Waste and Biomass Valorization

https://doi.org/10.1007/s12649-018-0352-4

ORIGINAL PAPER

Valorization of Kraft Lignin of Different Molecular Weights

as Surfactant Agent for the Oil Industry
Nacarid Delgado1,2   · Fredy Ysambertt3 · Gerson Chávez2 · Bélgica Bravo2 · Danny E. García4,5,6 · Jorge Santos1

Received: 15 February 2018 / Accepted: 22 May 2018

© Springer Science+Business Media B.V., part of Springer Nature 2018

Abstract
After cellulose, lignin is the second most abundant biopolymer in the vegetable world. Since lignin is a natural phenolic
polymer, there are a variety of potential products obtainable by its chemical modification, including surfactants. In this
regard, lignin is of great interest because represent a byproduct of pulp industries for papermaking; however, this byproduct
can be harnessed for obtaining aromatic derivatives of industrial interest. In this work, alkali lignin derivatives of different
molecular weights were synthesized from lignin fractions from Pinus caribaea obtained by ultrafiltration. Lignin and lignin-
fractions were modified with succinic anhydride (SA), and dodecyl-succinic anhydride (DSA) under microwave heating. The
reaction was monitored by Fourier Transform Infrared Spectroscopy. The surface activity of lignin, and lignin-derivatives
was evaluated through surface tension measurements, while the stability of suspensions and emulsions was evaluated by the
volumetric separation method. The lignin fractions, and the esterified derivatives were obtained in very short reaction times
(90–110 s) using a mixture of acetonitrile/ethanol. The lignin-derivatives showed higher surface activity in comparison to
the neat lignin. Derivatives prepared from the lower molecular weight fraction by using DSA showed the best emulsify-
ing properties. Lignin-derivatives also showed significant dispersing properties in comparison to a commercial dispersant
(lignosulfonate). The best dispersant properties were obtained from the higher molecular weight ultrafiltered lignin fraction
esterified with SA.

Keywords  Lignin · Derivatization · Succinic anhydride · Dodecyl-succinic anhydride · Dispersion · Emulsion

Statement of Novelty

We successfully synthetized bio-based surfactants by using

* Nacarid Delgado lignin fractions of different molecular weights modified with
n.delgado@udt.cl succinic anhydride and dodecylsuccinic anhydride, in a one-
1 step reaction.
Área de Bioproductos, Unidad de Desarrollo Tecnológico
(UDT), Universidad de Concepción (UdeC), Av. Cordillera
2634, Parque Industrial Coronel, Coronel, Biobío, Chile
2
Laboratorio de Petroquímica y Surfactantes (LPS), Introduction
Departamento de Química, Facultad Experimental de
Ciencias, Universidad del Zulia, Maracaibo, Venezuela The main source of fuels and chemicals is provide by the oil
3
Laboratorio de Instrumentación Analítica (LIA), industry. However, is necessary to explore alternative strate-
Departamento de Química, Facultad Experimental de gies for the conversion of biomass, abundant and renewable,
Ciencias, Universidad del Zulia, Maracaibo, Venezuela into added-value sustainable chemical products.
4
Laboratorio de Fitoquímica, Departamento de Química Lignin, as well as cellulose and hemicellulose, are the
Ambiental, Facultad de Ciencias, Universidad Católica de la main constituents of lignocellulosic biomass. After cellu-
Santísima Concepción (UCSC), Concepción, Biobío, Chile
lose, lignin is the most abundant macromolecule in nature.
5
Centro de Investigación en Biodiversidad y Ambientes Such heterogeneous biopolymer consists of phenylpropane
Sustentables (CIBAS), UCSC, Concepción, Biobío, Chile
moieties linked mainly by ether linkages, and comprise phe-
6
Investigador Asociado Área de Bioproductos, UDT, UdeC, nolic hydroxyls, aliphatic hydroxyls, methoxyls, carbonyls,
Concepción, Biobío, Chile

