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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 of oil resources. As concerns the dehydration product,


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

© 2013 American Chemical Society 11799 dx.doi.org/10.1021/ie4011854 | Ind. Eng. Chem. Res. 2013, 52, 11799−11815
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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 efficient accessibility of the Ni particles attached at the tip of the
the purification of sorbitol. As discussed above, it is speculated supports allows for immediate hydrogenation of glucose units.
that the high activity and stability of Mo and Cr modified Additionally, considerable effort should be directed to the
catalysts may be explained by the synergy among these active relationship between Ni particle size and related catalytic
metals, probably providing a lower activation energy of CO activity.
in glucose molecule. Much more work should focus on the Hydrotalcite-like compounds (HTlcs) were used as
synergy effect among used metals and calculating reaction precursors for the preparation of hydrogenation catalysts in
activation energy through performing kinetics experiments. The previous study.50 In our recent work, a series of catalysts were
phase of metal promoters may play a critical role in the prepared from Ni/Cu/Al hydrotalcite precursors and were
performance of modified catalysts. Overall, Mo and Cr applied in glucose hydrogenation. The obtained catalysts
modified catalysts hold great potential for possible application exhibited great sorbitol selectivity (93.4%) and glucose
in industrial-scale production after comprehensive comparison. conversion (78.4%) when the precursor was pretreated under
Considering the environment for producing sorbitol on H2 atmosphere at high temperatures. It was proposed that the
modified Raney-nickel catalysts, particular attention should be existing Al may be used as support for active Ni and Cu in
directed to the following aspects. First, proper H2 pressure is reduced samples and Ni species were mainly responsible for
deserved to achieve great glucose conversion, and higher high activity. For recycling experiments, Ni was obviously
reaction temperature leads to glucose carbonization and leached into the solution, while Cu showed excellent stability
generates some byproducts. Second, the desired pH value of according to the ICP-AES analysis of reaction solutions.
reaction solution was 8.0−9.0 when using Raney-nickel catalyst. With the modification of various metallic elements, an
However, glucose can be easily isomerized into mannose in interesting phenomenon came to us that the Co and Fe
alkaline condition and then hydrogenated into mannitol.47 modified catalysts were magnetic. It is known that products
Therefore a suitable pH value should be chosen so as to separation and catalyst reuse can be easily realized via the use of
prolong catalyst life and prevent glucose isomerization, and a magnetic catalysts. With the further research, Fe content also
pH of around 7.5 is proposed in industrial production. played a great important part in catalyst activity. It was inferred
Another method also attracts significant interest in catalyst that the synergy effect among metallic elements was weakened
preparation, i.e., the use of support to increase metal dispersion. with the further increase in Fe content; future studies on
Various carriers were examined to enhance catalyst activity, calculating reaction activation energy and leaching of Fe will
such as SiO2, TiO2, Al2O3, and so on. The research group of effectively address the present problems. When the magnetic
Claus had made great effort to the development in supported catalyst was applied in glucose hydrogenation, the optimal yield
Ni catalysts. They reported that the activity followed the and selectivity of sorbitol were 88.2 and 94.2% at reaction
sequence Al2O3 > TiO2 > SiO2 > C, while all these tested temperature of 398 K with a catalyst dosage of 35%. For
catalysts were leaching.48 In most cases, catalysts prepared by fructose hydrogenation, the desired yields of sorbitol and
impregnation exhibited higher activity compared to those mannitol on magnetic catalyst were 42.9 and 56.9% at reaction
prepared by incipient wetness. With in-depth study, the Ni temperature and initial H2 partial pressure of 383 K and 3.0
precursors were found to play an important role in the MPa, respectively. Concerning the conversion of biomass
performance of obtained catalysts. By comparison, Ni catalysts materials, the one-step synthesis of sorbitol could be realized
prepared by impregnation with nickel ethylenediamine over magnetic catalysts in combination with extremely low
complexes revealed small nickel particles (mean diameter: 2− acids.
3 nm) and showed almost no Ni leaching when compared to a For catalyst regeneration, various methods were investigated
commercial Ni/SiO2 catalyst, which confirmed that small nickel in detail to remove the adsorbed carbohydrates and prolong the
particles were more resistant to leaching than larger ones.49 In catalyst life, such as calcination or elution. Notably, the used
current research, some other carriers such as MCM-41 and catalyst after acetone elution showed better catalytic activity
HZSM-5 molecular sieves are of high interest that can provide when compared to that of other organic solvents. For methanol
high BET surface area, desirable porosity, and excellent metal or ethanol elution, Ni was easily leached into the solution due
dispersion for supported metal catalysts. In this manner, an 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 the superior stability of Raney Ni−P. It was speculated that the
metal catalysts, and the hydrogenation catalysts derived from disorder degree of catalyst was obviously increased by adding
HTlcs exhibit exciting activity for merits of smaller crystal size phosphorus, which facilitated hydrogen flowing during the
and higher surface area. reaction. For amorphous NiMoAl alloy, it exhibited excellent
Amorphous hydrogen storage alloy developed in recent years stability that could be recycled five times, and glucose was
has gained increasing interest as an alternative target for its completely converted with sorbitol selectivity of 99%.54 It was
hydrogenation/dehydrogenation properties. It was reported assumed that the diffusion rate of Ni active species decreased
that high yield and selectivity of sorbitol could be achieved due to greater atomic radius of Mo (0.139 μm) than Ni (0.124
under mild reaction conditions when using amorphous μm), which would prevent catalyst crystallization. The added
hydrogen storage alloy in glucose hydrogenation. For example, Mo increased the disorder degree and hydrogenation activity of
the glucose conversion reached 97% at 313 K and 834 kPa for catalyst. Follow-up studies are proposed to introduce supports
24 h when using LaNi5 as catalyst and HAc as additive. (molecular sieves, SiO2, active carbon, and γ-Al2O3) to improve
However, the conversion was only 35% under the same metal dispersion. Detail work on properly increasing disorder
conditions over Raney nickel.12,52 degree of amorphous structure by adding various additives (Fe,
In 2000, Li et al.53 reported that a skeletal Ni−P amorphous Zn, La, Ce, Co, etc.) is still necessary.
