molecules

Article
Lignin Refinery Using Organosolv Process for
Nanoporous Carbon Synthesis
Imam Prasetyo 1,2, *, Puspita Rahayu Permatasari 1 , William Teja Laksmana 1 ,
Rochmadi Rochmadi 1,2 , Won-Chun Oh 3 and Teguh Ariyanto 1,2, *
1 Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada Jl. Grafika No. 2
Kampus UGM, Yogyakarta 55281, Indonesia; puspitarahayup@gmail.com (P.R.P.);
william.teja.l13@gmail.com (W.T.L.); rochmadi@ugm.ac.id (R.R.)
2 The Carbon Material Research Group, Faculty of Engineering, Universitas Gadjah Mada,
Yogyakarta 55281, Indonesia
3 Department of Advanced Materials & Science Engineering, Hanseo University, Chungnam-do 356-706,
Korea; wc_oh@hanseo.ac.krn
* Correspondence: imampras@ugm.ac.id (I.P.); teguh.ariyanto@ugm.ac.id (T.A.);
Tel.: +62-274-649-2171 (I.P. & T.A.)

Academic Editor: Dipendu Saha




Received: 31 May 2020; Accepted: 20 July 2020; Published: 28 July 2020

Abstract: Porous carbon has been widely used for many applications e.g., adsorbents, catalysts,
catalyst supports, energy storage and gas storage due to its outstanding properties. In this paper,
characteristics of porous carbon prepared by carbonization of lignin from various biomasses are
presented. Various biomasses, i.e., mangosteen peel, corncob and coconut shell, were processed using
ethanol as an organosolv solvent. The obtained lignin was characterized using a Fourier transform
infrared (FTIR) spectrophotometer and a viscosimeter to investigate the success of extraction and
lignin properties. The results showed that high temperature is favorable for the extraction of lignin
using the organosolv process. The FTIR spectra show the success of lignin extraction using the
organosolv process because of its similarity to the standard lignin spectra. The carbonization process
of lignin was performed at 600 and 850 ◦ C to produce carbon from lignin, as well as to investigate
the effect of temperature. A higher pyrolysis temperature will produce a porous carbon with a high
specific surface area, but it will lower the yield of the produced carbon. At 850 ◦ C temperature,
the highest surface area up to 974 m2 /g was achieved.

Keywords: carbonization; extraction; organosolv process; porous carbon

1. Introduction
Porous carbon is a versatile material with wide applications, for example: in adsorption [1],
separation [2], purification [3], gas storage [4], electrochemical storage [5] and catalysis [6] due to the
advantageous properties of pore- and microstructures. There are many precursors for porous carbon
preparation, for instance: biomass (natural polymer), synthetic polymer and metal carbide. Biomass
materials occur in nature, for example: peat, coconut shell and wood. Porous carbons produced
from these natural materials are very dependable concerning elemental composition of materials.
These are controlled by e.g., plant age, location and management activities of a plantation. For a
synthetic polymer we can adjust the pore structure and purity of materials during synthesis of the
polymer [7]. Depending on the preparation method of the polymer, a hierarchical pore architecture and
a monomodal pore structure (a narrow pore size distribution) can be obtained [8]. It is important to note
that a narrow pore size distribution is important, especially for applications where diffusion limitation
is desirable. Metal carbide is new variety of carbon precursor from which high purity and a specific

Molecules 2020, 25, 3428; doi:10.3390/molecules25153428 www.mdpi.com/journal/molecules

Molecules 2020, 25, 3428 2 of 11

pore range of porous carbon can be obtained [9]. From three types of porous carbon precursors the
biomass material is provided in a large amount and is typically cheap. The biomass can be separated
into two major products i.e., cellulose and lignin. Lignin has promise as a carbon precursor since it has
a large portion of aromatic hydrocarbons [10] and high content of carbon element [11]. Yet, there are
still limited studies of lignin for porous carbon synthesis.
To solubilize lignin, a conventional process like the Soda or Kraft process can be employed. In the
Soda process, delignification occurs due to a breakdown of ether (-C-O-C-) bonding in lignocellulose.
Lignin is then solubilized in an ionic solution. Solubilized lignin can then be precipitated using
acids. However, the Soda process also breaks ether bonding in lignin polymeric structures. This
produces fragmented lignin polymeric structures with lower polymeric density. The Kraft process is a
modification of the Soda process, which uses the addition of sodium sulfide in a sodium hydroxide
solvent [12]. Therefore, these two processes are too harsh to solubilize lignin, producing a dramatic
change in polymeric structures of lignin. Ionic liquid and organosolv processes are two examples
of processes which can solubilize lignin without affecting its original structure. Ionic liquid works
due to interference of inter and intramolecular hydrogen bonding in lignocellulose [13]. Ionic liquids
include imidazolium, pyridinium, ammonium cations, etc. Despite being able to extract lignin in a
high yield, ionic liquid is very expensive [14]. The organosolv process dissolves lignin by breaking
lignocellulose in the ether linkage [15]. It employs solvents like dioxane, ethanol, butanol and ethylene
glycol. The organosolv solvent is relatively cheap [16]. Furthermore, some studies show promise in
extracting lignin using the method [17].
We described previously the possibility of preparation of porous carbon from mangosteen peel
lignin, which was extracted using an organosolv process at 70 ◦ C [18]. To evaluate the efficacy of
the method, it is necessary to expand the study using other lignin sources i.e., corncob and coconut
shell, and a higher extraction temperature. This paper presents a comparison of lignin extracted
from various biomasses and its use for porous carbon synthesis. To investigate lignin properties
and the respective porous carbon produced, characterizations like Fourier transform infrared (FTIR)
spectroscopy, scanning electron microscopy (SEM) and N2 -sorption analysis were employed. The results
demonstrate another approach to producing high quality porous carbon by using lignin as a precursor.

