Formic and Levulinic Acid from

Cellulose via Heterogeneous

Catalysis

Johan Ahlkvist
Copyright © Johan Ahlkvist 2014
This work is protected by the Swedish Copyright Legislation (Act 1960:729)
ISBN: 978-91-7459-798-1
Digital version available at http://umu.diva-portal.org/
Printed by: VMC-KBC Umeå
Umeå, Sweden 2014
Abstract
The chemical industry of today is under increased pressure to develop novel
green materials, bio-fuels as well as sustainable chemicals for the chemical
industry. Indeed, the endeavour is to move towards more eco-friendly cost
efficient production processes and technologies and chemical transformation
of renewables has a central role considering the future sustainable supply of
chemicals and energy needed for societies. In the Nordic countries, the
importance of pulping and paper industry has been particularly pronounced
and the declining European demand on these products as a result of our
digitalizing world has forced the industry to look at alternative sources of
revenue and profitability. In this thesis, the production of levulinic and
formic acid from biomass and macromolecules has been studied. Further,
the optimum reaction conditions as well as the influence of the catalyst and
biomass type were also discussed.

Nordic sulphite and sulphate (Kraft) cellulose originating from two Nordic
pulp mills were used as raw materials in the catalytic synthesis of green
platform chemicals, levulinic and formic acids, respectively. The catalyst of
choice used in this study was a macro-porous, cationic ion-exchange resin,
Amberlyst 70, for which the optimal reaction conditions leading to best
yields were determined. Cellulose from Nordic pulp mills were used as raw
materials in the catalytic one-pot synthesis of ‘green’ levulinic and formic
acid. The kinetic experiments were performed in a temperature range of
150–200 °C and an initial substrate concentration regime ranging from 0.7
to 6.0 wt %. It was concluded that the most important parameters in the one-
pot hydrolysis of biomass were the reaction temperature, initial reactant
concentration, acid type as well as the raw material applied. The reaction
route includes dehydration of glucose to hydroxymethylfurfural as well as its
further rehydration to formic and levulinic acids. The theoretical maximum
yield can hardly be obtained due to formation of humins. For this system,
maximum yields of 59 mol % and 68 mol % were obtained for formic and
levulinic acid, respectively. The maximum yields were separately obtained in
a straight-forward conversion system only containing cellulose, water and
the heterogeneous catalyst. These yields were achieved at a reaction
temperature of 180 °C and an initial cellulose intake of 0.7 wt % and belong
to the upper range for solid catalysts so far presented in the literature.

The reaction network of the various chemical species involved was

investigated and a simple mechanistic approach involving first order
reaction kinetics was developed. The concept introduces a one-pot procedure
providing a feasible route to green platform chemicals obtained via

i
conversion of coniferous soft wood pulp to levulinic and formic acids,
respectively. The model was able to describe the behaviour of the system in a
satisfactory manner (degree of explanation 97.8 %). Since the solid catalyst
proved to exhibit good mechanical strength under the experimental
conditions applied here and a one-pot procedure providing a route to green
platform chemicals was developed. A simplified reaction network of the
various chemical species involved was investigated and a mechanistic
approach involving first order reaction kinetics was developed.

ii
Table of Contents

Abstract i
Table of Contents iii
List of Papers v
Abbreviations vi
Introduction 1
Levulinic Acid 3
Reaction Network upon Production of Levulinic Acid from Biomass 3
The Influence of Reaction Parameters to the Yield of Levulinic Acid 4
The Influence of Raw Material Varieties 4
The Influence of Reaction Temperature 5
The Influence of Substrate Concentration 6
The Influence of Acid Type 7
The Influence of Acid 8
The Influence of Reaction Time 10
The Influence of Pre-treatment 11
The influence of Additives 13
The Influence of Agitation Speed 15
Materials and methods 17
Chemicals 17
Raw materials 17
Acidic polymer catalyst 18
Reactor system 18
Substrate and catalyst characterization 19
Nitrogen physisorption 20
Scanning electron microscopy 20
Acid-base titration 21
Product analysis 21
Liquid chromatography 22
Gas chromatography 23
Mass spectrometry 23
Derivatization for GC/MS 24
Definitions for the yield calculations of levulinic acid (LA) and formic acid (FA) 24
Modelling software and techniques 25
Results and Discussion 26
Catalyst Characterization 26
Substrate characterization 27
Auto-catalysis 29
Reusability of the catalyst, catalyst deactivation 29
Reaction network 30
The influence of reaction conditions and raw material on product yields 32

iii
 Comparison between different wood pulps 32
Reaction with D-glucose 33
The influence of reaction temperature and catalyst to substrate dosage 33
The influence of reaction gas and pressure 36
Selectivity 37
Kinetic modelling 38
Fit of the model to experimental data 41
Conclusions 46
Acknowledgements 48
References 49

iv
List of Papers
I Johan Ahlkvist, Samikannu Ajaikumar, William Larsson, Jyri-
Pekka Mikkola (2013). One-pot catalytic conversion of Nordic pulp
media into green platform chemicals. Applied Catalysis A, 454: 21-
29.

II Johan Ahlkvist, Samikannu Ajaikumar, William Larsson, Johan

Wärnå, Tapio Salmi, Jyri-Pekka Mikkola (2013). Reaction Network
upon One-pot Catalytic Conversion of Pulp. Chemical Engineering
Transactions, 32: 649-654.

III Johan Ahlkvist, Päivi Mäki-Arvela, Jyri-Pekka Mikkola. Macro-

molecules as a Source of Levulinic Acid (2013). The International
Review of Chemical Engineering. (submitted)

IV Johan Ahlkvist, Johan Wärnå, Tapio Salmi, Jyri-Pekka Mikkola

(2013). Experimental and Kinetic Modelling Studies upon
Conversion of Nordic Pulp into Levulinic Acid. Industrial &
Engineering Chemistry Research. (manuscript)

Authors’ contributions

I Planning, kinetic experiments, data analysis, most of the practical

work except some parts of the catalyst characterization, GC and
GC/MS measurements, writing article

II Planning, most of the practical work and data analysis except

mathematical modelling, major writing

III Major writing

IV Planning, kinetic experiments, most of the practical work and data

analysis except mathematical modelling, major writing

v
Abbreviations
5-HMF 5-hydroxymethylfurfural
AD Air dried
AHP Alkaline hydrogen peroxide pretreatment
APPO Aqueous phase partial oxidation
BET Stephen Brunauer, Paul Hugh Emmett and Edward Teller
BJH Barrett, Joyner and Halenda
CE-MS Capillary electrophoresis-mass spectrometry
CPD Critical point dried
D Domsjö
DP Degree of polymerization
FA Formic acid
GC Gas chromatography
GC-MS Gas chromatography-mass spectrometry
GVL Gamma-valerolactone
HAS High amylose corn starch
HMDS Hexametyldisilazane
HMF Hydroxymethylfurfural
HPLC High-performance liquid chromatography
IUPAC International Union of Pure and Applied Chemistry
LA Levulinic acid
LC-MS Liquid chromatography-mass spectrometry
MCMC Markov Chain Monte Carlo method
MG Mechanical grinding
MilliQ Deionized water
MGRS Mechanical grinding rice straw
MGSERS Mechanical grinding steam explosion rice straw
MS Mass spectrometry
M-S Metsä-Serla
MW Microwave
NS Normal starch
PAH Pressurized acid hydrolysis
RH Rice husk
RI Refractive index
RID Refractive Index Detector
RS Rice straw
SE Steam explosion
SEM Scanning electron microscopy
SERS Steam explosion rice straw
SG Superfine grinding
SGRS Superfine grinding rice straw

vi
SGSERS Superfine grinding steam explosion rice straw
TMCS Chloromethylsilane (Trimethylchlorosilane)
UV-vis Ultraviolet-visible spectroscopy

vii
Introduction
One of the main reasons for developing biorefinery processes for our
bioresources is to reduce the emission of carbon dioxide and other
greenhouse gases. Also, fossil fuels are a limited source of energy and will be
depleted in the future. However, today the cost of processing renewables to
chemicals and fuels is often too high, partly due to the fact that the
traditional synthesis routes developed and optimized for hydrocarbons are
not well adaptable for renewables [1]. Development of new processes for
woody biomass or other lignocellulosic materials has attracted increasing
attention for some time now. In fact, commercial operations and pilot units
are either integrated as biorefineries combined with adjacent pulp and paper
mills (utilizing e.g. black liquor and other secondary streams as sources of
new products) or built as stand-alone processing units. In order to combine
and re-invent the material streams of the old industry, together with other
processes and practices of chemical industry, a lot of new R&D efforts are
required thus utilizing the existing and new technology solutions to produce
a range of fossil-free alternatives of future.

Lignocellulosic biomass such as wood is a superb raw material for converting

renewables into fuels or fuel additives and chemicals, in view of the fact that
the utilization of this kind of biomass does not compete with feed or food
production. Chemical products produced from food-crops (e.g. corn) are
questionable in a world where there is a lack of adequate nourishment for all
its inhabitants. In fact, sugar crops like e.g. sugarcane is often grown for non-
food purposes (primarily transportation fuel blends) on farmland that
competes with human related food production. After the initial boom of first
generation biochemicals and fuels made from edible biomass, an ever
increasing number of the so-called second generation biofuels produced
from non-edible biomass (e.g. agricultural residues, lignocellulosics and
other waste materials) have been introduced.

Wood, the most common source of biomass in the world, is typically

composed of 40-50% cellulose, 23-33% lignin and 25-35% of hemicellulose
[2]. Cellulose is considered as a promising alternative to non-renewable
natural resources for the sustainable supply of fuels and chemicals in the
future. Currently, extensive research is being carried out worldwide to
identify and study chemical or biological transformation pathways to convert
cellulose into biofuels and feedstock chemicals [3, 4]. Furthermore, the
hydrolysis process of cellulose has been cited as the main gateway to a
biorefinery scheme based on the transformation of carbohydrates [5]. The
Scholler process, which was developed in Germany in the 1920’s, was the
first hydrolysis process for acidic conversion of lignocellulosic biomass [6].

1
To date, several studies have reported the conversion of biomass into
levulinic acid (LA) using a dilute mineral acid, such as HCl and H 2SO4 as
catalysts [7-10]. Although these hydrolysis reactions proceed smoothly, the
use of the mineral acids causes serious pollution and promotes equipment
corrosion. Moreover, any homogeneous catalysts are difficult to recover from
the reaction products for recycling [11]. Very limited attention has been given
to the use of solid acid catalysis for the depolymerization of cellulose in water
under realistic conditions for the possible exploitation, i.e. temperatures
below about 200 °C (to avoid secondary transformation of the produced
sugars). However, Rackemann et al. [12] summarizes the studies conducted
on the synthesis of levulinic acid using solid acid catalysts from various feed-
stocks. The catalyst used in this experimental study is a macro-porous,
cationic ion-exchange resin, Amberlyst 70 [13]. Today Amberlyst 70 is
reasonably well known and has been used with good results as a catalyst in
many types of reactions. Rinaldi et al. [14], Agirrezabal-Telleria et al. [15] as
well as Hu and Li [16] have recently used Amberlyst 70 in similar type of
reactions as our case.

Several kinetic studies using a various range of cellulosic materials can be

found in the literature. Saeman [17] was one of the pioneers when he in 1945
presented a modelling study based on hydrolysis reaction of Douglas fir into
glucose performed in batch mode. Also, several later studies are based on
Saemans model. In papers by Fagan et al. [18], Thompson et al. [19], and
Franzidis et al. [20], a plug-flow reactor was used to study the kinetics of the
hydrolysis reaction of Kraft paper slurries, Solka Floc as well as filter paper.
Also, Malester and co-workers [21, 22] were using Saemans model when the
kinetics of dilute hydrolysis of cellulose originating from municipal solid
wastes was investigated in a batch reactor. Nevertheless, only a few kinetic
reports [7, 23, 24] are available for the acid-catalyzed hydrolysis of cellulose
to levulinic acid before Girisuta et al. [9] who presented a more detailed
reaction mechanism of levulinic acid (LA) formation from cellulose through
glucose and 5-hydroxymethylfurfural (HMF), including the humin formation
reactions. Jing and Lu [25] also published a model describing LA production
based on a similar reaction mechanism performed in a batch autoclave using
glucose as the reactant. Further, Shen and Wyman [26] presented a
sophisticated model describing LA production in tubular batch reactors from
microcrystalline cellulose and their model accounted for the major
compounds as well as the side-reactions leading to by-products.

Hereupon we describe an experimental and modelling study of the acid-

catalyzed hydrolysis of soft wood dissolving pulp into levulinic acid through
glucose and HMF as well as xylose, furfural and formic acid from the
transformation of xylans in the pulp.

2
Our aim was to develop a procedure whereupon a reasonable cellulose-to-
catalyst ratio was applied. Also, avoiding the use of energy-intensive
pretreatments methods for cellulose, such as long-time ball-milling typically
used in most of the literature examples was the criteria set by ourselves [27].
Herein we report the direct catalytic conversion of wood pulp to levulinic
acid and formic acid by sequential hydrolysis, dehydration–hydration
reactions under relatively mild conditions.

Levulinic Acid

The first synthesis of LA by heating sucrose with mineral acids at high

temperature was reported in the 1840’s by the Dutch professor G. J. Mulder
[28]. This versatile renewable platform molecule has also been identified by
the US Department of Energy as one of the `12 top value-added biochemicals
[29].

Levulinic acid is a commodity chemical that finds applications for several

purposes, such as source of polymer resins, animal feed, food as well as
components of flavoring and fragrance industry, textile dyes, additives,
extenders for fuels, antifreeze products, antimicrobial agents, herbicides and
also plasticizers [12, 23]. Traditionally, the most convenient industrial route
to levulinic acid involves production from hexose sugars [23]. More recently,
the utilization of biomass and agricultural wastes for production of levulinic
acid has been subject to increased interest as a research topic, since it would
render the process cheaper due to the high availability and low cost of raw
materials. In fact, even ‘negative’ cost of the raw materials can be achieved
when wastes such as paper mill sludge are applied [30]. Importantly, a novel
process based on the use of waste products would not compete with food
supply. One-pot biomass hydrolysis to sugars followed by their dehydration
can be tuned to produce many different derivatives, including 5-
hydroxymethylfurfural and furfural. The former one can then consequently
be rehydrated to levulinic and formic acids. There are a few reviews available
that concern levulinic acid [12, 30, 31]. In a paper by Timokhin [31], mainly
the properties of levulinic acid and its utilization in organic synthesis were
reviewed, whereas transformation of lignocellulosics to levulinic acid is
emphasized in ref. [12].