13
Vol.:(0123456789)

carboxyls and sulfonates functionalities [1]. To this base
several functional groups from lignin provide active centers
for chemical and biological interactions [2], highly desirable
for the developing of bio-based products.
In the process of manufacturing cellulose pulp for the
production of paper, lignin is considered a by-product.
The amount of lignin extracted from pulp manufacturing
operations is ca. 70 million tons per year. Less than 2%
is recovered, mainly in the form of lignosulfonates or as
lignin derived from the Kraft process [3, 4]. In general,
lignin extracted from pulp and paper operations is burned
for energy recovery and regeneration of pulping chemicals.
However, its abundance in nature could potentially solve
the problem of the rapidly depleting resources if it was suc-
cessfully translated into a renewable resource or valorized
to higher value materials [5].
One of the most promising industrial applications of
lignin is as a renewable surfactant. Although that lignin from
black liquors is not a conventional amphiphilic molecule,
typical lignin contains both hydrophilic phenolic/aliphatic
hydroxyl groups and lipophilic carbon backbone, which
suggests a special affinity to polar and nonpolar phases.
Therefore, it owns great potential to be used as a surfactant.
However, a certain modification step is often necessary to
control its amphiphilicity and solubility [5]. Depending on
the specific application, the surface activity of the lignin can
be modified by derivatization. Variating of the functional
groups composition via grafting with polar or nonpolar func-
tionalities significantly change the hydrophilic-lipophilic
balance (HLB).
Recently, many scientific investigations have been con-
ducted on lignin to control its amphiphilicity so that the
resultant lignin can be applied in the field of dispersion
[6–10] and emulsification [11–13] as bio-based surfactants.
The usages of lignin in the oil industry are widely docu-
mented [14, 15]. The most extensively used lignin-based sur-
factants are lignosulfonates, hydrophilic anionic compounds
obtained from the liqueur of the sulphite pulping process.
Application ranging from the deflocculation of clay particles
in drilling muds, to the extraction of heavy and extra-heavy
crude oils of asphalt. In addition, another application com-
prises the stabilization of oil–water emulsions.
Despite the potential of application of lignin and lignin-
derivatives, one of the major limitation is associated to the
high polydispersity. The fractionation of lignin in low-poly-
disperse fractions is highly desirable for industrial applica-
tions. A useful technique for lignin fractionation is based on
ultrafiltration (UF) by using different molecular weight cut-
off [16–20]. The fractionation procedures become crucial for
the production of more uniform lignin-fractions.
The main objective of this work was to evaluate the emul-
sifying or dispersing properties of commercial Kraft lignin
derivatives synthesized from lignin-fractions of different
13
Waste and Biomass Valorization
molecular weights obtained by ultrafiltration. The chemi-
cal modification was carried out with succinic anhydride
(SA) and dodecyl-succinic anhydride (DSA) assisted by
microwave in a short reaction time. The physicochemical
properties of lignins, lignin-fractions, and lignin-derivatives,
in terms of emulsifying/dispersing behavior, are reported.
Materials and Methods
Ultrafiltration of Lignin
Pine (Pinus caribaea) alkali kraft lignin (AL), isolated by
acid precipitation (pH = 3) from the black liquor of Smurfit
Kappa Company, San Felipe, Venezuela, was used. The frac-
tionation was performed in a tangential UF module made of
stainless steel, operating in a semi-continuous mode, and
using a tubular ceramic membrane of α-alumina (nominal
pore size: 15 kDa) [21].
The procedure was developed by Rojas et al. [17] for the
fractionation of black liquor from the kraft process. Alkali
lignin solution dissolved in 0.1 M NaOH (Merck, 99%), was
pumped through the 15 kDa membrane from a tank at 25 °C
(P = 2 bar). The permeate and retained membrane currents
were treated with HCl (Riedel-de Haën, 37%) to precipitate
the lignin, which was then separated by centrifugation, dried
at 50 °C (24 h) and kept in a desiccator for further analysis.
The UF scheme is shown in Fig. 1.
Chemical Modification
Alkali lignin, and lignin-fractions obtained by UF (F1AL
and F2AL) were both reacted with succinic anhydride (SA,
