Figure 1.

Lignocellulosic framework

 Lignocellulose is a complex material synthesized by plants during the formation of the cell wall
 Cell wall is a semi-rigid structure external to the cytoplasmic membrane
 Function:
- protects the cytoplasm from physical, chemical and microbiological stresses
- facilitates the transports of water and nutrients
  Plant cell wall
 The most external layer, the middle lamella
made almost only of pectic molecules
 The primary wall, a polysaccharide rich layer
made mainly of cellulose, hemicellulose and
pectic polysaccharides.
 The last and innermost wall to be synthesized is
the secondary wall, where most of the lignin is
accumulated
Figure 2. Schematic representation of a plant cell wall. The main components of  Cell wall constituents
the primary and secondary wall are highlighted (right) - cellulose (40-50 %),
- hemicellulose (20-35 %)
- lignin (15-30 %)
Figure 3. Lignin derived potential products
Lignin isolation technology:
 physical pretreatments (ball milling,
etc.)
 solvent fractionation (organosolv
process, the use of ionic liquids, etc.)
 chemical pretreatment (acidic, alkaline,
etc.)
Forbiological
 medical and foodtreatment
lignocellulose products,
(fungi) lignin separation
using strong chemicals such as Kraft and Soda Process are
unfavorable

Hydrotropic separation of lignin

 A small molecular amphiphilic molecules composed of both

hydrophilic and a hydrophobic functional group
 Hydrotropes have a remarkable capability to dissolve other
sparingly soluble organic compounds in aqueous solutions
 Hydrotropes have been applied in separation of various
valuable solute (lignin, andrographolide, curcumin, etc.)
Figure 5. Hidrotrope salts: a) sodium benzoat, b) sodium salisilat, c)
sodium xylenesulphonate, d) sodium cymenesulphonate, e) sodium
benzenesulphonate, f) sodium phenolsulphonate, g) sodium
toluenesulphonate and h) sodium naphthalenesulphonate.
 Hydrotropic Reactive
Extraction

 The combination of two processes, physical and chemical processes, leading to:
 a higher solute distribution coefficient
 a higher extraction efficiency
 allowing transport processes intensification by increasing mass transfer and chemical
reactions rates
 Prized for its simplicity, technical accessibility, novelty and possibility of utilization of green,
cheap and efficient chemicals
 Hydrotropic reactive extraction of lignin:
- Ansari et al. 2014: sugarcane bagasse, NaXS, NaCS
- Devendra et al., 2018; rice straw, NaXS, NaCS
- Ma et al., 2018: wheat straw, p-Toluenesulfonic acid (p-TsOH)
- Denisova et al., 2015: oat hulls, sodium benzoate
- Hartati et al. 2018-2019: rice straw, urea, sodium benzoate
 Mathematical modelling of solid liquid reactive extraction to extract
valuable solute from a slab solid material (Hartati et al., 2018)
Model Validation

 Consistency test The numerical analysis of the model proposed was validated and
compared to the analytical solution of a simple cases

 Correspondence test The numerical analysis of the model proposed was validated and
compared to the experimental data

 Pragamatic test The mathematical model solution is utilized as one of basic consideration
in technical decision making

Validation of Mathematical Model of Hydrotropic-Reactive Extraction of Lignin:

The mathematical model parameters were determined by fitting the model to the hydrotropic reactive extraction experimental data
reported by Ansari et al. (2014).
 (a) (a) (b)
(b)

Figure 8. The predicted and experimental extraction percentage of sugarcane

bagasse hydrotropic reactive extraction performed at 5 wt% bagasse loading,
temperature of 338K and sodium xylene sulfonate concentration of 10-30% (w/w)
(a); and their accuracy (b)

 Sugarcane bagasse lignin concentration are reported by different  Makavana et al. [18]: porosity of sugarcane bagasse is 0.84,
authors, wherein some of them are of 18.1% [15], 22.2 ±0.1% [16], and  Zhang et al. [19]: sugarcane bagasse is having porosity of
30.62% (AI and ASL) [17], approximately 0.77.
 The initial sugarcane bagasse lignin concentration was taken to be 24%.  Sugarcane bagasse porosity was set of 0.80
 Model parameter Value
Effective diffusivity of hydrotrope (SXS) (m2/ s) 5 x10-11
Effective diffusivity of soluble lignin (m2/ s) 9.0 x10-12
Reaction rate constant m3/ (mol.s) 6.4 ×10-7
Reaction order of SXS 1.0
Reaction order of lignin 0.5
Pseudo stoichiometric mass ratio of hidrotrope:lignin 6.4

 The hydrotrope effective diffusivity of soluble lignin was slightly higher than those reported by Ansari et al (2014)
(DeC = 1.43×10-13 – 3.43 ×10-13 m2/s)
 Approximately one hundred times higher than ones reported by Zhao et al. (2014) which was 6.7×10−14–1.6×10−12
m2/s.

