Вы находитесь на странице: 1из 22


Potential routes for thermochemical

Pedro Haro,* Pedro Ollero, ngel L. Villanueva Perales and Fernando Vidal-Barrero, University of
Seville, Spain

Received January 17, 2013; revised February 22, 2013; accepted February 27, 2013
View online April 29, 2013 at Wiley Online Library (wileyonlinelibrary.com); DOI: 10.1002/bbb.1409;
Biofuels, Bioprod. Bioref. 7:551572 (2013)

Abstract: This critical review focuses on potential routes for the multi-production of chemicals and
fuels in the framework of thermochemical biorefineries. The up-to-date research and development
in this field has been limited to BTL/G (biomass-to-liquids/gases) studies, where biomass-derived
synthesis gas (syngas) is converted into a single product with/without the co-production of electricity
and heat. Simultaneously, the interest on biorefineries is growing but mostly refers to the biochemical
processing of biomass. However, thermochemical biorefineries (multi-product plants using thermo-
chemical processing of biomass) are still the subject of few studies. This scarcity of studies could be
attributed to the limitations of current designs of BTL/G for multi-production and the limited number of
considered routes for syngas conversion. The use of a platform chemical (an intermediate) brings new
opportunities to the design of process concepts, since unlike BTL/G processes they are not restricted
to the conversion of syngas in a single-reaction system. Most of the routes presented here are based
on old-fashioned and new routes for the processing of coal- and natural-gas-derived syngas, but
they have been re-thought for the use of biomass and the multi-production plants (thermochemical
biorefinery). The considered platform chemicals are methanol, DME, and ethanol, which are the
common products from syngas in BTL/G studies. Important keys are given for the integration of
reviewed routes into the design of thermochemical biorefineries, in particular for the selection of the
mix of co-products, as well as for the sustainability (co-feeding, CO2 capture, and negative emissions).
2013 Society of Chemical Industry and John Wiley & Sons, Ltd

Keywords: thermochemical biorefinery; methanol; DME; ethanol; butanol; acetic anhydride

Introduction mass yield of first-generation processes often makes them

unprofitable at current biomass prices. Furthermore,
urrently, the use of biomass as a renewable source expected future regulation of biofuels in the EU could

C accounts for the production of first-generation

ethanol and FAME (fatty acid methyl ester) biodie-
sel, in addition to the generation of heat and power.
exclude them or impose strong limitations in order to
fulfi ll the sustainability criterion.1 In response to that,
second- generation processes have been proposed and
Nonetheless, there is controversy over the use of food- several demonstration projects, based on the biochemi-
competitive biomass for the production of fuels. The low cal conversion of lignocellulosic biomass, are reported for

Correspondence to: Pedro Haro, Bioenergy Group, Chemical and Environmental Engineering Department. Escuela Tcnica Superior
de Ingeniera, University of Seville. Camino de los Descubrimientos s/n. 41092 Seville, Spain. E-mail: pedrogh@us.es

