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Cellulose Dissolution and Biomass Pretreatment Using Quaternary

Ammonium Ionic Liquids Prepared from H-, G-, and S-Type Lignin-Derived
Benzaldehydes and Dimethyl Carbonate

Article  in  Industrial & Engineering Chemistry Research · May 2019

DOI: 10.1021/acs.iecr.9b00640

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Cite This: Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX pubs.acs.org/IECR

Cellulose Dissolution and Biomass Pretreatment Using Quaternary

Ammonium Ionic Liquids Prepared from H-, G-, and S‑Type Lignin-
Derived Benzaldehydes and Dimethyl Carbonate
Victoria Diez,† Andrew DeWeese,† Roland S. Kalb,‡ David N. Blauch,§ and Aaron M. Socha*,†
†
Department of Environmental Science and Chemistry, Queens University of Charlotte, 1900 Selwyn Avenue, Charlotte, North
Carolina 28207, United States
‡
Proionic, GmbH, Parkring 18, A-8074 Grambach, Austria
§
Department of Chemistry, Davidson College, 405 North Main Street, Davidson, North Carolina 28035, United States
Downloaded by LAWRENCE BERKELEY NATL LABORATORY at 13:16:19:405 on May 31, 2019

*
S Supporting Information

ABSTRACT: The synthesis of novel benzyl alkylammonium

ionic liquids (IL) from starting materials derived from grass,
softwood, and hardwood lignin was performed using batch
reactor systems followed by facile methyl carbonate ion
from https://pubs.acs.org/doi/10.1021/acs.iecr.9b00640.

exchange chemistry. Approximately 90% yields of the ILs were

achieved over three synthetic steps, and all novel materials
were fully characterized by 1H and 13C nuclear magnetic
resonance spectroscopy and high-resolution mass spectrom-
etry. The structure−activity relationships of the lignin-derived
ILs were evaluated for their ability to dissolve microcrystalline
cellulose and convert switchgrass to fermentable sugars
(glucose and xylose). All ILs tested, including a 1:1:1 mixture
of ILs prepared from vanillin, syringaldehyde, and p-
anisaldehyde yielded 52−71% of the glucose and 50−71% of the xylose from the total amount of glucan and xylan available
in the raw feedstock. These data compared well to the yields obtained from switchgrass pretreatment with the IL, 1-ethyl-3-
methyl imidazolium acetate, which gave 71% of the glucose and 63% of the xylose from the total glucan and xylan in the raw
feedstock, respectively.

1. INTRODUCTION Because of lignin’s potential to provide diverse and versatile

Found in all vascular plant cell walls, lignin is a structurally
complex natural product representing the world’s most
abundant renewable source of aromatic carbon. There are
several major types of oxidatively generated linkages in the
lignin macromolecule,1 including β-aryl and phenolic ethers,
carbon−carbon bonds, and benzyl esters, phenylglycoside, and
acetal bonds between lignin and polysaccharides.2,3 Lignin
accounts for approximately 24−33, 19−28, and 15−25% of the
dry weights of softwood, hardwood, and grasses, respectively.4
Within these plant types, the phenylpropanoid monomeric
units comprising lignin macromolecules also vary in abundance
(Figure 1). Gymnosperms (e.g., softwoods such as pine and
spruce) have the most homogeneous lignin, with over 90%
being made of coniferyl alcohol (G-type lignin).5 Angiosperm
hardwood lignin, such as that of poplar, is made of
approximately 60% sinapyl alcohol (S-type lignin) and 40%
coniferyl alcohol.5 In addition to S- and G-type lignins, wild-
type grasses can contain 20−50% lignin as p-coumaryl alcohol
units (H-type lignin).6,7 The S/G/H lignin ratio of bioenergy
crops can now be genetically tuned, and modified lignin strains
often require lower pretreatment severities for cellulose
separation and subsequent conversion to fermentable sugars.8,9
feedstocks for materials science10 and organic synthesis,11
chemical and biological lignin depolymerization have been
studied extensively.12−15 Several oxidative lignin depolymeriza-
tion reviews16,17 and protocols specific to benzaldehyde
production18,19 include reactor design20 and purification
strategies.19−21 For example, yields of 2.4 mol % benzaldehyde
from alkali lignin,22 7.4 wt % 4-hydroxybenaldehyde, 14.8 wt %
3-methoxy-4-hydroxy benzaldehyde (vanillin), 8.9 wt % 3,5-
dimethoxy-4-hydroxybenzaldehyde (syringaldehyde) from
hardwood organosolv lignin,20 and 3.3 wt % syringaldehyde23
from eucalyptus kraft lignin have been reported. Because of the
commercial importance of vanillin in food and fragrances,
reports of lignin-derived vanillin have also appeared in
experimental reports from pulp mills24 and the Journal of
Chemical Education.25
Special Issue: Biorenewable Energy and Chemicals
Received: January 31, 2019
Revised: May 8, 2019
Accepted: May 16, 2019
Published: May 16, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.9b00640

Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 1. Monomers comprising lignin found in all grasses, softwoods, and hardwoods (left) and benzaldehyde oxidative depolymerization
products (right) used to prepare ILs in this study.
