Metal-Sulfide Catalysts Derived from Lignosulfonate and their Efficient Use in Hydrogenolysis

Article abstract of DOI:10.1002/cssc.201900677

Catalytic lignosulfonate valorization is hampered by the in situ liberation of sulfur that ultimately poisons the catalyst. To overcome this limitation, metal sulfide catalysts were developed that are able to cleave the C?O bonds of lignosulfonate and are

Full text of DOI:10.1002/cssc.201900677

Accepted Article
Title: Metal-sulfide catalysts derived from lignosulfonate and their
efficient use in hydrogenolysis.
Authors: Sijie Liu, Antoine P van Muyden, Lichen Bai, xinjiang cui,
Zhaofu Fei, Xuehui Li, Xile Hu, and Paul J. Dyson
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Metal-sulfide catalysts derived from lignosulfonate and their
efficient use in hydrogenolysis.
Sijie Liu,[a],[b] Antoine P. van Muyden, Lichen Bai, Xinjiang Cui, Zhaofu Fei, Xuehui Li,* Xile
[a]
[a]
[a]
[a]
[b]
[a]
[a]
Hu,* Paul J. Dyson.*
Abstract: Catalytic lignosulfonate valorization is hampered by the in
situ liberation of sulfur that ultimately poisons the catalyst. To
overcome this limitation, we developed metal sulfide catalysts able to
cleave the C-O bonds of lignosulfonate that are resistant to sulfur
poisoning. The catalysts were prepared using the lignosulfonate
substrate as a precursor to form well-dispersed carbon supported
metal (Co, Ni, Mo, CoMo, NiMo) sulfide catalysts. Following
optimization of the reaction conditions employing a model substrate,
the catalysts were used to generate guaiacyl monomers from
lignosulfonate. The Co catalyst was able to produce 23.7 mg of 4-
propylguaiacol per gram of lignosulfonate with a selectivity of 84 %.
The catalysts operate in water and can be recycled and reused
multiple times. Thus, we demonstrate that an inexpensive, sulfur
tolerant catalyst based on an Earth abundant metal and lignosulfonate
efficiently catalyzes the selective hydrogenolysis of lignosulfonate in
water in the absence of additives.
corrosion inhibitors [16], surfactants[17], dispersants[18], membranes
[
19]
and as a carbonaceous matrix for catalysts and electrodes [20–
2
2]
. The sulfur content in LS typically varies from 3-6%, depending
on the pulping process [
20,23]
, and therefore has been used in the
synthesis of S-doped porous carbon materials and was
succesfully applied in the acetalization of glycerol [20] and as a
cathode in lithium sulfur batteries [24]. Catalytic fractionation of LS
into bulk chemicals has also been widely investigated and vanillin
is already produced on an industrial scale via LS oxidation [25–27]
.
Hydrogenolysis and hydrogenation is another promising route to
valorize LS, producing aromatic and aliphatic derivatives
depending upon the catalyst used and the reaction conditions
[23,28]. However, the sulfur in LS tends to poisons most catalysts
[28,29], leading to rapid catalyst deactivation of hydrogenolysis
catalysts that typically operate in organic solvents [28,30].
Transition metal-sulfide catalysts based on Co [31–34], Mo [33,35] and
[
35,36]
Ni
have been intensively studied in hydrogenation,
hydrodeoxygenation (HDO) and hydrodesulfurization (HDS) of
petrochemicals and in the pyrolysis of bio-oil, due to their high
activity and low cost. Bimetallic CoMo- and NiMo-sulfide catalysts
Introduction
were applied recently in the hydrotreatment of lignin and lignin
Biomass has been extensively investigated as a source of
renewable fuels and chemicals [1–3], with the development of
competitive biorefineries requiring efficient processes able to
valorize all the components in biomass [1]. The utilization of
cellulose and hemicellulose to produce fuels and chemicals is a
mature technology [4–6], whereas utilization of the more recalcitrant
biopolymer, lignin, remains challenging despite excellent
progress [7]. Consequently, lignin is often considered a waste
which is usually burned to recover heat [8,9], and its valorization
continues to be widely studied [1,7]. Various lignins arise from
different biomass treatment protocols, and in general, most of
lignins are insoluble in common solvents, severely inhibiting
[37]
model compounds under solvent free conditions
and in
subcritical methanol [38], with the catalysts exhibiting good activity
towards the cleavage of C-O bonds. Metal-sulfide catalysts
2 2 3
immobilized on acidic supports (i.e. SiO , Al O ) result in rapid
coke formation [34–36,39] and therefore metal oxides are often
replaced by carbon support materials [40–43]. Carbon supported
metal-sulfide catalysts have been obtained from a traditional
multistep process comprising incipient wetness, co-impregnation
on activated carbon and sulfidized in a subsequent step under a
[36,44,45]
flow of H
2
S/H
2
or via heat treatment with sulfur containing
[37]
[2]
organics, i.e. dimethylsulfide
or thiourea . In order to by-pass
the sulfidation step, we decided to use LS as precursor to
synthesize highly dispersed metal-sulfide catalysts via pyrolysis
of LS impregnated with metal acetate salts. The resulting
catalysts were evaluated as hydrogenolysis catalysts as well-
dispersed catalysts such as single atom catalysts are unable to
hydrogenate aromatic rings [46], and therefore should lead to high
efforts to valorization lignin [1,10]
.