2013 Society of Chemical Industry and John Wiley & Sons, Ltd 551
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

the production of non-food-competitive bioethanol.2,3 In renewable source for carbon-based fuels and chemicals
a prior stage of development are the BTL/G (biomass to (essential for the production of, for example, fibers,
liquids/gases) processes, focusing on the thermochemical plastics, or jet fuel). For instance, the use of biomass via
conversion of biomass into synthesis gas (syngas) or pyrol- thermochemical processing is related to the former car-
ysis oil, which is then converted into products. Research bochemistry and the production of chemicals via reform-
on BTL/G processes is limited to various types of potential ing of natural gas. Being close to current petrochemical
bio-products,48 i.e. Fischer-Tropsch (FT) diesel,916 etha- facilities should be considered an advantage, since both
nol,1724 methanol,14,15,2531 DME,16,29,30,3236 H2, 25,26,30,37,38 the technology and the know-how from the processing
synthetic natural gas (SNG), and urea.11,14,15,3943 Each of of fossil fuels can be adapted and integrated in BTL/G
these processes has focused on the production of a single plants and thermochemical biorefi neries. Of course, the
fuel, either with or without the co-production of heat/ use of petrochemical technologies involves that BTL/G
electricity. Rather than producing a single product, a plants and thermochemical biorefi neries should be large
more interesting option is a multi-product plant, either by enough to achieve the benefits of the economy of scale as
combining two or more known BTL/G processes, or based in petrochemical facilities.
on a chemical intermediate (platform chemical).14,44 In a Contrary to current BTL/G processes, in a thermochem-
thermochemical biorefinery, fuel, chemicals, and power ical biorefinery, multi-production is the main objective. In
are co-produced. A first technoeconomic assessment of a thermochemical biorefinery, the existence of a platform
such a multi-product plant (thermochemical biorefinery) chemical brings different options for multi-production.
based on a platform chemical has shown there are impor- The platform chemical could be a product itself or con-
tant benefits compared to studied BLT/G plants, i.e. greater verted into more products, i.e. following two (or more)
profitability due to the co-production of high value prod- different routes resulting in different products. The design
ucts, the possibility of overcoming (e.g. in ethanol syn- of thermochemical biorefineries is of greater complexity
thesis) the limitations of product selectivity and a better than in the case of BTL/G processes. The chemical routes
energy and material integration.44 assessed in studied BTL/G processes could be used in the
Wit hin second-generation processes, different concepts design of thermochemical biorefineries (combining two
of biorefineries are the subject of special attention nowa- or more), but as they are not properly suitable for multi-
days. Despite the uncertain classification of biorefineries,* production, the review of other routes (especially for the
a thermochemical biorefinery involves (in the opinion production of chemicals) is of interest. In this context,
of the authors) the processing of biomass and carbon- several routes were proposed for the production of chemi-
based waste, i.e. organic fraction of municipal solid waste cals and fuels from syngas in the 1980s due to the crude oil
(MSW), to generate (simultaneously) products and serv- crisis, which promoted the search of an alternative feed-
ices covering fuels, chemicals, heat, and electricity from stock (i.e. natural gas or coal) to substitute crude oil for
syngas. chemical and fuel production. In some routes, syngas was
The production of fuels, chemicals, and services from converted into methanol, which is a platform chemical
syngas presents little or no differences if coal or natu- for the production of for example, gasoline (methanol-to-
ral gas are used as feedstock. However, the benefits of gasoline (MTG)) and olefins (methanol-to-olefins (MTO)).
the use of biomass instead of such fossil fuels are well Biomass and carbon-based waste are also suitable as crude
known. Biomass has a better GHG (greenhouse gas) bal- oil substitutes, since the processing downstream of syngas
ance (could even be negative regarding the process); it conditioning is identical. The main advantage of routes
enhances the security of the energy supply (in case bio- via platform chemicals for the design of new concepts
mass is produced in the same region); and it is the only of thermochemical biorefineries is their capability to be
combined or slightly modified to achieve multi-product
generation, as has already been demonstrated.44
*Classification of biorefineries is still under discussion, particu-
larly for the case of thermochemical processing of biomass. The In this review, the most appealing platform chemicals
Bioenergy Task 42 (International Energy Agency) has as its objec- suitable for the design of thermochemical biorefiner-
tive the classification of biorefinery systems and has proposed a ies have been identified: methanol, DME, and ethanol.
classification method based on four features (i.e. platforms, prod- Compiled routes via platform chemicals are described and
ucts, feedstocks, and processes).45 Although this classification
revised in detail, while the well-reported MTG and MTO
method is useful, for example, for C5/C6 sugars and lignin platform
systems, it may not be best option in order to make a thorough
routes are only briefly reviewed. Implications of the use of
classification of biorefineries using syngas as a platform.46 biomass and carbon-based waste are also detailed together