Scheme 1. Three-Step Synthesis of Lignin-Derived Ionic Liquids (10−12) from Methylated Lignin-Derived Benzaldehydes
To integrate all products of a biorefinery, we sought to
develop a “closed-loop” process similar to the γ-valerolactone
pretreatment strategy reported by Luterbacher et al.26 Instead
of γ-valerolactone as the pretreatment solvent, an alternative
strategy is to use low-cost, biobased ionic liquids (IL) derived
from lignin, hemicellulose, and/or amino acids.27−29 Ionic
liquids are defined as salts with loosely coordinated ions,
leading to solvents with melting points less than 100 °C and
negligible vapor pressures. Because of its favorable solvent
properties,30,31 1-ethyl-3-methyl-imidazolium acetate (EMIM
OAc, 1) can dissolve lignocellulosic biomass and is a well-
studied ionic liquid for biorefinery applications. Though
effective, IL pretreatment is resource-intensive.32 At a cost of
U.S. $20/kg, imidazolium ILs must be efficiently recycled and
dried for biomass processes. The cost estimate range of lignin-
derived ILs is U.S. $5−15/kg.27
IL pretreatment of lignocellulosic biomass typically dissolves
hemicellulose and lignin so that a purified cellulose stream can
be recovered and easily hydrolyzed to monomeric sugars by
cellulase and hemicellulase enzymes. Biomass applications
using ionic liquids have recently been identified as a highly
active research area,33 and commercial processes involving
ionic liquids and biomass have evolved beyond lignocellulosic
feedstocks.34 The first lignin-derived ionic liquids were tertiary
amines prepared from the reductive amination of benzalde-
hydes and furfurals, which were subsequently protonated with
phosphoric acid.27,35 These protic ILs showed over 40 and
50% lignin and xylan removal, respectively,27 but because of
their acidic nature, they did not dissolve cellulose. While protic
ILs are useful in biorefining36,37 and are recoverable via
distillation,38 they are not typically able to dissolve cellulose.
Protic ILs formed from superbases, such as those containing
guanidine and amidine cations, can dissolve approximately 10
wt % cellulose.39
Our work is motivated by the utility of biobased ILs as
solvents for biopolymers, such as cellulose,40,41 lignin,42
chitin,43 and silk,44 and biopolymer applications, including
fiber welding.45 Most of these applications require the IL to
dissolve the biopolymer so that the latter can be regenerated in
a new form. ILs with high Kamlet−Taft β values are
considered to be Brønsted bases and can accept a hydrogen
B DOI: 10.1021/acs.iecr.9b00640
Article
bond from cellulose hydroxyl groups, leading to its
solubilization46 and decrystallization.47 To a lesser extent,
cellulose dissolution depends on its degree of polymerization,
residence time, temperature, and concentration within the IL.
When holding the cation constant, it has been shown that
coordinating anions with greater hydrogen bond basicity have
a greater ability to dissolve cellulose, with a general trend of
diethylphosphate ≈ acetate > thioacetate > formate > chloride
> bromide.48 It is hypothesized that lignin-derived aprotic ILs
with acetate anions will dissolve cellulose, hemicellulose, and
lignin.
To more thoroughly assess the cellulose dissolution and
biomass pretreatment abilities of quaternary ammonium ILs
prepared from lignin-derived benzaldehydes, a structure−
activity study is presented using three prototypical products
of lignin oxidation: p-anisaldehyde, vanillin, and syringalde-
hyde. These feedstocks underwent reductive amination as
previously reported and were subsequently N-methylated using
dimethyl carbonate (Scheme 1). The carbonate-based ionic
liquid synthesis (CBILS) process was pioneered at Proionic,
GmbH in 2005 and today is used to produce ILs on the 100
ton scale annually.49 As compared to traditional ionic liquid
syntheses, carbonate-based IL chemistry runs in closed loops
and produces no waste or corrosive halogens in the final
product, and the ion exchange step proceeds with quantitative
yields due to the strong thermodynamic equilibrium resulting
from the loss of CO2.50 With lignin-derived quaternary
ammonium methyl carbonate “platform ILs” in hand, facile
ion exchange reactions were used to provide the corresponding
acetate ILs. We herein report the results of cellulose
dissolution and switchgrass pretreatment using these novel,
lignin-based, quaternary benzylammonium acetate ionic liquids
in direct comparison to EMIM OAc.
2. EXPERIMENTAL SECTION
2.1. Materials. All chemicals were purchased from Sigma-
Aldrich (97% pure or greater) and used without additional
purification unless otherwise stated. N,N-Dimethylbenzylamine
(≥99% pure) was used to prepare the trimethyl benzylammo-
nium methyl carbonate (5). Dimethyl carbonate was ≥99%
pure. Acetonitrile (Acros, 99.8% pure) was dried with 4 Å
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
molecular sieves. Avicel PH-101 cellulose (50 μm particle size)
was used for cellulose dissolution experiments. 1-Ethyl-3-
methyl-imidazolium acetate was prepared from 1-ethyl-3-
methyl-imidazolium methyl carbonate (30 wt % in methanol,
Proionic, GmbH) by adding 1 mol equiv of acetic acid and
allowing to stir for 30 min before removing methanol in vacuo.
A 600 mL Parr reactor vessel (Parr Instrument Company,
Moline, IL) was used to perform reductive amination
reactions. CBILS reactions, IL melting-point analysis, cellulose
dissolution, and biomass pretreatment experiments were
separately performed in 15 mL (25.4 mm OD x 11.9 cm
long) #15 Ace-thread pressure tubes with 4845 front-seal plugs
(Ace Glass). The tubes were temperature controlled using a
Fisher Isotemp stirring hot plate by placing in 5 cm × 5 cm ×
15 cm aluminum blocks drilled with three 2.5 cm deep × 2.6
cm diameter holes for the pressure tube and a 2.5 cm deep × 5
mm diameter hole for the thermoresistor.
