Review
pubs.acs.org/IECR
Advances in the Catalytic Production and Utilization of Sorbitol
Jun Zhang, Ji-biao Li, Shu-Bin Wu,* and Ying Liu*
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, Guangdong, 510640, China
ABSTRACT: Recently, research on the production and transformation of sorbitol has become exciting in chemical industry and
in catalysis studies for its broad applications. It opens up a new path for achieving sustainable energy supply and chemicals
production. Here we mainly review the catalytic routes for the synthesis of sorbitol and conversion of sorbitol into high value-
added compounds such as lower alcohols, paraffins, isosorbide, and other derivatives. Meanwhile, some promising and valuable
research directions are suggested based on the major challenges emerged in current research, such as the development of efficient
magnetic catalysts, microwave heating, and other hydrogen sources.
1. INTRODUCTION
For energy and economic reasons, extensive research has been
carried out worldwide to study the efficient conversion of
biomass resources into valuable biofuels and chemical materials
in the last decades (Figure 1), since they have great merits such
as abundance, renewable, and wide distribution when compared
to other raw materials.1−10 Among these explorations, one
attractive route is the preparation and utilization of sorbitol,
since it is known as one of the 12 important target chemicals in
their biomass program.11 Sorbitol being the most commonly
used sugar alcohol (it is the least costly) holds the biggest
market share among similar polyols, which is widely used in
food, drugs, cosmetics, toothpaste, and so on. For example, it is
an important precursor for the manufacture of L-ascorbic acid
that consumes almost 15% of world sorbitol production.12
Most importantly, sorbitol can be further degraded into polyols
that are the downstream products in the petrochemical
industry.13 Meanwhile, it can be used for the synthesis of
lactic acid under alkaline hydrothermal conditions.14 Recent
studies showed that the structure and the catalytic performance
of some catalysts were significantly enhanced with the addition
of sorbitol during catalyst preparation.15−18 As a selective
dehydration product of sorbitol, isosorbide has a special
application in cosmetic, biomedicine, and polymers materials
due to the rigid molecular structure and chiral centers.19−21 In
brief, the general preparation and conversion routes of sorbitol
are clearly shown in Scheme 1.
Usually the production of sorbitol is accomplished in a
hydrogenation process;22−25 however, reactions like hydrolysis
and hydrogenation may be involved in the same reaction
system due to the rapid development of research. Because
biomass materials such as starch26 and cellulose27−29 are
receiving increasing interest in recent work, leading to a great
need in the improvement in the catalysts and/or reaction
systems. Recently, the ruthenium catalysts showed higher
hydrogenation activity than that of nickel and alloy
catalysts.23,30,31 With in-depth studies, unavoidable phenomen-
on happens that sorbitol will be easily degraded in the presence
of H2 under high temperatures. Then lower alcohols, including
glycol, 1,2-propylene glycol, and methanol, are formed after
reaction.32,33 Notably, these chemicals can be used to
synthesize many high value-added products for the replacement
© 2013 American Chemical Society 11799
of oil resources. As concerns the dehydration product,
isosorbide is obtained by 2-fold dehydration of sorbitol via
sorbitan under acidic conditions. It was reported that sulfuric
acid and other inorganic acids were first used in the synthesis of
isosorbide.34−36 Due to high corrosion and environmental
pollution of inorganic acids, some pollution-free and effective
catalysts such as solid acids and acidic ion exchange resins are
developed. Through the above analysis, we can see that a
plethora of useful molecules will be obtained from multifunc-
tional sorbitol via a series of reactions by using various catalysts.
Although some published work deals with the topic of
sorbitol chemistry to a certain degree, including conversion of
cellulose into sorbitol and hydrogenolysis and dehydration of
sorbitol,37−39 this Review concentrates mainly on describing
and analyzing all aspects of the work on sorbitol chemistry
reported up to date. The improvement in catalytic synthesis
and conversion of sorbitol with suitable reaction systems are
discussed in greater detail, and some of the existing limitations
and unsolved challenges are put forward at the same time.
Owing to the rapidly expanding nature of this interesting field,
we hope that this Review provides a helpful overview and
insight to readers in this exciting research area.
2. SORBITOL PRODUCTION
In commercial terms, sorbitol is an ideal, versatile compound
that has been widely used in the fields of food and chemistry.
The detailed information for physical properties of sorbitol is
shown in Table 1. Three techniques are mainly introduced in
the industrial production, namely, batch, semicontinuous, and
continuous technology. It begins with raw materials like
cassava, corn, or wheat that are first converted into dextrose
through enzymatic hydrolysis and then was hydrogenated into
sorbitol at 403−423 K with H2 pressure ranging from 4.0 to
12.0 MPa. Among the manufacturers, Roquette Freres is the
biggest sorbitol producer around the world, together with
Cargill and SPI Polyols they hold a market share of over 70%.
By the way, the yield of mannitol is accompanied during
Received: April 14, 2013
Revised: July 28, 2013
Accepted: July 29, 2013
Published: July 29, 2013
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Industrial & Engineering Chemistry Research Review

Figure 1. Concept of a biorefinery.

Scheme 1. Specific Network for the Preparation and Utilization of Sorbitol

Table 1. Physical Properties of Sorbitol catalytic activity and stability of Raney-nickel were not desirable
due to the leaching of Ni.
molecular refractive density melting point boiling point
weight indexa (kg/m3)b (K) (K) Follow-up studies revealed that the activity of Raney-nickel
could be significantly enhanced by the addition of some
182.17 1.3477 1489 361−375 569
a
promoters.41−43 For the Mo modified sample, the specific
Value given for 10 wt % aqueous solution. bValue given for 268 K. surface area and hydrogenation activity increased from 56 to 77
m2/g and 0.35 to 0.46 (kg·s)−1, respectively.44,45 Mo was
present in the form of Mo3Al or Mo3Al8 in Ni2Al3, and the
sorbitol production, which has wide application in many fields leaching of Al and Ni was effectively avoided. Hoffer et al.
