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org/journal/ascecg Research Article

Interplay of Acid−Base Ratio and Recycling on the Pretreatment

Performance of the Protic Ionic Liquid Monoethanolammonium
Acetate
Pedro Y. S. Nakasu, Coby J. Clarke, Sarita C. Rabelo, Aline C. Costa, Agnieszka Brandt-Talbot,
and Jason P. Hallett*
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ABSTRACT: The use of protic ammonium ionic liquids (PILs) in the pretreatment of lignocellulosic biomass is a promising
alternative to using expensive aprotic ionic liquids such as 1-ethyl-3-methylimidazolium acetate, [Emim][OAc]. In this work, the PIL
monoethanolammonium acetate, [MEA][OAc], was used for the pretreatment of sugar cane bagasse. The study investigated
changing the acid base ratio (ABR) from 0.1 to 10 and recycling of the solvent. We determined the lignin extraction, lignin recovery,
solvent recovery, and enzymatic saccharification yield and compared the performance to that of the pure amine base,
monoethanolamine. We found that lignin extraction and glucose release during enzymatic saccharification increased with base
(amine) content, reaching up to 84% and 96%, respectively, after 72 h of saccharification for the 0.1 ABR. Up to 97% of the solvent
was recovered for the 1.0 ABR. A higher acid content led to increased hemicellulose extraction into the liquid phase and reduced
ionic liquid recovery. A partial conversion of the PIL into N-(hydroxyethyl) acetamide was observed after pretreatment, with up to
86% of conversion after the sixth use for the 1.0 ABR. A negative correlation (R2 = 0.96) was found between the acetamide content
in the solvent and the saccharification yield. The drop in pretreatment performance was also correlated with a decrease in
accumulated lignin recovery and the molecular weight of the isolated lignins. Acetamide formation was reduced when excess base
was present. Recycling of the mixture with 0.5 ABR showed that the performance was unchanged (97% saccharification yield) after
three uses, although 28% of the mixture was converted into the acetamide. The study shows that protic acetate ILs made from
primary amines form an equilibrium with their amide and a low ABR is required in order to maintain high pretreatment efficiency
when the PIL is reused.
KEYWORDS: Protic ionic liquid, Pretreatment, Sugar cane bagasse, Acid base ratio, Solvent recycling

■ INTRODUCTION
Sugar cane bagasse is a widely available lignocellulosic biomass Received: March 4, 2020
resource in Brazil, with a composition of around 32−48% Revised: April 13, 2020
cellulose, 19−24% hemicellulose (mainly composed of xylan Published: April 27, 2020
with minor amounts of arabinan), 23−32% lignin, and 1.5−5%
ash on a dry basis.1 In the past decades, several technologies
aimed at increasing accessibility of its polysaccharides have

© 2020 American Chemical Society https://dx.doi.org/10.1021/acssuschemeng.0c01311

7952 ACS Sustainable Chem. Eng. 2020, 8, 7952−7961
ACS Sustainable Chemistry & Engineering
been employed, such as hot water, dilute acid, alkaline, and
organosolv pretreatment.2 Despite focusing on low cost
solvents (water and ethanol) and low-cost catalysts (sulfuric
acid and ammonia), they usually suffer from one or several
drawbacks, such as low sugar yields due to high residual lignin
content after pretreatment, production of inorganic waste due
to the need for pH adjustment, a need for prior detoxification
of hydrolysates, or poor solvent recovery. Hence new
pretreatment technologies should be explored.3
Ionic liquids are organic salts whose melting points are
typically below 100 °C. They have been studied due to their
tunability, and different physicochemical properties such as
viscosity, thermal and electrical conductivity, dielectric
constant may be obtained by combining a variety of cations
and anions. Ionic liquids may be useful for applications in
catalysis, biocatalysis, electrochemistry, engineering fluids, etc.4
They have also been studied for use in biomass deconstruction
as they can modify lignocellulosic materials by either
solubilizing or swelling the entire lignocellulosic matrix,
including cellulose, or only solubilizing lignin and hemi-
cellulose. Combined with their potential low volatility
and high thermal stability, this makes them promising
pretreatment agents that can be recovered and recycled to
ensure the economic feasibility of the process.5 1-Ethyl-3-
methylimidazolium acetate, [C2C1Im][OAc], and 1-butyl-3-
methylimidazolium chloride, [C4C1Im]Cl, are examples of
aprotic ionic liquids and were first reported to dissolve wood
particles and then comprehensively studied as solvent
for pretreatment of a range of lignocellulose biomass including
wheat straw,6 swichtgrass,7 bagasse,8 and Norway spruce.9
Protic ionic liquids (PILs) can be produced in principle
at lower cost than aprotic ionic liquids10 and have recently
gained significant attention in the field of biomass pretreat-
ment. They typically cannot dissolve cellulose but some PILs
can extract lignin,5 producing a cellulose-rich pulp, paving the
way for a cost-effective production of second-generation
ethanol at sugar cane mills.
