Catalysis Today 223 (2014) 310

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Acid catalysed alcoholysis of wheat straw: Towards second

generation furan-derivatives
R.J.H. Grisel a, , J.C. van der Waal b , E. de Jong b , W.J.J. Huijgen a
a
b

Energy Research Centre of the Netherlands (ECN), Biomass & Energy Efciency, P.O. Box 1, 1755 ZG Petten, The Netherlands
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands

a r t i c l e

i n f o

Article history:
Received 9 January 2013
Received in revised form 30 May 2013
Accepted 1 July 2013
Available online 19 August 2013
Keywords:
Biomass
Wheat straw
Alcoholysis
Glucopyranoside
Glucoside
Furans

a b s t r a c t
The acid-catalysed alcoholysis of wheat straw has been studied in 95% methanol and 94% ethanol (w/w)
in the presence of various amounts of H2 SO4 and compared to the alcoholysis of wheat straw-derived
organosolv pulp and commercially available celluloses. Substrate liquefaction and the product distribution were found to depend mainly on the temperature and the amount of H2 SO4 added compared to the
acid neutralisation capacity (ANC) of the substrate. The process was optimised for the one-step conversion of wheat straw into methyl glucosides, dened as the sum of and anomers. The maximum total
methyl glucosides yield from wheat straw was 56 mol-% based on initial glucan after 120 min methanolysis at 175 C and 40 mM H2 SO4 . Concurrently, furfural was formed at 40 mol-% yield based on initial xylan.
The solid residue consisted of mainly acid insoluble (pseudo)lignin, humins and minerals. Switching to
ethanol resulted in a shift from glycosides to furfural, 5-(alkoxymethyl)-2-furfural and levulinates. Addition of MgCl2 , as well as substituting H2 SO4 by HCl led to poorer biomass liquefaction and lower glucosides
yield presumably due to consumption of protons under the typical reaction conditions. Alcoholysis of
delignied, cellulose-enriched pulp obtained via organosolv fractionation resulted in higher glucosides
yields and more concentrated product streams, as higher glucan loadings are possible and undesired
side-reactions are minimised. Furthermore, organosolv fractionation prior to alcoholysis allows for the
separation and valorisation of the lignin fraction. The glucosides can be separated, e.g. by means of chromatography, and may be converted into furan building blocks, for example for the production of plastic
precursors, such as 2,5-furandicarboxylic acid.
2013 Elsevier B.V. All rights reserved.

1. Introduction
A growing world population and its persistent drive for increasing the standard of living and the growing needs for mobility are
putting a large claim on the natural resources. It is commonly
believed that resources such as clean water, food, energy and raw
materials will become scarce in the foreseeable future. Worries
about running out of natural resources have been from all ages, but
has never led to insurmountable problems due to the adaptability and ingenuity of men. These days, declining known oil and gas
reserves are a major topic in international discussions. In the light
of anthropogenic global warming an obvious switch to alternative fossil carbon sources for energy production and petrochemical
building blocks is not recommendable.
In many instances, a petrochemical building block can be
substituted by natural alternatives. In this light, the U.S. Department of Energy published two reports identifying promising

Corresponding author. Tel.: +31 88 515 42 16.

E-mail address: grisel@ecn.nl (R.J.H. Grisel).
0920-5861/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2013.07.008

renewable building blocks that can be produced from biomass

sugars [1] and lignin [2]. Furan derivatives are considered to be
high-potential building blocks for bio-based fuels and polymers [1].
A key intermediate in the production of biomass-derived furans is
HMF (5-(hydroxymethyl)-2-furaldehyde) [3], which can be used
to produce, for example, 2,5-dimethylfuran (DMF) [4] and 2,5furandicarboxylic acid (FDCA) [5]. DMF is regarded as a potential
bio-gasoline [6] and FDCA can replace the petrochemical terephthalic acid, a precursor to the polyester PET, to make clothing and
plastic bottles [7].
HMF is an intermediate in the conversion of hexoses to levulinic acid and is produced in aqueous solution via acid-catalysed
dehydration of hexoses, such as fructose and glucose [812].
Herein, glucose rst needs to be converted to fructose by isomerisation. Under typical reaction conditions, the glucosefructose
isomerisation is rate-limiting, and HMF yields from fructose are
higher than starting from glucose [1113]. Addition of a base
is benecial for the production of HMF from glucose, by selectively accelerating the isomerisation reaction [8,14]. Increasing
the temperature will speed up both glucose isomerisation and
dehydration to form HMF, but even more the successive HMF

