Chapter 2

Chemical Conversion of Biomass

to Green Chemicals
Yijun Jiang, Xicheng Wang, Quan Cao, Linlin Dong,
Jing Guan and Xindong Mu

Abstract Biomass has the potential to serve as a sustainable source of energy and
organic carbon for our industrial society. The focus of this chapter is to provide a
survey of different strategies to achieve chemical catalytic conversion of
biomass-derived oxygenated feedstocks to value-added chemicals and fuels. The
key reactions involved in the processing of biomass are hydrolysis, dehydration,
isomerization, aldol condensation, reforming, hydrogenation/hydrogenolysis, and
oxidation. Here, a few specic examples, namely efcient hydrolysis of cellulose
over novel solid acids and synthesis of polyols by hydrogenation/hydrogenolysis of
cellulose and sugar have been chosen for this review. Further, the selective conversion of platform molecules, such as furan, HMF, and biogenic carboxylic acids
into intermediates, specialties, and ne chemicals has been considered. While many
challenges are involved in biomass processing, understanding of fundamental
reaction chemistry for different types of reactions can lead to the development of
new approaches for specic processes.
Keywords Biomass

2.1

Green chemicals
Chemical conversion techniques

Introduction

Production of chemicals highly depends on non-renewable fossil resources such as

petroleum, coal, and natural gas in modern society, which is widely acknowledged
as unsustainable. The diminishing fossil fuel reservoirs together with
ever-deteriorating environment associated with the worldwide fossil-fuel-based
industry makes the use of alternative feedstock imperative [13]. Biomass, which
has utilized directly via combustion to produce heat for thousands of years, has
Y. Jiang
X. Wang
Q. Cao
L. Dong
J. Guan
X. Mu (&)
CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy
and Bioprocess Technology, Chinese Academy of Sciences, 266101 Qingdao, China
e-mail: [email protected]
Springer Science+Business Media Dordrecht 2016
M. Xian (ed.), Sustainable Production of Bulk Chemicals,
DOI 10.1007/978-94-017-7475-8_2

19

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Y. Jiang et al.

been recalled for its renewable ability and enormous reserves. Biomass has been
regarded as a sustainable alternative to fossil resources, and therefore, the effective
utilization of biomass has greatly attracted the interest of the scientic and industrial
communities [46].
The transformation of biomass to chemicals and fuels can be generally realized
by three different techniques: thermal, biochemical, and chemical routes. Thermal
techniques, like pyrolysis and gasication, can take full advantage of the entire
organic substance of this resource. Nevertheless, these techniques still suffer from
the disadvantages of low selectivity and high energy input which are unacceptable.
Bioconversion of biomass possesses the advantage of good selectivity, but sometimes suffers from low efciency. Reasonable routes to promote biomass converted
into high value-added chemicals under relative mild circumstance in liquid phase at
a high selectivity are required. A variety of processes for the production of green
chemicals derived from biomass have been developed in the last few years, which
will be discussed in this chapter.

2.2

Depolymerization of Polysaccharide
with Catalytic Method

As we all know, glucose is an important platform compound which can be converted into various value-added chemicals with the fermentation or chemical processes. Cellulose is a polysaccharide with glucose as its monomer, which needs to
be hydrolyzed into glucose before being used as feedstock in most chemical and
bioprocesses. Therefore, the hydrolysis of cellulose into glucose is a key technology
for efcient biomass utilization. However, due to its highly crystalline structure,
together with the strong inner -1,4-glycosidic bonding and complex hydrogen
bonding, the hydrolysis of cellulosic biomass is quite difcult [7].
Currently, although a lot of efforts have focused on the hydrolysis of biomass by
enzymes, liquid acid, and supercritical water, drawbacks still exist in these processes. Liquid acid hydrolysis including dilute acid [8], concentrated acid [9], and
organic acid [10, 11] has a long industrial history, but is not recyclable and corrosive, which leads to various environmental problems. Enzymatic hydrolysis [12]
is one of the most promising hydrolysis technologies, but suffers from the low
hydrolysis efciency and high cost of the enzyme. The utilization of supercritical
water faces the problem of high energy consumption [13].
Compared with traditional mineral acid, solid acids are environment-friendly
catalysts that are less corrosive, easy to handle, separable and recyclable, which have
already been widely used to catalyze a variety of organic reactions. Recently, the
solid acid catalysts have attracted considerable attention in biomass conversion and
several solid acids have been developed to facilitate the hydrolysis of cellulose,
starch, or other polysaccharides with moderate to good glucose yield. Solid acid
catalysts such as carbonaceous solid acids (CSAs) [14, 15], inorganic oxides [16, 17],

2 Chemical Conversion of Biomass to Green Chemicals

21

zeolites [16, 1820], cation-exchanged resins [16, 17], clays [16], and hetero polyacids [2123] have been reported for the hydrolysis of cellulose due to their merits of
retrievability. Among them, the CSA bearing SO3H, COOH, and phenolic hydroxyl
(OH) groups in the framework of the amorphous carbon has been proven to be an
excellent candidate for the cellulose hydrolysis due to its high catalytic activity and
retrievability [20, 21]. The activity of CSA was reported to be much higher than
sulfuric acid and could be reused without obvious loss of activity. In order to enhance
the performance of CSA for the hydrolysis of cellulose, several groups including us
did some basic work to optimize the preparation of the CSA catalyst or to study the
mechanism of the solid-solid reaction. CSA prepared via sulfonating the amorphous
carbon or active carbon prepared at high temperature showed considerable catalytic
activity for the hydrolysis of cellulose [14, 15]. While these carbonaceous solid acid
still have the disadvantages of relative low activity and high energy consumption.
Highly dispersed carbonaceous spheres with sulfonic acid groups were successfully prepared from glucose by hydrothermal method [14] (Fig. 2.1). Under
hydrothermal conditions, the sugar was rst incompletely carbonized to carbon
nanospheres by dehydration. Then, the resulting carbon spheres were sulfonated to
form highly dispersive uniform CSA. More importantly, the uniform size and high
aqueous dispersibility of the CSA improve the accessibility to the polysaccharides,
and thus it exhibits excellent catalytic performances for the polysaccharides
hydrolysis. In the cellulose hydrolysis, ZrO2/WO3 and H-ZSM5 showed negligible
glucose yield less than 1 %; while Amberlyst-15 and C-673 gave glucose in 25.6,
49.0 % yield, respectively. Similarly, our CSA C-453 gave the highest glucose

Fig. 2.1 Stability of the CSA in the water solution (a), the cylinder of CAS powders before
(b) and after water wetting (c)

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Y. Jiang et al.

