C8GC00502H

Green Chemistry
Revisiting alkaline aerobic lignin oxidation
Journal: Green Chemistry
Manuscript ID GC-ART-02-2018-000502.R1
Article Type: Paper
Date Submitted by the Author: 25-Jun-2018
Complete List of Authors: Schutyser, Wouter; KU Leuven, Center for Surface Chemistry and
Catalysis; National Renewable Energy Laboratory, National Bioenergy
Center
Kruger, Jacob; National Renewable Energy Laboratory, National Bioenergy
Center
Robinson, Allison; National Renewable Energy Laboratory, National
Bioenergy Center
Katahira, Rui; National renewable Energy Laboratory,
Brandner, David; National Renewable Energy Laboratory,, National
Bioenergy Center
Cleveland, Nicholas; National Renewable Energy Laboratory, National
Bioenergy Center
Mittal, Ashutosh; National Renwable Energy laboratory, Biosciences
Censter
Peterson, Darren; National Renewable Energy Laboratory, National
Bioenergy Center
Meilan, Richard; Purdue University, Department of Forestry and Natural
Resources
Roman-Leshkov, Yuriy; MIT, Chemical Engineering
Beckham, Gregg; National Renewable Energy Laboratory, National
Bioenergy Center
Page 1 of 18 Green Chemistry
Revisiting alkaline aerobic lignin oxidation†

Wouter Schutysera,b, Jacob S. Krugera, Allison M. Robinsona, Rui Katahiraa, David G. Brandnera,
Nicholas S. Clevelanda, Ashutosh Mittala, Darren J. Petersona, Richard Meilanc, Yuriy Román-
Leshkovd, and Gregg T. Beckhama
Abstract: Lignin conversion to renewable chemicals is a promising means to improve the economic viability
of lignocellulosic biorefineries. Alkaline aerobic oxidation of lignin has long been employed for production of
aromatic compounds such as vanillin and syringaldehyde, but this approach primarily focuses on
condensed substrates such as Kraft lignin and lignosulfonates. Conversely, emerging lignocellulosic
biorefinery schemes enable the production of more native-like, reactive lignin. Here, we revisit alkaline
aerobic oxidation of highly reactive lignin substrates to understand the impact of reaction conditions and
catalyst choice on product yield and distribution. The oxidation of native poplar lignin was studied as a
function of temperature, NaOH loading, reaction time, and oxygen partial pressure. Besides vanillin and
syringaldehyde, other oxidation products include acetosyringone and vanillic, syringic, and p-
hydroxybenzoic acids. Reactions with vanillin and syringaldehyde indicated that these compounds are
further oxidized to non-aromatic carboxylic acids during alkaline aerobic oxidation, with syringaldehyde
being substantially more reactive than vanillin. The production of phenolic compounds from lignin is favored
by high NaOH loadings and temperatures, but short reaction times, as the products degrade rapidly, which is
further exacerbated by the presence of oxygen. Under optimal conditions, a phenolic monomer yield of 30
wt% was obtained from poplar lignin. Testing a range of catalysts showed that Cu-containing catalysts, such
as CuSO4 and LaMn0.8Cu0.2O3, accelerate product formation; specifically, the catalyst does not increase the
maximum yield, but expands the operating window in which high product yields are obtainable. We also
demonstrate that other native and isolated lignin substrates that are significantly chemically modified are
effectively converted to phenolic compounds. Finally, alkaline aerobic oxidation of native lignins was
compared to nitrobenzene oxidation and reductive catalytic fractionation, as these methods constitute
suitable benchmarks for lignin depolymerization. While nitrobenzene oxidation achieved a somewhat higher
yield, similar monomer yields were obtained through RCF and alkaline aerobic oxidation, especially for lignins
with a high guaiacyl- and/or p-hydroxyphenyl-content, as syringyl units are more unstable during oxidation.
Overall, this study highlights the potential for aerobic lignin oxidation revisited on native-like lignin substrates.
a. National Bioenergy Center, National Renewable Energy with β-ether bonds being the most prominent.1-5 Other
Laboratory, Golden CO 80401, USA important lignin building blocks are p-hydroxycinnamic
b. Center for Surface Chemistry and Catalysis, KU Leuven, acids (p-coumaric and ferulic acid), found in herbaceous
Celestijnenlaan 200F, 3001 Heverlee, Belgium crops,6, 7 and p-hydroxybenzoic acid, found in feedstocks
c. Department of Forestry and Natural Resources and Purdue
like poplar and palm.8, 9 These acids are mainly connected
Center for Plant Biology, Purdue University, West Lafayette,
IN 47907, USA to lignin through ester linkages and can account for a
d. Department of Chemical Engineering, Massachusetts Institute significant fraction of the lignin mass.
of Technology, Cambridge MA 02139, USA Due to its aromatic structure, lignin is regarded as a
Lignin valorization | Oxidation | Vanillin | Oxidative catalysis | promising source for renewable chemicals.1-4, 10-15 A
Lignocellulosic Biomass problem, however, is that traditional lignocellulosic
Email: [email protected]; [email protected] biorefinery processes primarily focus on the valorization of
† Electronic supplementary information (ESI) available. the carbohydrates, while the lignin is only utilized for low-
value applications (heat and power) without considering
Introduction the fate of the lignin stream. For instance, pulping
Lignin, a heterogeneous aromatic biopolymer, is one of the processes such as Kraft, sulphite, and organosolv, aim to
main constituents of lignocellulosic biomass, comprising remove lignin from wood to produce a pure carbohydrate
15 to 30% of its weight.1-4 It is an integral part of pulp.16, 17 In the production of cellulosic biofuels such as
terrestrial-plant cell walls, where it is responsible for bioethanol, a pretreatment step is applied to disrupt the
mechanical strength, defence against microbial and insect lignocellulosic cell-wall structure and remove or relocate
attack, and preventing the collapse of water-conducting the lignin, with the primary aim of making the
elements.1-5 Lignin is mainly assembled from three phenyl- carbohydrates more amenable for biological conversion.18,
propanoid units (p-coumaryl, coniferyl, and sinapyl 19
In these processes, the lignin either ends up in a
alcohols), which are linked through C-O and C-C bonds, pretreatment liquor (from which it can be precipitated), or
1
Green Chemistry Page 2 of 18
in a residue after enzymatic hydrolysis of the vanillin and syringaldehyde from lignin, it is performed
carbohydrates.10 In most biorefinery processes, the lignin commercially to produce vanillin from lignosulfonates.43, 44
is heavily degraded, which involves cleavage of labile The production volume has, however, dropped
ether bonds (mainly β-O-4 bonds) and condensation of considerably since 1980.
reactive intermediates through C-C bond formation.3, 4, 11,
20-22 Alkaline lignin oxidation has been extensively studied in
The resulting degraded lignin streams are resistant to
the last decade, mainly on condensed lignin substrates such
depolymerisation and are, therefore, usually incinerated for
as lignosulfonates51, 59, 68-70 and Kraft lignins.49-53, 71 For
energy recovery.10, 23 However, to improve the economics
instance, the influence of process parameters including
and sustainability of lignocellulosic biorefineries, a higher
temperature, oxygen pressure, and NaOH concentration on
value utilization of the lignin fraction is critical.10, 24
oxidation of Kraft lignin and lignosulfonates was studied
In this context, strategies to convert lignin into chemicals by Rodrigues,49, 50, 52 Tarabanko,54, 56, 70 and Evtuguin and
are receiving increasing attention. Research efforts are coworkers.59 New biorefinery processes, however, enable
directed both toward the development of biorefinery the generation of more reactive lignins, and, therefore, we
processes in which lignin degradation is avoided,3, 4, 14, 25 decided to examine the alkaline aerobic oxidation of a
and the development of effective and selective methods to highly reactive, non-degraded, unmodified substrate,
depolymerize the biorefinery lignin streams.1-4, 11-13 namely native poplar lignin. Oxidation of the entire poplar
Degradation of the lignin structure (C-C bond formation) substrate is likely not relevant from a process perspective
can, for instance, be prevented through chemical (although the carbohydrates are also converted to valuable
stabilization of the lignin structure during pulping, as in compounds, vide infra), but is performed here to assess the
formaldehyde-assisted pulping26 or reductive catalytic oxidation behaviour of unmodified lignin. We thoroughly
fractionation (RCF).27-32 In the latter case, pulping is investigated the influence of the process parameters and
combined with lignin depolymerization and reductive evaluated a series of catalysts on the reaction, in order to
stabilisation of the lignin products. Another option to gain more insight into the alkaline oxidation process and to
prevent degradation is to utilize mild conditions, as in the clarify some apparent contradictions between previous
isolation of native-like lignin substrates such as milled reports, for instance on the role of the catalysts.
wood lignin (MWL), cellulolytic enzyme lignin (CEL), or Furthermore, we assessed the conversion of other
enzymatic mild acidolysis lignin (EMAL).33, 34 biorefinery lignins and also compared the performance of
Pretreatment of biomass is often performed through alkaline aerobic oxidation to RCF for lignin valorisation in
thermochemical methods such as dilute-acid pretreatment a biorefining context.
(DAP) or hydrothermal pretreatment, which are known to
induce significant lignin degradation.13, 19, 21 Pretreatment Results
methods that do not use acids or high temperatures, such as Oxidation of poplar lignin: parameter investigation
deacetylation and mechanical refining (DMR)35 or To examine the oxidation of native-like lignin, we
anhydrous ammonia pretreatment (AAP),36, 37 likely cause performed reactions with poplar sawdust, with a total
less degradation, and are, thus, expected to generate more lignin content (Klason lignin and acid-soluble lignin) of
reactive lignin streams. 29.4 wt%. Reactions were performed in 2 M NaOH
aqueous solutions under an oxygen partial pressure of 5
Depolymerization of the resulting lignin streams has been
bar and a total pressure of 20 bar (He as make-up gas;
explored via reductive, oxidative, acid-catalyzed, base-
pressurized at room temperature) for temperatures ranging
catalyzed, and thermal methods, and many promising
from 125 to 200°C and reaction times of 0 to 60 min (the
results have been reported.1-4, 11-13 For instance, high yields
heating time of 30 min is not included in the reaction
of phenolic monomers can be obtained through reductive
time). After reaction, the reaction mixture was acidified
depolymerization, especially from native lignins (as in
and extracted with ethyl acetate. The ethyl acetate-
RCF)27-32 and other reactive lignins,26, 38 but also from
extracted phase (EA oil) was derivatized through silylation
recalcitrant substrates such as Kraft and soda lignin.39, 40
and subjected to gas chromatography (GC) analysis to
An effective depolymerization method that was recently
quantify the phenolic monomers. The results are shown in
introduced is acid-catalyzed depolymerization combined
Figure 1. Oxidation of poplar lignin mainly yielded the
with in situ stabilization of the products through acetal
aromatic aldehydes vanillin and syringaldehyde, along
formation.41, 42 Herein, ethylene glycol forms acetal
with other compounds such as vanillic and syringic acid,
structures with the reactive carbonyl functionalities in the
and acetosyringone. These compounds were also obtained
side-chains of the phenolic products. Through oxidation,
in the oxidation of isolated hardwood lignins.53, 58 In
lignin can be selectively converted to valuable chemicals
addition, p-hydroxybenzoic acid was obtained. This
such as aromatic aldehydes, aromatic acids, and aliphatic
compound is not an oxidation product, but is part of the
carboxylic acids.43-48 Lignin oxidation is mostly performed
structure of poplar lignin (it is esterified to the γ-OH
in alkaline reaction media with oxygen as oxidant (i.e.,
groups of syringyl structures).8, 9 During the reaction, it
aerobically),43, 49-61 but has also been successfully
was released through hydrolysis of the ester bond. Under
performed in acidic solutions, such as diluted inorganic
these oxidative conditions, the carbohydrates were also
acids62, 63 or concentrated acetic acid,64 organic solvents,65
transformed. Only under mild oxidation conditions (e.g.,
and ionic liquids.66, 67 As alkaline aerobic oxidation
low temperature and short reaction time) was some
enables the selective production of the aromatic aldehydes
2
carbohydrate-rich residue preserved, but increasing reactor with a much faster heating rate would likely further
temperature and reaction time induced almost complete enhance the product yield at temperatures above 175°C.
conversion of the substrate. Figure 2 shows a gas
chromatogram of the EA oil after poplar conversion at
175°C for 10 min. The main carboxylic acids were formic
acid and acetic acid (not shown in the chromatogram),
followed by lactic acid (A); glycolic acid (B); and smaller
amounts of other compounds, such as oxalic acid (D), 3-
hydroxypropionic acid (E), fumaric acid (H), and malic
acid (I). Most of these acids originated from the cellulose
and hemicellulose in poplar, although some of these also
derived from consecutive oxidation of the phenolic
compounds (vide infra). Thus, the carbohydrate fractions
were also converted to valuable compounds during
alkaline aerobic oxidation.
Figure 2 Gas chromatogram of the silylated EA oil from poplar

