Perspective

pubs.acs.org/acscatalysis

Biobased Chemicals from Conception toward Industrial Reality:

Lessons Learned and To Be Learned
Pierre Y. Dapsens, Cecilia Mondelli,* and Javier Pérez-Ramírez*
Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Wolfgang-Pauli-Strasse
10, CH-8093, Zurich, Switzerland

ABSTRACT: The development of innovative catalytic

technologies to transform biomass into chemicals attracts
increasing interest in both academic and industrial arenas as a
means to establish a sustainable economy. This Perspective
reviews relevant concepts developed in the field of chemo-
catalytic conversion of biomass and proposes strategies for
engineering the future generations of catalytic processes
devoted to the production of chemicals from lignocellulose-
derived compounds. We discuss (i) approaches currently
followed in the selection of biomass conversion routes to
chemicals; (ii) required operating conditions to process
bioderived feedstocks; (iii) design features for efficient catalysts; and finally, (iv) emerging reactor and separation options.
With regard to catalyst families, particular attention is given to zeolites in view of the promising utilization of these crystalline
microporous aluminosilicates in dehydration, isomerization, retro-aldolization, and oxidation reactions and of the potential of
tailored (hierarchical, functionalized, or both) zeolite-based systems to attain superior performances in the transformation of
biobased compounds. Throughout the way from idea to industrial reality, we put forward scientific and technological aspects of
the mature petrochemical industry that could be transposed or adapted to the biobased manufacture of chemicals and indicate
which knowledge will need to be developed ex novo.
KEYWORDS: biobased chemicals, sustainability, conversion routes, catalyst design, tailored hierarchical zeolites, reactors, separation,
petrochemicals

1. SETTING THE SCENE: BIOMASS TO CHEMICALS biofuels. Still, although significant progress has been achieved at
Fossil feedstocks constitute essential pillars of the economy in a lab-scale level7−9 and numerous routes proposed could be
modern society. They are the primary source of energy, technically implemented in industry, the major hurdle for the
accounting for three-quarters of the world’s energy supply.1 realization of large-scale biofuels production appears to be the
Moreover, the refining of crude oil (45% of the fossil raw shortage of biomass, as recently stressed considering the case of
materials)2 generates fuels and a wide variety of products that the U.S. as representative for a worldwide situation.10,11
improve the quality of our everyday life. Nevertheless, because As illustrated in Figure 1, the annual crude oil demand in the
of the accelerated consumption of these finite resources and the U.S. (1 billion tons) roughly corresponds to the quantity of
associated rise in anthropogenic CO2 emissions, scientists have lignocellulosic raw material that agricultural and forest
been exploring more sustainable sources of energy, fuels, and resources of the country could renewably supply.12 Never-
chemicals over the past 15 years.3,4 Biomass has received theless, since the carbon content in biomass is only half of that
particular attention because it represents the only abundant in crude oil, even considering full conversion and selectivity,
source of renewable organic carbon that can reduce our reliance two times more biomass than crude oil would be necessary to
on fossil feedstocks for all of the three purposes.5 Biomass generate an equivalent amount of transportation fuels. On the
allows for a wide variety of chemical transformations, and its other hand, the available lignocellulose could fully replace the
more even distribution and accessibility around the world with fossil feedstock for the manufacture of commodity chemicals
respect to fossil reserves should set a better scenario to and polymers.10,11 This is not the only reason to emphasize the
minimize price fluctuations and the raising of socioeconomic transformation of biomass into chemicals. More importantly, its
conflicts. Among the various types of biomass,6 lignocellulose is oxygenate nature and chemical diversity render biomass a
regarded as the main raw material of the future biorefinery. highly suitable raw material to manufacture a multitude of high-
This is essentially related to its nonedible nature, which implies added-value compounds.13
no competition with food.
Although the ideal concept of a biorefinery comprises a Received: February 17, 2012
synergy between the production of fuels and chemicals, most of Revised: May 4, 2012
the present research targets the conversion of biomass into Published: June 8, 2012

© 2012 American Chemical Society 1487 dx.doi.org/10.1021/cs300124m | ACS Catal. 2012, 2, 1487−1499
ACS Catalysis Perspective

Figure 1. Total consumption of oil in the United States compared with the potential harvested biomass divided into its main uses. Reproduced with
permission of Wiley-VCH Verlag from ref 10.

Figure 2. Routes for the production of chemicals from fossil feedstocks (left to center) and biomass (right to center).

The production of oxychemicals and biomaterials as a way to (Figure 2). Along any of them, heterogeneous catalysis
mitigate the dependency on fossil sources was envisaged some possesses a tremendous potential for rendering feasible and
30 years ago.14 Moreover, in the first half of the 20th century, economic biobased conversion processes.17
fermentation was industrially practiced to produce a number of The fascination with the field has led scientists and
bulk organic alcohols and acids.15 The lower price and higher technologists to pursue chemocatalytic-oriented research
purity of petroleum derivatives determined the progressive following different strategies and objectives. The result is that
abandonment of the enzymatic processes. Furthermore, the recent findings, although often individually valuable, appear
manufacture of petrochemicals was grounded on well- somehow complicated to rationalize or to categorize within the
implemented technologies allowing production at a larger overall picture. Therefore, this Perspective targets two aims: (i)
scale. Nowadays, the need to replace petrochemicals with for researchers getting initiated in the field, we synthesize the
biobased chemicals is becoming more likely. Three main most relevant concepts proposed in the vast literature and high-
catalytic routes for biomass-to-chemicals have emerged in the caliber reviews on biomass conversion,6,13 and (ii) for more
recent past;16 namely, gasification, pyrolysis, and hydrolysis experienced scientists, we delineate (on the basis of part i), key
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ACS Catalysis Perspective