as well like medicine, chemical industry, and so on. The reported that the activity of Raney-nickel modified with and
formation of mannitol is a result of the epimerization of glucose without Mo decreased from 0.46 to 0.32 (kg·s)−1 and from 0.35
to mannose in the case of alkaline medium. to 0.18 (kg·s)−1, respectively, in the third run.27 Note that Mo
The following sections summarize the research advances in showed excellent stability without leaching into reaction
the catalytic synthesis of sorbitol using various biomass solution. With in-depth studies, the specific surface area
carbohydrates. A series of efficient nickel and ruthenium increased by 30%−35% in Cr modified Raney-nickel catalyst,
catalysts are explored in glucose hydrogenation, as listed in and the activity depended on Cr content. The Cr replaced Ni in
Table 2. Ni2Al3 to form homogeneous alloy at certain degree when less
2.1. Production of Sorbitol from Glucose. 2.1.1. Nickel than 2 wt % Cr was added, and a new phase of Al9Cr4 would be
Catalysts. Sorbitol was introduced early by glucose hydro- created with further increasing Cr loading.45,46 With respect to
genation with the presence of suspension catalyst in 1942 for Fe modified catalyst, the specific surface area and activity were
the first time, and then fixed bed reactor was developed in obviously promoted, which increased from 56 to 112 m2/g and
combination with Raney-nickel catalyst.40 However, the from 0.35 to 0.90 (kg·s)−1, respectively. But more Ni, Al, and
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Table 2. Catalytic Hydrogenation of Glucose with Various Catalysts

glucose concn (wt%) catalyst T (K) Pa (MPa) glucose conversion (%) sorbitol selectivity (%) ref
10 Ru/MCM-41 393 3 100 94.4 29
10 Pd/C 393 3 41.1 39.9 29
10 Al−Ni 393 3 20.4 20.5 29
10 Ru/C 393 4 ―b >98 45
5 Ni1.85Cu1Al1.15 398 3 78.4 93.4 51
50 Raney Ni−P 393 4 55.8 99.5 53
50 Ru−B 353 4 95.1 ∼100 54
40 Ru/C 373 8 100 99.2 55
50 Ru/Cc 393 4 99.9 98.2 56
50 Ru−B/SiO2 373 4 100 ∼100 57
50 Ru/HMT 373 3 72.9 ― 62
50 Ru−Cr−B 353 4 99.7 ∼100 63
50 NiMoAl 408 4 100 >99 64
a
Initial hydrogen pressure measured at room temperature. bNot reported. cAdding carbonyl group promoted organic assistant.

Fe were lost during the reaction, which would raise the cost for
the purification of sorbitol. As discussed above, it is speculated
that the high activity and stability of Mo and Cr modified
catalysts may be explained by the synergy among these active
metals, probably providing a lower activation energy of CO
in glucose molecule. Much more work should focus on the
synergy effect among used metals and calculating reaction
activation energy through performing kinetics experiments. The
phase of metal promoters may play a critical role in the
performance of modified catalysts. Overall, Mo and Cr
modified catalysts hold great potential for possible application
in industrial-scale production after comprehensive comparison.
Considering the environment for producing sorbitol on
modified Raney-nickel catalysts, particular attention should be
directed to the following aspects. First, proper H2 pressure is
deserved to achieve great glucose conversion, and higher
reaction temperature leads to glucose carbonization and
generates some byproducts. Second, the desired pH value of
reaction solution was 8.0−9.0 when using Raney-nickel catalyst.
However, glucose can be easily isomerized into mannose in
alkaline condition and then hydrogenated into mannitol.47
Therefore a suitable pH value should be chosen so as to
prolong catalyst life and prevent glucose isomerization, and a
pH of around 7.5 is proposed in industrial production.
Another method also attracts significant interest in catalyst
preparation, i.e., the use of support to increase metal dispersion.
Various carriers were examined to enhance catalyst activity,
such as SiO2, TiO2, Al2O3, and so on. The research group of
Claus had made great effort to the development in supported
Ni catalysts. They reported that the activity followed the
sequence Al2O3 > TiO2 > SiO2 > C, while all these tested
catalysts were leaching.48 In most cases, catalysts prepared by
impregnation exhibited higher activity compared to those
prepared by incipient wetness. With in-depth study, the Ni
precursors were found to play an important role in the
performance of obtained catalysts. By comparison, Ni catalysts
prepared by impregnation with nickel ethylenediamine
complexes revealed small nickel particles (mean diameter: 2−
3 nm) and showed almost no Ni leaching when compared to a
commercial Ni/SiO2 catalyst, which confirmed that small nickel
particles were more resistant to leaching than larger ones.49 In
current research, some other carriers such as MCM-41 and
HZSM-5 molecular sieves are of high interest that can provide
high BET surface area, desirable porosity, and excellent metal
dispersion for supported metal catalysts. In this manner, an
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efficient accessibility of the Ni particles attached at the tip of the
supports allows for immediate hydrogenation of glucose units.
Additionally, considerable effort should be directed to the
relationship between Ni particle size and related catalytic
activity.
Hydrotalcite-like compounds (HTlcs) were used as
precursors for the preparation of hydrogenation catalysts in
previous study.50 In our recent work, a series of catalysts were
prepared from Ni/Cu/Al hydrotalcite precursors and were
applied in glucose hydrogenation. The obtained catalysts
exhibited great sorbitol selectivity (93.4%) and glucose
conversion (78.4%) when the precursor was pretreated under
H2 atmosphere at high temperatures. It was proposed that the
existing Al may be used as support for active Ni and Cu in
reduced samples and Ni species were mainly responsible for
high activity. For recycling experiments, Ni was obviously
leached into the solution, while Cu showed excellent stability
according to the ICP-AES analysis of reaction solutions.
With the modification of various metallic elements, an
interesting phenomenon came to us that the Co and Fe
modified catalysts were magnetic. It is known that products
separation and catalyst reuse can be easily realized via the use of
magnetic catalysts. With the further research, Fe content also
played a great important part in catalyst activity. It was inferred
that the synergy effect among metallic elements was weakened
with the further increase in Fe content; future studies on
calculating reaction activation energy and leaching of Fe will
effectively address the present problems. When the magnetic
catalyst was applied in glucose hydrogenation, the optimal yield
and selectivity of sorbitol were 88.2 and 94.2% at reaction
temperature of 398 K with a catalyst dosage of 35%. For
fructose hydrogenation, the desired yields of sorbitol and
mannitol on magnetic catalyst were 42.9 and 56.9% at reaction
temperature and initial H2 partial pressure of 383 K and 3.0
MPa, respectively. Concerning the conversion of biomass
materials, the one-step synthesis of sorbitol could be realized
over magnetic catalysts in combination with extremely low
acids.
For catalyst regeneration, various methods were investigated
in detail to remove the adsorbed carbohydrates and prolong the
catalyst life, such as calcination or elution. Notably, the used
catalyst after acetone elution showed better catalytic activity
when compared to that of other organic solvents. For methanol
or ethanol elution, Ni was easily leached into the solution due
to the chelation between Ni and hydroxyl.51 Above all, the
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Scheme 2. Reaction Mechanism for the Hydrogenation of D-Glucose to D-Sorbitol
preparation cost of HTlcs is lower compared to that of noble
metal catalysts, and the hydrogenation catalysts derived from
HTlcs exhibit exciting activity for merits of smaller crystal size
and higher surface area.
Amorphous hydrogen storage alloy developed in recent years
has gained increasing interest as an alternative target for its
hydrogenation/dehydrogenation properties. It was reported
that high yield and selectivity of sorbitol could be achieved
under mild reaction conditions when using amorphous
hydrogen storage alloy in glucose hydrogenation. For example,
the glucose conversion reached 97% at 313 K and 834 kPa for
24 h when using LaNi5 as catalyst and HAc as additive.
However, the conversion was only 35% under the same
conditions over Raney nickel.12,52
In 2000, Li et al.53 reported that a skeletal Ni−P amorphous
alloy (Raney Ni−P) was formed by alkali leaching of
amorphous Ni−Al−P precursor. This catalyst gave higher
turnover rates than Raney Ni, apparently as a result of
promotion of Ni-active sites by phosphorus. 55.8% glucose (50
wt % feed concentration) was hydrogenated, compared to that
of 17.2% in Raney nickel and 1.1% in commonly used Ni−P.