Riedel-de Haën, 99%) or n-dodecylsuccinic anhydride
(DSA, TCI 98%) (Fig. 2). Reactions were carried out in a
microwave oven (Panasonic, Japan, max. power 1200 W, fre-
cuency 2.45 GHz, temperature control 80 °C). The reaction
conditions in term of solvent, time of reaction, and amount
of the acylating agent were optimized in previous studies
[22].
Briefly, 100 mg of lignin or ultrafiltered fraction was
mixed with anhydride (2.0 mmol SA or 1.12 mmol DSA)
Fig. 1  Ultrafiltration of alkali lignin with 15 kDa ceramic membrane
Waste and Biomass Valorization
Fig. 2  Chemical modification
of lignin with alkyl succinic
anhydrides
in a glass reactor, adding 5 mL (4/1) acetonitrile/ethanol
(ACN/EtOH) mixture and heating in the microwave oven for
90–110 s at 80 °C. The reaction products were washed with
distilled water and 5% (v/v) HCl solution. The suspension
was centrifuged to a clear supernatant and dried at 50 °C
(24 h) until the analysis.
The derivatized products were washed with dichlorometh-
ane in order to remove the unreacted anhydride. Derivatives
were weighed (weight increase WI%, Eq. 1) after the chemi-
cal modification [23]:
[ ]
m1 − m0
WI (%) = × 100 (1)
m0
where m0 is the initial weight of dried lignin sample (g) and
m1 is the weight of lignin after esterification reaction (g).
Physicochemical Characterization
Lignin, lignin-fractions, and the anhydride-based derivatives
were characterized by Fourier Transform Infrared (FTIR
8400 Shimadzu) spectroscopy. FTIR spectra were perfor-
mance between 4000 and 400 cm−1, with a resolution of
4 cm−1 and 25 cumulative scans. Quantitative interpretation
(data not shown) was carried out by normalization using the
carbonyl (C=O) stretching bands from the modified lignin
or lignin fraction. Aliphatic C–H stretching (symmetric and
antisymmetric) were used as referential band.
The determination of the average molecular weight (Mw)
was performed by gel permeation chromatography (GPC),
using a liquid chromatography system (Waters Corp.) with a
set of columns Ultrastyragel® (Phenogel 7.8 × 300 mm) and
packaging of Styrene–divinylbenzene copolymer of 10 µm.
Three columns were used in series with selective permeation
ranges of 100, 500 and 1000 Å. The mobile phase (THF) at
a flow rate of 1 mL min−1, PDA detector (λ = 280 nm) and
100 µL sample injection volume was used.
Calibration was performed using polystyrene standards
with a narrow range of known Mw, as reported in previous
studies [24]. Samples were injected at a concentration of
0.2% (wt/v). The lignin and the corresponding ultrafiltered
fractions were acetylated with acetic anhydride (Fischer,
98.4%) prior to GPC analysis. Analyses were performed in
triplicate and the results were averaged.
Surface Tension Measurements
The surface activity of lignin, ultrafiltered fractions, and
lignin-derivatives was evaluated by surface tension meas-
urements using the Du Nouy ring method. Samples were dis-
solved in 0.1 M NaOH aqueous solution (1%, wt/v), which
was varied by successive dilutions. The solutions were
allowed to stand for 24 h for surface stabilization. Analyses
were performed in triplicate and the results were averaged.
Evaluation of the Dispersing Properties
The dispersing properties were compared with a commercial
dispersant “LS-CF” (M & P Supply and Services CA), a
sodium lignosulfonate commonly used in the oil industry
for the stabilization of drilling muds. The dispersing prop-
erties were evaluated by using aqueous bentonite (Baker &
Hughes) suspensions prepared in 0.1 M NaOH. The afore-
mentioned solution was prepared as follows:
0.05 g of the dispersant chemical (lignin, lignin fraction,
lignin-derivatives, and the commercial product) was dis-
solved in 100 mL of the aqueous solution of NaOH. Ben-
tonite (2.5%, wt/v) was added to the aqueous solution of the
dispersant, with continuous and controlled stirring (IKA®-
Werke mixer Eurostar model). Moreover, the suspension was
shaking for an additional 10 min (500 rpm).
It is worth to noting that the suspensions of bentonite
were prepared at a dispersant concentration of 0.05% (wt/v),
much lower than that commonly reported in the literature
(0.5–5.0% wt/v) [25–28].
The stability of the suspensions was determined under
static conditions by the volumetric separation method.
The suspensions were taken to graduated tubes, which
were maintained at 25 °C, measuring the volume of water
separated during a period of 72  h. The viscosity of the
13