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

polymerisation and decomposition yielding levulinic and formic

acid [9].
Preferably, HMF is produced from non-edible natural resources,
such as cellulose. When starting from lignocellulosic biomass, such
as wheat straw or wood chips, or from cellulose the rst step
is depolymerisation. Typical aqueous acid hydrolysis methods for
producing HMF from (ligno)cellulose are based on high temperatures. Consequently, the rate of HMF degradation via hydrolysis
and polymerisation reactions is high and the yield is limited. In
short, HMF is not stable under the typical acidic conditions required
for its formation from cellulose or lignocellulosic biomass in water
and the maximum yield from d-glucose is typically below 30%
[8,11,15]. The yield can be improved by reactive extraction of HMF
in a non-aqueous phase, preventing HMF degradation by hydration
and subsequent decomposition. Fan et al. [13] reported a 68% yield
of HMF from glucose in aqueous methyl isobutyl ketone, using the
solid heteropoly acid salt Ag3 PW12 O40 .
Recently, organic solvents such as N,N-dimethylacetamide
(DMA) [11,13,16] and ionic liquids [11,1719] were shown to have
potential for the selective production of HMF from glucose and
cellulose, especially in the presence of a metal chloride catalyst.
Herein, the improved yields originate from improved cellulose solubility, enhanced glucosefructose isomerisation, repressed HMF
hydration, or a combination of those. The inuence of loosely ionpared halide ions, such as chloride, was explained by effective
hydrogen bond disruption within the solid thus enabling cellulose
hydrolysis at reduced temperatures, while simultaneously lowering HMF degradation. In DMA/LiCl, the maximum HMF yield from
cellulose was circa 30% in the presence of Zr(O)Cl2 or CrCl3 [16]. For
a combination of CrCl3 , HCl and LiBr in DMA/LiCl a maximum HMF
yield of 37% was reported [11]. In both cases, the presence of large
amounts of 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl] and
1-butyl-3-methylimidazolium ([BMIm]Cl) resulted in a HMF yield
increase to 5457%. A mixture of CuCl2 and CrCl2 in [EMIm]Cl
yielded a maximum HMF of 55% from cellulose after 8 h at 120 C
[19]. After 1 h at 140 C, maximum HMF yields of respectively 53%
and 42% were reported for cellulose and corn stover in CrCl3 and
HCl containing [EMIm]Cl [11]. While in pure ionic liquids HMF can
easily be produced from fructose using a variety of metal chlorides,
the production from glucose and polymers thereof seems to specifically require the presence of chromium chloride [17,18]. Next to
the environmental disadvantages of chromium salts, the high cost
of ionic liquids limits the industrial application of such solvents
systems.
Alternatively, in acidied methanol and ethanol hexosecontaining material can be converted into stable HMF ethers [20].
These ethers can be isolated and converted further into valuable
building blocks, such as FDCA [7,12]. Thus far, etherication of HMF
has been shown successful with good yield and selectivity starting from fructose [21]. Etherication starting from glucose remains
challenging. Within the national Dutch Catfur project, ECN, Avantium Technologies and Utrecht University cooperate to develop
glucose-based, second generation furan-derivatives. Herein, the
rst step is liquefaction of lignocellulosic biomass using short-chain
alcohols. Garves reported that the main products from the cellulose
fraction are alkyl glucosides or alkyl levulinates, depending on the
process conditions [22]. Under water-lean conditions the formation of levulinic acid and humins is reduced [23]. The suppression
of humins formation is a major benet in the economics of biomass
valorisation, since humins are typically considered suitable for lowvalue applications only, such as heat and power generation. It is
noteworthy that obtained alkylated sugars are highly soluble in
alcohol and may be further converted to yield the same HMF ethers
as from glucose and fructose.
Liquefaction of lignocellulosic biomass in alcohols results in
product streams that also contain solubilised lignin fractions and

hemicellulose derivatives. Their presence may lead to a loss of sugars due to undesired condensation reactions. Alternatively, prior
to alcoholysis the biomass can be fractionated. Organosolv fractionation enables separation of the three main constituents of
lignocellulosic biomass, viz. lignin, hemicellulose and cellulose
[24,25]. The pulp can be used for the production of alkyl glucosides, whereas the lignin and hemicelluloses can be valorised
separately. When performing alcoholysis on delignied pulp, undesired side-reactions are expected to be minimised, the sugar yields
increased and more concentrated product streams will be possible
compared to alcoholysis on the whole biomass. Whereas methanol
seems the solvent of choice in alcoholysis of hexose-containing
material, ethanol is interesting when starting with lignocellulosic
biomass, due to the higher lignin solubility [26]. Besides, ethanol
is considered less toxic and can easily be obtained from renewable
resources. Moreover, in acid catalysed alcoholysis at elevated temperature the use of ethanol is preferred over methanol because of
its lower tendency to form dialkylether [27].
Previously, H2 SO4 , HCl, and MgCl2 have been compared and
tested as catalyst in organosolv fractionation of wheat straw in
ethanol/water (60% ethanol, w/w) [25]. Herein, the effect of the
acid catalysts was found to be primarily due to their effect on the
pH of the organosolv liquor rather than the type of anion. H2 SO4 was
found to be a weaker acid than HCl in 60% (w/w) aqueous ethanol.
The use of MgCl2 was found to enhance fractionation and enzymatic digestibility of the resulting pulp, however, to a lesser extent
than both acid catalysts.
In this study cellulose containing material is processed in acidied methanol and ethanol, targeting maximum total glucosides
yields. Herein, no difference is made between the yields of the
and anomer of the glucosides; both anomers can be used simultaneously as precursor for the formation of furan-derivatives. The
effect of substrate, catalyst concentration, temperature and reaction time are studied, as well as the effect of HCl and MgCl2 addition.