Meanwhile, only less than 1.0 ppm Ni was leached, indicating
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the superior stability of Raney Ni−P. It was speculated that the
disorder degree of catalyst was obviously increased by adding
phosphorus, which facilitated hydrogen flowing during the
reaction. For amorphous NiMoAl alloy, it exhibited excellent
stability that could be recycled five times, and glucose was
completely converted with sorbitol selectivity of 99%.54 It was
assumed that the diffusion rate of Ni active species decreased
due to greater atomic radius of Mo (0.139 μm) than Ni (0.124
μm), which would prevent catalyst crystallization. The added
Mo increased the disorder degree and hydrogenation activity of
catalyst. Follow-up studies are proposed to introduce supports
(molecular sieves, SiO2, active carbon, and γ-Al2O3) to improve
metal dispersion. Detail work on properly increasing disorder
degree of amorphous structure by adding various additives (Fe,
Zn, La, Ce, Co, etc.) is still necessary.
2.1.2. Ruthenium Catalysts. To completely overcome the
problem of nickel leaching and further increase sorbitol
selectivity, the increasing requirement for new catalysts is
essential. Ruthenium catalysts have attracted a great deal of
attention in recent years for high stability and superior
activity.31,47,55 Hoffer et al. first reported that carbon supported
Ru catalyst was a promising alternative for Raney-type Ni in the
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Table 3. One-Pot Aqueous Hydrolytic Hydrogenation of Cellulose and Cellobiose Using Various Metal/Carrier Catalysts or
Mixture Systems
catalyst substrate concn (wt%) time (h)
b
2.5 wt % Pt/γ-Al2O3 MC 0.8 24
1.0 wt % Ru/CNT MCc 0.8 24
4.0 wt % Ru/C MCb 2 0.5
HCl-0.2 wt % Ru/H-USY BMCd 2 3
CsHPA-5.0 wt % Ru/C BMC 10 8 463
H2SO4-5.0 wt % Ru/C α-cellulose 5 1
1.0 wt % Ru/CNT cellobiose 0.85 3 458
1.0 wt % Ru/CsPW12O40 BMC 0.67 24
1.0 wt % Ru/CsHPW12O40 cellobiose 2 6
Ru, pH 2.0 cellobiose 8.3 12
Ru/C cellobiose 1 1
a
Initial hydrogen pressure measured at room temperature. bMC = microcrystalline cellulose. cMicrocrystalline cellulose pretreated in 85% H3PO4 at
323 K for 40 min. dBMC = ball-milled microcrystalline cellulose. eSugar alcohol yield.
selective hydrogenation of glucose, providing clear direction
toward catalyst development in relevant fields. It was found that
Ru/C showed nearly 100% selectivity to sorbitol under 4 MPa
H2, above all, Ru exhibited excellent stability that effectively
addressed the issue of leaching in nickel catalysts.45 The activity
of Ru/C was proportional to Ru surface area (representing
metal dispersion) and independent of the preparation methods,
suggesting that great yield and selectivity could be achieved
over catalysts of high Ru dispersion. A novel anionic deposition
method rendered catalyst with Ru dispersion of up to 40%.45
In case of mass transfer and kinetics on glucose hydro-
genation, a first-order dependency with respect to hydrogen
was observed for low glucose concentrations (up to ca. 0.3
mol/L), while at higher concentrations the reaction rate
changed to zero-order behavior when the kinetic experiments
were carried out in the absence of mass transport limitations.30
Also, it was proposed that the conversion route involved the
formation of an ionized β-pyranose species, adsorbed on the Ru
surface by coordination of O-1, O-5, and O-6.
Follow-up studies focus on the influence of preparation
methods, supports (SiO2 and γ-Al2O3), and ruthenium
precursors (ruthenium acetate and ruthenium trichloride) on
catalyst activity.56−60 With different ruthenium complexes as
the precursors, the essential properties of catalyst may be of
considerable difference. For example, by comparison with
RuCl3, the glucose conversion increased by approximately 5%
when using ruthenium acetate as precursor.61 When Ru3+ was
supported on expanded graphite with HMT (hexamethylene
tetramine) as ligand by method of ultrasonic impregnation, the
obtained catalysts exhibited great dispersion and smaller grain
size (below 10 nm). A glucose conversion of 72.9% was
attained at 373 K under 3 MPa H2, while only 34.7% glucose
was converted by similar catalyst without HMT as ligand.62 In
another study, Ru/MCM-41 prepared by an impregnation-
formaldehyde reduction method showed almost 100% glucose
conversion and 94.4% selectivity toward sorbitol at 393 K
under 3 MPa H2.25 The mechanism for glucose hydrogenation
over Ru/MCM-41 involved a gas−liquid−solid three-phase
catalytic reaction, in which the carbonyl group in glucose
reacted with activated H (Scheme 2).
On the other hand, ultrafine Ru−B amorphous alloy reduced
by KBH4 was found to show perfect selectivity (∼100%) to
sorbitol compared to crystallized Ru−B, pure Ru powder, and
Raney Ni catalysts.63 Cr-promoted Ru−B amorphous alloy gave
∼98% glucose conversion at Cr content of 3.3%. The formation
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T (K) Pa (MPa) sorbitol yield (wt%) ref
463 5 26 23
458 5 69 24
518 6 29.6 68
463 5 66e 69
5 59e 70
433 5 33.2 71
5 87 76
433 2 40 77
413 2 93 77
393 4 100 78
458 3 87.1 79
of Cr2O3 improved the dispersion of Ru−B alloy particles by
acting as the support, preventing the coalescence of active Ru.64
However, excess Cr-dopant led to a rapid decrease in hydrogen
uptake rate due to negative effect on the intrinsic activity, since
Cr3+ may accept partial electrons from Ru atom. Concerning
the existing B element, it afforded the transformation of
electrons into the active Ru, resulting in an increase in the
specific area of catalyst.
Through the above analysis, we can give inspiration to the
following three points: first, the supports of high pore and BET
surface area are more favorable for the reaction. Second,
particular attention should be paid to the preparation methods
of Ru catalysts. Lastly, the selectivity to sorbitol is obviously
improved over Ru catalysts and the refining process will be
simple and clean. Therefore, subsequent studies on exploring
effective carrier for Ru catalysts should be focused, and
regeneration of Ru catalysts must be a second important
point, given the high price of metallic Ru. Only in this way can
we improve catalyst life and cut down the actual production
cost.
2.2. Production of Sorbitol from Biomass Feedstocks.
Recently increasing effort has been devoted to find ways to
utilize biomass as feedstocks for the production of organic
chemicals due to advantages of abundance, renewability, and
worldwide distribution. Discarding or burning away these
renewable resources will not be a feasible approach because of
environmental problems. Hence, efficient utilization of the
existing natural resources is now an urgent research to be
explored in great depth. In commercial terms, two steps
involving biomass hydrolysis and glucose hydrogenation are
generally adopted as an effective way in yielding sorbitol. With
the rapid development of research, one-pot conversion of
biomass into sorbitol captures our attention.