yield of about 74.0 %, which is much higher than previous reported sulfonated
activated carbon solid acid (40.5 %) [15], indicating that our CSA exhibits considerably high activity for cellulose hydrolysis.
However, in most reports, microcrystalline cellulose was always used as the
model feedstock which is far away from real industrial applications due to the
different compositions and structures between natural lignocellulosic biomass
(mainly composed of cellulose, hemicellulose, and lignin) and microcrystalline
cellulose. Additionally, the hemicellulose in the natural lignocellulosic biomass has
always been ignored as target feedstock for solid acid hydrolysis, although it is also
the main component in many plants and easier to be hydrolyzed. Therefore, it is
imperative to investigate the hydrolysis performance of CSA aiming at real biomass
substrates, especially the biomass containing signicant amount of hemicellulose.
Corncobs containing about 30 % hemicellulose are the popular and abundant
agricultural waste, which have been used as industrial raw material to produce
xylose and furfural by liquid acid hydrolysis. However, the environmental problems
from the large amount of liquid acids used and solid residues generated limit its
sustainable industrial application. A green and effective approach for the comprehensive utilization of corncobs (Scheme 2.1) was developed [24]. During this
process, the CSA catalyst was prepared from the hydrolyzed corncobs residue and
was used for the hydrolysis of corncob with only a small amount of water under
microwave irradiation. After reaction, the CSA and hydrolyzate can be easily
separated and recycled. There are two value-added products during the whole
process. One is sugars produced by hydrolysis, the other is CSA derived from the
unconverted solid residue, which can also be used as catalyst in the hydrolysis.
However, challenges still exist in this process; both the cellulose and the solid
acids are presented in solid state in this reaction and have resulted in difculties for
cellulose to get access to the active catalytic sites. Mass transfer between substrates
and catalysts is the main difculty in hydrogenolysis of cellulose. Generally, the
hydrolysis reaction catalyzed by solid acids needs higher temperature and gives low
glucose yield. In a word, despite the success of these techniques for the hydrolysis
of cellulose, each has its own pros and cons with respect to the economy, recyclability, and activity.
To mimic the functional sites in the real enzyme, sulfonated copolymer poly
(acrylic acid)-co-poly(styrene sulfonic acid) which showed high performance for

Scheme 2.1 Procedure for the corncobs hydrolysis by CSA derived from the hydrolysis residue

2 Chemical Conversion of Biomass to Green Chemicals

23

the hydrolysis of polysaccharides were also managed to be designed and synthesized [25]. However, the separation of the catalyst is still a main problem to block
its application. Well-dened sulfonated block copolymer poly(acrylic acid)block-poly(styrene sulfonic acid) (PAA-b-PSSH) and random copolymer poly
(acrylic acid)-random-poly(styrene sulfonic acid) (PAA-r-PSSH) were prepared by
direct thermolysis of the precursor copolymers poly(tert-butyl acrylate)-block-poly
(neopentyl styrenesulfonate) (PtBA-b-PNSS) and poly(tert-butyl acrylate)random-poly(neopentyl styrenesulfonate) (PtBA-r-PNSS), which were synthesized
by living radical polymerization (MWD < 1.10) catalyzed with CuBr. As shown in
Table 2.1, the well-dened sulfonated polymers exhibited excellent catalytic performance for polysaccharide hydrolysis under microwave irradiation at the low
effective acid concentration (0.4 mmol mL1). The best result was obtained by
using PAA-r-PSSH as a catalyst, with the glucose yield of 94.5 % for the hydrolysis
of starch at 373 K and 35 % for cellulose hydrolysis at 393 K. The remarkable
performance of PAA-r-PSSH for polysaccharide hydrolysis was achieved through
the synergetic combination of SO3H and COOH. The mechanism of the hydrolysis
of polysaccharide by the polymer acid catalyst established here will guide the
design of new acid catalyst for the polysaccharide hydrolysis.
To solve the problems of activity and recycling for solid acid, concentrated
H3PW12O40 (HPW) was also employed to decompose cellulose under microwave
irradiation at low temperature [26]. 75.6 % yield of glucose was obtained at 90 C
under microwave irradiation for 3 h, which was considerably high under such mild
condition using phosphotungstic acid as catalyst. With the same effective acid
concentration, HPW gave the highest cellulose conversion and glucose yield among
the Brnsted acid catalysts, indicating that the strong Brnsted acid played an
important role during cellulose hydrolysis. In the hydrolysis of cellulose with HPW

Table 2.1 Microwave-assisted hydrolysis of starch catalyzed by various catalystsa

Temp (C)
80

Catalyst

YGl/%

Rate of glucose formation (mol h1)

TOF (h1)b

PSSH
7.2
44
0.11
PAA-b-PSSH 12.6
78
0.19
14.4
89
0.22
H2SO4
PAA-r-PSSH
16.2
100
0.25
90
PSSH
20.7
128
0.31
PAA-b-PSSH 29.7
183
0.45
31.5
194
0.47
H2SO4
PAA-r-PSSH
38.7
238
0.58
100
PSSH
76.5
472
1.15
PAA-b-PSSH 88.2
544
1.33
90.9
561
1.37
H2SO4
PAA-r-PSSH
94.5
583
1.43
a
Starch: 100 mg; effective acid amount: 0.4 mmol; distilled water: 1 mL; reaction time: 60 min.
b
TOF is estimated from glucose formation per mole effective acid sites (SO3H) per hour

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Y. Jiang et al.

as catalysts, microwave irradiation led to higher glucose yields than the conventional heating method. The recovery and reusability of HPW were investigated by
extraction with diethyl ether from the reaction solution. In order to investigate the
performance of the concentrated HPW for the hydrolysis of real lignocellulosic
biomass, corncob, corn stover and bagasse were also employed to serve as feedstock under microwave irradiation. Before the reaction, the composition of the
lignocellulosic biomass was rst analyzed following the modied NREL laboratory
analytical procedures (NREL). Table 2.2 gives the results for the hydrolysis of
corncob, corn stover, and bagasse catalyzed by 88 % HPW solution at 90 C for 3 h
under microwave irradiation. For the hydrolysis of cellulose in corncob, corn
stover, and bagasse, 37.2, 43.3, and 27.8 % yields of glucose were obtained,
respectively, which were lower than that of microcrystalline cellulose (75.6 %)
under the same reaction conditions because of the recalcitrance of lignocellulose. It
is well established that the hydrolysis of hemicellulose (xylan + araban) is easier
than that of cellulose, but only 2.96, 2.30, and 3.94 % yields of xylose were
obtained from the xylan in corncob, corn stover, and bagasse, respectively, which
was attributed to the side reactions of xylose (xylose to furfural) under the reaction
condition. The yields of the side product for furfural were detected to be 11.6, 7.26,
and 7.47 %, respectively. The effect of the amount of corn stover on the glucose
yield was also evaluated by varying the amount of cellulose from 0.06 to 0.5 g.
With increasing the amount of corn stover from 0.06 to 0.5 g under the reaction
conditions, the yield of glucose decreased from 43.4 to 25.6 % because of the
saturation of the catalytic sites. After hydrolysis, the reusability of HPW in corn
stover hydrolysis was investigated just as that in microcrystalline cellulose
hydrolysis and the yield of glucose gradually decreased from 31.8 (the 2nd run),
19.9 (the 3rd run) to 12.6 % (the 4th run). It is believed that the by-products
(furfural and HMF) and the impurities such as extractives in the corn stover
(proteins, fat) generated in the hydrolysis reaction could be extracted by the diethyl
ether with HPW and damaged the catalytic site in the HPW.
In a word, despite the success of these techniques for the hydrolysis of cellulose,
each has its own pros and cons with respect to the economy, recyclability, and
activity. Therefore, it is imperative to develop some novel hydrolysis technologies
which not only can decompose the rigid cellulose structure effectively like cellulase
under mild temperature, but also can be recycled like solid acids.