2. Results and Discussion

2.1. Lignin Yield

Figure 1 shows the yield of lignin extraction from various biomasses using the organosolv process.
Mangosteen peel had a higher yield than the others. To study the influence of temperature, the extraction
condition was increased 70 ◦ C to 150 ◦ C. As a representative, mangosteen peel was chosen. When the
temperature of the organosolv process was increased from 70 ◦ C to 150 ◦ C, the yield of extraction of
mangosteen peel was higher (60.63%). Therefore, increasing temperature can enhance the yield of
lignin during organosolv extraction. Ethanol solutions reduce surface tension at high temperatures
thereby accelerating diffusion from the breakdown of lignin bonds into organic solutions [19]. As a
comparison, all biomasses were also treated using the conventional method of the Soda process (see
Figure 1). The solubility of lignin in soda solutions was higher than in organic solutions. The solubility
of lignin in a 0.25 M soda solution is 32 g/L [20] while the solubility of lignin in 60% ethanol solution is
16 g/L [21].
Molecules 2020, 25, 3428 3 of 11
Molecules 2020, 25, x FOR PEER REVIEW 3 of 11

100
Soda Process
Organosolv at 70 °C
Organosolv at 150 °C
80 76.33
72.68

60.63
60

Yield (%)
40
32.95
28.97
25.29

20 15.4

0
Mangosteen Corncobs Coconut
Peel Shell

Figure
Figure1. 1.Yield
Yieldcomparison
comparisonof oflignin
lignin extracted using organosolv
extracted using organosolvand
andsoda
sodaprocesses.
processes. Data
Data of of lignin
lignin
yield
yield ofof mangosteenpeel
mangosteen peelatat70 ◦
70 °C taken from our
C taken our previous
previousstudy
study[18].
[18].

2.2.
2.2Characteristics
Characteristics of
of Lignin
Lignin
TheTheextraction
extractionand and isolation
isolation processes
processes of of lignin
ligninhavehaveaacrucial
crucialrole
roleininseparating
separating lignin
lignin fromfrom
cellulose
cellulose and
and hemicellulose
hemicellulosewithoutwithoutbreaking
breakingthe thelignin
ligninoriginal
originalmolecular
molecular structure.
structure. TheThe derivations
derivations of
lignin monomers
of lignin monomersare p-hydroxyphenyl
are p-hydroxyphenyl monomers
monomers (H type), guaiacyl
(H type), monomers
guaiacyl monomers (G type), and syringyl
(G type), and
syringyl monomers
monomers (S type)
(S type) [22]. The[22]. Theobtained
lignin lignin obtained
from everyfrom every
type of type of biomass
biomass waste wastewaswas analyzed
analyzed with
withspectroscopy
FTIR FTIR spectroscopy
to ensure to that
ensure
thethat
ligninthewas
lignin was successfully
successfully obtained. obtained.
The graph Thewasgraphthen was then
compared
compared
with with the
the standard standardgroup
functional functional group of lignin.
of lignin.
The lignin functional group from
The lignin functional group from the organosolv the organosolv extractionsofof
extractions various
various biomass
biomass waste
waste cancanbebeseen
inseen in Figure
Figure 2. Lignin2. Lignin from mangosteen
from mangosteen peel, lignin
peel, lignin from from
corncob corncob and lignin
and lignin fromfrom coconut
coconut shell,
shell, which
which
were were extracted
extracted using theusing the organosolv
organosolv process at process
70 ◦ C, at are70labeled
°C, areaslabeled
LMP, LCC,as LMP, andLCC,
LCS, and LCS,
respectively.
respectively. Additionally, lignin from mangosteen peel, which was
Additionally, lignin from mangosteen peel, which was extracted using the organosolv process at aextracted using the organosolv
process at a higher temperature of 150 °C, is labeled as LMPT. For the spectra evaluation, several
higher temperature of 150 ◦ C, is labeled as LMPT. For the spectra evaluation, several publications
publications studying FTIR characterization of lignin were used [22–25]. At a wavelength−1of 1600
studying FTIR characterization of lignin were used [22–25]. At a wavelength of 1600 cm , lignin in
cm−1, lignin in (a), (b), (c), and (d) showed C=C stretching of the aromatic ring in lignin while in 1510
(a), (b), (c), and (d) showed C=C stretching of the aromatic ring in lignin while in 1510 cm−1 (c) and
cm−1 (c) and (d) showed the aromatic skeleton vibrations. C-H deformation (asymmetric in -CH3
(d) showed the aromatic skeleton vibrations. C-H deformation (asymmetric in -CH3 and -CH2 -) was
and -CH2-) was shown in the 1460 cm−1 wavelength of lignin (b), (c), and (d). At a wavelength
−1 wavelength of lignin (b), (c), and (d). At a wavelength of 1422 cm−1 , lignin (a),
of 1422
shown in the 1460 cm
cm−1, lignin (a), (c), and (d) showed C-H deformation in lignin. C-H stretching of G units was shown
(c),from
andlignin
(d) showed
(a) andC-H(b) indeformation
the 1283 cm−1in lignin.
. The peaks C-H stretching
in 1162 of G units
cm−1 showed was shown
by lignin (a), (b),from lignin
(c), and (d) (a)
and (b) typical
in the 1283 −1
cmG, and. TheS peaks in lignin.
1162 cm −1 showed by lignin (a),(a),
(b),(b),
(c),(c)
and (d)(d)
were typical
were for H, units of In 1110 cm-1 peak, lignin and showed
foraromatic
H, G, and S units of lignin. In 1110 cm −1 peak, lignin (a), (b), (c) and (d) showed aromatic C-H
C-H deformation of syringyl units, while in 917 cm , lignin (a) and (b) showed C-H bending
-1