alloy (Raney Ni−P) was formed by alkali leaching of 2.1.2. Ruthenium Catalysts. To completely overcome the
amorphous Ni−Al−P precursor. This catalyst gave higher problem of nickel leaching and further increase sorbitol
turnover rates than Raney Ni, apparently as a result of selectivity, the increasing requirement for new catalysts is
promotion of Ni-active sites by phosphorus. 55.8% glucose (50 essential. Ruthenium catalysts have attracted a great deal of
wt % feed concentration) was hydrogenated, compared to that attention in recent years for high stability and superior
of 17.2% in Raney nickel and 1.1% in commonly used Ni−P. activity.31,47,55 Hoffer et al. first reported that carbon supported
Meanwhile, only less than 1.0 ppm Ni was leached, indicating Ru catalyst was a promising alternative for Raney-type Ni in the
11802 dx.doi.org/10.1021/ie4011854 | Ind. Eng. Chem. Res. 2013, 52, 11799−11815
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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) T (K) Pa (MPa) sorbitol yield (wt%) ref
b
2.5 wt % Pt/γ-Al2O3 MC 0.8 24 463 5 26 23
1.0 wt % Ru/CNT MCc 0.8 24 458 5 69 24
4.0 wt % Ru/C MCb 2 0.5 518 6 29.6 68
HCl-0.2 wt % Ru/H-USY BMCd 2 3 463 5 66e 69
CsHPA-5.0 wt % Ru/C BMC 10 8 463 5 59e 70
H2SO4-5.0 wt % Ru/C α-cellulose 5 1 433 5 33.2 71
1.0 wt % Ru/CNT cellobiose 0.85 3 458 5 87 76
1.0 wt % Ru/CsPW12O40 BMC 0.67 24 433 2 40 77
1.0 wt % Ru/CsHPW12O40 cellobiose 2 6 413 2 93 77
Ru, pH 2.0 cellobiose 8.3 12 393 4 100 78
Ru/C cellobiose 1 1 458 3 87.1 79
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 of Cr2O3 improved the dispersion of Ru−B alloy particles by
toward catalyst development in relevant fields. It was found that acting as the support, preventing the coalescence of active Ru.64
Ru/C showed nearly 100% selectivity to sorbitol under 4 MPa However, excess Cr-dopant led to a rapid decrease in hydrogen
H2, above all, Ru exhibited excellent stability that effectively uptake rate due to negative effect on the intrinsic activity, since
addressed the issue of leaching in nickel catalysts.45 The activity Cr3+ may accept partial electrons from Ru atom. Concerning
of Ru/C was proportional to Ru surface area (representing the existing B element, it afforded the transformation of
metal dispersion) and independent of the preparation methods, electrons into the active Ru, resulting in an increase in the
suggesting that great yield and selectivity could be achieved specific area of catalyst.
over catalysts of high Ru dispersion. A novel anionic deposition Through the above analysis, we can give inspiration to the
method rendered catalyst with Ru dispersion of up to 40%.45 following three points: first, the supports of high pore and BET
In case of mass transfer and kinetics on glucose hydro- surface area are more favorable for the reaction. Second,
genation, a first-order dependency with respect to hydrogen particular attention should be paid to the preparation methods
was observed for low glucose concentrations (up to ca. 0.3 of Ru catalysts. Lastly, the selectivity to sorbitol is obviously
mol/L), while at higher concentrations the reaction rate improved over Ru catalysts and the refining process will be
changed to zero-order behavior when the kinetic experiments simple and clean. Therefore, subsequent studies on exploring
were carried out in the absence of mass transport limitations.30 effective carrier for Ru catalysts should be focused, and
Also, it was proposed that the conversion route involved the regeneration of Ru catalysts must be a second important
formation of an ionized β-pyranose species, adsorbed on the Ru point, given the high price of metallic Ru. Only in this way can
surface by coordination of O-1, O-5, and O-6. we improve catalyst life and cut down the actual production
Follow-up studies focus on the influence of preparation cost.
methods, supports (SiO2 and γ-Al2O3), and ruthenium 2.2. Production of Sorbitol from Biomass Feedstocks.
