional de Ciencia y

687 Tecnología (CONACyT) by the scholarship assigned to Castillo-Santos, K. and Aguirre-

us

688 Alonso, R.

689

an

690

691 References

692 AOAC. (2003). Official methods of analysis of AOAC international. 17th Ed. Gaithersburg,

693 MD.

M

694 Espinoza-Pérez, J.D.; Vargas, A.; Robles-Olvera, V.J.; Rodríguez-Jimenes, G.C.; García-

695 Alvarado, M.A. Mathematical modeling of caffeine kinetic during solid-liquid extraction

d

697 Garcia-Perez, J.V.; García-Alvarado, M.A.; Carcel, J.A.; Mulet, A. Extraction kinetics

te

698 modeling of antioxidants from grape stalk (Vitis vinifera var. Bobal): Influence of drying

699 conditions. J Food Eng 2010;101:49-58.

p

700 Gebreslassie, B.H., Diwekar, U.M. Efficient ant colony optimization for computer aided

ce

701 molecular design: Case study solvent selection problem. Comput Chem Eng

702 2015;78:1–9.

Ac

703 Grosberg, J.A. 1950. Solid-liquid extraction calculations. Ind Eng Chem 1950;42:154-62.

704 Kassing, M., Jenelten, U., Schenk, J., Strube, J. A New Approach for Process

705 Development of Plant-Based Extraction Processes. Chem Eng Technol 2010;33:377-

706 87.

707 Kassing, M., Jenelten, U., Schenk, J., Hänsch, R., Strube, J. Combination of Rigorous and

708 Statistical Modeling for Process Development of Plant-Based Extractions Based on

709 Mass Balances and Biological Aspects. Chem Eng Technol 2012;35:109–32.

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711 processes with constant distribution factor, when in the stationary state. I. Distribution of

712 one component only. Chem. Eng. Sci. 1951;1:86-93.

713 McCabe, W., Smith, J., Harriott, P. Unit Operations of Chemical Engineering. McGraw-Hill

714 2004.

t

715 Nayak, C.A.; Rastogi, N.K. Optimization of solid–liquid extraction of phytochemicals from

ip

716 Garcinia indica Choisy by response surface methodology. Food Res Int 2013;50:550-6.

717 Pan, G.; Yu, G.; Zhu, C.; Qiao, J. Optimization of ultrasound-assisted extraction (UAE) of

cr

718 flavonoids compounds (FC) from hawthorn seed (HS). Ultrason Sonochem

719 2012;19:486-90.

us

720 Perry, R.H., Green, D.W., Maloney, J.O. Perry’s Chemical Engineers Handbook 7th Ed.;

721 McGraw-Hill 2009.

an

722 Prakash-Maran, J., Sivakumar, V., Thirugnanasambandham, K., Sridhar, R. Microwave

723 assisted extraction of pectin from waste Citrullus lanatus fruit rinds. Carbohyd Polym

724 2014;101:786–91.

M

725 Ravenscroft, E.A. Extraction of Solids with Liquids: Multiple and Countercurrent Extraction.

726 Ind Eng Chem 1936;28:851-5.

727 Rodríguez-Jimenes, G.C.; Vargas-Garcia, A.; Espinoza-Pérez, D.J.; Salgado-Cervantes,

d

728 M.A.; Robles-Olvera, V.J.; García-Alvarado, M.A. Mass transfer during vanilla pods

te

730 50.

p

731 Ruiz-López, I.I.; Rodríguez-Jimenes, G.C.; García-Alvarado, M.A. Robust MIMO PID

732 controllers tuning based on complex/real ratio of the characteristic matrix eigenvalues.

ce

734 Satyanarayana KC, Abildskov J, Gani R. Computer-aided polymer design using group

Ac

736 Simeonov, E., Tsibranska, I., Minchev, A. Solid-liquid extraction from plants – experimental

737 kinetics and modelling. Chem Eng J 1999;73:255-9.

738 Veloso, G.O.; Krioukov, V.G.; Vielmo, H.A. Mathematical modeling of vegetable oil

739 extraction in a counter-current crossed flow horizontal extractor. J Food Eng

740 2005;66:477-86.