Figure 3. Illustration of the “product-targeted” approach in chemicals production from biomass. (a) Manufacture of acrylic acid: routes followed in
the petrochemical industry (left to center) versus envisaged routes from bioderived feedstocks (right to center), and (b) preparation of ethylene
glycol and adipic acid from biomass. The ethylene glycol case illustrates the “drop-in” strategy, as the preparation route takes advantage of the
existing petrochemical technology from a certain stage on, whereas adipic acid exemplifies the “substituting” strategy, because the preparation route is
completely different from the current petro-based one.

aspects for the development of catalytic processes that will help constituents (hydrolysis), from methanol obtained from
to drive the emergence of future biobased chemical factories. biosyngas (gasification) or from selected fractions of bio-oil
Our discussion covers all levels from idea to practical (pyrolysis) (Figure 2). The building blocks obtained by
application, starting with approaches and routes, spanning hydrolysis (i.e. glucose, mannose, xylose, galactose, and
through conditions and catalyst design, and finishing with an arabinose (from cellulose and hemicellulose)), and phenolic
analysis of emerging reactor types. With regard to catalyst derivatives (from lignin) preserve biomass intrinsic chemical
design, emphasis is set on zeolites. Their use in biomass diversity. Furthermore, selective enzymatic routes are estab-
conversion to chemicals is reviewed, and the potential of
lished to transform glucose, predominantly, into relevant C2−
tailored zeolite-based materials is uncovered. At each stage, we
highlight whether knowledge acquired at both scientific and C6 classes of compounds, the so-called platform molecules.
technological levels in the petrochemical industry can be Syngas production by gasification implies the complete loss
extrapolated to the manufacture of biobased chemicals or if the of all chemical functionalities in biomass and, additionally,
development of new technologies specific to the conversion of poses hurdles due to the production of tars, thus being less
bioderived molecules is necessary. favorable for this purpose than coal or natural gas.18 Bio-oil is
obtained in a substantially straightforward manner and without
2. STRATEGIES TO APPROACH THE RENEWABLE lowering the original O/C ratio of lignocellulose to a significant
CHEMICAL INDUSTRY extent, but hundreds of constituents have to be separated in
In the same manner as the production of petrochemicals rests clean fractions for manufacture of chemicals, and this still
on building blocks derived from fossil resources (namely, constitutes a big challenge. Thus, as the production of
methanol, light olefins, and BTX),14 biobased chemicals would chemicals emphasizes purity, sugars and their derived platforms
be generated from the units building up the lignocellulose are the most appealing starting molecules.
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ACS Catalysis Perspective

Two approaches to convert bioderived feedstocks into high- nestrøm et al.,10 who proposed two different overall strategies
added-value chemicals can be identified: (i) the “product- (namely, a “drop-in strategy” and an “emerging strategy”) and
targeted” approach that focuses on the replacement of petro- discussed their feasibility attending to the competitiveness with
derived with bioderived raw materials to generate specific end- petrochemicals. The drop-in strategy corresponds to the
products and (ii) the most commonly practiced “platform- transformation of a bioderived molecule into an intermediate
targeted” approach based on the curiosity-driven exploration of that is already obtained from fossil sources. Accordingly, it takes
selected starting molecules to produce any chemical.19 These advantage of the existing technology in terms of catalyst,
two strategies are briefly summarized in the following, and the reactor, and process from a more or less advanced step of the
respective main advantages and limitations are highlighted by value chain on. In this respect, we would like to point out that,
means of examples. although biobased molecules that can enter the petrochemical
2.1. Product-Targeted Approach. The product-targeted chain at an early stage are obviously highly desired, a careful
approach considers all possible pathways to synthesize one analysis of the overall process is needed to assess at which stage
specific chemical from biobased compounds. This is analogous biomass and petrol conversion trains should be connected. The
to the traditional retrosynthetic analysis in organic chemistry,20 emerging strategy represents a brand new route leading to a
but obviously, the pool of substrates must exclusively contain product with no correspondence in the petrochemical industry.
biomass building blocks and the derived platform molecules. Hence, its practical realization will benefit from the lack of
The most suitable route would be selected after a close competition with a petrochemical counterpart but suffer from
examination of the fundamental aspects of the process, such as greater technological challenges.
the catalyst’s activity, selectivity, and lifetime; reactor type; In the above analysis of the acrylic acid manufacture, the
energy balance; possible valorization of byproduct; etc. (vide route from ethanol could be classified as “drop-in” because it
infra). Since the availability and price of the starting molecules shares the β-lactone intermediate with the petrochemical route.
is also a relevant parameter, progress in fermentation On the other hand, the other routes cannot be labeled as
technologies is expected to play an important role in enhancing “emerging” because the final product is not a new chemical. In
the viability of chemocatalytic routes. the frame of a product-targeted approach, a complementary
The example of acrylic acid, a key compound in the polymer “substituting strategy” can thus be introduced to characterize
industry, nicely illustrates the product-targeted approach.21 the synthesis of a target chemical that already exists in the
Bioderived acrylic acid is potentially obtained through several petrochemical industry through a totally independent pathway.
routes (Figure 3a, right panel). Various starting molecules, As this strategy does not profit from the available technologies,
including glycerol, lactic acid, 3-hydroxypropionic acid, or the achievement of mature processes will require long-term
ethanol, can be suitable. On the basis of purely chemical commitment and substantial capital investment.
considerations, no pathway stems out as preferred, but all of the The syntheses of ethylene glycol (EG) and adipic acid are
routes comprising only one or two steps are environmentally illustrated in Figure 3b as examples of the drop-in and
and energetically much more attractive than those involving substituting strategies, respectively. EG is currently produced by
more steps. In view of the constant expansion of our knowledge oxidation of ethylene to ethylene oxide, which is further
and advances in technology, one expects that a route originally hydrolyzed to the target product. A future biobased route to
selected for the manufacture of a bioderived chemical might be bioEG could rely on the following steps: (i) sugar building
changed, improved, or replaced in the future. blocks are transformed into bioethanol via fermentation, (ii)
Also in the petrochemical industry, different routes were bioethanol is converted into bioethylene through catalytic
originally considered and even implemented at industrial scale dehydration, and (iii) bioethylene enters the fossil chain to
for one product. For example, the industrial manufacture of attain bioEG. Nowadays, the synthesis of adipic acid comprises
acrylic acid started at the beginning of the 20th century when the hydrogenation of benzene into cyclohexane, the oxidation
four commercially practiced technologies were introduced of the latter into a mixture of cyclohexanone/cyclohexanol (KA
more or less simultaneously. As shown in Figure 3a (left oil), and further oxidation by nitric acid. Bioadipic acid can be
panel), this chemical was produced from ethylene oxide obtained from glucose by oxidation to glucaric acid and
(ethylene cyanohydrin process), from acetylene (Reppe subsequent hydrogenation of this intermediate to the desired
process), from ethenone (propiolactone process), and from chemical.22 Although in the current approach the use of
acrylonitrile. These processes were eventually abandoned due stoichiometric amounts of nitric acid generates large amounts
to economic and environmental reasons and, since the end of of noxious nitrogen oxides, the benefits of the substituting
the 1960s, acrylic acid has been mostly produced via the strategy are the use of heterogeneous catalysts and the
catalyzed oxidation of propylene. Comparing the petro- and generation of only water as a byproduct. It is claimed that
biobased pathways to acrylic acid, it can be noticed that all this new process has a real potential for industrialization.22
bioroutes include different starting molecules or intermediates 2.2. Platform-Molecule Approach. In the attempt to
except for the one based on ethanol. Actually, all steps of the guide the emerging research in the production of biobased
latter pathway are well-known reactions in the petrochemical chemicals, the U.S. Department of Energy released in 2004 a
industry (used in the manufacture of acrylic acid or other list of 15 basic molecules23 that can be derived from cellulose
chemicals), and accordingly, this route appears as the most and hemicellulose and includes organic acids (e.g., succinic,
favorable. itaconic, fumaric, lactic, and levulinic acid) and polyols (e.g.,
The comparison between the existing petrochemical industry glycerol, sorbitol, and xylitol). Recently, Bozell and Petersen24
and the prospective biobased chemicals manufacture enables proposed a reduction of the original list to 10 molecules
one to discuss another important aspect that can guide the (Figure 4a). The widely spread “platform-molecule” strategy
selection of the route, which is the compatibility of biomass aims at exploring catalytic ways for the conversion of these
value chains with their fossil counterparts and with existing platform molecules into all possibly derivable high-value-added
infrastructure. This concept has been introduced by Ven- chemicals.
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3. TOWARD A GREENER INDUSTRY: LIQUID-PHASE