deformation
of the syringylof syringyl units, while
unit’s aromatic ring.inThe cm−1bending
917 C-H , lignin (a) of and (b) showed
syringyl units wasC-Hshown
bending in of
840thecmsyringyl
−1 of

unit’s
ligninaromatic ring.
(c) and (d). The observed
Peaks C-H bendingin FTIRof syringyl
spectra and units
thewas shown in 840
functionalities cm−1 of lignin
are tabulated in Table(c) 1.
and (d).
Peaks observed in FTIR spectra and the functionalities are tabulated in Table 1.

Table 1. Peaks Observed in FTIR Spectra.

Sample Wavenumber (cm−1 ) Functionality

LMP; LCC; LCS; LMPT 1600 C=C stretching of the aromatic ring
LCS; LMPT 1510 Aromatic skeleton vibrations
LCC; LCS; LMPT 1460 C-H deformation (asymmetric in -CH3 and -CH2 -)
LMP; LCS; LMPT 1422 C-H deformation in lignin
LMP; LMPT 1283 C-H stretching of G units
LMP; LCC; LCS; LMPT 1162 H, G, and S units of lignin
LMP; LCC; LCS; LMPT 1110 Aromatic C-H deformation of syringyl units
LMP; LMPT 917 C-H bending of syringyl units, aromatic ring
LCS; LMPT 840 C-H bending of syringyl units
Molecules 2020, 25, 3428 4 of 11
Molecules 2020, 25, x FOR PEER REVIEW 4 of 11

1460
1510 840
1422 1110
1600
1162 d

1283 917 b

1422
a

2000 1800 1600 1400 1200 1000 800 600

-1
Wavenumbers (cm )

Fourier transform
Figure 2. Fourier
Figure transform infra-red
infra-red(FTIR)
(FTIR)band
bandfrom
from(a)
(a)LMP,
LMP,(b)(b)
LCC, (c)(c)
LCC, LCS, dan
LCS, (d)(d)
dan LMPT. Y-axis
LMPT. Y-
is transmittance.
axis is transmittance.

