Catalysis Today 234 (2014) 2–12

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Evolving scenarios for biorefineries and the impact on catalysis夽

Paola Lanzafame, Gabriele Centi, Siglinda Perathoner ∗
Dipartimento di Ingegneria Elettronica, Chimica ed Ingegneria Industriale, University of Messina, INSTM/CASPE (Laboratory of Catalysis for Sustainable
Production and Energy) and ERIC (European Research Institute of Catalysis), V.le F. Stagno D’Alcontres 31, 98166 Messina, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The model of future biorefineries is changing driven from many motivations, particularly the need of
Received 2 December 2013 improving sustainability and integration with the chemical production. This conceptual review discusses
Received in revised form 2 March 2014 this change, with focus on the case of integrated chemical biorefineries, and how the new scenarios for
Accepted 6 March 2014
a sustainable chemical production require to develop new related models of biorefineries. Two cases
Available online 3 April 2014
are discussed in detail: (i) olefin biorefineries and (ii) biorefineries for sustainable chemical production.
In addition, some elements for an integrated solar biorefinery approach are also given. The status of
Keywords:
catalysis research to enable the development of these biorefinery models was discussed, together with
Biorefineries
Olefin
an analysis of the industrial developments in the field and some elements of assessment of the different
HMF routes. The aim was to provide fundamentals to understand how this area is evolving, and thus identify
Green energy where research effort has to be focused. It was also commented how the simple economic analysis, with
Sustainable chemistry boundary limits to plant gate, although important, is not enough to properly identify the future scenarios.

© 2014 Elsevier B.V. All rights reserved.

1. Introduction the bio-based economy on country/regional level rather than on a

The drivers pushing towards a bio-based economy are many:
(i) Kyoto and related politics to reduce carbon footprint, (ii) secu-
rity of supply, (iii) agricultural policies, (iv) sustainability and (v)
support of the local economics. There is thus a mix of motiva-
tions driving the development of these areas mostly based on
social and policy aims rather than purely economic and industrial
incentives [1]. For this reason, government policies drive change
in energy/chemical production from bio-based materials through
a mix of actions such as mandate fuel mix, subsidies, renewable
targets and carbon targets. The consequence is that there are dif-
ferent country/regional priorities. This is schematically illustrated
in Fig. 1 evidencing the different relevance given to aspects such as
greenhouse gas (GHG) emissions, energy and domestic economy
by some country/regions, reflecting then in different priorities and
targets for the development of a bio-based economy [2]. This is
clearly an evolving scenario, because (i) some expectations of few
years ago are not more valid or different and (ii) local socio-political
pushes determine different priorities conditioning the evolution of
夽 Based on the keynote presented at the 2nd International Congress on Catalysis
for Biorefineries (CatBior 2013) held in Dalian (China) on September 22–25, 2013.
∗ Corresponding author. Tel.: +39 0906765609; fax: +39 090391518.
E-mail addresses: perathon@unime.it, CENTI@UNIME.IT (S. Perathoner).
global scale.
Even taking into account that priorities could be different
depending on the specific country/region, it is necessary to analyze
the future scenarios for a bio-based economy, in order to discuss
the possible type of biorefineries and related needs of new cata-
lysts. In fact, the macro-trends of research in catalysis in the area
of bio-refinery appear not well aligned with the priorities which
may be identified for future biorefinery scenarios and briefly dis-
cussed in the following sections. This concept may be exemplified
using the topics discussed in the most recent review (March 1st,
2014) returned by Scifinder in searching with the keywords “catal-
ysis” and “biorefinery” [3]. The topics discussed for first generation
biorefineries are the following: (i) biodiesel production, (ii) con-
version of glycerol and (iii) bio-ethanol from starch-rich biomass.
For second generation biorefineries: (i) cellulosic ethanol, (ii) lac-
tic acid from glucose, (iii) pyrolysis of ligno-cellulosic biomass, (iv)
bio-oil upgrading and (v) gasification of biomass and bio-oil to syn-
gas. The discussion in the next sections about the future scenario
for biorefineries evidences that the priorities are probably different
and as a consequence the need in terms of catalysis development.
For the specific characteristics briefly outlined before, the field of
bio-refinery and -economy is depending largely on external factors
to techno-economic aspects. Therefore, it is not possible to leave
aside an analysis of these external factors to identify the possible
scenario for future biorefineries and as a consequence the priorities
and needs for catalysis. This paper is thus organized in two main

http://dx.doi.org/10.1016/j.cattod.2014.03.022
0920-5861/© 2014 Elsevier B.V. All rights reserved.
 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
Fig. 1. Different relevance given to aspects such as greenhouse gas (GHG) emis-
sions, energy and domestic economy by some country/regions, reflecting in different
priorities and targets for the development of a bio-based economy.
Adapted from Ref. [2].
sections. A first part discusses briefly the drivers and routes for
future sustainable biorefineries to identify the possible scenario. A
second part analyses more specifically two main concepts of future
biorefineries which derive from the preliminary evaluation. The
focus in this part is to analyse the current state of development in
the discussed routes, in terms of catalytic performances and indus-
trial targets. In fact, other papers and reviews (cited later) have
discussed aspects such as the relation between catalyst composi-
tion, reaction mechanism and performances, but an analysis of the
key priorities for catalyst development necessary is often missing.
As remarked before, often the aspects discussed in literature and
the objectives for catalyst development are not coincident with the
industrial needs.
2. Biorefineries of the future
It must be shortly introduced that in a region such as Europe,
sustainability and low carbon economy are two of the key elements
strongly influencing biofuel targets and in general bio-economy,
through government policies, such as subsidies and mandated use
of biofuels. The reason was the need to address concerns related
to the environment, energy security and rural development, but
the cost-effectiveness of achieving these goals under current sub-
sidy/policy schemes is often low [4]. On the average, the use of
bioenergy allows to save about 50% of CO2 emissions with respect to
fossil fuels, although many parameters affect LCA (life cycle assess-
ment) of the use of bioenergy [5]. In addition, some alternatives to
biofuels are possible today. Methanol produced from the reuse of
CO2 and renewable energy (RE) has a potentially larger impact in
terms of saving CO2 emissions, as well as in terms of resource and
energy efficiency [6]. Solar fuels derived from CO2 and RE [7–9]
could be an economic and more eco-efficient alternative to biofu-
els. It is thus possible a shift in the government policies on biofuel
targets, with a consequent impact on the future of biorefineries
[10].
On the other hand, reuse of CO2 emitted in biorefineries (fer-
mentation processes generate large volumes of carbon dioxide, for
example about 1 ton CO2 per ton of bioethanol produced by glucose
fermentation) and the integration of solar energy into the biore-
finery scheme are important elements determining the future of
biorefinery. They will be shortly discussed in Section 4.2.