CONVERSION OF BIOMASS
This section analyzes the requirements posed by the processing
of biomass in terms of reaction conditions and how an optimal
choice of the latter can help to control the selectivity of the
transformations. Furthermore, we discuss how the present
research attempts to incorporate the principles of sustainability
and green chemistry26 in the development of chemocatalytic
processes. It is important to note that the utilization of a
renewable feedstock such as biomass does not necessarily imply
that the biobased value chains introduced will be sustainable or
green. For instance, the use of a harmless solvent, energy
reduction, and the minimization of the waste generated should
be critically evaluated.
In contrast to fossil feedstocks, the abundant presence of
oxygen makes bioderived molecules soluble in water, of low
volatility, highly reactive, and prone to decomposition at a
moderate-to-high temperature. Accordingly, the harsh con-
ditions commonly applied to activate and functionalize
hydrocarbons in gas-phase reactions will not be appropriate,
at least at the first stages of the biomass conversion train,
whereas liquid-phase operation at mild temperatures and
pressures appears more suitable to control the chemical
reactivity of bioderived compounds.27
The dissolution of biobased molecules requires highly polar
media, which makes water the solvent of first choice. In this
case, the viscous fermentation broths containing the various raw
materials produced from biomass could be directly used
without going through intermediate isolation and purification,
thus decreasing energy consumption and waste generation.
Figure 4. (a) Platform molecules as defined by Bozell and Petersen.24 Alcohols are also suitable. The use of supercritical water and
(b) The furan platform is exemplified by the case of 5-HMF. The carbon dioxide28 and of bioderived solvents29−31 such as ethyl
products of proven marketable potential that can be directly derived
and that illustrate the “emerging” strategy are represented.
lactate and glycerol appears promising, too.
Ionic liquids (ILs) have recently attracted much interest due
to their ability to dissolve biopolymers. In particular, it has been
shown that in the presence of ILs, cellulose can be converted to
The case of 5-hydroxymethylfurfural (5-HMF) and its key intermediates through a multistep route in the same
derivatives serves as a good example to illustrate this approach. reactor, therefore overcoming the need for a prior production
5-HMF is typically obtained by acid-catalyzed dehydration of of the intermediate platform molecules by enzymatic routes
C6-based carbohydrates, such as glucose or fructose, and is an (Figure 2).32,33 Despite their very low volatility and the recent
important intermediate in the manufacture of a variety of advances in their purification,34 several drawbacks hamper the
large-scale utilization of ILs, such as their cost, high viscosity,
products.25 An overview of the main derivatives and their
and elusive information regarding toxicity, biodegradability, and
known or envisaged applications is presented in Figure 4b. The
modification of catalyst properties. Nevertheless, the perspec-
case of furan enables the highlighting of an important feature
tive to achieve one-step conversions will certainly trigger
common to most of the platform molecules. Because they
research efforts to circumvent some of these limitations. Most
directly derive from lignocellulosic building blocks (glucose, of the media mentioned have lower volatility, toxicity, and
mannose, xylose, galactose, and arabinose) by means of flammability than those typically used in the petrochemical
fermentation or direct chemocatalytic transformations, they industry (mainly, aliphatic or aromatic hydrocarbons, often
do not generally have petrochemical equivalents and easily lead halogenated; ethers; and alcohols) and better match the
to new chemicals. These new routes can be defined as principles of green chemistry.
“emerging” on the basis of the classification by Vennestrøm et However, to enable selection among different processes, a
al.10 quantitative description of their environmental footprint would
The platform-molecule approach is the most suited to be necessary. This issue has already been addressed for
discover molecules that can be used alternatively to those petrochemical processes, and metrics have been introduced
known from petrochemistry (that is, with similar function but for this purpose in the last few decades,35 the most popular
different backbone) or that exhibit novel characteristics and can possibly being the E(nvironmental) factor (kilograms of waste
enable the generation of new functional materials, thus generated per kilogram of desired product).36 The advantage of
broadening the current portfolio of chemicals and polymers. this metric is that the calculation of the waste produced in the
On the other hand, it might appear as less effective when the process takes into account the chemical yield and includes all
aim is developing a biobased route to replace one specific reagents, solvent losses, process aids, and energy consumption
petrochemical. (on a CO2 basis), although one limitation is that it neglects the
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ACS Catalysis Perspective