precursors (ruthenium acetate and ruthenium trichloride) on Recently increasing effort has been devoted to find ways to
catalyst activity.56−60 With different ruthenium complexes as utilize biomass as feedstocks for the production of organic
the precursors, the essential properties of catalyst may be of chemicals due to advantages of abundance, renewability, and
considerable difference. For example, by comparison with worldwide distribution. Discarding or burning away these
RuCl3, the glucose conversion increased by approximately 5% renewable resources will not be a feasible approach because of
when using ruthenium acetate as precursor.61 When Ru3+ was environmental problems. Hence, efficient utilization of the
supported on expanded graphite with HMT (hexamethylene existing natural resources is now an urgent research to be
tetramine) as ligand by method of ultrasonic impregnation, the explored in great depth. In commercial terms, two steps
obtained catalysts exhibited great dispersion and smaller grain involving biomass hydrolysis and glucose hydrogenation are
size (below 10 nm). A glucose conversion of 72.9% was generally adopted as an effective way in yielding sorbitol. With
attained at 373 K under 3 MPa H2, while only 34.7% glucose the rapid development of research, one-pot conversion of
was converted by similar catalyst without HMT as ligand.62 In biomass into sorbitol captures our attention.
another study, Ru/MCM-41 prepared by an impregnation- As the most abundant source, cellulose, a linear polymer of
formaldehyde reduction method showed almost 100% glucose glucose with β-1,4-glycosidic bonds, can be hydrolyzed into
conversion and 94.4% selectivity toward sorbitol at 393 K glucose and subsequently hydrogenated into sorbitol, while
under 3 MPa H2.25 The mechanism for glucose hydrogenation starch that consisted of glucose by α-1,4-glycosidic bonds also
over Ru/MCM-41 involved a gas−liquid−solid three-phase can be used as an ideal source with excellent hydrolysis rate.26
catalytic reaction, in which the carbonyl group in glucose However, starch should primarily be considered as a source of
reacted with activated H (Scheme 2). food, so a great effort has been directed to the conversion of
On the other hand, ultrafine Ru−B amorphous alloy reduced cellulose. Above all, this conversion route involves both
by KBH4 was found to show perfect selectivity (∼100%) to hydrolysis and hydrogenation reactions that play an important
sorbitol compared to crystallized Ru−B, pure Ru powder, and role in yielding sorbitol. Table 3 lists the main data on the most
Raney Ni catalysts.63 Cr-promoted Ru−B amorphous alloy gave recent advances in the catalytic conversion of cellulose into
∼98% glucose conversion at Cr content of 3.3%. The formation sorbitol.
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In an earlier research, Fukuoka and Dhepe investigated a new by forming hydride compounds to increase H2 solubility.73 Zhu
green catalytic process for the conversion of cellulose into sugar et al.74 reported that an IL connected to an additional binding
alcohols. Among the metals examined, Pt/γ-Al2O3 gave high agent with a boronic acid-containing functional group could be
yields (sorbitol: 25%, mannitol: 6%) in sugar alcohols at 463 K used for the stabilization of Ru nanoparticles, and yields of up
and 5 MPa H2, compared to Pd, Ir, and Ni catalysts.23 Cellulose to 94% for the conversion of cellulose to sorbitol (main
hydrolysis was found to be a rate-determining step, and the Pt product) and mannitol were observed. By using metal
catalysts promoted both hydrolysis and hydrogenation steps.65 nanoparticles as catalysts, ILs feature certain advantages as
It was suggested that the metal−support match made hydrogen solvents, such as the stabilization of the nanoparticles to avoid
spill over from the metal onto the support, which generated aggregation to maintain high surface area and catalytic
protic sites on the support surface and led to an increased pool activity.75
of H+ in the system consequently.66 Subsequently, Essayem and However, the use of ILs poses other problems, such as the
co-workers performed a series of controlling reactions to clarify separation of high polar products from equally highly polar ILs.
the functional details of Pt/γ-Al2O3 catalyst in cellulose Usually all chemicals in the reactions described above have high
degradation.67 It was demonstrated that the presence of Pt/γ- boiling points or decompose at elevated temperatures, which
Al2O3 increased the initial rate of dissolution-conversion hinders separation by distillation. Therefore, biphasic systems
significantly as well as the total yields of monomer sugars. Pt have been discussed, which enable the extraction of the
associated with hydrogen was proposed to intervene not only in products from the IL to facilitate a more efficient product
glucose hydrogenation but also most likely in H+ generation via separation. However, most extraction solvents exhibit low
H2 heterolytic dissociation and/or hydride transfer steps. separation coefficients, which result in inefficient extraction. An
Much work still focuses on the development of Ru catalysts advanced separation of products and catalysts could be an
for the hydrolytic hydrogenation of cellulose due to superior important factor for an efficient catalytic conversion of cellulose
catalytic performance in glucose hydrogenation. For example, a to isosorbide with the present system. Besides, the corrosion of
two-step transformation of cellulose into polyols was conducted ILs to the commonly used stainless steel equipment has to be
in hot water by using Ru/C catalyst. The elevated temperatures avoided. On the basis of the above discussion, there are still
resulted in the formation of H+ from water that was capable of some very intriguing questions about this novel process yet to
performing acid-catalyzed reactions; finally a 29.6% yield in be answered.