oxidation at 175°C for 10 min (2 M NaOH, 5 bar O2 + 15 bar He at RT).
The external standard (ES) is 4-n-propylguaiacol.
To examine the oxidative degradation of the phenolic

monomers, we performed reactions with vanillin and
syringaldehyde at 150°C for 10 min (Table 1).
Syringaldehyde was much more reactive than vanillin,
with a conversion of 88%, compared to 31% for vanillin.
The higher reactivity of syringyl (S)-type compounds
compared to guaiacyl (G)-type compounds observed here
Figure 1 Phenolic monomer yields (on a lignin basis) from alkaline is in accordance to previous studies53, 59, 60, 73 and is
aerobic oxidation of poplar at various temperatures and reaction obvious from the time-course plots in Figure 1, which
times. Reaction conditions: 0.5 g poplar (150 mg lignin), 30 mL of 2 M shows a faster degradation of syringaldehyde and syringic
NaOH aqueous solution, 5 bar O2 + 15 bar He (at RT).
acid compared to their guaiacyl analogues.
Figure 1 shows that, especially in oxidation at higher Both vanillin and syringaldehyde were mainly converted to
temperatures, the phenolic monomers were rapidly small carboxylic acids, with formic acid as the main
produced, but also quickly consumed through oxidative product from vanillin. Syringaldehyde yielded both formic
degradation, resulting in sharp maxima in monomer yield and malonic acid as main products. Malic acid was
as function of reaction time. The maximum product yield obtained from syringaldehyde, while this was only
increased with temperature, from 7 wt% at 125°C up to scarcely obtained from vanillin. Other products from both
about 30 wt% at 175°C, but did not increase further by aldehydes are acetic acid, glycolic acid, lactic acid, and
raising the temperature to 200°C. The 30 wt% monomer oxalic acid, although the latter could not be quantified.
yield obtained after 10-min reaction at 175°C comprises 24 Vanillin oxidation yielded a small amount of vanillic acid,
wt% oxidation products (including 13 wt% syringaldehyde while reaction with syringaldehyde generated only trace
and 7 wt% vanillin) and 6 wt% p-hydroxybenzoic acid. As amounts of syringic acid. So although these acids are
was also observed in the oxidation of condensed lignin usually proposed to be derived from vanillin and
substrates such as Kraft lignin,50, 52, 59, 72 these results show syringaldehyde,68 the majority of vanillic and syringic acid
that increasing the reaction temperature enhances the obtained during lignin oxidation is likely produced via a
maximum product yield, but also shortens the reaction different route, such as that proposed by Gierer et al.74
time needed to reach this maximum, because both the
formation and degradation of phenolic monomers are
accelerated. Thus, the reaction necessitates careful control
of the reaction time. For a high product yield, a very short
reaction at high temperature is ideal. However, this is
difficult to accomplish with a batch Parr reactor setup,
because it requires a long heating time (~ 30 min), during
which considerable lignin conversion takes place. Using a
3
Table 1 Conversion and product yields from alkaline aerobic oxidation of vanillin acid, which was expected from base-catalyzed hydrolysis
and syringaldehyde.a of ester linkages). Other studies have found that
conversion of lignosulfonates in the absence of oxygen
Substrate Vanillin Syringaldehyde yields a considerable amount of depolymerization products
time (min) 10 10 (vanillin, syringaldehyde, vanillic acid, and syringic
acid),59, 69 but the different functional structure of
conversion (wt%) 31 88 (4)b
lignosulfonates compared to native lignin likely facilitates
yield (wt%) the different chemistry. In contrast, high monomer yields
were obtained from reaction under 5 bar oxygen, but
vanillic /syringic acid 2 0
increasing the pressure up to 10 bar resulted in a drop in
formic acid 12 28 yields. Increasing the oxygen pressure is known to
accelerate both product formation and degradation,50, 72
acetic acid 3 5
and, therefore, shortens the time needed to reach the
glycolic acid 1 3 maximum product yield. The fact that oxygen facilitates
product degradation is also illustrated in Table 1 by the
lactic acid 3 5
high conversion of syringaldehyde under oxygen (88
malonic acid 5 31 wt%), compared to only slight conversion under an inert
atmosphere (4 wt%, in brackets). Due to the long heating
malic acid 0 5
time, the maximum yield under 10 bar oxygen was likely
sum 23 76 obtained during the heating period. This again indicates
a
that while oxygen is needed to generate oxidation products
Reaction conditions: 100 mg substrate, 30 mL of aqueous 2 M NaOH from native lignin, rapid heating of the reaction mixture is
solution, 150°C, 5 bar O2 + 15 bar He (at RT). Substrate conversion and
vanillic and syringic acid yield were determined via GC-FID. The yield of the
also critical to avoid subsequent oxidation of the desired
other acids was determined via HPLC. Oxalic acid was observed in both the products.
GC and HPLC analyses, but could not be quantified. bSyringaldehyde
In Figure 3b, the GPC profiles of the EA oils for reaction
conversion under inert atmosphere (20 bar He) is indicated in brackets.
under inert atmosphere and 5 bar oxygen are depicted. The
Mn, Mw, and PD values are provided in Table S1. The
peak at 200 Da corresponds to the aromatic aldehydes and
acetosyringone, the peak at 300 Da to the aromatic acids
(vanillic, syringic, and p-hydroxybenzoic) and the broad
signal at higher molecular weights (> 350 Da) to the
oligomeric products. Reaction under inert atmosphere
mainly yielded oligomeric products, while reaction under
oxygen primarily generated monomeric products, which
underpins the need for oxygen to depolymerize lignin. To
further assess the chemical transformations occurring
under oxygen and inert atmosphere, poplar and the
reaction products (EA oils) were analyzed through HSQC
NMR (Figure 4). Poplar wood showed large peaks of aryl
ether (β-O-4), phenylcoumaran (β-5), and resinol units (β-
β), while there were almost no aldehyde peaks (Figure
4a). In the aromatic region, the poplar spectrum mainly
displayed signals of guaiacyl (G), syringyl (S), and p-
hydroxybenzoate (PB) units. The correlation peaks of p-
hydroxyphenyl units (H2/6) at δC/δH 128.0/7.2 ppm were
extremely small, with the H/G ratio being only 0.0004.
Figure 3 Impact of oxygen partial pressure (at RT) on phenolic This indicates that H-units (other than PB) are only present
monomer yields (a) and molecular weight distribution of the EA oils in minor amounts in poplar. Based on the peak integral, an
(b) obtained from alkaline aerobic oxidation of poplar. The EA oils for
S/G molar ratio of 1.18 was estimated, which was
GPC analysis were obtained after 10 min reaction and were
acetylated prior to analysis. Reaction conditions: 0.5 g poplar, 30 mL
calculated using both normal and oxidized S components.
of 2 M NaOH aqueous solution, 175°C, 20 bar total pressure (at RT; He Besides the S-, G- and H-signals, a clear signal of PB2/6 is
as make-up gas). present at 131/7.71 ppm. The EA oil generated under inert
atmosphere contained less resinol and phenylcoumaran
Subsequently, we assessed the influence of the oxygen units than poplar, and had no aryl ether and cinnamyl
pressure on poplar oxidation. Figure 3a shows the product alcohol units (Figure 4b), suggesting, as expected, that β-
yields for poplar oxidation in 2 M NaOH at 175°C, under O-4 linkages were also cleaved under non-oxidative
oxygen partial pressures of 0, 5, and 10 bar (20 bar total conditions, likely through base-catalyzed transformations.
pressure). Under inert atmosphere (0 bar oxygen), no Phenylcoumaran and resinol structures appeared to
oxidation products were obtained (only p-hydroxybenzoic partially withstand these conditions. In the aromatic
4
region, the PB signal decreased because the ester bonds in aromatic region, the S2/6 and G2/5/6 peaks drastically
PB units were readily saponified to generate p- reduced and the S’2/6 and G’2 signals increased,
hydroxybenzoic acid, which is evidenced by the phenolic supporting that 30% of the poplar lignin was degraded into
monomer yield distribution (Figure 3a). Also, oxidized α-ketone monomers by 5 bar O2 treatment. (Figure 5). The
guaiacyl unit (G’2) signals at around 110-114/7.4-7.7 ppm decrease of aromatic peaks also suggests that some
and G’6 at 124.5/7.57 ppm clearly appear, suggesting that aromatic ring cleavage occurred.74 The interunit linkages
α-ketone structures were generated from β-O-4 units under were thus effectively disrupted under the oxidative
alkaline conditions. The S/G ratio in the EA oil generated conditions. The S/G ratio in the EA oil generated under
under inert atmosphere was 1.73, higher than that in oxygen decreased to 1.14, likely due to a faster oxidative
poplar, likely due to base-catalyzed repolymerization of G- degradation of S-type units compared to G-type units. In
units.3 The spectrum of the EA oil obtained under oxygen addition, the aldehyde peak was much more prominent in
exhibited far fewer signals than the spectra of the poplar the EA oil generated under oxygen than in the oil obtained
and the EA oil obtained in absence of oxygen (Figure 4c). without oxygen, due to generation of vanillin and
Specifically, there were no β-O-4, phenylcoumaran, syringaldehyde.
resinol, and much fewer carbohydrate peaks. In the
Figure 4. HSQC NMR spectra of (a) Poplar wood, (b) EA oils for poplar conversion under inert atmosphere and (c) 5 bar oxygen. Reaction conditions for
(b) and (c): 0.5 g poplar, 30 mL of 2 M NaOH aqueous solution, 175°C, 10 min, 20 bar He at RT (b) and 5 bar O2 + 15 bar He at RT (c). G: Guaiacyl, G’:
Guaiacyl with Cα=O, S: Syringyl, S’: Syringyl with Cα=O, PB: p-Hydroxybenzoate, AL: Benzaldehydes, CA: Cinnamyl alcohol, A: β-Aryl ether (β-O-4), B:
Phenylcoumaran (β-5), C: Resinol (β-β)
Figure 5 Impact of NaOH concentration on the phenolic monomer