Figure 2 shows that the lignin from

Table organosolv
1. Peaks Observed extraction of various biomass waste had syringyl
in FTIR Spectra
and guaicyl groups. They are like a typical lignin standard. Meanwhile, the functional group from
soda extraction Wavenumberdid not have the group of syringyl and guaicyl but only
Samplefor various biomass waste Functionality
had the stretching unit in the aromatic (cm−1group
) of lignin. This confirms that the organosolv process can
LMP;
extract LCC;
lignin LCS;saving most of the original structure of lignin.
while 1600 C=C stretching of the aromatic ring
LigninLMPTmolecular weight can be indicated by the viscosity of the lignin solution [26]. Lignin
LCS;have
precursors LMPT different fractions of1510lignin-forming monomers Aromatic
so they canskeleton
produce vibrations
different molecular
weights. The viscosity was measured by a vapor pressureC-H deformation
osmometer (asymmetric
with NaOH 0.5 in
N -CH
as a 3solvent.
LCC; LCS; LMPT 1460
Table 2 displays the viscosity of lignin solutions. and -CH2-)
LMP; LCS; LMPT 1422 C-H deformation in lignin
LMP; LMPT 1283 Table 2. Viscosity of lignin.C-H stretching of G units
LMP; LCC; LCS;
1162 Viscosity H,(cP)
G, and S units of lignin
LMPT Lignin Source
LMP; LCC; LCS; Organosolv Process Soda Process
1110 Aromatic
◦ C-H deformation of syringyl units
LMPT Mangosteen peel 1.43/1.97 (at 150 C) 1.23
LMP; LMPT Corn cob 917 1.63
C-H bending of syringyl 1.17 units, aromatic ring
Coconut shell 1.53 1.20
LCS; LMPT 840 C-H bending of syringyl units
Figure 2 shows that the lignin from organosolv extraction of various biomass waste had syringyl
As can be seen in Table ◦ C,
and guaicyl groups. They are2,like
lignin, whichlignin
a typical was extracted
standard. using the organosolv
Meanwhile, process
the functional at 150
group from
features
soda the highest
extraction value ofbiomass
for various viscositywaste
compared to the
did not other
have thelignin
groupsources. It canand
of syringyl be an indication
guaicyl that
but only
the molecular
had weight
the stretching unitof
in the
the mangosteen
aromatic group peelofislignin.
higherThis
compared
confirmstothatthe the
other lignin sources.
organosolv processWith
can
respect to the Soda process, the viscosity of lignin obtained
extract lignin while saving most of the original structure of lignin. from the organosolv method has a higher
value. The low
Lignin viscosityweight
molecular of lignincanobtained from the
be indicated bySoda process suggests
the viscosity that the
of the lignin molecular
solution structure
[26]. Lignin
of lignin was
precursors fragmented
have different into smaller
fractions offorms [27,28]. Interestingly,
lignin-forming monomers using so they thecan
organosolv
produceextraction
different
process, the
molecular structures
weights. Theofviscosity
the lignin wasaremeasured
more or lessby apreserved, as indicated
vapor pressure osmometerby the high
with viscosity.
NaOH 0.5 N as
a solvent. Table 2 displays the viscosity of lignin solutions.
2.3. Characteristics of Porous Carbon Produced from Lignin
Table preparation
The precursors used in porous carbon 2. Viscosity ofwere
ligninlignin extracted from mangosteen peel
(MP), corncob (CC), and coconut shell (CS). The temperatures used for the carbonization process were
Viscosity (cP)
600 C and 850 C. Figure 3 shows that at 600 C, more carbon products were obtained than at 850 ◦ C
◦ ◦ Lignin Source ◦
Organosolv Process Soda Process
for all of biomass waste precursors. The increase of carbonization temperature resulted in decreasing
Mangosteen peel 1.43/1.97 (at 150 °C) 1.23
the product. This was because of a thermal degradation process in the molecular structures of lignin.
Corn cob 1.63 1.17
Lignin extracted using the Soda process was also carbonized at 600 ◦ C. The yield was lower than 10%,
Coconut shell 1.53 1.20
 2.3 Characteristics of Porous Carbon Produced from Lignin
The precursors used in porous carbon preparation were lignin extracted from mangosteen peel
(MP), corncob (CC), and coconut shell (CS). The temperatures used for the carbonization process
were
Molecules 2020,600 ℃ and 850 ℃. Figure 3 shows that at 600 °C, more carbon products were obtained than at
25, 3428 5 of 11
850 ℃ for all of biomass waste precursors. The increase of carbonization temperature resulted in
decreasing the product. This was because of a thermal degradation process in the molecular
which structures
is likely due to low
of lignin. thermal
Lignin degradation
extracted of lignin
using the Soda obtained
process was alsofrom the Soda
carbonized process
at 600 °C. The(data
yield not
shown,was seelower
literature [18]).which
than 10%, The carbon
is likelyproduced
due to lowwas labeled
thermal in accordance
degradation of ligninwith the type
obtained fromofthe
lignin
Sodaand
process (data not shown, see literature [18]). The carbon produced was
carbonization temperature. For instance, LMP-850 means porous carbon produced by pyrolysis labeled in accordance with of
the type of lignin and
lignin from mangosteen peel at 850 C.carbonization
◦ temperature. For instance, LMP-850 means porous carbon
produced by pyrolysis of lignin from mangosteen peel at 850 °C.