2. Experimental
2.1. Materials
Wheat straw was selected as a representative lignocellulosic
biomass substrate, because it is an abundant agricultural residue in
Europe. The wheat straw used in this study was dried winter wheat
straw grown in the vicinity of Delftzijl, the Netherlands, and cut to
<2 cm pieces. The average moisture content was 8% (w/w) dry
biomass. The bulk composition of the wheat straw was: 8.4% water
extractives, 2.0% ethanol extractives, 36.9% glucan, 19.9% xylan,
1.9% arabinan, 0.7% galactan, 0.2% mannan, 0.1% rhamnan, 16.7%
acid-insoluble lignin, and 1.1% acid-soluble lignin. The ash content
was 6.1%. The elemental composition of the biomass was 44.3% carbon, 42,7% oxygen, 5.4% hydrogen, 2.2% silicium, 0.2% potassium,
0.2% calcium (other elements <0.1%) [25]. All percentages are based
on dry biomass weight. The straw was stored dry in closed bags at
room temperature until use. The material was used without further
treatment.
Cellulose-enriched lignocellulosic pulp (68.9%, w/w glucan;
7.9%, w/w xylan, 15.7%, w/w acid-insoluble lignin, and 0.4%, w/w
acid-soluble lignin) was obtained from organosolv pulping of wheat
straw [28]. For this, the wheat straw was mixed with 50% (w/w)
aqueous ethanol in a ratio of 10 L/kg dry biomass and the slurry
was heated to 210 C while being mixed. The reactor was kept
isothermal for 90 min and then cooled to below 40 C. After organosolv treatment, the product was ltered. The solid fraction was
washed with 50% (w/w) aqueous ethanol and dried in vacuo at
50 C. The pulp was stored in closed vessels until further use.
As lignin and hemicellulose-free reference samples Avicel PH-101

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

microcrystalline cellulose (50 m particle size) and -cellulose

(50500 m particle size distribution) were purchased from
SigmaAldrich and used without further purication.
Methanol (99.9%, w/w), ethanol (92.695.2%, w/w, average 94%,
w/w used in the calculations), H2 SO4 (98%, p.a.), HCl (32%, p.a.)
and MgCl2 6H2 O (p.a.) were all purchased from Merck and used
without further purication. Alkyl-glycosides used in the analysis standards were obtained from Carbosynth, Berkshire, UK, with
the exception of -ethyl-d-xylopyranoside. To be able to determine
the elution time of -ethyl-d-xylopyranoside, a mixture of and
-ethyl-xylosides was prepared by heating xylose in 94% (w/w)
ethanol containing 50 mM H2 SO4 to 70 C and injected onto the
corresponding column.
2.2. Alcoholysis process
2.2.1. Reactor set-up
Alcoholysis experiments were performed in two different
reactor types. Screening experiments on the effect of H2 SO4
concentration and the alcoholysis experiments with alternative
catalysts (HCl, MgCl2 ) or alternative substrates (organosolv pulp,
cellulose) were carried out in parallel 125 mL batch reactors (acid
digestion bomb type 4748, SS 316 with Teon liner, Parr Instrument Company, Moline, IL). The substrate was suspended in the
solvent and subsequently the catalyst or a mixture of catalysts was
added. The closed reactor vessels were placed in a heating block
(adapted RS600, Thermo Fisher Scientic, Rochford, UK) and the
block temperature was set to the desired temperature. The slurries
were stirred by a magnetic bar, located at the bottom of each vessel (1000 rpm). After 180 min the power to the heating blocks was
switched off and the reactors were cooled while kept in the blocks.
Time at temperature within 5 C of the set-point was estimated at
circa 30 min [25]. This reactor type is referred to as reactor A.
Screening experiments on the combined effect of temperature
and acid concentration, as well as the methyl-glucosides optimisation experiments were carried out in an autoclave reactor (0.5 L
Hastelloy Kiloclave, Bchi Glas Uster AG, CH). The substrate was
mixed with either 95% (w/w) methanol or 94% (w/w) ethanol, balance H2 O. Sulphuric acid was added in catalytic amounts. Under
agitation (100 rpm, propeller stirrer), the slurry was heated to reaction temperature and kept at this temperature for 30150 min. The
reactor was equipped with a standard sampling system consisting
of a Hastelloy dip tube with a 7 micron lter (Bchi Glas Uster AG,
CH) to allow sampling at temperature and pressure. The samples
were quenched in an ice-water cooled coil attached directly to the
dip tube. After reaction, the reactor was cooled actively to below
40 C in less than 30 min. This reactor type is referred to as reactor
B. Due to divergent heating and cooling transients of both reactors,
the results can only be compared within their series.
2.2.2. Screening experiments on the effect of acid dose,
temperature, and incubation time
The screening experiments on the effect of acid dose were carried out in reactor A with 6 g wheat straw (as received) in 45.6 g
methanol and 2.4 g H2 O obtaining 95% (w/w) methanol and a
liquid-to-solid ratio of 11.3 L/kg (dry weight). Subsequently various
amounts of H2 SO4 were added (050 mM). The block temperature
was set at 200 C. The effect of the acid concentration was studied in
terms of solvolysis performance and total glucosides yield. Herein,
the glucosides yield is the sum of -methyl-d-glucopyranoside and
-methyl-d-glucopyranoside anomers being produced.
The methanolysis yielding the highest glucosides yield was
repeated at 25 g wheat straw scale (as received) in reactor B 200 C
for 30 min. The solvent to substrate ratio was 11 L/kg (dry weight).
Additional experiments were carried out in which the reaction
temperature was varied between 160 and 200 C. The incubation