yields from alkaline aerobic oxidation of poplar. Reaction conditions:
0.5 g poplar, 30 mL of 1 or 2 M NaOH aqueous solution, 175°C, 5 bar
O2 + 15 bar He (at RT).
Finally, we assessed the impact of the NaOH concentration

on poplar oxidation. Figure 5 shows the monomer yields
for oxidation at 175°C under 5 bar oxygen partial pressure
in 1 and 2 M NaOH solutions. In line with previous studies
on Kraft lignin and lignosulfonates,43, 50, 54, 71 the highest
monomer yields were obtained in 2 M NaOH. A high
NaOH concentration is suspected to be necessary to
5
facilitate lignin oxidation, viz. for ionization of the In Figure 6b, the catalytic results for a range of oxide-
phenolic hydroxyl groups43, 44 and likely also for the based catalysts are depicted. A range of oxides,
conversion of reactive intermediates (see Discussion),43, 54- perovskites, and noble metal catalysts were tested. Co3O4
57
and to retard degradation of the phenolic compounds.43, is a commonly used oxidation catalyst,81, 82 and CuO has
72
For instance, Rodrigues et al. showed that raising the pH been used frequently in lignin oxidation, either in the
of the reaction solution over 12 significantly slows down absence (itself being the oxidant)83, 84 or presence of
the oxidative degradation of vanillin.72 On the other hand, oxygen.60, 75 The use of perovskites is based on the work of
utilizing an NaOH concentration that is too high (e.g., 4 Lin and co-workers, who found that Co-, Mn-, and Fe-
M) causes operational problems such as salt deposition and based perovskites significantly enhanced the product
fouling in the reactor, and, therefore, a 2 M concentration yields in alkaline lignin oxidation, and that their
is usually advised.43 performance can be further improved by Cu doping.77-80
Sales et al. showed that Pd/Al2O3-catalyzed lignin
Catalytic oxidation of poplar: catalyst screening and
oxidation enabled much higher product yields than
examination of the catalyst effect
uncatalyzed oxidation,76 while Villar et al. observed that
Alkaline oxidation of lignin is often performed in the
the use of Pt/Al2O3 had an adverse effect on the product
presence of a catalyst. The catalyst is suggested to
yield.71 In poplar oxidation, the highest yield was achieved
facilitate lignin oxidation through electron abstraction
with CuO (17 wt%), similar to the yield obtained with
(oxidation) of the phenolate groups to phenoxy radicals,
CuSO4. Following oxidation with Co3O4, Pd/Al2O3, and
after which the catalyst is reoxidized by oxygen (thus
Pt/Al2O3, no increase in product yield was observed
completing the redox cycles).43, 59, 75 The catalyst is usually
compared to the uncatalyzed reaction. To test the catalytic
CuSO4 or another metal salt, but also solid catalysts such
activity of perovskites, we prepared Fe-, Co-, and Mn-
as metal oxides and noble metal catalysts have been
based perovskites through sol-gel synthesis and confirmed
studied. Numerous studies have shown that the catalyst
their perovskite crystal structure confirmed via XRD
accelerates product formation and also raises the maximum
(Figure S1). The highest yield was obtained when poplar
product yield,58-60, 76-80 although a few studies did not
was oxidized with LaMnO3, while the use of LaFeO3 or
observe an increase in maximum product yield.50, 71 To
LaCoO3 resulted in no or a very minor yield increase,
verify the catalyst effect in alkaline lignin oxidation, we
compared to the uncatalyzed reaction. In line with the
first compared the catalytic activity of a range of reported
results of Lin et al., the catalyst performance could be
catalysts in the alkaline oxidation of poplar. The oxidation
enhanced by doping the perovskites with Cu (see results
was performed in 2 M NaOH at 150°C under 5 bar oxygen
for LaCo0.8Cu0.2O3 and LaMn0.8Cu0.2O3). The highest yield
for 0 min. Figure 6a shows the catalytic results for
of oxidation products was achieved with LaMn0.8Cu0.2O3
reactions with metal salts. The uncatalyzed reaction
(13 wt%).
reached a total monomer yield of 14 wt%, including 8 wt%
oxidation products (without p-hydroxybenzoic acid). The
latter yield is used as benchmark and is indicated with a
dashed line. CuSO4 reached the highest yield of oxidation
products (17 wt%), followed by CoCl2 and MnCl2 (11-12
wt%). Reactions with FeCl3 and Cr2(SO4)3 achieved
approximately the same yields as the uncatalyzed run. The
superior catalytic performance of CuSO4 is likely due to
the intermediate reduction potential of Cu2+ (-0.16 V for
the CuO/Cu2O redox pair at pH 14), as was postulated by
Tarabanko et al. to be sufficient for oxidation of lignin to
aldehydes with limited subsequent oxidation of
aldehydes.57 The promising performance of Cu relative to
other metals explains why it is a commonly used catalyst
in alkaline lignin oxidation.50, 58, 59, 68, 70 Regarding the Co,
Mn, and Fe salts, Lin et al. also found that Co and Mn salts
improve lignin oxidation,78, 79 while FeCl3 had no effect on
the reaction.80 This can be explained by the fact that Fe3+
cannot abstract an electron from the phenolate groups and,
thus, cannot follow the oxidation-reduction cycles.75
However, some studies reported that FeCl3 facilitates
lignin oxidation, which was attributed to the formation of
O2-Fe-lignin complexes that act as oxygen carriers that can
attack the lignin.58, 60, 75 These studies also showed that
CuSO4 and FeCl3 exert a synergistic effect on the
oxidation. However, in this work, no further increase in
product yield was observed with the addition of FeCl3 to
CuSO4 (Figure 6a).
6
LaCoO3, its reduction started at lower temperature (the