Reaction Network upon Production of Levulinic Acid from

Biomass
All in all, one-pot synthesis of levulinic acid from biomass is a demanding
reaction since the whole process most conveniently starts with acid

3
hydrolysis of biomass thus giving rise to various issues in terms of waste
produced as well as the occurrence of multiple side reactions. The desired
raw material, lignocellulosic biomass, is mainly composed of cellulose,
hemicelluloses and lignin of which the first two can yield the desired
hexoses, the key intermediates in the production of levulinic acid.
Thereafter, sugars need to be dehydrated and rearranged to 5-
hydroxymethylfurfural and furfural depending on whether hexoses or
pentoses, respectively, are to be dehydrated. Consequently, hexoses can then
further rehydrate to formic and levulinic acids also requiring two equivalents
(moles) of water. Since two different organic carboxylic acids are formed, the
theoretical yield of levulinic acid from hexoses and cellulose has been
reported to reach 64.5 wt % and 71.5 wt % only, respectively [32]. It should,
however, be stated that the real yields of levulinic acid are typically lower
than the theoretical yields due to the harsh reaction conditions required for
the hydrolysis of macromolecules. Thus, the formation of humins is hardly to
be avoided.

The Influence of Reaction Parameters to the Yield of Levulinic

Acid

The influence of various reaction parameters during transformation of

biomass to levulinic acid, such as biomass type, reaction temperature, initial
concentration of feedstock, liquid-to-solid ratio, agitation speed in the
reactor, potential adjacent pretreatments of biomass as well as the influence
of additives is elucidated in this Section. The main emphasis was directed
towards selection of optimal reaction conditions to the yield of levulinic acid
and how it actually can be maximized.

The Influence of Raw Material Varieties

The influence of raw material upon production of levulinic acid is important

since, for example, the presence of lignin results in changes in the optimum
reaction conditions and usually more drastic conditions are needed for
lignocellulosic raw material compared to cellulose. It should be pointed out
here that it is difficult to directly compare the results on the basis of levulinic
acid yield, since in some cases the yield has been given on the basis of initial
raw material, cellulose content (as well as C6 content) in the raw material
(mass) or based on the theoretical yield of levulinic acid. The highest
theoretical yield of levulinic acid reported amounted to 92 % corresponding
to 65.9 % yield, based on the cellulose content in the raw material (paper
sludge) and achieved by a two-stage process at a temperature of 200–215 °C
[33]. Comparative theoretical yields of levulinic acid were achieved from rice
husk (82.9 %) [34], tabacco chops (82.5 %) [30], paddy straw (79.6 %) [10],

4
bagasse (78.8 %) [10] and wheat straw (77.4 %) [30]. All produced with a
strong acid, hydrochloric acid (HCl) and from a waste material. When
comparing different raw materials and the yield of levulinic acid, it was
observed that - as also stated by Kang et al. [35] - marine biomass can be
grown rapidly and is easily cultivated without the need for expensive
equipment, compared to land biomass. In addition, annual CO2 absorption
by marine biomass can be five to seven times higher than that of wood-
biomass and the carbohydrate content is higher and can easily be converted
to chemicals through proper chemical processes.

The Influence of Reaction Temperature

The influence of reaction temperature on the levulinic acid production has

been intensively investigated using different feedstock’s, such as cellulose [9,
36-38] wheat straw [8, 30], kernel grain sorghum [23], water hyacinth [39],
poplar sawdust [30], paper sludge [30], olive tree pruning [30] bagasse and
paddy straw [10]. The effect of reaction temperature on the cellulose
conversion into LA was investigated by Peng et al. [38] and the experiments
were conducted at 180–220 °C, respectively. The temperature has a
significant effect on LA yield. When the reaction temperature was increased
above 200 °C, the yield of LA began to fall, and intermediates such as
glucose and HMF couldn’t be detected any more. Higher temperatures thus
could accelerate the rate of chemical reactions, but undesired side reactions
like formation of humins also appeared at the same time. Therefore, higher
temperatures are unfavorable for the extent of reaction. Analogously to the
study of Peng et al. [38], an optimum temperature giving rise to high yield of
levulinic acid has been reported for the transformation of wheat straw at
about 210 °C [40]. Similar results with an optimum temperature was also
obtained by Szabolcs et al. (cellobiose) [41] and Shen et al. (cellulose) [26].
However, by contrast to cellulose transformation by Girisuta et al. [42], the
yield of levulinic acid was greater in the study by Fang et al. [23] at higher
temperatures (200 °C) than that obtained at lower ones (160 °C) using
kernel grain sorghum as the raw material. Very high yields of levulinic acid
were also obtained from bagasse and paddy straw at 220 °C [10]. These
results indicate that the presence of lignin requires a higher temperature in
order to maximize the yield of levulinic acid compared to the case when
cellulose is the raw material of choice although it is known that the humins
originate from glucose and HMF [36]. Furthermore, it has been confirmed
that levulinic acid is stable at 180 °C, even after 24 h [36]. However, it was
also observed that at very high temperatures, above 230 °C, the amount of
levulinic acid decreased in water solution due to dehydration to α- and β-
angelica lactone [10]. Generally, around 170 °C is considered the optimal
reaction temperature above which the humins are readily forming due to

5
higher equilibrium concentration of protonated pyranose forms of the sugars
[41].

The Influence of Substrate Concentration

Theoretically, a higher liquid-to-solid ratio should result in a higher yield of

levulinic acid. However, it has further been found that high carbohydrate
loading had an adverse effect on levulinic acid yield in the reaction mixture.
Therefore, one method to maximize the yield is to slowly add the
carbohydrate material to the reaction mixture in order to reduce the
concentration of the carbohydrate in the mixture at any given time and
increase the yield of levulinic acid. In this manner the final concentration of
levulinic acid will be gradually built up, resulting in a decreased cost of
materials and handling [43]. Generally, lower concentration of cellulose
resulted in higher yields of levulinic acid. For each levulinic acid molecule
generated, two molecules of water are needed; otherwise 5-
hydroxymethylfurfural (HMF) may be converted into humins [42]. These
observations are in line with other studies on the acid-catalyzed
decompositions of HMF and glucose, where the low substrate concentrations
favored high LA yields. The highest levulinic acid yield (60 mol %), at full
cellulose conversion, could be obtained at a temperature of 150 °C,
whereupon an initial cellulose addition of 1.7 wt % and a sulfuric acid
concentration of 1 M were applied [9]. The same phenomena have also been
noted in transformation of sorghum flour [23], corn starch [44], cotton straw
[45], and cellulose [26, 46].

Chang et al. [8] observed that the yield of levulinic acid in fact deteriorated
after a certain optimum ratio was reached as noted by Carlson [47]. Also,
Peng et al. [38] observed that the optimal concentration of substrate is very
important in terms of the efficient use of cellulose and the final levulinic acid
(LA) concentration reached. Higher LA yield was achieved at lower substrate
concentrations, but a higher LA concentration in the product is extremely
favorable since it results in lower energy consumption upon purification of
LA and also reduces the amount of waste water produced. When catalyst
dosage was fixed, increasing substrate concentration resulted in more
cellulose available for conversion which, in turn, meant that higher LA
concentration was achieved in the reaction product. However, the yield of LA
was found to decrease significantly by increasing substrate concentration
from 10 wt % to 15 wt %. The plausible reason for this is the product
feedback inhibition, reactivity diminution or insufficient catalyst dosage for
the additional cellulose [38]. In accordance to Yan et al. [10] also too much
or too little water inhibits the hydrolysis process. The primary hydrolysis of
the reaction system is significantly depressed if the water-to-solid ratio is too

6
low, at least in the case of bagasse. The reaction with paddy straw shows a
much less sharp change in terms of the yield of levulinic acid reached. The
highest practical yield was achieved when the water-to-solid wt-ratio was 8.5
for both raw materials.

The Influence of Acid Type

In terms of the mineral acid used, it seems that the use of hydrochloric acid
results in better selectivities than that of sulphuric acid. This was observed
e.g. by Galetti et al. [30] when levulinic acid was produced from paper
sludge. However, the highest theoretical yield ever, 92 %, is produced from
paper sludge by sulfuric acid [33]. When water insoluble biomass is
processed, homogeneous acid catalysts generally appear more suitable in
comparison to heterogeneous ones, considering their ability to deliver the
active species into the solid or swelled biomass [48]. So far H2SO4 has been
the most commonly used mineral acid, even if HCl, HBr, and H 3PO4 also
have been frequently reported as applicable homogeneous catalysts [49].
However, HBr and H2SO4 have been attempted, albeit with poor
performance compared to HCl at low temperatures [50]. In all cases, diluted
HCl always demonstrated superior behavior in comparison to H 2SO4 as the
catalyst. Also, significant deposition of humin solid by-products on the
reactor walls was observed and when the raw biomass had a significant
content of calcium salts, like paper-mill cellulose wastes or tobacco chops,
significant deposition of calcium sulphate was observed, even at lower H 2SO4
concentrations. When higher H2SO4 concentrations were adopted, reactor
clogging took place. On the contrary, when HCl was the catalyst of choice
under optimized reaction conditions and at limited exposure times, no
precipitation of salts and humins deposition was observed. Consequently,
HCl always afforded higher LA yields with respect to H 2SO4. However, when
Chang et al. [8] reported the optimization of levulinic acid production from
wheat straw using H2SO4 under optimal conditions the yield reached, based
on the weight of raw material, 19.86 %, which is comparable with the 19.3 %
value obtained upon use of HCl. The use of this volatile acid catalyst enables
furthermore the recovery of the produced LA by atmospheric/vacuum
distillation and steam stripping whereupon about 95 % of the acid catalyst
and water can be recycled [51]. These results are important in terms of the
economics of the whole process and considering the possible exploitation of
the solid residue, mainly due to lignin component. In fact, the residual lignin
has great potential for many applications such as a substrate for soil
conditioning, as a free radical scavenger for antioxidation, as a low-density
filler taking place of inorganic fillers, as a component for biodegradable
formulations or to be incinerated to energy. Again, if water-soluble
carbohydrates are employed as substrates, heterogeneous acid catalysts

7
appear attractive. A key property of heterogeneous catalysts is their very easy
separation from the reaction products. Furthermore, heterogeneous catalysts
are easily recycled. Also, they are environmentally friendly with respect to
safety and corrosiveness. Up until now, very few heterogeneous acid catalysts
have been tested for the conversion of carbohydrates to yield LA. Examples
thereof include ion-exchange resins [52], zeolites [53], pillared clays [54],
nafion [55], and solid super acid S2O82-/ZrO2-SiO2-Sm2O3 [20]. NbP was
observed to be active in the conversion of inulin to yield LA under traditional
heating. Yields in the range of 20 wt % were achieved in 1 hour without
significant formation of solid by-products. LA was the predominant
monomer product, while a soluble monomer by-product identified in very
low concentrations was the intermediate 5-HMF. Interestingly, the use of
microwave (MW) irradiation allowed for significant time savings and, at the
same time, enhanced the yield from 20 up to about 30 wt %, corresponding
to 40 % of the theoretical yield [30]. This investigation, carried out in a
slurry batch reactor, appears very promising. Many heterogeneous catalysts
up to now investigated in the synthesis of LA generally required very long
reaction times (15-25 h) to reach comparable yields as e.g. in refs. [52-55].
The results of the study presented above can well be compared with those
obtained with homogeneous HCl under similar thermal treatment
conditions. Nevertheless, the heterogeneous NbP has one significant
drawback which is that NbP remains encapsulated in the solid lignin. The
encapsulated catalyst can be recovered and recycled only after suitable
thermal treatments [30]. In terms of Lewis or Brönsted acids, the former
types are assumed more efficient concerning levulinic acid production [56].
As a general observation, hydrochloric acid appears to be slightly better
catalyst than sulfuric acid although the potential release of chlorine into the
biosphere speaks against the use of HCl [41].

The Influence of Acid

Fang and Hanna [23] observed that higher sulfuric acid concentration also
significantly increased the levulinic acid yield. Yield of levulinic acid was
positively correlated with mineral acid concentration, which greatly boosted
the yield of levulinic acid by the higher rate of hydrolysis of carbohydrates to
organic acids. As observed by many authors, also Peng et al. [38] noticed
that the yield of LA increased rapidly with increasing catalyst dosage until an
optimum level was reached. After this only a minor increase of the LA yield
was achieved. Consequently, the addition of excess catalyst has little or even
negative effect on the LA yield. Accordingly, when the requirements of the
reaction are satisfied, no more should be added. Similar observation was
noted upon LA production catalyzed by other catalysts such as H 2SO4 [39]
and HCl [8]. When working with CrCl3 (0.02 M), less catalyst was needed

8
than in the case of H2SO4 (0.1–1 M) [8, 9, 39] and HCl (~1.2 M) [10]. In this
case, the most beneficial concentration of CrCl3 was found to be 0.02 M
when considering the economic aspects and the efficiency. Too high
concentration and long reaction time were in favor of causing side-reactions
that may negatively affect the rate of hydrolysis of the cellulose to levulinic
acid [37]. The plausible reason for this is the existence of parallel reactions
upon transformations occurring [45]. A higher catalyst concentration was
not only unnecessary but undesirable in that it was found to complicate the
purification of the final product [57]. If higher acid concentrations are used,
difficulties are encountered in terms of the operation of the process and, at
the same time, no beneficial yield gains could be observed [44]. Chang et al.
[8] also observed that mineral acid with higher concentration also caused
severe corrosion in the reactor equipment – a well known fact. Mineral acid
concentration in combination with increasing reaction temperature,
determines how corrosive the reactants are to the metal parts of the reactor.
At a given temperature there is a maximum allowable concentration of a
mineral acid for a specific metal or alloy [23]. The disposal of the catalysts
will not only waste resources, but also cause environmental pollution, so it is
extremely important that particularly metal catalysts like chromium are
recycled [38].

In order to verify the optimum acid concentration, Szabolcs et al. [41]

performed dehydration of cellulose and cellobiose in a concentration range
of 0.1–2.5 M H2SO4. The optimum conditions for cellobiose were found to be
2 M H2SO4 at 170 °C for 10 min; and for cellulose 2 M H 2SO4 at 170 °C for 30
min. In fact, Yan et al. [10] also found that low concentration of
hydrochloride acid resulted in too low concentration of H + ions thus being
unable to facilitate cellulose hydrolysis and, consequently, a low reaction rate
was observed. In the case of raw materials containing primarily C 5 sugars,
low acid concentrations and high temperatures were beneficial when aiming
at high furfural yields. Typical streams of this kind are e.g. pre-hydrolysis
liquors or pulping/papermaking waste streams. On the other hand, as
expected, low acid concentrations and short reaction times lead to low
levulinic acid yields. However, using low acid concentrations is problematic,
because the lignin present in the biomass consumes a fraction of the acid
during the reaction. Due to the low initial concentration of acid, the amount
of acid lost is significant, and the LA yield decreased from 57 % to 27 % upon
third batch of corn stover being added to the reaction mixture [58]. In case
of starch, higher sulfuric acid concentrations favor levulinic acid formation
and a large weight ratio of 0.3 (sulfuric acid-to-starch) was found optimal
[59]. In case of sulfuric acid, the yield of levulinic acid falls at higher
temperatures due to oxidation of raw material by the acid demonstrated by
the presence of hydrogen sulfide formed [50]. Shen and Wyman observed

9
that an increase in HCl acid concentration caused a slight increase in the
maximum LA yield from 54.8 % to 59.7 %, respectively. This outcome is
consistent with the role of hydrochloric acid as a catalyst not changing
chemical equilibrium under ideal conditions even though the chemical
reaction rate would increase with increasing acid concentration. As a result,
the maximum LA concentration and yield changed little for the three acid
concentrations applied. However, increasing acid concentration reduced the
time needed to attain the maximum LA yield from about 20 min with an acid
concentration of 0.309 M to only 6 min at 0.926 M. This result confirmed
that acids accelerated the reactions. Moreover, LA concentrations and yields
dropped if the solution was held beyond the optimum time due to by-
product formation [26].