2.2. Instrumental Methods. Nuclear magnetic resonance
(NMR) spectroscopy was performed on a Bruker AVANCE III
HD spectrometer at frequencies of 400 MHz for 1H and 100
MHz for 13C. Samples dissolved in D2O contained acetone as
an internal standard. 1H and 13C chemical shifts were
referenced to the acetone CH3 signals at 2.22 and 30.89
ppm, respectively. For samples dissolved in CDCl3, 1H
chemical shifts were referenced to the residual proton signal
at 7.26 ppm and 13C chemical shifts were referenced to the
solvent signal at 77.16 ppm.51 High-resolution mass spectrom-
etry (HR-MS) was performed on an Agilent accurate-mass
6520B Q-TOF mass spectrometer operating in positive-ion
mode with 3500 V capillary and 120 V fragmenter voltages.
The dual-spray electrospray ionization source was operated at
a nebulizer pressure of 40 psi and a 12 L/min flow of N2 drying
gas at 340 °C. The Agilent ESI-L tuning mix was used for
calibration, and the ESI source continuously introduced a
reference solution containing ammonium trifluoroacetate,
purine ([M + H]+ 121.0509), and hexakis (1H,1H,3H-
tetrafluoropropoxy)phosphazine ([M + H]+ 922.0098) during
measurements. Samples were dissolved in methanol or water
and introduced into the ion source by flow injection analysis
using a 50/50 mixture of methanol and 0.1% formic acid
flowing at 0.300 mL/min. GC/MS was performed on dimethyl
benzylamines using a Thermo Trace 1300/ITQ 900 instru-
ment with a Thermo TG-SQC column (30 m, 25 mm, 0.25
μm) and a 15 °C/min temperature ramp from 75 °C (hold for
3 min) to 190 °C (hold for 2 min). The retention time of
starting benzaldehydes was approximately 11.0 min, and that of
dimethyl benzylamine products was approximately 11.4 min.
HPLC was performed on CBILS reactions using a Shimadzu
UFLC instrument with an SPD-M20A diode array detector
using a mobile phase (1 mL/min) gradient of 15−65%
methanol in water + 0.1% TFA in 12.0 min using a Restek
Ultra C18 column (5 μm, 250 mm × 4.6 mm) with the
column oven set at 40 °C. The retention time of starting
dimethyl benzylamines was approximately 6.5 min, and that of
trimethyl benzylammonium products was approximately 6.3
min. Thin layer chromatography (TLC) was performed on
Grace Reveleris aluminum-backed normal phase TLC plates
using a mobile phase of 2:1 hexane/EtOAc (+1% dihexylamine
buffer) for dimethyl benzylamines and 4:2:1 hexane/EtOAc/
methanol (+1% dihexylamine buffer) as the mobile phase for
dimethyl benzylammonium methyl carbonates. Citrate buffer
(0.1 M ) was prepared to pH 5.2 in a 1.0 L volumetric flask
with 18.0 g of sodium citrate and 3.7 g of citric acid and used
C DOI: 10.1021/acs.iecr.9b00640
Article
to prepare enzyme cocktails and dilute enzymatic saccha-
rification reactions.
2.3. Reductive Amination of Lignin-Derived Benzal-
dehydes to Dimethyl Benzylamines (2−4). Example
protocol: 4-methoxybenzaldehyde (p-anisaldehyde, 12.00 g,
88.14 mmol, 1.0 equiv) and sodium triacetoxyborohydride
(26.15 g, 123.39 mmol, 1.4 equiv) were dissolved in 294 mL of
anhydrous MeCN and added to the reactor vessel with stirring
at 200 rpm. At 33 °C, the vessel was evacuated to a pressure of
400 Torr and then filled to atmospheric pressure (760 Torr)
with dimethylamine. This cycle was repeated four additional
times. The cylinder of dimethylamine was situated on a scale
during this procedure to ensure MeCN and the reactor
headspace contained at least 1.2 equiv of dimethylamine (4.77
g, 105.77 mmol). The reactor was heated to 50 °C and allowed
to stir for 20 h. The reaction was quenched with approximately
200 mL of DI water, acidified to pH 1.8 with 4 M HCl, and
placed under reduced pressure to remove MeCN. The
remaining aqueous mixture was extracted with 3 × 75 mL of
methyl-tert-butyl ether (MTBE) before the pH was increased
to 11.1 with 4 M KOH. The latter was extracted with 2 × 75
mL of MTBE and dried over MgSO4. Solvent was removed
under reduced pressure to yield 1-(4-methoxyphenyl)-N,N-
dimethylmethanamine (2) as an amber, nonviscous oil (13.30
g, 80.49 mmol, 91.3% yield). TLC: Rf of starting material/
product = 0.6/0.2.
2.4. CBILS of Trimethyl Benzylammonium Methyl
Carbonates (5−8) from Dimethyl Benzylamines (2−4)
and Dimethyl Benzylamines. Example protocol: Com-
pound 2 (1-(4-methoxyphenyl)-N,N-dimethylmethanamine,
5.00 g, 30.26 mmol, 1.0 equiv) was dissolved in 4.68 g of
methanol, and dimethyl carbonate (4.36 g, 48.42 mmol, 1.6
equiv) was added. The reaction mixture was sparged with N2
and then heated in an aluminum block to 140 °C for 16−24 h
in a pressure tube. The reaction was monitored by HPLC, and
upon complete disappearance of the starting material,
methanol and residual dimethyl carbonate were removed
under reduced pressure to yield 1-(4-methoxyphenyl)-N,N,N-
trimethylmethanaminium (6) as a white crystalline solid (7.61
g, 29.81 mol, 98.5%). TLC: Rf of starting material/product =
0.9/0.1.