maximum of the first TPR signal of LaMnO3 and LaCoO3
was at about 320°C and 380°C, respectively), which might
also have contributed to its higher activity in lignin
oxidation. Incorporation of Cu in LaMnO3 and LaCoO3 did
not affect the specific surface area of the catalysts (Figure
7a), but clearly lowered the temperature at which reduction
takes place (Figure 7b). The first TPR signal (at about
200-350°C) is due to both Cu2+ and Mn4+/Co3+ reduction.88
The higher activity of the Cu-doped catalysts is, thus,
attributed to their easier reducibility, which can also
explain the high activity of CuO.89
Figure 6 Phenolic monomer yields from oxidation of poplar with

various metal salts (a) and oxide-based catalysts (b). Reaction Figure 7 Brunauer–Emmett–Teller specific surface areas (SBET) obtained
conditions: 0.5 g poplar, 30 mL of 2 M NaOH aqueous solution, 40 from N2 adsorption isotherms (a) and H2-TPR profiles (b) of the
µmol metal salt or 10 mg solid catalyst, 150°C, 0 min (the reactor was perovskite catalysts.
quenched when reaching the reaction temperature, 30 min heating
time), 5 bar O2 + 15 bar He (at RT). The dashed line indicates the yield
of oxidation products obtained in the uncatalyzed reaction (8 wt%).
Due to their high catalytic activity, CuSO4 and
LaMn0.8Cu0.2O3 were further used to examine the influence
of the catalyst in alkaline aerobic oxidation. First, the
To elucidate the catalytic behaviour of the perovskite
conversion of poplar was studied with CuSO4 at 150°C and
catalysts, some physicochemical properties were
175°C at times ranging from 0 to 60 min. The monomer
determined. Figure 7a shows the specific surface area,
yields for catalyzed and uncatalyzed oxidation are depicted
determined by N2 physisorption, and Figure 7b the
in Figure 8. At both temperatures, CuSO4 accelerated
temperature programmed reduction (TPR) profiles, which
product formation and retarded product degradation,
provide valuable information about the reducibility of
compared to uncatalyzed oxidation, but did not increase
oxidation catalysts.85, 86 A high specific surface area is
the maximum monomer yield. As shown in Figure 8c-d,
advantageous because more active surface sites are
LaMn0.8Cu0.2O3 exerted the same effect on the product
available, while a high catalyst reducibility facilitates the
yields. So, although addition of a catalyst does not enhance
oxidation (electron abstraction) of the lignin. Regarding
the product yield, it accelerates the reaction and widens the
the Cu-free perovskites, LaMnO3 exhibited a considerably
time window in which a high product yield is obtained,
higher specific surface area than LaFeO3 and LaCoO3 (22
which makes the process less time sensitive.
vs. 6-9 m2/g), which can explain its higher catalytic
LaMn0.8Cu0.2O3 was further employed in oxidation of other
activity. The TPR profiles indicated a negligible hydrogen
substrates, as discussed in the next section.
uptake for LaFeO3, in line with the very low reducibility of
Fe3+.80, 87 LaMnO3 showed a higher hydrogen LaMn0.8Cu0.2O3-catalyzed oxidation of other substrates
consumption, which can be attributed to reduction of Mn4+ In addition to poplar, we subjected other lignocellulosic
to Mn3+ at lower temperature and Mn3+ to Mn2+ at higher feedstocks, viz. high-S poplar, pine, and corn stover to
temperature.79, 88, 89 The highest hydrogen consumption alkaline aerobic oxidation with LaMn0.8Cu0.2O3. Figure 9
was observed for LaCoO3, due to reduction of Co3+ to Co2+ shows the monomer yields for oxidation at 175°C for 0
at lower temperature (300-450°C) and Co2+ to Co0 at min under 5 bar oxygen partial pressure. From wild-type
higher temperature (500-650°C).88, 90 Although LaMnO3 (WT) poplar, a 31 wt% monomer yield was obtained,
showed a much lower hydrogen consumption than
7
comprising 25 wt% oxidation products. Oxidation of

transgenic poplar with a high S-lignin content (high-S
poplar; line F5H-64-E)91, 92 resulted in a higher selectivity
towards S-type compounds (syringaldehyde,
acetosyringone, and syringic acid) than WT poplar, but the
yield of oxidation products was only a little higher (29 vs.
25 wt%) and the total monomer yield was the same (31
wt%). This is quite unexpected because a higher S content
in lignin results in a higher β-ether content,93, 94 and,
therefore, should enable a higher monomer yield.
However, the maximum attainable monomer yield was
likely limited due to the fast oxidative degradation of S-
type compounds. High-S poplar oxidation also generated
p-hydroxybenzoic acid, but with a considerably lower
yield than WT poplar (2 vs. 6 wt%).
The oxidation of pine yielded only G-type compounds
(vanillin, acetovanillone, and vanillic acid), in line with the
lignin composition of softwoods, with high selectivity
towards vanillin. While the maximum product yield was
obtained at a reaction time of 0 min for all other substrates
(Table S2 for the monomer yields after 0 and 10 min), the
maximum yield from pine (22 wt%) was reached after 10
min, which indicates that oxidation of G-rich lignin occurs
more slowly than oxidation of S-rich lignin. In oxidation
of corn stover, p-coumaric acid, ferulic acid, and p-
hydroxybenzaldehyde were obtained, along with the
previously described products. Similar to p-
hydroxybenzoic acid in poplar, the hydroxycinnamic acids
p-coumaric and ferulic acid were not produced through
lignin oxidation, but through alkaline hydrolysis of ester
bonds. These compounds were obtained in 9 and 2 wt%
yield, respectively, with the total monomer yield being 27
wt%.
Figure 8 Phenolic monomer yields from uncatalyzed and catalyzed

oxidation of poplar wood at 150°C (a and b) and 175°C (c and d).
Panels a and c depict the total monomer yield, while the yields of the
individual compounds are indicated in panels b and d. Reaction
conditions: 0.5 g poplar, 30 mL of 2 M NaOH aqueous solution, 40
µmol CuSO4 or 10 mg LaMn0.8Cu0.2O3, 5 bar O2 + 15 bar He (at RT).
8
In addition to the native lignins, we examined the

oxidation of a range of isolated lignins, comprising one
softwood lignin (spruce Kraft lignin) and three herbaceous
lignins (corn stover DMR-EH, DAP-EH, and AAP-AE
lignin) (Figure 9). The results not only indicated the
potential of oxidation to yield phenolic products from
these substrates, but also made it possible to evaluate the
impact of the isolation method on the structural integrity of
the lignin, by comparing the results of the native and
isolated lignins for the same (or similar) feedstocks.
Oxidation of spruce Kraft lignin, an isolated softwood
lignin, yielded 12 wt% monomers, with a very similar
monomer distribution as from pine oxidation. The
monomer yield, however, was much lower, which is due to
the degraded state of the Kraft lignin structure. Next, three
isolated corn stover lignins were subjected to oxidation,
which enables a direct evaluation of the isolation method
on the reactivity of lignin toward depolymerization.
Oxidation of DMR enzymatic hydrolysis residue (DMR-
EH lignin) from corn stover rendered a similar monomer
yield (27 wt%) and monomer distribution as corn stover
oxidation, thus, indicating that the original lignin reactivity
is well preserved during the mechanical pretreatment and
enzymatic hydrolysis steps. On the other hand, oxidation
of dilute acid-pretreated enzymatic hydrolysis residue
Figure 9 Monomer yields (on lignin basis) from LaMn0.8Cu0.2O3- (DAP-EH lignin) from corn stover generated a much lower
catalyzed oxidation of various lignocellulosic feedstocks and isolated
monomer yield (13 wt%), indicating that the lignin
lignins. Reaction conditions: 0.5 g lignocellulose (95-150 mg lignin),
150-300 mg isolated lignin (140-160 mg lignin) or 15 g corn stover AAP-
structure is significantly degraded during DAP. The
AE liquor (150 mg lignin), 30 mL of 2 M NaOH aqueous solution (for individual yield of most monomers was lower than in
reaction with the corn stover AAP-AE lignin, 15 mL of the liquor (0.1 M oxidation of corn stover or DMR-EH lignin, but the main
NaOH) was combined with 15 mL of a 3.9 M NaOH aqueous solution difference is observed for the hydroxycinnamic acids. The
to obtain 30 mL of a 2 M NaOH solution), 10 mg LaMn0.8Cu0.2O3, 175°C, p-coumaric acid yield was only 3 wt% and almost no
0 min (10 min for pine), 5 bar O2 + 15 bar He (at RT).
ferulic acid was obtained, compared to a p-coumaric and
ferulic acid yield of 10 and 1 wt%, respectively, for corn
The molecular weight distribution of the oxidation stover DMR-EH lignin. These acids were likely removed
products from the lignocellulosic feedstocks is depicted in during the DAP step, as aqueous acid can also hydrolyse
Figure 10 (see Table S1 for Mn, Mw and PD values). For ester bonds. Lastly, we tested alkaline-extracted lignin
the woody substrates, the peaks at about 200 and 300 Da from anhydrous ammonia-pretreated corn stover (AAP-AE
correspond to the monomeric compounds. The signal of lignin) in the reaction. The ammonia pretreated corn stover
the oligomeric compounds (> 350 Da) decreased in the was treated with a 0.1 M NaOH aqueous solution, which
following order: pine > WT poplar > high-S poplar. The extracted 70 wt% of the lignin. A portion of this alkaline
GPC profile of the corn stover oxidation product showed a extraction liquor was subsequently combined with a
large peak at 350-400 Da, corresponding to the concentrated NaOH solution to obtain a 2 M NaOH
hydroxycinnamic acids. aqueous solution, and subjected to oxidation. The
monomer distribution was quite similar to that from corn
stover and DMR-EH lignin oxidation, while the monomer
yield was even higher (31 wt% on extracted lignin basis).
However, in oxidation of corn stover and DMR-EH lignin,
the yields were based on the entire corn stover lignin
fraction (given that no lignin is lost during DMR-EH),
while in oxidation of AAP-AE lignin, only the extracted
lignin was considered (i.e., 70 wt% of the total lignin).
Taking into account the extracted lignin yield, 22 wt% of
the original corn stover lignin was converted to phenolic
monomers through AAP-AE and oxidation. Although this
yield is somewhat lower than the yields from raw corn
stover and corn stover DMR-EH lignin (27 wt%), it can be
Figure 10 GPC profiles of the lignocellulose oxidation products. The
concluded that AAP-AE is also an effective method to
reaction conditions are indicated in the caption of Figure 9. isolate a highly reactive lignin substrate from corn stover.
9
carboxylic acid stream that is obtained in addition to the