Figure 5. Main catalyst families employed in the conversion of bioderived molecules described in terms of suitability to perform different types of
reaction (orange boxes) versus main benefits and drawbacks (green boxes).

nature of the solvent. Sheldon has recently indicated that this indicating the reactions catalyzed and the main benefits and
metric can be transposed to characterize bioprocesses, as well, drawbacks.
but possibly, integration with some form of life cycle Bulk Metal Oxides. These materials have been successfully
assessment will be needed.37 applied in isomerization and dehydration. TiO2 and ZrO2, for
example, catalyze the conversion of glucose in hot-compressed
4. THE CORE PROBLEM: CATALYST DESIGN water through isomerization to fructose and further dehy-
dration (to HMF, mainly),43 whereas CeO2 shows remarkable
Considering that more than 80% of the petrochemical activity and selectivity in the dehydration of 1,3-propanediol to
processes rely on the use of heterogeneous catalysts,38 the 2-propen-1-ol.44 Despite their typically low cost, their structural
engineering of materials played a key role in this success story. instability in polar media hinders the vast utilization of these
To place the biobased chemical industry at the same materials. Solubilization is particularly enhanced when water
technological level, one of the major scientific challenges is under supercritical conditions is used,45 as often required for
the development of selective, stable, and active (in this priority dehydration reactions. Thus, metal oxides might be more suited
order) catalysts that are able to convert biomass with a for transformations at late stages of the biomass conversion
comparable efficiency.39,40 To this end, materials’ properties, chain, which involve substrates with reduced O/C ratio and,
process conditions, and reactor configurations should be hence, less polar solvents.
optimized. Nevertheless, the intrinsically different chemical Metal-Oxide-Supported Metals. These systems have
properties of the molecules that have to be converted as well as shown good performances in hydrogenation, oxidation, and
the different processing environments needed to control and C−C bond breaking of cellulose and platform molecules as well
preserve their reactivity pose additional requirements on the as subsequent chemical intermediates.46 For instance, Taarning
catalysts' features that have to be tuned with respect to the et al.47 report the formation of methyl lactate with 72%
petrochemical scenario. These critical factors and their impact selectivity by oxidation of 1,2-propanediol over 1 wt % Au/
on the catalyst design have been addressed in recent TiO2. The aqueous-phase oxidation of glucose to gluconic or
reviews.27,41 glucaric acid is obtained with high yields over Au/Al2O348 and
On the basis of these premises, is the extrapolation of supported Pt catalysts, respectively.22 Pt/Al2O3 has been
catalytic technologies developed for petrochemical trans- reported to be highly active in the dehydration−hydrogenation
formations to the conversion of biobased compounds possible, of cellulose into sugar alcohols, such as sorbitol and mannitol.49
and which catalyst families appear more promising? In recent The low water tolerance of metal oxides mentioned above
years, several catalytic systems, widely and effectively employed would imply their unfavorable use as carriers for metals. At
in the preparation of petrochemicals, have been used for present, the information reported with regard to the stability of
transformations along the production lines of biobased metal-oxide-supported metals is very limited. Nevertheless, the
chemicals.13,42 Figure 5 reports the main catalyst families, Au/Al2O3 catalyst employed for the oxidation of glucose to
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ACS Catalysis Perspective

Table 1. Main Zeolites and Zeotypes Used in the Liquid-Phase Conversion of Biobased Molecules under Mild Conditions and
Most Prominent Catalytic Data Obtained

a
M = Al for H-beta, H-ZSM-5, H-Y, Na-X, Na-Y, H-mordenite, H-ferrierite. M = Sn for Sn-beta and Sn-silicalite. M = Ti for TS-1 and Ti-Y. bTi-/
Zr-/Al-/Si-beta have also been employed to demonstrate the role of Lewis acidity but the conversion and selectivity values are lower than for Sn-
beta. c,dSi/Sn ratios. eYield.