The Influence of Reaction Time

The normal trend in the most reactions carried out at moderate reaction
temperatures is that increasing reaction time also results in significantly
increased levulinic acid yield. However, Chang et al. [8] also observed that
time had a relative significant correlation with other variables. Temperature,
acid concentration and liquid-to-solid ratio influenced significantly the time
required for the over-all reaction to proceed. Moreover, an optimum
temperature existed in the conversion process. It was suggested that if the
hydrolysis was continued for too long a time, the yield decreased, again as
the result of side reactions occurring that consumed the levulinic acid
already formed. Peng et al. [38] noted that the amount of LA increased very
fast during the first 140 min. After this it was observed that only a slight rise
occurred after 140 min of reaction time. Finally, it was found that 180 min
was sufficient for completion of the hydrolysis reaction. Yan et al. [10]
observed that bagasse was hydrolyzed rapidly during the first 10 min after
which the hydrolysis rate slowed down and the yield rose gently during the
last 20 min. whereas the rate of the hydrolysis reaction for paddy straw
reached its highest point after 25 min. The reaction proceeded well for 10
min, and then the reaction progressed much more sluggishly. The reason for
these differences in kinetics may lie in the different cellulose content,
different cellulose type and the intrinsic composition structures. The
reaction was interrupted after 45 min because side reactions started to occur
when the degradation products were exposed to high temperatures for a
prolonged period of time. Thomas [57] also noticed that continuing the
digestion of levulose, dextrose or starch with hydrochloric acid for periods
longer than one hour actually resulted in decreased yields of levulinic acid,
the effect decreasing in this order. Alonso et al. [58] observed that short
reaction times and low acid concentrations prevent furfural degradation
reactions and leave the cellulose mostly unconverted, leading to low LA

10
yields (less than 11 %). On the other hand, Cha et al. [59] were using a
reactive extrusion process to hydrolyze starch in the presence of 5 wt %
sulfuric acid. They noticed that the levulinic acid yield increased as reaction
time increased from 20 to 60 min. However, the yields in the samples
containing 25 wt % extruded starch and further reacted at 40 and 60 min of
reaction time were not significantly different. Wang et al. [37] also
investigated the effect of the reaction temperature on the levulinic acid yield.
It was concluded that the reaction rate is very sensitive to the temperature
and the rate was reduced dramatically at lower temperatures. As already
stated, higher temperatures favor the production of more LA, also observed
by Kang et al. [35].

The Influence of Pre-treatment

First of all it should be pointed out here that it is extremely difficult to

directly compare the values of levulinic acid yield reported in the literature.
It is very important to note that some of the raw materials were not really
‘pure’ raw materials in its proper sense. In fact, several starting materials
had already been exposed to some type of pre-treatment or purification
processes. Because of these reasons the results obtained may display various
‘unfair’ advantages in comparison to studies where the starting materials
were not pre-treated in any form. When Galletti et al. [30] were using poplar
sawdust as a substrate, the performance could be improved not only by
adopting MW irradiation, but also by carrying out traditional heating in two
steps: a pre-hydrolysis at lower temperature and a successive conversion
step at 200 °C. The pretreatment at a lower temperature, such as 120 °C for
2 h, dissolves part of the hemicelluloses thus yielding cellulose more easily
accessible and, consequently, increasing the yield of levulinic acid during the
second hydrolysis step. Upon a preliminary screening, the adoption of the
pre-hydrolysis step appears as a more immediate approach in order to
improve the LA yields from raw biomass in comparison to MW irradiation
[30].

Chen et al. [60] found out that steam explosion (SE) combined with
superfine grinding (SG) of rice straw (RS) could effectively increase levulinic
acid (LA) yield due to the reduction of particle size and the increase of
specific surface area which would enhancing the accessibility of cellulose
[61]. It was found that LA yield reached upon a SGSERS sequence amounted
to 22.8 %, accounting for 70 % of the theoretical value, which was 61 %
higher than obtained when applying the sequence mechanical grinding (MG)
SERS. When comparing MGRS and SGRS sequences, LA yield of MGSERS
and SGSERS were increased by 95 % and 68 %, respectively. Pretreatment
lowers the polymerization grade and the crystallinity of the cellulose, which

11
can exert a significant influence on the hydrolysis yield. Additionally, the
chemical pretreatment stage of the raw material aims to partially remove the
lignin bound to the hemicelluloses without degrading the cellulosic chain
[62]. For this reason Bevilaqua et al. [34] conducted in their study some
pretreatments focusing on the delignification of the biomass and the
elimination of non-contributing substances, like extractives and metals. To
establish the best precondition for pressurized acid hydrolysis (PAH), rice
husk (RH) was submitted to different pretreatments. From an analysis of the
pretreatment procedures, it can be seen that the strategy of applying aqueous
extraction via Soxhlet extraction resulted in a higher LA yield (18.2 g L-1),
probably due to the elimination of interfering metals and an improved
performance PAH on RH. There was no apparent advantage in pretreatment
with oxalic acid aiming at removing metals or with hydrogen peroxide upon
an alkaline medium (delignification). It is evident, in this case, that a part of
the glucose was released during the pretreatment. Soxhlet extraction of RH
with an organic solvent, with the aim of eliminating extractives and
pretreatment with chlorite (RH delignification and facilitation of cellulose
hydrolysis), did not exert any significant influence on the LA yield. Also,
Ghorpade and Hanna [63] patented a process for producing levulinic acid
using an extrusion process, which is advantageous in that it is continuous,
requires fewer steps and reduces reaction time compared with a batch
reactor process. However, the extrusion process is limited due to the loss of
evaporated gases containing HMF. In Cha and Hanna’s [59] study extrusion
has been used as pre-treatment in a ‘two-stage’ process. After extrusion, the
extrudates were reacted with additional water and sulfuric acid in a
pressurized reactor. Extrusion processing increased levulinic acid yield
because the extrusion processing increased the hydrolysis of starch in the
presence of an acid. The yields of glucose and levulinic acid increased at the
higher extrusion temperature and slower screw speed (longer residence
time). High amylose corn starch (HAS) was also converted more readily to
glucose and levulinic acid than normal starch (NS). Extrusion of both starch
varieties resulted in even higher yields.

The cellulose hydrolysis study of Stijn Van de Vyver et al. [64] indicates that
the reaction rate is strongly dependent on the degree of crystallinity, well in
agreement with previous studies. Since the cleavage of the b-1,4-glycosidic
bonds is considered to be rate-determining, hydrolysis of ball-milled
cellulose gave the highest conversion, carbon efficiency and selectivity
among the five cellulose fractions, with a LA yield higher than 27 %.
Interestingly, the observed LA yield corresponds well to the results for
cellobiose, cellohexaose and even starch. The latter observation should be
explained based on the low crystallinity index of 4.1 % for ball-milled
cellulose when compared to the substantially higher crystallinities for

12
commercial cellulose substrates. Generally, a limited accessibility of the b-
1,4-glycosidic linkages of cellulose is likely responsible for slower hydrolysis
rates at higher crystallinity. Alonso et al. [58] have been using corn stover
which has been subjected to an alkaline hydrogen peroxide pretreatment
(AHP), which partially removes the lignin [65, 66]. By using AHP corn
stover, the yield of LA increases slightly to 69 % in the first batch, and
remained high (overall 53 %) after the third batch of stover. Removing the
lignin was not necessary for the process; however the sulfuric acid was
retained in the reactor, and not consumed by the lignin. The use of the AHP
corn stover allows for lower acid concentrations and shorter reaction times
to be employed, resulting in furfural yields up to 96 %, with low conversion
of cellulose.

The influence of Additives

Already in the 1940’s Thompson [43] noticed when converting hydrol

(mother liquor from industrial, crystalline corn sugar) that the presence of
sodium chloride in the hydrolysis mixture will not only increase the speed of
the reaction but will also increase the yield of levulinic acid. The
phenomenon was at that time not fully understood, but it was speculated
that the presence of the sodium chloride in the reaction mixture increases
the activity of the mineral acid. The best results were obtained when the salt-
to-water wt-ratio was 6. Galletti et al. [30] also observed that the addition of
a cheap electrolyte to the reaction medium, such as NaCl, increased the LA
yield for some substrates such as wheat straw and tobacco chops. When
water slurry of tobacco chops powder containing 25 wt % of cellulose was
employed as the starting material, the actual yield of LA reached about 83 %
of the theoretical yield. The reason given was the combined effect of both the
addition of the electrolyte and the pre-hydrolysis step at 120 °C. This yield is
one of the highest ever reported using a waste biomass in a batch process.
Also, more generally, the yields reached with the different substrates are
promising if compared with those that have been reported until now [51]. In
essence, it is known that the addition of an electrolyte can increase the rate
of the heterogeneous acid hydrolysis of cellulose to convert to glucose and
then LA, while enhancing the accessibility of the rest portion of the cellulose
[67]. Liu et al. [68] also reported that inorganic salts could increase the
hydrolysis rate of hemicellulose components during dilute acid
pretreatment. This salt-effect has been explained by applying the Donnan’s
theory of membrane equilibria to the heterogeneous hydrolysis of the
cellulose in dilute acid. The difference of concentration of H 3O+ ions in the
two phases can be minimized by the addition of an inert, diffusible salt. The
addition of an electrolyte should result in an increase in the concentration of
H3O+ ions in the cellulose phase, thus increasing its swelling and the rate of

13
protonation of reaction sites [30]. The effect of added salts on Nafion as a
solid acid catalyst for the hydrolysis of cellulose was also investigated by
Potvin et al. [69]. The result of the investigation was that the yield of
levulinic acid can be increased 5-fold from 14 % to 72 % upon incorporation
of a 25 wt % NaCl solution. The use of a different salt, such as potassium
chloride, was also investigated to determine if the salt effect was general.
Reactions using 10 wt % KCl was less powerful than reactions with
comparable concentrations of NaCl. On the contrary, 5 wt % KCl solution
induced higher product yields than the use of 5 wt % NaCl solution. The
yields were not significantly different between the sodium and potassium
chloride trials indicating that cation size may not have a large influence on
the product yield. They hypothesize that the greater concentration of NaCl
allows for a greater concentration of ions in solution. These charged particles
interact with the hydrogen bonding network of the cellulose structure. The
dramatic increase in yield indicates that sodium chloride is effective in
interrupting the hydrogen bonding network at high temperatures and
pressures. Wettstein et al. [70] have also been using a solute additive for the
conversion of cellulose. They have demonstrated a biphasic process to make
GVL (gamma-valerolactone), in which cellulose is deconstructed to produce
LA and FA using a dilute aqueous solution of hydrochloric acid (HCl) with a
sufficient amount of a dissolved solute in the solution to yield a biphasic
system with GVL. The top phase is an organic phase rich in GVL and LA,
while the bottom phase is an aqueous phase rich in mineral acid. The
maximum yield of LA achieved was 72 % after the first batch of cellulose and
using 1.25 M HCl saturated with 35 wt % NaCl and a 1:1 aqueous-to-organic
wt-ratio. During the reaction, the GVL continuously extracts the LA and FA
from the aqueous phase, and solubilizes the humins that form. The aqueous
phase can be used to carry out additional cellulose deconstructions. The
organic phase is then transferred to a hydrogenation reactor, where the LA is
converted into GVL (using a Ru–Sn/C catalyst) that can be used directly or
further upgraded to chemicals [71-73] or transportation fuels [74, 75]. A
biphasic reaction system using an aqueous phase containing a phase
modifier (e.g., salt and sugars) and GVL as a solvent offers significant
advantages in the production of GVL from biomass derived cellulose. This
system solves the following three important issues that limit current
processing approaches: eliminating the need for a filtration step after
cellulose deconstruction, eliminating the need for a step to separate the
product from the solvent (the product is the solvent), and using a renewable
solvent. Alonso et al. [58] have taken the use of GVL a step further in the
conversion of lignocellulosic biomass (corn stover). By using GVL as a
solvent broadens the optimal processing conditions allowing the conversion
of hemicelluloses and cellulose simultaneously in a single reactor, thus
eliminating pre-treatment steps to fractionate biomass and simplifying

14
product separation since GVL is a product of the process. Other important
advantages are elimination of reactor clogging and other solids handling
problems because GVL effectively solubilizes the biomass (and humins). The
GVL solvent also increases the rate of cellulose conversion and decreases the
rate of furfural degradation and is completely miscible with water, allowing
wet biomass to be used in the process.

Lin et al. [46] was converting cellulose over a ZrO2 catalyst by a one-pot
catalytic aqueous phase partial oxidation (APPO) process. Under the APPO
conditions, the molar ratio of formic acid to LA was only ~0.35 with a ZrO2
catalyst. The low formic/levulinic acid molar ratio implies that, unlike acid
hydrolysis, APPO follows a pathway in which formic acid is no longer a
major by-product. Nevertheless, the LA yield is sensitive to the oxygen
partial pressure and the maximum yield of LA was obtained with 2.8 % O 2.
Redox, rather than acid-base, properties of the ZrO2 catalyst play the central
role in the oxidative deconstruction of cellulose in the APPO reactions.
Higher oxygen partial pressures resulted in lower LA yields as LA is further
degraded to acetic acid and CO2 by strong oxidation. The results also show
that there is a decrease of 5 % in LA yield when not feeding O 2 compared to
the case with 2.8 % O2 loading. Another unique feature of the APPO process
is the low yield of water insoluble humins. It is proposed that HMF is the
precursor of humins during the acid hydrolysis of cellulose [76]. However,
the proposed APPO reaction mechanism indicates that gluconic acid and not
HMF, is the key intermediate to produce LA. This is very likely the reason
why the yield of humins was lower than in a pure acid catalyzed hydrolysis
reaction.