Lignosulfonate (LS) is a typical highly condensed lignin waste
from the pulping industry produced in about 50 million tons per
year [9] and which easily dissolves in water. LS is often used as a
[
11,12]
for plasticizers [13–14],
cheap and renewable material
selectivities toward hydrogenolysis. Moreover, the prepared
catalysts are naturally sulfur tolerant due to the presence of metal-
sulfide bonds.
[
[
a]
S.Liu, A.P. van Muyden,L.Bai, Dr. X. Cui, Prof. X.Hu, Prof.
P.J.Dyson.
Institute of Chemical Sciences and Engineering (ISIC)
École Polytechnique Fedérale de Lausanne (EPFL)
1015 Lausanne, Switzerland
Results and Discussion
pjd@epfl.ch
Xile.Hu@epfl.ch
S.Liu, Prof. X. Li
b]
The metal-sulfide catalysts were prepared via dispersion of the
Laboratory of Pulp and Paper Engineering
South China University of Technology
Guangzhou, Guangdong, 510640, China.
cexhli@scut.edu.cn
2
appropriate metal acetate salts with Mg(OH) onto LS in methanol
[
46]
followed by pyrolysis for 4 h at different temperatures under N
2
(
Scheme 1), to afford the appropriate metal sulfide and MgO. The
Supporting information for this article is given via a link at the
end of the document
MgO was subsequently removed by washing the solid with HNO
3
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3 4
Scheme 1. Illustration of the synthetic route used to prepare the Co S /C catalyst.
Table 1. Surface area, pore volume and acidic properties of the catalysts calcined at 700 oC.
Metala
mmol/g)
Sb
(mmol/g)
168
221
165
162
190
180
S
SA
c
Tot. PV
(cm /g)
c
Acid sitesd
(µmol/g)
excess
Catalyst
Co /C
2
3
(
(equ.)
1.3
2.6
1.2
-0.4
0.4
/
(m /g)
379
560
630
485
412
571
3
S
4
56
61
37
62
47
/
0.41
0.77
0.93
0.88
0.50
0.68
165
349
196
196
219
150
NiS/C
MoS /C
Co MoS
2
/Ce
/Ce
3
6
NiMoS
S/C
3
[
a] Determined by ICP-AES. [b] Determined by elemental analysis. [c] Determined by physisorption of N
2
. [d] Determined by
chemisorption of NH
3
.
(
see Experimental for full details and Table 1 for the structural
were used to observe the catalyst at atomic resolution. The well-
dispersed bright dots in the HAADF-STEM image indicates the
presence of both single Co atoms (Fig. 2 left f) or small clusters
properties of the catalysts).
The metal loading varies from 3.3 to 3.6 wt% with the
exception of Co
wt%. The sulfur content exceeds that of the metals except for
Co MoS , which implies, as expected, that more than one sulfur
3
MoS
6
/C, which has a higher metal content of 5.0
of Co atoms (Fig. 2 left g). The TEM images of MoS
to those of the Co /C catalyst (Fig. S2).