2.5. Ion Exchange of Trimethyl Benzylammonium
Methyl Carbonates to Trimethyl Benzylammonium
Acetate Ionic Liquids. Example protocol: Compound 6 (1-
(4-methoxyphenyl)-N,N,N-trimethylmethanaminium, 5.00 g,
19.58 mmol, 1.00 equiv) was dissolved in 5 mL of methanol,
and glacial acetic acid (99.9% pure, 1.177 g, 19.58 mmol, 1.00
equiv) was added dropwise while stirring at room temperature.
After 1 h or the complete evolution of CO2, methanol was
removed under reduced pressure (0.3 Torr) at 75 °C to yield
10 as a light-pink crystalline solid (4.68 g, 19.58 mmol, 99.9%).
2.6. Cellulose Dissolution. Example protocol: Compound
10 (536 mg) was added to a 15 mL pressure tube and heated
in a temperature-controlled aluminum block. Once the melting
point was reached (130 °C), 20 mg of Avicel cellulose was
added. Constant temperature was maintained throughout the
experiment, and 10 mg aliquots of cellulose were added every
5−10 min until saturation was observed. Table 1 summarizes
the melting points of each IL, which is also the temperature
studied for cellulose dissolution, and the observed cellulose
solubility limits. Experiments were conducted in triplicate, and
average weight percentages and standard deviations are shown.
Compound 1 is a liquid at room temperature, but cellulose
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Table 1. Cellulose Dissolution Experiments with Acetate ILs
IL temp (°C) cellulose solubility (wt %) standard deviation
1 100 15
9 115 9 0.87
10 130 10
11 100 4 0.38
12 110 3 0.75
dissolution experiments were conducted at 100 °C to approach
the temperatures used to test cellulose dissolution with lignin-
derived ILs.
2.7. Biomass Pretreatment. Switchgrass (SG) was
obtained from Lawrence Berkeley National Laboratory and
found to be 33.5% glucan, 24.1% xylan, 5.3% arabinan, and
13.8% lignin as determined by the NREL method for
determining structural carbohydrates in biomass.52 Dry
switchgrass (400 mg) was mixed with 3.6 g of IL and 0.4
mL of water to give 10 wt % biomass loading in 15 mL glass
pressure tubes. All pretreatment reactions were run in
duplicate, and an EMIM OAc (1) positive control was run
in triplicate. Tubular reactors were placed vertically in
aluminum blocks and held at 160 °C for 3 h in a Thermo
Heratherm laboratory oven without stirring. After pretreat-
ment, the reactors were allowed to cool to room temperature.
The mixture of IL, water, and pretreated biomass was
transferred to a 50 mL falcon tube using DI water to a final
volume of 45 mL and then centrifuged (22 °C, 5000 rpm, 15
min) to separate the solid and liquid phases. The solid fraction
was sequentially washed and centrifuged with 40 mL of
methanol, 3 × 40 mL of water (70 °C), and 40 mL of 0.1 M
citrate buffer (pH 5.2) to remove any residual IL and/or
sugars. Washed solids were either stored at 4 °C for 48 h or
used directly in enzymatic saccharification. The water negative
control used 400 mg of SG and 4.0 mL of water and was held
at 160 °C for 3 h. The 1:1:1 combined IL sample used 400 mg
of SG with 1.27 g of 10, 1.20 g of 11, 1.23 g of 12, and 0.4 mL
of water.
2.8. Mass Balance. Following pretreatment with com-
pounds 1, 9, and 11, washed solids were dried in the laboratory
oven (105 °C, 18 h) and weighed to determine the percent
solid recovery. A mass balance was then performed using
standard analytical methods.52 To determine the extent of
cellulose, hemicellulose, and lignin removal after IL pretreat-
ments, the recovered biomass was subjected to 72% H2SO4
hydrolysis (30 °C, 60 min, 200 rpm stirring) followed by 4%
H2SO4 hydrolysis (121 °C, 60 min, autoclave). The samples
were filtered to quantify acid-insoluble lignin content and then
subjected to HPLC (as described in Section 2.9) to quantify
glucan and xylan contents. Lignin, glucan, and xylan
concentrations were compared to compositional analysis values
Table 2. Compositional Analysis of Switchgrass after Pretreatment with Selected Ionic Liquids As Compared to the
Nonpretreated Switchgrass (SG) Controla
IL pretreatment solid recovery, % glucan, %
1 51.2 ± 1.5 46.0 ± 1.8
9 46.4 ± 1.2 49.5 ± 0.6
11 60.5 ± 3.5 42.0 ± 0.2
untreated SG N/A 33.5 ± 0.5
a
± = standard deviation.
Article
from nonpretreated switchgrass, and the results are presented
in Table 2.
2.9. Enzymatic Saccharification. Enzymatic saccharifica-
1.50 tion reactions were conducted on the individual pretreated
samples and water negative control following NREL LAP 9
0.35 “Enzymatic Saccharification of Lignocellulosic Biomass”. After
the final centrifugation cycle, the washed and decanted
biomass was suspended in 4.0 mL of citrate buffer
(approximately 10% solids loading for the original 400 mg of
biomass sample) and transferred to 15 mL falcon tubes. The
CTec2 cellulase enzyme blend (1.5 g, Sigma-Aldrich product
number SAE0020) and 225 mg of hemicellulase enzymes from
Aspergillus niger (Sigma-Aldrich product number H2125) were
diluted in 0.1 M citrate buffer to a final volume of 10.0 mL.