As the most abundant source, cellulose, a linear polymer of
glucose with β-1,4-glycosidic bonds, can be hydrolyzed into
glucose and subsequently hydrogenated into sorbitol, while
starch that consisted of glucose by α-1,4-glycosidic bonds also
can be used as an ideal source with excellent hydrolysis rate.26
However, starch should primarily be considered as a source of
food, so a great effort has been directed to the conversion of
cellulose. Above all, this conversion route involves both
hydrolysis and hydrogenation reactions that play an important
role in yielding sorbitol. Table 3 lists the main data on the most
recent advances in the catalytic conversion of cellulose into
sorbitol.
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In an earlier research, Fukuoka and Dhepe investigated a new
green catalytic process for the conversion of cellulose into sugar
alcohols. Among the metals examined, Pt/γ-Al2O3 gave high
yields (sorbitol: 25%, mannitol: 6%) in sugar alcohols at 463 K
and 5 MPa H2, compared to Pd, Ir, and Ni catalysts.23 Cellulose
hydrolysis was found to be a rate-determining step, and the Pt
catalysts promoted both hydrolysis and hydrogenation steps.65
It was suggested that the metal−support match made hydrogen
spill over from the metal onto the support, which generated
protic sites on the support surface and led to an increased pool
of H+ in the system consequently.66 Subsequently, Essayem and
co-workers performed a series of controlling reactions to clarify
the functional details of Pt/γ-Al2O3 catalyst in cellulose
degradation.67 It was demonstrated that the presence of Pt/γ-
Al2O3 increased the initial rate of dissolution-conversion
significantly as well as the total yields of monomer sugars. Pt
associated with hydrogen was proposed to intervene not only in
glucose hydrogenation but also most likely in H+ generation via
H2 heterolytic dissociation and/or hydride transfer steps.
Much work still focuses on the development of Ru catalysts
for the hydrolytic hydrogenation of cellulose due to superior
catalytic performance in glucose hydrogenation. For example, a
two-step transformation of cellulose into polyols was conducted
in hot water by using Ru/C catalyst. The elevated temperatures
resulted in the formation of H+ from water that was capable of
performing acid-catalyzed reactions; finally a 29.6% yield in
sorbitol was achieved at 518 K and 6 MPa H2.68 However, the
use of around 0.1 wt % inorganic acids will be of great
effectiveness, and the acidity of reaction system can be
enhanced in an almost environmentally friendly manner.
Desirable hexitols yield of 66% (mainly consisted of sorbitol
and mannitol) at 463 K for 24 h was presented in 106 ppm
HCl.69
Subsequent studies focus on the exploration of multifunc-
tional Ru catalysts for the replacement of inorganic acids that
will address the issues of catalyst reuse and green environment.
The hydrolysis activities of functional catalysts are found to be
very dependent on the presence of acidic functional groups on
the acid-pretreated surface of the supports. With the
introduction of acidic supports, one-step conversion of
bioresources into sorbitol can be accomplished under the
catalyzing of supported noble metal catalysts. For instance, a
40% yield of hexitols (including 36% sorbitol) was achieved
over Ru/CNT for the conversion of commercial cellulose
(crystalline, 85%) at 458 K for 24 h.28 Decreasing cellulose
crystallinity favored the formation of sorbitol, and a 69% yield
was obtained at crystallinity of 33% due to the rapid rate in
hydrolysis of amorphous cellulose. In related research, a series
of heterogeneous heteropoly acids, hydrotreated cesium salts of
heteropoly acids and the like combining with metal supported
catalysts were examined,29,70,71 but the main problems
presented in achieving high sorbitol from cellulosic materials
are low cellulose dissolution and complex side products.
In recent years, ionic liquids (ILs) have gained increasing
interest as alternative solvents as they enable the complete
dissolution of cellulose to facilitate hydrolytic depolymeriza-
tion.72 Hence, the hydrolytic hydrogenation reaction that
results in sugar alcohols has been actively investigated by using
ILs as the media.37 For instance, the combination of a
heterogeneous Pt or Rh catalyst with a homogeneous Ru
complex in 1-butyl-3-methylimidazolium chloride under a H2
atmosphere achieved full cellulose conversion and 51%−74%
selectivity to sorbitol.73 The Ru complex acted as a H2 carrier
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by forming hydride compounds to increase H2 solubility.73 Zhu
et al.74 reported that an IL connected to an additional binding
agent with a boronic acid-containing functional group could be
used for the stabilization of Ru nanoparticles, and yields of up
to 94% for the conversion of cellulose to sorbitol (main
product) and mannitol were observed. By using metal
nanoparticles as catalysts, ILs feature certain advantages as
solvents, such as the stabilization of the nanoparticles to avoid
aggregation to maintain high surface area and catalytic
activity.75
However, the use of ILs poses other problems, such as the
separation of high polar products from equally highly polar ILs.
Usually all chemicals in the reactions described above have high
boiling points or decompose at elevated temperatures, which
hinders separation by distillation. Therefore, biphasic systems
have been discussed, which enable the extraction of the
products from the IL to facilitate a more efficient product
separation. However, most extraction solvents exhibit low
separation coefficients, which result in inefficient extraction. An
advanced separation of products and catalysts could be an
important factor for an efficient catalytic conversion of cellulose
to isosorbide with the present system. Besides, the corrosion of
ILs to the commonly used stainless steel equipment has to be
avoided. On the basis of the above discussion, there are still
some very intriguing questions about this novel process yet to
be answered.
Recently, a sorbitol yield of 87% was attained at 458 K, and
little mannitol (around 2%) was detected using Ru/CNT
catalyst with cellobiose as raw material.76 During the reaction,
the catalysts with larger mean sizes of Ru nanoparticles and
higher acidity presented a better sorbitol yield. While those
with smaller Ru nanoparticles and less acidic sites afforded
about 93% 3-β-D-glucopyranosyl-D-glucitol, and smaller Ru
particles accelerated the degradation of sorbitol. Polyoxometa-
late-supported Ru nanoparticles were also served as bifunc-
tional heterogeneous catalysts for the conversions of cellobiose
and cellulose into sorbitol under mild conditions. Liu et al.
confirmed that H2-originated Brønsted acid sites played a key
role in the conversions, and Keggin-type Ru/Cs2PW12O40
showed outstanding activity and stability.77 Increasing the pH
value from 2.0 to 10.0 resulted in an acceptable decrease in the
conversion rate of cellobiose, and a new chemical with formula
of C6H14O4 (2,6-dideoxy-hexitol) was formed in neutral and
basic mediums.78
In our work, the deactivation mechanism of Ru/C catalyst
was discussed in conversion of cellobiose to sorbitol in
extremely low phosphoric acid. Based on the ICP-AES analysis,
Ru could stably exist in acidic reaction solution without any
loss. XRD and XPS tests of recycled catalysts indicated that
almost all the Ru element was presented in zero valence state.
The study on surface properties of used Ru/C indicated that
the BET surface area and pore volume decreased significantly
due to the adsorption of organic chemicals, resulting in an
obvious decrease in catalyst activity.79 This work may provide a
remarkable level of understanding for catalyst activation and
recycling in future work.