2
/C are similar
3
S
4
3
6
atom interacts with the metal atoms. Moreover, XPS analysis of
the S region shows that sulfur is present in both sulfide and
sulfonate forms (Fig. 3). The acid sites of the catalyst support
material were determined by temperature programmed
desorption of ammonia (NH
mol/g. In general, the utilization of LS as a precursor results in
more acidic sites than in classical carbon supported catalysts
3
-TPD) and varies from 150 to 349

[
37]
(
3
typically 40-100 mol/g) .The NH -TPD analysis (Fig. 1a, 1b)
also shows that the nickel-sulfide catalyst, NiS/C, possesses a
higher number of weak acid sites than the other catalysts, which
is in agreement with a computational study showing that the
strength of the acid-base interaction depends on the metal ion [
.
47]
2
The surface areas of the catalysts range from 379 to 630 m /g
3
and the pore volumes varies from 0.4 to 0.9 cm /g, which is in line
with the carbon supported metal sulfide catalysts prepared with
H
2
S or dimethyl disulfide [ . XRD patterns of the metal-sulfide
41]
catalysts are similar to the S/C material (Fig. 1c, 1d), with a broad
peak centered at ca. 25° corresponding to amorphous carbon
Figure 1. (a) NH
TPD analysis of the bimetallic-sulfide catalysts. The support (S/C) and the
Mo S/C catalyst are shown in both figures for comparison. (c) XRD patterns of
the monometallic-sulfide catalysts. (d) XRD patterns of the bimetallic-sulfide
catalysts.
3 3
-TPD analysis of the monometallic-sulfide catalysts. (b) NH -
2
(
002). Sharpe peaks characteristic of crystalline structures are
absent, except in the XRD patterns of the Ni containing catalysts,
3
i.e. NiS/C and NiMoS /C, which exhibit some crystallinity
attributable to NiS nanoparticles [48–50].
The catalysts were further characterized by TEM (Fig. 2). The
bright field image of Co S /C (Fig. 2 left a) reveals a porous
3 4
The TEM images of the NiS/C catalyst confirmed the presence of
NiS nanoparticles (Fig. 2 right). The enlarged image (Fig. 2 right
b) shows that the NiS nanoparticles are anchored on the porous
carbon support. HRTEM images confirm the structure of the
crystals (Fig. 2 right c, d) with lattice fringes of 0.195 and 0.293
amorphous carbon structure. The enlarged images (Fig. 2 left b
and c) indicates that distinct Co nanoparticles are not present in
the carbon matrix. EDX mapping was recorded in HAADF-STEM
mode, and confirmed that the material consists mainly of
homogeneously dispersed C, O, S and Co (Fig. 2 left d) atoms.
Spherical aberration corrected HAADF-STEM (Fig. 2 left e-g)
nm corresponding to the (101) and (110) planes of αNiS, [51]
.
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Figure 2. Purple rectangle. (a) Bright field TEM image of the Co
3
S
4
/C catalyst. (b) Enlarged image corresponding to the blue rectangle in a. (c) Enlarged image
corresponding to the blue rectangle in b. (d) EDX mapping. (e) Spherical aberration corrected HAADF-STEM image. (f) Spherical aberration corrected HAADF-
STEM image showing single atoms. (g) Enlarged region of e showing the presence of clusters. Green rectangle (a) Dark field TEM image of the NiS/C catalyst. (b)
HRTEM enlarged image corresponding to the red rectangle in a. (c) HRTEM enlarged image corresponding to the blue rectangle in a. (d) HRTEM of red squares
in b (with lattices fringes corresponding to α-NiS). (e) HAADF images of the blue square in a. (f) EDX mapping.
The blue region (Fig. 2 right e) highlights the presence of
many NiS nanoparticles. EDX mapping analysis revealed that the
nanoparticles are composed mainly of S and Ni (Fig. 2 right f).
The TEM images of the bimetallic-sulfide catalysts are presented
in Figs. S3-S4 and they have similar characteristics to the
monometallic catalysts (i.e. Co S /C catalysts are well dispersed
3 4
and NiS/C catalysts form αNiS nanoparticles).