Table 2.2 Hydrolysis of real lignocellulosic biomass catalyzed by HPWa

Biomass

YGl (%)b

YXy (%)b

YAr (%)b

YTs (%)b

YFu (%)

YHM (%)c

Corncob
37.2
2.96
28.0
24.6
11.6
0.24
Corn stover
43.4
2.30
26.5
30.0
7.26
0.21
Bagasse
27.8
3.94
34.1
19.0
7.47
0.29
a
Biomass: 60 mg; HPW solution: 3 mL; temperature: 90 C; reaction time: 180 min
b
YGl, YXy, YAr, and YTs were the carbon-based yield of glucose, xylose, arabinose, and total sugar
respectively
c
YFu (%) and YHM (%) were the carbon-based yield of furfural and HMF, respectively

2 Chemical Conversion of Biomass to Green Chemicals

2.3

25

Production of Polyols from Lignocellulosic Biomass

and Biomass-Derived Compounds

Biobased polyhydroxy compounds, including sugars, sugar alcohols, and glycerol

can be converted into high value-added chemicals via catalytic conversion [2730].
However, unlike petroleum, biomass possess high oxygen content and specic
carbon skeleton. In order to transform the biobased polyhydroxy compounds into
high value-added chemicals, the selective removal of oxygen is the key
step. Catalytic hydrogenolysis is an efcient way for biomass valorization. Here, we
will provide a general overview of the catalytic conversion of polyhydroxy compounds into high value-added chemicals via hydrogenolysis. Figure 2.2 illustrated
the value-added glycols with carbon chain in the range of 26, which can be
derived from fatty acid esters and lignocellulose.

2.3.1

Cellulose Hydrogenation and Hydrogenolysis

Cellulose, mainly from agricultural and forestry residues, is one of the worlds
largest organic raw material resource (nearly 40 billion tones production every
year). Different from starch, cellulose cannot be digested by human. Therefore
instead of starch, humans main food source, cellulose was regarded as a promising
resource that can be transformed into energy and chemicals in the post-petroleum
era. To date, the one-pot chemical transformation of cellulose to polyols over
heterogeneous catalyst is one of the most promising routes for the effective

Fig. 2.2 Value-added glycols with carbon chain in the range of 26 from fatty acid esters and
lignocelluloses

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Y. Jiang et al.

utilization of cellulose in a more efcient and convenient manner [31]. In this part,
we will focus on the recent advances of one-pot hydrogenation and hydrogenolysis
of cellulose.
Supported metal catalyzed hydrogenation of cellulose was rst reported by
Fukuoka in 2006 [32]. Among the metal catalysts they had tested, Pt and Ru
showed superior activity in conversion of cellulose at 463 K under 5 MPa H2.
A yield of 30 % sugar alcohol was obtained over Pt/-Al2O3. The reaction of
cellulose hydrolysis to glucose was catalyzed by in situ generated acid sites, while
noble metals catalyze the following process of glucose hydrogenation. In order to
reduce the crystallinity and particle size of cellulose which impeded the conversion
of cellulose into high value-added chemicals via heterogeneous catalytic transformation, ball milling was applied in their experiment for the purpose of degradation
the cellulose more efciently. To improve the efciency, the in situ generated
protons produced by high temperature liquid water (above 473 K) was employed to
act as acid catalyst in Lius research [33]. The acid will disappear when the reaction
system is cooled down to the room temperature, making it a green process. Ru/C
was chosen as the hydrogenation catalyst in this research for its superior glucose
hydrogenation activity. After 30 min, yield of hexitol was 39.3 % at the conversion
of 85.5 % under the reaction of 518 K, 6 MPa H2. Zhang et al. [34] performed the
hydrogenation of cellulose under the catalysis of tungsten carbide in order to
replace the high-price noble metal catalysts used previously. Tungsten carbide was
found to give a higher yield of ethylene glycol (EG) than platinum and ruthenium
catalysts at the reaction condition of 518 K, 6 MPa H2, 30 min. Furthermore, the
yield of EG increased from 27 to 61 % signicantly with the promotion of a small
amount of nickel. The following study showed that HxWO3 was the authentic active
species which promoted the CC cleavage of cellulose for the formation of EG in
this reaction [31]. Tungsten trioxide promoted ruthenium catalysts was also proved
to show high activity in hydrogenolysis of cellulose to yield glycols by Liu et al.
[35]. WO3 was found to promote the hydrolysis of cellulose as well as the CC
bond cleavage of the sugar. EG and propylene glycol were produced by selective
hydrogenolysis of glucose and fructose, respectively.
Although non-noble nickel is generally considered as efcient hydrogenation
and hydrogenolysis catalyst, supported nickel catalysts investigated currently and
consistently exhibited poor performances towards the production of target polyols.
In order to explore a catalyst that can effectively convert cellulose at low cost, Mu
et al. [36] evaluated Ni catalysts supported on a series of supports and found that
20 % Ni/ZnO catalyst can convert the cellulose completely and give a 70.4 % yield
of total glycols. The main drawback of this catalyst lies in its poor hydrothermal
stability, resulting in the decrease of catalytic activity after repeated reaction runs.
Further study showed that NiCu/ZnO bimetallic catalysts could be successfully
applied to the hydrogenolysis of cellulose and real biomass substrates (including
cornstalk and corncob) for the purpose of producing 1,2-alkanediols as the major
products [37]. The mole ratio of Ni and Cu not only dominated the activity,
selectivity, and product distribution, but also played synergetic roles for the formation of 1,2-alkanediols during the reaction. Other than nickel, non-noble metal

2 Chemical Conversion of Biomass to Green Chemicals

27

copper was also employed in the reaction of hydrogenolysis of cellulose.

Concentrated cellulose (up to 15 wt%) can be converted into 1,2-propylene glycol
and EG through the reaction of hydrogenolysis with no coke-like precipitates
formed over CuCr catalysts promoted by Ca(OH)2 [38]. 1,2-propylene glycol and
EG was obtained at the yield of 42.6 and 31.6 % under the reaction condition of
518 K, 6.0 MPa H2, respectively.
Apart from acid sites from solid acid, water with high temperature and pressure,
mineral acids like phosphoric acid and sulfuric acid were also introduced into
cellulose hydrogenation under the catalysis of supported noble metal catalysts
based on Pt, Ru, and Pd at relatively low temperature and short reaction time [21,
3941]. The reaction network of cellulose hydrogenolysis is shown in Fig. 2.3.
Based on the progress made in cellulose hydrogenolysis, the real biomass was
also used as starting materials for the production of polyols over similar catalysts
used in cellulose conversion. However, researches still focus on the pure cellulose
feedstocks because the real cellulose raw material contained some components that
are difcult to transform or some elements that are poisonous to the catalysts. It is
signicant to spare additional efforts to investigate the influence of feedstocks in
hydrogenolysis of cellulose.

H OH

H
H O

HO
HO

OH

OH

HO
O

H O
O
HO

H O
H

H OH

H OH

OH
H

OH

Cellulose
Acid
CHO

CH2OH
H

OH
HO

isomerization

H
H

HO

OH

OH

Fructose

HO

H2 O

OH
OH

Hydrogenation

HO

H2

OH

OH

Mannitol
H2

Hydrogenolysis

OH

HO
H2

HO

HO
OH

HO

1,2-Propanediol

OH

Hydrogenation

OH

Ethylene glycol

HO

H2
OH

Glycerol

Hydrogenolysis

HO

HO
HO

OH

1,3-Propanediol

HO

OH
1,2-Hexanedioll

HO
OH
1,2-Butanediol

OH

HO

OH

OH
Glycerol

OH

Hydrogenolysis

1,2-Propanediol

OH

H
OH

Sorbitol

O
HO

OH

OH

CH2OH

CH2OH

Glucose

Retro-Aldol

Aldol Cond.