The ionoSolv pretreatment promotes lignin and hemi-
cellulose solubilization with acidic PILs such as triethylammo-
nium hydrogen sulfate, [TEA][HSO4], and leaves a cellulose-
rich pulp that could be further processed into bioethanol or
cellulose materials.11
A work by Sun et al.12 showed that an acetate based PIL,
monoethanolammonium acetate, [MEA][OAc], also demon-
strated effectiveness for lignocellulose pretreatment, but with a
different selectivity. It dissolved lignin (up to 80 wt % at 160
°C for 0.5 h) while leaving the majority of the hemicellulose in
the pulp. Considerable sugar yields upon saccharification were
reported, above 80% for glucose,12−14 with good water
tolerance of up to 20 wt %. [MEA][OAc] synthesis is a
simple acid base neutralization using two bulk chemicals
without the need for dilution in water, resulting in low solvent
cost of around $1.8 kg−1,11 which is more than an order of
magnitude cheaper than the widely used aprotic ionic liquid 1-
ethyl-3-methylimidazolium acetate, [Emim][OAc], which
has an estimated solvent cost of $20−50 kg−1 at bulk scale.5
The acid−base ratio (ABR) in PILs is an important
parameter that affects the pretreatment.15 Varying the ABR
of sulfate-based PILs has been subject to several studies.11,15,16
Verdiá et al.15 systematically changed the ABR of [HBIm]-
[HSO4] for the pretreatment of miscanthus; a slight excess of
acid promoted higher cellulose content in the pulp and sped up
pretreatment, whereas a slight excess of base resulted in a
7953
pubs.acs.org/journal/ascecg Research Article
higher hemicellulose recovery. Weigand et al.16 tested small
ABR variations (0.98 to 1.02) in [TEA][HSO4] on the
pretreatment of willow. A slightly higher ABR, 1.02, provided
higher glucose yield during the enzymatic saccharification of
the pulp. The better performance with excess acid was assigned
to the higher recalcitrance of hardwood, but longer pretreat-
ment times led to lower saccharification yields than observed
for the lower ABR. However, there are currently no reports of
variable ABR pretreatments with acetate-based PILs. There-
fore, this work aims to investigate the impact of ABR on
pretreatment efficiency in enzymatic saccharification, selectiv-
ity toward lignin solubilization/carbohydrate preservation, and
solvent recycling to understand how the ABR further affects
the pretreatment process.
Ionic liquids with ABRs other than 1 can be classified as
mixtures. As the ratio increases, it is expected that the liquid
behaves more like the pure acid,17 while with decreasing ABRs,
the liquid is expected to behave more like the pure base.18 Pure
MEA is a reactive chemical19,20 and requires the use of pipes
and reactors made from expensive alloys. The addition of
acetic acid is known to decrease its corrosivity.21 Acetic acid is
also 1.5−2 fold cheaper than MEA, so high ABRs decrease the
overall solvent price. Moreover, the 1.0 ABR [MEA][OAc] is a
supercooled PIL at ambient temperature,22 so it might
crystallize at low water contents (below 10 wt % water) and
could potentially clog pipes or equipment. Therefore, mixtures
with excess acid or amine are good solvent alternatives to 1.0
PILs and pure amines.
■
MATERIALS AND METHODS
Materials. Reagents were purchased from Sigma-Aldrich and used
as received. Sugar cane bagasse was provided by São João Mill
(Araras-SP, Brazil). The material was collected by mechanical
harvesting. It was air-dried, ground, and sieved (180−850 μm, 20 +
80 US mesh scale) before compositional analysis and pretreatment
assays. Feedstock, lignin, and pulp characterization protocols can be
found in the Supporting Information (SI).
PIL and Acid−Base Mixtures Synthesis. Monoethanolammo-
nium acetate, [MEA][OAc], was synthesized as described previously
by Pin et al.23 Acetic acid was added dropwise to cooled
monoethanolamine in a round-bottom flask while stirring. The
moisture content in the synthesized IL was verified by Karl Fischer
titration (Mettler Toledo V20) in triplicate and was less than 100
ppm.
For the solution with different ABRs, the same procedure was
followed as aforementioned, but different amounts of acetic acid were
added to monoethanolamine to generate acid−base mixtures with 11
ABRs. Five ABRs corresponded to excess base0.1, 0.2, 0.5, 0.8, and
0.9five to excess acid1.1, 1.25, 2.0, 5.0, and 10.0plus the
neutral PIL with 1.0 ABR. Two controls, pure monoethanolamine
(MEA) and pure acetic acid, were also used. However, pretreatment
with acetic acid resulted in charring of the biomass and the data are
not presented here. ABR determination experiments were carried out
in duplicate.
The ABRs were confirmed via 1H NMR spectroscopy. 1H NMR
spectra were recorded on a Bruker 400 MHz spectrometer. Chemical
shifts (δ) are reported in ppm. The integrals for the methyl group of
the acetate anion and the protons of the methylene group adjacent the
amino group in monoethanolamine were compared. The ABRs deter-
mined by NMR analysis are shown in the SI.
Biomass Pretreatment. Pretreatment with [MEA][OAc] and its
acid−base mixtures was carried out according to a standard protocol24
with slight modifications. 10.67 ± 0.05 g of ionic liquid (or mixture)
and 2.67 ± 0.05 g of water were weighed into a 100 mL glass pressure
tube with a silicone front sealing ring (Ace Glass), and the exact
weight was recorded. A total of 2 g of ground sugar cane bagasse (15
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wt % solids loading) was added, the vials capped, and the content Scheme 1. Experimental Workflow Employed in This
mixed with a vortex shaker. The water content in the solvent was 20% Studya
w/w. The samples were placed into a convection oven (OMH60
Heratherm Advanced Protocol Oven) preheated to 150 °C. After the
pretreatment (2 h), they were immediately cooled. Pretreatment ex-
periments were carried out in triplicate.