2.1. Drivers for future biorefineries
Few years ago, discussing the alternative routes in the catalytic
transformation of lignocellulosic materials [11,12], some elements
driving the future of biorefineries were analyzed from the perspec-
tive of sustainability and low-carbon economy: (i) use of waste
3
biomass and marginal lands, (ii) minimize intensive cultivations
and transport, (iii) no food competition and (iv) reduce impact
on water. Between the consequences the need of (a) developing
efficient technologies of transformation at small-scale, (b) realiz-
ing small plants (low investments) with a tight integration with
chemical production (common platform molecules) and food (e.g.
development of agro-chemical/energy districts), and (c) avoiding
high temperature processes (thermochemical treatments are com-
plex, costly particularly for small-scale and show a low energy
efficiency, in terms of ratio between final and input energy, when
applied on small scale).
Although a detailed discussion is out of the scope, it is necessary
to remark that new factors/trends influencing the strategic choices
for future biorefinery scenarios are emerging today in response to
new options and requests for energy, climate and environmental
issues, energy security. We believe that the following aspects are
critical from this perspective, and motivate the aspects discussed
later, even if it is correct to evidence that there is not a general
consensus on the statements reported below:
- Biofuel expectations for 2050 have to decrease from 27% of total
transport fuel (IEA Blue Map scenario [13]) to about 15%, due to
increased availability of non-conventional fossil fuels (particu-
larly, shale gas in US and coal in China), and also some alternative
fuels such as those deriving from CO2 using renewable energy.
- The transition from 1G (1st generation) to 2G/3G biofuels will
be probably less fast than expected; a main reason is that 1G
technologies are simpler, and require less investments.
- 2G biofuel routes will be dominated from routes with full use
of biomass and which well-integrate within the actual refinery
scheme. In this context alternatives such as bio-crude vs. platform
molecules, waste biomass vs. dedicated crops have to be analyzed.
- Higher efficient biomass production minimizing land use is nec-
essary. Algae utilization, in particular using seawater, is a required
direction to proceed, but technologies to allow their economic
processing (besides growing) are crucial.
- Integration with chemical production will be a key factor for plat-
form molecules. Integrated chemical biorefineries is the direction
to valorize the higher added value of chemical production.
- Integration of bio- and solar-refineries, in order to exploit and
valorize the CO2 produced in biorefineries as well as to integrate
RE sources in biorefinery production (solar biorefineries).
2.2. Routes for sustainable biorefineries
An analysis of the routes for sustainable biorefineries, accord-
ing to the drivers briefly outlined above, should start from current
identification of the potential routes for the development of biore-
fineries up to 2030 [14]. There are different possible biorefinery
schemes identified in this report, although the relative impact on
the future scenario is different. They were classified depending on
the prevailing type of raw materials:
- Starch and sugar biorefineries: processing starch crops, such as
cereals (e.g. wheat or maize) and potatoes, or sugar crops, such
as sugar beet or sugar cane.
- Oilseed biorefineries: currently produce mainly food and feed
ingredients, biodiesel and oleochemicals from oilseeds such as
rape, sunflower, and soybean.
- Green biorefineries: processing wet biomass, such as grass, clover,
lucerne or alfalfa. They are pressed to obtain two separate product
streams: fibre-rich press juice and nutrient-rich pressed cake.
- Lignocellulosic biorefineries: processing a range of lignocellulosic
biomass via thermochemical, chemiocatalytic or biochemical
routes.
4 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
Fig. 2. Some of the emerging biorefinery concepts possibly developed and implemented by 2030.
Adapted from Ref. [14].
- Aquatic (marine) biorefineries: processing aquatic biomass –
micro-algae and seaweed.
Some of these biorefinery concepts are schematically shown
in Fig. 2. Many different models and concepts of biorefineries are
thus foreseen, even if the large variety of technologies necessary to
develop will affect the fixed costs and in turn profitability of the dif-
ferent routes. As a consequence, only a part of these concepts will
be effectively implemented on commercial scale. Sustainability is
another critical element which will drive the effective implemen-
tation on a large scale of the different biorefinery concepts.
3. Impact of bioroutes on chemical production and
relevance for biorefinery scenario
Current discussion on the use of biomass derived products and
their impact on current petrochemical production chain is often
limited to end or even consumer products. We should remark
here that instead a more relevant contribution to the goal of sus-
tainability and low-carbon economy could be achieved when the
production of base building blocks is addressed. A more detailed
discussion on these aspects is reported elsewhere [15] and will be
thus not further examined here, except to highlight how biomass
could change the scenario of sustainable chemical production by
providing new alternative raw materials for: (i) base building
blocks (light olefins, CO/H2 , aromatics), (ii) drop-in intermediates,
(iii) other intermediates and (iv) fine/specialty chemicals. These
aspects integrate with those related to the use of CO2 and RE to
produce also raw materials (building blocks) and specific interme-
diates for the chemical industry [16]. It is anticipated in the cited
recent papers [15,16] that a new scenario for a sustainable chem-
ical production based on the reuse of CO2 and of biomass is fast
approaching.
Many indications, from socio-economic to technological, sup-
port this indication of a transition to a new production scenario
for the chemical industry. Biorefinery is another critical factor for
this transition. Therefore, emphasis is given here to discuss the
elements and priorities facing this transition.
Catalysis is a key enabling factor to allow the development of
new sustainable processes and technologies [17] and thus plays
a critical role to enable this transition. Consequently, the devel-
opment of catalysts and related catalytic technologies for the use
of biomass to produce the raw materials and green energy sources
for chemical production [18] is becoming a key area of the research.
Many recent reviews have discussed these topics recently. A limited
selection is represented by the reviews of Dumesic et al. [19,20],
Kobayashi and Fukuoka [21], Corma et al. [22,23], Miertus et al.
[24], Stocker [25], Rinaldi and Schüth [26], and Gallezot [27] and
the book of Triantafyllidis et al. [28] on different aspects of the
catalytic chemistry in biomass conversion to chemicals and fuels.
However, the relevance of the different paths on the development
of new scenarios for chemical produced has been not typically dis-
cussed. Similarly, it has not clearly identified the priority targets for
research in relation to industrial needs. These aspects are instead
the focus of the discussion in the following section.