time and acid concentration were varied as well, thus taking into
account combined effects. The reaction conditions are summarised
in Table 1.
After cooling, the product was centrifuged and the liquid
was analysed with a combination of HPLC, HPAEC and GCMS
techniques as described in Section 2.3. The solid residue was
washed, dried and weighed to calculate the pulp yield or liquefaction efciency. The resulting pulps of the top-three performing
experiments in terms of glucosides yield were analysed for their
composition and the amount of non-converted glucan was determined according to the methods described in Section 2.3. Based
on the combined results of glucosides yield, pulp yield and pulp
composition, a set of process conditions was dened and taken as
the starting point for further optimisation to yield a maximum of
methyl glucosides from wheat straw.
2.2.3. Optimising glucosides yield
Based on the screening experiments a set of condition was
dened in terms of processing temperature, incubation time and
added acid dose. A set of optimisation experiments was carried
out in reactor B with 30 g wheat straw (as received) in 95% (w/w)
methanol (11 L/kg dry weight) at xed temperature, ranging from
175 to 190 C, and a H2 SO4 concentration, ranging from 25 to
40 mM. After 105 min at temperature the sampling line was ushed
with 5 mL and consequently a 5 mL sample was drained from the
reactor and quenched in ice water to stop the reaction and condense
the product mixture. This was repeated at a 15 min interval until
4 samples were isolated per set of conditions. The liquid samples
were analysed for methyl glucosides by HPAEC-PAD, as described
in Section 2.3. The set of conditions yielding the highest amount of
methyl glucosides in the sampling experiments were veried single
batch experiment, to eliminate possible effects of volume changes
and a different cooling transient as a result of the sampling in the
optimisation experiments.
2.2.4. Effect of ethanol and chloride
The usability of ethanol for the production of glucosides from
wheat straw was evaluated qualitatively by comparing the results
of ethanol alcoholysis at 200 C and 30 mM H2 SO4 with those
obtained after methanolysis under similar conditions. The effect of
chloride on the alcoholysis of wheat straw was tested by the addition of 50, 100 and 200 mM MgCl2 and, in a separate series replacing
30 mM H2 SO4 by 60 mM HCl. The MgCl2 experiments were carried
out in 95% (w/w) methanol at 180 C in the absence and presence of
H2 SO4 . The HCl experiments were performed in 94% (w/w) ethanol
at 200 C. All results were compared to a H2 SO4 reference.
2.3. Analyses
2.3.1. Summative composition of wheat straw and obtained solids
The ash content of the wheat straw was determined by calcination according to NREL/TP-510-42622 [29]. The elemental
composition was measured with an elemental analyser (Carlo Erba
Instruments FLASHEA1112, Wigan, UK) (C, H, N, and O), ion chromatography after bomb combustion (Cl), and inductively coupled
plasma atomic emission spectroscopy (ICP-AES) (other elements).
The further composition of the raw materials and obtained solid
residues, i.e. lignin, hemicellulose and cellulose, were analysed
using a modied hydrolysis protocol based on TAPPI methods T 222
and 249 [30]. In this, the solids were hydrolysed in subsequently
12 M H2 SO4 at 30 C for 1 h and 1.2 M at 100 C for 3 h. The amount
of solid residue, i.e. acid-insoluble lignin and ash, was determined
gravimetrically and the ash content herein was determined by calcination. The hydrolysate was analysed for acid-soluble lignin by
UVvis absorption spectroscopy at 205 nm and monomeric reducing sugars by HPAEC-PAD (see Section 2.3.2). In case of the wheat

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

Table 1
Glucan-based product yields after methanolysis of wheat straw.
Entry

Temperature ( C)

Incubation time (min)

H2 SO4 (mM)

Solid residue (wt-%)

Unconverted substrate and main product groups

Solid glucan (%)b

Glucosides (mol-%)c

Furans (mol-%)

Levulinates (mol-%)

1
2
3
4
5
6

200
200
200
200
200
200

30a
30a
30a
30a
30a
30a

10
20
30
40
50

84.2
72.8
33.7
14.9
15.5
20.1

96.8
96.0
61.7
6.0
1.6
0.1

0.0
0.2
23.3
37.7
d
d

0.0
0.1
0.7
7.1
3.0
2.5

0.0
0.0
0.7
15.3
26.4
40.4

7
8
9
10
11
12
13

200
200
180
180
170
160
160

30
60
60
120
120
120
120

30
30
30
30
50
50
150

15.1
18.0
29.5
22.9
20.3
32.6
22.4

6.0
d
d
28.4
15.9
d
d

41.0
29.2
35.2
43.9
44.4
30.6
33.2

6.2
3.0
d
2.9
3.3
d
d

18.6
26.4
d
7.0
12.6
d
d

a
b
c
d

Performed in reactor A: estimated time at temperature.

Unconverted glucan as percentage of glucan present in the wheat straw sample.
-Methyl-d-glucopyranoside/-methyl-d-glucopyranoside molar ratio 1.71.8.
Not analysed.

straw, the extractives were removed with two successive Soxhlet

extractions using water and ethanol according to NREL/TP-51042619 [29] prior to hydrolysis. The moisture content of the solid
samples was measured with a halogen moisture analyser (Mettler Toledo HR83, Columbus, OH). Unless otherwise indicated, all
mentioned solid masses are on dry weight basis.