40 mL water was added to the pretreatment mixture and the
suspension transferred into a 50 mL centrifuge tube. The tube was
shaken for 1 min and centrifuged at 4000 rpm for 50 min. The
supernatant was transferred into a 250 mL round-bottom flask. The
washing step was repeated three more times. The pulp was transferred
into a cellulose thimble and washed by Soxhlet extraction with
refluxing water (150 mL) for 15 h. The thimbles were air-dried
overnight. The pulp yield was determined by weighing the recovered
biomass from the cellulose thimbles (calculations section in the SI).
The water used for the Soxhlet extraction was combined with the
previous washes and evaporated under reduced pressure at 40 °C,
leaving a concentrated mixture of water and PIL (or solvent mixture).
The suspension was transferred into a pre-weighed 50 mL centrifuge
tube, shaken for 1 min, and left at room temperature for at least 1 h.
The tube was centrifuged and the supernatant was collected in a
round-bottom flask. This washing step was repeated twice more. The
lignin in the centrifuge tube was freeze-dried for 72 h, weighed and
stored in plastic containers. Based on the freeze-dried lignin weight,
a
the lignin recovery was calculated (calculations section in the SI). The solid lines depict the workflow for the ABR experiments, while
Pretreatment with 0.1 ABR and MEA were repeated in 500 mL the recycle experiments included IL recovery indicated by the dotted
stainless steel reactors according to Pin et al.23 line.
Recycling Experiments. The recycling experiments were
performed in glass pressure tubes in a procedure similar to the one cane bagasse used in this study, as percentage of dry mass, was
detailed under Biomass Pretreatment. The concentrated PIL/mixture
was reused 5 times without additional IL added to it.
as follows: cellulose, 42.0 ± 1.4%; hemicelluloses, 25.4 ± 0.7%;
Enzymatic Saccharification. The enzymatic saccharification lignin, 23.8 ± 1.3%; extractives, 2.1 ± 0.5%; acetyl groups, 3.5
assay was carried out according to the NREL protocol “Enzymatic ± 0.1%; and ash, 3.0 ± 0.8%. The pulp yields (oven-dried
saccharification of lignocellulosic biomass” in triplicate. The cellulase weight) for the pretreatment of sugar cane bagasse with
cocktail Cellic Ctec2 (Novozymes) was employed with a loading of [MEA][OAc] with different ABRs are summarized in Figure 1.
15 FPU per g dry biomass and at 1 wt % solids loading. All Since pretreatment with acetic acid at these conditions resulted
saccharification experiments were performed in 20 mL centrifuge in charring of the biomass, the data were not reported.
tubes incubated in a Stuart Orbital Incubator (S1500) at 250 rpm, 50
°C, for 72 h and held at pH 4.8 with a 0.05 mol L−1 sodium citrate
buffer. Samples were filtered, and the filtrate was analyzed by HPLC
(Shimadzu, Aminex HPX-87P from Bio-Rad, 300 × 7.8 mm) for
glucose, xylose, and arabinose. Mobile phase conditions were
employed based on a previously developed method.11 Cellulose and
hemicelluloses yields were calculated as a percentage of the cellulose
and hemicelluloses content of raw bagasse, as determined by
compositional analysis (calculations section in the SI).

■ RESULTS AND DISCUSSION

The experimental workflow used in this study is summarized in
Scheme 1. The first part of the study evaluated the impact of
the ABR on the pretreatment performance using freshly
synthesized [MEA][OAc] with different ABRs. Varying
amounts of acetic acid were added to monoethanolamine to
generate 11 ABRs. Five excess base ABRs and five excess acid
ABRs were investigated, in addition to the PIL with 1.0 ABR.
Pure monoethanolamine (MEA) and pure acetic acid were also
investigated as controls. Previously optimized pretreatment
conditions (time, temperature, water content and solids
loading)25 were used.
The second part of the study investigated pretreatment
performance during repeated use of [MEA][OAc] for two
selected ABRs. Carbohydrate recovery and release of sugars by
cellulose hydrolyzing enzymes were again monitored. Changes
to the chemical properties of the isolated lignins were also
evaluated.
Effect of the ABR on Pretreatment Performance and
Solvent Recovery. The chemical composition of raw sugar
7954
Figure 1. Pulp yield (non-gray fill) and composition after pretreat-
ment of bagasse with [MEA][OAc] with different ABRs with 20 wt %
water at 150 °C for 2 h and 15 wt % solids loading. The composition
of untreated (UTD) sugar cane bagasse is also displayed.
For the lowest ABR values, 0.1−0.5 ABR, there were no
major differences in the amount of biopolymer extraction. We
note that there was very little cellulose solubilizations
regardless of the ABR in the [MEA][OAc], while hemi-
cellulose solubilization increased when the ABR was above 1.
This trend was not surprising, as it is known that hemi-
celluloses hydrolyze readily in acidic solvents while they are
more stable in alkaline conditions. Analysis of the liquid
fraction by HPLC (Figure S1 in the SI) did not detect any
cellulose degradation products, i.e., glucose, HMF, formic
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acid and levulinic acid, regardless of the ABR. Furfural, a

hemicellulose degradation product, was only detected for the
highest ABRs, 5 and 10, which confirmed that [MEA][OAc] is
very selective toward isolating both cellulose and hemi-
cellulose. We show here that this is the case for a wide range
of ABRs. Ash solubilization was observed at low ABRs, as
indicated by the lower ash content in the pulps obtained with
these PIL mixtures. The solubilization of extractives also
followed this trend, which was probably due to their affinity
toward alkali. Tannins, lignans, fats, and proteins are
commonly found in the extractives fraction and they have
increased solubility in alkaline solvents.26 It was observed that
lignin was the major solubilized component and that
delignification increased with increasing base content, with
up to 84 wt % of delignification found for the lowest ABR, 0.1.