4. Advanced concepts for biorefineries and the role of
catalysis
4.1. Olefin biorefineries
Light olefins are the base building blocks for current petrochem-
istry. They are produced currently for over 98% from fossil fuels,
mainly by steam cracking of oil and NG (natural gas) fractions, but
new opportunities are given from the use of biomass-derived raw
materials. Fig. 3 reports an overview of the main routes of produc-
tion of olefins from biomass and of their interconversion. A new
 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
Fig. 3. New routes of production of olefins from biomass.
process route, already at an industrial level, is the dehydration of
ethanol produced from biomass fermentation. An alternative, but
less attractive from an industrial perspective (complex, multistep,
economic only at a large scale, with severe problems of purifica-
tion and quality of products, etc.), is the production of methanol
via syngas from biomass (eventually, via intermediate fast pyroly-
sis). Methanol can be then converted to olefins (MTO – methanol
to olefins) or even selectively to propylene (MTP – methanol to
propylene). The methanol synthesis is well established commer-
cially, while MTO/MTP are industrial processes, even if there are
still some critical aspects regarding productivity/deactivation. A
shorter alternative path is to produce directly olefins from syngas
by FTO (Fischer–Tropsch to Olefin) process, although catalysts for
this reaction have to be further improved as discussed shortly later.
In order to analyze the industrial feasibility of the production of
light olefins starting from biomass, some comments are necessary.
The last years have seen a large capacity addition of petrochemi-
cal plants in the Middle East mainly based on associated gas from
oil production leading to a superior cost position. Furthermore, the
substantial reduction of prices for ethane due to shale gas exploita-
tion in US has pushed ethane use in most US crackers. This shift from
naphtha to ethane has caused a supply shortage of propylene and
C4 olefins (deriving mainly from naphtha steam cracking), deter-
mining, in combination with the high demand of these olefins, new
opportunities for alternative production routes. Another important
element regards the size of the plants for light olefin produc-
tion. Steam-cracking plants have a typical size between 1.5 and
3.0 Mtons/year and they are not profitable for smaller sizes or at
low operation capacity. There is thus interest to develop dedicated,
small sizes olefins production plants (on-purpose). There is thus
the opportunity for the production of light olefins from alternative
routes to fossil-fuel, because (potentially) cheaper and more sus-
tainable raw materials, and suited for on-purpose productions, can
be used.
Ethanol to ethylene. This route depends greatly on the cost of
production of ethanol. In Brazil, where cheap ethanol is avail-
able by sugar fermentation, already a couple of industrial plants
(by Braskem, Dow and Solvay Indupa) produce ethylene from
bioethanol, but cost of ethanol production in Europe is larger. How-
ever, ethanol could be easy transported by ship, for example, van
Haveren et al. [29] indicated that bio-based ethylene production
will significantly increase in the short and medium terms, first
in Brazil and then extending to regions such as US and Europe.
They suggested that this route would lead also to the production of
bio-based vinyl chloride, with thus the two most dominant thermo-
plastic materials (polyethylene and polyvinylchloride) produced
to a significant extent from biomass. Production of other olefins
5
would require converting further ethylene, for example by olefin
methathesis. Fig. 3 shows the existing possibilities of conversion of
light olefins, some discussed in more detail later.
The profitability of the process depends essentially on the cost of
production of bioethanol, which may vary considerably depending
on the raw materials and technology of production. Energy integra-
tion of the process is also critical. Actual ethanol to ethylene plants
have a production capacity about one order of magnitude lower
than that typical of steam cracking plants, but this aspect could be
an advantage in terms of on-purpose plants. Process intensifica-
tion is one of the ways to make profitable also small-medium size
plants.
The catalytic dehydration of ethanol to ethylene [30–32] is a
reaction apparently simple. It is acid-catalyzed, but is necessary
to tune carefully the catalyst properties to maximize the selectiv-
ity, because it is necessary to avoid the (i) consecutive reaction of
ethylene with surface acid sites and (ii) redox reaction leading to
dehydrogenation rather than dehydration. Fig. 4b reports the sim-
plified reaction mechanism of ethanol catalytic conversion over
mixed oxides. An acido-base concerted mechanism with forma-
tion of a surface ethoxy species is prevailing [32]. This is an easy
reaction occurring typically in very mild conditions and the rate
limiting step of the reaction is thus water desorption to regenerate
the active sites.
Selected catalytic results are reported in Fig. 4a [32]. One of
the most used industrial catalysts (Syndol catalyst, from Halcon
SD) is based on alumina doped with KOH and/or ZnO as well as
other dopants. Yield of ethylene is over 96–97%, but relatively high
temperatures (about 450 ◦ C) are necessary. This is a quite stable
catalyst working at high liquid hourly space velocities (LHSV about
100–250 h−1 ). Research on new catalysts is mainly focused at devel-
oping catalysts active at lower temperatures, although this is not
necessarily a critical issue, being stability, productivity and possi-
bility of heat recovery more relevant industrial parameters.
Zeolites, particularly H-ZSM-5, are catalysts giving good per-
formances at low temperatures (200–300 ◦ C), as shown in Fig. 4. At
300 ◦ C, HZSM-5 can reach an ethanol conversion level of 98% and
95% ethylene selectivity. The main disadvantage of HZSM-5 is its
acidity, which reduces its stability and coking resistance. Modifica-
tion with phosphorous to reduce acidity improves both selectivity
(over 99%) and stability. Modification with La (eventually as co-
dopant with P) leads also to interesting results. With almost 100%
ethylene selectivity and ethanol conversion and low temperatures
(about 240 ◦ C), 0.5% La–2% P-HZSM-5 is currently one of the best
catalysts [33]. Due to diffusional limitations, the use of nano-scale
zeolites [34] leads to better results. SAPO zeolites, such as the SAPO-
34 that is between the best catalysts for methanol to olefin (MTO)
reaction together with H-ZSM-5, show also good performances in
ethanol dehydration.
Another class of catalysts investigated was based on het-
eropolyacids. Ag3 PW12 O40 shows good performances, giving 99.2%
selectivity at 100% ethanol conversion in rather mild conditions
(220 ◦ C, GHSV = 6000 h−1 ) [35], but long term stability has to be
demonstrated. Supported heteropolyacids, particularly on meso-
porous silica [36], also give interesting performances (Fig. 4a).
Fischer-Tropsch to olefin. An alternative to produce light olefins
is the synthesis of syngas from biomass and then the conversion of
syngas via FTO (Fischer–Tropsch to olefin) process. The potential
advantage over bioethanol route is the possibility of using a larger
range of biomass sources, including especially biowaste, and the
possible higher degree of utilization of carbon in biomass. How-
ever, quality of syngas from biomass and the possibility to develop
an efficient and economic process at relatively small scale are still
challenges. The catalysts for FTO process have also to be improved.
Catalysts for FT reaction are well established, also in terms of reac-
tion mechanism and kinetics [37–40], but those for FTO still need
6 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12

Fig. 4. (a) Selected catalytic results for the dehydration of ethanol to ethylene. (b) Simplified reaction mechanism of ethanol conversion over mixed oxide catalysts.