On the whole, efficient catalysts and reaction systems are still
in high demand in one-pot conversion of biomass carbohy-
drates. The Ru and Pt based catalysts are to be preferred for the
excellent performance in previous work. Otherwise, some
magnetic catalysts can be properly considered through the
introduction of Fe or Co in noble metal catalysts, and efficient
supports are deserved to be explored to enhance the activity of
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magnetic catalysts. Inspired by the related work, noble metal
catalysts also show excellent performance in the production of
H2 from 2-propanol and formic acid,80−84 so the attempts for
the use of other hydrogen sources are suggested to be given
increasing attention. In this manner, the production cost and
equipment requirement for high H2 pressure will be lowered. In
our current study, various hydrogen donors were tested in
glucose hydrogenation by using supported noble metal
catalysts. It was found that sodium formate was much better
than other formate salts (HCOOK and HCOONH4) and other
agents of donating-hydrogen (CH3COOH, HCOOH, and
(CH3)2CHOH) for the catalytic transfer hydrogenation of
glucose. Among the examined noble metal catalysts, the
catalytic transfer hydrogenation activity for Pd/C was far
superior to that of Pt/C and Ru/C. At the reaction conditions
of using sodium formate as hydrogen donor at 363 K for 2.5 h,
the conversion of glucose and selectivity to sorbitol reached
71.7 and 94.1%, respectively. It can be observed that low
reaction temperature and low N2 pressure are advanced in
sorbitol production.
3. SORBITOL CONVERSION
Sorbitol has a considerable potential for the production of
versatile chemicals from renewable resources as its hydroxyl
groups allow for further functionalization or direct processing
via a series of hydrogenolysis, dehydration, and aqueous-phase
reforming reactions. In the following sections, the most
important advances in the catalytic conversion of sorbitol
with regard to potential fields of applications are summarized.
3.1. Synthesis of Lower Alcohols. Lower alcohols,
including ethylene glycol, propylene glycol, and glycerol, are
important platform molecules with extensive applications. For
example, 1,2-propylene glycol is primarily used as a monomer
in polyesters and as an antifreeze or cooling liquid. Strikingly,
glycerol is an interesting starting material for further chemical
derivatization as it can be used for the synthesis of ethylene
glycol and propylene glycol as well by deep hydrogenolysis.
The state of the art of processing of downstream
petrochemical products (oxirane and epoxypropane) into
these chemicals is of incredible efficiency after so many years
of research. One can reasonably argue that today’s society is not
only addicted to oil as a fuel but also to its products. Generally,
the mass productions of ethylene glycol and 1,2-propylene
glycol are accomplished through a hydration process at ∼473 K
under high pressure. Due to gradual diminishment of fossil fuel
reserves and further deterioration of environment and
ecosystem, the switch from oil-derived chemicals to biorenew-
able ones calls for a considerable effort in recent years. One-
step rapid hydrogenolysis of biomass holds great advantage that
offers a new route for lower alcohols production under a
relatively lower reaction pressure, principally addressing the
issues of cheap material and diverse sources. On the other side,
it opens up a feasible pathway in the synthesis of these high-
grade alcohols and accords with the demands of sustainable
development strategy in converting cellulosic biomass into bulk
chemicals.
The C−C and C−O bonds in polyols tend to be cleaved at
high temperatures under H2 atmosphere. The first evidence on
sorbitol hydrogenolysis was made by Zartman and co-authors,
when they studied the degradation of sugar alcohol (sucrose,
glucose, maltose, sorbitol, and mannitol) at 30 MPa H2 using
Cu/Cr2O3 catalyst.85
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Subsequently, a series of supported Ni catalysts are
extensively developed. Clark used Ni supported diatomite to
catalyze sorbitol hydrogenolysis at temperatures of 488 to 513
K under 13.78−38.58 MPa H2 for the production of glycerol.
However, many byproducts such as ethylene glycol, propylene
glycol, and xylitol were created at the same time.86 According to
the patents of DuPont, under the catalyzing of Ni/silica/
alumina catalyst, basic promoter Ca(OH)2 favored the
proceeding of hydrogenolysis; however, the selectivities toward
ethylene glycol and 1,2-propylene glycol decreased significantly
by using Cl−C4 alkoxides as solvents.87,88 Follow-up study
further demonstrated that the use of Ca(OH)2 remarkably
increased sorbitol conversion, and the selectivity to 1,2-
propylene glycerol was obviously improved by using Pt-NaY
as compared to Ni-NaY.89 The addition of Ce into Ni/Al2O3
slightly lowered the reduction temperature of nickel oxide but
considerably enhanced the H2-chemisorption amount. The
overall selectivity to glycols was around 55% at sorbitol
conversion of 90%.90 It is concluded that high H2 pressure is
required to achieve desirable conversion when using Ni-based
catalysts. Another point to consider is that selecting one or two
chemicals as the main products is a must, with the aim of
increasing corresponding yield and selectivity.
Low ruthenium loading catalysts are found to be a good
replacement to address the present problems in combination
with the use of alkaline mediums. Various supports were
investigated to increase the activity of Ru catalysts, such as
Al2O3, SiO2, TiO2, activated carbon, and so on. The maximum
1,2-propylene glycol yield reached up to 37.8% at desirable Ru
dispersion of 2.5% Ru/CTC-20.91 Sorbitol hydrogenolysis was
found to show a dependence on pH and reaction temperature.
In a basic medium, the main reaction was a reverse aldolization
which gave, among others, a mixture containing two or three
carbon atoms independently of the temperature.92 As a
comparison, the application of neutral medium and low
temperature led to an increase in selective hydrogenolysis in
the middle carbon chain of sorbitol, giving mainly glycerol and
1,2-propanediol. Montassier et al. proposed that the cleavage of
C−C bond belonged to a retro-Michael reaction under the
action of adsorbed nucleophilic species.93
In recent years, active carbon nanofibers (CNFs and CNF/
GF) were used in sorbitol hydrogenolysis, which provided high
Ru dispersion and proper porosity.94−96 Supported Ru catalysts
are shown to have an attracting behavior compared to
commercial Ru/C, especially in terms of selectivity to glycols.
Ru/CNF/GF presented higher selectivities to ethylene glycol,
propylene glycol, and glycerol (79.1% in total). The addition of
Ca(OH)2 remarkably increased the selectivities to glycols, as
compared with that of soluble NaOH.