From the enzyme solution described above, 100 μL was added
to each saccharification experiment to achieve approximate
cellulase and hemicellulase concentrations of 125 mg/g of
glucan and 25 mg/g of xylan, respectively. Saccharifications
were placed horizontally on a Thermo Scientific Compact
Digital Mini Rotator inside a Fisher Scientific Isotherm
incubator and allowed to incubate (50 °C) with gentle mixing
(100 rpm). Aliquots of supernatant (1.0 mL) were sampled at
48 and 70 h, centrifuged (14 700 rpm, 5 min, 23 °C), and
directly analyzed by HPLC for monosaccharide content as
described previously.53 Briefly, sugars were detected by the
refractive index using a Biorad Aminex 87-P column (300 ×
7.8 mm) with 100% water as the mobile phase. Five-point
calibration curves of glucose and xylose each had an R2 value of
0.99. The glucose and xylose yields presented in Figure 3 were
calculated from the maximum possible glucan (e.g., 134.0 mg)
and xylan (e.g., 96.4 mg) in 400 mg of raw (untreated)
biomass.
3. RESULTS AND DISCUSSION
3.1. Synthesis, NMR, and Mass Spectra of ILs. The
quaternization of amines 2−4 to yield methyl carbonates 6−8
results in the expected downfield shifts in the 1H NMR spectra
owing to the strong diamagnetic effect of creating a positive
charge on the amine nitrogen, while losing the nitrogen lone
pair. This downfield shift is strongest (Δδ 1.07 and 0.86 ppm)
for the α methylene protons and α methyl protons,
respectively. NMR spectra of the free amines (2−4) and
ionic liquids (5−12) were obtained in CDCl3 and D2O,
respectively, owing to solubility considerations. For a wide
range of compounds, changing solvents from CDCl3 to D2O
results in less than a ±0.2 ppm change in the chemical shift.51
The observed downfield shift of the α CH2 and CH3 sites
resulting from quaternization is larger than the expected
solvent effect. Downfield shifts for the benzene ring and
methoxy groups are smaller and cannot be reliably
distinguished from the solvent effects.
xylan, % arabinan % lignin, % xylan removal, % lignin removal, %
20.8 ± 2.0 4.7 ± 0.4 14.8 ± 0.1 51.3 ± 0.8 44.5 ± 1.1
25.3 ± 0.1 3.2 ± 0.1 13.6 ± 0.4 51.0 ± 0.1 57.5 ± 1.3
27.9 ± 0.3 4.5 ± 0.1 17.3 ± 1.4 23.3 ± 0.5 24.1 ± 6.6
24.1 ± 1.5 5.3 ± 0.2 13.8 ± 0.4 N/A N/A
D DOI: 10.1021/acs.iecr.9b00640
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
1
H NMR spectra for 5−8 show no signals for the anion,
while the only anion signal in the 13C spectra appears at 161.0
ppm. NMR spectra of potassium methyl carbonate in D2O are
reported to show 1H peaks at 2.86 ppm and 13C peaks at 53.2
and 160.2 ppm.54 For 5−8, the chemical shifts for the
N(CH3)3 13C peaks are nearly identical to the expected
location of the methyl carbonate CH3 signal. However, the 1H
spectra for 5−8 show no peaks near 2.86 ppm that would be
consistent for the methyl carbonate CH3 group (Supporting
Information). The 13C chemical shift for NH4HCO3 in D2O
has been reported at 160.87 ppm55 and that for NaHCO3 has
been reported at 161.20 ppm56 and 160.4 ppm.54 The
observed peak at 161.0 ppm for 5−8 is consistent with
hydrogen carbonate, but the methyl carbonate and carbonate
ions also show signals close to this position. On the basis of the
NMR data, it seems possible that reaction or workup
conditions for 5−8 led to the hydrolysis of the methyl
carbonate ion to the hydrogen carbonate ion.
Ion-exchanged ionic liquids (9−12) show the expected 1H
and 13C signals for the acetate ion at 1.91 (CH3), 23.90 (CH3),
and 181.93 (COO) ppm as well as the absence of the 13C peak
at 161.0 ppm. All ionic liquids showed good purity by NMR
with the exception of 12, which contains residual acetic acid
from the ion-exchange process. For this compound, the
“acetate” CH3 1H signal integrates to 4H instead of the
expected 3H, indicating 25 mol % or 6% (w/w) acetic acid in
the sample. As a solute in D2O, the acetate ion and acetic acid
will rapidly exchange hydrogen ions, leading to a single NMR
signal for the CH3 site. The acetate signal is observed at 1.91
ppm (9−11), and the reported chemical shift for acetic acid is
2.08 ppm.51 For 25 mol % acetic acid, the methyl 1H signal is
predicted to be 1.95 ppm; the observed chemical shift for 12 is
1.95 ppm.