2.3.2. Composition of alcoholysis liquors

The alcoholysis liquors were analysed for their acidity and
content of glycosides, monomeric reducing sugars, sugar dehydration products, and organic acids. Analysis of the alpha
and beta anomers of the glucosides (alkyl-d-glucopyranosides)
and xylosides (alkyl-d-xylopyranoside) was performed with
High Performance Anion Exchange Chromatography with Pulsed
Amperometric Detection (HPAEC-PAD, ICS3000, Dionex, Sunnyvale, CA) equipped with a CarboPac MA1 column and a post
column addition of 0.3 mL/min 0.25 M NaOH. A gradient of NaOH
was used as eluent (0.25 mL/min): 50 mM (05 min), increasing
from 50 to 425 mM (537.5 min), increasing from 425 to 800 mM
(37.540 min), 800 mM (4060 min), and decreasing from 800 to
50 mM (6062 min), 50 mM (6270 min). With this set-up it was
not possible to completely separate ethyl--glucopyranoside and
ethyl--xylopyranoside. Due to the low yields of xylopyranosides
in ethanol alcoholysis, the error made herein is small.
Analysis of monomeric sugars was performed by HPAEC-PAD
equipped with a CarboPac PA1 column and a post column addition
of 0.2 mL/min 0.25 M NaOH. A gradient of NaOH was used as eluent (0.25 mL/min): 15 mM (02 min), 0 mM (219 min), increasing
from 0 to 200 mM (1935 min), 200 mM (3550 min), decreasing
from 200 to 15 mM (5051 min) and 15 mM (5159 min). Lactose
was used as an internal standard.
The concentration of furfural (furan-2-carbaldehyde), HMF
(5-(hydroxymethyl)-2-furaldehyde), MMF (5-(methoxymethyl)-2furaldehyde) and EMF (5-(ethoxymethyl)-2-furaldehyde), as well
as acetic acid, formic acid, and levulinic acid (4-oxopentanoic acid),
was determined with High Performance Liquid Chromatography
(HPLC, Agilent 1100 series) equipped with an RI analyser, UV detector and a Bio-Rad Aminex HPX-87H column (65 C, 5 mM H2 SO4 ,
0.60 mL/min).
Analysis of levulinate esters was performed with GCMS
(Trace GC ultra DSQ II, Thermo Scientic, with Phenomenex ZBWAXplus column) starting at 40 C (05 min), increasing to 245 C
(10 C/min) and 25 min dwell time at 245 C. The samples were
diluted in isopropanol before analysis.

2.3.3. Acid-neutralisation capacity

Several typical minerals in biomass (fractions) have an acidneutralising effect, inuencing the effect of added acid catalyst. The
acid-neutralisation capacity (ANC) of the wheat straw was determined using pH dependence leaching tests at pH 2 and pH 4 [31].
A mixture of 50 g wheat straw (as received) in 500 g water was
titrated with concentrated HNO3 (65%) until the pH of the solution
reached the desired value. The closed vessel was placed on a roller
bank. After 4, 24 and 48 h of equilibration, a measured amount of
additional HNO3 was added to retain the desired pH. Hereafter, a
further change in pH is negligible and the total HNO3 consumption
was determined. The ANC of the wheat straw was 0.10 and 0.26 mol
H+ /kg wheat straw (dry weight) at pH 4 and pH 2, respectively.
3. Results and discussion
3.1. Screening and optimisation of glucosides yield
Initial screening experiments were carried out in reactor A on
untreated wheat straw in 95% methanol (w/w) at 200 C and varying amounts of H2 SO4 . Table 1 (entry 16) shows the inuence of
the H2 SO4 concentration on the products yields obtained after alcoholysis of wheat straw in methanol. The solid residue is based on the
weight change of dried solids before and after reaction; the product
yields are given in mol-% based on initial glucan input. The furans
yield is the sum of HMF and MMF yields and the levulinates yield
is the sum of levulinic acid and methyl levulinate yields. Typically,
the methylated compounds constitute >90% for both main product
groups.
Based on the degree of solubilisation and glucosides yield, the
optimum concentration of H2 SO4 under given reaction conditions
was 30 mM. Lower acid concentrations led to poor glucan conversion and a limited glucosides (and furans) yield. Higher acid
concentrations as well as doubling the incubation time (Table 1,
entry 8) led to high yields of levulinates as well as an increase
in solid residue after methanolysis, implying the formation of
insoluble humins. Moreover, at the higher acid concentrations
the pressure build-up in the reactor was considerably higher
than may be expected from the vapour pressure equilibrium of
water/methanol mixtures. This was found to be related to the formation of the more volatile dimethyl ether from the acid-catalysed
dehydration of methanol. In the range studied, the formation of
dimethyl ether was kinetically limited and methanol losses due
to the formation of dimethyl ether were found to vary roughly
from 5 to 30%, depending on the reaction conditions. The glucose

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

Fig. 1. Methyl glucosides yield after 120 min (left) and 150 min (right).