It is known that alkaline conditions favor lignin extraction, due
to susceptibility of the β-O-4 ether bond, the most common
linkage in lignin, to hydrolysis in alkaline conditions and due
to deprotonation/coordination of phenol groups by bases,
leading to dissolution of hydrolyzed lignin fragments. Alkaline
pretreatment solvents utilising hydrogen peroxide,27 sodium
hydroxide,28 and ammonia fiber explosion, AFEX (with
switchgrass as feedstock),29 also remove a great portion of
the lignin, with up to 74, 91, and 81 wt % of delignification,
similar to the delignification achieved in this work. However,
carbohydrates can also be solubilized during alkaline pretreat- Figure 2. (a) Glucose (blue) and pentose (xylose and arabinose;
ment, with up to 4, 10, and 3 wt % of cellulose and 27, 12, and green) yields relative to the sugar content in untreated biomass after
71 wt % of hemicellulose being solubilized during AFEX, 72 h of enzymatic saccharification following pretreatment with
[MEA][OAc] with different ABRs. (b) Lignin recovery after
hydrogen peroxide, and sodium hydroxide pretreatment of
[MEA][OAc] pretreatment with different ABRs relative to the lignin
sugar cane bagasse, respectively.27−29 In this work, less than 2 content in the untreated biomass.
wt % of hemicelluloses and no cellulose (below the detection
limit) were solubilized when solutions with low ABR were
used, which showed that [MEA][OAc] mixtures have selectiv-
ity advantages over other alkaline pretreatments. The composi- experimental data, confirming that the saccharification yields
tional analysis results confirmed that PILs can not only be obtained by HPLC are correct.
tailored by choosing the anion and cation configuration but The lignin recovery upon variation of ABR is shown in
also by adjusting the ratio of the acid and base used. Figure 2b. For low ABRs, ranging from 0.1 to 0.9, the amount
Figure 2a illustrates the glucose and pentose sugar yields of recovered lignin increased as the ABR increased. The trend
(xylose and arabinose) after 72 h of enzymatic saccharification. was likely due to high lignin solubility in highly alkaline media,
Both glucose and pentose sugar yields were higher for lower which makes antisolvent preciptiation less effective in such
ABRs, i.e. the excess base conditions. The highest yields were conditions. For the ABRs above 1, i.e., 1.1 to 10:1, there was a
observed for the MEA control. Pentose yields in particular further increase in precipitate recovery. We note that for the
decreased when the acid content increased, which was due to 5:1 and 10:1 ABR, the lignin recovery exceeded the lignin
more hemicellulose solubilization during pretreatment (Figure extraction (Figure 1), which indicates pseudolignin formation
1). Interestingly, glucose release was also lower for excess acid from the hemicellulose fraction. Excess lignin recovery has
solutions. This is likely due to lignin redeposition on the pulps. been reported for acidic PILs before.11,15
Redeposited lignin can act as a physical barrier to enzyme Pseudolignin, also called humins, is a by-product of the
access and may also reduce enzyme activity by adsorbing decomposition of hemicellulose sugars in acidic media.32 The
enzymes onto lignin surfaces.30 It is very interesting that, for extensive hemicellulose solubilization in acidic conditions
the excess base conditions, the glucose yield decreased with likely promoted pseudolignin formation here. The 1.0 PIL
increasing acid content, despite there being no quantitative provided 32.7 ± 1.9 wt % of recovered precipitate (relative to
difference in the carbohydrate and lignin content in the total lignin in the raw bagasse), which is similar to 27.8 wt %
pulps as shown in Figure 1. Therefore, addition of acetic acid lignin recovery for [MEA][OAc] pretreatment of sugar cane
not only reduces lignin removal but also induces morpho- bagasse in a previous study.14 In comparison, nearly 50 wt % of
logical changes in the pretreated pulps. Although this was not the lignin in sugar cane bagasse was recovered as a separate
investigated, cellulose crystallinity and the amount of fraction during fractionation with the acidic PIL [TEA][HSO4]
pseudolignin in the residual lignin was likely higher when at 120 °C for 4 h;33 nearly 80 wt % of the lignin in miscanthus
acid is present. It is known that amine solutions swell cellulose was recovered by using the same PIL at 120 °C for 9 h.11 A
and that decrystallized cellulose can be hydrolyzed more higher amount, 90 wt %, was obtained in the pretreatment of
quickly than crystalline cellulose.31 Hydrolysis residues were willow with [TEA][HSO4] at 170 °C for 40 min,16 which
also weighed (Figure S2 in the SI) and compared with the indicates lignin recovery depends on biomass type and PIL
predicted residue weights based on the saccharification yields. used. It should be noted that the first pretreatment cycle does
There was a good correlation between calculated and not necessarily reflect the lignin recovery that would be
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obtained at equilibrium in a process that uses recycled ionic scans can be found in Figures S4−S7 in the SI; binding
liquid.11 energies in Table S2 in the SI). Lignin from [TEA][HSO4]
We also monitored lignin quality using elemental anal- pretreatment was also analyzed for comparison with an acidic
ysis (Table S1 in the SI). We observed that the nitrogen PIL pretreatment methodology. [TEA][HSO4] pretreatment
content of the lignins was higher than the values found for the conditions were similar to Chambon et al.33
pulps, showing that [MEA][OAc] is interacting with the All lignin samples, including [TEA][HSO4] pretreated
precipitate regardless of ABR. This may explain why lignin, showed N 1s signals in the survey spectra, confirming
lignin recovery was not quantitative. Other studies have also the nitrogen incorporation on the lignin samples found by
reported nitrogen incorporation into the lignin during elemental analysis. Except for the MEA lignin, all samples had
AFEX34,35 and [TEA][HSO4]11 pretreatments, which seems higher carbon content than the elemental analysis values. One
to be a common feature of delignifying pretreatments using reason is related to the fact that XPS provides surface
amines. The most interesting trend, however, was the composition while elemental analysis does bulk and surface
significant decrease in carbon content as the ABR decreased. composition. Except for the MEA sample, lignin particles may
The CHN content in the MEA lignin corresponded to less have aggregated in such a way during precipitation in water
than 25 wt %; oxygen only cannot account for the large mass that the more hydrophobic aromatic moieties would be in the
difference, suggesting there are inorganic elements in the surface.