552 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

with one example of thermochemical biorefineries based bed (i-CFB) operated with air are the proposed gasification
on DME as the platform chemical. technologies for syngas production from lignocellulosic
biomass.13,14,20,26,39,52 Gasification of carbon-based waste
General aspects of thermochemical is also feasible, but the variability of its chemical composi-
processing tion makes it technologically more difficult.51 Raw syngas
from the gasifier needs different cleaning and condition-
Selection of the thermal treatment of biomass depends
ing treatments, which depend on the further processing of
on further use of the product. For BTL/G processes, the
thermochemical processing of biomass usually involves
gasification or pyrolysis .4750 This review will focus only
on synthesis routes via gasification. Routes via platform chemicals
The chemistry of these routes is always characterized by
Gasification, gas cleaning, and conditioning
the presence of at least one chemical intermediate (plat-
Gasification of all carbon-based feedstocks (biomass, coal, form chemical) generated from syngas. The platform
carbon-based waste) undergoes the same basic chemistry chemical can be directly converted into products or con-
and thermodynamics.51 The gasification process can take verted into a new chemical intermediate. Most routes were
place at temperatures in the range of 800C to 1800C, initially proposed in the 1980s as consequence of the crude
but in the case of biomass gasification, temperatures are oil crisis, since they allow replacing crude oil with coal
always below 1300C due to softening and melting tem- and natural gas with the production of commodities and
peratures of the biomass ashes.51 Currently, entrained flow fuels. The recovery of crude oil prices led to their abandon-
bed (EFB) and circulating fluidized bed (CFB) operated ment; however, their use has recently been reconsidered
with oxygen and steam, and indirect circulating fluidized for the processing of biomass. Figure 1 shows the routes

Figure 1. Thermochemical routes via platform chemicals (methanol/DME and ethanol) for the
production of chemicals and fuels from syngas.

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 553
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

via platform chemicals which have been reviewed. Most C2H5OH C2H4 + H2O (20)
routes are based on the use of methanol or DME, which is
easily generated from methanol (dehydration). Ethanol is 2C2H5OH C4H9OH + H2O (21)
also included as a platform chemical, although bioethanol
is usually not produced from syngas, but directly from Methanol/DME as a platform chemical
The chemical equations which are involved in routes via The production of methanol from syngas is well docu-
platform chemicals are presented below: mented and represents one of the most important indus-
trial applications of syngas.2527,53 Methanol synthesis
CO + 2H2 CH3OH (1) (Eqn (1)) can be described as a set of two exothermic
reversible reactions, namely conversion of CO via water
CO + H2O CO2 + H2 (2) gas shift reaction to CO2 (Eqn (2)), and hydrogenation of
CO2 to methanol (Eqn (3)).54 The catalyst used for metha-
CO2 + 3H2 CH3OH + H2O (3) nol synthesis is a Cu-ZnO supported on alumina (Al 2O3),
which has been improved to achieve selectivity to metha-
2CH3OH CH3OCH3 + H2O (4) nol over 99%.54 Typical reaction conditions for methanol
synthesis are 200300C and 40100bar.54,55 Industrial
3CO + 3H2 CH3OCH3 + CO2 (5) production of methanol is carried out using different
reactor configurations. The most important reactors for
CH3OH + CO + 2H2 C2H5OH + H2O (6) commercial production of methanol are: tube cool con-
verter, radial flow steam raising converter (R-SRC), axial
CH3OH + 2CO + H2 C2H5OH + CO2 (7) flow steam raising converter (A-SRC), quench converter
(Johnson Matthey Company);56,57 combined synthesis
CH3OH + CO CH3COOH (8) converter (Lurgi Air Liquid Group);58 methanol super
converter (Mitsubishi Heavy Industries); 56,59 collect-mix-
CH3COOH + 2H2 C2H5OH + H2O (9) distribute (CMD) reactor, boiling water reactor (Haldor
Topsoe);56,57 axial radial concept (ARC) quench type reac-
CH3COOH + CH3OH CH3COOCH3 + H2O tor, horizontal steam raising reactor, pseudo isothermal
(10) reactor (Methanol Casale);56,60 Variobar converter (Linde
AG);55,61 MRF-Z converter (Toyo Engineering);61 and liq-
CH3COOH + C2H5OH CH3COOCH2CH3 uid-phase methanol (LPMEOH) reactor (Air Products and
+ H2O (11) Chemicals, Inc.).56,62
DME can be produced directly from syngas (Eqn (4)) or
CH3COOCH3 + 2H2 C2H5OH + CH3OH(12) indirectly via methanol dehydration (Eqn (5)).63,64 Typical
reaction conditions are 250400C and up to 20 bar, using
CH3COOCH2CH3 + 2H2 2C2H5OH (13) a dehydration catalyst, for example, -alumina or zeo-
lites.65,66 Direct synthesis of DME from syngas is described
2CH3OH + CO CH3COOCH3 + H2O (14) in the literature.6769 Typical reaction conditions are close
to methanol synthesis and the catalyst employed is a mix-
CH3OCH3 + CO CH3COOCH3 (15) ture of methanol synthesis and dehydration catalyst.70 In
the case of methanol dehydration, industrial production
CH3OCH3 + CO + 2H2 C2H5OH + CH3OH (16) of DME is carried out using fi xed-bed reactors, whereas in
the case of direct synthesis similar reactors to those used
CH3COOCH3 + CO (CH3CO)2O (17) for methanol synthesis are employed.