lignin products could, for instance, be separated into
individual acids analogously to recovery of acids from
fermentation broth,95 or they could be upgraded
biologically to other value-added products.96 In Table 2,
the yields of phenolic compounds and aliphatic carboxylic
acids (on total substrate basis) are indicated. Spruce Kraft
lignin has a very high lignin content (93 wt%) and, thus,
almost all carboxylic acids derived from the lignin
fraction. On the other hand, the isolated corn stover lignins
have a much lower lignin content (30-63 wt%) and contain
a significant fraction of carbohydrates (15-33 wt%). Thus,
for these substrates, the carboxylic acids originated from
both the lignin and carbohydrates. Besides the phenolic
monomer compounds, spruce Kraft lignin oxidation
mainly yielded formic acid and smaller amounts of acetic,
glycolic, lactic, malonic, and oxalic acid (the lattermost
was not quantified). Only traces of succinic acid and no
malic acid were obtained. The carboxylic acid distribution
was, thus, rather similar to that from vanillin oxidation
(Table 1). A total product yield of 39 wt% was obtained.
In oxidation of the corn stover lignins, formic acid was
also the main product, followed by acetic, glycolic, and
Figure 11 GPC profiles of the isolated lignins (a) and oxidation
lactic acid. Malonic and malic acid were minor products
products of the isolated lignins (b). The reaction conditions used to
obtain the oxidation products are indicated in the caption of Figure 9.
(2-3 wt% yield), while succinic acid was only present in
trace amounts. Also some oxalic acid was obtained from
these lignins, although not quantified. Remarkably, AAP-
In Figure 11, the molecular weight distribution of the
AE lignin oxidation generated similar amounts of formic
isolated lignins (a) and their oxidation products (b) is
and acetic acid, while the acetic acid yield was much lower
displayed (see Table S1 for Mn, Mw and PD values). The
than the formic acid yield for the other corn stover lignins.
GPC profiles of the isolated lignins and the oxidation
The total quantified product yields from the corn stover
products are plotted together in Figure S2 for each lignin
lignins amounted to 46-49 wt%. Thus, a targeted
substrate. Spruce Kraft lignin, corn stover DMR-EH, and
valorization strategy can be rationally designed for up to
DAP-EH lignin exhibited a high molecular weight (Figure
half of the substrate mass.
11a) and were clearly converted to low-molecular-weight
products (200-4,000 Da) by oxidation (Figure 11b). Comparison of lignocellulose alkaline aerobic oxidation
Similar to Figure 10, the main peaks were present at 200 with nitrobenzene oxidation and RCF
Da, corresponding to the aromatic aldehydes and Through alkaline aerobic oxidation, the native lignin in
acetovanillone and -syringone (especially for spruce Kraft lignocellulosic feedstocks can be effectively converted to
lignin), and 350-400 Da, corresponding to the phenolic monomers. To evaluate the effectiveness of this
hydroxycinnamic acids (for the corn stover lignins). In depolymerization method, we compared alkaline aerobic
contrast to the other isolated lignins, corn stover AAP-AE oxidation to nitrobenzene oxidation and reductive
lignin exhibited a low molecular weight (Figure 11a). The depolymerization. Nitrobenzene oxidation is commonly
GPC profile showed a large signal at 350-400 Da, used for lignin characterization, as it enables an effective
indicating that the lignin in the AAP-AE liquor was mainly depolymerization of lignin into phenolic monomers.51, 53, 83
composed of ‘free’ (hydrolyzed) hydroxycinnamic acids. However, as the oxidant (nitrobenzene) and its products
Oxidation of the AAP-AE lignin enabled the conversion of are harmful, nitrobenzene oxidation is only relevant from a
other lignin structures in the liquor to small monomeric characterization perspective. Reductive depolymerization
compounds, as indicated by the signal strength at 200 Da of native lignin, which is usually termed RCF when
(Figure 11b and Figure S2). applied to whole biomass, enables very high (close-to-
theoretical) monomer yields from native lignin (based on
Besides phenolic compounds, alkaline aerobic oxidation of
ester and β-O-4 ether cleavage).3, 11, 13, 14 Both of these
the lignocellulosic feedstocks and isolated lignins also
methods constitute suitable benchmarks for alkaline
generated a large amount of aliphatic carboxylic acids,
aerobic oxidation. It should be noted that while RCF is an
which derived from both the lignin and the carbohydrate
appropriate method to valorize the entire lignocellulose
fractions. While this study only focuses on the lignin
substrate (i.e., both the lignin and carbohydrates; the latter
fraction in the reactions with the lignocellulosic feedstocks
are largely retained in a pulp that can be used for further
(and, therefore, only looks at the phenolic compounds), the
processing), alkaline aerobic oxidation is likely not, as the
fate of the entire substrate is of interest in the reactions
carbohydrates are converted into a complex mixture of
with the isolated lignins, because these represent highly
aliphatic carboxylic acids. Therefore, alkaline aerobic
relevant feedstocks for chemical production. The mixed
10
oxidation and RCF are solely compared at the lignin level Table 2 Product yield from alkaline aerobic oxidation of isolated lignin on total
here. substrate basis.a
Figure 12 depicts the monomer yields obtained through Spruce Corn stover Corn stover Corn stover
alkaline aerobic oxidation (Ox; same results as in Figure Substrate Kraft DMR-EH DAP-EH AAP-AE
9), nitrobenzene oxidation (OxNB) and RCF (Red). Only lignin lignin lignin ligninb
poplar was subjected to nitrobenzene oxidation. The same m substrate
150 300 250 520
products and a similar product distribution were obtained (mg)
as in alkaline aerobic oxidation of poplar, but a rather lignin content
93 53 63 30
higher total monomer yield was achieved (35 vs. 31 wt%). (wt%)
RCF was applied to all lignocellulose substrates in Figure m lignin (mg) 140 160 158 154
9, and was performed with Pd/C in methanol at 225°C yield (wt%)
under hydrogen pressure. The main products were
phenolic
propanolguaiacol and -syringol, with minor products being 12 14 8 9
compounds
guaiacol and syringol with a propyl, propenyl,
methoxypropyl, or ethyl side-chain (these compounds are formic acid 15 13 16 11
combined under ‘other guaiacols’ and ‘other syringols’). acetic acid 4 4 5 11
The p-hydroxybenzoic acid in poplar and high-S poplar
was converted to methyl p-hydroxybenzoate (through glycolic acid 3 7 6 6
esterification) and phenol (through decarboxylation)97 and lactic acid 3 7 5 7
the p-coumaric and ferulic acid in corn stover were
converted to methyl dihydrocoumarate and dihydroferulate malonic acid 2 2 3 2
(through side-chain hydrogenation and esterification, succinic acid <1 <1 <1 <1
respectively).28 Because the monomeric compounds
produced through oxidation and reduction are different malic acid 0 2 2 2
and, thus, have different molecular weights, the product sum 39 49 46 49
yields cannot be compared on weight basis. Therefore, the
a
yields presented in Figure 12 are indicated on a molar Reaction conditions: 30 mL of 2 M NaOH aqueous solution, 10 mg
basis (mmol/g). The total monomer yields on weight basis LaMn0.8Cu0.2O3, 175°C, 0 min, 5 bar O2 + 15 bar He (at RT). The yield of
phenolic compounds and other acids was determined via GC-FID and HPLC,
are also shown.
respectively. Oxalic acid was observed in both the GC and HPLC analyses,
but could not be quantified. b15 mL of the AAP-AE liquor (0.1 M NaOH,
containing 520 mg solids and 154 mg lignin) was combined with 15 mL of a
3.9 M NaOH aqueous solution to obtain 30 mL of a 2 M NaOH solution.
For poplar, pine, and corn stover, alkaline aerobic