gluconic acid seems to offer encouraging durability. No loss in Acid-Functionalized Mesoporous Materials. In view of
activity or selectivity was observed during 70 days of their strong acidity, high specific area, and well-ordered
continuous operation.48 mesoporosity, acid-functionalized mesoporous materials are
Carbon-Supported Metals. Carbon-supported metals able to catalyze esterification, hydrolysis, and dehydration
attained encouraging results in hydrogenation, hydrogenolysis, reactions attaining high conversions and selectivities.55 For
and oxidation.50 As an example, Pd/C enabled the formation of instance, sulfonic-acid-functionalized MCM-41 is reported to
glycerate by oxidation of glycerol under basic conditions with dehydrate xylose into furfural with a selectivity of 82% at 91%
high selectivity (77%),51 whereas Ru/C has been recently conversion.56 Recent work by Diaz et al. suggests that superior
described as an efficient catalyst in the hydrogenolysis of xylitol performances can be attained by selecting materials with
to ethylene glycol.52 Carbons seem to represent a suitable adequate porous characteristics and controlling the strength
alternative to metal oxides to support metals because they are and distribution of the functional groups grafted.57 In particular,
highly resistant in acidic and alkaline media, display specific the authors report a MCM-41−SO3H catalyst featuring a
surface areas up to 3000 m2/g, and have a relatively low cost. specific balance between lipophilic and hydrophilic species that
Moreover, the carbon can be burned off the catalyst after use, selectively attains the monoesterification of glycerol with fatty
thus enabling recovery of the loaded active phase, which is acids. Owing to the presence of mesoporosity, it is expected
particularly advantageous in the case of expensive metals. that these materials could be beneficial for the processing of
On the other hand, the heterogeneity of the surface (i.e., bulky substrates. Nevertheless, because of their amorphous
nature and number of oxygenated surface chemical species) and nature, the hydrothermal and mechanical stabilities of these
the presence of nonordered and small-size pores negatively solids are typically limited, which may lead to disintegration of
affect the dispersion of the active phase.53 This, along with the the structure within a few hours upon use in aqueous
lack of mechanical strength, makes the commercial application solutions.58
of conventional carbons rather unattractive, whereas the use of Ion-Exchanged Resins. Ion-exchanged resins, such as
carbon replicas of ordered mesoporous materials (MCM-41, Amberlyst, Nafion, and Dowexes, have long been employed for
MCM-48, or SBA-15), which offer well-ordered and tunable hydrolysis and esterification and more recently for alkylation or
mesoporosity, is indicated as promising.54 Nonetheless, even if deformylation.59 Still, their moderate thermal stability (e.g., up
these materials demonstrated superior properties, their complex to 280 °C for Nafion-NR50, 190 °C for Amberlyst 70, and 150
and expensive synthesis would likely hamper a broad utilization. °C for Dowexes) strongly restricted the utilization of this
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ACS Catalysis Perspective