H2

HO

CH2OH

CH2OH

CH2OH

CH2OH

OH

1,3-Propanediol

OH

Ethylene glycol

Fig. 2.3 Typical pathways for the hydrolytic hydrogenation of cellulose to glycols

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Y. Jiang et al.

Though great advances have been made in the conversion of cellulose to polyols,
challenges still exist in this process. For example, both the substrate and the catalysts are presented in solid state in this reaction, resulting in difculties for cellulose to get access to the active catalytic sites. Mass transfer between substrates
and catalysts is the main difculty in hydrogenolysis of cellulose.

2.3.2

Hydrogenolysis of Sugars and Sugar Alcohols

Glucose hydrogenation/hydrogenolysis is an important step not only in one-pot

hydrogenation/hydrogenolysis of cellulose but also in cellulose utilization step by
step. Study on catalytic hydrogenation and hydrogenolysis of glucose is essential
for it can give an insight in the process of glycols production, thus leading us to
gain insights how to coordinate the reaction rate of glucose production and rate of
hydrogenation/hydrogenolysis reaction in one-pot catalytic reaction. Until now, the
hydrogenolysis of sugars and sugar alcohols has been abundantly investigated.
Glycols such as propanediol, EG, and butanediol can be obtained by hydrogenating
sugars or sugar alcohols under the transition metal catalysts with Ni, Ru, and Pt as
major active components and other catalysts via selective cracking of CC and CO
bonds [42]. Nickel- and copper-based catalysts usually suffer from disadvantages of
nickel leaching, activity deactivation, and challenges in product purication, which
restricted their application. To avoid the problems, the robust noble metal catalysts
were generally used for their high hydrogenation activity and high stability [43].
In the conversion of sugar alcohols to glycols, base promoters such as NaOH or
Ca(OH)2 were always needed in hydrogenolysis of sugar alcohols because base can
catalyze the CC cleavage of dehydrogenation intermediate products. However, the
use of alkali brings about problems like difculties in recycle of the alkali. MgO, a
kind of solid base was employed to support the metal of nickel to promote the
hydrogenolysis of sorbitol under a relative mild condition [44]. Bimetallic catalysts
promoted by solid bases were rational materials for the upgrading of sugar alcohols
to lower polyols, which is under intensive study [45].

2.3.3

Hydrogenolysis of Glycerol

Glycerol is produced by hydrolysis of vegetable oil as a by-product of soap and by

transesterication of oil and fats in the production of biodiesel [46, 47]. Due to the
intensive interest in biofuels, the production of glycerol has increased enormously
and the disposal of glycerol waste in biodiesel manufacture has limited the spread
of the use of biodiesel. In this context, several ways of glycerol valorization have
been described. One of the most promising ways to generate value-added products
is hydrogenolysis especially 1,2-propanediol, 1,3-propanediol, and also EG (see
Fig. 2.4) [48].

2 Chemical Conversion of Biomass to Green Chemicals

29

HO

H2O

H2O

CH3OH

OH

1,2-Propanediol
HO

OH
OH

Glycerol

HO

OH

1,3-Propanediol

HO

OH

Ethylene glycol

Fig. 2.4 Conversion of glycerol to 1,2-propanediol, 1,3-propanediol and ethylene glycol

The hydrogenolysis of glycerol involves the dissociation of the CC bonds and

the CO bonds followed by hydrogen addition. CC hydrogenolysis of glycerol
generates EG. On the other hand, in the CO hydrogenolysis, 1,2-propanediol or
1,3-propanediol could be obtained depending on the catalyst used. The general
challenge in the hydrogenolysis of glycerol lies in the selective cleavage of CO
versus CC bonds. Effective catalytic systems have been developed to selectively
discriminate between CC and CO bonds. Cu-based catalysts were found to be
selective for the formation of 1,2-propanediol with over 95 % selectivity, while
with the more active Ni and noble metal based catalysts, both 1,2-propanediol and
EG can be obtained due to the capability of cleaving both CO and CC bonds.
However, the selective hydrogenolysis of the secondary hydroxyl group in the
cleavage of CO bonds is a different problem. Several catalyst systems have been
described which resulted in a signicant selectivity for 1,3-propanediol [48]. For
example, WO3 promoted Pt catalysts and ReOx promoted Ir or Rh catalysts were
especially effective in 1,3-propanediol formation among the reported materials.

2.4

Catalytic Synthesis of Value-Added Furanic Products

from Biomass

The dehydration of pentose (xylose) and hexose (fructose or glucose) can yield
furfural and 5-hydroxymethylfurfural (HMF), which are both promising intermediates to synthesize high-value products. By now, numerous works have been
carried out on their conversion and a lot of value-added products have been successfully synthesized. Their detailed synthetic methods are described below.

2.4.1

Furfural Derivatives

Furfural has been produced in million tons annually all over the world from the
hydrolysis of hemicellulose and subsequent dehydration of the intermediate xylose.

30

Y. Jiang et al.

Therefore, scientists are keen to develop methods on furfural conversion for its easy
availability and acceptable price. By hydrogenation, furfural can be converted into
furfuryl alcohol (FA), 2-methylfuran (MF), and tetrahydrofurfuryl alcohol with
their synthetic method very mature in industry [49]. Scheme 2.2 shows the compounds that have been successfully synthesized from furfural, FA and MF. Those
compounds can be divided into two categories, fuels (pathways 14) and ne
chemicals (pathways 58).
Due to the high polarity and instability of furfural from the presence of aldehyde
group, it cannot be added directly into gasoline or diesel. Therefore, converting
furfural into fuels is a process that can obtain a molecule with low polarity and
long-term stability. Moreover, the octane number or cetane number of the products
should be considered to meet the requirement of gasoline or diesel. Such molecules
as alkane, ether, ester, and acetal have been designed and synthesized.
Base-catalyzed aldol reaction occurred between furfural and acetone to produce
compound 1 (4-(2-furyl)-3-buten-2-one) as an intermediate. Subsequent
hydrodeoxygenation of 1 yields octane, which is used in gasoline (pathway 1) [50].
The yield of 1 can be improved by increasing the molar ratio of acetone to furfural,
aiming at avoiding the formation of difurfurylideneactone (double aldol adduct).
The Pt/NbOPO4 catalyst was reported to achieve ca. 76 % octane yield from 1
under a mild condition, in particular, P = 2.5 MPa, T = 175 C, and
WHSV = 0.6 h1.
Through acid-catalyzed hydroxyalkylation with carbonyl-containing compounds
and subsequent hydrodeoxygenation, MF was converted to a diesel-range alkane
(pathway 2). Acid catalysts such as strong Brnsted inorganic, organic and solid
acid can all catalyze hydroxyalkylation reaction with more than 90 % yield
achieved. Hydrodeoxygenation could be realized by Pt catalyst supported on active
carbon, TiO2, SiO2Al2O3, Nb2O5, and ZrP [5153].
It is notable that 6 mol of hydrogen were needed to synthesize alkanes (pathways
1 and 2) when furfural was adopted as the primary substrate. Besides, all the
oxygen atoms of the reactants are removed, against the atom economy. Therefore,
pathways 3 and 4 were put forward that could consume less hydrogen and keep
more atoms. In pathway 3, FA rst etheries with monohydric alcohol to produce
the intermediate alkyl furfuryl ether (AFE). AFE was then hydrogenated to alkyl
tetrahydrofurfuryl ether (ATE), a promising cetane number improver for diesel.
Further hydration of AFE can synthesize alkyl levulinate (AL) for gasoline additive.
Mu et al. developed a synthetic method of methyl tetrahydrofurfuryl ether
(MTE) and ethyl tetrahydrofurfuryl ether (ETE) using acidic ZSM-5 zeolite and
Raney Ni catalytic system. The highest selectivity of the intermediates methyl
furfuryl ether (MFE) and ethyl furfuryl ether (EFE) reaches 59 and 45 %, respectively. Nearly quantitative hydrogenation of MFE and EFE to MTE and ETE was
achieved by Raney Ni catalyst6. However, the main drawback of MTE and ETE lies
in their low flash point [54]. The one-pot conversion of FA to AL has been performed using various acidic catalysts in the corresponding alcohol solution with
more than 80 % AL yield achieved [5558].