precipitated solids. We also found a characteristic methyl signal Inorganic Si was present in all the pretreated lignins, except
at δ1 ≈ 1.2 ppm and δ2 ≈ 20 ppm in the HSQC NMR for lignin obtained from [TEA][HSO4] pretreatment (Table
spectrum of the recovered lignin that indicates the presence of 1). MEA pretreated lignin contained the most silicon, which
acetyl groups in the lignin36 (Figure S3 in the SI). was present in 20.4 at. %, while all [MEA][OAc] samples
The elemental surface composition of selected ligin precip- showed small quantities of silicon (<1 at. %); this
itates was therefore measured with X-ray photoelectron indicates that MEA either reacted with the glass from the
spectroscopy (XPS). pressure tubes during pretreatment or retained Si from the ash
XPS analysis is a non-destructive technique that can
present in the biomass.
fill information gaps left by the elemental analysis. The survey
For MEA pretreated lignin, the Si 2p photoemissions
scans of lignins isolated from [MEA][OAc] with 0.8, 1, and 2
(Figure 3a) showed two chemical states in the high-resolution
ABRs, MEA, and [TEA][HSO4] pretreatments were quantified
spectrum which indicated a mixture of organosilicon
and the atomic percentages are shown in Table 1 (lignin survey
compounds (102.6 eV), such as siloxane, and inorganic silica
(103.5 eV), i.e., SiO2. The presence of additional oxygen also
Table 1. Atomic Percentages of Each Lignin Sample
caused a significant deviation in the expected O/C ratio, which
Measured from Survey Spectra in Avantage Using the
should fall within a certain range to give a linear relationship
ALThermo1 Database
with the C 1s component 1 percentage (Figure 3b).37 To find
at. % out whether the silicon present in MEA lignin originated from
C N O Si S Ca the pressure tubes or the ash in the biomass, we then analyzed
RSFa 1.00 1.68 2.89 0.90 1.89 5.97
lignins obtained from pretreatments with MEA and [MEA]-
MEA 30.4 3.0 45.7 20.4 0.5 [OAc] with 0.1 ABR in a stainless steel reactor. The results
0.8 ABR 78.6 2.8 17.7 0.9 show that overall silicon content was lower than in the samples
1.0 ABR 85.4 1.9 12.3 0.4 pretreated in glass tubes (6.7 and 6.6 at. %) which confirmed
2 ABR 79.5 2.1 18.1 0.3 that MEA reacted with the borosilicate pressure tubes.
[TEA][HSO4] 74.6 0.1 24.3 1.1 However, the small amounts of Si present in the lignin
MEA (steel reactor) 77.6 1.5 14.2 6.7 obtained using the reactor most likely originated from the
0.1 ABR (steel reactor) 78.2 1.4 13.9 6.5 biomass ash, and show that MEA has a high affinity for Si,
a
ALThermo1. which can be subsequently recovered.
[TEA][HSO4] pretreated lignin contained less nitrogen in
comparison to [MEA][OAc] pretreated lignins; however,
sulfur was present (1.1 at. %) in the survey scans just like

Figure 3. High resolution XPS Si 2p scans (a) showing MEA lignin (purple) and MEA lignin from stainless steel reactor pretreatment (green) with
additional all Si containing lignin photoemissions (inset). Plot of C 1s component 1 vs O/C atomic ratios for MEA lignin (purple) and all other
lignin samples (green).

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the lignin obtained from pretreatment of miscanthus.11 The
presence of additional carbon chemical states at high B.E. (i.e.,
>288 eV) and the small amount of nitrogen suggest that the
hydrogen sulfate anion has chemically functionalized the lignin.
GPC analysis monitors the molar weight of lignins and can
help understand structural changes in lignin such as
fragmentation and condensation/humin formation. The
average molar weights (weight-average molar weight Mw and
number-average molar weigth, Mn) and the polydispersity
(PD) for the ABR experiments were obtained (Table S3 in the
SI), while molar weight profiles can be found in Figure S8 in
the SI.
The 1.0 PIL and the PILs with higher ABRs showed Mn, Mw
and PD values consistent with the ones obtained with
[TEA][HSO4] and [Emim][OAc] pretreatments of miscan-
thus11 and poplar,38 respectively. Similar Mw values were also
reported for the lignins obtained from lignin depolymerization
experiments with diisopropylammonium acetate.39 We assume
that the 1.0 PIL and the solutions containing excess acid
generated a largely pure lignin. Under excess base conditions,
however, the Mw and therefore the PD (Mw/Mn) increased,
indicating that the precipitate is more heterogeneous. we note
that the excess base recovered lignins were pooly soluble in
solvents such as DMSO, alkaline water solutions, chloroform
and DMF, which further supports the hypothesis that
they contained inorganic compounds. The covered lignins
are shown in Figure S9 in the SI.