The Influence of Agitation Speed

It is well known that agitation speed is an important factor in solid-liquid

phase catalytic reaction systems. If the agitation speed is too low the reaction
may suffer from low reaction rate, low conversion and low product yields etc.
This is a result of high interfacial mass transfer resistances between the two
phases. Increasing the agitation speed might increase the contacting area
and relative velocity between the two phases, and hence diminish any
external diffusion limitations [77]. The effect of agitation speed on the yields
of reaction products was, in fact, investigated by Peng et al. [38]. The
hydrolytic reaction was carried out by varying the agitation speed from 0–
600 rpm using cellulose as a feedstock and chromium chloride as a catalyst.
As can be seen, the interfacial mass transfer resistances between the solid
surface and water phase appear as negligible when the agitation speed is
higher than 200 rpm considering levulinic acid yield. However, one could
not observe any clear influence of the agitation speed in terms of the yields of

15
glucose and 5-hydroximethylfurfural (HMF) - most probably because they
are properly dissolved in the liquid and thus can be well contacted with the
catalyst. Nevertheless, the reader should be reminded that the design of the
stirrer as well as the baffling of the reaction vessel have a significant
influence in terms of the mixing performance.

16
Materials and methods
Chemicals

The commercially acquired reagents and chemicals used were of analytical

grade and used without further purifications or other treatment procedures.
D-glucose (VWR International, >99 %), 5-hydroxymethylfurfural (Aldrich,
99 %), levulinic acid (Janssen Chimica, 98+ %) and formic acid (Sigma-
Aldrich, 98-100 %) were used to facilitate the calibration curves needed to
follow the reaction kinetics. HPLC grade sulfuric acid (Fluka, 50 %) was used
for eluent preparation. Pyridine (Fluka, ≥99 %), hexamethyldisilazane
(Fluka, ≥99 %) and chloromethylsilane (Fluka ≥99 %) were used for the
silylation. Phenolphthalein (Fluka) and Sodium chloride (Sigma-Aldrich,
≥99 %) were used for the acid titration of catalyst. Whenever water was used,
deionized water (MilliQ) was used to prepare all the solutions.

Raw materials

Most of the focus has been given to investigate the hydrolytic conversion of
Nordic, bleached, industrial pulp obtained as a gift from the Aditya Birla
Domsjö pulp mill in Sweden (a mixture of softwoods Norway Spruce and
Scots Pine), however Metsä-Serlas kraft pulp from Finland (hardwood birch,
Betula pendula) were compared as a competing raw material. The softwood
pulp utilized has a typical degree of polymerization (DP) in the range of 950
as an average whereas the DP of hardwood approaches 1900 on the basis of
viscosity measurements (Scandinavian Standard SCAN-CM 15:99) [78].
Kraft (sulphate) cellulose typically contains significant amounts of residual
hemicelluloses (16 wt % xylose pentose) [79] whereas sulphite pulp is lean on
hemicelluloses (sum of xylose and mannose pentoses comprise 4.2 wt %)
[80]. Native Birch wood (Betula pendula) has been reported to contain 23 %
of xylose, bound in the form of the hemicellulose xylanes [81].
Monosaccharide’s originating from hemicelluloses of four different bleached
birch pulps from Finnish paper mills has been studied earlier and it was
found that the average amount of xylose found in the pulps resides in the
range of 14.3 wt % (13.6–15.3 wt %) [82]. The pulps were utilized without
any prior chemical treatments but both the sulphite and sulphate pulp were
initially disintegrated by a centrifugal mill (ZM 200, Retch, Germany) with a
cutting sieve to an average particle size of 0.35 mm in order to facilitate a
realistic comparison. Since the degradation and transformations of the
cellulose polymers initially proceeds via hydrolysis to glucose, also
transformation of pure D-glucose was investigated in order to obtain insight
into the general reaction behaviour.

17
Acidic polymer catalyst

The acidic polymer based catalyst, Amberlyst 70, was obtained as a gift from
the Rohm and Haas Company [13]. The catalyst is a macro-porous,
polymeric, cationic ion exchange resin material applicable in high-
temperature applications and is designed to be used in various processes
such as olefin hydration, esterification and aromatic alkylation. In the
aforementioned applications, Amberlyst 70 offers good performance over
conventional resins due to its high thermal stability (up to 190 °C), catalytic
activity and good mechanical strength. Importantly, very low sulphonate
leaching has also been confirmed. The catalyst has an appearance as dark
brown and spherical particles with an effective particle size of around 0.50
mm. The average pore diameter corresponds to 220 Å (22 nm) and the
nitrogen physisorption (BET area) to 36 m2 g−1 [13, 83, 84].

Reactor system

All kinetic experiments were carried out batch wise in a standard 300 ml
laboratory scale, three-phase stainless-steel autoclave (Parr Inc, USA)
designed for high pressures and temperatures (see Fig. 1.). The temperature
was measured with a thermocouple and automatically adjusted with the
inbuilt temperature regulator (Parr 4848 Reactor Controller). The autoclave
was equipped with a sampling outlet fitted with a 7 μm metal sinter frit
designed to prevent the catalyst particles as well as pulp pieces to leave the
reaction vessel upon sampling of the liquid phase. The hydrolytic
degradation of wood pulp took place in the presence of catalysts in an
aqueous media and high stirring rates (1000 rpm) were applied in order to
eliminate any external mass transfer limitations. The reaction parameters
studied, such as the reaction time, temperature, pressure as well as the
nature of the catalyst was of crucial importance in terms of optimal
conversion of the biopolymers to platform chemicals. Each and every
experiment was commenced by charging the reaction vessel with a slurry
containing 1–9 g of pulp dispersed in 141–149 ml of deionized water along
with 1–9 g of catalyst. Before heating the reaction mixture to the intended
temperature (150–200 °C), the system was degassed (<0.01 atm) with a high
power vacuum pump to remove any residual air in the solution. After
reaching the preset temperature the agitation was engaged, gas atmosphere
(CO2, Ar, H2) was applied at set pressure (3–50 bar excluding vapour
pressure from water) and this was considered as the initial start of the
reaction. A blank reaction (without catalyst) has also been performed at 200
°C with a higher CO2 pressure than normal reaction conditions (90 bar
instead of 50 bar) to exclude that carbonic acid catalyzes the reaction.
Throughout the experimental run, samples were taken at suitable intervals

18
and the sampling line was flushed with small volumes of the reaction
solution in between the samples to avoid any contamination between
consecutive samples. For the sake of precaution, the samples were once more
filtered and the composition was determined by means of high-performance
liquid chromatography (HPLC).

Gas inlet

Water in/outlet

RPMI
TI
Reactor Controller
Sampling PI
RPMIC

TIC

PI
PI Pressure indicator
Reactor
TI Temperature indicator
Heating jacket
TIC Temperature indicator & Thermocouple
controller PC
Coil
RPMI RPM indicator
Sinter
RPMIC RPM indicator & controller Agitator

Figure 1. Schematic picture of the experimental set-up used for the catalytic transformation
of wood pulp in batch mode.

Substrate and catalyst characterization

The substrates and catalyst were characterized by means of the following

methods: scanning electron microscopy, nitrogen physisorption and acid-
base titration. Also the wood pulps were characterized by scanning Electron
Microscopy (SEM): The morphology of the two wood pulps, kraft pulp from
Metsä-Serla and the sulfite pulp from Aditya Birla (Domsjö) was investigated
by SEM (Cambridge Leica Stereoscan 360). The samples were prepared with
a thin layer (50 Å) of gold and carbon before they were introduced to the
measurement chamber. Some of the samples were also critical-point-dried
for a comparison with air-dried samples. Also the morphology of the
Amberlyst 70 catalyst was investigated by SEM (Cambridge Stereoscan 360).
Further nitrogen adsorption–desorption measurements were conducted for
the fresh and spent catalyst using Micromeritics TriStar 3000 porosimeter.
Adsorption–desorption isotherms were recorded at −196 °C after degassed
the samples at 120 °C. Surface areas were calculated by B.E.T method and
pore volumes were calculated from desorption isotherm. Pore size

19
distribution was estimated using the Barrett, Joyner and Halenda (BJH)
algorithm (ASAP-2010) available as built-in software from Micromeritics.
The acid site concentration of the catalyst was measured by means of a
conventional titration method [85]. 1 g of the resin was added to about 50 ml
of NaCl solution (200 g L-1). The cation exchange between H+ and Na+ was
allowed to take place for 24 h upon stirring of the system. The mixture was
then titrated with a 0.1 N NaOH solution. The measurement was carried out
on fresh catalyst and on spent catalysts exposed to the reaction temperatures
of 190 and 200 °C, respectively.

Nitrogen physisorption

Surface area, pore size distribution and pore volume is an attribute that is
used by catalyst manufacturers and users to monitor the activity and stability
of catalysts as well as a quality control tool during catalyst manufacture.
There are different methods used to measure surface area and each method
can yield different results. In physisorption, a monolayer formation of inert
gas, mostly nitrogen, is adsorbed by weak Van der Waals attractions on the
surface of a solid material or, in case of porous materials, also on the surface
of pores. Most widely known is the determination of the B.E.T (Stephen
Brunauer, Paul Hugh Emmett, and Edward Teller) surface area by gas
adsorption. Adsorption of nitrogen at a temperature of 77 K leads to a so-
called adsorption isotherm, sometimes referred to as the B.E.T. isotherm,
which is the most common way to express measured porosity of materials.
The principle of capillary condensation is usually applied to assess the
presence of pores, pore volume and pore size distribution. Pre-treatment of
the sample is performed at elevated temperature in vacuum or either by a
flowing inert gas in order to remove any contaminants.

Scanning electron microscopy

A scanning electron microscope (SEM) is a type of electron microscope that

produces micrographs of a solid specimen by scanning it with a focused
beam of high-energy electrons. The electrons interact with atoms in the
sample, producing signals that can be detected and that contain information
about the surface topography, chemical composition, crystalline structure
and orientation of materials making up the sample. In most applications,
information is collected over a selected area of the surface of the sample, and
a micrograph is generated that displays spatial variations in these properties.
Generally the electron beam is scanned in a raster scan pattern, and the
beam's position is combined with the detected signal. A two-dimensional
micrograph with a resolution better than 1 nanometer can be produced. The
most common mode of detection is by secondary electrons emitted by atoms

20
excited by the electron beam. The number of secondary electrons is a
function of the angle between the surface and the beam. On a flat surface, the
plume of secondary electrons is mostly contained by the sample. However on
a tilted surface, the plume is partially exposed and more electrons are
emitted. By scanning the sample and detecting the secondary electrons, a
micrograph displaying the tilt of the surface is generated.

Acid-base titration

The acid-base titration process consists of the addition of a solution with

known concentration, from a buret, to a measured volume of a solution of
the other reactant or to a weighed sample dissolved in water, until the same
number of equivalents of each substance has been used. The end point in the
titration is detected by means of a suitable indicator. Phenolphthalein, which
is red in basic solution and colorless in acid solution, is often used for acid-
base titrations. The end point, where the permanent color change just occurs
after thorough mixing, is usually very sharp. Often a drop or a fraction of a
drop will bring about a color change.

Product analysis

The quantitative composition of the samples in the liquid-phase was

analyzed off-line with high-performance liquid chromatography (HPLC,
Agilent Technologies 1200 Series) equipped with a refractive index (RI)
detector, a degasser, a double-channel binary pump and an auto sampler.
The analytical column of choice (Bio-Rad Aminex HPX-87H) is a 300 x 7.8
mm, a pre-packed HPLC column suited for carbohydrate and acidic
compounds analysis supplied in the proton form containing 9 μm particle
size with 8 % cross linkage and is designed to operate at a pH range of 1–3. 5
mM H2SO4 was utilized as the mobile phase with a flow rate of 0.5 cm 3 min-1
and temperature of 60 °C. The samples were injected into the HPLCs directly
after the sample was taken without any pre-treatment other than filtering (2
µm) to prevent column damage. The analysis for a sample was completed
within 1 h. The concentrations of each compound in the liquid-phase mixture
were determined using calibration curves obtained by analyzing standard
solutions with known concentrations. For the sake of the clarity, instead of
more commonly applied UV-vis detector, refractive index (RI) detection is a
must upon analysis of carbohydrates and their derivatives since UV detection
is not capable of resolving most of the species. A Bio-Rad Aminex HPX-87C
carbohydrate column was also tested, however the acidic main compounds,
formic- and levulinic acid, peaks overlapped each other (same retention
times).

21
Other possible by-products of the acid-catalyzed hydrolysis of cellulose are
gas-phase components from thermal degradation (eventually catalyzed by
the autoclave walls) reactions of reactants, intermediates and/or products.
To gain insights into the extent of these reactions, a GC study has been
carried out to analyze the gas phase composition during an experiment
performed at 180 ◦C without any gas addition. A sample of non-condensable
gases were taken with a gas syringe and analyzed with a Varian 490-GC
Micro-GC. To identify the compounds in the liquid phase gas
chromatography-mass spectrometry (GC-MS) analysis have been performed.
The samples were derivatized to make the compounds volatile and stable,
suitable for gas chromatography analysis. About three drops (150 µl) of the
liquid samples were transferred to a little test tube and evaporated in a water
bath operating at 40 °C under nitrogen flow. As a reference a blank sample
containing only distilled water was dried and used. The dried samples were
silylated by addition of 150-200 µl of pyridine, 200 µl of HMDS silylation
reagent (hexametyldisilazane) and, finally, 100 µl of TMCS reagent
(chloromethylsilane). After half an hour of stirring at room temperature the
samples were ready for analysis. The samples were transferred into small
ampoules and analyzed with GC-MS. The GC-MS was equipped with an HP-1
column (25 m x 0.2 mm x 0.11 µm) and a flow of 0.8 ml/min (helium) was
used and the split was 15 ml/min. The heating program started at 60 °C with
a heating rate of 8 °C/min up to 325 °C.

Liquid chromatography

Although gas chromatography is widely used, it is limited to samples that are

thermally stable and easily volatilized. Nonvolatile samples, such as peptides
and carbohydrates, can be analyzed by GC, but only after they have been
made more volatile by a suitable chemical derivatization. For this reason, the
various techniques included within the general scope of liquid
chromatography are among the most commonly used separation techniques.
In high-performance liquid chromatography (HPLC), a liquid sample, or a
solid sample dissolved in a suitable solvent, is carried through a
chromatographic column by a liquid mobile phase. Separation is determined
by solute/stationary-phase interactions, including liquid–solid adsorption,
liquid–liquid partitioning, ion exchange and size exclusion, and by
solute/mobile-phase interactions. In each case, however, the basic
instrumentation is essentially the same [86]

Over the past three to four decades, high-performance liquid

chromatography (HPLC) has been the method of choice for the
determination of carbohydrate species, and as a result a large number of
HPLC methods have been developed to determine a wide variety of

22
carbohydrate samples. One of the most challenging areas of analytical
chemistry is the development of selective and sensitive methods for analyses
of carbohydrates. The main difficulties in the analysis of carbohydrates arise
from their considerable number of isomeric forms due to the various
possible configurations of the monosaccharides. Oligo- and polysaccharides
are composed of different combinations of them, forming linear or branched
polymeric species, many of which may differ only in the position of
attachment and anomeric configuration of the glycosidic linkages. RI
detection is the most popular detection technique for carbohydrates in HPLC
but a serious drawback is that it can only be used to monitor isocratic
separations [87].