2 Chemical Conversion of Biomass to Green Chemicals

O

base

+
acetone

Furfural

31

H2

Octane

4-(2-Furyl)-3-buten-2-one 1

pathway 1
R

hydroxylalkylation

H2

H+

MF
H+

O
OH

ROH

diesel range alkane

O
O

FA

pathway 2

H2

ATE
H+
O
H 2O

AFE

pathway 3

AL
O
O

HO

O
O

H2

OH

Furfural

acid

OH

OH

glycerol

OH

Ac2O
O

O
O

O
O

O
O

pathway 4

O
O

HO
O

H2

OH

OH

1,5-pentanediol

HO
OH

OH

1,2-pentanediol

pathway 5
O
O

1/2 O2

1/2 O2

Furfural

O2

Maleic anhydride

pathway 6
O
O

Furfural

OH

H2

H+

FA

OH

4-HO-2-CPEO

H2

+
CPO

2-CPEO

pathway 7
O
O

Furfural

+ HN

R1

R1

R2

pathway 8

OH

H2

Scheme 2.2 Reaction pathways for the conversion of furfural

R2

R1
R2

CPL

32

Y. Jiang et al.

Glycerol is the by-product yielded during the production of biodiesel. Expanded

use of biodiesel will generate large amount of glycerol [59]. The pathway 4 presents
a way of utilizing both furfural and glycerol in fuel production. The acetal reaction
of glycerol with furfural and subsequent hydrogenation produced compounds 3 and
4. To further reduce the polarity of the nal products, the hydroxyl group in 3 and 4
reacts with acetic anhydride to produce compounds 5 and 6. In the acetal reaction,
ZnCl2 was proved to be the best choice from the pool of Lewis acids with 90 % of
acetal products obtained. The solid acids aluminosilica MCM-41 (Al = 3 %) and
montmorillonite K-10 clay could achieve around 80 % acetal yield. Hydrogenation
of the furan ring can be carried out using Pd/C catalyst. Acetylation of the free
hydroxyl group was performed by combining 3 and 4 with two equivalents each of
acetic anhydride and triethylamine [60]. Although the targeted products 5 and 6
showed no problems with solubility, cloud point, density and flash point in diesel,
the more signicant parameter cetane number was not investigated.
Furfural contains ve carbon atoms and two oxygen atoms. Hydrogenation of
furfural and its downstream products FA and tetrahydrofurfuryl alcohol (THFA)
produces 1,2-pentanediol (1,2-PeD) or 1,5-pentanediol (1,5-PeD) depending on the
substrate and catalyst employed (pathway 5). The Ru/MnOx catalyst was reported
to hydrogenate FA to 1,2-PeD in aqueous solution with 42.1 % yield achieved [61].
The hydrotalcite-supported Pt nanoparticles (Pt/HT) was capable of achieving 73 %
yield of 1,2-PeD from furfural in isopropanol [62]. No work has been reported to
hydrogenate tetrahydrofurfuryl alcohol into 1,2-PeD. With respect to 1,5-PeD, the
PdIrReOx/SiO2 catalyst showed good performance from furfural obtaining the
maximum yield of 71.4 % [63]. The Pt/Co2AlO4 catalyst prepared by
co-precipitation method was able to achieve 35 % 1,5-PeD yield from FA [64]. The
most efcient way of preparing 1,5-PeD is by hydrogenating tetrahydrofurfuryl
alcohol. More than 90 % 1,5-PeD selectivity could be obtained using RhMoOx,
IrMoOx, RhReOx, and IrReOx supported on SiO2 or carbon [6569]. Recently,
we developed a highly efcient and green catalytic system comprising MoO3 and a
supported Rh catalyst for the hydrogenolysis of THFA with 1,5-PeD selectivity up
to 80 % is achieved [70]. Moreover, a very interesting phase-transfer behavior for
MoO3 during the reaction was observed with the assistance of different characterization techniques. In this process, MoO3 dissolves partially in the liquid phase
under the reaction conditions and is transformed into the soluble hydrogen
molybdenum oxide bronzes (HxMoO3) in the presence of H2, which are recognized
as the genuinely active sites for the secondary CO bond breaking of THFA. The
furan ring and aldehyde group of furfural were both sensitive to oxygenation.
Oxygenation of furfural yields maleic anhydride (MA) using VOx/Al2O3 catalysts
(pathway 6). The highest selectivity to MA reached 73 % [71].
Copper and nickel supported on Co3O4 and ZrO2 prepared by co-precipitation or
sol-gel method can catalyze hydrogenation of FA into cyclopentanone (CPO) and
cyclopentanol (CPL) as main products in aqueous solution [72]. Possible mechanism is presented in Scheme 2.2 pathway 7.
Erbium (III) chloride [73] in ethyl lactate is used for the reaction of furfural and
amines at room temperature to yield diastereoselectively differently N,N-substituted

2 Chemical Conversion of Biomass to Green Chemicals

33

trans-4,5-diaminocyclopent-2-enones as versatile synthetic intermediates to the

formation of densely functionalized derivatives as shown in pathway 8.

2.4.2

HMF Derivatives

Different from furfural, there are two substituents in the furan ring of HMF, aldehyde, and hydroxymethyl, which are both active during hydrogenation or oxygenation. Hence, HMF is considered to be more valuable than furfural especially in
the synthesis of polymer monomer [74]. Scheme 2.3 shows some value-added
products that have been synthesized from HMF. They can be divided into two
categories. One is fuel and the other is monomer.
As HMF itself is highly polar, oxygen-rich, and non-volatile, it is necessary to
lower the polarity and the boiling point to obtain liquid fuels or fuel additives. By
hydrogenation, HMF can be converted into 2,5-dimethyl-furan (DMF) and
2,5-dimethyl-tetrahydrofuran (DMTHF), which possess both a high octane number
and high energy content to replace gasoline directly [7581]. Dumesic et al.
developed a CuRu/C catalyst that could in situ hydrogenate HMF produced in a
water/1-butanol biphasic system into DMF [76]. The neat HMF can be converted
into DMF using most of the precious metal catalysts such as Pd, Pt, Ru, and Rh
supported on active carbon [79]. In the case of HMF conversion to DMTHF, RhCl3
in aqueous solution can be used as catalyst to in situ hydrogenate HMF from fructose
dehydration into DMTHF with more than 80 % DMTHF yield achieved [81].
The processes to DMF and DMTHF consume 3 and 5 mol of hydrogen,
respectively, and remove two oxygen atoms in HMF, which are not favorable from
the viewpoint of atom economy. Therefore, work was carried out on the conversion
of HMF into 2,5-bis-alkoxymethylfurans (BAMF), which could consume less
hydrogen and retain more mass than those of DMF and DMTHF [82, 83].