With the progress of research, biomass materials are explored
for direct synthesis of lower alcohols via sorbitol production
during the past years, due to the advantages of broad source,
splendid reserve, and cheap cost. Ji et al. investigated single-step
conversion of cellulose into ethylene glycol using nickel-
promoted tungsten carbide catalysts. The Ni−W2C/AC gave a
remarkable selectivity toward ethylene glycol than that of Pt/
Al2O3 and Ru/C, and the highest yield of 61% was achieved at a
temperature of 463 K.97 Ni5−W25/SBA-15 gave 75.4% ethylene
glycol at 100% conversion.98 They claimed that the addition of
Ni into tungsten phosphide (WP) promoted catalytic hydro-
genation due to a remarkable synergy between Ni and WP,
leading to an increase in ethylene glycol yield to 46.0 mol %,
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Industrial & Engineering Chemistry Research Review

Scheme 3. Reaction Mechanism of Sugar and Sugar Alcohol Hydrogenolysis

Scheme 4. Route for Continuous Conversion of Biomass into Useful Chemicals

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Industrial & Engineering Chemistry Research
compared to a 25.4 mol % yield over 20% WP/AC at 6 MPa H2
and 518 K.99
In 2010, a novel one-pot approach for alkaline hydrolysis and
hydrogenation of cellulose on supported Ru catalysts was
proposed by Deng et al.100 A wide range of bases including
solid bases, e.g., Ca(OH)2 and La2O3, and phosphate buffers
were examined. It was found that the cellulose conversions and
products distribution depended largely on the basicity and pH
values of the solutions. The findings may provide a scientific
basis for efficient conversion of cellulose into targeted polyols
by using various alkaline conditions. Similar research is found in
recent studies on the conversion of cellulose into polyols using
supported noble metals catalysts.101−103
As is well-known that the basic compounds are used as the
promoters, the properties of base (NaOH, KOH, Ba(OH)2,
Mg(OH)2, CaO, and so on) play a critical role in conversion
rate and selectivities. Originally, it was assumed that the base
could prevent the dissolution of metal ions from the
catalyst.104−106 However, subsequent experiments showed
that the base played a more important role in the reaction
process. Several hydrogenolysis mechanisms were advanced to
illustrate the cleavage of C−C and C−O bonds in polyols in the
following research.93,107−109 On the basis of previous work,
Wang et al.109 had systematically studied the mechanism of
breaking bonds in the reaction of polyols hydrogenolysis by
using 1,3-diol as the model. The results had fully demonstrated
that the addition of bases facilitated the proceeding of reverse
aldol condensation and dehydration, thus leading to the
cleavage of C−C and C−O bonds (as shown in Scheme 3).
According to the above analysis, noble metal catalysts are
widely used in the production of lower alcohols, especially Ru
based catalysts. Improving metal dispersion by selecting
excellent supports can be a pronouncing research direction.
Nickel catalysts also are promising ones if the problem of
leaching can be well addressed. Suitable alkaline conditions are
conducive to the formation of these valuable chemicals. Most
work focuses on cellulose conversion, while the utilization of
existing resources, such as secondary fiber, agricultural waste
(cotton stalks, saw dust, coconut husks, and rice husks), and
forestry residues (bark, branches, and trunk) has not been given
enough attention. Besides, an efficient and recyclable solid base
is deserved to be investigated in more detail.
In practical production, various high value-added chemicals
can be achieved by a method of continuous processing
(Scheme 4). For the initial step, biomass materials are
hydrolyzed into glucose in acidic mediums under high
temperature. Then the hydrolysates are hydrogenated into
sorbitol under H2 atmosphere or using other H2 sources. The
obtained mixtures will be purified by crystallization to produce
high purity sorbitol. Furthermore, the final solutions in Reactor
2 can be successively used for deep hydrogenolysis to obtain
useful lower alcohols without separation and purification.
Besides, the metal catalysts developed in the second step are
proposed to be further applied in Reactor 3 without any
treatment. Usually alkaline mediums offer good selectivities
toward these valuable platform chemicals in Reactor 3, so
properly increasing pH value of the reaction solutions provides
a good choice for sorbitol hydrogenolysis.
3.2. Synthesis of Hydrogen and Alkane. Processing of
renewable carbohydrates to produce fuels and/or chemicals
invariably requires the removal of oxygen to form compounds
with lower molecular weights and higher volatility that can be
subsequently upgraded using gas-phase processes. Previous
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Review
studies showed that H2 was produced from ethylene glycol and
methanol by aqueous-phase reforming (APR) using supported
noble metal catalysts.110,111 With a detailed study, sorbitol can
also be directly used for the production of H2 and alkanes that
opens up a new field in sorbitol chemistry. The conversion of
sorbitol into clean fuel is of great significance for the shortage of
energy and partial replacement of oil resource, given the rising
demand for fossil resource and natural gas.
The catalytic route for the production of H2 and alkanes by
APR of oxygenated hydrocarbons involves cleavage of C−C
bonds as well as C−H and/or O−H bonds to form adsorbed
species on the catalyst surface. Cleavage of these bonds occurs
readily over Group VIII metals, such as Pd and Rh.112 The
production of alkanes by APR of sorbitol is presented in a
bifunctional pathway, involving the formation of H2 and CO2
on metal catalysts and then dehydration of sorbitol on a solid
acid catalyst. In 2002, the research group of Dumesic declared
that H2 was formed by APR of sugar alcohols over Pt/Al2O3
catalyst.113 Although paraffin mixtures were synthesized by one-
step reforming of sorbitol, the specific reaction network was
complex due to the presence of parallel and cascade reactions.
The selectivities of H2 and alkane reached up to 66 and 15%
separately, and the addition of ethanol into sorbitol enhanced
the formation of H2.114
For the non-noble metal catalyst, the Raney Ni−Sn catalyst
gave selectivities of H2 and alkane at 65 and 19%, respectively,
that may be a good choice to replace Pt/Al2O3.115,116 The
essential features of bifunctional pathway for production of
alkanes from sorbitol were briefly described in Scheme 5.117
Scheme 5. Reaction Network for the Production of Alkanes
from Sorbitol over Bifunctional Catalysts
Hydrogen is produced on the metal by cleavage of C−C bonds
followed by the water-gas shift reaction. Dehydrated species
such as ring compounds (e.g., isosorbide) or enolic species are
formed on acid sites,118 which migrate to metal sites where they
undergo hydrogenation reactions. Repeated cycling of dehy-
dration and hydrogenation reactions under H2 atmosphere
leads to the production of heavier alkanes (such as hexane).
Formation of lighter alkanes takes place by cleavage of C−C
bonds compared to hydrogenation of dehydrated reaction
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Industrial & Engineering Chemistry Research Review

Scheme 6. Pathways for Sorbitol Dehydration

Table 4. Catalytic Preparation of Isosorbide with Different Catalysts

catalyst substrate concn t (h) T (K) isosorbide yield ref
SnPO sorbitol 10 wt % 2 573 47.2 mol % 135
0.8P/NBO-400 sorbitol 10 wt % 5 498 62.5 mol % 136
CuSO-650 sorbitol 10 wt % 4 473 67.3 wt % 137
SZ-0.05 sorbitol 20 wt % 2 483 61 wt % 138
S-TiO2 sorbitol 20 wt % 2 483 75 wt % 139
30% PW/SiO2 sorbitol 10 wt % 6 423 56 mol % 140
none sorbitol 1 mol/dm−3 1 590 57 wt % 143
Amberlys 35a sorbitol ― 5 413 70 wt % 144
5 wt % Ru/C celluloseb 2 wt % 6 488 49.5 mol % 145
H4SiW12O40 lignocellulosec 2 wt % 1 483 63 wt % 148
a
Microwave heating. b6 MPa H2 cWheat straw pulp (CIMV, delignified), 5 MPa H2.