The change of the ABR in the IL recovered after the
pretreatment was also monitored by 1H-NMR spectroscopy
(Figure S10 in the SI). For the excess base conditions (Figure
S10a), there was a slight decrease in the ABR. For the excess
acid conditions (Figure S10b), the drop in ABR was even more
pronounced. We assign this to the evaporation of acetic acid
during the drying step.
When examining 1H NMR and 13C NMR spectra of the
recovered PIL more closely, we also found signals for a new
compound which was assigned to N-(2-hydroxyethyl)-
acetamide. The mechanism for producing the amide is
shown in Scheme 2, using an chemical equilibrium between
Scheme 2. Mechanism for the PIL Conversion into N-(2-
Hydroxyethyl)acetamide
PIL and the amine and acid, with the latter pair reacting via an
amidation reaction. Although the formation of amides is not
kinetically favored between alkylamines and carboxylic acids,
as they usually require a catalyst at room temperature,40 the
high pretreatment temperatures in this study appear to
have enabled the reaction towards the thermodynamically
more stable amide. Partial conversion of an acetate based PIL
into an acetamide has been reported before for an PIL made
using a secondary amine, pyrrolidinium acetate, [Pyrr]-
[OAc].41 This suggests that primary and secondary acetate
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PILs are not inert at conditions used for lignocellulose
pretreatment. Tertiary aliphatic amines would not participate
in such a reaction but they are reported to exhibit low ionicity
and poor water solubility, due to the lack of multiple hydrogen
bonding sites on the cation,42 making them less suitable for
this application.
The influence of the ABR on the extent of amide formation
can be seen in the 1H NMR spectra (Figure S11 and S12 in the
SI). At low ABR (Figure S12), the peaks for the acetamide (δ
= 1.8, 3.05 and 3.35) decreased in intensity as the ABR
decreased, suggesting that amide formation was suppressed,
especially for ABRs below 0.5. This is likely due to more
acetate being present, which is deactivated for nucleophilic
attack by the amine. When the ABR was high (Figure S11 in
the SI), the amide formation was also suppressed for ABRs
higher than 2, which is likely associated with a decrease in the
concentration of the nucleophile, monoethanolamine, due to
its protonation.
Chen et al.42 investigated changes in the ABR in order to
estimate the ionicity of this group of PILs. The ABR was varied
from 0.6 to 1.5 in 1-methylimidazolium acetate, and it was
shown that acetate-based ammonium PILs are highly ionized,
even though the pKa difference between the acid and conjugate
bases is not greater than 10.43
We also examined IL recovery rates (Figure S13 in the SI),
which are key to commercial viability of such a solvent-based
process. High recovery of 94−97% was reported for the low
ABRs (0.1 until 1.1). The highest recovery, 97%, was found for
[MEA][OAc] with 1.0 ABR. Klein-Marcushammer et al.44
reported that a minimum recovery of around 97% is needed for
a low-cost IL with a solvent price of USD 2.5/kg. Based on this
recovery and an estimated bulk price for [MEA][OAc] of USD
1.8/kg, pretreatment with this PIL has the potential to be
economically viable. Lower ABRs, i.e., the solutions with excess
MEA, generally resulted in higher solvent recovery compared
to the solutions where excess acetic acid was present. This is
likely due to the high boiling point of MEA (170 °C)
compared to that of acetic acid (118 °C). The recovery data
suggest that the acetic acid evaporated during solvent recovery,
while most of the MEA did not. Achinivu et al.41 also
investigated recovery of acetate PILs after pretreatment of corn
stover. Unlike here, they employed low pressure distillation
(0.1 mbar). They were able to recover up to 98% of the PIL
pyridinium acetate, [Py][Ac], with 1.0 ABR.
For the conditions where recovery rates were not near-
quantitative (<99 wt %), it is possible that either [MEA][OAc]
or MEA itself has been chemically incorporated in the pulps or
recovered lignins during pretreatment. Hence, we employed
elemental analysis of the pulps to check for amine
incorporation (Table S4 in the SI). Elemental analysis showed
that the nitrogen content was the same for raw bagasse and the
pulps, suggesting that no substantial nitrogen/amine incorpo-
ration in the pulps occurred, even in conditions when solvent
recovery was low. There was a slight trend towards less
incorporation for pure MEA and when a large excess of amine
was present. In comparison, palm oil empty fruit bunch
pretreatment with ammonia fiber expansion34 resulted in
nitrogen incorporation in the pulp, which indicates
that [MEA][OAc] is less reactive than ammonia, probably
due to steric and electronic effects. Pretreatment of miscanthus
with [TEA][HSO4]11 resulted in very low nitrogen content in
the pulps, but there was sulfur, which may indicate inorganic
sulfate salts remain with the pulps.
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ACS Sustainable Chemistry & Engineering
Figure 4. Glucose (a) and pentose (xylose and arabinose) (b) yields after 72 h of enzymatic saccharification upon repeated pretreatment with
[MEA][OAc] with 1.0 ABR. Yields for pure acetamide (purple bar) are shown for comparison. The purple line indicates the acetamide content in
the solvent (relative to sum of amide and [MEA][OAc]).