suspensions was measured with a rheometer (Brookfield,
model LVDV-III+, Software Rheocal). All measurements
were made in triplicate, and the average value was reported.
Evaluation of Emulsifying Properties
The emulsifying properties were compared with those of
the commercial anionic surfactant named dodecylbenzene
sodium sulfonate (DBSS). The emulsions were prepared
using a 0.1 M NaOH solution containing several lignin con-
centrations (0.25, 0.5, and 1% wt/v), ultrafiltered fraction,
lignin-derivatives or DBSS surfactant, and xylene (Riedel
of Haën, 96%) as oleic phase, at a water/oil ratio of 50/50
(WOR = 1). The emulsification protocol comprises the mix-
ing of the organic and the aqueous phases with a homog-
enizer (Heidolph Silent Crusher M), at a speed of 9000 rpm
during 60 s.
The stability of the emulsions was determined under
static conditions by the volumetric separation method: emul-
sions were taken to graduated tubes at 25 °C, measuring the
volume of water separated after 24 h. The type of emulsion
formed was determined by electrical conductivity measure-
ments (WTW LF 320 conductivity meter). The viscosity of
the emulsions was measured with a rheometer immediately
after preparation. All measurements were made in triplicate,
and the average value was reported.
Results and Discussion
Molecular and Structural Characterization
The UF process was performed in order to obtain homo-
geneous lignin fractions of different Mw, since the lignin
shows high polydispersity, which influence negatively on
the surface activity.
Table  1 shows the number average molecular weight
(Mn), and mass average molecular weight (Mw), as well as
the polydispersity (D: Mw/Mn). Less polydisperse lignin frac-
tions were obtained in comparison to the starting lignin.
Table 1  Molecular features of alkali lignin, and lignin-fractions
obtained by ultrafiltration
Polyphenol Mw (Da) Mn (Da)
AL 15,375 1598
F1AL 3876 1466
F2AL 1972 1544
AL alkali kraft lignin, F1AL higher molecular weight ultrafiltered
lignin fraction, F2AL lower molecular weight ultrafiltered lignin frac-
tion, D polydispersity
13
Waste and Biomass Valorization
In Table 1, F1AL show an Mw (3876 Da) lower than that
of the neat AL (15,375 Da). There are two reasons that could
explain these results:
(i) The composition of lignin in terms of concomitant
compounds. This industrial lignin contains other
compounds such as residual sugars, hemicellulose,
and other polyphenols which could affect the filtering
process, even though this was washed to collect the
retained fraction. This potential loss of low molecu-
lar weight fractions during the filtration overestimate
the molecular weight of the neat lignin [29]
(ii) Intrinsic limitations associated to the method for
Mw distribution analysis. It is well-known that the
variation of hydrodynamic volumes associated with
the lignin analysis significantly affects the Mw aver-
age. Chemistry interactions of polyphenols with the
stationary phase during the elution process might
affect the results. Artifacts as consequence of non-
derivatized –OH groups might induce overestimation
or underestimations of the Mw average [29–31]. The
hypothesis arises considering that lignin, as well as
other polyphenols such as selected condensed tan-
nins, are fully acetylated in drastic conditions in term
of temperature and esterification time.
The FTIR spectra of the neat lignin, and the lignin-frac-
tions is provided (Fig. 3). In all cases, the typical signals
are observed. A broad band around 3400 cm−1, attributed
to the stretching of hydroxyl groups in phenolic and ali-
phatic structures, as well as the bands appearing at 2941 and
2846 cm−1 associate to C–H stretching in methyl and meth-
ylene groups of side chains, and methoxyl aromatic groups
in lignin is observed. In addition, the bands at 1595, 1510,
and 1427 cm−1 related to the vibrations of the aromatic skel-
eton is also visible. In addition, bands between 1000 and
1250 cm−1, associated with the C–O stretching of methoxyl
groups and of alcohols, are identified [32–35].
In comparison to the neat lignin, the F1AL-, and F2AL-
fractions show a sharp band (1700 cm−1), associated to
carbonyl groups, and probably due to the acid precipitation
process used for the isolation of the lignin fractions after UF
process. Such apparent degradation of lignin has been also
reported by Boeriu et al. [36] as consequence of the oxi-