Gas chromatography

In gas chromatography (GC) the sample, which may be a gas or liquid, is

injected into a stream of an inert gaseous mobile phase (carrier gas). The
sample is carried through a packed or capillary column where the sample’s
components separate based on their ability to distribute themselves between
the mobile and stationary phases. The most common mobile phases for GC
are He, Ar, and N2, which have the advantage of being chemically inert
toward both the sample and the stationary phase. The choice of which carrier
gas to use is often determined by the instrument’s detector [86].

Mass spectrometry

A mass spectrometer consists of three major parts: the ion source, the mass
analyzer, and the detector. The first mass spectrometer was used in England
by JJ Thompson in 1912, and by F. W. Aston in 1919, but the instrument that
resembles today's mass spectrometers was first constructed in 1932 [88].
Over the last two decades mass spectrometry has become one of the central
techniques in analytical chemistry. Its importance is now comparable to that
of the more traditional electrophoresis, liquid and gas separations
techniques, and it is often used in conjunction with them as so-called
“hyphenated” techniques, such as CE-MS, LC-MS and GC-MS. Mass
spectrometry is used for both quantitative and qualitative analysis and is
based on production of unstable ions from neutral species, that is, atoms,
molecules or clusters and the study of the decomposition (fragmentation) of
these. The separation should also be independent of the chemical
conformation of the species. When a compound is ionized in vacuum the
compound decays whereby new ions are formed. The apparatus must be kept
under vacuum (typically <10-6 mmHg) to prevent reactions between the
unstable fragment ions and gases, resulting in mass spectra that cannot be
interpreted. The ions are separated and deposited in a chart relative to the

23
proportion of ions towards the ion mass, resulting in a so-called mass
spectrum. Each compound decomposes in a manner which is unique
precisely for this compound and thus a mass spectrum is obtained that is
specific for that molecule. The decomposition gives us information about the
association structure, which allows the mass spectrum can be interpreted
and compound can be identified. All mass analyzers presently in use are
based on electromagnetism so ions are required to obtain separation. The
different types of mass spectrometers differ in regard to the mechanism by
which ions are separated. There are several types of mass analyzers used in
mass spectrometric research and they can be divided into different
categories, such as magnetic or pure electric, scanning/non-scanning (pulse
based), and trapping/non-trapping analyzers [89].

Derivatization for GC/MS

Silylation is the most widely used derivatization procedure for gas

chromatography and mass spectrometry analysis and have been used since
the late fifties. A wide variety of products (and functional groups) like
alcohols, carboxylic acids, amines, thiols, and phosphates etc. can be
derivatized by silylation. The process involves the replacement of an active
proton with a trialkylsilyl group, typically trimethylsilyl (-SiMe3). Compared
to their parent compounds, a silyl derivative generally are more volatile, less
polar, and more thermally stable and enables the GC-MS analysis of many
involatile and too unstable compounds [90].

Definitions for the yield calculations of levulinic acid (LA) and

formic acid (FA)

The yield of levulinic acid (LA) on molar basis (𝒀𝑳𝑨 ) was defined as the ratio
between the LA concentration in the reaction product (𝑪𝑳𝑨 ) and the
concentration of the available C6-sugars (𝑪𝑪𝟔 ) in cellulose and hemicelluloses
fractions in the pulp:

𝐶𝐿𝐴
𝑌𝐿𝐴 (𝑚𝑜𝑙 %) = × 100 % (1)
𝐶𝐶6

It is also possible to define the yield of LA on a weight base (𝒀𝑳𝑨,𝒘𝒕 ),

corresponding to the mass ratio between the LA and the available C6-sugars
in the pulp:

24
 𝐶𝐿𝐴 × 𝑀𝐿𝐴
𝑌𝐿𝐴,𝑤𝑡 (𝑤𝑡 %) = × 100 % (2)
𝐶𝐶6 × 𝑀𝐶6

In eq. (2), the terms and represent the molecular weight of LA (116 g mol –1)
and C6-sugars (180 g mol–1), respectively.

The yield of LA can also be defined as the ratio between the mass of LA and
the total mass of the oven-dried pulp:

𝐶𝐿𝐴 ×𝑀𝐿𝐴
𝑌𝐿𝐴,𝑡𝑜𝑡𝑎𝑙 (𝑤𝑡 %) = × 100 % (3)
𝑚𝑝𝑢𝑙𝑝

where 𝒎𝒑𝒖𝒍𝒑 represent the mass of the oven-dried pulp.

The yield of formic acid (FA) on molar basis (𝒀𝑭𝑨 ) was calculated in the
same manner except that the sugar concentration was based on the available
C6- and C5-sugars in cellulose and hemicelluloses fractions in the pulp. The
theoretical yield of LA from C6-sugars is 100 mol %, or 64.5 wt % due to the
co-production of formic acid.

Modelling software and techniques

For the modeling of the reaction kinetics, the software Modest® was used
[91]. The software solves the reactor model equations (system of ordinary
differential equations) with the backward difference method and optimizes
the parameter values using a hybrid method involving Simflex and
Levenberg-Marquardt methods.

The software minimizes the following objective function

𝑄 = ∑ ∑(𝑐𝑖,𝑡,𝑒𝑥𝑝 − 𝑐𝑖,𝑡,𝑚𝑜𝑑𝑒𝑙 )2 𝑤𝑖,𝑡 (4)

𝑡 𝑖

25
Results and Discussion
Catalyst Characterization

In Fig. 2 we find the N2 adsorption–desorption isotherms of the fresh and

spent Amberlyst 70 catalysts. The results exhibit that the materials have a
sharp inflection at higher relative pressures in the range of 0.7–1.0p/p0.
This corresponds to type-V curves according to the IUPAC classification,
characteristic to large pore materials. The hysteresis loop observed at the
inflection, reflects the irregularity of the pore sizes over the surface. The
results indicate that the surface areas of fresh and spent catalysts are 0.165
and 35.72 m2 g−1, respectively; at the same time, the pore volumes were
measured to reside at 0.0015 and 0.168 cm3 g−1; and the average pore sizes at
37.5 and 18.16 nm, respectively. The results of the spent catalysts revealed
that the morphological properties are clearly altered during the reaction. The
surface area and pore volume of the spent catalyst were increased
enormously; this might be due to swelling nature of the catalyst in aqueous
reaction conditions.

Fig. 2. Nitrogen adsorption–desorption curves for (a) fresh Amberlyst 70 and (b) spent
Amberlyst 70.

The changes in the surface properties were further evidenced with SEM
images of the catalysts. The scanning electron micrographs (SEM) show
sponge like porous surface over the spent catalyst (see Fig. 3).

The exchange capacity of the fresh resin determined by the dry weight
titration method resulted in a capacity of 2.50 mequiv. g-1. This value was
rather well in line with the manufacturer’s data (2.55 mequiv. g-1). However,
when the catalyst was exposed to the reaction temperature of 190 °C, a
reduction in the number of acid sites at around 70 % of the original value
was obtained whereas 200 °C reaction temperature resulted in a reduction in
the number of acid sites of around 60 %, in comparison to the fresh catalyst.

26
Figure 3. Scanning electron micrographs of fresh (top) and spent (below) Amberlyst 70
catalyst (scales correspond to 500, 20, and 2 respective 0.5 µm).

Substrate characterization

Typical scanning electron micrographs of the wood pulps from Metsä-Serla

(M-S) and Domsjö (D), respectively, are depicted in Fig. 4. When looking at
the sample M-S 0.35 AD with fibres from Metsä-Serla, one can see that the
fibre surface is much smoother than the fibre surface of the sample from
Domsjö, D 0.35 AD. A probable reason for this is that all the hemicellulose
contained within the pulp was not dissolved from the kraft pulp from Metsä-
Serla; however, the sulfite pulp from Domsjö turned out to be almost
hemicellulose-free, resulting in a less glossy surface appearance. Upon a
comparison between air-dried and freeze-dried pulp, it was a bit more
difficult to draw any further conclusions. In theory, freeze drying should be
less destructive to the fibers; however, in this case it was difficult to see any
differences between the micrographs obtained for the wood fibre samples.

27
M-S 0.35 AD

D 0.35 AD

D 0.35 CPD

D CPD

D AD

Figure 4. Scanning electron micrographs of wood pulps. Scales correspond to 200, 20, and
10 µm. M-S (Metsä-Serla), D (Domsjö), AD (air-dried), CPD (critical-point-dried), 0.35
(grinded to; mm).

28
Auto-catalysis

Initially, reactions were also carried out without catalyst until to the reaction
temperature of 200 °C containing 10, 30, 50 and 80 mM formic and levulinic
acid, which corresponds to the concentration range we work within.
Consequently, we could observe that we have very little or negligible
autocatalysis occurring during our experiments. What could be observed was
that the hemicellulose and a very small part of the cellulose were converted
to intermediates and final products before the reaction subsided. It appeared
as if the solution was not sufficiently acidic to react the crystalline part of the
cellulose, but enough acidic (LA pKa = 4.59, FA pKa = 3.75 [92, 93]) to react
some of the amorphous part. However, the reaction rates were very slow
(particularly at low concentrations) and approximately around 5 wt% of the
total mass of pulp was converted before reaction died. In an experiment with
catalyst (heterogeneous catalysis), the contribution of autocatalysis in the
system is likely to be very negligible. The reason is that all the hemicellulose
and probably also the most part of the amorphous cellulose is already
converted before the concentration of formic acid and levulinic acid becomes
so high that it could contribute to autocatalysis. A blank reaction without the
catalyst was also performed at 200 °C and under higher CO2 pressure than at
normal reaction conditions (90 bars instead of 50 bars). The goal was to
determine whether the carbonic acid formed catalyzes the reaction. No pulp
conversion was observed; i.e. no. reaction products or intermediates (or
humins visually) were observed upon analysis.

Reusability of the catalyst, catalyst deactivation

The catalyst reusability was studied at a reaction temperature of 190 °C and

200 °C, respectively. After the first hydrolysis reaction, the resin was
separated from the reaction solution and washed with distilled water and
dried at 100 °C for 24 h. At 190 °C, the yield of LA an FA was approximately
similar as upon the first batch, but the reaction time was significantly longer.
At 200 °C reaction temperature, the catalyst activity reflects the results of
the acidic capacity measurements, i.e. lower product yields, lower reaction
rate and a higher formation of humins. The manufacturer, Rohm and Haas,
has suggested a maximum operating temperature of 190 °C, but some
investigators have reported that the resin could be considered as quite stable
even above this temperature [83]. Consequently, the loss of sulfonic groups
as a result of extended reaction times leads to the lower activity of the
catalyst. Nevertheless, an acid treatment should at least partially restore the
catalytic performance, but it has never been examined in practice.

29
Reaction network

A simplified reaction network for the acid-catalyzed hydrolysis of wood pulp

to levulinic and formic acids is introduced in Fig. 5.

Wood pulp
H2 O H2 O

OH OH OH OH
O O OH
OH
OH OH OH OH

Glucose Xylose
Humins
(or Tar)
3 H2 O 3 H2 O

O O

HO O O
decarbonylation
Furfural
HMF

2 H2O

O
OH + O OH O OH
H3C

Levulinic acid O Formic acid Formic acid

Decomp. prod.

Figure 5. The reaction network upon production of the platform chemicals levulinic and
formic acid from wood pulp.

In fact, the one-pot synthesis of levulinic acid from wood is a demanding

reaction since the whole process most conveniently starts with acid
hydrolysis of pulp thus giving rise to various issues in terms of waste
produced as well as the occurrence of multiple side reactions. Two reaction
pathways are involved: degradation of cellulose results into formation of
glucose, while the degradation of hemicelluloses generates xylose. The
glucose formed is under the experimental conditions further transformed to
5-hydroxymethylfurfural (HMF) which, in turn, is further converted in a
consecutive hydration-dehydration reaction sequence to levulinic (LA) and
formic acids (FA). The xylose pentoses originating from the hemicellulose
fractions transform to furfural which is finally decomposed to formic acid.
Furthermore, HMF can be decarbonylated into furfural [78]. The desired
raw material, lignocellulosic biomass, is mainly composed of cellulose,
hemicelluloses and lignin of which the first two can yield the desired
hexoses, the key intermediates in the production of levulinic acid.

30
Thereafter, sugars need to be dehydrated and rearranged to 5-
hydroxymethylfurfural and furfural depending on whether hexoses or
pentoses, respectively, are to be dehydrated. Consequently, hexoses can then
further rehydrate to formic and levulinic acids also requiring two equivalents
(moles) of water.

Since two different organic carboxylic acids are formed, the theoretical yield
of levulinic acid from hexoses and cellulose has been reported to reach 64.5
wt % and 71.5 wt % only, respectively [32]. It should, however, be stated that
the real yields of levulinic acid are typically lower than the theoretical yields
due to the harsh reaction conditions required for hydrolysis of
macromolecules. Thus, the formation of humins is hardly to be avoided and
throughout all kinetic experiments, black insoluble-substances known as
humins/tar were also found on the reactor walls and the amount was visibly
increased with reaction time. These are well known products of side-
reactions upon acid-catalyzed decomposition of pulp. Girisuta et al. [94]
confirmed by elemental analysis that the solids are a mixture consisting
mainly of humins (typical composition: C, 63.1; H, 4.2) and some unreacted
cellulose (C, 42.2; H, 6.1). In addition to the anticipated products, Girisuta et
al. [42] also detected small amounts of glucose-reversion products (e.g.,
levoglucosan, isomaltose and gentiobiose). The formation of the reversion
products was also observed in this study, but the maximum amount of these
products was very low and not accurately quantified in this work. A typical
example of an HPLC chromatogram of a sample taken in the beginning
during a reaction is given in Fig. 6.

Fig. 6. Typical HPLC chromatogram for the acid-catalyzed hydrolysis of soft wood pulp.

Other possible by-products of the acid-catalyzed hydrolysis of cellulose are

gas-phase components from thermal degradation (eventually catalyzed by
the autoclave walls) reactions of reactants and/or products. To gain insights
into the extent of these reactions, a GC study was carried out to analyze the
gas phase composition during an experiment performed at 180 °C without

31
any gas addition. CO, CO2 and H2 are typically detected. The amounts
observed were less than 0.1 wt% of the cellulose intake. This implies that the
formation of gas-phase compounds is only a minor reaction pathway under
the investigated reaction conditions, at lower temperatures. However, we
could not quantify the presence of any formed carbon dioxide since it was
used to pressurize the reactor system during most of our experiments. On
the other hand on the basis of the graphic illustrations of the kinetic
experiments, we can clearly see that formic acid decomposes at higher
temperatures. Most likely increases the levels of CO and CO 2 with increasing
reaction temperatures, but no conclusive investigations were performed.
Formic acid decomposes primarily to CO and H 2O in the gas phase
(dehydration), but to CO2 and H2 (decarboxylation) in the aqueous phase
[95] and indicating an increase in the total pressure of the reaction vessel.