(a) Adapted from Ref. [15], (b) adapted from Table 2 of Ref. [32].

further development as well the reaction mechanism better under- aspects, even if important, determine the industrial development
standing. There is a growing research activity to improve activity, routes in this specific area. We have shown how different aspects
selectivity, and stability of the catalytic system [41]. have to be considered for a correct assessment of the novel routes
In terms of reaction mechanism, the probability for the selec- in producing olefins [16]. We thus suggest that both bioethanol
tive formation of lower olefins increases with temperature (in the dehydration and syngas/FTO route have to be considered valuable
200–400 ◦ C temperature range, the typical one for FT reaction) routes to be assessed based on the specific local conditions and
and decreases at higher pressures and H2 :CO ratios in the feed. value chain.
Olefins can also be incorporated into the growing chain involving Conversion of C3/C4 alcohols or diols. In addition to the routes
a metallo-cyclobutane transition state followed by ␤-H transfer to from bioethanol or syngas, other opportunities are offered through
form ␣-olefins. It is thus necessary to prevent the re-adsorption of the intermediate synthesis of C3 or C4 alcohols (or alternatively
olefins which increases the formation of longer-chain compounds. diols) via fermentation processes. There are also microorgan-
Shorter contact times are preferable, but also the choice of the reac- ism strains which could produce directly propylene from glucose
tor is important. Operations in liquid phase (slurry-type reactors) media (together with various other hydrocarbons, such as propane,
allow limiting olefin readsorption and surface overheating due to
the exothermic reaction. Operations in a slurry reactor lead to max-
imize the yields of lower olefins.
Fig. 5 reports selected relevant literature results [41] in FTO reac-
tion. Selection has been based on the following constrains, which
are all relevant for the possibility of industrialization of the pro-
cess: (i) selectivity in CO conversion should be at least above 50%,
(ii) methane selectivity should be below 15%, (iii) testing has been
made at a pressure at least above 10 bar and using a H2 to CO ratio of
around 1.0. All the selective catalysts [42–44] are active in a temper-
ature range of about 320–340 ◦ C. Results refer mainly to lab-scale
experimentation. Although still improvements are necessary with
respect to indicative industrial targets (besides to have stable cat-
alytic performances), already quite interesting results have been
obtained. It is thus reasonable to expect that industrial targets can
be reached within few years of research.
It has to be remarked that Ruitenbeek and coworkers [31] con-
cluded in a feasibility study that bioethylene from sugar beet is
not commercially viable under current market conditions, neither
probably in the near future. They suggest that it would be prefer-
able for an integrated process route where a higher part of the
original carbohydrate backbone is retained in the final product
(ethylene), such as the syngas/FTO route. Although the Ruitenbeek
and coworkers [31] careful study has considered different busi-
ness cases, including imported ethanol and different options for Fig. 5. Selected catalytic results for synthesis of C2–C4 olefins from syngas. The
indicative industrial target (yield C2–C4 olefins higher than 75% with selectivity to
integrated ethanol production (50%) from upgraded raw juice (30%
methane lower than 10%) is also shown. Fe–Mn–Zn–K and Fe–Ti–Zn–K bulk cat-
sugar) or thick juice (70% sugar), in comparison with the fossil-fuel alysts: Ref. [42]; Fe–Na–S supported on CNF and ␣-Al2 O3 Ref. [43]; Fe/o-CNT Ref.
reference case, we have to remark that not only pure economic [44].
 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
butane, butene, pentene, etc.), but productivities are low and sep-
aration cost high.
Propylene could be synthesized from 1-propanol or 2-propanol
produced by fermentation, but actual productivities of the latter
are still low. Currently, it would be preferable to synthesize 1,2-
propanediol via biochemical pathways [45,46]. Dehydration of the
diol to 2-propanol and further to propylene occurs through a reac-
tion mechanism analogous to that discussed for ethanol, although
the selectivity is lower, being present more reactive hydrogen
species.
The alternative is the ABE fermentation process [47,48] leading
to ethanol, butanol and acetone, the latter reduced to propylene.
ABE fermentation (acetone–butanol–ethanol) with wild and genet-
ically modified strains (from the Clostridium family) is known from
long time, but has received renewed interest recently. However,
there are still many aspects to improve in order to produce n-
butanol at commercially attracting prices, such as (i) improve yields
of butanol, (ii) expanding substrate utilization and (iii) minimizing
energy consumption during separation and purification. Cost of n-
butanol is thus still high. It is necessary to develop micro-organisms
able to give the selective fermentation to butanol to make compet-
itive the synthesis.
In addition, it would be preferable to use directly the glycols
(1,2-propanediol, for example) obtained by catalytic conversion of
sugars or other platform molecule (glycerol, lactic acid) as sub-
stitute of those derived from fossil fuels (catalyzed ring-opening
of propylene oxide). Polyol Chemical Inc., for example, produces
propylene and ethylene glycols (together with other products such
as glycerine and butanediol) starting from sorbitol/glucose. The
process economics, however, are positive only using waste sugar
streams.
Production of butadiene. Butadiene is another interesting olefin
which can be produced from biomass-based routes alternative
to those starting from fossil fuels (naphtha steam cracking frac-
tions, or by dehydrogenation of butane). The reaction mechanism
of butadiene synthesis involves the dehydrogenation of ethanol
to acetaldehyde, followed by aldol condensation and dehydra-
tion. The reaction thus requires a bifunctional catalyst, having
both dehydrating and dehydrogenating functionalities. Although
known from long time, the exact reaction mechanism is still unclear
[49]. It is generally accepted that the aldol condensation between
two acetaldehyde molecules produces 3-hydroxybutanal which
then can be dehydrated to yield crotonaldehyde further hydro-
genated and dehydrated to give butadiene. However, still questions
exist about the rate determining step in the reaction, whether is
acetaldehyde or crotonaldehyde formation or instead other steps
such as the reduction to crotyl alcohol.
A one-pot process over MgO–SiO2 (doped with Na2 O) catalysts
(Lebedew process) is possible with an overall yield of 70% or more
[49]. Hüls is using this process from over three decade, but buta-
diene could be economic only using cheap bioethanol. Butadiene
could be used to produce various rubbers, or converted (via epox-
idation) to tetrahydrofuran and 1,4-butanediol. Posada et al. [50]
indicate the conversion of ethanol to ethylene or 1,3-butadiene
as promising routes for an integrated biorefinery concept, in con-
trast to other possibilities (for example, ethanol conversion to acetic
acid, n-butanol, isobutylene, hydrogen and acetone). Butanol dehy-
dration to butenes followed by dehydrogenation to butadiene has
been also presented as a value and an economic route [51].
