Extraction of a tricarboxylic acid from a sugar-cane by-product – Study and modeling of the anion-exchange step . 16. Congrès de la Société Française de Génie des Procédés "Le Génie des Procédés au Service de l'Homme" (SFGP 2017

Fargues, Claire

Lameloise, Marie-Laure

Petit, Arnaud

Wu-Tiu-Yen, Jenny

English

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Extraction of a tricarboxylic acid from a sugar-cane
by-product – Study and modeling of the anion-exchange
step
Jenny Wu-Tiu-Yen, Marie-Laure Lameloise, Arnaud Petit, Claire Fargues
To cite this version:
Jenny Wu-Tiu-Yen, Marie-Laure Lameloise, Arnaud Petit, Claire Fargues. Extraction of a tricar-
boxylic acid from a sugar-cane by-product – Study and modeling of the anion-exchange step. 16.
Congrès de la Société Française de Génie des Procédés ”Le Génie des Procédés au Service de l’Homme”
(SFGP 2017), Société Française de Génie des Procédés (SFGP). FRA., Jul 2017, Nancy, France. 1054
p. ￿hal-01774738￿
EXTRACTION OF A TRICARBOXYLIC ACID FROM A SUGAR-CANE BY-PRODUCT – 
STUDY AND MODELING OF THE ANION-EXCHANGE STEP 
Jenny Wu-Tiu-Yen
1,2
, Marie-Laure Lameloise
1
, Arnaud Petit
2
, Claire Fargues*
1,3 
 
1-UMR Ingénierie Procédés Aliments, AgroParisTech, INRA, Université Paris-Saclay, 91300 Massy, 
France 
2-eRcane, 97494 Ste Clotilde Cedex, Réunion, France 
3-Université Paris-Sud, 91400 Orsay, France 
*claire.fargues@agroparistech.fr 
Key-words: Anion-exchange, aconitic acid, biorefinery, electrodialysis, modeling 
 
In a context of biorefinery development, it is essential to find new feedstock for the extraction of 
biobased molecules. In the case of agroindustry by-products valorization, the component of interest to 
be extracted is generally diluted in a complex mixture.Sugarcane industry by-products are still rich in 
compounds such as carboxylic acids, phenol derivatives, amino acids and proteins [1].The aim of this 
study was to separate a multivalent organic acid (aconitic acid, AAco) from sugar-cane distillery 
stillageby a combination of processes including ananion-exchange chromatography step. A food-
grade weak-anionic resin had already been selected, the Lewatit S4528 resin (Lanxess, Courbevoie, 
France) [2, 3]. 
First, the major species competing for the ion exchange sites were determined. They are the acid of 
interest and chloride and sulfate ions. In order to understand the selectivity of this support for AAco 
and obtain equilibrium data useful to further predict and improve the column separation, ion exchange 
equilibrium measurements were obtained in batch mode at room temperature on ion-pairs. Aconitic 
acid being a multivalent acid, its valence is pH-dependent. It is monovalent at pH about 3 and 50% 
mono/ 50% divalent at pH 4.5, the natural pH of the stillage.Ion pairs studied were H2AAco
-
/Cl
-
, 
H2AAco
-
/SO4
2-
andHAAco
2-
/SO4
2-
. The isotherms obtained led to the determination of therational 
selectivity coefficients Kx(expressedrelative to ionic fractions) (Example Fig 1): Kx H2AAco
-
/Cl
-
 = 5.6; Kx 
H2AAco
-
/SO4
2- 
= 0.07 and KxHAAco
2-
/SO4
2-
= 7.1, showing the following affinity order: HAAco2- >SO4
2-
 > H2AAco
- > Cl-.Running the separation at pH 4.5 then appears more relevant, as affinity for the 
divalent species is the best. 
 
 
 
 
 
 
 
 
 
Figure 1.H2AAco
-
/Cl
-
 ion-exchange equilibrium on Lewatit S4528 resin. Experimental points and simulation 
(KxH2AAco-/Cl- = 5.6).
 