 Li and van Heiningen (2000) reported a higher values of soluble lignin effective diffusivity from the magnesium bi-
sulfite pulping of wood chips in which the values are equal to 2.78×10−10, 6.67×10−10 and 1.39×10−9 m2/s for the wood
chips cooked at the temperatures of 155, 165 and 175 °C, respectively.
  The higher the sodium xylene sulfonate
concentration, the higher the yield of the
extraction was observed.
 Firstly sodium xylene sulfonate is absorbed in
the biomass cell wall, and then disrupts the cell
structure, finally penetrates the cell and
solubilizes the lignin (Devendra et al., 2018 )
 The more the disrupting agent available in the
system, the more lignin solubilized and
extracted from the system would be.

(a)
Figure 8. The predicted and experimental extraction percentage of (b)
sugarcane bagasse hydrotropic reactive extraction performed at 5 wt%
bagasse loading, temperature of 338K and sodium xylene sulfonate
concentration of 10-30% (w/w)
Time function profile of concentration fraction in the bagasse particle

(a) (b)
(a) (b)

(c)
(c)

Figure 9. The sodium xylene sulfonate concentration fraction profile in bagasse Figure 11. The lignin concentration fraction profile in the bagasse particle as time function
particle as time function for sugarcane bagasse hydrotropic reactive extraction for sugarcane bagasse hydrotropic reactive extraction performed at 5wt% bagasse loading,
performed at 5wt% bagasse loading, temperature of 338K and sodium xylene temperature of 338K and sodium xylene sulfonate concentration of (a) 10%, (b) 20% and (c)
sulfonate concentration of (a) 10%, (b) 20% and (c) 30%. 30%
 (a) (b)

Sodium xylene sulfonate diffuses to the inner part of the

biomass

The cell wall structure is disrupted

(c)
Figure 13. The soluble lignin concentration profile in bagasse particle as time function for
sugarcane bagasse hydrotropic reactive extraction performed at 5wt% bagasse loading,
temperature of 338K and sodium xylene sulfonate concentration of (a) 10%, (b) 20% and (c)
30%
The cell wall lignin is reacted with the hydrotrope and
solubilized into soluble fragments product
 The sodium xylene sulfonate and lignin concentration
start to be consumed and decreasing in its concentration
 The soluble lignin concentration increasing
Concentration fraction profile in axial direction

(a) (b)

(c)

Figure 10. The sodium xylene sulfonate concentration fraction profile in Figure 12. The lignin concentration fraction profile in the bagasse particle in axial direction
bagasse particle in axial direction for sugarcane bagasse hydrotropic reactive for sugarcane bagasse hydrotropic reactive extraction performed at 5wt% bagasse loading,
extraction performed at 5wt% bagasse loading, temperature of 338K and temperature of 338K and sodium xylene sulfonate concentration of (a) 10%, (b) 20% and (c)
sodium xylene sulfonate concentration of (a) 10%, (b) 20% and (c) 30%. 30%
  There are an internal concentration gradient
(a) (b) of soluble lignin product since soluble lignin
product diffuses slower than sodium xylene
sulfonate does.

 The diffusion of soluble lignin product and

the reaction between lignin and sodium
xylene sulfonate are the two steps that
influence the overall rate of hydrotropic
reactive extraction of lignin from sugarcane
(c)
bagasse.
Figure 14. The soluble lignin concentration profile in bagasse particle in axial position for
sugarcane bagasse hydrotropic reactive extraction performed at 5wt% bagasse loading,
temperature of 338K and sodium xylene sulfonate concentration of (a) 10%, (b) 20% and (c)
30%
(a)(a) (b) (b)

Figure 15. The sodium xylene sulfonate concentration profile in liquid phase
(a) and soluble lignin concentration profile in liquid phase (b)
 Conclusion

 Simulations show that the mathematical model of the hydrotropic-reactive extraction were well fitted
to the experimental data
 Mathematical model parameters comprised of hydrotrope effective diffusivity (DeA), effective
diffusivity of soluble lignin product (DeC), reaction rate constant (kr), reaction order of hydrotrope (n),
reaction order of lignin (m) and pseudo-stoichiometric mass ratio of hydrotrope to lignin (FA) were
obtained
 Concentration profile of hydrotrope, lignin, and soluble lignin product in both axial position and time
function, as well as the hydrotrop and soluble product concentration in the liquid phase obtained from
this hydrotropic reactive extraction mathematical modelling were able to give a better understanding
related to the mechanism of the hydrotropic reactive extraction.
 The validated proposed model can be applied for predicting the behavior of reactive extraction system
for various materials in which having slab geometry.