40

Carbonization Product/Precursors (%)

600 35.01
850
30

23.94
20.44
20

13.62

10 8.57
6.82

0
Mangosteen Corncobs Coconut
Peel Shell

3. Percentage
FigureFigure of product/precursor
3. Percentage at carbonization
of product/precursor at carbonizationtemperatures
temperatures 600 ◦ Cand
600℃ and850
850℃.◦ C. Data
Data of of
carbonization
carbonization yieldyield of mangosteen peel
of mangosteen peel taken
takenfrom
fromourour
previous study
previous [18]. [18].
study

Scanning Scanning
electronelectron microscopy
microscopy (SEM)
(SEM) analysiswas
analysis was performed
performed to toevaluate
evaluatethethe
details of the
details of the
microscopic
microscopic surface surface structure
structure of theofcarbon
the carbon material.
material. TheThe carbon
carbon morphology
morphology in in Figure
Figure 4a4a shows
shows a
a rigid
rigid and ordered pore structure similar to Figure 4c. The LMPT-850 carbon
and ordered pore structure similar to Figure 4c. The LMPT-850 carbon in Figure 4b shows morphology in Figure 4b shows
morphology like a sponge with more voids. The SEM result of LMP-850 in Figure 4D shows flake
like a sponge with more voids. The SEM result of LMP-850 in Figure 4D shows flake structures. For
structures. For the LCC-600 and LCC-850 (Figure 4e,f), these carbons possess rigid flakes. For carbon
the LCC-600 and LCC-850 (Figure 4e,f), these carbons possess rigid flakes. For carbon from coconut
from coconut shell, the LCS-850 in Figure 4h shows flatter surfaces with many voids compared with
shell, the LCS-850
LCS-600 in Figure
in Figure 4h shows
4g Therefore, flatter surfaces
morphologies with depend
of carbon many voids
on thecompared with LCS-600
material precursors and in
Figurecarbonization
4g Therefore, morphologies of carbon depend on the material precursors and carbonization
temperature, which is in agreement with the literature [7]. It is important to note that
temperature, which is inofagreement
the morphologies with the by
carbon synthesized literature [7]. It is
carbonization of important to note thatcarbon)
lignin (lignin-derived the morphologies
are very
of carbon synthesized
different from theby carbonization
morphologies of lignin
of porous (lignin-derived
carbon produced directlycarbon)
fromare very different
biomass from the
of mangosteen
peel [29],of
morphologies corncob
porous[30]and
carboncoconut
producedshelldirectly
[31]. from biomass of mangosteen peel [29], corncob [30]
and coconut shell
Molecules 2020, 25,[31].
x FOR PEER REVIEW 6 of 11

A B C D

E F G H

Figure 4. SEM
Figure 4. SEMimages
imagesof
of carbon fibers:a) (a)
carbon fibers: LMPT-600;
LMPT-600; (b) LMPT-850;
b) LMPT-850; (c) LMP-600;
c) LMP-600; d) LMP-850;(d) LMP-850;
e) LCC-
(e) LCC-600; (f) LCC-850;
600; f) LCC-850; (g) LCS-600;
g) LCS-600; h) LCS-850.(h)Figure
LCS-850. Figure
(c) and (c) and
(d) taken from(d)
ourtaken fromstudy
previous our [18],
previous
studyCopyright AIP Publishing,
[18], Copyright 2020.
AIP Publishing, 2020.

The carbon materials, from the carbonization process for various precursors and carbonization
temperatures were characterized by nitrogen adsorption and desorption. From N2-sorption
isotherms, pore structure, pore size distribution and micropore structure were evaluated. The
characterization of pore size distribution was used to evaluate the uniformity of pore sizes formed in
 Figure 4. SEM images of carbon fibers: a) LMPT-600; b) LMPT-850; c) LMP-600; d) LMP-850; e) LCC-
600; f) LCC-850; g) LCS-600; h) LCS-850. Figure (c) and (d) taken from our previous study [18],
Molecules 2020, 25, 3428 6 of 11
Copyright AIP Publishing, 2020.

TheThecarbon
carbonmaterials,
materials,fromfromthethecarbonization
carbonizationprocess
processfor forvarious
variousprecursors
precursorsand andcarbonization
carbonization
temperatures were characterized by nitrogen adsorption and desorption. From N2 -sorptionNisotherms,
temperatures were characterized by nitrogen adsorption and desorption. From 2-sorption