XPS was used to determine the surface chemical
compositions of the catalysts (Fig. 3). The Co region showed the
presence of Co in both 2+ and 3+ oxidation states [50] and a
characteristic peak of CoSO
of Co-S species (785 eV). The two oxidation states suggest that
cobalt clusters of formula Co are present. Nickel is in the 2+
oxidation state and shows two distinct species that may be
attributed to NiS and NiSO
[52]. Mo is only observed as Mo4+
4
resulting from the surface oxidation
3
S
4
4
linked to either S or O. To rule out the possibility of metal oxides,
the O 1s region was examined and only peaks corresponding to
C-O and C=O carbon are present (at 532.5 and 533.7 eV,
respectively). The S 2p region confirms the presence of sulfide
bonded to metals and to oxygen as sulfate [52], with the latter
attributed to the excess sulfur atoms presents in the LS support
material and surface oxidation of the metal sulfides into the
corresponding sulfate. Since the Co and Mo catalysts are well
dispersed, the ratio of each species varies and the XPS
experiment should be considered as qualitative. The XPS spectra
of the bimetallic-sulfide species exhibit similar patterns to the
monometallic-sulfide catalysts (Fig. S5).
Figure 3. Left, Metal region. Middle S 2p region. Right O 1s region for the Co
top), Ni (center) and Mo (bottom) monometallic-sulfide catalysts. The dashed
line in the O 1s region highlights the absence of metal oxides on the surface.
(
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The six catalysts were evaluated in the hydrogenolysis of 2-
propylsyringol was obtained with no sign of propanol substituted
monomers. Therefore, the catalysts appears to be selective
towards alkyl-substituted monomers. It should be noted that the
selectivity to four main products is unusual as lignins usually
afford large numbers of different products following their catalytic
(
2-Methoxyphenoxy)-1-phenylethanol (MPP-ol) at 150 and 180°C
for 5 h (Fig. 4a, 4a). At 150 °C (low conversion rate, Fig. 4a), three
catalysts are reasonably active (Co /C, NiS/C and Co MoS /C)
3
S
4
3
6
with conversions between 40-50%. The support alone catalyzes
the reaction to a modest extent due to the presence of the weakly
acidic surface sites on the support [8,53]. The selectivity of the
catalysts was assessed and, at 180 °C (high conversion rate, Fig.
3 4 3 6
degradation. The stability of the Co S /C and Co MoS /C
catalysts was assessed in recycling experiments (Fig. 5b, 5c) with
the bimetallic-sulfide catalyst appearing to be slightly more stable
than the monometallic catalyst with both catalysts being
reasonably stable for this challenging process. Presumably, the
4
b), all the catalysts afford 1, with the Co
in the highest yield of 95%. Notably, Co
NiS/C (12% to 5%), whereas the bimetallic (Co
NiMoS /C) catalysts produce, preferentially, the aldehyde
products (4, 5). Styrene (3) is produced with Co MoS /C (note that
at 180 °C, the activity of NiMoS /C is similar to Co MoS /C). In all
3
S
4
/C catalyst resulting
/C affords more 6 than
MoS /C,
3
S
4
3
6
Mo in the Co
enhancing the stability of the Co-S bonds
integrity of the Co /C and Co MoS /C catalysts TEM (Fig. S10,
3 6
MoS /C catalyst favors the stabilization by
[
47]
3
. To assess the
3
6
3
S
4
3
6
3
3
6
S11) and XPS (Fig. S12) were performed after the recycling
experiments, i.e. after the seventh cycle. The structure and
dispersion of the metals remained similar to that of the fresh
catalyst and no sign of aggregation were apparent, suggesting
that the catalysts are resistant to leaching due to the mechanism
the experiments hydrogenation of the aromatic ring was not
observed. This is in agreement with small clusters and single
atom catalysts being unable to catalyze this reaction [54] and,
3
surprisingly, the NiS/C and NiMoS /C (which contain NPs) also
showing the same selectivity. In an attempt to improve the catalyst, hypothesized above. However, the EDX mapping revealed the
+
Co
3
S
4
/C was calcined at different temperatures and 700°C
presence of Na ions (derived from the LS substrate), which is
presumably adsorbed into the pores of the carbon support during
reaction. The accumulation of Na+ ions in the support may
account for the slight deactivation of the catalysts over time.
appears to be the optimum one (Fig. S6). We further investigated
the effect of different lignin precursors (alkali lignin, Russia LS and
dealkalize lignin). The catalysts exhibit similar selectivities, but the
conversion varies from 70-90 % (Table S2, Fig. S7).
Figure 4. Conversion of the model compound and product distribution at low
conversion (a) and high conversion (b).
All the prepared catalysts show good activities for the
hydrogenolysis of the MPP-ol, but leaching of the metals takes
place due to the formation of H
from the catalyst support thus allowing the metal to leach) [28]
Note that H S was detected at the end of the reaction (see
Experimental). We hypothesized that the LS as substrate could
prevent such a leaching mechanism as H S would be generated
2
S and product 6 (the S is derived
.