In C4 diols, there is a considerable effect of the acidity on
the reaction network and mechanism [52]. Strong acid catalysts
such as SiO2 –Al2 O3 catalyze the dehydration at reaction temper-
atures below 250 ◦ C, while weak acid catalysts such as ZrO2 and
TiO2 require temperatures above about 300 ◦ C. This influences
also the paths of transformation. For example, SiO2 –Al2 O3 catal-
yses the dehydration of 1,3-butanediol into unsaturated alcohols,
7
consecutively dehydrated into 1,3-butadiene. Alumina alone
instead forms 4-methyl-1,3-dioxane, which is the acetal compound
of 1,3-butanediol and formaldehyde. Several compounds were pro-
duced over TiO2 and ZrO2 owing to the side reactions such as
dehydrogenation and hydrogenation.
On strong solid acids, the butadiene selectivity is still unsatis-
factory and thus more research is needed. On strong solid acids, the
butadiene selectivity is still unsatisfactory and thus more research
is needed. On the other hand, the method could be interesting
for the synthesis of unsaturated alcohols (raw materials for the
synthesis of various fine and specialty chemicals for applications
as medicines, perfumes, agricultural products). Over weak basic
oxides such as CeO2 at 325 ◦ C, 3-buten-2-ol and trans-2-buten-1-ol
are produced with selectivities of about 58% and 36%, respectively
[53].
An alternative route to butadiene is to produce 2,3-butanediol
(2,3-BDO) by fermentation of sugars, followed by dehydrated to
butadiene. LanzaTech has developed on a pilot-scale a fermentation
process to produce 2,3-BDO (using CO/H2 as feed). In joint venture
with other companies (Invista, a global nylon producer interested
to convert butadiene to adiponitrile, intermediate to manufacture
of Nylon 6,6), LanzaTech is also developing a process to convert 2,3-
BDO to butadiene via fermentation (leading in perspective to the
single-step production of butadiene via gas fermentation). Versalis
in joint venture with Genomatica is also developing the produc-
tion of butadiene via 2,3-BDO obtained by fermentation. There are
good perspectives that these routes (by sugar or gas fermentation)
will become commercially attractive, but productivity and cost of
separation are still critical elements.
Other olefins interesting for rubbers are also developed using
biomass. Genecor in joint venture with Goodyear is developing
a bio-isoprene production process, and Glycos Biotechnologies
plan also to commercialize the production of isoprene from crude
glycerine. Global Bioenergies and Gevo/Lanxess are developing
processes to produce isobutene from glucose or from isobutanol,
respectively. The latter is produced by fermentation, as demon-
strated on already relatively large scale by Gevo and claimed to be
competitive to the fossil-fuel based route to C4 olefins.
This short overview of the possible, and under development,
routes to make olefins from biomass shows that this is an area
with quite active research. It will significantly influence the future
scenario of biorefineries for chemical production. Although some
economic feasibility study put a question mark on the production of
olefin from biomass as shortly discussed before, we strongly believe
that by making a more extensive assessment than limited to only
economic parameters (with boundary limits at the plant gate), it is
possible to indicate that olefin biorefineries will play a significant
role on the future scenarios of chemical production. From the catal-
ysis perspective, there is need to still develope some of the catalysts,
both heterogeneous and bio-catalysts, particularly the latter rea-
sonably via metabolic engineering. At the same time, it is necessary
to strength synergies between these two areas, in order to lower
the costs and optimize productivities. The latter are still the critical
issue in biocatalytic routes, together with the costs of separation.
4.2. Biorefineries for sustainable chemical production and
towards integrated solar biorefineries
As discussed in more detail elsewhere [15,16], there is an evolv-
ing scenario for sustainable chemical production, driven from many
motivations going beyond the simple economic scenario. The lat-
ter is clearly important, but has to be assessed in the more general
perspective of competitiveness, governmental policies and pushes,
ecological aspects, etc. (see also Fig. 1). From this broader and less
conservative perspective, there is thus the need to develop alter-
native routes to produce intermediates in the chemical production
8 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
Fig. 6. Possible model for an integrated solar biorefinery approach.
value chain, which contribute to reduce the use of fossil fuels as raw
materials for the chemical industry (at least of 30% by year 2030). In
order to facilitate this transition, by reducing the investment costs,
it is important that these intermediates are drop-in products, e.g.
which can be inserted into the actual value chain. Drop-in prod-
ucts can be faster commercialized, being not necessary to create a
market and overcome many barriers (authorization, REACH, etc.)
necessary to introduce new chemicals/products.
The concept is thus of biorefineries which integrate into the
chemical production value chain by supplying building blocks
(olefins as discussed before or other base raw materials such as aro-
matics and syngas) or intermediate chemicals. There is the need
to fully exploit biomass as carbon source. The biomass compo-
nents which cannot be used for producing chemicals, can be used
to prepare energy products, from fuels to biogas or other options.
It will be also necessary to better exploit biorefinery emissions:
(i) water emissions, for example by using wastewater to feed a
microalgae plant together with some of the CO2 emitted during
fermentation and (ii) gaseous emissions, particularly CO2 , which is
rather pure and can be a suitable way to introduce solar energy in
the biorefinery chain to improve the carbon footprint [54].
There are different options possible to valorize CO2 emissions
from biorefinery [6a,16,54] and use this possibility to both decrease
the carbon footprint and increase the added value. However, sev-
eral of them do not fit well with the needs for future biorefineries
outlined before. We will thus discuss in the following section some
possibilities that we believe are more appropriate for future (sus-
tainable) biorefinery value chain. Similarly, we have focused the
discussion below on some key intermediates for chemical pro-
duction that we believe are more relevant for future schemes of
biorefineries and having more opportunities to become large vol-
ume productions. On the other hand, it is out of the scope and limits
of this review to discuss in detail all the possible paths. For the same
reason, discussion is centred mainly on outlining the aspects less
frequently discussed, but relevant to define the practical outlooks
for the discussed path. Limited space has been dedicated instead
to a detailed analysis of the catalyst structure–reactivity relation-
ships and reaction mechanism, because these aspects have been
analyzed in other cited papers.
Integrated solar biorefineries. This concept of integrated solar
biorefineries is emerging as an interesting opportunity. A possible
scheme for an integrated solar biorefineries is presented in Fig. 6.