The influence of reaction conditions and raw material on product

yields

Comparison between different wood pulps

In Fig. 7, one can see the results from the two experiments performed with
different wood pulps. One can clearly see that the yield of formic acid
compared to levulinic acid in the wood pulp from Metsä-Serla is much
higher than in the wood pulp from Domsjö. The underlying reason lies in the
high hemicelluloses content found in the wood pulp from Metsä-Serla. The
main difference when comparing the catalytic transformation of pulp from
Domsjö and pulp from Metsä-Serla over Amberlyst 70 is the absence of
xylose and, consequently, lower formation of furfural from the former raw
material.

60
LA Domsjö

50 FA Domsjö

40 LA Metsä-Serla
Yield / mol-%

FA Metsä-Serla
30

20

10

0
0 10 20 30 40 50 60
Reaction time / h

Fig. 7. The comparison of formic and levulinic acid yields for soft wood pulp from Domsjö
(sulfite pulp) and Metsä-Serla (sulfate pulp) (the reaction atmosphere is CO2, the catalyst and
substrate amount is 3 g respectively and the temperature is 180 ◦C).

32
Reaction with D-glucose

The conversion of wood pulp to LA and FA is a complex multistep process. It

is generally believed that the polymer chains of cellulose are broken down
into low molecular weight fragments and finally to glucose. Then, glucose is
decomposed to HMF, which is further converted into LA and FA in a molar
ratio of 1:1 [9]. However, HMF has also been reported to react into furfural
(carbonylation) which is further converted to formic acid [78]. Fructose is
also a known intermediate in acid catalyzed decomposition of glucose, but
could not be detected in this study. The epimerization step is very rapid and,
consequently, fructose was omitted as an individual chemical species. To
find out if we also have the same plausible reaction mechanism for the
Amberlyst 70 catalyzed conversion of wood pulp we did an experiment with
glucose. We can clearly see (Fig. 8) that LA and FA are not formed in a molar
ratio of 1:1. It is even clearer if we take into account the decomposition of FA
during time. All above-mentioned products (except fructose) were detected
in this study, which means we also detected furfural in our product samples
taken from the reactor during reaction with glucose. Furfural formed in
experiments with D-glucose originated most probably from the
decarbonylation of HMF, but also most certainly from the transformation of
some of the impurities, C5 sugars, in the D-glucose.

100
90
D-glucose
80
70
Yield / mol-%

60
Levulinic acid
50
40
Formic acid
30
20
10
0
0 5 10 15 20 25 30
Reaction time / h

Fig. 8. Experiment with d-glucose (the reaction atmosphere is CO2, the catalyst and substrate
amount is 3 g respectively and the temperature is 180 ◦C).

The influence of reaction temperature and catalyst to substrate

dosage

Hydrolysis of wood pulp by Amberlyst 70 is highly dependent upon the

reaction temperature. The effect of reaction temperature on the cellulose
conversion into LA and FA was investigated, and the experiments were
conducted at 150, 170, 180, 185, 190 and 200 °C, respectively. At lower
temperatures (150 °C), there is little conversion of cellulose to levulinic acid
as well as to formic acid. Note however, that the experiments at 150 and 170

33
°C were interrupted before all the wood pulp was consumed because of low
reaction rate. As the temperature was increased, the conversion rates
improved very rapidly. The increased conversion is likely related to increased
solubility of cellulose at higher temperatures. The conversion at 190 and 200
°C is very fast as can be seen in Fig. 9.

60 60
200 C 190 C 180 C
50 185 C 50 200 C 190 C 185 C
180 C

40 40
ƳLA / mol-%

ƳFA / mol-%
170 C
170 C
30 30

20 20

10 150 C 10 150 C

0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Reaction time / h Reaction time / h

Fig. 9. The influence of reaction temperature on levulinic and formic acid yields (the reaction
atmosphere is CO2 and the catalyst and substrate amount is 3 g respectively).

It has been reported that when the reaction temperature was increased
above 200 °C, the yield of LA began to fall. Higher temperatures could thus
accelerate the rate of chemical reactions, but unwanted side reactions also
appear at the same time. For example, LA is unstable above 230 °C, which
would be dehydrated to unsaturated lactones. Additionally, more humins
may occur during the reaction [10]. Therefore, an increase in the
temperature is unfavorable for the extent of reaction, and, consequently, the
reaction temperature was limited to 200 °C in this work. Another reason that
the maximum reaction temperature was limited to 200 °C is that the
manufacturer of Amberlyst 70 recommends a maximum reaction
temperature of 190 °C. However, it has been reported that the catalyst could
be considered as stable in some conditions even above this temperature [84].
Fig. 9 also shows the effect of the temperature on the decomposition of FA. It
can be observed that temperature has a significant effect on the
decomposition rate of FA. When the reaction temperature was increased
from 180 to 200 °C, there was a huge increase in the decomposition rate of
FA. The amount of FA decreased quickly very likely forming carbon
monoxide, carbon dioxide and hydrogen gas [95] indicated by a small but
notable rise of the pressure in the autoclave. The effect of catalyst dosage on
the yields of products is shown in Fig. 10.

34
 60 60

50 185 C, 3 g cat 50 185 C, 3 g cat

180 C, 3 g cat 180 C, 3 g cat

40 40

ƳFA / mol-%
ƳLA / mol-%

180 C, 2 g cat
180 C, 2 g cat
30 30

20 20

10 10

0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Reaction time / h Reaction time / h

Fig. 10. The effect of temperature and catalyst amount on levulinic and formic acid yields (the
reaction atmosphere is CO2 and substrate amount is 3 g).

The amount of catalyst in the reaction mixture was varied from 2 to 4 g at

180 °C and 1 to 3 g at 185 °C, respectively. As can be seen, the amount of
catalyst affected the extent of cellulose conversion, but not as much as the
reaction temperature does. Fig. 11 illustrates the maximum levulinic acid
yields obtained upon kinetic experiments conducted at different acid and
substrate concentrations. Theoretically, a higher liquid-to-solid ratio should
result in a higher yield of levulinic acid. However, it was further observed
that higher substrate loadings had an adverse effect in terms of the final
levulinic acid yields detected in the reaction mixture. These observations are
in line with other studies on the acid-catalyzed decompositions of HMF and
glucose, whereupon low substrate concentrations favored high LA yields.
Generally, lower concentration of cellulose resulted in higher yields of
levulinic acid. For each levulinic acid molecule generated, two molecules of
water are needed; otherwise 5-hydroxymethylfurfural (HMF) may be
converted into humins [42]. As also depicted by Fig. 11, evidently there exists
an optimal catalyst loading. Consequently, the addition of excess catalyst has
little or even negative effect on the LA yield. In fact, Yan et al also observed
that low concentration of hydrochloride acid resulted in too low
concentration of H+ ions thus being unable to facilitate cellulose hydrolysis
and, consequently, a low reaction rate was observed. Using low acid
concentrations is problematic, because the lignin and other impurities
present in the biomass consumes a fraction of the acid during the reaction.
In our case a load of 9 g substrate and 1 g catalyst resulted in only 5.9 mol %
yield of levulinic acid, at a reaction temperature of 190 °C.

35
 67.8
70 65.4 66.1
Levulinic acid yield [mol %] 60.2 70 62.1 62.7

Levulinic acid yield [mol %]

57.4 59.9 61.2
51.5 59.2 57.0
60 55.5 54.3
60
51.7
43.1 43.9
50 50.7
46.9 50 48.2
1 1
3 5.9 3
40 6 Substrate 40 6 Substrate
1 9 [g] 1 9 [g]
3 3
180 °C 6
9 190 °C 6
9
Catalyst [g] Catalyst [g]

Figure 11. Maximum levulinic acid yields formed at 180 °C and 190 °C at different acid and
substrate concentrations (the reaction atmosphere is CO2).

The influence of reaction gas and pressure

In this study, carbon dioxide was used as the reaction atmosphere. However,
to investigate whether various gases affect the conversion of wood pulp,
some tests with other gases and pressures were also performed. Fig. 12
illustrate the results of these experiments.

60 No gas addition 60
Ar 3 bar Ar 3 bar

50 CO2 50 bar 50 Ar 50 bar

Ar 50 bar CO2 50 bar
40 40
ƳFA / mol-%
ƳLA / mol-%

No gas addition
30 30

20 20

10 10

0 0
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80
Reaction time / h Reaction time / h

Fig. 12. The influence of reaction atmosphere and pressure on levulinic and formic acid yields
(the catalyst and substrate amount is 3 g respectively and the temperature is 180 ◦C).

As can be observed, argon as the reaction atmosphere seems to promote the

reaction rates, whereas the presence of carbon dioxide acted as a mild
inhibitor. This was surprising since we expected the significantly better
soluble CO2 to yield carbonic acid that would enhance the performance of
our system. However, the much less soluble and supposedly inert argon (by a
factor of roughly 103 [96]) seemed to yield better performance. The reason
for this is at present not clear to us. Our hypothesis is that the argon gas and
formic acid are capable of forming relatively strong argon–HCOOH
complexes [97] resembling hydrogen bonding networks. Thus, the
equilibrium in between the gas and the liquid phase is presumably shifted
toward the gas phase (low solubility of noble gases in water) and,
consequently, any possible product inhibition contribution to the additional

36
formation of HCOOH from cellulose (in liquid phase) is diminished,
resulting in increased amounts of the final desired products. Similar
phenomena might also contribute in the case of levulinic acid. In addition it
is well known that CO2 can be hydrogenated to formic acid (reversible
reaction). Further, particularly at higher temperatures, formic acid tends
easily to decompose. Thus, it might be that since these reactions are typically
metal catalyzed that our reactor setups (stainless steel and zirconium) could
to certain extent interact with the species emerging. A system containing at
least water, CO2 and HCOOH, in the presence of metals could provide
conditions that inhibit the initial HCOOH formation from cellulose.

Selectivity

Overall, we can conclude that the catalysis reaction is highly selective, and
there are very little by-products formed (except humins). Nevertheless, if we
compare our main products formic and levulinic acid, we can perhaps
discern small differences among the selectivity under different reaction
conditions. The molar yield of formed levulinic acid as a function of the
molar yield of produced formic acid in the catalytic transformation of wood
pulp over Amberlyst 70 resin is presented in Fig. 13, respectively.

60
No gas addition
50 CO2 50 bar
Ar 50 bar
40 Ar 3 bar
LA / mol-%

30

20

10

0
0 10 20 30 40 50 60
FA / mol-%

60 60
200 C 185 C, 3 g cat
190 C 185 C, 1 g cat
50 185 C 50 180 C, 4 g cat
180 C 180 C, 3 g cat
40 170 C 40 180 C, 2 g cat
LA / mol-%

LA / mol-%

150 C
30 30

20 20

10 10

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
FA / mol-% FA / mol-%

Fig. 13. The influence of the reaction atmosphere, temperature and catalyst amount on the
molar yield of levulinic acid as a function of the molar yield of formic acid (the reaction
atmosphere is CO2, the substrate and catalyst amount is 3 g respectively and the temperature
is 180 ◦C).

37
The most striking difference is perhaps that an atmosphere with low
pressure of argon seems to favor formic acid transformation. However, up to
40% yield level, the differences are extremely small. It seems likely that in
the end of a reaction the decomposition of formic acid affects to a greater
degree the selectivity. Ultimately, more experiments are needed to draw
more accurate conclusions.

Kinetic modelling

Upon modelling of the reaction kinetics, Modest ® was used [91]. The
software uses the backward difference method to solve the reactor mass
balances (a system of ordinary differential equations, ODEs) and a hybrid
method involving Simflex and Levenberg-Marquardt methods for the
estimation of the kinetic parameters (rate constants and activation energies)
defined in the kinetic model. The Levenberg-Marquardt method [98], is a
more effective modification of the well-known Newton-Raphson method and
the Simplex algorithm is based on the Simplex method introduced by
Spendley et al. [99]. If the two methods are compared, one can conclude that
the Simplex algorithm is slightly better at finding the way to the optimum
from a poor initial guess of parameters, while the sharp optimum is easier
and faster achieved by the Levenberg-Marquardt method, provided that the
initial guess is sufficiently close to the optimum. Consequently, the rate
equations for the proposed elementary reaction kinetic model and batch
reactor model were implemented in the software which also provides the
graphical interface.

38
 Wood pulp
H2 O H2 O
A1 / A2
r1 r2

OH OH OH OH
O O OH
OH
OH OH OH OH

Glucose Xylose
Humins
(or Tar) r4
r3
3 H2 O 3 H2 O

O O

HO O O
decarbonylation
Furfural
HMF

r5 r6
2 H2O

O
OH + O OH O OH
H3C

Levulinic acid O Formic acid Formic acid

r14

Decomp. prod.

Figure 14. The reaction network upon production of the platform chemicals levulinic and
formic acid from cellulose as well as the reactions used in the mathematical model.

For the parameter estimation the following objective function was

minimized

𝑄 = ∑ ∑(𝑐𝑖,𝑡,𝑒𝑥𝑝 − 𝑐𝑖,𝑡,𝑚𝑜𝑑𝑒𝑙 )2 𝑤𝑖,𝑡 (5)

𝑡 𝑖

where ci,t,exp and ci,t,model are the experimentally recorded concentrations and
the concentrations predicted by the model, respectively. The weight factors,
wi, were at this time set equal to unity (1) for all experimental data.

The reaction system was described with the following reactions

𝑟1 𝑟3 𝑟5
𝐴1 → 𝐺𝑙𝑢𝑐𝑜𝑠𝑒 → 𝐻𝑀𝐹 → 𝐿𝑒𝑣𝑢𝑙𝑖𝑛𝑖𝑐 𝑎𝑐𝑖𝑑 + 𝐹𝑜𝑟𝑚𝑖𝑐 𝑎𝑐𝑖𝑑 (6)

𝑟2 𝑟4 𝑟6
𝐴2 → 𝑋𝑦𝑙𝑜𝑠𝑒 → 𝐹𝑢𝑟𝑓𝑢𝑟𝑎𝑙 → 𝐹𝑜𝑟𝑚𝑖𝑐 𝑎𝑐𝑖𝑑 (7)

39
 𝑟14
𝐹𝑜𝑟𝑚𝑖𝑐 𝑎𝑐𝑖𝑑 → 𝐷𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 (8)

In the initial approach, only the experimental runs at higher temperature

range, i.e. 180–200 °C, were concerned since the reaction proceeds
extremely sluggishly at lower temperatures and batch experiments lasting
for several days had to be carried out. Nevertheless, some preliminary
modeling revealed that a first order reaction kinetics model was able to
describe the reactions in a reasonable and simple way. Thus, the reaction
rates were determined as follows:

𝑟𝑗 = 𝑘𝑗 𝑐𝑖 (9)

where rj denote the individual reaction rates for the reaction j, kj denote the
reaction rate constants and ci the concentration of component i. On the other
hand, the temperature influence on the reaction rate was taken into account
with the Arrhenius equation

𝐸𝐴𝑗 1 1
− ( − ) (10)
𝑘𝑗 = 𝑘0𝑗 𝑒 𝑅 𝑇 𝑇𝑚𝑒𝑎𝑛

and thus, kj denote the reaction rate constants, koj the frequency factor, R is
the ideal gas constant, T is the temperature and EAj the activation energy.
The modeling approach chosen verified that the experimental results
obtained at 180–200 °C, in the heterogeneously catalyzed reaction displayed
prominent Arrhenius-type temperature dependence demonstrated for the
reaction products identified.