concentration in the liquors was <0.3% at H2 SO4 concentrations

20 mM and around 4% at higher acid doses.
At a H2 SO4 concentration of 30 mM the xylan fraction of the
substrate was completely solubilised. The major product was furfural (>43 mol-% based on xylan). The xylose yield dropped from
5.9% in the absence of H2 SO4 to below 1% at a H2 SO4 concentration
20 mM.
The pH of the resulting liquors was around 2 and lower for experiments carried out with an initial H2 SO4 concentration 20 mM.
The ANC of the wheat straw was 0.26 mol H+ /kg at pH 2, corresponding to an effective H2 SO4 concentration reduction of about
12 mM in these experiments. Based thereon, the sudden increase
in acid-catalysed glucan solvolysis between 10 and 20 mM initial
H2 SO4 concentration is understandable, since at these concentrations not all added acid will have been neutralised. It is noted that
during solvolysis of biomass some organic acids are being produced
as well, such as acetic acid, formic acid and levulinic acid. However, in alcohol-rich environments large part of the organic acids is
esteried and will not contribute to the acidity of the nal mixture
(esterication typically >90%).
The screening experiments were extended by lowering the temperature and varying the incubation time and acid concentration.
The highest methyl glucoside yields were obtained after 30 min at
200 C with 30 mM H2 SO4 (Table 1, entry 7), after 120 min at 180 C
with 30 mM H2 SO4 (Table 1, entry 10) and after 120 min at 170 C
with 50 mM H2 SO4 (Table 1, entry 11). The selectivities for glucosides were 48%, 61%, and 53% respectively. This corresponds with
the trends observed for levulinates yield, indicative for the reaction
severity, and the solid residues. The extent of methanol dehydration
at temperatures below 180 C seemed to be limited.
Compositional analysis of the three corresponding solid
residues showed that nearly all the ash ends up in the residue,
whereas no xylan and virtually no acid-soluble lignin (<0.2%, w/w)
were detected in the solids. The amount of acid-insoluble lignin in
the solids was reduced to 32% of the initial amount after alcoholysis
at 180 and 200 C and 44% after alcoholysis at 170 C, suggesting a
lower delignication at lower temperature. This fraction will also
include lignin-condensates and acid-insoluble humins, if formed.
Based on the work by Hu et al. [23], however, the amount of humins
produced under these conditions is probably limited. The amount of
glucan in the solid, expressed as a percentage of the initial amount,
is tabulated in Table 1. The mass balance of the composition analysis
was >95% for all solids.
Based on results of the screening experiments an experimental
matrix was dened in which the temperature was varied between
180 and 190 C and the acid concentration between 25 and 35 mM
H2 SO4 . Subsamples were collected after 105, 120, 135 and 150 min
and analysed for methyl glucosides. During the methanolysis

experiments the amount of solvent changes, as a result of hydrolysis and condensation reactions, especially when dimethyl ether
(DME) is formed. At typical methanolysis conditions, methanol loss
due to the formation of dimethyl ether is estimated to be 520%
[32]. Net water will be produced and methanol will be consumed,
resulting in a lower volume and total weight of the solvent. Since
during sampling the amount of remaining liquid cannot be quantied, the yields are given in g per kg initial solvent. It should be
noted that sampling itself also slightly reduces the total amount
of solvent, affecting the glucosides concentration, especially after
multiple samplings. Consequently, the concentrations found for
longer incubation times will be relatively larger. The concentrations were corrected for the solvent loss due to sampling and the
results after 120 and 150 min incubation are depicted in Fig. 1.
The optimum yield per temperature follows the diagonal from
highest temperature and lowest acid concentration to the lowest
temperature and highest acid concentration. At less severe reaction
conditions, i.e. lower temperature and/or lower acid concentration
an increase in incubation time led to increased methyl glucosides
production, whereas more severe reaction conditions, i.e. higher
temperature and acid concentration, led to a decrease in yield
with increasing incubation time. The increase is explained by prevailing alcoholysis of the remaining glucan in time; the decrease
is a result of enhanced and dominating glucosides degradation,
yielding higher amounts of furans and, especially, levulinates. The
trend implies that an optimum can be found along, or in the
vicinity of the mentioned diagonal. Indeed, after 150 min the highest yield, 25.9 g/kg, was obtained at 185 C with 30 mM H2 SO4 .
The highest yield after 120 min was 26.2 g/kg, obtained at 180 C
with 35 mM H2 SO4 . Although the direction towards optimum reaction conditions is clear, no overall maximum glucosides yield was
found in this set of experiments. Therefore, the optimisation set
was extended along the diagonal by performing methanolysis
at 175 C with 35 and 40 mM H2 SO4 and at 180 C with 40 mM
H2 SO4 .The highest methyl glucosides yield was observed after
120 min at 175 C with 40 mM H2 SO4 (Table 2). Although an absolute maximum in methyl glucosides yield is still not unambiguously
established, based on the screening experiments (Table 1) it was
concluded that the optimum reaction conditions for this wheat
straw should be near 175 C and 40 mM H2 SO4 for a 120 min process
and that further optimisation will result in marginal improvements,
at best. The maximum yield was estimated at 27.9 g/kg or 55.5 mol%, assuming no weight changes in the solvent. The concluding pH
of the liquor was 1.5.
To validate the results, methanolysis was repeated using the
same reactor set-up at 175 C with 40 mM H2 SO4 without intermediate sampling using 30 g wheat straw in 238 g methanol 95%
(w/w). After 120 min at temperature the reactor was cooled to

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

Table 2
Optimisation of methyl glucosides yield from wheat straw in reactor B.
Temperature ( C)