ESI mass spectra of amines 2−4 displayed signals for the
protonated amine, [M + H]+, while quaternary amines 5−8
and 9−12 gave signals for the M+ cation. The m/z values and
isotopic distributions were in good agreement with the
expected chemical formulas. Attempts to prepare longer-
chain amines (i.e., N,N-diethyl, N,N-dipropyl, and N,N-
dihexyl) by reductive amination were successful, but these
tertiary benzylamines decomposed by Hoffman elimination
reactions upon attempting N-methylation with dimethyl
carbonate at 120−140 °C (MS data not shown). In our
hands, N-ethylation with diethyl carbonate was also
unsuccessful because of a lack of reactivity. Our previous
results showed the importance of phenol methylation on
protic, lignin-derived cations.27 While the free phenols were
not tested in this study of quaternary alkylammonium acetate
salts, it is noteworthy that dimethyl carbonate has been
reported as a “greener” alternative to dimethyl sulfate for the
O-methylation of eugenol and vanillin.57
Figure 2. Ionic liquids evaluated in this study.
E DOI: 10.1021/acs.iecr.9b00640
Article
3.2. Cellulose Dissolution. Cellulose dissolution experi-
ments showed that lignin-derived aprotic ILs, at their melting
points, can dissolve microcrystalline cellulose (Avicel) between
3 and 10 wt %. Compounds 9 and 10, derived from
benzaldehyde and 4-methoxybenzaldehyde, respectively,
showed the highest melting points and highest cellulose
dissolution. Compound 10 dissolved 10 wt % cellulose, and
saturation was observed upon increasing the cellulose
concentration to 11.6 wt %. As compared to 9 and 10,
compounds 11 and 12 showed the swelling of the cellulose
particles but less dissolution. When raising the temperature to
130 °C in cellulose dissolution experiments with 11, the
cellulose solubility did not increase beyond 5%. Therefore, it
seems that cation structure is more critical than temperature
for cellulose dissolution in this aprotic, lignin-derived IL. It
appears that increasing the degree of methoxylation decreases
the cellulose solubility in these lignin-derived IL cations.
In contrast to previously reported biomass pretreatment
studies using protic ILs with the basic, coordinative acetate
anion38 and protic lignin-derived ILs with the acidic,
coordinative H2PO4− anion,27 the quaternary ammonium
compounds reported here carry the OAc− anion, and some
have the ability to dissolve cellulose. Protic ILs transfer a
proton from a Brønsted acid to a Brønsted base58 but typically
lack the requisite basicity to dissolve cellulose.59 However,
many protic ILs effectively pretreat biomass through their
ability to dissolve and remove lignin,38,27 which renders the
cellulose more accessible for enzymatic hydrolysis to
monomeric sugars.
3.3. Mass Balance. A mass balance was performed with
ILs 1, 9, and 11 using the aforementioned pretreatment
conditions and showed 51.2, 46.4, and 60.5% solids recovery,
respectively (Table 2). The data for 1 and the untreated
switchgrass controls were consistent with those previously
reported.27 Glucan represented 49.5% of the solids recovered
from pretreatment with 9 and 42.0% of the solids recovered
from pretreatment with 11. Compared to 33.5% glucan in the
untreated switchgrass, this represents 47.8 and 25.3% increases
in glucan for 9 and 11, respectively. As anticipated from their
solubilization in the ILs, the amounts of lignin and xylan
decreased in the pretreated biomass. Compounds 9 and 11
show 57.5 and 24.1% lignin removal, respectively. Xylan
removal was 51.0% for 9 and 23.3% for 11. Notably,
pretreatment with IL 11 provided slightly less glucan in the
recovered biomass and removed significantly less lignin and
xylan, as compared to 1 and 9. However, the higher solid
recovery after pretreatment with 11 led to glucose and xylose
yields comparable to those of 1 and 9 after enzymatic
saccharification (Figure 3).
3.4. Biomass Pretreatment and Enzymatic Saccha-
rification. Overall, the lignin-derived ILs (9−12) performed
well, as compared to EMIM OAc (1), in terms of both glucose
and xylose yields (Figure 3). After pretreatment at 160 °C for 3
h followed by enzymatic saccharification, EMIM acetate
pretreatment provided 71% of the total possible glucose and
63% of the total possible xylose from raw switchgrass.
Trimethyl benzylammonium acetate (9) and the trimethyl
benzylammonium IL derived from vanillin (11) gave
comparable results with glucose yields of 69 and 70% and
xylose yields of 71 and 67%, respectively. The IL derived from
p-anisaldehyde (10) gave a glucose yield of 64% and a xylose
yield of 62%, and the IL derived from syringaldehyde (12)
gave the lowest glucose and xylose yields of any of the ILs
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 3. Glucose and xylose yields obtained after pretreatment and
70 h of enzymatic saccharification of switchgrass using individual
lignin-derived ILs (9-12), a 1:1:1 mixture of 10:11:12, and EMIM
OAc (1).
tested. The decreased ability to dissolve cellulose and pretreat
switchgrass, as observed in 12, is most likely due to the 25%
molar excess of acetic acid, as described in Section 3.1.
Interestingly, lignin-derived ILs 9 and 11 had higher xylose
yields as compared to 1, and this could result from greater
lignin removal by 9 and lesser xylan removal by 11.
An experiment using a 1:1:1 mixture (by mass) of 10:11:12
gave 62% glucose and 61% xylose yields. While the glucose
yields obtained by pretreatment with these quaternary
ammonium ILs are slightly lower than those reported using
protic lignin-derived ILs,27 it is likely due to the fact that the
sugar yields reported from the protic ILs were calculated from
the total possible glucose available from glucan in the
pretreated biomass. In the current work, the glucose yields
were calculated on the basis of the total amount of glucan
available in the untreated switchgrass. This assumption is
corroborated by the fact that switchgrass pretreated with
EMIM OAc also gave decreased glucose yields as compared to
previous results,27,28 which were calculated on the basis of the
total glucan available after pretreatment. The water-pretreated
switchgrass control gave 32% glucose and 20% xylose yields,
which represents a 1.60-fold-higher yield of glucose as
compared to that of xylose. The IL-pretreated samples gave
an average of 1.04-fold higher glucose than xylose, also
indicating that some glucan was lost during pretreatment.