741 Yu, C.H.; Chen, J.; Xiong, Y.K.; Li, X.X.; Daia, X.Y.; Shi, C.C. Optimization of multi-stage

742 countercurrent extraction of antioxidants from Ginkgo biloba L. leaves. Food Bioprod

743 Process 2012;90:95-101.

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25

744

745

746

747 Fig. 1. Ideal multistage solid-liquid batch extractors’ representation.

748

t

749

ip

750 Fig. 2. Specific retained solution (kg retained solution per kg inert) experimentally obtained

751 for 1x and 3x vanilla extract with ethanol-water 60% w/w 50 oC.

cr

752

753

us

754 Fig. 3. Extractable equilibrium distribution experimentally obtained for 1x and 3x vanilla

755 extract with ethanol-water 60% w/w at 50 oC (o). Continuous linear line represents fitted

an

756 Nernst´s distribution law; the non-linear line represents a hypothetic Langmuir type law.

757

758

M

759

760

761 Table 1

d

te

763

764

Component Mass fraction

p

765

766

ce

Extractable solids b 0.365 ( x F2 )

0.293 ± 0.08a ( x F3 )

Ac

Water

Vanillin c 0.023 ± 0.003a ( x F21 )

767

768 a: standard deviation

769 b: calculated by difference x F = 1 − x F − x F

2 1 3

770 c: as part of extractable solids

771

772

773

774

Page 25 of 32

26

775

776

777

778 Table 2a

779

780 Simulation of a 1 single stage solid-liquid extraction of vanilla. Feed ( F ) 100 kg of vanilla

t

ip

781 pods pieces. Solvent ( S ) ethanol-water (60 % w/w) at 50oC (Nernst´s distribution law, Eq.

782 36a).

cr

783

784

η

us

S kg Extract Underflow

785

786

an

880 (1x) E1 = 844.8 kg, xE12 = 0.03 R1 = 135.2 kg, xR11 = 0.25 0.77

M

xR14 = 0.40

440 (2x) E1 = 400.5 kg, xE12 = 0.05 R1 = 139.5 kg, xR11 = 0.25 0.60

d

te

xR14 = 0.37

220 (4x) E1 = 174.6 kg, xE12 = 0.08 R1 = 145.4 kg, xR11 = 0.23 0.37

p

ce

xR14 = 0.32

787

Ac

788

789

790

791

792

793

794

795

796

Page 26 of 32

27

797

798

799

800 Table 2b

801

t

802 Simulation of a 1 single stage solid-liquid extraction of vanilla. Feed ( F ) 100 kg of vanilla

ip

803 pods pieces. Langmuir type distribution law, Eq. (36b).

804

cr

805

S kg Extract Underflow η

us

806

807

E1 = 848.4 kg, xE12 = 0.04 R1 = 131.5 kg, xR11 = 0.26

an

880 (1x) 0.86

xR14 = 0.41

M

440 (2x) E1 = 405.6 kg, xE12 = 0.06 R1 = 134.4 kg, xR11 = 0.25 0.71

d

xR14 = 0.38

te

220 (4x) E1 = 177.4 kg, xE12 = 0.09 R1 = 142.6 kg, xR11 = 0.24 0.43

p

ce

xR14 = 0.32

808

Ac

809

810

811

812

813

814

815

816

817

Page 27 of 32

28

818 Table 2c

819

820 Simulation of a 1 single stage solid-liquid extraction of vanilla. Feed ( F ) 100 kg of vanilla

821 pods pieces. Infinite distribution with saturation, Eq. (36c).

822

t

823

ip

S kg Extract Underflow η

824

cr

825

880 (1x) E1 = 850.0 kg, xE12 = 0.04 R1 = 130.0 kg, xR11 = 0.26 0.90

us

xE13 = 0.40 , xE14 = 0.56 xR12 = 0.03 , xR13 = 0.30

xR14 = 0.41

440 (2x) E1 = 410.0 kg, xE12 = 0.07

R1 = 130.0 kg, xR11 = 0.26

0.81

M

xR14 = 0.38

220 (4x) E1 = 187.5 kg, xE12 = 0.12 R1 = 132.5 kg, xR11 = 0.26 0.62

d

te

xR14 = 0.34

p

826

827

ce

828

829

830

Ac

831

832

833 Table 3a

834

835 Process variables (extreme stages) for counter-current multistage solid-liquid extraction of

836 vanilla. Feed ( F ) 100 kg of vanilla pods pieces. Solvent ( S ) ethanol-water (60 % w/w) at