oxidation and reduction achieved comparable monomer
yields. Also, starting from poplar and corn stover, a similar
distribution of S-, G-, and p-hydroxyphenyl (H)-type
compounds (indicated in red, blue, and green, respectively,
in Figure 12) was obtained through both methods. Pine
conversion yielded only G-type products. For corn stover,
reduction generated a significantly higher yield of p-
coumaric acid (as methyl dihydrocoumarate) and ferulic
acid (as methyl dihydroferulate) than oxidation, while the
total yield of H- and G-type products was fairly similar.
This can be explained by the fact that these acids were
further transformed to other H- and G-type products
during oxidation,61 while they were stabilized during
reduction (as methyl dihydrocoumarate and
dihydroferulate). Oxidation achieved a considerably lower
monomer yield than reduction only for high-S poplar. The
main difference was in the S-type products. This yield
difference is likely due to the low stability of S-type
compounds during oxidation, while they are stable under
reductive conditions. These results show that an effective
oxidative depolymerization is especially difficult for S-rich
lignins.
11
the ester-linked p-hydroxybenzoic acid, are produced

while heating without oxygen, as indicated in Figure 3,
but significant monomer production is evident by the time
the reactors reach reaction temperature when they are
heated under 5 bar O2. These results are consistent with
Rodrigues et al., who showed that pine Kraft lignins
produce minimal vanillin under non-oxidizing alkaline
hydrolysis conditions, but that vanillin is both rapidly
produced and consumed when O2 is present.50 On the other
hand, Pacek et al. found significant vanillin production
without O2 from Na-lignosulfonates.69 In future work, it
would be useful to assess the influence of introducing the
oxidizing atmosphere before and after heating the reactor,
although it is expected that heating in absence of oxygen
will induce lignin degradation through base-catalyzed
transformations, as illustrated by the loss of β-ether
structures in the reaction under inert atmosphere (see
Figure 4) and, therefore, lower the product yields. While
not typically reported, the stirring rate, which affects the
gas-liquid mass transfer of O2 into solution, may also
influence reported yields, though Pacek et al. found
Figure 12 Monomer yields (on lignin basis) from alkaline aerobic vanillin yields in lignosulfonate oxidation were relatively
oxidation (Ox), nitrobenzene oxidation (OxNB) and reductive catalytic insensitive to agitation, at least for stirring speeds above
fractionation (Red) of various lignocellulosic substrates. Syringyl (S)-,
500 rpm at pH > 12.69
guaiacyl (G)- and p-hydroxyphenyl (H)-type products are indicated in
red, blue and green, respectively. Reaction conditions for alkaline Second, the observation in the literature that a catalyst
aerobic oxidation: 0.5 g lignocellulose (95-150 mg lignin), 30 mL of 2 M
sometimes increases lignin monomer yields and other
NaOH aqueous solution, 10 mg LaMn0.8Cu0.2O3, 175°C, 0 min (10 min
for pine), 5 bar O2 + 15 bar He (at RT). Reaction conditions for
times does not may be due to both heating rate
nitrobenzene oxidation: 0.5 g poplar, 27 mL of 2 M NaOH aqueous (with/without O2) and lignin chemistry. Lignin in the
solution, 3 mL nitrobenzene, 170°C, 120 min. Reaction conditions for native biomass substrates explored here has a high
reduction: 1 g lignocellulose, 30 mL methanol, 0.1 g Pd/C, 225°C, 6 h, reactivity even without catalyst, and while some catalysts
30 bar H2 (at RT). appear to have a substantial effect at lower temperatures
and short reaction times (150°C, 0 min in Figure 6 and
Discussion and Conclusions Figure 8a), the apparent benefit is not as prominent at
higher temperatures or intermediate reaction times. At
Consistent with previous work, we have shown that
longer reaction times, monomer yields are again higher
alkaline oxidation is an effective lignin depolymerization
with catalyst than without, though overall yields are again
strategy for both native and technical lignins, provided that
lower. There are at least three mechanisms by which the
the latter are not overly degraded in upstream operations.
catalyst could lead to these trends, which would be
Up to about 30 wt% aromatic monomers can be achieved,
sensitive to the chemistry of the substrate. First, the
depending on the substrate and conditions, with short
catalyst may be breaking lignin linkages that are not
reaction times, high temperatures, and high NaOH
broken (or not broken as quickly) without a catalyst,
concentrations being favourable. Addition of Cu-based
leading to higher aldehyde yields initially. Second, as the
catalysts does not appear to improve phenolic monomer
aldehyde-producing linkages in the lignin are consumed,
yields, but makes the process less sensitive to reaction
the catalyst may preserve the aldehyde products, inhibiting
time.
their degradation. Third, the catalyst may preferentially
These results provide some insight into the puzzling and shuttle active oxygen species to other reactions (e.g.,
sometimes contradictory results of previous work. First, converting carboxylic acids to CO2), reducing the O2
because short reaction times are required and reactors are pressure in the reactor and leading to slower aldehyde
typically pressurized with O2 or air at room temperature, degradation. The first mechanism is difficult to prove
the heating rate of the reactors is a critical parameter that because the HSQC NMR spectra are somewhat
could significantly affect results across experimental ambiguous. The second mechanism is unlikely, as
setups. For example, Wu et al. employed a system that preliminary results suggest that Cu catalysts increase the
could be heated from room temperature to 170°C in 3-5 rate of degradation of vanillin and syringaldehyde. In the
min.60, 75 In contrast, other configurations, including the third mechanism, the reactor pressure should decrease
one used here, were limited by a 30-min heating time, more during the reaction with catalyst as more O2 is
which we show allows the reaction to proceed to a consumed. However, in our reactions, the reactor pressures
significant extent. The reaction during heating is likely due with and without catalyst were similar, rendering the third
to both hydrolysis of ether and ester bonds in the alkaline mechanism unlikely, as well. Therefore, the catalytic
solution and oxidation reactions. Few monomers, such as
12
trends cannot yet be explained, and further research efforts have to rely on differences in molecular weight and/or
are needed to understand the role of the catalyst. boiling point between monomers, dimers, and oligomers.
Alkaline oxidation, on the other hand, yields a highly
Third, further study is needed regarding the congruence of
alkaline reaction solution containing a mixture of
monomeric product yields in oxidative and reductive lignin
phenolics (aromatic aldehydes, aromatic acids,
depolymerization approaches. RCF has been proposed to
acetophenone-like compounds, and oligomer fragments)
cleave mainly inter-unit ether and ester linkages,
and aliphatic carboxylic acids. Isolation of the phenolics
generating stabilized products. On the other hand, aromatic
from the reaction is typically performed through
monomers are rapidly degraded under alkaline oxidation
acidification and extraction with organic solvents.43, 44, 99
conditions, with loss of aromaticity as a primary
This procedure, however, requires large amounts of acid
contributor. This, combined with the much shorter reaction
and organic solvent, and generates a significant amount of
times in alkaline oxidation, indicates that the reported
highly saline wastewater. To avoid extraction of the
maximum aromatic monomer yields are more snapshots of
acidified solution with organic solvents, alternatives such
a much more dynamic reaction system than an indication
as extraction with supercritical CO2 or adsorption of the
that both depolymerization strategies attack the same
phenolics on zeolites or macroporous resins have been
functional linkages (although there is clear NMR evidence
examined.43, 44, 99 To circumvent the acidification of the