sorbitol was achieved at 518 K and 6 MPa H2.68 However, the Recently, a sorbitol yield of 87% was attained at 458 K, and
use of around 0.1 wt % inorganic acids will be of great little mannitol (around 2%) was detected using Ru/CNT
effectiveness, and the acidity of reaction system can be catalyst with cellobiose as raw material.76 During the reaction,
enhanced in an almost environmentally friendly manner. the catalysts with larger mean sizes of Ru nanoparticles and
Desirable hexitols yield of 66% (mainly consisted of sorbitol higher acidity presented a better sorbitol yield. While those
and mannitol) at 463 K for 24 h was presented in 106 ppm with smaller Ru nanoparticles and less acidic sites afforded
HCl.69 about 93% 3-β-D-glucopyranosyl-D-glucitol, and smaller Ru
Subsequent studies focus on the exploration of multifunc- particles accelerated the degradation of sorbitol. Polyoxometa-
tional Ru catalysts for the replacement of inorganic acids that late-supported Ru nanoparticles were also served as bifunc-
will address the issues of catalyst reuse and green environment. tional heterogeneous catalysts for the conversions of cellobiose
The hydrolysis activities of functional catalysts are found to be and cellulose into sorbitol under mild conditions. Liu et al.
very dependent on the presence of acidic functional groups on confirmed that H2-originated Brønsted acid sites played a key
the acid-pretreated surface of the supports. With the role in the conversions, and Keggin-type Ru/Cs2PW12O40
introduction of acidic supports, one-step conversion of showed outstanding activity and stability.77 Increasing the pH
bioresources into sorbitol can be accomplished under the value from 2.0 to 10.0 resulted in an acceptable decrease in the
catalyzing of supported noble metal catalysts. For instance, a conversion rate of cellobiose, and a new chemical with formula
40% yield of hexitols (including 36% sorbitol) was achieved of C6H14O4 (2,6-dideoxy-hexitol) was formed in neutral and
over Ru/CNT for the conversion of commercial cellulose basic mediums.78
(crystalline, 85%) at 458 K for 24 h.28 Decreasing cellulose In our work, the deactivation mechanism of Ru/C catalyst
crystallinity favored the formation of sorbitol, and a 69% yield was discussed in conversion of cellobiose to sorbitol in
was obtained at crystallinity of 33% due to the rapid rate in extremely low phosphoric acid. Based on the ICP-AES analysis,
hydrolysis of amorphous cellulose. In related research, a series Ru could stably exist in acidic reaction solution without any
of heterogeneous heteropoly acids, hydrotreated cesium salts of loss. XRD and XPS tests of recycled catalysts indicated that
heteropoly acids and the like combining with metal supported almost all the Ru element was presented in zero valence state.
catalysts were examined,29,70,71 but the main problems The study on surface properties of used Ru/C indicated that
presented in achieving high sorbitol from cellulosic materials the BET surface area and pore volume decreased significantly
are low cellulose dissolution and complex side products. due to the adsorption of organic chemicals, resulting in an
In recent years, ionic liquids (ILs) have gained increasing obvious decrease in catalyst activity.79 This work may provide a
interest as alternative solvents as they enable the complete remarkable level of understanding for catalyst activation and
dissolution of cellulose to facilitate hydrolytic depolymeriza- recycling in future work.
tion.72 Hence, the hydrolytic hydrogenation reaction that On the whole, efficient catalysts and reaction systems are still
results in sugar alcohols has been actively investigated by using in high demand in one-pot conversion of biomass carbohy-
ILs as the media.37 For instance, the combination of a drates. The Ru and Pt based catalysts are to be preferred for the
heterogeneous Pt or Rh catalyst with a homogeneous Ru excellent performance in previous work. Otherwise, some
complex in 1-butyl-3-methylimidazolium chloride under a H2 magnetic catalysts can be properly considered through the
atmosphere achieved full cellulose conversion and 51%−74% introduction of Fe or Co in noble metal catalysts, and efficient
selectivity to sorbitol.73 The Ru complex acted as a H2 carrier supports are deserved to be explored to enhance the activity of
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magnetic catalysts. Inspired by the related work, noble metal Subsequently, a series of supported Ni catalysts are
catalysts also show excellent performance in the production of extensively developed. Clark used Ni supported diatomite to
H2 from 2-propanol and formic acid,80−84 so the attempts for catalyze sorbitol hydrogenolysis at temperatures of 488 to 513
the use of other hydrogen sources are suggested to be given K under 13.78−38.58 MPa H2 for the production of glycerol.
increasing attention. In this manner, the production cost and However, many byproducts such as ethylene glycol, propylene
equipment requirement for high H2 pressure will be lowered. In glycol, and xylitol were created at the same time.86 According to
our current study, various hydrogen donors were tested in the patents of DuPont, under the catalyzing of Ni/silica/
glucose hydrogenation by using supported noble metal alumina catalyst, basic promoter Ca(OH)2 favored the
catalysts. It was found that sodium formate was much better proceeding of hydrogenolysis; however, the selectivities toward
than other formate salts (HCOOK and HCOONH4) and other ethylene glycol and 1,2-propylene glycol decreased significantly
agents of donating-hydrogen (CH3COOH, HCOOH, and by using Cl−C4 alkoxides as solvents.87,88 Follow-up study
(CH3)2CHOH) for the catalytic transfer hydrogenation of further demonstrated that the use of Ca(OH)2 remarkably
glucose. Among the examined noble metal catalysts, the increased sorbitol conversion, and the selectivity to 1,2-
catalytic transfer hydrogenation activity for Pd/C was far propylene glycerol was obviously improved by using Pt-NaY
superior to that of Pt/C and Ru/C. At the reaction conditions as compared to Ni-NaY.89 The addition of Ce into Ni/Al2O3
of using sodium formate as hydrogen donor at 363 K for 2.5 h, slightly lowered the reduction temperature of nickel oxide but
the conversion of glucose and selectivity to sorbitol reached considerably enhanced the H2-chemisorption amount. The
71.7 and 94.1%, respectively. It can be observed that low overall selectivity to glycols was around 55% at sorbitol
reaction temperature and low N2 pressure are advanced in conversion of 90%.90 It is concluded that high H2 pressure is
sorbitol production. required to achieve desirable conversion when using Ni-based
catalysts. Another point to consider is that selecting one or two
3. SORBITOL CONVERSION chemicals as the main products is a must, with the aim of
Sorbitol has a considerable potential for the production of increasing corresponding yield and selectivity.