Recycling of [MEA][OAc] with 1.0 ABR. The formation
of acetamide and the changes in the ABRs observed upon
solvent recovery led us to investigating solvent recycling in
more detail and use the same solvent repeatedly for 6 times.
The results for the saccharification yields after repeated use of
the 1.0 ABR [MEA][OAc] are shown in Figure 4. A decrease
for both glucose (Figure 4a) and pentose (Figure 4b) release
was noted, following the same trend found in studies with 1.0
ABR [MEA][OAc] pretreatment of sugar cane14 and apple
cashew bagasse.13 However, we also observed some differ-
ences. In the previous work on [MEA][OAc] pretreatment of
sugar cane bagasse, where glucose saccharification yield
remained steady for the first three cycles at around 74%. In
this work, the glucose and pentose yields dropped steadily to
50%. The main reason for the difference is likely that fresh PIL
was added before the new pretreatment cycles in the previous
work, due to low PIL recovery rates of around 83 ± 2%, which
masked the yield decrease noted in this work. The solvent
recovery rates obtained in this work remained stable at around
97% (Figure S14 in the SI) over the cycles and there was no
need to use top-up solvent.
Recycling of [TEA][HSO4] during the pretreatment of
miscanthus11 led to higher recovery rates of 99%, which is
probably related to the non-volatility of sulfuric acid.
The acetamide content in the mixtures was tracked along the
use cycles and is shown in Figure 4. By the end of the sixth
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cycle, the acetamide content approached 86%. The saccha-
rification yield (40% for glucose and 43% for pentose yield)
was higher than the yields observed for bagasse pretreated
with pure acetamide (purple bar).
The data suggest that the PIL/acetamide mixture reached a
thermodynamic equilibrium after a number of recycles. We
conclude that the main reason behind the drop in [MEA]-
[OAc] performance during recycling is PIL conversion into the
acetamide. A negative correlation between glucose saccha-
rification yield and acetamide content after pretreatment can
be found (Figure S15 in the SI), with a very good fit (R2 =
0.96). A poor (R2 = 0.40), slightly positive correlation was
found between glucose saccharification yield and high ABRs,
which may be due to acetic acid being present in the recovered
solvent. However, even though the reaction tubes were sealed
so that no water could evaporate and shift the equilibrium to
the amide, the high temperatures employed in the pretreat-
ment favored the formation of the more thermodynamically
stable amide.
Lignin recovery for the recycling experiments is shown in
Figure 5. A slight increase in recovery was observed as
recycling progressed, with a tendency towards plateauing by
the sixth cycle. However, the delignification and the cumulative
lignin recovery (lignin recovery summed over all previous
cycles) decreased. The cumulative lignin recovery was lower
than the lignin extraction, which means that lignin is
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ACS Sustainable Chemistry & Engineering
Figure 5. Lignin recovery (red bars), delignification (green line), and
cumulative lignin recovery (black line) from aqueous solutions of
[MEA][OAc] during solvent recycling. Lignin recovery after pretreat-
ment with the pure acetamide (purple bar) is also shown for
comparison.
accumulating in the solvent. It is interesting to note
that lignin recoveries for the IL/acetamide mixtures were
higher than for the acetamide control, even though over 80%
of the pretreatment mixture was acetamide in the last
cycle. This shows that even a small amount of the ionic liquid
has a substantial positive effect on pretreatment performance.
The compositional analysis for the pulps obtained during
recycling experiments was also performed (Figure S16 in the
SI). Lignin extraction decreased as the solvent was recycled.
The change in ABR was also tracked for the recycling
experiment (Figure S17 in the SI). As expected, the ABR did
not change much upon reuse. Formation of the amide
consumes both acetic acid and monoethanolamine, so the
reaction would not significantly change the ABR. In a study
using the PILs pyrrolidinium acetate (a secondary amine) and
pyridinium acetate (a tertiary amine), the authors also reported
that the ABR ratio was unchanged at the end of the
pretreatment.41
Recycling of [MEA][OAc] with 0.5 ABR. To limit the
effect of PIL condensation into acetamide, we studied the
recycling of [MEA][OAc] with a 0.5 ABR, an excess base
solvent that should not favor the amide formation. The glucose
and hemicellulose saccharification yields for three uses is
shown in Figure 6. We observed that the yields remained stable
over the three uses. The acetamide content reached 30% by the
end of the third cycle. This confirms the assumption that
conversion into acetamide is a major driver of the efficiency
loss observed during recycling. We observed high saccha-
rification yields for pentose, yields that were similar to those
obtained with pure MEA. As shown earlier, MEA and the
excess base solutions are more selective in terms of
delignification, polysaccharide preservation and carbohydrate
digestibility.
Data for ABR changes during recycling were also collected
(Figure S18 in the SI). There was a small decrease in the ABR
after the first cycle, which was also observed at the end of the
single cycle ABR experiments. It is important to note that
suppression of acetamide formation with [MEA][OAc] is
essential to guarantee efficiency during recycling. Acetate-
based PILs tend to form acetamides with cations of primary
and secondary amines. When using tertiary amines, there is a
high chance the PIL has a low ionicity. In fact, tertiary amines
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Figure 6. Glucose (light green) and xylose/arabinose (dark green)
yields after 72 h of enzymatic saccharification for three consec-
utive pretreatment cycles with [MEA][OAc] with 0.5:1 ABR. A
pretreatment control with pure MEA (glucose yield, light purple;
xylose/arabinose yield, dark purple) is shown for comparison. The
acetamide content (purple line) was also plotted.
with acetic acid have been shown to form complex oligomeric
liquid systems of amine:acid in the range 1:2−3.45,46
Molar weight parameters for the lignin obtained in the
recycling experiments were also obtained (Table S5 in the SI).