intermediates. Lighter alkanes can also be formed by hydro-
genation of CO and/or CO2 on metals such as Ni and Ru.119
The selectivities of alkanes depend on the relative rates of
C−C bond cleavage, dehydration, and hydrogenation reactions,
which can be varied by changing the catalyst composition, the
reaction conditions, and modifying the reactor design.117 In
addition, these selectivities can be modified by cofeeding H2
with the aqueous sorbitol feed, leading to a process in which
sorbitol can be converted to alkanes and water without the
formation of CO2. Meanwhile, the production of alkanes can be
accomplished by replacing the solid acid with a mineral acid
that is cofed with the aqueous sorbitol. The alkane distribution
shifts to heavier alkanes when the pH of the aqueous sorbitol
feed is lowered by the addition of HCl. By changing the nature
of the metal component in the catalyst, one can vary the relative
rates of C−C bond cleavage versus hydrogenation, thereby
controlling the selectivities for the production of different
alkanes. For example, using the optimized Pd/SiAl catalyst, the
selectivity to n-hexane, n-pentane, and n-butane increased to
56%, 28%, and 8%, respectively.117 The selectivities to heavier
alkanes increased obviously when more solid acid sites (SiAl)
were added to a nonacidic Pt−Al catalyst.
Zhang et al. investigated the aqueous-phase processing of
sorbitol to isoparaffins under the catalyzing of Ni/HZSM-5
catalyst, and the maximal i-C6H14 selectivity of 45.4% and the
total yield of i-C6H14 and i-C5H12 in 32.3% were obtained over
calcined catalyst.120,121 Higher calcination temperature resulted
in a decrease in catalyst activity that may be caused by the
sintering and pore changes. In addition, Vilcocq first observed
that Pt sintering occurred in the atmosphere of steam and
11808
liquid water, because the existing liquid water led to a severe
decrease in metal dispersion even at room temperature.122 The
steaming pretreatment of Pt/SiO2−Al2O3 allowed a first aging
of the catalyst that limited the modification induced by the
hydrothermal environment on metal dispersion and support
texture. Thereby new catalysts with better hydrothermal
stability and appropriate metal/acid sites ratios are still
necessary for further advances in sorbitol chemistry. Metal
catalysts toward improving certain product selectivities may be
an interesting research direction. Last but not least, attention to
the reuse and regeneration of supported metal catalysts will be
a promising direction in one-step aqueous-phase reforming of
sorbitol.
Recently, biomass gasification/pyrolysis has attracted huge
interest by producing a gas rich in H2 and CO, which can be
further processed to produce liquid alkanes by Fischer−
Tropsch synthesis.123,124 An advantage of the above process is
that it is relatively simple, usually requiring only one reactor
(thus having a low capital cost); however, this process is
nonselective, producing a wide range of products under various
temperatures. Based on our previous work, typical products
made from thermochemical processing of biomass include H2,
CO, CH4, tars, acids, chars, alcohols, aldehydes, esters, ketones,
and aromatic compounds.125−128 Unfortunately, unacceptable
levels of tars produced in this process can cause operational
problems in downstream processes by blocking gas coolers,
filter elements, and engine suction channels. Moreover, tars
may deposit on the surface of the catalysts used in the
downstream process (reforming, shift and methanol or
Fischer−Tropsch synthesis), deactivating them. Most applica-
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Industrial & Engineering Chemistry Research
Scheme 7. One-Pot Conversion of Cellulose to Isosorbide in a Molten Salt Medium
tions also require removal of at least part of the dust and tar
before the gas can be used. Hence, the tar removal is a key issue
for a successful application of biomass generated gases.
Catalytic cracking/reforming is currently one of the most
effective ways for both reducing tar content and enhancing H2
content in syngas at relatively low temperature. Several kinds of
catalysts were developed and applied in this process, such as
mineral, Ni-based, and noble metal catalysts.129−132 Therefore
one-step conversion of biomass into clean fuels is receiving
increasing interest for both environmental and economic
reasons, and the APR of high value-added sorbitol also provides
a promising avenue for the production of high-quality fuel
molecules.
3.3. Synthesis of Isosorbide. Isosorbide is known as an
important biobased industrial chemical like polylactic acid in
the future. The conversion of sorbitol into isosorbide includes
two steps that are cyclodehydration to 1,4-sorbitan and 3,6-
sorbitan and afterward dehydration to isosorbide (Scheme 6).
In earlier studies, various inorganic acids such as HF, H2SO4,
and HCl were extensively used in sorbitol dehydration at 293−
408 K.35,133,134 However, the neutralization treatment is
required to remove those hazardous inorganic acid, and the
separation of dehydration products from the salt solutions will
be a problem. For this reason, a considerable research effort has
been directed to the environmentally benign techniques. A
series of efficient catalysts and reaction systems are developed
in isosorbide production, as summarized in Table 4.
Metal(IV) phosphates of tin, zirconium, and titanium
synthesized by the hydrothermal method were used for
selective dehydration of sorbitol to isosorbide.135 Among the
three catalysts studied, SnPO showed the highest stability and
selectivity to isosorbide (65.4%) with a 72.1% sorbitol
conversion at 573 K. Interestingly, TiPO exhibited the excellent
conversion (97.1%), but over 50% side products were detected
during the reaction. It was found that the deactivation rate was
in accordance with coke deposition by thermal analysis, and the
acidity provided by functional groups of catalysts was the key
factor for prolonging catalyst lifetime. Thereby much work
should be directed to prevent coke deposition and retain the
acidity, and the reasons for coke deposition must be
investigated in detail to avoid such phenomenon. Meanwhile,
the acid types of synthesized catalysts are required to be
identified clearly that will be beneficial to the development of
new catalysts in latter studies. As for the determination of acid
amount and strength for solid catalysts, NH3-TPD analysis is
suggested to be mastered.
As the study develops in depth, several solid acid catalysts are
developed with the aim of improving selectivity and conversion,
such as phosphated Nb2O5,136 sulfated copper oxide,137 sulfated
zirconia,138 sulfated titania,139 silicotungstic acid,140 and PW/
SiO2.141 For instance, the selectivity to isosorbide increased
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Review
obviously over phosphated Nb2O5, due to the increment in
surface acid strength after phosphoric acid modification.136 The
excellent performance with 100% conversion and 62.5%
isosorbide selectivity was achieved over 0.8P/NBO-400 at a
temperature of 498 K. It was revealed that the modification of
phosphoric acid could well prevent the crystallization of Nb2O5.