837 50oC. (Nernst´s distribution law, Eq. 36a). Final extract concentration xE12 = 0.08

838

839

Page 28 of 32

29

840

841

N =2 373.2 E1 = 337.2 kg, xE12 = 0.08 R2 = 135.9 kg, xR 21 = 0.25 0.74

t

xR 24 = 0.40

ip

N =3 438.0 E1 = 405.6 kg, xE12 = 0.08 R3 = 132.4 kg, xR 31 = 0.26 0.90

cr

xE13 = 0.41 , xE14 = 0.51 xR 32 = 0.03 , xR 33 = 0.29

us

xR 34 = 0.43

N =4 465.2 E1 = 434.1 kg, xE12 = 0.08 R4 = 131 kg, xR 41 = 0.26 0.95

an

xE13 = 0.41 , xE14 = 0.51 xR 42 = 0.014 , xR 43 = 0.29

xR 44 = 0.44

M

842

843

844

d

845

te

846

847

p

848

849

ce

850

851 Table 3b

Ac

852

853 Process variables (extreme stages) for counter-current multistage solid-liquid extraction of

854 vanilla. Feed ( F ) 100 kg of vanilla pods pieces. Langmuir type distribution law, Eq. (36b).

855 Final extract concentration xE12 = 0.09

856

857

Stages S kg Extract Underflow η

858

859

Page 29 of 32

30

xR 24 = 0.41

N =3 416.7 E1 = 386.3 kg, xE12 = 0.09 R3 = 130.4 kg, xR 31 = 0.26 0.95

t

xE13 = 0.41 , xE14 = 0.50 xR 32 = 0.01 , xR 33 = 0.29

ip

xR 34 = 0.43

cr

N =4 431.1 E1 = 401.0 kg, xE12 = 0.09 R4 = 130 kg, xR 41 = 0.26 0.99

us

xR 44 = 0.44

860

861

862

an

M

863

864

865

d

866

te

867

868

p

869

870

ce

871 Table 3c

872

Ac

873 Process variables (extreme stages) for counter-current multistage solid-liquid extraction of

874 vanilla. Feed ( F ) 100 kg of vanilla pods pieces. Infinite distribution with saturation, Eq.

875 (36c). Final extract concentration xE12 = 0.119

876

877

Stages S kg Extract Underflow η

878

879

Page 30 of 32

31

xR 24 = 0.42

N =3 330.9 E1 = 300.9 kg, xE12 = 0.119 R3 = 129.9 kg, xR 31 = 0.26 0.98

t

xE13 = 0.41 , xE14 = 0.47 xR 32 = 0.005 , xR 33 = 0.30

ip

xR 34 = 0.43

cr

N =4 335.2 E1 = 305.2 kg, xE12 = 0.119 R4 = 129.9 kg, xR 41 = 0.26 0.995

us

xR 44 = 0.44

880

881

882

an

M

883

884

885

886

d

887 Table 4

888 Vanilla extract composition obtained with 3 stages counter-current solid-liquid extraction

process in 5th, 6th and 7th sequences

te

889

890

Mass fraction

p

891

ce

892

Ac

893 a: Predicted with Eqs. (21) to (33) and Table 1 values as feed composition.

894 b: Predicted with Eqs. (39) and (40) and Table 1 values as feed composition.

895

896

897

898

899

900

901

902

Page 31 of 32

32

903 >Counter-current N-stage solid-liquid extractors mechanistic model with composite solvent

904 and two equilibrium relations was conceptualized.

905

906 >Differences between thermodynamic and apparent equilibrium were demonstrated.

907

t

908 >An optimization based algorithm for model solution was proposed.

ip

909

910 >Equilibrium properties of vanilla-ethanol-water system were evaluated experimentally.

cr

911

912 >Experimental counter-current 3 stages solid-liquid vanilla extraction had 10% of average

us

913 deviation with respect to model solution.

914

an

915

916 M

d

p te

ce

Ac

Page 32 of 32