versatile chemicals from renewable resources as its hydroxyl Low ruthenium loading catalysts are found to be a good
groups allow for further functionalization or direct processing replacement to address the present problems in combination
via a series of hydrogenolysis, dehydration, and aqueous-phase with the use of alkaline mediums. Various supports were
reforming reactions. In the following sections, the most investigated to increase the activity of Ru catalysts, such as
important advances in the catalytic conversion of sorbitol Al2O3, SiO2, TiO2, activated carbon, and so on. The maximum
with regard to potential fields of applications are summarized. 1,2-propylene glycol yield reached up to 37.8% at desirable Ru
3.1. Synthesis of Lower Alcohols. Lower alcohols, dispersion of 2.5% Ru/CTC-20.91 Sorbitol hydrogenolysis was
including ethylene glycol, propylene glycol, and glycerol, are found to show a dependence on pH and reaction temperature.
important platform molecules with extensive applications. For In a basic medium, the main reaction was a reverse aldolization
example, 1,2-propylene glycol is primarily used as a monomer which gave, among others, a mixture containing two or three
in polyesters and as an antifreeze or cooling liquid. Strikingly, carbon atoms independently of the temperature.92 As a
glycerol is an interesting starting material for further chemical comparison, the application of neutral medium and low
derivatization as it can be used for the synthesis of ethylene temperature led to an increase in selective hydrogenolysis in
glycol and propylene glycol as well by deep hydrogenolysis. the middle carbon chain of sorbitol, giving mainly glycerol and
The state of the art of processing of downstream 1,2-propanediol. Montassier et al. proposed that the cleavage of
petrochemical products (oxirane and epoxypropane) into C−C bond belonged to a retro-Michael reaction under the
these chemicals is of incredible efficiency after so many years action of adsorbed nucleophilic species.93
of research. One can reasonably argue that today’s society is not In recent years, active carbon nanofibers (CNFs and CNF/
only addicted to oil as a fuel but also to its products. Generally, GF) were used in sorbitol hydrogenolysis, which provided high
the mass productions of ethylene glycol and 1,2-propylene Ru dispersion and proper porosity.94−96 Supported Ru catalysts
glycol are accomplished through a hydration process at ∼473 K are shown to have an attracting behavior compared to
under high pressure. Due to gradual diminishment of fossil fuel commercial Ru/C, especially in terms of selectivity to glycols.
reserves and further deterioration of environment and Ru/CNF/GF presented higher selectivities to ethylene glycol,
ecosystem, the switch from oil-derived chemicals to biorenew- propylene glycol, and glycerol (79.1% in total). The addition of
able ones calls for a considerable effort in recent years. One- Ca(OH)2 remarkably increased the selectivities to glycols, as
step rapid hydrogenolysis of biomass holds great advantage that compared with that of soluble NaOH.
offers a new route for lower alcohols production under a With the progress of research, biomass materials are explored
relatively lower reaction pressure, principally addressing the for direct synthesis of lower alcohols via sorbitol production
issues of cheap material and diverse sources. On the other side, during the past years, due to the advantages of broad source,
it opens up a feasible pathway in the synthesis of these high- splendid reserve, and cheap cost. Ji et al. investigated single-step
grade alcohols and accords with the demands of sustainable conversion of cellulose into ethylene glycol using nickel-
development strategy in converting cellulosic biomass into bulk promoted tungsten carbide catalysts. The Ni−W2C/AC gave a
chemicals. remarkable selectivity toward ethylene glycol than that of Pt/
The C−C and C−O bonds in polyols tend to be cleaved at Al2O3 and Ru/C, and the highest yield of 61% was achieved at a
high temperatures under H2 atmosphere. The first evidence on temperature of 463 K.97 Ni5−W25/SBA-15 gave 75.4% ethylene
sorbitol hydrogenolysis was made by Zartman and co-authors, glycol at 100% conversion.98 They claimed that the addition of
when they studied the degradation of sugar alcohol (sucrose, Ni into tungsten phosphide (WP) promoted catalytic hydro-
glucose, maltose, sorbitol, and mannitol) at 30 MPa H2 using genation due to a remarkable synergy between Ni and WP,
Cu/Cr2O3 catalyst.85 leading to an increase in ethylene glycol yield to 46.0 mol %,
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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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compared to a 25.4 mol % yield over 20% WP/AC at 6 MPa H2 studies showed that H2 was produced from ethylene glycol and
and 518 K.99 methanol by aqueous-phase reforming (APR) using supported
In 2010, a novel one-pot approach for alkaline hydrolysis and noble metal catalysts.110,111 With a detailed study, sorbitol can
hydrogenation of cellulose on supported Ru catalysts was also be directly used for the production of H2 and alkanes that
proposed by Deng et al.100 A wide range of bases including opens up a new field in sorbitol chemistry. The conversion of
solid bases, e.g., Ca(OH)2 and La2O3, and phosphate buffers sorbitol into clean fuel is of great significance for the shortage of
were examined. It was found that the cellulose conversions and energy and partial replacement of oil resource, given the rising
products distribution depended largely on the basicity and pH demand for fossil resource and natural gas.