dation, where the characteristic band of carbonyl/carboxyl
groups increased in several lignin fractions extracted with
D
organic solvents or acid precipitation.
9.62 The chemical modification of lignin and the corre-
2.64 sponding lignin-fractions obtained by UF with ASA was
1.28 confirmed by FTIR spectroscopy (Fig. 4). The spectra of
the esterified AS-based products (ALSA, F1ALSA, and
F2ALSA) show a sharp band around 1714–1729 cm−1, cor-
responding to the absorption of carbonyl groups, in which
Waste and Biomass Valorization
Fig. 3  FTIR spectra of alkali
lignin, and the corresponding
lignin-fractions (F1AL and
F2AL)
the signals of the ester groups (1750 cm −1), and carbox-
ylic acids (1712 cm−1) are overlapped. In the case of the
F1ALSA-, and F2ALSA-derivatives, the band increases
the intensity in comparison to the F1AL-, and F2AL-frac-
tions. Such signals highlight that SA-based esterification
was successful [37–39]. The increasing in the absorption
band around 1166 cm −1 (stretching of the CO bond of
esters and carboxylic acids), as well as a slight change
of the aliphatic CH tension intensity (2950–2871 cm −1),
and of the flexural vibration (1460 cm−1) are structural
evidence of the incorporation of the methylene carbons
from the SA. The absence of absorption bands between
1850–1800 cm −1 suggests that the products are free of
unreacted SA.
The results are in accordance with those reported by
Xiao et al. [37] who performed the chemical modification of
lignin with SA using conventional heating (1–12 h), and by
Liu et al. [39] by using shorter reaction times (30–120 min).
The modified products showed similar structural features
in function of the FTIR data. However, the MW assistance
allowed the preparation of esters from lignin in a single step
in very short reaction times.
In the FTIR spectra of the DSA-esterified derivatives
(ALDSA, F1ALDSA and F2ALDSA) the carbonyl carbon
signals are observed around 1700 cm−1, which increases its
intensity in the F1ALDSA- and F2ALDSA-derivatives in
comparison to F1LA-, and F2LA-derivatives. The decrease
in intensity corresponding to the hydroxyl group bands
around 3440 cm−1 is highlighted. Additionally, an increase
in the absorption band is observed around 1166 cm−1 associ-
ated to the stretching of the C–O bond of esters and carbox-
ylic acids as complementary evidence of the esterification.
In addition, the absence of absorption bands in the region
of the spectrum between 1870–1850 cm−1 indicates that the
products are also free of unreacted DSA.
On the other hand, the weight increase (WI%) of AS-
based derivatives was 12.9%. Such value is higher than the
values reported by Xiao et al. [37] (WI%: 2.8–8.6) using an
alternative method of synthesis (SA-conventional heating).
In contrast, the chemical modification of lignins with DSA,
show a significant WI (290%). However, the values obtained
in this study are in accordance with those reported in our
previous study [22].
Surface Activity
When a substance with surface activity is added to the water
(or oil), it spontaneously adsorbs to the surface, and the sur-
face tension (γ) decreases. The surface tension values as a
function of the concentration of lignin, lignin-fractions, and
lignin-derivatives is provided (Fig. 5).
In all cases a decrease of the surface tension suggests the
adsorption of the molecules at the water–air interface.
Considering the influence of the lignin fractionation on
the surface activity, lower surface tension values for the
F2LA fraction was observed. However, highly functional-
ized molecules become more soluble in the aqueous solu-
tion, enabling migration to the interface.
Apparently, the incorporation of the new functional
groups had a positive effect on the surface activity of the
lignin-derivatives, since the surface tension was decreased.
The DSA based-derivatives presented lower surface
tension values as a function of the concentration; the
results suggest that the steric repulsion effect of the graft-
ing (dodecylsuccinic-chain) and the electrostatic effect of
the carboxylate anion in basic medium dictate the interac-
tion. Parallely, the surface tension of the derivative name
F1ALDSA (Fig. 5c) remain constant from a concentration
around 0.25% (wt/v). In monomeric surfactants, this concen-
tration indicates the critical micelle concentration (CMC).
13
 Waste and Biomass Valorization