2
Figure 5. (a) Hydrogenolysis of LS with different catalysts. (b and c) Recycling
experiments with the Co S /C and Co MoS /C catalysts, respectively.
3 4 3 6
2
from the substrate rather than from the catalyst, thereby
protecting the catalyst from decomposition. Consequently, the
hydrogenolysis of LS was investigated, albeit under harsher
conditions (230 °C, 5 MPa, 10 h) than those used for the model
Conclusions
substrate. Of the six catalysts, the Co
3
S
4
/C catalyst is the most
A series of sulfur-tolerant, highly selective hydrogenolysis
active and produce 27.9 mg of products per gram of substrate (Fig. catalysts were obtained using LS as precursor/support material
5
a). The four major products comprise guaiacyl (G) derived
for single atom/small cluster or nanoparticle catalysts depending
upon the metal(s) used. Additionally, to avoid hydrogenation of
aromatic rings during the hydrogenolysis process (favored by
monomers (the major monomer in softwood lignin) and differ by
the alkyl chain length. A 2D HSQC NMR of LS did not reveal any
traces of the syringyl unit (S) (Fig. S8). When using beech
sawdust as substrate, a mixture of 4-propylguaiacol and 4-
nanoparticles), the metals were dispersed using Mg(OH)
2
.
Although small nanoparticles were formed with the Ni based
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catalysts, the entire series of catalysts to not appear to catalyze
arene hydrogenation. Studies using the model substrate, 2-(2-
methoxyphenoxy)-1-phenylethanol, showed that the bimetallic
equipped with a Mo-K radiation. Transmission electron microscopy
(TEM) was performed on an FEI Talos instrument operated at 200 kV high
tension. Atomic resolution imaging measurements were performed on an
FEI Titan Themis 60-300 operated at 200 kV with an aberration-corrected
electron probe and using high angle annular dark field scanning
transmission electron microscopy (HAADF-STEM) mode. Energy-
dispersive X-ray spectroscopy (EDX) mapping was used for elemental
characterization. X-Ray photoelectron spectroscopy (XPS) was measured
on a PHI Versa Probe II scanning X-ray electron spectrometer with Al Kα
X-ray sourced the curve fitting was performed by the PHI Multipak software.
NiMoS
3
/C catalyst is more selective than the other catalysts and
/C
avoids condensation of the products. Although the Co
3
S
4
catalysts are less selective with the model compound, they exhibit
the highest activity with LS substrate. Importantly, the quantitative
selectivity towards guaiacyl monomers is achieved and the
catalyst favors the formation of 4-propylguaiacol with 84 %
selectivity. The use of LS prevents the metals from leaching due
to a sacrificial/compensation mechanism and the presence of Mo
Hydrogenolysis of 2-(2-Methoxyphenoxy)-1-phenylethanol
as a second metal appears to enhance this stabilization by
augmenting the Co-S bond strength [47]. Overall, we demonstrated
that an inexpensive catalyst comprising well-dispersed earth
abundant cobalt anchored on a carbon support derived from LS
can be used to depolymerize LS with high selectivity in water in
the absence of additional additives.
MPP-ol (0.1 mmol) and the catalyst (10 mg) were dispersed in D.I. water
(2 mL) under sonication (700 Hz, 1 min). Then the reaction mixture was
inserted in an autoclave (Parr, 75 mL) and pressurized with H
The autoclave was heated at the desired temperature (150 to 180 C) for
2
(1 MPa).
o
5
h. After reaction, the products were extracted with ethyl acetate (2 × 5
mL) and the catalyst was recovered by centrifugation (6000 rpm. 2 min.).
S was detected by bubbling the gas after the reaction into a Pb(OAc)
H
2
solution. The products were analyzed using an Agilent 7890B Gas
Chromatograph Mass Spectrometer equipped with an Agilent 7000C
GC/MS triple quad detector and a capillary column from Agilent (30 m ×
Experimental Section
0
.25 mm × 0.25 μm) with a flame ionization detector (FID). For
Materials
quantification, dimethyl phthalate was used as the standard. See figure
S13 for a representative chromatogram with each compound assigned and
their corresponding mass spectra.