isotherms,
pore structure, pore
porestructure, pore size
size distribution anddistribution and micropore
micropore structure structureThe
were evaluated. were evaluated. The
characterization of
pore size distribution was used to evaluate the uniformity of pore sizes formed in the sizes
characterization of pore size distribution was used to evaluate the uniformity of pore formed in
carbonization
the carbonization
process. The uniformityprocess.
of pore The uniformity
size can be seenoffrom
porea narrow
size canpore be size
seendistribution.
from a narrow pore size
The quenched
distribution.
solid The quenched
density functional solid
theory density method
(QSDFT) functionalwastheory
used(QSDFT)
to evaluatemethod was size
the pore useddistribution
to evaluate the
of
pore size distribution of produced carbon. According to the International
produced carbon. According to the International Union of Pure and Applied Chemistry (IUPAC), Union of Pure and Applied
pores
Chemistry
with a size of(IUPAC),
2–50 nm pores with a as
are classified size of 2–50 nmwhile
mesoporous are classified
below 2 nm as mesoporous
categorized as while below 2[32].
micropores nm
categorized as micropores [32].
Figure 5A displays the nitrogen adsorption-desorption curves of LMPT for the carbonization
Figure of
temperature 5A displays
600 the ◦nitrogen
◦ C and 850 adsorption-desorption
C. Both carbons show the isotherm curves
of typeofIVLMPT
(IUPAC forClassification
the carbonization
[32]),
temperature of 600 ℃ and 850 ℃. Both carbons show the isotherm of type
where the shape of this isotherm curve type becomes more vertical in the range of relative pressureIV (IUPAC Classification
[32]),1.0.
near where
In thethe shaperange,
specific of thisthe
isotherm curve
desorption type
line does becomes more with
not coincide vertical
the in the rangeline,
adsorption of relative
which
is called the hysteresis phenomenon. This phenomenon happens because there is a difference in line,
pressure near 1.0. In the specific range, the desorption line does not coincide with the adsorption the
which is called the hysteresis phenomenon. This phenomenon happens because
contact angle of the gas molecules in the pore when adsorption and desorption happen. Condensation there is a difference
ininthe
thecapillaries
contact angle of the
of carbon gasismolecules
pores in reason
also another the pore forwhen adsorption and
this phenomenon [33]. desorption happen.
Condensation in the capillaries of carbon pores is also another reason for this phenomenon [33].

A 390 Adsorption B 0.48 0.20

Desorption LMPT-600

dV/dD (cc/nm/g)
360 LMPT-850
0.15
0.40
330
Volume @STP (cc/g)

dV/dD (cc/nm/g)

0.10
300 LMPT-850
0.32
270 0.05

240 0.24 0.00

4 8 12 16
210 Pore Width (nm)
0.16
180
LMPT-600
150 0.08
120
0.00
0.0 0.2 0.4 0.6 0.8 1.0 1 2 4 8 16 32 64
Relative Pressure (P/P0) Pore Width (nm)

Figure 5. (A) Adsorption and desorption of nitrogen in carbon mangosteen peel lignin extracted using
Figure 5. (A) Adsorption and desorption of nitrogen in carbon mangosteen peel lignin extracted using
organosolv at 150 ◦ C; (B) QSDFT-N2 pore size distribution of carbon mangosteen peel lignin extracted
organosolv at 150 °C; (B) QSDFT-N2 pore size distribution of carbon mangosteen peel lignin extracted
by using organosolv at 150 ◦ C.
by using organosolv at 150 °C.
Figure 5B shows the pore size distribution of mangosteen peel lignin extracted using the organosolv
process at 150 ◦ C. Both carbons feature a pore size in the range of 1–50 nm, which is in the micropore
and mesopore ranges. The pore size distribution for both carbons is broad and diverse. The majority
of pores are in the micropore range as indicated by a high fraction of pores below 2 nm. Interestingly,
LMPT-600 also features pores in a mesopore range and a narrow pore size distribution with a peak of
ca. 5 nm. This peak becomes more intense in LMPT-850, indicating that more mesopores are produced
at a higher carbonization temperature. The presence of mesopore is likely associated with a large
amount of decomposition of material [34] and a minor fraction of mineral in the lignin [35].
Figure 6 displays the nitrogen adsorption-desorption curves for carbon produced from lignin
of corncob and coconut shell. The LCC-600 in Figure 6A and LCS-600 in Figure 6B show the type II
isotherm (IUPAC Classification [32]) while LCC-850 in Figure 6A and LCS-850 in Figure 5B show the
type IV isotherm. The change of the isotherm curve is likely caused by effective pore formation during
the carbonization process at higher temperature [35].
Figure 7A shows the pore size distribution of LCC at the carbonization temperatures of 600 ◦ C and
◦
850 C while Figure 6B displays the pore size distribution of LCS at the carbonization temperatures of
600 ◦ C and 850 ◦ C. All carbons had a pore size between 1–50 nm, which is in the range of micropores
and mesopores, where all the carbons had multimodal or broad pore size distribution.
The majority of pores are in the micropore range as indicated by a high fraction of pores below 2 nm.
240 240
A
Interestingly, LMPT-600 B range and
Adsorption also features pores in a mesopore a narrow pore size distribution
Adsorption
Desorption Desorption
with a peak
210 of ca. 5 nm. This peak becomes more intense in LMPT-850, indicating that more
210
mesopores are produced at a higher carbonization temperature. The presence of mesopore is likely

Volume @STP (cc/g) Volume @STP (cc/g)