Fig. 4  FTIR spectra of a alkali

lignin, and lignin-derivatives, b
F1AL-fraction and F1AL-based
derivatives, and c F2AL-
fraction, and F2AL-based
derivatives

However, lignin molecules unable association in the form of
micelles and therefore this concentration is rather described
as a pseudo-CMC, or as a critical aggregation concentra-
tion (CAC), term used to indicate the concentration at which
the surface tension levels off [11]. It is worth to notice that
under the tested conditions it was only possible to obtain the
pseudo-CMC of the F1ALDSA derivative.
In general, the lignin-derivatives behave as polymeric
surfactants in aqueous media. Adsorption of conventional
surfactants is generally very rapid, but for larger molecules
such as Kraft lignin, as well as lignin-derivatives the adsorp-
tion process apparently is slower.
Dispersing Properties
Lignin and lignin-derivatives are able to stabilize the
bentonite particles, since the water separated from the

13
Waste and Biomass Valorization
Fig. 5  Isotherms surface tension-concentration of a alkali lignin, F1AL-, and F2AL-fractions; b alkali lignin, and lignin-derivatives; c F1AL,
and F1AL-based derivatives; d F2AL, and F2AL-based derivative (T = 25 °C)
suspension as a function of time is smaller than the sus-
pension prepared without any dispersant (Fig. 6a).
The stability of dispersed systems depends on two types
of repulsive forces: (i) electrostatic and (ii) steric. The
effect of the addition of lignin on the dispersability of
the bentonite particles can be explained considering that
adsorption occurs via both steric, and electrostatic repul-
sive forces.
In addition, the stability of the suspension prepared
with F1AL was comparable to the LS-CF-based solution
behavior. The UF method proved to be a suitable strategy
in order to get homogeneous lignin fractions.
The chemical modification of alkali lignin with ASA
favors the stabilization of the bentonite suspensions
(Fig. 6b). This is probably related to the increase in both
steric and electrostatic repulsive forces, mainly due to car-
boxylate anion from the esterified derivatives.
The influence of the molecular size and the polydisper-
sity on the repulsive forces behavior is shown (Fig. 6c, d).
In order to synthesize esterified lignin with remarkable
dispersing properties, it is appropriate to combine either
(i) smaller and less polydisperse lignin molecules with
long side-chain anhydrides or (ii) larger lignin molecules
with short-chain anhydrides, in order to tailor an adequate
balance between steric, and electrostatic repulsive forces.
The aforementioned trend is highlighted in Fig. 7. The
stability of the suspension as the time taken to reach V/
V∞ = 0.15 (separate water volume/total volume) condi-
tion is shown.
According to the results, ALSA-, F1ALSA-, and
F2ALDSA-based derivatives showed better stabilizing
properties of aqueous bentonite suspensions than LS-CF.
All the suspensions behave as a non-Newtonian fluid
of the pseudo-plastic type (Fig. 8), where the viscosity
decreases as the shear speed or shear rate increases [40]. In
all cases the viscosity of the slurry prepared with LS-CF
was lower. In contrast, the viscosity of the reference sus-
pension prepared without dispersant was greater. Such
results emphasize that the dispersants show reofluidizing
properties, since the aforementioned chemical decreases
the apparent viscosity of the suspensions in comparison
to the reference.
The apparent viscosity of the suspensions prepared with
lignin, as well as lignin-fractions obtained by UF proved to
be rather similar. However, chemically modified fractions
show differences in terms of apparent viscosity values of
the bentonite suspensions. Despite a clear trend cannot be
established, it is observed that the suspensions prepared
with the F2AL-derivatives showed higher viscosity values.
In this regard, Yang et al. [41] reported that the higher
Mw of the LS the better the effect on the reduction of the
viscosity of aqueous carbon suspensions. Similarly, other
studies have concluded that the Mw is an important fac-
tor that affects the dispersant capacity of aqueous carbon
suspensions, and that the fractions of high Mw have lower
viscosity and greater dispersing capacity for this type of
systems [42, 43].
13
 Waste and Biomass Valorization

Fig. 6  Stability expressed as the percentage of water separated as atives, c F1AL, and F1AL-based derivatives, d F2AL, and F2AL-
a function of time for bentonite suspensions prepared with a alkali based derivatives (T = 25 °C)
lignin, F1AL-, and F2AL-fractions, b alkali lignin and lignin-deriv-