Glucose and xylose yields were quantified at 48 h of enzyme
incubation and were approximately 4−6% lower for all ILs as
compared to respective yields after 70 h. There was no
statistical difference among the ILs tested. These data indicate
that the enzymatic hydrolysis rate reached a maximum in the
first 48 h. To compare glucose yields to those observed after
pretreatment with aprotic lignin-derived ILs,27 glucose yields
for ILs 1, 9, and 11 were also calculated from glucan recovery
(Table 2). As expected, glucose yields were found to be 97%
for 1, 94% for 9, and 95% for 11. Standard deviations for the
aforementioned monosaccharide yields were between 2 and
7%.
F DOI: 10.1021/acs.iecr.9b00640
Article
4. CONCLUSIONS
A series of novel quaternary ammonium ILs were synthesized
in high purity and high yield over three steps from
benzaldehydes derived from H-, G-, and S-type lignin. The
lignin-derived ILs prepared in this study showed the ability to
dissolve cellulose up to 10 wt % and pretreat biomass as
effectively as 1-ethyl-3-methyl imidazolium acetate for the
production of fermentable sugars (glucose and xylose). A
structure−activity relationship was observed whereby increas-
ing the methoxylation of the cation led to decreased
biopolymer solubility. This phenomenon was studied in
cellulose dissolution experiments of ILs 9−12, and observed
through lignin and xylan removal in mass balance experiments
with 9 and 11. The trend in cellulose dissolution did not
accurately predict the pretreatment efficacy, with the most
notable differences being with IL 11, derived from vanillin.
This compound showed only 4% cellulose dissolution but
provided the highest glucose yields of any lignin-derived ILs
(70%), as compared to that of 1 (71%). This finding is likely
due to the fact that 11 gave higher solids recovery and
comparable glucan recovery as compared to the other ILs
examined in mass balance experiments.
It is well known that IL viscosities can be lowered by
optimizing the N-alkyl chain length, branching, degree of
unsaturation,60 and incorporation of the ether functionality.
Future studies will be aimed at preparing lignin-derived ILs
with lower viscosities by generating asymmetry via N-alkyl
substituents. To fully investigate the properties, pretreatment
mechanisms of action, and the overall utility of these new
lignin-derived ILs, Kamlet−Taft measurements, spectroscopic
studies including NMR of recovered lignin, and X-ray
diffraction along with glycome profiling of pretreated biomass
are warranted.
5. SPECTRAL DATA
Compound 1 (1-ethyl-3-methyl-imidazolium acetate) clear
liquid. 1H NMR: 1.49 (3H, t, J = 7.3 Hz), 1.90 (3H, s), 3.89
(3H, s), 4.22 (2H, q, J = 7.3 Hz), 7.42 (1H, s), 7.49 (1H, s),
8.72 (1H, s). 13C NMR: 15.09, 23.77, 36.19, 45.38, 122.48,
124.06, 136.18, 181.48. HR-MS: [C6H11N2]+, found 111.0919,
calcd 111.0917, Δ = 2 ppm.
Compound 2 (1-(4-methoxyphenyl)-N,N-dimethylmethan-
amine) clear liquid. 1H NMR: 2.22 (6H, s), 3.36 (2H, s), 3.78
(3H, s), 6.85 (2H, d), 7.21 (2H, d). 13C NMR: 45.19, 55.29,
63.72, 113.68, 130.39, 130.76, 158.82; HR-MS: M =
C10H15NO, [M + H]+, found 166.1225, calcd 166.1225, Δ =
0.6 ppm.
Compound 3 (1-(3,4-dimethoxyphenyl)-N,N-dimethyl-
methanamine) clear liquid. 1H NMR: 2.21 (6H, s), 3.35
(2H, s), 3.84 (3H, s), 3.86 (3H, s), 6.78 (2H, s), 6.87 (1H, s).
13
C NMR: 45.25, 55.92, 64.18, 110.75, 112.12, 121.31, 131.28,
148.20, 148.97. HR-MS: C11H17NO2, [M + H]+, found
196.1328, calcd 196.1332, Δ = 2 ppm.
Compound 4 (N,N-dimethyl-1-(3,4,5-trimethoxyphenyl)-
methanamine) clear liquid. 1H NMR: 2.24 (6H, s), 3.35
(2H, s), 3.82 (3H, s), 3.84 (6H, s), 6.54 (2H, s); 13C NMR:
45.43, 56.19, 60.92, 64.77, 105.84, 134.50, 137.03, 153.19; HR-
MS: C12H19NO3, [M + H]+, found 226.1435, calcd 226.1438,
Δ = 1 ppm.
Compound 5 (N,N,N-trimethyl-1-phenylmethanaminium
methyl carbonate) clear liquid. 1H NMR: 3.10 (9H, s), 3.35
(2H, s), 4.48 (2H, s), 7.6 (5H, m). 13C NMR: 53.97 (t, J = 16
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Hz), 70.23 (t, J = 10 Hz), 128.02, 129.81, 131.46, 133.43,
160.94. HR-MS: [C10H16N]+, found 150.1276, calcd 150.1277,
Δ = 0.7 ppm.