It is based on a 2G bioethanol plant, where wastewater (still con-
taining significant amounts of carbon) is used, together with part
of CO2 emitted in the fermentation process, to feed a microalgae
plant producing high-added-value chemicals (nutraceuticals, such
as omega-3, etc.) and fuels (from the lipidic fraction, to produce
green diesel and jet fuel). The not used part of microalgae is then
fed to an anaerobic digestion to produce biogas, with the CO2 sent
again to microalgae plant while methane is used as substituted nat-
ural gas. Lignin produced as byproduct in the 2G bioethanol plant
is transformed to bio-oil by solar thermal pyrolysis, and the bio-oil
(after further upgrading) used as fuel additive. Furfural and part
of HMF, produced in the 2G bioethanol plant, are used to syn-
thesize chemicals and polymers along one or more of the routes
discussed later. Finally, part of CO2 , together with H2 deriving from
water and biowaste photoconversion, is catalytically converted to
methanol (or other chemicals/fuels). Methanol could be also used
to convert catalytically some of the less used fractions (furfurals,
for example) to high added value fine chemicals (fragrances and
flavouring agents, such as methyl-2-furoate, 2-acetylfuran, and
methyl-furfural).
There are other possible options for integrated solar biorefiner-
ies, but the model shown in Fig. 6 evidences a possible direction
towards the full use of carbon in biomass and the integration of
solar energy within the biorefinery scheme. In order to focus dis-
cussion, however, we will not further discuss this model of solar
biorefineries, but centre the analysis on the different routes to pro-
duce chemicals (intermediates) from biomass.
Intermediates for chemical production chain value. Several new
routes are under development for the production of interme-
diates starting from biomass or biowastes instead that from
fossil-fuels. An example is the production of 1,4-BDO which cur-
rent market is about 1.5 Mtons (mainly to polymers such as
polybutylene terephthalate, copolyester ethers and thermoplas-
tic polyurethanes). 1,4-BDO can be converted to tetrahydrofuran
(THF, used in some polymers synthesis or as solvent) and to
␥-butyrolactone (GBL), used in various syntheses for fine and spe-
cialty chemicals. Current production is a multi-step process, via
synthesis of maleic anhydride (MA) by catalytic selective oxidation
of n-butane, esterification of MA with ethanol followed by hydro-
genation to diethylsuccinate converted then to GBL and finally to
1,4-BDO with THF as co-product. It is thus a complex multistep
route. A key advantage of alternative routes is the possibility to
reduce the number of steps.
The current main alternative route passes through the pro-
duction of biosuccinic acid from sugars [55], eventually in
the presence of CO2 . Various companies (BASF, DSM, Rochette,
 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
Fig. 7. Selected routes in the conversion of 5-HMF to chemicals and fuels.
BioAmber, Purac, etc.) are working on pilot/demo scale production
of biosuccinic acid. Reverdia, the joint venture between DSM and
Roquette, started operations of the first commercial bio-succinic
acid plant (10,000 tonnes/year) in Cassano Spinola (Italy) in 2013.
Succinic acid can be then hydrogenated to BDO/THF. BDO can be
alternatively produced by direct fermentation of sugar (Genomat-
ica), or via formation of PHA (polyhydroxyalkanoate) (Metabolix).
Biosuccinic acid route is currently the most advanced, with good
perspective to become a main route to produce BDO/THF, mainly
because it reduces the process complexity and improves energy
& resource efficiency with respect to current path starting from
n-butane. Global succinic acid market is expected to reach about
half billion US$ by 2016, growing at a CAGR (compounded annual
growth rate) of 18.7% from 2011 to 2016. In fact, succinic acid is
a platform chemical that has a broad range of applications, from
high-value but niche applications such as personal care products
and food additives, to large volume applications such as plasticiz-
ers, polyurethanes, resins and coatings. The possible applications
for succinic acid, which are expected to grow in the near future,
are plasticizers, polyurethanes, bioplastics, and chemical inter-
mediates. The actual cost of biosuccinic acid is still about 20%
higher than from fossil fuel sources, but cost is expected to become
soon competitive. Biggest future potential for bio-based succinic
acid is for the production of BDO, PBS/PBST (polybutylene succi-
nate/polybutylene succinate-terephthalate) and polyester polyols.
Succinic acid is thus a valuable platform chemical for biobased
polymers from renewable resources [55–57], but there are also
other valuable platform chemicals, between which particularly
furfurals (also called furanics): 5-hydroxymethylfurfural (5-HMF),
furfural, 5-methyl-2-furaldehyde [58–60]. HMF finds application in
the production of various chemicals as well as fuels [58]. Some of
them are highlighted in Fig. 7 which reports selected conversion
routes to valuable high-volume chemicals and fuel components.
Between these routes, the following can be evidenced:
9
- caprolactam: commercially produced in a multistep process from
benzene; it is the monomer for Nylon-6;
- 1,6-hexanediol: commercially prepared by hydrogenation of
adipic acid; it is widely used for industrial polyester and
polyurethane production;
- adipic acid: commercially produced in a multistep process from
benzene; it is the monomer for Nylon-66.
5-HMF forms by acid-catalyzed dehydration of hexoses, par-
ticularly fructose which is the most reactive and selective. It is
thus necessary to isomerize glucose to fructose, if starting from the
former. Fructose dehydration is acid catalyzed, but a critical role is
played from the solvent, because it is necessary to minimize side
reactions of polymerization. With the best catalysts and reaction
conditions (temperatures of about 120 ◦ C, 2 h of reaction, dimethyl
sulfoxide – DMSO – or dimethylformamide – DMF – as solvents)
high yields in 5-HMF could be obtained even for high fructose con-
centrations [58]. Very high yields (>90%) are shown by a number
of catalysts, such as zeolites, heteropolyacids and acidic resins in
DMSO, but a continuous water removal is necessary. Amberlyst 15
is claimed to yield 100% HMF, even after recycling (three times) and
using a fructose concentrations higher than 50% [61]. In the case of
FePW12 O40 and H-BEA zeolite, the HMF yields decreased to below
50% at 50 wt% fructose concentration, while yields are above 90%
at low fructose concentration [58]. The same catalysts giving excel-
lent yield in HMF from fructose show lower performances starting
from glucose, and even worse starting from polysaccharides. The
HMF yields from cellulose are generally very low (<10%). There is
thus the need to develop novel multifunctional catalysts for the
selective HMF synthesis starting from polysaccharides.
Different catalysts are able to perform selectively the oxidation
of 5-HMF to 2,5-FDCA:
10 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12
- Pt supported on carbon or Al2 O3 gives 98% FDCA yield at complete
HMF conversion in the liquid phase oxidation with oxygen in the
presence of a base (need to keep the FDCA formed in aqueous
solution as dialkaline salt) [62]; reaction conditions are 100 ◦ C,
40 and 260 min for carbon and alumina supports respectively,
and 150 psi O2 .
- Au supported on hydrotalcite, which under similar reaction con-
ditions as above, gives nearly 100% FDCA yield [63]. This catalyst,
due to the use of a basic support, may avoid the use of a base,
being the support itself a base. However, strong chemisorption of
FDCA on the support may not cause complete recovery and possi-
ble catalyst deactivation over time. In addition, Pt-based catalysts
oxidize HMF to FDCA an order of magnitude faster than Au-based
catalysts.