values of the solutions. The findings may provide a scientific The catalytic route for the production of H2 and alkanes by
basis for efficient conversion of cellulose into targeted polyols APR of oxygenated hydrocarbons involves cleavage of C−C
by using various alkaline conditions. Similar research is found in bonds as well as C−H and/or O−H bonds to form adsorbed
recent studies on the conversion of cellulose into polyols using species on the catalyst surface. Cleavage of these bonds occurs
supported noble metals catalysts.101−103 readily over Group VIII metals, such as Pd and Rh.112 The
As is well-known that the basic compounds are used as the production of alkanes by APR of sorbitol is presented in a
promoters, the properties of base (NaOH, KOH, Ba(OH)2, bifunctional pathway, involving the formation of H2 and CO2
Mg(OH)2, CaO, and so on) play a critical role in conversion on metal catalysts and then dehydration of sorbitol on a solid
rate and selectivities. Originally, it was assumed that the base acid catalyst. In 2002, the research group of Dumesic declared
could prevent the dissolution of metal ions from the that H2 was formed by APR of sugar alcohols over Pt/Al2O3
catalyst.104−106 However, subsequent experiments showed catalyst.113 Although paraffin mixtures were synthesized by one-
that the base played a more important role in the reaction step reforming of sorbitol, the specific reaction network was
process. Several hydrogenolysis mechanisms were advanced to complex due to the presence of parallel and cascade reactions.
illustrate the cleavage of C−C and C−O bonds in polyols in the The selectivities of H2 and alkane reached up to 66 and 15%
following research.93,107−109 On the basis of previous work, separately, and the addition of ethanol into sorbitol enhanced
Wang et al.109 had systematically studied the mechanism of the formation of H2.114
breaking bonds in the reaction of polyols hydrogenolysis by For the non-noble metal catalyst, the Raney Ni−Sn catalyst
using 1,3-diol as the model. The results had fully demonstrated gave selectivities of H2 and alkane at 65 and 19%, respectively,
that the addition of bases facilitated the proceeding of reverse that may be a good choice to replace Pt/Al2O3.115,116 The
aldol condensation and dehydration, thus leading to the essential features of bifunctional pathway for production of
cleavage of C−C and C−O bonds (as shown in Scheme 3). alkanes from sorbitol were briefly described in Scheme 5.117
According to the above analysis, noble metal catalysts are
widely used in the production of lower alcohols, especially Ru Scheme 5. Reaction Network for the Production of Alkanes
based catalysts. Improving metal dispersion by selecting from Sorbitol over Bifunctional Catalysts
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 Hydrogen is produced on the metal by cleavage of C−C bonds
toward these valuable platform chemicals in Reactor 3, so followed by the water-gas shift reaction. Dehydrated species
properly increasing pH value of the reaction solutions provides such as ring compounds (e.g., isosorbide) or enolic species are
a good choice for sorbitol hydrogenolysis. formed on acid sites,118 which migrate to metal sites where they
3.2. Synthesis of Hydrogen and Alkane. Processing of undergo hydrogenation reactions. Repeated cycling of dehy-
renewable carbohydrates to produce fuels and/or chemicals dration and hydrogenation reactions under H2 atmosphere
invariably requires the removal of oxygen to form compounds leads to the production of heavier alkanes (such as hexane).
with lower molecular weights and higher volatility that can be Formation of lighter alkanes takes place by cleavage of C−C
subsequently upgraded using gas-phase processes. Previous bonds compared to hydrogenation of dehydrated reaction
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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- liquid water, because the existing liquid water led to a severe
genation of CO and/or CO2 on metals such as Ni and Ru.119 decrease in metal dispersion even at room temperature.122 The
The selectivities of alkanes depend on the relative rates of steaming pretreatment of Pt/SiO2−Al2O3 allowed a first aging
C−C bond cleavage, dehydration, and hydrogenation reactions, of the catalyst that limited the modification induced by the
which can be varied by changing the catalyst composition, the hydrothermal environment on metal dispersion and support
reaction conditions, and modifying the reactor design.117 In texture. Thereby new catalysts with better hydrothermal
addition, these selectivities can be modified by cofeeding H2 stability and appropriate metal/acid sites ratios are still
with the aqueous sorbitol feed, leading to a process in which necessary for further advances in sorbitol chemistry. Metal
sorbitol can be converted to alkanes and water without the catalysts toward improving certain product selectivities may be
formation of CO2. Meanwhile, the production of alkanes can be an interesting research direction. Last but not least, attention to
accomplished by replacing the solid acid with a mineral acid the reuse and regeneration of supported metal catalysts will be
that is cofed with the aqueous sorbitol. The alkane distribution a promising direction in one-step aqueous-phase reforming of
shifts to heavier alkanes when the pH of the aqueous sorbitol sorbitol.