Volume @STP (cc/g) Volume @STP (cc/g)

associated
Molecules 180with
2020, aLCC-850
large amount of decomposition of material
25, 3428 180 [34] and a minor fraction of mineral
LCS-850 7 of in
11
the lignin [35].
150 150
240 240
A 120 Adsorption B 120 Adsorption
Desorption Desorption
210 LCC-600 210
90 LCS-600
90
180 LCC-850
60 180 LCS-850
60
150 0.0 0.2 0.4 0.6 0.8 1.0
150
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/P0) Relative Pressure (P/P0)
120
120
Figure 6. Adsorption and desorption of nitrogen in carbon (A) corncob lignin; (B) coconut shell
90 LCC-600 LCS-600
lignin. 90
60
Figure 6 displays the nitrogen adsorption-desorption60curves for carbon produced from lignin of
0.0 coconut
corncob and 0.2 0.4 The
shell. 0.6 LCC-600
0.8 in1.0 Figure 6A and 0.0LCS-600
0.2 in 0.4
Figure0.66B show0.8 the 1.0
type II
isotherm (IUPACRelative Pressure[32])
Classification (P/Pwhile
0) LCC-850 in Figure 6A and Relative Pressure
LCS-850 (P/P0) show the
in Figure5B
type IV isotherm. The change of the isotherm curve is likely caused by effective pore formation
Figure
during the6.
Figure Adsorption and
6.carbonization
Adsorption and desorption
desorption
process of
of nitrogen
at highernitrogen in
incarbon (A)
(A)corncob
carbon[35].
temperature corncoblignin;
lignin;(B)
(B)coconut
coconutshell
shelllignin.
lignin.

Figure 6 displays the nitrogen adsorption-desorption curves for carbon produced from lignin of
corncob and coconut shell. The LCC-600 in Figure 6A and LCS-600 in Figure 6B show the type II
isotherm (IUPAC Classification [32]) while LCC-850 in Figure 6A and LCS-850 in Figure5B show the
type IV isotherm. The change of the isotherm curve is likely caused by effective pore formation
during the carbonization process at higher temperature [35].

Figure7.7.QSDFT-N
Figure QSDFT-N2 2pore
poresize
sizedistribution
distributionof
ofcarbon
carbon(A)
(A)corncob
corncoblignin;
lignin;(B)
(B)coconut
coconutshell
shelllignin.
lignin.

The isotherm
Figure 7Ashowscurves of nitrogen
the pore adsorption-desorption
size distribution of LCC at the from Figures 5temperatures
carbonization and 6 were used
of 600for
℃
determining
and 850 ℃ the poreFigure
while structure. The calculation
6B displays of size
the pore specific surface area
distribution (SBET ),
of LCS at mesopore specific
the carbonization
surface area (Smeso ), pore volume (V), mesopore volume (Vmeso ) and average pore diameter (Davg ) for
various precursor are shown in Table 3.

Table 3. Structural
Figure 7. QSDFT-Npore properties
2 pore of carbon. of
size distribution Data of LMP-600
carbon and LMP-850
(A) corncob lignin; (B)taken fromshell
coconut our lignin.
previous
study [18].
Figure 7Ashows the poreLMP
Characteristics
size-600
distribution of LCC at the carbonization
LMPT -850 LMP-600 LMP-850 LCC-600
temperatures
LCC-850 LCS-600
of 600 ℃
LCS-850
T
and 850 ℃ while Figure
Surface area (S ), m /g
2 6B displays
567
the
974
pore
205
size distribution
595 349
of LCS
820
at the carbonization
333 781
BET
Mesopore area (Smeso ), m2 /g 110 153 85 42 28 59 58 50
%Smeso 19.5 15.67 41.76 7.06 8.06 7.18 17.55 6.34
Total pore volume, cm3 /g 0.37 0.55 0.21 0.28 0.16 0.38 0.21 0.35
Mesopore volume (Vmeso ), cm3 /g 0.18 0.22 0.16 0.07 0.03 0.09 0.09 0.07
%Vmeso 48.4 40.21 72.40 23.8 17.03 22.61 45.27 20.64
Mean pore diameter, nm 2.50 2.04 3.04 1.47 1.38 1.64 1.88 1.45

From Table 3, it is shown that LMPT-850 (974 m2 /g) possesses a higher specific surface area than
the LMPT-600 (567 m2 /g) but both carbons are microporous carbons because of the low percentage of
mesopore surface area (<20%). The average diameter for LMPT-850 is 2.04 nm, while LMPT-600 is
Molecules 2020, 25, 3428 8 of 11

2.50 nm. For LMP, the one carbonized at 600 ◦ C features a high percentage of mesopore surface area
(41.76%) with an average pore diameter of 3.04 nm, while that with a carbonization temperature of
850 ◦ C shows a lower percentage of mesopore area (7.06%) with an average pore diameter of 1.47 nm.
LMP-850 carbon is a micropore carbon, which gives a higher specific surface area (595 m2 /g) than
LMP-600 carbon (205 m2 /g). All LCC and LCS carbons show similar carbon pore characteristics with
a low percentage of mesopore surface area less than 20%. Both LCC-850 (820 m2 /g) and LCS-850
(781 m2 /g) feature a higher specific surface area than LCC-600 (349 m2 /g) and LCS-600 (333 m2 /g) with
average diameters in the range of 1.4–1.9 nm.
In this work, porous carbon produced by carbonization of lignin had specific surface area in
the range of 205–974 m2 /g depending on lignin material and carbonization temperature. A higher
temperature was favorable to obtain a high specific surface area. The highest specific surface area
was 974 m2 /g, which can compete with commercially available porous carbon [36] and lignin-derived
carbon as in the literature [37].