(CH3CO)2O + C2H5OH CH3COOCH2CH3 Methanol homologation to ethanol

+ CH3COOH (18) The methanol homologation, or methanol reductive
carbonylation, route was the first studied route via a
(CH3CO)2O +CH3OH CH3COOCH3 platform chemical (1951) to produce ethanol from syn-
+ CH3COO (19) gas; it remains the most investigated to date.71 Methanol

554 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

homologation was envisioned along with direct conversion molecule. However, promoters and additives are required
of syngas to ethanol as an alternative process to produce in order to increase the rate of reaction and selectivity,
ethanol from coal.72 Despite great interest in the 1980s, the and avoid complex irreversible degradation.78 Promoters
methanol homologation route has been almost disregarded can be present in different chemical species, for example,
and neither a pilot plant nor a commercial process based CH3I, phosphine.79,80 Additives, mainly oxygenate com-
on this route has been constructed.4 For a profitable appli- pounds, affect product distribution since most are prod-
cation of the methanol homologation route, development ucts of the secondary reactions during homologation.8185
of non-toxic homogeneous catalysts which could be easily These additives shift secondary reactions, which are in
(and economically) recovered, or heterogeneous/supported equilibrium, at operating conditions of methanol homolo-
catalysts achieving yields to ethanol similar to those in the gation. Attempts to use heterogeneous or supported cata-
case of homogeneous catalysts, are needed. lysts are reported in the literature but the results obtained
The methanol homologation route consists of two con- are still unsatisfactory.86,87
secutive steps to make ethanol from syngas: methanol Despite the great number of patents and publications
synthesis (Eqn (1)) and methanol homologation (Eqn(6) available on the methanol homologation route, neither
or Eqn (7)). In a possible process based on this route, a commercial process, nor even an industrial program
syngas would be first converted in a methanol synthesis has been developed. The only active project, at laboratory
reactor and the outlet stream would be directly fed to the scale, the Dry Ethanol Process, is being carried out by the
homologation reactor where unconverted syngas and pre- Argonne National Laboratory.9397 This process follows
viously generated methanol react at 150200C and high Eqn (7), so no water is generated, and uses an Fe-Mn-
pressures (100300bar) producing ethanol, and to a lesser based homogeneous catalyst with n-methylpiperidine
extent, oxygenates and hydrocarbons. as the promoter. The main advantage of this route is the
The methanol homologation step can be carried out via absence of water in products, which makes the recovery of
different kinds of homogeneous catalysts. The first study ethanol easier.93
of methanol homologation was presented by Wender There is a lack of knowledge on the deactivation of the
etal. using a Co-based homogeneous catalyst in a batch methanol homologation catalyst. According to Ishogai,
reactor.71 Depending on the H2/CO molar ratio in the it would be possible to use syngas with low contents of
homologation reactor feed, the homologation can occur methane, ethylene and CO2 without a significant negative
by Eqn (6) or Eqn (7), resulting in the generation of either impact on the catalyst.85 Due to the scarcity of informa-
water or CO2 as a by-product. Table 1 shows the common tion, the experience gained from the most similar proc-
chemical states for the studied homologation catalysts ess, acetic acid synthesis (Monsanto Process), could be
along with the main promoters for the reaction. A detailed helpful.54,78
description of the kinetics and reaction mechanism of the Research on methanol homologation following Eqn
homologation reaction is presented elsewhere.7377 The (6) is limited at laboratory scale, but there are some pat-
main active complex in the homologation reaction can be ents describing preliminary conceptual designs.81,88 In
described by the formula [M(CO)n]d, where M represents a similar way to LPMEOH synthesis, the homogeneous
the active component, n is the coordination factor (fre- catalyst requires the presence of an inert solvent to carry
quently: 3, 4, 12) and d is always negative (often -1). This out the reaction.81 The solvent, for example, the same
complex allows itself the CO insertion in the methanol used in LPMEOH, has to ensure liquid-liquid equilibrium