catalyst family in petrochemistry. On the other hand, their high (Sn-silicalite) attained lower LA selectivity (66%).73 In the case
water compatibility and strong acidity, as well as the possibility of the isomerization of glucose into fructose, the selectivity
to generate materials with high surface areas and improved dependency on the framework structure is stronger, and due to
microstructures point to a successful application of resins to the the larger size of the substrate, the conversion level is also
liquid-phase processing of biomass derivatives at mild temper- affected. Tin silicalite converts glucose to a very low extent
atures. Nafion 117 is reported to dehydrate xylose to furfural (9%) with moderate selectivity (44%),73 whereas much more
with considerable yield (60%) and to maintain the original relevant data (56% conversion, 75% selectivity) are obtained
activity level upon utilization in several catalytic runs.60 The using Sn-beta.63,64 It is worth noting that also the Sn-free
main drawbacks of acidic resins are poisoning by bases, such as zeolites H-MOR, H-ZSM-5, and H-Y exhibit significant
amines, and poor resistance to abrasion, detrimental for use in performances in the isomerization of DHA to LA (99%
stirred reactors.61 conversion; 39, 22, and 71% selectivity, respectively), indicating
Zeolites and Zeolite-Supported Metals. Their high that zeolites purely containing Si and Al can be active for this
specific area, strong acidity, remarkable (hydro)thermal reaction.72 In this respect, extraframework aluminum sites
stability, and the presence of pores of molecular dimensions should be responsible for the activity. With regard to retro-
rendered zeolites hegemonic catalysts in the petrochemical aldolization Sn-beta achieves full conversion in most cases and
industry. These characteristics set a highly promising basis for selectivities ranging between 44 and 64%, depending on the
the adaptation of this catalyst family to production of biobased starting sugar (Table 1).
chemicals. Furthermore, exploration of zeolites for this purpose By ion exchange, metal ions with redox properties can also be
has already attracted research and produced encouraging inserted in the material. Titanium-containing zeolites, such as
results. The use of Lewis acidic zeolites for the conversion of Ti-Y and TS-1, have been reported to catalyze the oxidation of
sugars to lactates and furans, glycerol to acrolein, and terpenes glucose to gluconic acid, although the conversion and selectivity
to selected starting materials for the manufacture of fine reported are rather low. Supported noble metals (e.g., Au) have
chemicals has been recently reviewed.62 Herein, we present a performed much better in this reaction, but such catalysts
broader overview of the main zeolites and zeotypes used and typically are more costly.81 Although the amount of titanium in
the most prominent catalytic data obtained in the trans- the framework FAU is not reported, the selectivity is double
formation of various platform molecules in liquid phase and (28%) using Ti-Y with respect to TS-1 (12%).74 In view of the
under mild conditions (below 150 °C). This information is clear impact of the porous structure, it is expected that zeolites
collected in Table 1. We do not aim to give exhaustive can be improved to reach more significant conversion and
reference to every zeolite-catalyzed reaction reported in the selectivity levels.
field of biomass to chemicals, but rather, to highlight the most The deposition of metals in the form of nanoparticles onto
prominent examples that demonstrate the potentially wide the external surface of zeolites enables generation of catalysts
applicability of these catalysts. So far, zeolites of BEA, MFI, featuring both strong acid and redox sites. The use of such
FAU, MOR, and FER frameworks have successfully catalyzed bifunctional materials is advantageous for performing a two-
dehydration, isomerization, retro-aldolization, oxidation, and step reaction in one pot. For instance, Pt/NaY is reported as a
hydrogenation reactions. The capability of zeolites to perform a highly active and selective catalyst for the conversion of glycerol
broad spectrum of transformations descends from their to 1,2-propanediol, which involves the acid-catalyzed dehy-
structural versatility. This involves both the availability of a dration of the reactant to hydroxyl acetone and the metal-
large number of frameworks featuring different pore shape, size, catalyzed hydrogenation of the latter to a desired product
and connectivity and the possibility to modify existing or insert (Table 1). This reaction can be performed even in the absence
new types of catalytic centers by means of well-established of an external hydrogen supply, since platinum enables its in
methods into a specific zeolite structure. situ production through the aqueous-phase reforming of a small
As expected from their strong Brønsted acidity, zeolites are amount of glycerol.79
able to accomplish dehydration reactions, such as fructose to 5- When applicable, information on catalyst productivity and
HMF or xylose to furfural, with remarkable to very high reusability, two aspects that become particularly relevant in
conversion. Some of these catalysts are equaled or surpassed view of the implementation of the processes developed at an
only by certain resins60,80 and sulfonated mesoporous silica,56 industrial scale, has been included in Table 1. Concerning the
activity-wise. Remarkably, the selectivity of the zeolite-catalyzed former, the substrate concentrations in the feed, with the
processes can be modulated by the specific porous character- exception of the isomerization of glucose to fructose, were
istics of different frameworks. Thus, at present, H-mordenite generally rather low (below 10 wt %). An economically viable
dominates the dehydration scene offering the highest and environmentally friendly process would require operation
selectivities to the desired products (90% in both cases) with more concentrated solutions. This implies that more
among all catalyst types. efforts should be put in ensuring that catalysts are able to
With regard to the structural modifications, Lewis acid sites process highly viscous solutions without suffering from
can be introduced by exchanging framework aluminum or excessive mass transfer limitations and active site blocking/
silicon atoms with other heteroatoms. The presence of this type deactivation via depositions of side products, for instance. With
of acidity has been demonstrated important for isomerization regard to catalyst reusability, little information is available. Only
and retro-aldolization reactions. A very remarkable example is for Sn-beta and Ti-Y was it confirmed that the catalyst could be
the isomerization of dihydroxyacetone (DHA) to lactic acid employed with no appreciable loss in activity for 3−6 runs.
(LA), which is realized with full conversion and a selectivity of Further research should try to put more emphasis on this
90% over Sn-beta (Table 1).66 Still, although the nature of the essential aspect, too.
active sites is crucial, the micropore characteristics seem to play Along our discussion of activity data, we have encountered
a role in driving the selectivity toward the desired product, as conversion and, most importantly, selectivity figures that are
well. Thus, the incorporation of tin into the MFI framework only moderate or even rather low. We would like to stress that
1494 dx.doi.org/10.1021/cs300124m | ACS Catal. 2012, 2, 1487−1499
ACS Catalysis Perspective

Figure 6. Intrinsic properties of purely microporous zeolites and additional features that can be incorporated by means of postsynthetic modification
and functionalization.

these less attractive examples were included to underline the The creation of a mesoporous surface paves the way for
ample margin for improving catalysts and reaction conditions. further possibilities (Figure 6). The use of a hierarchical zeolite
The selectivity values reported are state-of-the-art for zeolites as a carrier for a metal phase is expected to be favorable for
and all other catalyst classes. Isolated exceptions have been obtaining a bifunctional material with superior properties in
pointed out along the discussion. We think that significant view of the availability of an even larger external surface onto
advances could be achieved via rational catalyst design in which the metal phase can be deposited, thus achieving higher
zeolite-based conversion of biomass, as explained hereon. dispersion,89 and of the closer proximity of the metal and acid/
In addition to the modifications mentioned above, a wide base sites in the solid with respect to the parent zeolite.
array of treatments82−85 has recently become available that Another interesting alternative is the grafting of organic
enables the obtaining of tailored zeolites with superior functionalities over the freshly developed mesoporous area.
properties. Herein, we focus on the postsynthetic modification This might include the introduction of sulfonic acid groups90 or
options (Figure 6) as the scalability, simplicity, and versatility of the heterogeneization of homogeneous metal complexes,91−93
these methods offer real potential for implementation for which currently is attracting much interest as a way to combine
industrial manufacture of modified zeolites.86 Sequential the intrinsically outstanding stereoselectivity of these catalysts
desilication (by base leaching) and dealumination (by acid with the ease of separation of a solid material.
treatment) mediated by the use of so-called pore-directing Catalytic data attained with the use of hierarchically
agents allow one to obtain hierarchically structured zeolites that structured materials for the conversion of fossil-derived
couple the original microporosity with an auxiliary intercon- compounds have indicated enhanced activity, reduced
nected mesopore network.87 These mesoporous zeolites retain deactivation, and improved selectivity.94−96 Initial results
the intrinsic features of the parent zeolites but benefit from obtained using conventional and postsynthesis-modified H-
higher accessibility. Remarkably, the mesoporous surface and ZSM-5 and H-USY zeolites in the isomerization of DHA into
pore size distribution can be tuned by simple adjustments of LA provide the first tangible evidence that tailored zeolites
parameters such as the concentration of the reactants or the could be successfully upgraded for the preparation of biobased
temperature.87 Most of the zeolite frameworks widely used in chemicals. Although of preliminary nature, we believe that these
the petrochemical industry (FAU, MFI, MOR, BEA, MTW, findings are important to strengthen our perspective.
AST, FER, MWW, IFR, STF, CHA, TON) can be prepared in Figure 7 depicts the DHA conversion (green bars) and LA
mesoporous form at present. Although the literature does not selectivity (blue bars) after 6 h of reaction. Conventional H-
report a full compositional investigation for each zeolite, recent ZSM-5 and H-USY zeolites exhibit remarkable activity and
studies performed on ZSM-5 and Y/USY88 suggest that any appreciable selectivity. The activity of the modified zeolites is
zeolite can be obtained in hierarchical form. Zeolite Y is almost unaltered. The small size of the DHA molecule and,
particularly interesting in view of its prominent role in thus, the low benefit on reducing the diffusion limitations might
petrochemistry, the deep knowledge on this material, and explain this. Clearer positive effects should be obtained when
especially because its synthesis does not require the use of an converting substrates of larger size. Remarkably, for both the
expensive template, as in the case of all other zeolites. The frameworks, the modified zeolites attain ca. 50% higher
textural properties of modified zeolite Y resemble those of selectivity to LA with respect to the parent samples (81%
mesoporous MCM-41, but the aluminosilicate displays better versus 55% for ZSM-5 zeolites and 71% versus 53% for USY
intrinsic acidity, selectivity, and (hydro)thermal stability. In zeolites). It is worth noting that the selectivity to LA obtained
addition, simultaneously with the textural alteration, modifica- with mesoporous H-ZSM-5 by far surpasses the literature data
tion of the native acid/base properties of the zeolite can be for conventional ZSM-5 (32%) and other conventional
achieved. In particular, the number, type (Brønsted or Lewis), zeolites72 and approaches the selectivity of the Sn-beta zeotype
and distribution of sites can be tuned. (90%, Table 1). An accurate speciation and quantification of
1495 dx.doi.org/10.1021/cs300124m | ACS Catal. 2012, 2, 1487−1499
ACS Catalysis Perspective