Furthermore, the catalytic activity of used phosphated Nb2O5
could be retained by calcination compared to an unmodified
sample.136
When using 30% PW/SiO2 as catalyst, over 56% isosorbide
selectivity was achieved at a 95% sorbitol conversion under the
temperature of 423 K.141 The acidity of the supported PW
catalyst was determined by the PW species presenting on the
supports and interaction between PW and supports. Through
dichloromethane elution, the regenerated PW/SiO2 showed no
loss after recycling five runs. Employing NiO/AC as catalyst,
the preparation methods were found to have a significant
influence on NiO distribution and catalyst surface acidity. The
catalysts prepared through the simultaneous loading-reduction
procedure had stronger acidity and higher NiO dispersion on
the outer surface of activated carbon, which contributed jointly
to high sorbitol conversion and slightly low selectivity to
anhydro sugar alcohols (ca. 66%). The stronger acidity and
greater moderate acid amount of catalysts were beneficial to
high sorbitol conversion and excellent selectivity to isosorbide,
respectively, especially for the one reduced by NaBH4.142
In near future study, a green process was applied in sorbitol
dehydration without using any acidic catalysts. Based on the
properties of high temperature liquid water, high isosorbide
yield could be realized by properly controlling reaction
temperature and time, and the maximum yield of isosorbide
reached up to 57% at 590 K.143 They ascribed the success to
the higher concentration of H3O+ and OH− owing to the
temperature-dependent autoprotolysis of water. In spite of the
higher energy consumption at high temperatures, no obvious
byproducts were identified in the reaction. With in-depth study,
a more environmentally friendly and economical process was
introduced for the conversion of sorbitol to isosorbide, and
energy consumption and reaction time were significantly
reduced with the use of microwaves. Meanwhile, the obtained
isosorbide yield could be up to 70%.144 As for the kinetic study
in sorbitol dehydration under microwave heating, several
models considering first-order reactions or Langmuir−Hinshel-
wood type equations were detailed investigated by Polaert et al.
They claimed that kinetics of the reaction was only correctly
described by a Langmuir−Hinshelwood type model, including
the adsorption−desorption equilibrium of sorbitol.144 Based on
the resulting kinetic parameters, a continuous microwave
reactor could be rationally designed after further chemical
engineering calculations.
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Industrial & Engineering Chemistry Research
Scheme 8. Route for Continuous Conversion of Biomass Feedstocks into Isosorbide
Another interesting development in the field of chemo-
catalytic conversion of carbohydrate is the recent reported one-
pot conversion of cellulose into isosorbide using hydrogenation
catalyst, in combination with ZnCl2 as both Lewis acid catalyst
and molten salt reaction medium, as depicted in Scheme 7.8
During this cascade procedure, cellulose was first converted
into glucose in the presence of ZnCl2 hydrate and afterward
hydrogenated into sorbitol using Ru/C catalyst under 5 MPa
11810
Review
H2. A subsequent 2-fold dehydration in the ZnCl2 hydrate
media, alone or with additional CuCl2 and NiCl2 catalysts,
followed to form isosorbide. The authors claimed that the
hydrolysis and hydrogenation steps could occur with complete
conversion, while the dehydration exceeded 95% conversion. In
another work, under the circumstances of dilute HCl and
superheated water, Ru/C showed excellent selectivity toward
isosorbide compared to Pt/C and Pd/C, and a isosorbide yield
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Industrial & Engineering Chemistry Research
of 49.5% was obtained at 488 K.145 It was proposed that much
more produced glucose was converted into sorbitol under a
hydrogen atmosphere due to the superior hydrogenation
activity of Ru/C, so more isosorbide was attained under the
same acidic system. For Pt/C and Pd/C catalysts, levulinic acid
and other degradation products accounted for the major parts
by means of the acid−catalyzed degradation of glucose.
As cellulose is one of the most abundant biomass materials
on earth, the conversion of cellulose into important fine
chemicals presents a great challenge and opportunity in the
fields of energy and environment.146,147 Obviously, formation
of isosorbide from biomass resources instead of glucose will be
preferred from an availability point of view. In recent work,
three different lignocellulosic biomass feedstocks were used:
hardwood (Populus x canadensis), softwood, and wheat straw.
It was shown that hemicellulose, lignin residues, and other
impurities impeded cellulose conversion to isosorbide and
lignocellulose pretreatment methods were of high importance
as they could increase accessibility of cellulose for the catalyst.
As a result, the delignified CIMV (Compagnie Industrielle de la
Matière Végétale, organosolv) wheat straw pulp was rapidly and
efficiently converted to 63% isosorbide after 1 h of reaction
over SiW and Ru/C catalysts. Notably, the disadvantage of a
high crystallinity index was overturned by the advantage of a
small particle diameter and large specific surface area, originated
from the activity comparison between ball-milled Avicel PH-
101 cellulose and delignified CIMV wheat straw pulp.148
According to the above work, a reaction diagram in converting
biomass feedstocks into isosorbide was generally described in
Scheme 8, which provides a promising direction for the future
study in isosorbide production.
4. CONCLUSIONS
The production and utilization of sorbitol hold great potential
due to the rapid development of food and chemical industry,
especially in the fields of energy and fuel. In this review, we
focus on developing effective methods for the synthesis of
sorbitol and its derivatives. In summary: (1) glucose and
biomass feedstocks can be converted into sorbitol by using
nickel-based catalysts, hydrogen storage alloy, and ruthenium
catalysts; (2) for lower alcohols, the major routes include
sorbitol hydrogenolysis and one-pot hydrolytic hydrogenation
of biomass resources with multifunctional catalysts; (3) in
particular, hydrogen and alkanes are generally produced
through aqueous phase reforming of sorbitol; (4) isosorbide
is attained by 2-fold dehydration of sorbitol or one-step
conversion of lignocellulose materials with designed reaction
systems.
Although great progress has been achieved for the catalytic
preparation and transformation of sorbitol, further improve-
ment in productivity and selectivity are still necessary in many
cases for achieving the goal of industry production of those
processes. On the one hand, metal catalysts, especially Ni, Ru,
and Pt, exhibit excellent catalytic performance in sorbitol
production and downstream chemicals. Much work should
focus on the realization of regulation mechanism of target
products. However, efficient and cheap catalysts or rational
reaction systems are also in great need for further
commercialization. As far as one-pot reactions on the
production and conversion of sorbitol are concerned, that is,
several steps are completed in one reactor, such as biomass
hydrolysis, glucose hydrogenation, and sorbitol hydrogenolysis,
aqueous-phase reforming and dehydration reactions, so multi-
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Review
functional catalysts should deserve the priority in the following
research. Furthermore, the supports of multifunctional catalysts
provide acidity and high metal dispersion. Meanwhile cellulosic
materials can be dissolved significantly by using acidic solvents
or ionic liquids, thus leading to an obvious increase in the
conversion and yield.
With the introduction of the concept of green chemistry,
efforts in biomass conversion should be devoted to the
economical, rapid, and eco-friendly production of sorbitol
based chemicals. High temperature liquid water and microwave
heating are of great interest in catalytic reactions. A feasible
pathway for the industrial conversion of biomass into these
chemicals is still needed to be progressed in depth. This
suggests that steps involving material pretreatment and
subsequent sectional processing can be clearly considered.
Another point worth noting is that the activation and reuse of
the catalyst and effective separation of the target products are
always the hottest topics for catalytic processing research.
■ AUTHOR INFORMATION
Corresponding Author
*Phone/Fax: +86 020 22236808. E-mail: shubinwu@scut.edu.
cn (S.-B.W.), amyliu@scut.edu.cn (Y.L.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the supported by National Key
Basic Research Program of China (No. 2013CB228101),
National Natural Science Foundation of China (No.
31270635), and the National High Technology Research and
Development Program of China (863 Program,
2012AA101806).
■
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