feed is lowered by the addition of HCl. By changing the nature Recently, biomass gasification/pyrolysis has attracted huge
of the metal component in the catalyst, one can vary the relative interest by producing a gas rich in H2 and CO, which can be
rates of C−C bond cleavage versus hydrogenation, thereby further processed to produce liquid alkanes by Fischer−
controlling the selectivities for the production of different Tropsch synthesis.123,124 An advantage of the above process is
alkanes. For example, using the optimized Pd/SiAl catalyst, the that it is relatively simple, usually requiring only one reactor
selectivity to n-hexane, n-pentane, and n-butane increased to (thus having a low capital cost); however, this process is
56%, 28%, and 8%, respectively.117 The selectivities to heavier nonselective, producing a wide range of products under various
alkanes increased obviously when more solid acid sites (SiAl) temperatures. Based on our previous work, typical products
were added to a nonacidic Pt−Al catalyst. made from thermochemical processing of biomass include H2,
Zhang et al. investigated the aqueous-phase processing of CO, CH4, tars, acids, chars, alcohols, aldehydes, esters, ketones,
sorbitol to isoparaffins under the catalyzing of Ni/HZSM-5 and aromatic compounds.125−128 Unfortunately, unacceptable
catalyst, and the maximal i-C6H14 selectivity of 45.4% and the levels of tars produced in this process can cause operational
total yield of i-C6H14 and i-C5H12 in 32.3% were obtained over problems in downstream processes by blocking gas coolers,
calcined catalyst.120,121 Higher calcination temperature resulted filter elements, and engine suction channels. Moreover, tars
in a decrease in catalyst activity that may be caused by the may deposit on the surface of the catalysts used in the
sintering and pore changes. In addition, Vilcocq first observed downstream process (reforming, shift and methanol or
that Pt sintering occurred in the atmosphere of steam and Fischer−Tropsch synthesis), deactivating them. Most applica-
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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 obviously over phosphated Nb2O5, due to the increment in
before the gas can be used. Hence, the tar removal is a key issue surface acid strength after phosphoric acid modification.136 The
for a successful application of biomass generated gases. excellent performance with 100% conversion and 62.5%
Catalytic cracking/reforming is currently one of the most isosorbide selectivity was achieved over 0.8P/NBO-400 at a
effective ways for both reducing tar content and enhancing H2 temperature of 498 K. It was revealed that the modification of
content in syngas at relatively low temperature. Several kinds of phosphoric acid could well prevent the crystallization of Nb2O5.
catalysts were developed and applied in this process, such as Furthermore, the catalytic activity of used phosphated Nb2O5
mineral, Ni-based, and noble metal catalysts.129−132 Therefore could be retained by calcination compared to an unmodified
one-step conversion of biomass into clean fuels is receiving sample.136
increasing interest for both environmental and economic When using 30% PW/SiO2 as catalyst, over 56% isosorbide
reasons, and the APR of high value-added sorbitol also provides selectivity was achieved at a 95% sorbitol conversion under the
a promising avenue for the production of high-quality fuel temperature of 423 K.141 The acidity of the supported PW
molecules. catalyst was determined by the PW species presenting on the
3.3. Synthesis of Isosorbide. Isosorbide is known as an supports and interaction between PW and supports. Through
important biobased industrial chemical like polylactic acid in dichloromethane elution, the regenerated PW/SiO2 showed no
the future. The conversion of sorbitol into isosorbide includes loss after recycling five runs. Employing NiO/AC as catalyst,
two steps that are cyclodehydration to 1,4-sorbitan and 3,6- the preparation methods were found to have a significant
sorbitan and afterward dehydration to isosorbide (Scheme 6). influence on NiO distribution and catalyst surface acidity. The
In earlier studies, various inorganic acids such as HF, H2SO4, catalysts prepared through the simultaneous loading-reduction
and HCl were extensively used in sorbitol dehydration at 293− procedure had stronger acidity and higher NiO dispersion on
408 K.35,133,134 However, the neutralization treatment is the outer surface of activated carbon, which contributed jointly
required to remove those hazardous inorganic acid, and the to high sorbitol conversion and slightly low selectivity to
separation of dehydration products from the salt solutions will anhydro sugar alcohols (ca. 66%). The stronger acidity and
be a problem. For this reason, a considerable research effort has
greater moderate acid amount of catalysts were beneficial to
been directed to the environmentally benign techniques. A
high sorbitol conversion and excellent selectivity to isosorbide,
series of efficient catalysts and reaction systems are developed
respectively, especially for the one reduced by NaBH4.142
in isosorbide production, as summarized in Table 4.
In near future study, a green process was applied in sorbitol
Metal(IV) phosphates of tin, zirconium, and titanium
dehydration without using any acidic catalysts. Based on the
synthesized by the hydrothermal method were used for
selective dehydration of sorbitol to isosorbide.135 Among the properties of high temperature liquid water, high isosorbide
three catalysts studied, SnPO showed the highest stability and yield could be realized by properly controlling reaction
selectivity to isosorbide (65.4%) with a 72.1% sorbitol temperature and time, and the maximum yield of isosorbide
conversion at 573 K. Interestingly, TiPO exhibited the excellent reached up to 57% at 590 K.143 They ascribed the success to
conversion (97.1%), but over 50% side products were detected the higher concentration of H3O+ and OH− owing to the
during the reaction. It was found that the deactivation rate was temperature-dependent autoprotolysis of water. In spite of the
in accordance with coke deposition by thermal analysis, and the higher energy consumption at high temperatures, no obvious
acidity provided by functional groups of catalysts was the key byproducts were identified in the reaction. With in-depth study,
factor for prolonging catalyst lifetime. Thereby much work a more environmentally friendly and economical process was
should be directed to prevent coke deposition and retain the introduced for the conversion of sorbitol to isosorbide, and
acidity, and the reasons for coke deposition must be energy consumption and reaction time were significantly
investigated in detail to avoid such phenomenon. Meanwhile, reduced with the use of microwaves. Meanwhile, the obtained
the acid types of synthesized catalysts are required to be isosorbide yield could be up to 70%.144 As for the kinetic study
identified clearly that will be beneficial to the development of in sorbitol dehydration under microwave heating, several
new catalysts in latter studies. As for the determination of acid models considering first-order reactions or Langmuir−Hinshel-
amount and strength for solid catalysts, NH3-TPD analysis is wood type equations were detailed investigated by Polaert et al.