Table 1. Chemical state for the catalyst used in the methanol homologation route.
chemical state
component Acetate Carbonate Carbonyl Formate Oxide Carboxylate Elemental Chloride Organic Ref.
active 72,90
promoter I

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 555
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

(water-products/solvent-catalyst-syngas).83 Hence, the

methyl acetate
benzoic acid

homologation of methanol should be carried out, for

example, in a batch reactor, a continuous stirred tank reac-
tor (CSTR), a bubbling column with internal recycle, or
another kind of reactor available for homogeneous cata-

P (bar) time (min) molar ratio XCO XMethanol Ethanol Propanol acetate Oxygenatesc CO2 CH4 Others Water
lysts. Table 2 shows a collection of reaction data for metha-

nol homologation following Eqn (6). Although general
references claim that methanol homologation needs pres-


sure of about 300 bar, that was only true in the first stage
of development of the homologation catalyst.98 The use

of promoters allowed a reduction of operating pressure,

which is limited by the condition of retaining methanol

as liquid in the reactor (usually limited to a total pressure

product yield (%)

of 50 bar). Detailed information on product selectivity
for a catalyst with Ru can be found in Jenner.99 Through

Table 2. Reaction conditions, product distribution and main additives for homologation catalysts.

the use of additives, ethanol selectivity is improved up to


Methanol to ethanol via acetic acid


The acetic hydrogenation route consists of a set of com-

mon steps: methanol synthesis (Eqn (1)), acetic acid syn-

thesis (Eqn (8)) and acetic acid hydrogenation (Eqn (9)).
As shown in Fig. 2, syngas is used for methanol synthesis,
and also to provide CO for the synthesis of acetic acid. 52.71

Produced methanol is carbonylated using a homogene- 89f
ous catalyst. Acetic acid is then directly hydrogenated to

ethanol and water. Regarding the conditions of the acetic

acid hydrogenation, i.e. considered catalyst and reaction

conditions, more steps could be needed for subproduct

conversion by recycling or chemical conversion in addi-

tional reactors.101
reaction conditionsa

The acetic acid hydrogenation route was developed in


the early 1980s.4 This route is based on the hydrogena-

tion of acetic acid to yield ethanol, and to a lesser extent,

acetates using heterogeneous catalysts. The employment


of a heterogeneous catalyst is the main advantage of this

route compared with the methanol homologation route.
All collected data refers to batch reactors.

As in the case of methanol homologation, the end of the

Propanol, propanal and methyl acetate.

Selectivity to ethanol and acetic acid.


crude oil crisis was the main reason for its withdrawal,
but in the case of the acetic acid hydrogenation route, the

corrosiveness of the reaction mixture (with a detrimen-

T (C)


tal effect on the life of hydrogenation catalyst) was also

Refers to all catalysts.

The synthesis of acetic acid is one of the most impor-

Other oxygenates.