For the reactor, the ideal batch reactor model was used.

𝑑𝑐𝑖
= 𝑟𝑖 𝑚𝑐𝑎𝑡 (11)
𝑑𝑡

where ci denote the concentration of component i, ri the generation rate for

component i and mcat the catalyst amount.

The parameters (frequency factors k0j, activation energies EAj) were

estimated using the parameter estimation software. Estimation of the

40
reaction kinetics parameters were split into two parts, whereupon first only
parameters for the reactions r2, r4 and r6 were estimated, after which the
parameters for r2, r4 and r6 were fixed and the rest of the parameters were
estimated. Initially an estimation of all parameters simultaneously was tried
but it did not give good results for the reactions r2 and r4 (formation of
xylose and furfural), mainly due to large differences in the concentration
levels of the compounds present thus leading to unstable behavior of the
solver. The values of the estimated parameters are enlisted in Table 1.

Table 1. Numerical values for the estimated parameters (degree of explanation 97.8 %).
Parameter / (for units see Value Parameter error / %
below)
k01 2.7 1.5
k02 15.3 11.8
k03 18.9 4.3
k04 30.8 8.4
k05 291 130
k06 40.7 14.2
k014 0.429 2.7
EA1 163 2.8
EA2 33.3 82.7
EA3 163 7.2
EA4 64.5 34.1
EA5 8.83 2705
EA6 16.7 203
EA14 134 7
Tmean = 185 °C, Frequency factor (koj) in h-1 and activation energy (EAj) in kJ/mol.

Fit of the model to experimental data

The most common measure for the goodness of fit is the degree of
explanation, the R2 value. The idea is to compare the residuals given by the
model to the residuals of the simpliest model one may think of, the average
value of all the data points. The R2 value is given by the expression
2
(𝑦𝑚𝑜𝑑𝑒𝑙 − 𝑦𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 )
𝑅2 = 100 2 (12)
(𝑦𝑚𝑜𝑑𝑒𝑙 − 𝑦̅𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 )

where the y values denotes the estimated vs. measured values of the
respective parameters. The closer the R2 value is 1, the better is the fitting of
the model. For the parameter estimation the degree of explanation of 97.8 %
was obtained.

41
The distribution and sensitivity of the parameters were controlled with the
Markov Chain Monte Carlo method (MCMC) [100], see Figure 16. These
figures also show low correlations between parameters and confirm well
identified optimal values.

42
Figure 15. Sensitivity analysis for the parameters.

43
Figure 16. Fit of model to experimental data for one of the experiments performed at 190 °C
with 6 g catalyst and 6 g substrate. Levulinic acid (○), formic acid (+), glucose (*), 5-HMF (□),
xylose (∆) and furfural (◊) vs. time.

25 0.7

0.6
Levulinic acid
20

0.5
Formic acid Xylose

15
0.4
mmole

mmole

0.3
10

0.2 Furfural

5
0.1

Glucose HMF
0 0
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40 45
time (h) time (h)

Figure 17. Fit of model to experimental data for one of the experiments performed at 180 °C
with 6 g catalyst and 9 g substrate. Levulinic acid (○), formic acid (+), glucose (*), 5-HMF (◊),
xylose (∆) and furfural (□) vs. time.

7 0.8

6 0.7

0.6
5
Formic acid
0.5
4
mmole

mmole

0.4
3
Levulinic acid 0.3

2
0.2

1 0.1
Xylose HMF
Glucose Furfural

0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
time (h) time (h)

Figure 18. Fit of model to experimental data for one of the experiments performed at 200 °C
with 1 g catalyst and 3 g substrate. Levulinic acid (○), formic acid (+), glucose (*), 5-HMF (◊),
xylose (∆) and furfural (□) vs. time.

The figures depicting the fit of model to experimental data (Figs. 16-18) show
that the model can predict the behavior of the reaction rather well at

44
different conditions as displayed in the parity plot Figure 19. Nevertheless,
the fit could be better for the components present in low concentrations.

Figure 19. Fit of model to all experimental data (levulinic acid (○), formic acid (+) and
glucose (*)).

45
Conclusions
Levulinic acid can be successfully produced from biomass using either
homogeneous or heterogeneous catalysts albeit with variations in
performance. Besides more traditional approaches like taking advantage of
mineral acids, in particular hydrochloric and sulfuric ones, many solid acids
have shown comparable performance. New, unorthodox processing
alternatives such as application of microwave dielectric heating or various
mechanical commutator designs have also been demonstrated for this
process. In general, the beneficial conditions involve relatively low acid
concentrations, low initial concentrations of feedstock and moderate
temperatures.
In this thesis solid acid catalyzed degradation of bleached Nordic industrial
dissolving pulp (a mixture of softwoods Norway Spruce and Scots Pine) was
investigated under mild batch wise reaction conditions and the goal was to
obtain versatile platform chemicals – levulinic and formic acids. The optimal
reaction conditions were determined and a simple, first-order kinetic
approach was developed to describe the experimental data with satisfactorily
accuracy. Sulphite-cellulose, being lean on pentose sugar containing
hemicelluloses was revealed as a good raw material compared to sulphate
pulp (birch kraft pulp), thus resulting in about 59 and 68 mol % theoretical
yields of levulinic vs. formic acid, respectively, obtained at a reaction
temperature of 180 °C and at a low initial cellulose concentration. It was also
observed that excessively high reaction temperatures contribute to thermal
degradation of the formed formic acid, since formic acid tends to degrade to
carbon dioxide, carbon monoxide, hydrogen and water, which in turn led to
lower overall yields of the desired products. Further it was observed that a
low substrate load favors a high levulinic acid yield and that the catalyst
loading has an optimum, i.e. whether the amount of catalyst is too high or
too low reduces the yield. One can also observe that a low acid
concentrations is problematic, because the lignin and other impurities
present in the biomass consumes a fraction of the acid during the reaction.
Consequently, the loss of sulfonic groups as a result of extended reaction
times leads to the lower activity of the catalyst. Nevertheless, an acid
treatment should at least partially restore the catalytic performance, but it
has never been examined in practice.
More surprisingly was that argon as the reaction atmosphere seems to
promote the reaction rates, whereas the presence of carbon dioxide acted as
a mild inhibitor. We expected the significantly better soluble CO 2 to yield
carbonic acid that would enhance the performance of our system. The reason
for this is at present not clear to us.

46
Also we have observed very little auto-catalysis occurring during our
experiments. What could be observed was that the hemicellulose and a very
small part of the cellulose were converted to intermediates and final
products before the reaction subsided. It appeared as if the solution was not
sufficiently acidic to react the crystalline part of the cellulose, but enough
acidic to react some of the amorphous part. In an experiment with catalyst
(heterogeneous catalysis), the contribution of auto-catalysis in the system is
likely to be very negligible.

47
Acknowledgements
First of all, I would like to express my deepest gratitude to my supervisor and
closest colleague, Prof. Jyri-Pekka Mikkola for giving me the opportunity to
work at the laboratory.

I would like to give special thanks to Prof. Johan Wärnå for his contribution
in the computational modelling and Dr. William Larsson for his assistance
with laboratory equipment.

Also my assistant supervisors Prof. Leif Jönsson and Doc. Torbjörn

Lestander are acknowledged for their invaluable advices and discussions.
Markku Reunanen and Dr. Carina Jonsson for carrying out the GC–MS
analysis and Per Hörstedt are acknowledged for carrying out the SEM
analysis.

I also would like to thank all the co-authors and co-workers and all the rest
of my collages.

Finally, I would like to express gratitude to my parents Gunvor and Runar

for their love and encouragement throughout my education. Special thanks
go also to my two sisters, Karin and Ingrid, and their families for their
support.

It would not have been possible without you all!

The Bio4Energy programme, Knut and Alice Wallenberg and Kempe

Foundations are gratefully acknowledged for the financial support. Further,
COST action CM0903 (UBioChem) and the Academy of Finland are
acknowledged and greatly appreciated. Collaboration with Processum
Biorefinery Initiative AB is acknowledged. This work is also a part of
activities at the Åbo Akademi Process Chemistry Centre, a center of
excellence financed by the Åbo Akademi University.

48
References

[1] P. Gallezot, Process options for converting renewable feedstocks to

bioproducts, Green Chemistry, 9 (2007) 295-302.

[2] D. Mohan, C.U. Pittman, P.H. Steele, Pyrolysis of wood/biomass for

bio-oil: A critical review, Energy & Fuels, 20 (2006) 848-889.

[3] S.N. Naik, V.V. Goud, P.K. Rout, A.K. Dalai, Production of first and
second generation biofuels: A comprehensive review, Renewable &
Sustainable Energy Reviews, 14 (2010) 578-597.

[4] G.W. Huber, S. Iborra, A. Corma, Synthesis of transportation fuels

from biomass: Chemistry, catalysts, and engineering, Chemical
Reviews, 106 (2006) 4044-4098.

[5] R. Rinaldi, F. Schuth, Acid hydrolysis of cellulose as the entry point

into biorefinery schemes, Chemsuschem, 2 (2009) 1096-1107.

[6] W.L. Faith, Development of the scholler process in the United-States,

Industrial and Engineering Chemistry, 37 (1945) 9-11.

[7] A.A. Efremov, G.G. Pervyshina, B.N. Kuznetsov, Production of

levulinic acid from wood raw material in the presence of sulfuric acid
and its salts, Chem Nat Compd, 34 (1998) 182-185.

[8] C. Chang, P. Cen, X. Ma, Levulinic acid production from wheat straw,
Bioresource Technology, 98 (2007) 1448-1453.

[9] B. Girisuta, L.P.B.M. Janssen, H.J. Heeres, Kinetic study on the acid-
catalyzed hydrolysis of cellulose to levulinic acid, Industrial &
Engineering Chemistry Research, 46 (2007) 1696-1708.

[10] L. Yan, N. Yang, H. Pang, B. Liao, Production of levulinic acid from

bagasse and paddy straw by liquefaction in the presence of
hydrochloride acid, CLEAN – Soil, Air, Water, 36 (2008) 158-163.

[11] J.-P. Lange, W.D. van de Graaf, R.J. Haan, Conversion of Furfuryl
Alcohol into Ethyl Levulinate using solid acid catalysts, Chemsuschem,
2 (2009) 437-441.

[12] D.W. Rackemann, W.O.S. Doherty, The conversion of lignocellulosics

to levulinic acid, Biofuels, Bioproducts and Biorefining, 5 (2011) 198-
214.

49
[13] Amberlyst 70 high temperature strongly acidic catalyst
http://www.amberlyst.com/literature/a4/70.pdf, (accessed
6.11.2011).

[14] R. Rinaldi, R. Palkovits, F. Schüth, Depolymerization of cellulose

using solid catalysts in ionic liquids, Angewandte Chemie
International Edition, 47 (2008) 8047-8050.

[15] I. Agirrezabal-Telleria, A. Larreategui, J. Requies, M.B. Güemez, P.L.

Arias, Furfural production from xylose using sulfonic ion-exchange
resins (Amberlyst) and simultaneous stripping with nitrogen,
Bioresource Technology, 102 (2011) 7478-7485.

[16] X. Hu, C.-Z. Li, Levulinic esters from the acid-catalysed reactions of
sugars and alcohols as part of a bio-refinery, Green Chemistry, 13
(2011) 1676-1679.

[17] J.F. Saeman, Kinetics of wood saccharification-hydrolysis of cellulose

and decomposition of sugars in dilute acid at high temperature,
Industrial & Engineering Chemistry, 37 (1945) 43-52.

[18] R.D. Fagan, H.E. Grethlein, A.O. Converse, A. Porteous, Kinetics of

the acid hydrolysis of cellulose found in paper refuse, Environmental
Science & Technology, 5 (1971) 545-547.

[19] D.R. Thompson, H.E. Grethlein, Design and evaluation of a plug flow
reactor for acid hydrolysis of cellulose, Industrial & Engineering
Chemistry Product Research and Development, 18 (1979) 166-169.

[20] J.-P. Franzidis, A. Porteous, J. Anderson, The acid hydrolysis of

cellulose in refuse in a continuous reactor, Conservation & Recycling,
5 (1982) 215-225.

[21] M. Green, S. Kimchie, A. Malester, B. Rugg, G. Shelef, Utilization of

municipal solid wastes (MSW) for alcohol production, Biological
wastes, 26 (1988) 285-295.

[22] I.A. Malester, M. Green, G. Shelef, Kinetics of dilute acid hydrolysis of

cellulose originating from municipal solid wastes, Industrial &
Engineering Chemistry Research, 31 (1992) 1998-2003.

[23] Q. Fang, M.A. Hanna, Experimental studies for levulinic acid

production from whole kernel grain sorghum, Bioresour Technol, 81
(2002) 187-192.

[24] T. Frost, E. Kurth, Tappi, 1951.

50
[25] Q. Jing, X. LÜ, Kinetics of non-catalyzed decomposition of glucose in
high-temperature liquid water, Chinese Journal of Chemical
Engineering, 16 (2008) 890-894.

[26] J. Shen, C.E. Wyman, Hydrochloric acid-catalyzed levulinic acid

formation from cellulose: data and kinetic model to maximize yields,
AIChE Journal, 58 (2012) 236-246.

[27] A. Onda, T. Ochi, K. Yanagisawa, Selective hydrolysis of cellulose into

glucose over solid acid catalysts, Green Chemistry, 10 (2008) 1033-
1037.

[28] G.J. Mulder, J. Prakt. Chem., 21 (1840).

[29] T. Werpy, G. Petersen, A. Aden, J. Bozell, J. Holladay, J. White, A.

Manheim, D. Eliot, L. Lasure, S. Jones, in, Top value added chemicals
from biomass. Volume 1-Results of screening for potential candidates
from sugars and synthesis gas, DTIC Document, 2004.

[30] A.M.R. Galletti, C. Antonetti, V. De Luise, D. Licursi, N. Nassi,

Levulinic acid production from waste biomass, BioResources, 7 (2012)
1824-1835.

[31] B. V. Timokhin, V. A. Baransky, G. D. Eliseeva, Levulinic acid in

organic synthesis, Russian Chemical Reviews, 68 (1999) 73-84.

[32] R.H. Leonard, Levulinic acid as a basic chemical raw material,

Industrial & Engineering Chemistry, 48 (1956) 1330-1341.

[33] S.W. Fitzpatrick, Production of levulinic acid from carbohydrate-

containing materials (US Patent 5,608,105, 1997).