Incubation time (min)

H2 SO4 (mM)

Methyl glucosides (g/kg)a

175
175
180
175
175
180

120
120
120
150
150
150

35
40
40
35
40
40

26.4
27.9
23.2
24.9
25.3
21.8

-methyl-d-glucopyranoside/-methyl-d-glucopyranoside molar ratio 1.8.

below 40 C. The concluding pH of the liquor was 1.5 and the liquid
weight loss due to the consumption of methanol, by methanolysis and DME formation was less than 3%. The products yields were
corrected for the liquid mass loss and are depicted in Fig. 2. The
glucosides yield was 53.9 mol-% based on initial glucan, which is
in agreement with the data obtained in the optimisation series.
Other identied, glucan-derived products were glucose (3.7 mol-%),
HMF (0.2 mol-%), 5-(methoxymethyl)-2-furaldehyde (3.8 mol-%),
methyl levulinate (11.0 mol-%) and levulinic acid (1.0 mol-%).
The solid residue after alcoholysis was virtually free of unconverted xylan. The xylan in the wheat straw has preferentially been
converted into furfural, 40.6 mol-%. Other products were methylxylosides (17.9 mol-%) and xylose (1.4 mol-%).

3.2. Methanol versus ethanol alcoholysis

Compared to methanol, alcoholysis of wheat straw at 200 C in
94% (w/w) ethanol acidied with 30 mM H2 SO4 resulted in a lower
(alkyl) glycosides yield (Fig. 3). However, due to a relatively high
furans production, the sum of alkyl glucosides and alkoxymethylfurfural yield is higher than in methanolysis. Since the formation
of alkoxymethylfurfural is a consecutive step in alkyl glucosides
valorisation, e.g. for the production of 2,5-furandicarboxylic acid,
ethanol seems a suitable solvent to replace methanol in alcoholysis of wheat straw, if furan-based products are desired. Moreover,
in acid catalysed alcoholysis at elevated temperature the use of
ethanol is preferred over methanol because of its lower toxicity
and lower tendency to form dialkylether [27]. The liquefaction efciencies in methanol and ethanol were 85.1% and 83.2% (w/w),
respectively.
In ethanol, the production of levulinates is not promoted per
se and there are no indications of increased humins formation.
Still, the higher amount of alkoxymethylfurfural and levulinates

observed after alcoholysis in ethanol suggest that the reaction

conditions in ethanol were slightly more severe. This is in agreement with the lower alkyl xylosides and the higher furfural yield
found for the xylan fraction of the wheat straw (Fig. 3). The difference in severity experienced at similar acid concentration may be
explained by a difference in behaviour of H2 SO4 in both alcohols. It
should be noted that, for both alcohols, the reaction conditions in
these experiments were not optimised for glucosides production.

3.3. Substrate effect (in ethanol)

After alcoholysis of untreated wheat straw, next to the identied
compounds, also minerals, lignin fractions and (other) hemicelluloses derivatives are present in the product liquors. Obviously,
the presence of these species will complicate isolation of the
desired products. However, their presence may also inuence the
nal product distribution. For example, dissolved lignin fractions
may react with furan-like species and form soluble and insoluble species [25] and minerals may act as co-catalysts or proton
scavengers. To visualise the possible effects of reduction of typical
non-carbohydrate constituents from lignocellulosic biomass, alcoholysis was performed on pure cellulose and cellulose-enriched
pulp (glucan 68.9%, w/w) obtained from organosolv treatment. The
results are compared with the results obtained with untreated
wheat straw containing 36.9% (w/w) glucan (Fig. 4).
At similar acid concentration the sugars and furans yield for
both the pulp and wheat straw were signicantly higher than those
obtained from Avicel PH-101 and -cellulose (Fig. 4). Apparently,
the (pure) celluloses experience more severe reaction conditions,
in which relatively large amounts of levulinates (and carbonaceous
residue) are formed. This is explained by the absence of acid neutralising minerals, resulting in a higher net acid concentration. The
differences found in concluding pH of the resulting liquors, pH 1.4

Fig. 2. Product spectrum after methanolysis of wheat straw at variable conditions.

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

Fig. 3. Products yield of wheat straw alcoholysis in methanol and ethanol at 200 C (reactor A).

is only slightly higher than that of wheat straw, 16.8% (w/w). Therefore, the larger part of the condensation products, if formed, seem
soluble in the resulting liquor.
3.4. Effect of chloride

Fig. 4. Products yield of different substrates: alcoholysis in ethanol and 30 mM

H2 SO4 (reactor A).

for the celluloses and pH 1.8 for the pulp and wheat straw, support
this assumption.
Under studied conditions, the total glucosides molar yields from
organosolv pulp and untreated wheat straw were comparable, but
the furans and levulinates yields from pulp were signicantly lower
(Fig. 4). The relatively lower yields of furans and levulinates, as secondary products, do not correspond with the lower ANC found for
the pulp, 0.19 mol H+ /kg versus 0.26 mol H+ /kg for the wheat straw
at pH 2. At similar substrate loading, however, as a direct result
of the cellulose enrichment, the pulp led to signicantly higher
product concentrations. For example, the total ethyl glucosides
concentration in the liquor was twice as high. Higher glucosides
and/or furans concentrations are expected to result in increased
product losses due to condensation reactions, especially in the presence of (residual) lignin. Hereby, furans will be consumed and the
formation of levulinates will be reduced, resulting in a lower yield
for both compounds, as is observed for the pulp (Fig. 4). The amount
of solid residue obtained after alcoholysis of the pulp, 18.2% (w/w),