Compound 6 (1-(4-methoxyphenyl)-N,N,N-trimethyl-
methanaminium methyl carbonate) clear liquid. 1H NMR:
3.06 (9H, s), 3.35 (2H, s), 3.87 (3H, s), 4.42 (2H, s), 7.10
(2H, d, J = 8.2 Hz), 7.49 (2H, d, J = 8.2 Hz). 13C NMR: 52.69
(t, J = 16 Hz), 56.11, 69.80 (t, J = 10 Hz), 115.15, 120.50,
134.98, 160.95, 161.36. HR-MS: [C11H18NO]+, found
180.1378, calcd 180.1383, Δ = 3 ppm.
Compound 7 (1-(3,4-dimethoxyphenyl)-N,N,N-trimethyl-
methanaminium methyl carbonate) clear liquid. 1H NMR:
3.08 (9H, s), 3.87 (3H, s), 3.88 (3H, s), 4.41 (2H, s), 7.1 (3H,
m). 13C NMR: 52.85 (t, J = 16 Hz), 56.35, 56.43, 70.15 (t, J =
10 Hz), 112.36, 116.18, 120.72, 127.07, 148.84, 150.70,
160.96. HR-MS: [C12H20NO2]+, found 210.1490, calcd
210.1489, Δ = 0.5 ppm.
Compound 8 (N,N,N-trimethyl-1-(3,4,5-trimethoxyphenyl)-
methanaminium methyl carbonate) clear liquid. 1H NMR:
3.12 (9H, s), 3.82 (3H, s), 3.89 (6H, s), 4.42 (2H, s), 6.86
(2H, s). 13C NMR: 53.14 (t, J = 16 Hz), 56.86, 61.58, 70.35,
111.02, 124.40, 139.25, 153.34, 160.97. HR-MS:
[C13H22NO3]+, found 240.1594, calcd 240.1594, Δ = 0 ppm.
Compound 9 (N,N,N-trimethyl-1-phenylmethanaminium
acetate) clear liquid. 1H NMR: 1.91 (3H, s), 3.10 (9H, s),
4.49 (2H, s), 7.6 (5H, m). 13C NMR: 23.87, 52.96 (t, J = 16
Hz), 70.22 (t, J = 10 Hz), 128.01, 129.81, 131.46, 133.42,
181.85. HR-MS: [C10H16N]+, found 150.1274, 150.1277, Δ =
2 ppm.
Compound 10 (1-(4-methoxyphenyl)-N,N,N-trimethyl-
methanaminium acetate) clear liquid. 1H NMR: 1.91 (3H,
s), 3.06 (9H, s), 3.87 (3H, s), 4.43 (2H, s), 7.10 (2H, d, J = 8.2
Hz), 7.49 (2H, d, J = 8.2 Hz). 13C NMR: 23.90, 52.69 (t, J =
16 Hz), 69.80 (t, J = 10 Hz), 115.16, 120.49, 134.98, 161.37,
181.93. HR-MS: [C11H18NO]+, found 180.1377, calcd
180.1383, Δ = 3 ppm.
Compound 11 (1-(3,4-dimethoxyphenyl)-N,N,N-trimethyl-
methanaminium acetate) clear liquid. 1H NMR: 1.91 (3H, s),
3.08 (9H, s), 3.88 (3H, s), 3.90 (3H, s), 4.42 (2H, s), 7.1 (3H,
m). 13C NMR: 23.89, 52.84 (t, J = 16 Hz), 56.38, 56.47, 70.15
(t, J = 10 Hz), 112.41, 116.27, 120.77, 127.10, 148.87, 150.74,
182.02. HR-MS: [C12H11NO2]+, found 210.1489, calcd
210.1489, Δ = 0 ppm.
Compound 12 (N,N,N-trimethyl-1-(3,4,5-trimethoxy-
phenyl)methanaminium acetate) clear liquid. 1H NMR: 1.95
(4H, s), 3.12 (9H, s), 3.82 (3H, s), 3.89 (6H, s), 4.43 (2H, s),
6.87 (2H, s). 13C NMR: 23.19, 53.14 (t, J = 16 Hz), 56.86,
61.59, 70.35, 111.03, 124.40, 139.26, 153.35, 180.83. HR-MS:
[C13H22NO3]+, found 240.1596, calcd 240.1594, Δ = 1 ppm.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.9b00640.
EMIM acetate, 1H and 13C NMR spectra of compound
1; benzylammonium, 1H and 13C NMR spectra of
compounds 5 and 9; 4-methoxy benzylammonium, 1H
and 13C NMR spectra of compounds 2, 6, and 10; 3,4-
dimethoxy benzylammonium, 1H and 13C NMR spectra
of compounds 3, 7, and 11; 3,4,5-trimethoxy benzy-
lammonium, 1H and 13C NMR spectra of compounds 4,
8, and 12 (PDF)
G DOI: 10.1021/acs.iecr.9b00640
Article
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: sochaa@queens.edu.
ORCID
Roland S. Kalb: 0000-0002-8462-4317
Aaron M. Socha: 0000-0002-9976-3184
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The LCMS used for mass spectrometry was acquired through
an NSF-MRI grant (CHE-1624377) awarded to D.N.B.
Student support for this project was made possible by an
NSF-ATE grant (1601636) awarded to A.M.S. The authors
thank collaborators at Lawrence Berkeley National Laboratory
(Joint Bioenergy Institute) for the gift of switchgrass.
■ DEDICATION
This article is dedicated to Professor Yuzuru Shimizu.
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I DOI: 10.1021/acs.iecr.9b00640
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