suggested to be mastered. They claimed that kinetics of the reaction was only correctly
As the study develops in depth, several solid acid catalysts are described by a Langmuir−Hinshelwood type model, including
developed with the aim of improving selectivity and conversion, the adsorption−desorption equilibrium of sorbitol.144 Based on
such as phosphated Nb2O5,136 sulfated copper oxide,137 sulfated the resulting kinetic parameters, a continuous microwave
zirconia,138 sulfated titania,139 silicotungstic acid,140 and PW/ reactor could be rationally designed after further chemical
SiO2.141 For instance, the selectivity to isosorbide increased engineering calculations.
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Scheme 8. Route for Continuous Conversion of Biomass Feedstocks into Isosorbide

Another interesting development in the field of chemo- H2. A subsequent 2-fold dehydration in the ZnCl2 hydrate
catalytic conversion of carbohydrate is the recent reported one- media, alone or with additional CuCl2 and NiCl2 catalysts,
pot conversion of cellulose into isosorbide using hydrogenation followed to form isosorbide. The authors claimed that the
catalyst, in combination with ZnCl2 as both Lewis acid catalyst hydrolysis and hydrogenation steps could occur with complete
and molten salt reaction medium, as depicted in Scheme 7.8 conversion, while the dehydration exceeded 95% conversion. In
During this cascade procedure, cellulose was first converted another work, under the circumstances of dilute HCl and
into glucose in the presence of ZnCl2 hydrate and afterward superheated water, Ru/C showed excellent selectivity toward
hydrogenated into sorbitol using Ru/C catalyst under 5 MPa isosorbide compared to Pt/C and Pd/C, and a isosorbide yield
11810 dx.doi.org/10.1021/ie4011854 | Ind. Eng. Chem. Res. 2013, 52, 11799−11815
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of 49.5% was obtained at 488 K.145 It was proposed that much functional catalysts should deserve the priority in the following
more produced glucose was converted into sorbitol under a research. Furthermore, the supports of multifunctional catalysts
hydrogen atmosphere due to the superior hydrogenation provide acidity and high metal dispersion. Meanwhile cellulosic
activity of Ru/C, so more isosorbide was attained under the materials can be dissolved significantly by using acidic solvents
same acidic system. For Pt/C and Pd/C catalysts, levulinic acid or ionic liquids, thus leading to an obvious increase in the
and other degradation products accounted for the major parts conversion and yield.
by means of the acid−catalyzed degradation of glucose. With the introduction of the concept of green chemistry,
As cellulose is one of the most abundant biomass materials efforts in biomass conversion should be devoted to the
on earth, the conversion of cellulose into important fine economical, rapid, and eco-friendly production of sorbitol
chemicals presents a great challenge and opportunity in the based chemicals. High temperature liquid water and microwave
fields of energy and environment.146,147 Obviously, formation heating are of great interest in catalytic reactions. A feasible
of isosorbide from biomass resources instead of glucose will be pathway for the industrial conversion of biomass into these
preferred from an availability point of view. In recent work, chemicals is still needed to be progressed in depth. This
three different lignocellulosic biomass feedstocks were used: suggests that steps involving material pretreatment and
hardwood (Populus x canadensis), softwood, and wheat straw. subsequent sectional processing can be clearly considered.
It was shown that hemicellulose, lignin residues, and other Another point worth noting is that the activation and reuse of
impurities impeded cellulose conversion to isosorbide and the catalyst and effective separation of the target products are
lignocellulose pretreatment methods were of high importance always the hottest topics for catalytic processing research.
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
■ AUTHOR INFORMATION
Corresponding Author
efficiently converted to 63% isosorbide after 1 h of reaction *Phone/Fax: +86 020 22236808. E-mail: shubinwu@scut.edu.
over SiW and Ru/C catalysts. Notably, the disadvantage of a cn (S.-B.W.), amyliu@scut.edu.cn (Y.L.).
high crystallinity index was overturned by the advantage of a
Notes
small particle diameter and large specific surface area, originated
The authors declare no competing financial interest.


from the activity comparison between ball-milled Avicel PH-
101 cellulose and delignified CIMV wheat straw pulp.148 ACKNOWLEDGMENTS
According to the above work, a reaction diagram in converting
biomass feedstocks into isosorbide was generally described in This work was supported by the supported by National Key
Scheme 8, which provides a promising direction for the future Basic Research Program of China (No. 2013CB228101),
study in isosorbide production. National Natural Science Foundation of China (No.
31270635), and the National High Technology Research and
4. CONCLUSIONS Development Program of China (863 Program,
2012AA101806).


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