N/A = not available.


tant examples of industrial processes using homogene-

Co-I catalyst88

Acetic acid.

ous catalysts. When the hydrogenation of the acetic acid


route was in the first stage of development, conventional

synthesis of acetic acid was mainly conducted via the
Monsanto process operating at 150200C and 3060 bar



556 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

Figure 2. Chemical scheme for the acetic acid
hydrogenation to ethanol.
Oxygenatesb CO2
product yield (%)

with very high selectivity to acetic acid.104 The Monsanto

process uses an Rh-based homogeneous catalyst, which is
converted in-situ into an active Rh-carbonyl catalyst for
methanol homologation.104 Currently, BPs Cativa process

has emerged as the best available technology for acetic acid

production.105 The Cativa process is similar to Monsantos

except for the catalyst. In the Cativa process, an Ir-based


catalyst is used, featuring a higher catalyst lifetime and

better stability and recovery.105,106

The hydrogenation of acetic acid is carried out at liquid


phase (and high H2 pressure) using a conventional catalyst

for organic compound hydrogenation.107,108 Typical reac-
XMethanol Ethanol

tion conditions for the ENSOL process are 230270C and

40120 bar.108 A detailed description of kinetics and reac-

tion mechanisms along with catalyst behavior can be found

elsewhere.103,109111 Catalysts considered in the literature for
acetic acid hydrogenation to ethanol are Co, Cu, Fe-based

dispersed on silica support,112 supported Pt-based and

Pd-based catalyst.103,109,110,111,113 These studies differ from
Table 3. Reaction conditions for the Dry Ethanol Process.

the ENSOL process in operating conditions. Whereas the

BASF process achieves near complete conversion of acetic
H2/CO molar

acid at moderately high pressures (40120bar),108 the other

reaction conditionsa

studies always operated at near atmospheric pressure and


achieve very low per pass conversion of acetic acid (around


5%) with high lights formation.107,112 According to the reac-

tion mechanism, acetaldehyde is the main intermediate of
time (min)

the reaction and sometimes the reaction could not proceed

further depending on catalyst and operating conditions
All collected data refers to batch reactors.

(partial pressure of H2).111 Therefore, acetic acid conversion

to acetaldehyde is the subject of more studies in the litera-
P (bar)

ture than to ethanol. The reaction is quite selective to etha-


nol, ethyl acetate and n-butanol being the only by-products

in the aqueous phase, and with low gas formation (CO and
T (C)

methane).108 Both liquid by-products can be partially con-

Other oxygenates.
N/A = not available.

verted into ethanol by recycling them into the reactor.108

The reaction mixture (aqueous phase) is highly corrosive,

which leads to rapid catalyst degradation, and becomes


the main limitation for the reaction. Although reaction in

the vapor phase could avoid catalyst degradation by reduc-

ing the corrosiveness of the reaction mixture, extremely


2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 557
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

Table 4. Reaction conditions and product distribution for acetic acid hydrogenation catalysts.
reaction conditiona product yield (%)
GSHV H2/acetic Ethyl
Catalyst T (C) P (bar) (h1) acid Conversion Ethanol acetate Oxygenatesb CO2 CH4 Others
Co-Cu-Mn-Mo108 230270 40120 N/A 2.1 100 97 N/A N/A N/A 0 N/A
Pt-Sn 250 1422 2500 10-4 2243 1540 37 0 0 0 N/A
114 c d
Co-Mo-S-K 325 100 6372 N/A 100/72.2% NA N/A N/A N/A N/A N/A
Referred to all catalysts.
Other oxygenates.
Defined as L/(kgcath).
Conversion of acetic acid.
N/A= not available