2-(2-Methoxyphenoxy)-1-phenylethanol (MPP-ol) was synthesized
[
55]
according to
a
literature method
and characterized by NMR
spectroscopy (Fig. S1). Sodium lignosulfonate was purchased from TCI
L0098, Lot: V3G6G), alkali lignin was purchased from Sigma-Aldrich,
Russia LS was purchased from Xingzhenghe Chemical Factory Co. Ltd.
Shenyang, China) and dealkalize lignin was purchased from J&K China
Chemical Ltd (Beijing, China). All other chemicals were obtained from
Acros or Sigma-Aldrich and used without further purification.
Hydrogenolysis of LS
(
LS (100 mg) and the catalyst (20 mg) were dispersed in D.I. water (4 mL)
and inserted in an autoclave (Parr, 75 mL) and pressurized with H (5 MPa).
2
(
Then the autoclave was heated to 230 oC. After 10 h, the reactor was
cooled to room temperature and the pressure released. The products were
extracted with ethyl acetate (2 × 5 mL) and the catalyst was recovered by
centrifugation (6000 rpm. 2 min.). The products were analyzed by an
Agilent 7890B Gas Chromatograph Mass Spectrometer equipped with an
Agilent 7000C GC/MS triple quad detector and a capillary column from
Agilent (30 m × 0.25 mm × 0.25 μm) with a flame ionization detector (FID)
for quantification, dimethyl phthalate was used as the standard.
Catalyst synthesis
LS (600 mg) and the appropriate metal acetate salt(s) (0.5 mmol or 0.25
mmol based on the metal in the acetate salt(s)) in methanol (120 mL) were
sonicated for 30 min. Next, Mg(OH) (3 g, 52 mmol) was added and the
2
solution was sonicated for an additional 30 min. The resulting suspension
was heated to reflux for 6 h at 60 °C. The reaction mixture was cooled to
RT and the solvent was removed under reduced pressure and the resulting
powder was calcined at 700 °C under a N
cooling to room temperature, the powder was stirred in nitric acid (80 mL,
M) for 2 h to remove the MgO and Na O residues. The catalyst was
washed with D.I. water (3 × 100 mL) and dried under reduced pressure at
0 °C. Thre other Co-based sulfide catalysts obtained from alkali lignin,
Russia LS and dealkalize lignin were prepared using a similar procedure
to that used to prepare the Co /C catalyst, except the lignosulfonate
TCI) was replaced by alkali lignin (Co /C-A), Russia LS (Co /C-R) or
dealkalize lignin (Co /C-DA), respectively.
2
atmosphere for 140 min. After
Acknowledgements
1
2
We thank the Swiss National Science Foundation, the European
Research Council (681292), Natural Science Foundation of China
6
(
21736003) and Oversea Study Program of Guangzhou Elite
Project for financial support. We also thank the Interdisciplinary
Center for Electron Microscopy at EPFL assistance in electron
microscopic measurements and XPS, Dr. Wu Lan, Florent
3 4
S
(
S
3 4
3 4
S
3 4
S
Héroguel and Prof. Jeremy Luterbacher (EPFL) for the N
2
Catalyst characterization
adsorption-desorption measurements and Weiyan Ni for the XRD
analysis.
The surface area (SA) and pore volume (PV) were analyzed by N
physisorption at 77 K using a Micromeritics ASAP 2000M apparatus.
Temperature programmed desorption of ammonia (NH -TPD) was used to
determine the acid property of the catalysts (Micromeritics Pulse
Chemisorb 2700 instrument equipped with a thermal conductivity detector,
TCD). Inductively coupled plasma atomic emission spectroscopy (ICP-
AES) was used to determine the metal and sulfur content (NexIon 350,
Perkin Elmer). X-ray diffraction spectroscopy (XRD) patterns were
recorded on a Bruker Nonius Apex II Advance X-ray diffractometer
2
Keywords: lignosulfonate • hydrogenolysis • sulfide • biomass
valorization • guaiacyl monomers
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ChemSusChem
10.1002/cssc.201900677
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S. Liu, A. P. van Muyden, L. Bai, X. Cui,
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Page No. – Page No.
Metal-sulfide catalysts derived from
lignosulfonate and their efficient use
in hydrogenolysis.
Lignosulfonate was used as precursor to form sulfur tolerant catalysts. The
catalysts were successfully used to transform lignosulfonate into guaiacyl
monomers.
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