709
Experiments further run in column with synthetic and real stillage for different pH and resin initially 
under chloride or sulfate form confirmed that the best aconitic acid capacity was the natural pH 4.5. 
Chloride form gives a slightly better result than sulfate one with qAAco = 0.22 g/gdry resin, about 60% of 
the maximal capacity (obtained with aconitic acid alone). Furthermore, sulfates are less retained by 
the resin when it is in chloride form (qsul = 0,045 g/gdry resin) than are the chlorides when the sulfate 
formis used(qCl = 0,051 g/gdry resin).Elution by HCl 0,5N (flow-rate 1BV/h) was used to recover the 
chloride form and elute the aconitic acid. The compromise fraction, corresponding to an acid recovery 
of 80% and apparent purity at least 80% (as compared to the global quantity of anions it contains) 
contains 13.8 g AAco/L and only 0.17 g SO4/L and still 2.2 g Cl/L. Other organic acids are less than 
0.35 g/L, when their concentration wasabove 11 g/L in the initial stillage. This corresponds to a 
purification factor for this step of at least x 3. 
In parallel, modeling through a classical mathematical description of ion exchange in the fixed-beds 
was used, where the bed is treated as a continuous medium with assumption of a local equilibrium 
between liquid and sorbent, and of plug-flow of the stream, taking axial dispersion into account. This 
modeling gives good result once Kx coefficients are adjusted on a synthetic stillage (Figure 2). 
 
 
Figure 2 :Experimental and simulated breakthrough curves for a synthetic stillage pH 4.5 on Lewatit S4528 resin 
sulfate form (CE AAco = 5 g/L, CE Cl = 4.5 g/L, CE SO4 = 2 g/L; Bed Volume (BV)= 64 mL; Flow-rate 2 BV/h; 
simulation with Dax = 5 10
-6
 m
2
 s
-1
 ; Kx Cl-/HSO4- = 0,5 ; Kx H2AAco-/HSO4- = 3,5) 
 
Combination of the ion-exchange step with elimination of chloride ions through conventional 
electrodialysis process was considered. Two strategies were studied: electrodialysis can be used 
previously to the ion exchange step (resin under sulfate form) in order to increase aconitic acid fraction 
and thus improve the resin capacity for this solute. A second combination consists in treating the 
eluate obtained (HCl elution) by elimination of the chloride afterwards. Run on the initial stillage pH 
4.5, electrodialysis process under constant voltage of 18V andwith AMX and CMX membranes allows 
elimination of at least 90% of the chloride content (in concentrate compartment), when only 15% of the 
aconitic acid is lost. Concerning the first strategy,demineralized stillage through electrodialysis was 
sent on the Lewatit S4528 resin under sulfate form. The capacity for aconitic acid then reaches 
qAAco = 0.34 g/gdry resin, quite the maximal value obtained for a synthetic solution of aconitic acid alone. 
Combination of ion exchange and electrodialysis leads to a global purification factor close to 4 with a 
recovery about 60% for the aconitic acid and purity of about 30% (MS). The extract still contains some 
colorants and its purity could be improved by adsorption on active carbon support or crystallisation, 
that are still to be studied. 
 
[1] Caderby E, Baumberger S, Hoareau W, Fargues C, Decloux M, Maillard M-N. Sugar cane stillage : A potential 
source of natural antioxidants. Journal of agricultural and food chemistry 2013, 61: 11494-11501. 
[2] Petit A, Wu-Tiu-Yen J, Pislor E, Pontalier P-Y, Albet J, Hoareau W, Corcodel L. 2015. Procédé d'extraction de 
l'acide aconitique à partir de produits issus de l'industrie de la canne à sucre. FR1452245. 
[3] Pislor E. Extraction d'un acide organique à partir de co-produits issus de l'industrie de la canne à sucre. 2011 
Thèse Université de Toulouse. 
710


Extraction of a tricarboxylic acid from a sugar-cane by-product – Study and modeling of the anion-exchange step

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Extraction of a tricarboxylic acid from a sugar-cane by-product – Study and modeling of the anion-exchange step

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