configurations, the latter should be carefully optimized to

ensure efficient mass and heat transfer.
For some applications, monoliths98 could gain interest
because they offer the possibility to have a fixed bed and
retain high effectiveness due to short diffusion distances. In
addition, recently proposed reactor concepts such as the
spinning disk reactor (SDR)99 and the oscillatory flow reactor
(OFR),100 operated in continuous mode, are interesting ideas.
Thanks to the large centrifugal forces generated, the SDR is
characterized by increased heat transfer coefficients, which
renders it extremely suitable for highly exothermic processes.
This reactor could represent a convenient alternative to stirred
tank reactors, which may suffer from poor mixing in viscous
environments and complicated temperature control, for
polymerizations. On the other hand, the OFR would be a
Figure 7. DHA conversion (green bars) and LA selectivity (blue bars) more appropriate choice for reactions that require long times
over conventional and postsynthesis-modified H-ZSM-5 (CBV3024E, because its combination of baffles and oscillatory motion leads
Zeolyst International, Si/Al = 15) and H-USY (CBV720, Zeolyst to increased heat and mass transfer and plug flow behavior.
International, Si/Al = 15) zeolites. Modification was achieved by Case by case assessment of the overall effect of parameters such
alkaline treatment (AT) as reported in refs 87 and 88. Conditions:
Wcat = 80 mg, cDHA = 3 wt %, water solvent, T = 140 °C, t = 6 h. as reaction kinetics and enthalpy, temperature, viscosity,
catalyst characteristic length and porosity, and substrate shape
and size will indicate the optimal reactor concept.
Because of the highly functionalized nature of bioderived
the acid sites will enable understanding if and to what extent molecules, one crucial issue in their transformation is
extraframework Al species were already present in the parent selectivity. Therefore, the development of more efficient and
zeolites and if their amount was increased upon desilication, as targeted separation methods nowadays receives much interest.
expected. Because the synthesis of zeotypes such as the In this respect, distillation, extraction, adsorption with
mentioned Sn-beta is long and the presence of a metal makes it molecular sieves, filtration, crystallization, and osmosis hold
costly,72 tuning the Lewis acidity by varying the aluminum great promise and have been thoroughly reviewed by Huang et
content and distribution via postsynthetic treatments appears
al.101 A significant example is the extractive separation of an
much simpler, faster, and more economical in view of a
aqueous solution of 3-hydroxypropionic acid (nonconverted
practical application. The establishment of structure−prop-
starting platform molecule) and acrylic acid (desired dehy-
erty−function relationships will indicate which combination of
dration product). Separation is attained by addition of an
modifications will render optimized catalysts.
accurately selected extrinsic phase (ethyl acetate) for which the
5. TOWARD THE PROCESS two molecules have different partitioning coefficients.102
Purification of the recovered acrylic acid could be performed
Describing the detailed configuration of a biobased chemical
by fractional crystallization. In the process described, a salt (e.g.,
factory is premature. Nevertheless, because the success of any
sodium chloride) is added, which eliminates the eutectic point
industrial process finds its origin in the optimal synergy
existing between water and acrylic acid and, thus, enables its
between catalyst and reactor, we would like to analyze which
selective crystallization upon decrease of the temperature.103
reactor concepts appear suited to drive the liquid-phase
preparation of biobased chemicals from lab-scale toward This method is claimed to constitute a good alternative to
practical application. Furthermore, because selectivity con- distillation, which suffers from limited yields due to partial
stitutes a critical aspect in the conversion of biobased polymerization of acrylic acid.
compounds, other unit operations such as separations will be Recently, research efforts have determined the appearance of
addressed, too. a few highly attractive systems, in which “reaction” and
Virtually all reactions studied so far at an academic level are “separation” are integrated in the same unit (so-called “hybrid
carried out in simple vessels such as round-bottomed glass process”). One such example is the biphasic reactor proposed
flasks or stainless steel autoclaves.74,79 Consequently, slurry by Román-Leshkov et al.80,104 for the catalytic dehydration of
reactors operated in batch mode seem to be the natural choice fructose to HMF (Figure 8a). The desired product forms in the
in the design of a process. These reactors are typically used in aqueous phase and is continuously extracted into a separation-
the low-volume pharmaceutical and fine-chemicals industries. friendly organic phase. This procedure minimizes the
In contrast, the high-volume production of bulk petrochemicals occurrence of side reactions in water and, thus, boosts the
relies on the use of gas-phase processes under continuous HMF yield of the process. According to a recent analysis by
operation.97 The paradox imposed by bioderived molecules is Torres et al.,105 the biobased HMF manufactured in a process
the necessity to produce commodity chemicals in the liquid based on this biphasic reactor would cost only about twice as
phase. To achieve this goal, we expect that a transition toward much as petro-derived HMF. The versatility of this system has
operation in slurry reactors in continuous mode will be been demonstrated through the utilization of various feed-
required. Although we believe that slurry reactors will be stocks, such as glucose or cellulose.106 It has also been shown
predominantly employed, reactor designs based on an that biphasic reactors can be combined in series and with
immobilized catalyst, such as the trickle-bed reactor, might intermediate separation and reaction units to achieve multistep
receive increased attention in view of the easier catalyst or cascade reactions, such as the conversion of xylose into
recovery. Still, because structured catalysts are applied in these levulinic acid.107
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ACS Catalysis Perspective