Fig. 7  Comparison of stability
of lignin-, ultrafiltered frac-
tions-, esterified derivatives-,
and commercial LS-based
bentonite suspensions, and the
corresponding reference (V/
V∞ = 0.15)

Emulsifying Properties
The electrical conductivity of the emulsion as a function of
the concentration of alkali lignin, lignin-fractions and lignin-
derivatives is shown (Fig. 9).
All emulsions prepared are of the O/W type (oil in
water), with values of electrical conductivity between 2
and 6 m S cm−1. Such values are greater than the electrical
conductivity of the oil phase of the emulsion (xylene) whose
value is 0.0002 m S cm−1. The electrical conductivity of the
pure aqueous phase was 21 m S cm−1. The values decrease
in the emulsion due to the presence of lignin, lignin-fractions
or the esterified derivatives. The electrical conductivity of
lignin-based emulsions solutions decreases at higher con-
centrations. However, this effect was not observed for the
commercial surfactant (DBSS).

13
Waste and Biomass Valorization

Fig. 8  Apparent viscosity as a function of the shear rate of aqueous bentonite suspensions prepared with a alkali lignin, F1AL- and F2AL-frac-
tions; b alkali lignin, and lignin-derivatives; c F1AL, and F1AL-based derivatives; d F2AL, and F2AL-based derivatives (T = 25 °C)

Fig. 9  Electrical conductivity as a function of the concentration of a alkali lignin, F1AL-, F2AL-fractions, and DBSS b alkali lignin and lignin-
derivatives, c F1AL, and F1AL-based derivatives, d F2AL, and F2AL-based derivatives (T = 25 °C)

13
 Waste and Biomass Valorization

The stability expressed as the time taken by the system The stability of the emulsions prepared with lignin,
to reach the V/V∞ ratio (0.15), is observed (Fig. 10). The lignin-fractions, and esterified derivatives are similar to
stability of the emulsions increases as the concentration those observed in relation to the stability of the bentonite
of the lignin or lignin-fraction increases, as the number of suspensions, where the best results are obtained by combin-
molecules capable of being adsorbed at the xylene/water ing the higher molecular size molecules (AL and F1AL)
interface increases. with SA, and the smaller molecular size molecules (F2AL)
Unmodified lignin-based emulsions stability increases with the long alkyl-chain anhydride (DSA).
as the molecular size increases (Fig. 10a), indicating that The results show that lignin-derivatives esterified with
the steric stabilization dominates. In the case of the ASA- ASA exhibited a differentiate behavior in comparison to the
based derivatives, the influence of electrostatic repulsions commercial surfactant (DBSS). The stability of the emul-
between drops caused by the ionized carboxylate anion sions prepared at 1% (wt/v) DBSS exceeds by three times
in basic medium must be considered. It is worth to notice
that emulsions prepared with alkali lignin at low concen-
trations are more stable than the emulsions prepared with
their esterified derivatives (Fig. 10b). The polydispersity and
structural features of alkali lignin, as well as the grafting of
alkyl-succinic chain unable adequate orientation of the mol-
ecules around the dispersed phase droplets. This behavior
is completely opposite to that observed in Fig. 10d. In this
case, the emulsions prepared with the esterified derivatives
(F2AL) are more stable than the emulsions prepared with
the aforementioned fraction.
The results highlight that the incorporation of the alkyl-
succinic chain enable less polydispersity values. In addition,
the UF process has also a positive effect on the molecular
homogeneity since lignin derivatives can be better accom-
modated on the surfaces of the dispersed phase droplets. Fig. 11  Stability of emulsions prepared with alkali lignin, lignin-frac-
tions, esterified derivatives, and DBSS (C = 1% wt/v; V/V∞ = 0.15)

Fig. 10  Stability of emulsions prepared at different concentrations of a alkali lignin, F1AL-, and F2AL-fractions; b alkali lignin, and lignin-
derivatives; c F1AL, and F1AL-based derivatives; d F2AL, and F2AL-based derivatives (V/V∞ = 0.15)