H2

DMF H

ROH

RO

Caprolactam
H2

HO

BHMF

DFF

+O

H2

O
O

BAMF

MA

+ HO

HO

O
O
OH

FDCA

Scheme 2.3 Reaction pathways for the conversion of HMF

OH

THFDM

R
O

O
O

OH

O2
O

ROH

O
HO

HMF

AMF

O
O

NH3

DMTHF

34

Y. Jiang et al.

As shown in Scheme 2.3, such a process needs hydrogenation and etherication

catalysts. Mu et al. employed a low-cost supported Cu/SiO2 catalyst in the efcient
hydrogenation of HMF into 2,5-bis-hydroxymethylfuran (BHMF) and acidic
ZSM-5 zeolite in the etherication of BHMF with methanol. In their work, 97 %
BHMF and 70 % 2,5-bis-methoxymethyl-furan (BMMF) yield could be achieved.
The high cetane number of 80 (much higher than that of the commercial diesel),
high flash point (90 C), and low cold lter plugging point (<37 C) make BMMF
a good candidate for diesel [83]. Although direct etherication of HMF with
monohydric alcohol can produce 5-alkyloxymethyl furfural (AMF), the presence of
aldehyde group in AMF makes its stability and solubility in diesel limited.
Furthermore, its cetane number has not been measured [84].
The monomer production from HMF can be carried out by hydrogenation,
oxygenation, or hydrogenation and subsequent amination. The hydrogenation of
HMF can produce BHMF and 2,5-bis-hydroxymethyltetrahydrofuran (THFDM)
[83, 85]. Except the aforementioned Cu/SiO2 catalyst, Pt or PtSn supported on
active carbon or Al2O3 demonstrated good performance in hydrogenation to BHMF
[82]. Nearly quantitative hydrogenation of HMF to THFDM can be realized by
Raney Ni catalyst [85].
Oxygenation of HMF can synthesize three products using different catalysts. The
Cu(NO3)2/VOSO4 catalyst was reported to selectively oxidize the hydroxymethyl
to aldehyde with 99 % 2,5-diformylfuran (DFF) yield achieved only at room
temperature [86]. Besides, Fe3O4/Mn3O4 and V2O5/C also exhibited high selectivity in HMF oxygenation to DFF [87]. Deeper oxygenation of HMF to
2,5-furandicarboxylic acid (FDCA) was performed typically using supported platinum catalysts with the aid of homogeneous base, resulting in near quantitative
FDCA yield [88]. Gorbanev et al. demonstrated that Au/TiO2 could oxidize HMF
into FDCA in 71 % yield. At near room temperature [89], Casanova et al. showed
that Au/CeO2 was more active and selective [90]. However, these catalysts require
addition of homogeneous base (120 equiv. NaOH) and high oxygen pressure (10
20 bar). Navneet et al. reported a base-free oxidative system using
hydrotalcite-supported gold nanoparticle catalyst [91].
Using vanadium compounds, the furan ring of HMF can be further oxidized to
MA. About 3050 % yields of MA were obtained using VO(acac)2, VO(pic)2 [bis
(pyridine-2-carboxylato) oxovanadium (IV)], VO(mal)2 [bis (maltolato) oxovanadium (IV)], and VOSO4 catalysts [92].
Vries et al. developed a route that could convert HMF into caprolactone, which
needed four steps with THFDM, 1,2,6-hexanetriol (1,2,6-HT), 1,6-hexanediol (1,
6-HD) as the intermediates. Caprolactone was considered to be the intermediate of
caprolactam, the monomer for nylon-6, a widely used polymer [85].
It should be noted that although HMF may be converted into a lot of high-value
compounds, the bottlenecks that hinder the industrial application of those products
is the availability of HMF in large scale. The price of HMF precursor fructose is too
high. In addition, the high boiling point and high polarity of HMF make it difcult
to be separated from the reaction system.

2 Chemical Conversion of Biomass to Green Chemicals

2.5

35

Catalytic Conversion of Biological Fermentation

Products into Value-Added Chemicals

A core part of modern biotechnology is the modern fermentation engineering like

genetic engineering. The fermentation products can be used in drug, cosmetics,
food, and other chemical industries. Biotechnology itself as a hot research eld has
signicant advantages: high selectivity in the biological fermentation; high conversion efciency, mild reaction conditions. However, the existing biological
conversion technology based on microbes and enzymes has its inherent limitations,
such as the enzyme specicity, serious environmental pollution, and expensive
equipments. The problems greatly limit the large-scale application of biological
technology. Chemical catalytic conversion can realize flexible product structures.
With breakthroughs in bio-fermentation technology and reduction in the production
costs, succinic acid, lactic acid (LA), itaconic acid (IA), etc., have become a cheap
and abundant supply of raw material products [9395]. Selective conversion of
biogenic carboxylic acids has become an important biorenery transformation
concept based on platform chemicals. With the development of science and technology, the combination of biological technology and chemical conversion technology to produce chemical products would be gradually applied into industrial
productions.

2.5.1

Succinic Acid

Succinic acid (SA, C4H6O4) [96] produced from fermentation anaerobically with
bacteria from glucose and CO2 has been identied as one of the most important
platform chemicals according to the US Department of Energy (DOE) Report in
2004 [97]. As a C4-dicarboxylic acid, succinic acid could be converted into some
key building blocks in chemical markets and industries via hydrogenation, dehydration, esterication, amination, and cyanation reactions (Scheme 2.4) [98]. The
hydrogenation of succinic acid will be discussed in details.
Ruthenium-based catalyst was considered as an efcient catalyst for the
hydrogenation of succinic acid [99101]. A series of important chemical products
including 1,4-butaniol (BDO), tetrahydrofuran (THF), and -butyrolactone
(GBL) could be obtained via direct hydrogenation of SA or diethyl succinate [101,
102]. BDO is an important raw material for the production of polyesters and
polyurethanes. GBL could be used to produce THF, N-methyl-2-pyrrolidone
(NMP), and 2-pyrrolidone. THF as an important chemical was widely used as
solvent or chemical intermediate in the production of polyvinyl chloride (PVC) and
paints. It was usually obtained from fossil fuels, including the dehydration of
1,4-butanediol (BDO), hydrogenation of maleic anhydride (MAN), hydrogenation
of SA or diethyl succinate. The product distribution in the hydrogenation of SA is
varied with different catalysts and experimental conditions. In order to obtain the