3. Materials and Methods

3.1. Materials
The biomass precursors used in this experiment were obtained from different places. Mangosteen
peel, which had 180–355 µm particle size, was obtained from Bina Agro Mandiri, Bantul, D.I. Yogyakarta,
Indonesia. The corncob was obtained from old pearl corn in Sripendowo Village, South Lampung,
Indonesia. The coconut shell with dark brown color and size of 80 mesh was obtained from Ruko
Taman Niaga, Semarang, Indonesia. The solvent for lignin extraction was ethanol (96%, Sigma Aldrich,
Singapore). Sulfuric acid (98%, Sigma Aldrich, Singapore) was employed for lignin precipitation.

3.2. Methods
Extraction using the organosolv process at low temperature was carried out based on the method
described in the literature [18,38]. Firstly, mangosteen peel was poured in ethanol (60%) in a three-neck
flask. The ratio of solid:liquid was set to 1:8 (w/v). The extraction process was carried out at 70 ◦ C for 4 h.
After that, the black liquor obtained was separated from the solid phase using filtration. Precipitation
of lignin was carried out by adding sulfuric acid 1 N until the pH was 2. The lignin obtained was
then taken from solution by centrifugation and dried in an oven overnight. Similar procedures of
the organosolv process at low temperature were carried out for the corncob and coconut shell as raw
materials of biomass. The lignin produced was labeled depending on the type of biomass i.e., LMP
(lignin from mangosteen peel), LCC (lignin from corncob) and LCS (lignin from coconut shell). The
extraction process at high temperatures was carried out in an autoclave reactor at a temperature of
150 ◦ C and a pressure of 10 bar under nitrogen pressure. For extraction using the Soda process, a
similar procedure was employed but the solvent was 10% sodium hydroxide (see the literature [18]).
The properties of lignin were investigated by Fourier-transform infrared (FTIR) spectroscopy (Thermo
Nicolet iS10 by Thermo Fisher Scientific, MA, USA) and lignin solution viscosity (DV-E Viscometer by
Brookfield, Toronto, Canada).
Conversion of lignin to carbon was conducted by a carbonization process in a furnace at 600 ◦ C
and 850 ◦ C under a flow of nitrogen. The detailed procedure is available elsewhere [38]. The carbon
produced was labeled in accordance with the type of lignin after carbonization temperature. For
instance, LMP-600 means porous carbon produced by pyrolysis of lignin from mangosteen peel at
600 ◦ C. The pore structure of carbon was characterized by N2 -sorption analysis (NOVA 2000 by
Quantachrome Instruments, Boynton Beach, FL, USA) and scanning electron microscopy, SEM (JSM
6510 LA by JEOL, Tokyo, Japan).
Molecules 2020, 25, 3428 9 of 11

4. Conclusions
Lignin was successfully extracted by the organosolv process. The yield of lignin depended on the
types of biomass and extraction conditions. A higher extraction temperature was more favorable to
obtain a greater amount of lignin. The FTIR spectra of lignin showed peaks of syringyl and guaiacyl
units, which are typical features for a lignin standard. When lignin was converted to porous carbon, the
temperature of pyrolysis significantly affected the yield and properties of the porous carbon produced.
Pore structure analysis displayed that carbon from lignin of mangosteen peel, corncob, and coconut
shell synthesized at 850 ◦ C exhibited a high surface area of >550 m2 /g. The highest surface area, up to
974 m2 /g, was obtained in this work. The results showed that lignin-derived carbon is promising and
could be beneficial for porous carbon applications.

Author Contributions: Conceptualization, I.P. and R.R.; methodology, I.P., R.R., T.A.; investigation, P.R.P.; data
curation, P.R.P.; writing—original draft preparation, I.P. and T.A.; writing—review and editing, I.P., R.R., W.-C.O.
and T.A.; visualization, W.T.L.; supervision, I.P., T.A. and R.R.; funding acquisition, R.R. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was funded by World Class Research, Ministry of Research, Technology and Higher
Education of the Republic of Indonesia, grant number 1987/UN1.DITLIT/DIT-LIT/LT/2019.
Conflicts of Interest: The authors declare no conflict of interest.

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Sample Availability: Samples of the compounds of lignin-derived carbons are available from the authors.

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