Both Mw and Mn values decreased as recycling progressed.
However, since the decrease in Mw values was more
pronounced, the PD also decreased. Decreasing Mw values
can indicate harsher pretreatment conditions for acetate ILs,38
which is not the case when the pretreatment conditions were
kept constant. As previously mentioned, there is a drop in
delignification and cumulative lignin recovery along the cycles,
and lower Mn and Mw values may indicate a decrease in
delignification efficiency, with smaller lignin fragments being
released to the PIL solution during pretreatment with recycled
PIL. The rationale behind this is that PIL conversion into
acetamide depletes the ammonium cation in the medium, the
main source of interaction between lignin/cellulose and the
PIL containing mixture, therefore decreasing the permeability
of the catalyst; lignin deconstruction might then be limited to
the primary peeling reactions.47
■
CONCLUSIONS
In this study, pretreatment of bagasse with the low-cost protic
IL [MEA][OAc] and its corresponding acid−base mixtures
was investigated. We studied in detail the effect of the ABR on
pretreatment performance and solvent recovery. Low ABRs
and monoethanolamine provided the best performance, with
nearly quantitative glucose and pentose yield during
saccharification with ABR 0.1. We showed that up to 96%
glucose and up 85% hemicellulose (C5) sugar release can be
achieved at 150 °C in 2 h. Although the pretreatment time is
longer than hydrothermal pretreatment, the pretreatment here
was shown to be selective toward delignification (up to 84 wt
% with nearly 100% carbohydrate recovery). We observed a
solvent recovery up to 97% for the 1.0 ABR PIL and for
mixtures with excess base, however, solvent recovery decreased
significantly with increasing ABR, due to loss of acetic acid in
the evaporation steps. We found that pure MEA was corrosive
and reacted with the borosilicate present in the walls of the
glass tubes used as reaction vessels and the silicates present in
the ash of the biomass. Even though glass was not the best
materials choice for the pretreatment vessels, it revealed how
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ACS Sustainable Chemistry & Engineering
reactive/corrosive monoethanolamine solutions are during
pretreatment, and that using a PIL version of the amine can
provide key process benefits.
We also discovered that the PIL [MEA][OAc] partially
converted into an acetamide, and that the acetamide became
the dominant component in the 1.0 PIL. This shows that
acetate based PILs containing primary and secondary amines
are not inert when used for lignocellulose pretreatment. A
balance between lignin recovery, efficiency in saccharification,
and PIL mixture corrosivity and reactivity must be found in
order to make a [MEA][OAc] pretreatment process fully
operational and feasible.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.0c01311.
Additional results for the ABR experiments: degradation
products content in the liquid fractions, hydrolysis
residues, recovered lignins, Molar weight profiles of the
recovered lignins, elemental analysis data, XPS data, and
1 (1) Saini, J. K.; Saini, R.; Tewari, L. Lignocellulosic agriculture
H-NMR spectra of the recovered PIL mixtures;
additional results for the recycling experiments: PIL
recovery rates, ABR changes during PIL recycling, and
molar weight profiles of the recovered lignins after
recycling; 1H-NMR spectra of the synthesized PIL and
for acetamide; calculations for pulp yield, saccharifica-
tion yield, degree of delignification, lignin recovery,
ABR, and acetamide content; feedstock, pulp, and lignin
characterization (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Jason P. Hallett − Department of Chemical Engineering,
Imperial College London, London SW7 2AZ, United Kingdom;
orcid.org/0000-0003-3431-2371; Phone: +44 (0)20 7594
5388; Email: j.hallett@imperial.ac.uk
Authors
Pedro Y. S. Nakasu − Process and Products Development
Department, Faculty of Chemical Engineering, State University
of Campinas (UNICAMP), Campinas 13083-970, SP, Brazil;
Department of Chemical Engineering, Imperial College London,
London SW7 2AZ, United Kingdom
Coby J. Clarke − Department of Chemical Engineering, Imperial
College London, London SW7 2AZ, United Kingdom;
orcid.org/0000-0003-2698-3490
Sarita C. Rabelo − Department of Bioprocess and Biotechnology,
College of Agricultural Sciences, São Paulo State University
(UNESP), Botucatu 01049-010, SP, Brazil; orcid.org/
0000-0002-3153-7674
Aline C. Costa − Process and Products Development
Department, Faculty of Chemical Engineering, State University
of Campinas (UNICAMP), Campinas 13083-970, SP, Brazil
Agnieszka Brandt-Talbot − Department of Chemical
Engineering, Imperial College London, London SW7 2AZ,
United Kingdom
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c01311
7960
pubs.acs.org/journal/ascecg Research Article
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are thankful for the financial support from
FAPESP São Paulo Research Foundation [Grant Nos.
2015/14042-2, 2015/20630-4, 2016/06142-0, and 2017/
06116-1].
■ ABBREVIATIONS
ABR, acid base ratio; AFEX, ammonia fiber expansion; IL,
ionic liquid; PIL, protic ionic liquid; MEA, monoethanol-
amine; [MEA][OAc], monoethanolammonium acetate;
[EMIM][OAc], 1-ethyl-3-methylimidazolium acetate; [TEA]-
[HSO4], triethylammonium acetate
■
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