that ester and β-O-4 linkages do not survive either
entire reaction mixture, strategies to directly isolate the
process).28-30
phenolates from the mixture, such as extraction with
Fourth, and similarly, further study is needed to specific solvents (e.g., butanol), adsorption on cation-
conclusively elucidate the mechanism of alkaline oxidation exchange resins (in the Na+ or H+ form), or ultrafiltration
with and without catalysts. Several mechanisms have been to remove high-molecular-weight lignin fragments, have
proposed in literature, comprising both radical and ionic been investigated.43, 44, 99 Despite advances being made,
pathways.48, 54-57, 74, 75 The requirement of a highly alkaline further research is necessary to enable a more sustainable
solution can in part be rationalized on the basis of isolation of the phenolic products from the reaction
deprotonating phenolic functional groups and maintaining solution, and, in addition, separation of individual products
alkalinity in the presence of produced acids. However, from the phenolics mixture. For instance, separating
even in presence of the produced acids, which constitute vanillin in high purity requires an elaborate purification
much less than 0.5 M of neutralizing equivalents, procedure, involving crystallization, extraction, and
deprotonation of the phenolic groups should still be distillation steps. However, an advantage of alkaline
possible at much lower NaOH concentrations than 2 M, as oxidation compared to reductive procedures is that the
the pKa of phenolic groups is around 10-11.5 at 25°C.43 market for certain oxidation products, such as vanillin, is
Thus, the need for high alkalinity likely indicates a critical well established, while the market for reductively
step in the depolymerization that depends on deprotonation produced monomers is smaller and/or less-defined.
of different functional groups with higher pKa. According
to the mechanism proposed by Tarabanko et al. (Figure Materials and methods
S3), a high alkalinity is necessary for deprotonation of Chemicals and materials
certain reaction intermediates and retro-aldol cleavage of a N,O-Bis(trimethylsilyl)trifluoroacetamide (BSFTA),
cinnamaldehyde-like intermediate to obtain the final pyridine (anhydrous, +99%), dichloromethane (+99%),
aromatic aldehydes and acetophenone-like products.54-57 nitrobenzene (+99%), 2-isopropylphenol (+98%), HCl
The mechanism involving retro-aldol cleavage is (37%), 4-propylguaiacol (+99%), citric acid (+99%),
supported by the fact that the kinetics of vanillin formation spruce Kraft lignin (alkali lignin; 93.2 wt% lignin content),
from lignin are similarly affected by the pH of the reaction Na2SO4 (+99%), Pt/Al2O3 (5 wt%), Pd/Al2O3 (5 wt%),
medium as oxidation of vanillideneacetone, which is a CuO nanopowder, La(NO3)2·6H2O (+99%),
representative compound for the cinnamaldehyde-like Co(NO3)2·6H2O (+99%), CuSO4·5H2O (+99%), FeCl3
intermediate. Furthermore, this mechanism can also (+99%), MnCl2 (+99%), CoCl2 · 6H2O (+97%), Cr2(SO4)3
explain the formation of the acetophenone-derived · xH2O (+99%), were all purchased from Sigma-Aldrich.
products, and is, therefore, considered to be a plausible NaOH (99%), acetone (+99%), tetrahydrofuran (THF,
mechanism for alkaline lignin oxidation. However, a more Baker, HPLC grade), methanol (+99%) and ethyl acetate
conclusive elucidation of the reaction mechanism likely (+99%) were purchased from Fischer Scientific.
requires a combined experimental (model compound) and Fe(NO3)3·9H2O (98%), Mn(NO3)2·4H2O (99%),
computational study, as was previously performed to Cu(NO3)2·3H2O (99%), Co3O4 nanopowder (99%) were
verify the mechanism of acid- and base-catalyzed lignin purchased from Alfa Aesar. H2SO4 was purchased from
conversion.22, 98 Ricca Chemical Company.
Finally, alkaline oxidation requires a different workup The poplar wood used for this project was obtained from a
procedure than reductive approaches, such as RCF. farm in Alexandria, Minnesota, provided through the
Reductive methods are usually performed in low-boiling USDA Northern Research Station in Rhinelander,
reaction solvents, which can be easily removed and Wisconsin. The poplar sawdust was extracted with water
recycled by distillation. The products exhibit similar and ethanol for 48 h, respectively. The total lignin content
functionality and polarity, implying that separations will (Klason lignin and acid-soluble lignin) of the (extractives-
13
free) poplar sawdust is 29.1 wt%. Pine sawdust was concentrated HCl to pH < 2 and extracted with ethyl
provided by Idaho National Laboratory (total lignin acetate (4 x 5 mL). The nitrobenzene oxidation reaction
content of 29 wt%). Corn stover was provided by Idaho mixtures were first extracted with dichloromethane (3 x 5
National Laboratory (total lignin content of 15.1 wt%). mL) before acidification. The ethyl acetate was evaporated
The genetically engineered high-S poplar line (F5H-64-E) with a rotavap, resulting in a brown lignin oil (EA oil). 25
was originally produced as described by Franke et al.91 and mg of 4-n-propylguaiacol was added as a standard and 7
was provided by Carl Huetteman (Managing Director, mL acetone was added to solubilize the EA oil and
C3Bio, Purdue University) (total lignin content of 22.9 standard. 200 µL of this solution was added to a GC vial
wt%).92 The preparation of corn stover DMR-EH and and subsequently dried under vacuum. Next, 1 mL of
DAP-EH lignin is described elsewhere (total lignin content pyridine and 100 µL of BSTFA were added, the vial was
of 52.8 and 67.3 wt%, respectively).100 Corn stover AAP- sealed, thoroughly shaken and left for 24 h before GC
AE lignin was prepared as described elsewhere.36 Briefly, analysis.
50 g milled corn stover was treated with anhydrous
For GPC and NMR, the remainder of the reaction solution
ammonia (3 g/g corn stover) in a stainless steel Parr batch
(~ 20 mL) was acidified and extracted with ethyl acetate in
reactor at 130°C for 60 min. After evaporation of the
a separatory funnel (4 x 25 mL). The ethyl acetate phase
ammonia, alkali extraction was performed by treating the
was dried with NaSO4 and the ethyl acetate evaporated
pretreated corn stover in an Erlenmeyer flask with 500 mL
using a rotavap, yielding the EA oil.
of a 0.1 M NaOH solution at 25°C for 2 h. The insoluble
material was subsequently separated by centrifugation. The Gas chromatography (GC) analysis
separated solid was mixed with 30 mL of deionised water For quantitative analysis of the volatile fraction, the
and the obtained slurry was centrifuged again. This step duplicate samples were analyzed on an Agilent GC (6890
was repeated twice, and the two wash fractions were added series) equipped with a HP5-column and a flame
to the supernatant from the first centrifugation, making up ionization detector (FID). The following operating
the corn stover AAP-AE liquor. A portion of this liquor conditions were used: injection temperature of 260°C;
was neutralized with H2SO4 and freeze-dried to determine column temperature program: 50°C, 2-min hold, 10°C
the total solids concentration (34.4 g/L, corrected for min-1 to 280°C, 5-min hold; detection temperature of
Na2SO4 weight) and lignin concentration (10.3 g/L). 300°C. Sensitivity factors of the reagents and products
were obtained by calibration with commercial standards.
Oxidation experiments
When using lignocellulosic feedstocks and isolated lignins,
Alkaline aerobic oxidation reactions were performed in a
the product yields were calculated on a weight basis using
Parr multi-batch reactor system. 30 mL of a NaOH
the following equation:
aqueous solution (deionized water; typically 2 M
concentration), substrate and catalyst were added to 75-mL
= × 100 %%
reactor cups (type 316 stainless steel). The reactors were , × !"
closed and stirring was performed using magnetic stir bars In the experiments with vanillin and syringaldehyde
at 800 rpm. Next, the reactors were flushed with high- (Table 1), the conversion and yield were calculated as
pressure He (three cycles), pressurized with He, and follows:
further pressurized with O2 to achieve a total pressure of −
,
20 bar. The applied He pressure depended on the targeted '" ( " =