[34] D.B. Bevilaqua, M.K.D. Rambo, T.M. Rizzetti, A.L. Cardoso, A.F.
Martins, Cleaner production: levulinic acid from rice husks, Journal
of Cleaner Production, 47 (2013) 96-101.

[35] M. Kang, S.W. Kim, J.-W. Kim, T.H. Kim, J.S. Kim, Optimization of
levulinic acid production from Gelidium amansii, Renewable Energy,
(2012).

[36] D.-m. Lai, L. Deng, Q.-x. Guo, Y. Fu, Hydrolysis of biomass by

magnetic solid acid, Energy & Environmental Science, 4 (2011) 3552-
3557.

[37] P. Wang, S. Zhan, H. Yu, Production of levulinic acid from cellulose

catalyzed by environmental-friendly catalyst, Advanced Materials
Research, 96 (2010) 183-187.

51
[38] L. Peng, L. Lin, J. Zhang, J. Zhuang, B. Zhang, Y. Gong, Catalytic
conversion of cellulose to levulinic acid by metal chlorides, Molecules,
15 (2010) 5258-5272.

[39] B. Girisuta, B. Danon, R. Manurung, L.P.B.M. Janssen, H.J. Heeres,

Experimental and kinetic modelling studies on the acid-catalysed
hydrolysis of the water hyacinth plant to levulinic acid, Bioresource
Technology, 99 (2008) 8367-8375.

[40] V.S. Minina, A.E. Sarukhanova, K.U. Usmanov, Preparation of fural

and levulinic acid by hydrolysis of pressed cotton stems, Fiz. i Khim.
Prirodn. i Sintetich. Polimerov, Akad. Nauk Uz. SSR, Inst. Khim.
Polimerov, 1962, pp. 87-93.

[41] A. Szabolcs, M. Molnar, G. Dibo, L.T. Mika, Microwave-assisted

conversion of carbohydrates to levulinic acid: an essential step in
biomass conversion, Green Chemistry, 15 (2013) 439-445.

[42] B. Girisuta, L. Janssen, H. Heeres, Green Chemicals: A kinetic study

on the conversion of glucose to levulinic acid, Chemical Engineering
Research and Design, 84 (2006) 339-349.

[43] A. Thompson, Method of making levulinic acid (US patent 2,206,311,

1940).

[44] W.W. Moyer, Preparation of levulinic acid (US patent 2,207,328,

1942).

[45] Z. Yang, H. Kang, Y. Guo, G. Zhuang, Z. Bai, H. Zhang, C. Feng, Y.

Dong, Dilute-acid conversion of cotton straw to sugars and levulinic
acid via 2-stage hydrolysis, Industrial Crops and Products, 46 (2013)
205-209.

[46] H. Lin, J. Strull, Y. Liu, Z. Karmiol, K. Plank, G. Miller, Z. Guo, L.

Yang, High yield production of levulinic acid by catalytic partial
oxidation of cellulose in aqueous media, Energy & Environmental
Science, 5 (2012) 9773-9777.

[47] L.J. Carlson, Process for the manufacture of levulinic acid (US patent
3,065,263, 1962).

[48] H. Mehdi, V. Fábos, R. Tuba, A. Bodor, L. Mika, I. Horváth,

Integration of homogeneous and heterogeneous catalytic processes for
a multi-step conversion of biomass: From sucrose to levulinic acid, γ-
valerolactone, 1,4-pentanediol, 2-methyl-tetrahydrofuran, and
alkanes, Top Catal, 48 (2008) 49-54

52
[49] Y. Takeuchi, F. Jin, K. Tohji, H. Enomoto, Acid catalytic hydrothermal
conversion of carbohydrate biomass into useful substances, J Mater
Sci, 43 (2008) 2472-2475.

[50] A.A. Efremov, G.G. Pervyshina, B.N. Kuznetsov, Thermocatalytic

transformations of wood and cellulose in the presence of HCl, HBr,
and H2SO4, Chem Nat Compd, 33 (1997) 84-88.

[51] W.O.S. Doherty, P. Mousavioun, C.M. Fellows, Value-adding to

cellulosic ethanol: Lignin polymers, Industrial Crops and Products,
33 (2011) 259-276.

[52] R.A. Schraufnagel, H.F. Rase, Levulinic acid from sucrose using acidic
ion-exchange resins, Product R&D, 14 (1975) 40-44.

[53] J. Jow, G.L. Rorrer, M.C. Hawley, D.T.A. Lamport, Dehydration of d-

fructose to levulinic acid over LZY zeolite catalyst, Biomass, 14 (1987)
185-194.

[54] K. Lourvanij, G.L. Rorrer, Dehydration of glucose to organic acids in

microporous pillared clay catalysts, Applied Catalysis A: General, 109
(1994) 147-165.

[55] J. Hegner, K.C. Pereira, B. DeBoef, B.L. Lucht, Conversion of cellulose

to glucose and levulinic acid via solid-supported acid catalysis,
Tetrahedron Letters, 51 (2010) 2356-2358.

[56] R. Weingarten, W.C. Conner, G.W. Huber, Production of levulinic acid

from cellulose by hydrothermal decomposition combined with
aqueous phase dehydration with a solid acid catalyst, Energy &
Environmental Science, 5 (2012) 7559-7574.

[57] R.W. Thomas, H.A. Schuette, Studies on levulinic acid. I. It’s

preparation from carbohydrates by digestion with hydrocloric acid
under pressure, Journal of the American Chemical Society, 53 (1931)
2324-2328.

[58] D.M. Alonso, S.G. Wettstein, M.A. Mellmer, E.I. Gurbuz, J.A.
Dumesic, Integrated conversion of hemicellulose and cellulose from
lignocellulosic biomass, Energy & Environmental Science, 6 (2013)
76-80.

[59] J.Y. Cha, M.A. Hanna, Levulinic acid production based on extrusion
and pressurized batch reaction, Industrial Crops and Products, 16
(2002) 109-118.

53
[60] H. Chen, B. Yu, S. Jin, Production of levulinic acid from steam
exploded rice straw via solid superacid, Bioresource Technology, 102
(2011) 3568-3570.

[61] Y. Bin, C. Hongzhang, Effect of the ash on enzymatic hydrolysis of

steam-exploded rice straw, Bioresource Technology, 101 (2010) 9114-
9119.

[62] V. Chang, M. Holtzapple, Fundamental factors affecting biomass

enzymatic reactivity, M. Finkelstein, B. Davison (Eds.) Twenty-First
Symposium on Biotechnology for Fuels and Chemicals, Humana
Press, 2000, pp. 5-37.

[63] V.M. Ghorpade, M.A. Hanna, Method and apparatus for production
of levulinic acid via reactive extrusion (US Patent 5,859,263, 1999).

[64] S. Van de Vyver, J. Thomas, J. Geboers, S. Keyzer, M. Smet, W.

Dehaen, P.A. Jacobs, B.F. Sels, Catalytic production of levulinic acid
from cellulose and other biomass-derived carbohydrates with
sulfonated hyperbranched poly(arylene oxindole)s, Energy &
Environmental Science, 4 (2011) 3601-3610.

[65] G. Banerjee, S. Car, T. Liu, D.L. Williams, S.L. Meza, J.D. Walton, D.B.
Hodge, Scale-up and integration of alkaline hydrogen peroxide
pretreatment, enzymatic hydrolysis, and ethanolic fermentation,
Biotechnology and Bioengineering, 109 (2012) 922-931.

[66] G. Banerjee, S. Car, J.S. Scott-Craig, D.B. Hodge, J.D. Walton,

Alkaline peroxide pretreatment of corn stover: effects of biomass,
peroxide, and enzyme loading and composition on yields of glucose
and xylose, Biotechnol Biofuels, 4 (2011) 16.

[67] M.F. Zaranyika, M. Madimu, Heterogeneous dilute acid hydrolysis of

cellulose: A kinetic model for the hydrolysis of the difficultly accessible
portion of cellulose based on donnan's theory of membrane equilibria,
Journal of Polymer Science Part A: Polymer Chemistry, 27 (1989)
1863-1872.

[68] L. Liu, J. Sun, C. Cai, S. Wang, H. Pei, J. Zhang, Corn stover

pretreatment by inorganic salts and its effects on hemicellulose and
cellulose degradation, Bioresource Technology, 100 (2009) 5865-
5871.

[69] J. Potvin, E. Sorlien, J. Hegner, B. DeBoef, B.L. Lucht, Effect of NaCl

on the conversion of cellulose to glucose and levulinic acid via solid
supported acid catalysis, Tetrahedron Letters, 52 (2011) 5891-5893.

54
[70] S.G. Wettstein, D.M. Alonso, Y. Chong, J.A. Dumesic, Production of
levulinic acid and gamma-valerolactone (GVL) from cellulose using
GVL as a solvent in biphasic systems, Energy & Environmental
Science, 5 (2012) 8199-8203.

[71] I.T. Horvath, H. Mehdi, V. Fabos, L. Boda, L.T. Mika, [gamma]-

Valerolactone-a sustainable liquid for energy and carbon-based
chemicals, Green Chemistry, 10 (2008) 238-242.

[72] J.-P. Lange, J.Z. Vestering, R.J. Haan, Towards 'bio-based' Nylon:
conversion of [gamma]-valerolactone to methyl pentenoate under
catalytic distillation conditions, Chemical Communications, (2007)
3488-3490.

[73] M. Chalid, H.J. Heeres, A.A. Broekhuis, Ring-opening of γ-

valerolactone with amino compounds, Journal of Applied Polymer
Science, 123 (2012) 3556-3564.

[74] J.Q. Bond, D.M. Alonso, D. Wang, R.M. West, J.A. Dumesic,
Integrated catalytic conversion of γ-valerolactone to liquid alkenes for
transportation fuels, Science, 327 (2010) 1110-1114.

[75] J.C. Serrano-Ruiz, D.J. Braden, R.M. West, J.A. Dumesic, Conversion
of cellulose to hydrocarbon fuels by progressive removal of oxygen,
Applied Catalysis B: Environmental, 100 (2010) 184-189.

[76] S.K.R. Patil, C.R.F. Lund, Formation and growth of humins via aldol
addition and condensation during acid-catalyzed conversion of 5-
hydroxymethylfurfural, Energy & Fuels, 25 (2011) 4745-4755.

[77] V.G. Devulapelli, H.-S. Weng, Synthesis of cinnamyl acetate by solid–

liquid phase transfer catalysis: Kinetic study with a batch reactor,
Catalysis Communications, 10 (2009) 1638-1642.

[78] M. Käldström, N. Kumar, D.Y. Murzin, Valorization of cellulose over

metal supported mesoporous materials, Catalysis Today, 167 (2011)
91-95.

[79] A. Sundberg, K. Sundberg, C. Lillandt, B. Holmbom, Determination of

hemicelluloses and pectins in wood and pulp fibres by acid
methanolysis and gas chromatography, Nordic Pulp and Paper
Research Journal, 11 (1996) 216-219.

[80] P. Strunk, T. Öman, A. Gorzsás, M. Hedenström, B. Eliasson,

Characterization of dissolving pulp by multivariate data analysis of
FT-IR and NMR spectra, Nordic Pulp and Paper Research Journal,
26 (2011) 398.

55
[81] S. Willför, A. Sundberg, A. Pranovich, B. Holmbom, Polysaccharides
in some industrially important hardwood species, Wood Science and
Technology, 39 (2005) 601-617.

[82] A. Sundberg, S. Emet, P. Rhen, l. Vähäsalo, B. Holmbohm, Estimation

of proportions of different pulp types in recycled paper and deinked
pulp by acid methanolysis, Proc. of 13th International Symposium on
Wood, Fibre and Pulping Chemistry, Auckland, New Zealand, 2005,
pp. 361-365.

[83] P.F. Siril, H.E. Cross, D.R. Brown, New polystyrene sulfonic acid resin
catalysts with enhanced acidic and catalytic properties, Journal of
Molecular Catalysis A: Chemical, 279 (2008) 63-68.

[84] R. Bringué, M. Iborra, J. Tejero, J.F. Izquierdo, F. Cunill, C. Fité, V.J.

Cruz, Thermally stable ion-exchange resins as catalysts for the liquid-
phase dehydration of 1-pentanol to di-n-pentyl ether (DNPE), Journal
of Catalysis, 244 (2006) 33-42.

[85] Z.P. Xu, K.T. Chuang, Effect of internal diffusion on heterogeneous

catalytic esterification of acetic acid, Chemical Engineering Science,
52 (1997) 3011-3017.

[86] D. Harvey, Modern analytical chemistry, McGraw-Hill Boston,

(2000).

[87] C. Corradini, Liquid Chromatography, (2000).

[88] Willard, H.H., Dean, J.A., Settle, F.A., and Merritt, L.L., Instrumental
methods of analysis, 7th ed.; Wadsworth: Belmont, CA (1988).

[89] A. Kraj, D.M. Desiderio, N.M. Nibbering, Mass spectrometry:

instrumentation, interpretation, and applications, John Wiley &
Sons, (2008).

[90] Silylating agents, http://www.sigmaaldrich.com/content/dam/sigma-

aldrich/docs/Aldrich/General_Information/silylation_overview.pdf,
(accessed 10.2.2014).

[91] H. Haario, Modest user´s guide, Profmath Oy, Helsinki, 1994.

[92] M. Saeed, M. Depala, D. Craston, T. Lynch, A standard addition

method for the quantitative determination of succinic acid and
levulinic acid in processed acid stream extracts employing indirect UV
capillary electrophoresis, Chromatographia, 47 (1998) 709-715.

56
[93] A. Gildberg, J. Raa, Properties of a propionic acid/formic acid
preserved silage of cod viscera, Journal of the Science of Food and
Agriculture, 28 (1977) 647-653.

[94] B. Girisuta, L.P.B.M. Janssen, H.J. Heeres, A kinetic study on the

decomposition of 5-hydroxymethylfurfural into levulinic acid, Green
Chemistry, 8 (2006) 701-709.

[95] N. Akiya, P.E. Savage, Role of water in formic acid decomposition,

AIChE Journal, 44 (1998) 405-415.

[96] W. Hayduk, W. Landie, A.I.Ch.E.J, 19 (1973) 1233.

[97] J.J. Panek, P.K. Wawrzyniak, Z. Latajka, J. Lundell, Interaction energy

decomposition analysis for formic acid complexes with argon and
krypton atoms, Chemical Physics Letters, 417 (2006) 100-104.

[98] D.W. Marquardt, An algorithm for least-squares estimation of

nonlinear parameters, Journal of the Society for Industrial & Applied
Mathematics, 11 (1963) 431-441.

[99] W. Spendley, G.R. Hext, F. Himsworth, Sequential application of

simplex designs in optimisation and evolutionary operation,
Technometrics, 4 (1962) 441-461.

[100] N. Metropolis, A.W. Rosenbluth, M.N. Rosenbluth, A.H. Teller, E.

Teller, Equation of state calculations by fast computing machines, The
journal of chemical physics, 21 (1953) 1087.

57