Figure 8. (a) Illustration of the biphasic reactor patented by Dumesic et al.104 for the continuous production of HMF by dehydration of fructose
(figure adapted from refs 80 and 105). The system comprises (i) a CSTR, in which the HMF formed in the aqueous phase (bottom) migrates into
the organic phase (top) according to its repartition coefficient; (ii) an evaporator, which serves to purify HMF and to recycle the organic phase; and
(iii) an extractor, used to recover the fraction of HMF remaining in the aqueous phase. (b) Scheme of the biphasic reactor proposed by Kröger et
al.108 for the conversion of fructose into 2,5-furandicarboxylic acid (FDCA). The reactor is composed of two compartments separated by a porous
membrane and containing the aqueous and an organic phases, respectively. Fructose is dehydrated to HMF over an acidic resin in water. In view of
its smaller size, only HMF is allowed to transfer to the organic phase through the membrane. In this medium, an oxidation catalyst (Pt−Bi/C) is
present, which converts HMF to FDCA.

A few years earlier, Kröger et al.108 reported a reactor system Future efforts might also be focused to develop tailored
that could be considered as an evolution of the biphasic reactor membrane reactors. This concept has been already proven in
by Román-Leshkov et al. The main difference in the design is the area of biocatalytic biomass conversion. Arora et al.109 have,
the additional presence of a PTFE membrane separating the in fact, developed a “separative bioreactor” which enables the
continuous enzymatic production and recovery of organic acids
aqueous and organic phases into two distinct compartments,
owing to the immobilization of the biocatalyst on an ion-
whose porosity is chosen to disable the transfer of fructose from exchange resin, which also functions as a membrane. With
the aqueous to the organic phase (Figure 8b). This makes it regard to chemocatalytic transformations, we think that zeolites,
possible to combine the dehydration of fructose into HMF with which combine catalytic and molecular-sieve properties,110
a further oxidation step that leads to 2,5-furandicarboxylic acid could be highly suited for this purpose.
(FDCA). Moreover, the selectivity of the process is high,
thanks to the removal of the intermediate product (HMF) by 6. CONCLUSIONS AND OUTLOOK
transfer through the membrane and the preservation of fructose Although the market of bioderived chemicals is still in its
from degradation by oxidation, as it is constrained into the infancy, the progressive shift toward biobased chemical factories
aqueous phase. is starting to become a reality. Aiming at a faster and effective
1497 dx.doi.org/10.1021/cs300124m | ACS Catal. 2012, 2, 1487−1499
ACS Catalysis Perspective

transition, key aspects to engineer suitable chemocatalytic Liotta, C. L.; Mielenz, J. R.; Murphy, R.; Templer, R.; Tschaplinski, T.
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AUTHOR INFORMATION Practice; Oxford University Press: New York, 1998; p 30.
Corresponding Author (27) Serrano-Ruiz, J. C.; Luque, R.; Sepúlveda-Escribano, A. Chem.
*Fax: +41 44 633 1405. E-mail: jpr@chem.ethz.ch, cecilia. Soc. Rev. 2011, 40, 5266−5281.
(28) Savage, P. E. J. Supercrit. Fluids 2009, 47, 407−414.
mondelli@chem.ethz.ch.
(29) Jessop, P. G. Green Chem. 2011, 13, 1391−1398.
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The authors declare no competing financial interest. Cadierno, V. Chem. Commun. 2011, 47, 6208−6227.

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(31) Pereira, C. S. M.; Silva, V. M. T. M.; Rodrigues, A. E. Green
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ACKNOWLEDGMENTS (32) Schoevaart, R.; Kieboom, T. Top. Catal. 2004, 27, 3−9.
This work was supported by the Swiss National Science (33) Zhang, Q.; Zhang, S.; Deng, Y. Green Chem. 2011, 13, 2619−
Foundation (Project Numbers 200021-134572 and 200021- 2637.
140496). (34) Dibble, D. C.; Li, C.; Sun, L.; George, A.; Cheng, A.; Persil
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