× 100 %%
,
O2 partial pressure and was typically 15 bar

(corresponding with an O2 partial pressure of 5 bar). The = × 100 %%
,
reactors were then heated to the desired temperature
(heating time of 30 min), at which point the reaction was The yields and conversions indicated in the manuscript
started (i.e., reaction time was set to 0 min). After reaction, constitute the average of the yields from the duplicate
the reactors were quenched in water and depressurized at samples. The standard deviation was always less than 1%.
room temperature. Selected reactions were performed in triplicate, with the
standard deviation being less than 1%. Qualitative analysis
For the nitrobenzene oxidation reactions of poplar, 27 mL
of the product solution was performed by analyzing the
of a 2 M NaOH aqueous solution, 3 mL nitrobenzene and
samples on an Agilent GC (6890 series) equipped with a
0.5 poplar were added to the reactor cups. After flushing
HP5-column and a 5973N MS detector (Agilent
with He, the reactors were heated to 170°C and left at this
Technologies). The following operating conditions were
temperature for 120 min.
used: injection temperature of 260°C; column temperature
CAUTIONARY REMARK: Using highly alkaline program: 50°C, 2-min hold, 10°C min-1 to 280°C, 5-min
solutions at high temperature can cause stress corrosion hold; MS transfer line temperature: 280°C.
cracking in stainless pressure vessels. Therefore, Monel
HPLC analysis
400 pressure vessels were purchased for future research.
High-performance liquid chromatography (HPLC) analysis
Work-up procedure was performed to quantify the aliphatic carboxylic acids in
For GC analysis, the following procedure was performed the reaction mixture. Before HPLC analysis, a 1 mL
in duplicate for each reaction: 5 mL of the reaction reaction sample was acidified with concentrated HCl to pH
solution was added to a 15-mL glass vial, acidified with < 2 and filtered with a 0.45 µm nylon membrane syringe
14
filter. The samples were analyzed on an Agilent HPLC For the synthesis of the LaCoO3, LaFeO3, and LaMnO3
(1100 series, Santa Clara, CA, USA) outfitted with a perovskite catalysts, 15 mmol of La(NO3)2·6H2O (6.495
refractive index detector and using an Aminex HPX-87H g), 15 mmol of either Co(NO3)2·6H2O (4.3655 g),
(300 × 7.8 mm) organic acid column and Cation H+ guard Fe(NO3)3·9H2O (6.06 g) or Mn(NO3)2·4H2O (3.765 g), and
cartridge (Biorad Laboratories, Hercules, CA, USA). The 45 mmol citric acid (8.645 g) were added to a 200-mL
column was maintained at 65°C with mobile phase glass beaker together with 120 mL deionized water. For
consisting of 0.05 N sulfuric acid with a flow rate of 0.6 the LaCo0.8Cu0.2O3 and LaMn0.8Cu0.2O3 catalysts, 12 mmol
mL min-1. The mobile phase was prepared from 10 N of either Co(NO3)2·6H2O (3.492 g) or Mn(NO3)2·4H2O (g)
sulfuric acid (Ricca Chemical Company, Arlington, TX, and 3 mmol Cu(NO3)2·3H2O (0.7248 g) were combined
USA). Analytes were identified by comparing retention with 15 mmol La(NO3)2·6H2O, 45 mmol citric acid, and
times and spectral profiles with pure standards. 120 mL deionised water. The mixture was stirred with a
magnetic stirring bar, heated to 90°C and left until most of
Gel permeation chromatography (GPC) analysis
the water was evaporated and a gel remained. The sample
GPC analysis was performed to assess the molecular
was subsequently dried at 100°C overnight and calcined at
weight distribution of the aromatic lignin oxidation
650°C for 6 h (5°C min-1 heating rate). XRD was
products. The EA oils and the lignin substrates (20 mg)
performed on a Rigaku Ultima IV X-ray diffraction system
were acetylated in a mixture of pyridine (0.5 mL) and
using Cu Kα radiation, with operating voltage and current
acetic anhydride (0.5 mL) at 40°C for 24 h with stirring.
of 40 kV and 44 mA, respectively, scan speed of 5° min-1,
The reaction was terminated by addition of methanol (0.5
and point spacing of 0.02°. N2 physisorption was carried
mL). The acetylation solvents were then evaporated from
out at 77K with a Quantachrome Quadrasorb SI
the samples at 40°C under a stream of N2 gas. Additional
instrument, with outgassing under vacuum at 350°C for a
methanol was added in 1-mL increments during N2 drying
minimum of 12 h before analysis, and equilibration time of
to assist in removing the remaining acetylation solvents by
30 s for both adsorption and desorption. Temperature
converting any remaining acetic anhydride to methyl
programmed reduction (TPR) was performed on an AMI-
acetate. The samples were further dried overnight in a
390 (Altamira Instruments) system equipped with a
vacuum oven at 40°C. The dried, acetylated samples were
thermal conductivity detector (TCD) to measure hydrogen
dissolved in THF. The dissolved samples were filtered
consumption during a temperature ramp. A molecular
(0.2-µm nylon membrane syringe filters) before GPC
sieve was placed before the TCD to trap water coming
analysis. GPC analysis was performed using an Agilent
from the catalyst bed. Approximately 100 mg of catalyst
HPLC with 3 GPC columns (Polymer Laboratories, 300 ×
was loaded between quartz wool plugs into a quartz U-tube
7.5 mm) packed with polystyrene-divinylbenzene
reactor. A thermocouple located in the furnace wall was
copolymer gel (10-µm beads) having nominal pore
used to control the experiment temperature and another
diameters of 104, 103, and 50 Å. The eluent was THF and
thermocouple located on top quartz wool plug monitored
the flow rate 1 mL min-1. An injection volume of 25 µL
the sample temperature. A pretreatment step consisting of
was used. The HPLC was attached to a diode array
heating in 10% O2/He at 10°C min-1 up to 500°C, followed
detector measuring absorbance at 260 nm (bandwidth 80
by holding for 30 min, was performed in situ. TPR
nm). Retention time was converted into molecular weight
experiments were then carried out in 35 sccm of 5% H2/Ar
(MW) by applying a calibration curve established using
with a ramp rate of 10°C min-1 from 100 to 800°C.
polystyrene standards of known molecular weight (1 × 106
to 580 Da) plus toluene (92 Da). The detection method is RCF experiments
mainly sensitive to aromatics, while other (sugar and RCF experiments were performed in a Parr multi-batch
lignin-derived) products only contribute little to the signal. reactor system. 30 mL of methanol, 1 g of substrate and
100 mg of Pd/C catalyst were added to the 75-mL reactor
NMR analysis
cups. The reactors were closed and stirring was performed
Heteronuclear Single Quantum Coherence (HSQC) nuclear
(800 rpm). The reactors were flushed with high-pressure
magnetic resonance (NMR) spectra were acquired for the
He (three cycles), pressurized with 30 bar H2, heated to
EA oils and poplar wood. The EA oil (80 mg) was
225°C (heating time of 30 min) and left at this temperature
dissolved in 0.5 mL of deuterated acetone. The MWL (100
for 6 h. After reaction, the reactors were quenched in water
mg) was dissolved into 0.5 mL of d6-DMSO/d5-pyridine
and depressurized at room temperature. The reaction
(4:1, v/v). Spectra were acquired on a Bruker 400 MHz
solutions were subsequently filtered to separate the pulp
spectrometer using a BBO probe with Z gradient, with
and catalyst from the liquor. The liquors were dried in a
1,024 points and a sweep width of 15 ppm in the F2 (1H)
rotavap and the resulting brown oils were subjected to a
dimension and 512 points and 220 ppm of sweep width in
three-fold liquid-liquid extraction with dichloromethane
the F1 (13C) dimension. The delay time was 1.5 s. TMS
and water. The dichloromethane phase, containing the
was used as an internal reference for the oil samples and
lignin products, was dried, 40 mg 2-isopropylphenol was
DMSO peak (δH 2.5, δC 39.51 ppm) for the MWL. Peak
added as a standard and 7 mL acetone was added to
assignment was performed according to the literature.101-103
solubilize the standard and lignin products. The resulting
Synthesis and characterization of the perovskite mixtures were quantitatively and qualitatively analysed by
catalysts GC-FID and GC-MS, respectively. The operating
conditions of the GC-FID and GC-MS, and the yield
15
calculations were the same as described for the oxidation J. N. Saddler, T. J. Tschaplinski, G. A. Tuskan and
reactions. C. E. Wyman, Science, 2014, 344, 709.
11. R. Rinaldi, R. Jastrzebski, M. T. Clough, J. Ralph,
Conflicts of Interest M. Kennema, P. C. A. Bruijnincx and B. M.
There are no conflicts of interest to declare. Weckhuysen, Angewandte Chemie International
Edition, 2016, 55, 8164-8215.
Acknowledgements 12. S. Gillet, M. Aguedo, L. Petitjean, A. R. C. Morais,
A. M. da Costa Lopes, R. M. Lukasik and P. T.
This work was authored in part by Alliance for Sustainable
Anastas, Green Chemistry, 2017, 19, 4200-4233.
Energy, LLC, the manager and operator of the National
13. W. Schutyser, T. Renders, G. Van den Bossche, S.
Renewable Energy Laboratory for the U.S. Department of
Van den Bosch, S.-F. Koelewijn, T. Ennaert and B.
Energy (DOE) under Contract No. DE-AC36-08GO28308.
F. Sels, in Nanotechnology in Catalysis, Wiley-VCH
Funding provided by the U.S. Department of Energy
Verlag GmbH & Co. KGaA, 2017, DOI:
Office of Energy Efficiency and Renewable Energy
10.1002/9783527699827.ch23, pp. 537-584.
BioEnergy Technologies Office. W.S. acknowledges the
14. T. Renders, S. Van den Bosch, S. F. Koelewijn, W.
Research Foundation Flanders (FWO Vlaanderen) and the
Schutyser and B. F. Sels, Energy & Environmental
internal funds of KU Leuven for funding. R.M. was
Science, 2017, 10, 1551-1557.
supported by the Center for Direct Catalytic Conversion of
15. L. Shuai and B. Saha, Green Chemistry, 2017, 19,
Biomass to Biofuels (C3Bio), an Energy Frontier Research
3752–3758.
Center funded by the U.S. Department of Energy, Office
16. M. Ragnar, G. Henriksson, M. E. Lindström, M.
of Science, Office of Basic Energy Sciences, Award DE-
Wimby, J. Blechschmidt and S. Heinemann, in
SC0000997. The views expressed in the article do not
Ullmann's Encyclopedia of Industrial Chemistry,
necessarily represent the views of the DOE or the U.S.
Wiley-VCH Verlag GmbH & Co. KGaA, 2000, DOI:
Government. The U.S. Government retains and the
10.1002/14356007.a18_545.pub4.
publisher, by accepting the article for publication,
17. P. Sannigrahi and A. J. Ragauskas, in Aqueous
acknowledges that the U.S. Government retains a
Pretreatment of Plant Biomass for Biological and
nonexclusive, paid-up, irrevocable, worldwide license to
Chemical Conversion to Fuels and Chemicals, John
publish or reproduce the published form of this work, or
Wiley & Sons, Ltd, 2013, DOI:
allow others to do so, for U.S. Government purposes.
10.1002/9780470975831.ch10, pp. 201-222.
18. S. P. S. Chundawat, G. T. Beckham, M. E. Himmel
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Green Chemistry

Revisiting alkaline aerobic lignin oxidation

Journal: Green Chemistry

Article Type: Paper

Date Submitted by the Author: 25-Jun-2018

Revisiting alkaline aerobic lignin oxidation†

Figure 2 Gas chromatogram of the silylated EA oil from poplar

To examine the oxidative degradation of the phenolic

Figure 5 Impact of NaOH concentration on the phenolic monomer

Finally, we assessed the impact of the NaOH concentration

LaCoO3, its reduction started at lower temperature (the

Figure 6 Phenolic monomer yields from oxidation of poplar with

comprising 25 wt% oxidation products. Oxidation of

Figure 8 Phenolic monomer yields from uncatalyzed and catalyzed

In addition to the native lignins, we examined the

carboxylic acid stream that is obtained in addition to the

For poplar, pine, and corn stover, alkaline aerobic

the ester-linked p-hydroxybenzoic acid, are produced

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