Bimetallic catalysts, for example Au–Cu/TiO2 giving 99% FDCA
yield at 110 ◦ C for 4 h under 20 bar O2 [64], are used to improve
catalyst stability, but the latter remains a critical aspect in these
catalysts.
Direct synthesis routes of FDCA from fructose by combining
dehydration and oxidation have also been reported using Pt–Bi/C
in combination with a solid acid in water/MIBK. However, an FDCA
yield of only 25% was obtained. Direct (base-free) oxidative ester-
ification of HMF into the diester (which may be directly used
to produce polymers) was instead demonstrated by Corma and
coworkers [65] using Au/CeO2 as catalyst in methanol under 10 bar
oxygen in an autoclave reactor (yield about 99% at about 65 ◦ C).
Therefore, although some improvements in catalysts could be
still necessary, for example to avoid the use of a base and to have
more stable operations, catalysts for the selective oxidation of 5-
HMF to 2,5-FDCA are available. The potential market for FDCA is
huge mainly due to the variety of applications in which FDCA can be
used as a substitute. Chemicals, which can be potentially replaced
by FDCA, include:
- terephthalic acid in the production of PET, PBT and polyamides;
- bisphenol A in polycarbonates;
- adipic acid in the polyester polyols and plasticizers;
- phthalic anhydride in the polyester polyols and plasticizers;
- isophthalic acid in the production of modified PET.
In the field of polyamides market, FDCA may play a role for
completely novel polyamides. FDCA has also strong potential to be
used in the production of solvents, especially novel solvents. The
addressable market volume for FDCA is approximately 50 Mtons.
This could occur only when the price of FDCA will be competitive
with the price of chemicals, which would be replaced by FDCA or
derivatives. The current price for FDCA is over US$ 2300/ton and
is influenced by purity and quantity. From 2016, when large pro-
duction is expected, FDCA price will go down to approximately US$
1000/ton [66]. Emerging markets for FDCA are also polyester poly-
ols, used in polyurethanes, and polycarbonates, in which FDCA can
replace the toxic bisphenol A. Including these possibilities, the pro-
jected market for FDCA could increase to approximately 500 Mtons
[66], although probably this value is overestimated.
The initial driver for the development of FDCA market, how-
ever, will be for the synthesis of furanoate (PEF) (Fig. 7) and its use
as new material for packaging (alternatives to PET – polyethylene
terephthalate), particularly for bottles and other packaging which
are the main areas of use of bioplastic. This market is sensitive to
the green image of the product and thus there is interest from lead-
ing companies in this field (Coca Cola, Danone, for example) to use
bio-based containers which reduce, if not eliminate, the use of fos-
sil fuels. Avantium is between the companies with more advanced
development in the production of PEF via oxidation of 5-HMF to
2,5-FDCA.
FDCA and MEG (mono ethylene-glycol) are then used to pro-
duce polyethylene furanoate (PEF) (Fig. 7), a valid alternative to
PET with better O2 -barrier capacity. MEG can be also produced from
bio-resources, for example by one-pot catalytic conversion of cel-
lulose in the presence of H2 [67]. The reaction is quite selective and
could be alternative to the two-step current process involving the
synthesis of ethylene oxide (EO) by ethylene epoxidation, followed
by catalytic hydratation of EO. It is thus possible to produce 100%
biobased PEF which can substitute commercial PET. The driving
force for the development is from one side the social push to have
more sustainable commodities and from the other side the forma-
tion of a final product with superior performances (5-time higher
resistance barrier to O2 permeation).
Eerhart et al. [68] evaluated the energy and greenhouse gas
(GHG) balance in the production of the bioplastic polyethylene
furandicarboxylate (PEF) starting from corn based fructose and
compared to its petrochemical counterpart polyethylene tereph-
thalate (PET). The production of PEF can reduce the non-renewable
energy use (NREU) approximately 40–50% while GHG emissions
can be reduced approximately 45–55%, compared to PET for the
system cradle to grave. These reductions are higher than for other
biobased plastics, such as polylactic acid (PLA) or polyethylene (PE).
2,5-FDCA can be used also to make other valuable large-volume
chemicals, such as adipic acid. The hydrogenation of FDCA to
adipic acid occurs in a two-step process [69]. In the first step,
2,5-tetrahydrofuran-dicarboxylic acid is produced in 88% yield by
hydrogenating FDCA at 140 ◦ C for 3 h in acetic acid, catalyzed by Pd
on silica. Yields up to 99% of adipic acid were claimed by reacting
this product under hydrogen at 160 ◦ C for 3 h in acetic acid in the
presence 0.2 M of HI and 5% Pd on silica catalyst.
It should be observed that start-up companies such as Rennovia,
Verdezyne, BioAmber, Celexion, and Genomatica have developed
some alternative bio-based routes to produce adipic acid; some
have reached advanced pilot or demonstration scales. Adipic acid
has traditionally been produced from various petroleum-based
feedstocks (e.g., phenol, benzene, and cyclohexane), but shifts in
the hydrocarbon market have resulted in the virtual elimination of
phenol as a feedstock. In recent years, cyclohexane-based processes
have accounted for about 93% of global production capacity. Two
steps are involved in adipic acid production: (1) oxidation of cyclo-
hexane to produce KA oil (cyclohexanone and cyclohexanol) and (2)
nitric acid oxidation of KA oil to produce adipic acid. An example
is the DuPont/Invista cyclohexane-based process. The alternative
bio-based processes, in addition to that discussed above starting
from HMF, are developed by (1) Verdezyne using genetically mod-
ified enzymes to ferment glucose directly to adipic acid and (2)
Rennovia for using air oxidation to catalytically convert glucose to
glucaric acid, followed by hydrodeoxygenation to convert glucaric
acid to adipic acid. The latter process has a high potential to be cost
competitive with the conventional cyclohexane oxidation process.
The advantage of both bio-routes is their use of US$ 300/ton glucose
feedstock, compared to the conventional process using cyclohex-
ane having a market price of US$ 1250/ton in 2012 [70]. However,
selectivity and catalyst productivity have to be improved, and as
well as higher enzyme turnover rates should be achieved.