The effect of MgCl2 addition is ambivalent. In the absence

of H2 SO4 the presence of MgCl2 promoted alcoholysis, whereas
in the presence of 40 mM H2 SO4 it had a clear inhibiting effect
(Table 3). Compared to a non-acidied experiment, addition of
100 mM MgCl2 resulted in a decrease in solid residue after reaction from 89.8 to 70.4%, as well as a decrease in concluding pH
from 6.6 to 4.9. Paszner and Cho [33] hypothesise that adsorption
of Mg2+ on carboxylic acid groups of the biomass causes a release
of protons, thus lowering the pH. It was also suggested that MgCl2
effectively hydrolyses the hemicellulose and lignin fraction. The latter hypothesis would explain an increase in solvolysis of the wheat
straw without an increase in soluble glucan derived products. If the
effects are related is not known.
Another explanation may be that this effect is originating from
dissociation of hydrated magnesium cations, releasing protons into
the solution according to: [Mg(H2 O)6 ]2+ = [Mg(H2 O)5 (OH)]+ + H+ .
Hydrated magnesium cations are only weakly acidic. The pKa
in water is about 11.2 at 25 C [34]. Upon addition of H2 SO4
the measured pH of the mixture rapidly drops below the point
that deprotonation of Mg-hydrate cation, and hence its promoting effect, is no longer expected. Quite the reverse, the presence
of MgCl2 was found detrimental to the alcoholysis in acidied
methanol and the methyl glucosides yield. At the same time it was
noticed that, after reaction, the concluding pH of the liquor was 1.5
in the absence and 2.2 in the presence of 100 mM MgCl2 . Compared
to the MgCl2 -free experiments a lot of protons, initially present,
must have been consumed. The consumption of H+ will suppress
the alcoholysis reaction. One such a mechanism consuming H+
may be chlorination of methanol: CH3 OH + Cl + H+ = CH3 Cl + H2 O.

Table 3
Effect of MgCl2 and HCl on the alcoholysis of wheat straw.
T ( C)

Catalyst

Solvent (balance H2 O)

Solid residue (wt-%)

180
180
180
180
200
200
200

a
40 mM H2 SO4
40 mM H2 SO4 a
30 mM H2 SO4
60 mM HCl
100 mM HCl

95% methanol
95% methanol
95% methanol
95% methanol
94% ethanol
94% ethanol
94% ethanol

89.8
70.4
21.4
52.7
15.3
52.1
48.2

a
b

Added 100 mM MgCl2 .

Not analysed.

Main product groups

Glucosides (mol-%)

Furans (mol-%)

Levulinates (mol-%)

<0.1
0.4
44.6
3.4
31.9
3.2
4.7

b
0.2
2.8
0.8
19.3
1.4
2.0

b
0.1
10.9
0.2
10.3
<0.3
<0.3

10

R.J.H. Grisel et al. / Catalysis Today 223 (2014) 310

At given reaction conditions it made little difference whether 50,

100 or 200 mM MgCl2 was added.
A similar effect was observed in ethanol at 200 C when 30 mM
H2 SO4 was replaced by 60 mM HCl. At equal normality the concluding pH increased from 2.0 to 3.6 and the ethyl glucosides
yield dropped by an order of a magnitude. An increased initial HCl
concentration of 100 mM led to a concluding pH of 3.2 and the
alcoholysis was improved only a little (Table 3).
4. Conclusions
Lignocellulosic biomass can be converted in a single step via
acid catalysed alcoholysis using small chain, linear alcohols yielding
mainly furfural and alkyl glucosides. Maximum yields simultaneously obtained from wheat straw are 40% furfural (xylose
equivalents) and 56% methyl glucosides (glucose equivalents). The
major by-products are levulinic acid and its alkyl ester. The amount
of insoluble humins that are formed is limited.
The depolymerisation and alkylation of carbohydrates (chains)
are mainly Brnsted acid catalysed and the presence of proton consuming compounds, such as acid-neutralising native minerals or
chloride, hamper the liquefaction efciency and the alkyl glucosides yields. The optimum acid dose needs to be adjusted to the
acid neutralisation capacity of the biomass.
A second important parameter is the process temperature. In
this study, the best results were obtained around 175 C. The
optimum temperature will depend on the heating and cooling
transients of the equipment. The amount of dimethyl ether formed
from methanol under these conditions was limited, but became
readily more prominent at higher temperatures. Solvent loss due
to ether formation from ethanol condensation was much smaller.
The incubation time had only a limited effect.
Delignication prior to alcoholysis did not inuence the results
much, but allowed higher product concentrations and enables a
separate lignin valorisation.
Acknowledgements
The authors acknowledge Arjan Smit and Ron van der Laan for
their contribution to this work and Ben van Egmond and Karina
Vogelpoel-de Wit for their analytical work. This work was funded
by Agentschap NL in the framework of the EOS-LT Catfur project
(EOS-LT 08030). Additional funding from the Dutch Ministry of Economic Affairs as part of the Biomass research programme of ECN is
acknowledged.
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