13
Waste and Biomass Valorization
fold the values reported from the emulsions prepared at the
same concentration by using F2ALDSA (Fig. 11).
Another important property of emulsified systems is their
rheological behavior. The apparent viscosity as a function
of the shear rate of lignin-stabilized emulsions, lignin-frac-
tions, lignin-derivatives, and DBSS surfactants at 1% (wt/v)
is provided (Fig. 12). All emulsions are characterized by
initial viscosities which rapidly decrease as the rate or shear
rate increases, typical behavior of non-Newtonian fluids of
the pseudo-plastic type. This behavior can be associated to
molecular features. In more stable emulsions, small droplets
formed remain separated from each other by steric and elec-
trostatic, increasing the viscosity, whereas in the less stable
emulsions the droplets tend to coalesce rapidly, increasing
the size and decreasing the apparent viscosity. It emphasizes
that the emulsions prepared both with lignin and with its
esterified derivatives of different molecular weight, showed
lower viscosity values than the emulsions prepared with the
commercial surfactant DBSS.
In general, for the AL-based derivatives, as well as the
F1AL-, and F2AL-fractions, a slight emulsifying property
were showed. In addition, is necessary to evaluate the influ-
ence of the component composition on the stability of the
emulsions prepared with lignin-derivatives. It is possible that
by using a WOR different from 1, the stability of the emul-
sions can be increased by dispersing more of the internal
phase. Another possibility is to perform additional structural
Fig. 12  Apparent viscosity as a function of the shear rate of the emulsions prepared at 1% (wt/v) of a alkali lignin, F1AL- and F2AL-fractions; b
alkali lignin, and lignin-derivatives; c F1AL, F1AL-based derivatives; d F2AL, and F2AL-based derivatives
modification in order to increase the potential emulsifying/
dispersing in view of novel applications.
Conclusions
The ultrafiltration of alkali kraft lignin using a ceramic mem-
brane of 15 kDa allowed two fractions of lignin of lower
polydispersity in comparison to the neat feedstock. The
molecular fractionation had a significant impact on the sur-
face activity of the lignin-derivatives obtained by chemical
modification with succinic-, and dodecylsuccinic-anhydride.
The synthesis of the aforementioned lignin-derivatives was
carried out in very short reaction times, and in the absence
of catalyst.
F1ALSA derivative showed better dispersing properties,
while the best emulsifying properties corresponding to the
F2ALDSA derivative. The result indicating that either (a)
the combination of smaller lignin molecules (less polydis-
perse), with long chain anhydrides, or (b) larger lignin mol-
ecules with short-chain anhydrides, are adequate in order
to tailor a proper balance between steric and electrostatic
repulsive forces.
All aqueous bentonite suspensions and oil/water emul-
sions prepared with lignin, ultrafiltered fractions or esterified
derivatives showed rheological behavior of non-Newtonian
fluids.
13

Lignin-derivatives and their ultrafiltered fractions esteri-
fied with alkyl-succinic anhydrides generally show good
dispersing properties of bentonite suspensions since a sig-
nificant stability based on the commercial lignosulfonate
behavior was observed.
In contrast, the lignin-derivatives esterified with alkyl-
succinic anhydrides showed low emulsifying properties.
All emulsions prepared with the lignin derivatives and their
ultrafiltered fractions esterified with alkyl-succinic anhy-
drides were O/W type. The stability of such emulsions was
greater as the concentration of lignin, lignin-fraction or
lignin-derivative is increased. In all cases, the stability of
the emulsions prepared with the lignin-derivatives of the
corresponding fractions was higher that the stability of the
emulsions prepared with the non-fractionated lignin deriva-
tives. Such result emphasize that ultrafiltration is a conveni-
ent technique for obtaining less polydisperse lignin.
Acknowledgements  The authors thank the Laboratory of Mixing, Sep-
aration and Industrial Synthesis (LMSSI) of the Faculty of Engineering
of the University of Los Andes (ULA), Merida-Venezuela, especially
to professor Dr. Johnny Bullón, for the technical support (tangential
UF equipment). In addition, authors like to thanks to “Proyecto Basal
PFB-27”, Technological Development Unit (UDT), Concepción Uni-
versity, Chile, and to the Scientific, Humanistic and Technological
Development Council (CONDES) of the University of Zulia (LUZ),
Maracaibo-Venezuela (project CC-0260-15).
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