Another valuable high-volume chemical which can be produced
from HMF is caprolactam. A multistep route to produce caprolac-
tam (the monomer for nylon-6) or 1,6-hexanediol (monomer for
high performance polyesters, polyurethane resins, and adhesives)
has been proposed by de Vries and co-workers [71]. HMF is hydro-
genated in >99% yield to 2,5-bishydroxymethyl-tetrahydrofuran
which can be then further hydrogenated to 1,6-hexanediol in 86%
yield, by using a Rh–Re/SiO2 catalyst in the presence of Nafion. This
is a tandem three-step process proceeding through the formation of
1,2,6-hexanetriol, which is cyclized under the influence of the acid
to tetrahydropyran-2-methanol, which in turn is hydrogenated to
 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12 11

1,6-hexanediol using the same catalyst. The diol can be then con- gasification, syngas fermentation and distillation of ethanol from
verted into caprolactone using a ruthenium catalyzed Oppenauer the reactor effluent is still at semi-commercial development (BRI
oxidation in virtually quantitative yield. Overall selectivity from energy), as well the use of CO fermentation to produce ethanol from
HMF to caprolactone was 86%. Conversion of ␧-caprolactone into steel mill off-gas (LanzaTech). However, the extension to the direct
caprolactam can be made selectively using ammonia at 170 bar and use of CO2 is still challenging. However, it is known that Ni and Fe
300–400 ◦ C (UCC process), but an alternative catalytic route would containing metalloenzyme such as Clostridium thermoaceticum cat-
be preferable. alyzes the reversible oxidation of CO to CO2 , and purple non-sulfur
Glycerol, produced in large amounts as by-product during bacteria are able to produce H2 in a process similar to the WGS
bio-diesel production, is another example of renewable plat- (water–gas shift) reaction.
form molecule. Glycerol can be catalytic converted to C3 diols These examples outline some of the possibilities existing in the
(alternative method to the production by fermentation, or from frame of biorefineries to valorize the CO2 emissions and at the same
propylene). 1,2-Propanediol (1,2-PDO or propylene glycol; it is cur- time reduce the carbon footprint.
rently produced from propylene via propene oxide) is used as
chemical feedstock for the production of unsaturated polyester
5. Conclusions
resins, besides other uses. 1,3-Propanediol (1,3-PDO) has also a
wide range of applications, from the synthesis of polytrimethy-
There are many factors influencing a significant evolution in the
lene terephthalate (PTT, mainly used in carpet industry) to the
model of biorefineries of the future with respect to few years ago.
potential substitution of propylene glycol, 1,4-butanediol (BDO),
Sustainability and integration with chemical production are two of
and butylene glycol in number of applications. Glycerol can be also
them driving the need to explore new concepts. We have limit dis-
catalytically dehydrated to acrolein and then catalytically oxidized
cussion to the case of integrated chemical biorefineries, and how
to acrylic acid and acrylate esters [72,73], which are also important
the new scenarios for a sustainable chemical production require
monomers for polymer industry. The main current limitation for
to develop new models of biorefineries, which probably should be
the industrial development of this process is the large uncertain
better indicated as bio-factories. In fact, the use of biomass as well
in definying the long-term trend in price of glycerol. This is one of
as of other resources such as bio-waste and CO2 , particularly in
the main motivations having inhibited the industrial exploitation
regions poor of other resources such as Europe, open new scenarios
of these processes.
to develop a sustainable and low carbon chemical production. The
CO2 valorization in biorefineries. As commented shortly before,
chemical production will be thus the target for bio-economy rather
there are many possible options to use the CO2 streams produced in
than biofuel production. There are many motivations for this tran-
biorefineries, particularly those from fermentation processes being
sition to a new economy and some of them were shortly discussed,
characterized from high CO2 concentration (>99%) [54]. In addition
although not the focus of this contribution centred on analysing
to the possibilities shortly described in the section on integrated
how this new scenario will impact on new concepts and models for
solar biorefineries, other interesting possibilities regard
biorefineries.
Two cases are discussed in detail: (i) olefin biorefineries and
i) the production of succinic acid from glucose and CO2 via
(ii) biorefineries for sustainable chemical production. In addition,
biotechnological routes (discussed above);
some elements for an integrated solar biorefinery approach are also
ii) the Evonik process of production of acetone from CO2 and H2
given. The status of catalysis research to enable the development of
also via enzymatic routes;
these biorefinery models was discussed, together with an analysis
iii) the CO/CO2 gas fermentation process (particularly developed
of the industrial developments in the field and some elements of
by LanzaTech, but actively studied also by other companies) to
assessment of the different routes. The aim was to provide funda-
produce bioethanol, but also other products such as acetic acid
mentals to understand how this area is evolving, and thus identify
and 2,3-butandiol;
where research effort has to be focused. It was also commented
iv) chemo-catalytic routes to produce drop-in intermediates, an
how the simple economic analysis, with boundary limits to plant
interesting example (although still under development) being
gate, although important, is not enough to properly identify the
represented from the synthesis of acrylic acid from CO2 and
future scenarios.
ethylene, the latter derived from bioethanol. This route is devel-
In conclusion, the panorama for chemical production is fast
oped especially by BASF researchers, although the possible
evolving and new raw materials derived from biomass, substituting
industrialization is still rather challenging [74,75].
fossil fuels for sustainability motivations and to develop a low car-
bon society, will become a main driver to develop novel production
The latter example, may be a competitive route to produce
routes. Catalysis is a key element to enable this possibility, but it is
acrylic acid from glycerol, shortly discussed above. It is also possi-
necessary to clearly identify both the new directions of research
ble, as a potential alternative, the reaction of CO (obtained from CO2 ,
and the remaining critical aspects on which focus the research.
either using water–gas-shift bacteria or electro- or photo-processes
For this reason, we have limited discussion here on aspects such
using RE sources) with ethylene oxide (derived from ethylene gly-
as structure–activity relationships and reaction mechanism in the
col, also produced via enzymatic routes) to form propiolactone then
discussed catalysts (being these aspects discussed in other papers),
converted to either glacial acrylic acid or acrylate esters. This route
to try to first identify the most promising routes and then the key
is developed by Novomer using its proprietary catalysts.
aspects on which focus investigation from an exploitation perspec-
The carboxylation of alkenes occurs instead through the forma-
tive.
tion of metallolactones, particularly of Ni and Pd, but which are
We hope that this conceptual review was contributing to
quite stable molecules. The difficulty is thus how close is the cycle.
achieve these goals.
Recently, however, BASF researchers [75] realized the first catalytic
synthesis of acrylate from CO2 and alkene, although the turnover
number is still low (about ten) and two separate steps are necessary. Acknowledgements
Interesting possibilities are also offered from gas fermentation
processes. Acetogens microorganisms (for example, Clostridium The authors acknowledge the PRIN10-11 project “Innovative
ljungdahlii) can produce fuels and chemicals by syngas utiliza- processes for the conversion of algal biomass for the production
tion. The production of ethanol by a process combining biomass of jet fuel and green diesel” and the EU IAPP project nr 324292
12 P. Lanzafame et al. / Catalysis Today 234 (2014) 2–12

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