36

Y. Jiang et al.
HO

OH

1,4 - butanediol
O

esterification
MeOOC

COOMe

OH

tetrahydrofuran (THF)
hydrogenation

HO
HO

OH

OH

-butyrolactone

fermentation
dehydration
cyclization

HOOC

HOOC

COOH
fumaric acid

COOH

COOH

succinic acid

COOH
maleic acid
H 2N

amination

NH2

1,4 - diaminobutane
CN
NC
succinonitrile
O

cyanation

H 2N

amination

NH2
O
succindiamide

Scheme 2.4 Succinic acid as a platform chemical [94]

above chemicals more effectively, it is important to understand the hydrogenation

mechanism of succinic acid. A simple reaction pathway for the hydrogenation of
succinic acid was shown in Scheme 2.5 [103].
As early as 1988, DuPont Company has applied a patent for making butyrolactones, butanediols, and mixtures thereof by hydrogenating maleic acid, fumaric

+ H2
COOH

+ H2
COOH -2H O
2

succinic acid

OH

OH
1,4 - butanediol

- butyrolactone

+ H2
-H2O

Scheme 2.5 Reaction pathway for the hydrogenation of succinic acid

tetrahydrofuran

2 Chemical Conversion of Biomass to Green Chemicals

37

acid, succinic acid, IA, or mixtures thereof over palladium or combinations with
rhenium using at least one support selected from the oxides of titanium, zirconium,
and hafnium [104]. Piero Frediani et al. [99] studied the hydrogenation of -butyrolactone, succinic and fumaric acid into 1,4-butanediol with the homogeneous
catalytic system [Ru(acac)3]/triphos] [triphos:MeC(CH2PPh2)3]. A 96 % yield and
100 % isotopomeric selectivity of 1,4-butanediol were achieved under mild reaction
conditions. In order to simplify the separation process of the products, researches
committed to nding heterogeneous catalyst replacing homogeneous catalytic
system. Many studies focused on nding suitable support materials for
ruthenium-based catalysts. Palladium-mesoporous alumina (PdAX) catalysts
prepared by Song et al. via sol-gel method were rst used in the liquid-phase
hydrogenation of SA to GBL [103]. The yield for GBL increased with increasing
the acid density of PdAX catalysts. Lee and co-workers examined the effect of
different mesoporous supports (MCM-41 and SBA-15) impregnated by palladium
solutions on the product distributions for the hydrogenation of SA [105]. With the
same preparation and reaction process, Pd/MCM-41 catalyst favorably produced
BDO, while the Pd/SBA-15 catalyst preferred to produce cyclic compounds THF
and GBL. The HRTEM results indicated that for MCM-41, larger Pd particles were
located on the outside of the pore channels predominantly; for SBA-15, smaller Pd
particles preferred to incorporate to the inside channels while the larger particles
located on the mesopores. Besson examined the effect of 2 wt% Pd/TiO2 catalysts
for the hydrogenation of SA in aqueous phase, and titania support showed better
stability than other support materials under hydrothermal conditions [106].
Nowadays, carbon is usually selected as support materials for its controllable
porosity, non-toxicity, interactive functions at the surface, and hydrophobic property [107]. Song et al. introduced ruthenium-mesoporous carbon composite
(Ru-XC) catalysts, which was prepared by an incipient wetness impregnation
method into this system [102]. They found that ruthenium dispersion played a key
role in determining the catalytic performance in the hydrogenation of succinic acid.
Ruthenium particle size depended on the HCl solution concentration during the
RuCl3 impregnation process. THF yield in the hydrogenation of SA increased with
decreasing average ruthenium particle size.
Ru-mesoporous carbon catalyst served as an efcient and reusable catalyst in the
hydrogenation of succinic acid to GBL. Petitjean et al. studied the effect of addition
of Re to Pd/C and Ru/C catalysts over the hydrogenation of 15 wt% SA aqueous
solutions to BDO [108]. By addition of 4 % Re to 2 % Pd/C and 2 % Ru/C, the
selectivity of BDO increased from 44 and 49 %, to 62 and 66 % at 180 C and
150 bar H2, respectively. Liangs group also conrmed the results above [109]. In
the following studies, X-ray diffraction and TEM results illustrated that Re and Cu
metals which were introduced into the carbon support step by step could improve
the ruthenium dispersion signicantly [110]. Re/Cu-MC catalyst showed a better
catalytic activity than Re/Cu/MC catalyst in the liquid-phase hydrogenation of
succinic acid to BDO. In the real reaction process, all the reactions are reversible
[111], there are still some other by-products including butyric acid, propionic acid
and butanol.

38

Y. Jiang et al.

Mu et al. have also carried out the hydrogenation of SA to BDO over Pd/C
catalysts. By the addition of iron, the size of Pd particles and the iron dispersion on
carbon support were improved effectively. The yield and selectivity of BDO were
further changed. Fan et al. have developed a new gold-catalyzed aqueous hydrogenation protocol with syngas as hydrogen source [112]. The conversion of SA
reached 100 % and the selectivity of GBL reached 99 % with Au/m-ZrO2 (Au
0.2 mol%) and syngas (4 MPa, H2/CO = 2:1) at 180 C for 6 h. Furthermore, the
catalyst could also be readily adapted to IA hydrogenation.
However, there are still some problems in expanding this chemical catalytic
system: hash reaction conditions, higher reaction temperature, excess hydrogen,
high cost of precious metals. Using soluble mineral acids one can realize the fast
esterication of succinic acid, but it would lead to hazardous waste and complex
separation process. Traditional heterogeneous solid acid catalysts including acidic
zeolites, metal oxide, sulfated zirconia, heteropoly acids or resins were also considered, but the above catalysts could not keep stable in water. Hu et al. reported the
esterication of valeric acid over amino acid ionic liquids catalysts. A 99.9 % yield
of ethyl valerate with 100 % selectivity was obtained after 7 h at 80 C and the
catalysts kept activities after 5 recycles [113]. To resolve the catalyst stability
problems, we speculate that acidic ionic liquids may help a lot in future.
Furthermore, in order to obtain special products selectively, some theoretical
studies about the catalytic mechanism would be considered.

2.5.2

Itaconic Acid

IA [114], also called methylene succinic acid, was rstly produced from citric acid
in 1837 via dehydration reaction at high temperature. It was widely used as an
important precursor to synthesis pharmaceuticals, resins, adhesives, plasticizers,
coatings, deodorants, herbicides, and surfactants [115117]. IA has conjugated
double bonds and two carboxyl groups according to its structure which can be used
as co-monomer with acrylamide or self-polymerized to polyitaconic acid
(PIA) [115]. It could also be estericated to a series of itaconate esters using
Ln SO42/TiO2SiO2 catalysts [118] (Scheme 2.6). Many researches paid
attention to the enantioselective hydrogenation of IA. Bartvk et al. carried out a
detailed study on the enantioselective hydrogenation of IA over cinchona alkaloid
modied supported Pd catalyst in presence of benzylamine with the ee values up to
58 % [119].
More than 80 % of IA was converted to 2-methylbutanediol (MeBDO) and
methyl--butyrolactone (MeGBL) over a 1 % Pd and 4 % Re on titanium oxide
catalyst in the itaconic hydrogenation according to DuPont Companys patent.
BASF Aktiengesellschafts invention in 2001 found that 100 % of IA could be
hydrogenated to 45.2 % of MeBDO and 47.9 % of MeGBL in the presence of a
catalyst comprising Pt and Re [120]. In order to prolong the life of catalyst, many
itaconate esters were synthesized rstly, then, researchers tested the catalytic

2 Chemical Conversion of Biomass to Green Chemicals

H3C

39

CH3

O
3-&4 methyl GBL

H2N

NH2
2-methyl-1,4-butane diamine

H3C
CH2 O
O

CH2 O

3-methyl THF

HO

NH2
O

OH
O
Itaconic acid

CH3
HO

H2N

Itaconic diamide
H
N

OH

2-methyl-1,4-BDO

H3C
O

3-methylpyrrodine

3-&4 methyl NMP

Scheme 2.6 Itaconic acid as a platform chemical

hydrogenation activity of itaconate esters over CuCrMnBa or CuoZnO composite catalysts on a xed bed. The conversion of itaconates reached 100 % [121].
A theoretical study about the selective homogeneous hydrogenation of biogenic
carboxylic acids supposed that for [Ru(TriPhos)H]+ as the catalytically active unit,
the energetic spans for the reduction of the different functional groups follows the
order: lactone carboxylic acid > ketone > aldehyde [122]. Mu and co-workers
have studied the aqueous-phase hydrogenation of biomass-derived IA to methyl-butyrolactone over Pd/C catalysts. They found that the pretreatments of active
carbon with concentrated nitric acid and sodium hypochlorite solution changed the
properties of the carbon, and the best catalyst showed complete conversion with
89.5 % total selectivity to MeGBL [123].
Besides, decarboxylation reactions of IA were carried out with solid Pd/Al2O3,
Pt/Al2O3, Pd/C, and Ru/C catalysts. The isolation of methacrylic acid reached up to
50% yield with high selectivity of 84% [124].

2.5.3

Lactic Acid

LA is one of the important biomass-derived platform chemicals, which could be

industrially produced by fermentation of sugars on medium-size scale. The production is nearing 260,000 tons per year. As a platform molecule with hydroxyl
group and carboxyl group, some important chemicals could be produced via

40

Y. Jiang et al.
O
*
O

CH3

*
C
O

*
O

H3C

C
O

LMW prepolymers
LMW poly-lactic acid (PLA)
OH

- H2O
esterification
OH

OH
HO
HO

O
OH
glucose

fermentation

COOH

reduction

COOEt
lactate esters
OH

dehydration

OH

OH
propylene glycol

lactic acid

O
propylene
oxide

dehydration
COOR
acrylic acid and esters

Scheme 2.7 Overview of lactic acid conversions

selective esterication, reduction, or dehydration reactions (Scheme 2.7). The

chemicals were usually used as green solvents, fuel precursors, and commodity
chemicals [125].
Burns et al. rstly used LA as raw material to produce acrylic acid (AA) in 1935
[126], and this was followed by Fisher and co-workers in the 1940s [127] and a
patent led in 1949 by Atwood [128]. Holmen reported the one-step conversion of
LA into acrylic acid via direct dehydration over CaSO4/Na2SO4 heterogeneous
catalyst, and 68 % yield of AA was obtained at 400 C [129]. From then, NaX and
NaY zeolites [130], Ca3(PO4)2Ca2(P2O7) [131] catalyst and NaY zeolites modied
with alkali phosphates [132] have been introduced into this system.
1,2-propanediol (PeD) is a promising precursor for building unsaturated
polyester resins [133]. The reduction of LA to PeD is very difcult because of the
low reactivity of the carboxyl group, so that the screening of catalysts was of great
importance. Ru catalysts including RuO2 [134], Ru/C [135], MgONH2Ru [136],
RuSnB/Al2O3 [137] and Ru/TiO2 [138] for the aqueous-phase hydrogenation
of LA were thoroughly studied. Dumesic et al. reported that a 88 % yield of PG was
achieved at full LA conversion over a 10 wt% Cu/SiO2 catalyst at 200 C with a
partial H2 pressure of 0.72 MPa. The catalyst kept stable during its 22 days on
stream [139]. 10 wt% Co/SiO2 catalyst also performed good activity in the
hydrogenation of ethyl lactate [140].
Polylactic acid (PLA) obtained from direct polycondensation of LA has
numerous applications from industrial to clothes and biocompatible materials for
medical application [141, 142]. The direct polycondensation yield was quite low,
and therefore lactide from intramolecular esterication process was primarily separated. Then high molecular weight PLA was produced via ring-opening polymerization (ROP) of lactide. However, mainly tin-based homogeneous catalysts
worked in intramolecular esterication which could not be recycled. Few studies
about heterogeneous catalysts were reported [143].

2 Chemical Conversion of Biomass to Green Chemicals

Scheme 2.8 Catalytic
conversion of amino acids

41
NH2

hydrogenation

OH

NH2
OH

deamination

HO
glutaric acid

O
OH

decarbonylation

2.5.4

H2N
NH2
pentane diamine
NH2
H2N
butanediamine

Amino Acid

As essential building blocks of proteins, amino acids could be produced in high

volume from glucose via fermentation. They are important intermediates in metabolism [144] and widely applied in agriculture, medicine and industry elds [145,
146]. Aminoalcohols especially for chiral aminoalcohols are of important chiral
auxiliaries to prepare pharmaceuticals or insecticidal reagents [147]. Direct
hydrogenation of amino acids with hydrogen was considered as the most promising
method (Scheme 2.8), and Ru/C, RuRe, Pd/C, and Pt/C hydrogenation catalysts
were brought to this system appropriately. However, the above catalysts usually
need high temperature with low activity and loss of optical purity. Tomishige et al.
[144] reported selective aqueous hydrogenation of amino acids to amino alcohols
with Rh-MoOx/SiO2 catalyst. The catalyst activity and the selectivity and ee for the
product were enhanced after the modication of Rh with MoOx.
As important precursors to synthesis polymers, glutaric acid could be prepared
via deamination of glutamic acid and pentamethylene diamine via decarbonylation
theoretically (Scheme 2.8). However, pentamethylene diamine was usually
obtained from biological decarboxylation of 1,5-diaminopentane over lysine
decarboxylase. Butanediamine was prepared similarly. Reports about the catalytic
conversion of amino acid are still very limited.

2.6

Summary

So far, biomass is the only renewable carbon resources that can be converted into
chemicals and liquid fuels. The global issues such as greenhouse effect and the
shortage of energy can be eventually solved by the rational utilization of biomass
resources. Owning to the ideal carbon skeleton and oxygen content in biomass and
biomass-derived compounds, the endeavor in the industrialized catalytic transformation of biomass into high value-added chemicals via more environmentally
friendly approaches would pave the way for the future chemical manufacture.

42

Y. Jiang et al.

To selectively produce liquid hydrocarbon fuels, it requires oxygen removal reactions (i.e., dehydration, hydrogenolysis, hydrogenation, decarbonylation/decarboxylation,
etc.) and in some cases in combination with the adjustment of the molecular weight via CC
coupling reactions (e.g. aldol condensation, ketonization, oligomerization) of reactive
intermediates. In this context, the development of a new family of highly active and selective
catalyst systems is an essential prerequisite for chemoselective catalytic conversion of
lignocellulosic biomass into desired products.

References
1. Chheda JN, Huber GW, Dumesic JA (2007) Liquid-phase catalytic processing of
biomass-derived oxygenated hydrocarbons to fuels and chemicals. Angew Chem Int Ed
46:71647183
2. Petrus L, Noordermeer MA (2006) Biomass to biofuels, a chemical perspective. Green Chem
8:861867
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