high partial pressures of H2 (of at least 270 bar) would be from biomass. A new process configuration has been
needed.108 Recent efforts to produce new catalysts for the recently described by Jetvic et al.118
hydrogenation of acetic acid have been conducted by Range
Fuels Inc. and Celanese International Corp.114,115 Celanese Methanol to ethanol via acetic acid
has developed a Pt-Sn catalyst (Table 4) that allows higher esterification
productivity for acid acetic hydrogenation to an ethanol/
The acetic acid esterification route consists of a set of
ethyl acetate mixture with remarkably high space velocity
different processes in which one mole of acetic acid is
and global selectivity (to both ethanol and ethyl acetate).115
esterified with one of alcohol to give one mole of the corre-
Other recent improvements in hydrogenation catalysts, i.e.
sponding ester. The produced ester is easily hydrogenated
nano Pd-based catalyst, have been carried out by BASF.116
(hydrogenolysis) to alcohols, yielding two moles of alco-
The ENSOL process was developed by a joint-venture
hol per mole of ester. One mole of alcohol is used for the
between Humphreys & Glasgow Ltd, Monsanto, and
esterification of acetic acid, whereas the other would be the
BASF based on the acetic acid hydrogenation route, but
product. To our knowledge, only two alcohols have been
neither a pilot plant nor further research has been done.107
studied, i.e. methanol and ethanol. Chemical schemes for
According to the original scheme of the process, methanol
both cases are shown in Figs 3 and 4. Although this route
is produced either on-site or off-site using natural gas as
feedstock. If methanol is produced on-site, it can be used
as raw methanol without enhanced purity.107 Acetic acid is
produced from CO and methanol, and further converted
into ethanol by hydrogenation (Fig. 2). As water is pro-
duced in the hydrogenation of acetic acid, a dewatering
section is also required in the process.107 A combination
of cryogenic distillation and pressure swing adsorption
(PSA) was considered the technical solution to achieve the
required purity of CO and H2 streams.107 The requirement Figure 3. Chemical scheme for the acetic acid esterification
of high purity CO and H2 streams represents a disadvan- with methanol.
tage of this route, since it is intensive in both energy and
economy. However, the main limitation for further devel-
opment of this route lies in the degradation of the catalyst
for the acetic acid hydrogenation.
On the basis of reaction data from the Pacific
Northwest National Laboratory, which made a tech-
noeconomic assessment of this route, the calculated
ethanol minimum selling process was higher than cur-
rent market price.108,117 In this assessment, CO and H2
for both acetic acid production and hydrogenation were Figure 4. Chemical scheme for the acetic acid esterification
assumed as raw materials, i.e. they were not produced with ethanol.

558 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

was developed in the early 1980s, only recently have some for the catalyst.139 There are also studies on vapor-phase
processes become commercial, such as that by Enerkem esterification, including in a supercritical CO2 atmosphere,
Inc., which uses MSW as feedstock.101,119,120 but they are not commercially viable.139,141,142
In this route, acetic acid can be produced as described Hydrogenation (hydrogenolysis) of methyl or ethyl
earlier, or via acid carbonylation (a combination of Eqns acetate is carried out with heterogeneous catalysts in
(8) and (14)). The first case is applicable for both methanol fi xed-bed reactors. Various catalysts have been used for
and ethanol, whereas the second makes sense only if the both reactions but at reaction conditions. For common
considered alcohol for the esterification is methanol. The Cu-Cr (Adkins) catalysts reaction conditions are severe,
methanol acid carbonylation is close to common acetic i.e. 250350C and a partial pressure of H2 of 100300
acid synthesis but, in this case, it is carried out in acid bar.122,143 Other catalysts used for acetate hydrogenation
conditions leading to in situ esterification of part of the are Cu-Fe,144 Re-based,145 Pd-ZnO,146 hydrotalcites,143
generated acetic acid with methanol.121127 For acid carbo- Ni-based and Rh-based catalysts.147,148 Reaction conditions
nylation, typical molar selectivity to both acetic acid and for these catalysts are close to those from the Cu-Cr cata-
methyl acetate is up to 80%, with a 3:1 molar distribution lyst, but with lower H2 pressures (up to 60 bar).143 Ethanol
of acetic acid and methyl acetate, respectively.121,126,127 selectivity ranges from 60 to 95%, the main by-products
Reaction conditions for the acid carbonylation of metha- being higher acetates (produced by homologation of the
nol are presented in Table 5. The in situ esterification original acetate) and acetaldehyde. However, in these
reduces the size of the acetic acid esterification section, previous studies, acetate hydrogenation (hydrogenolysis)
since a fraction of methyl acetate is produced in the car- is carried out in the absence of CO. Recent publications
bonylation reactor. More information about methanol based on a Cu-ZnO catalyst claim that the hydrogenation
carbonylation over heterogeneous catalysts can be found of acetates (methyl and ethyl acetates) can be carried out
elsewhere.128133 in the presence of CO with a H2 to CO molar ratio of 1, at
The esterification of methanol and acetic acid is an equi- lower partial pressures of H2 (<15 bar) and with similar or
librium-limited reaction, like most esterification reactions, higher selectivity to corresponding alcohols.149151
which can be conducted in regular fi xed-bed reactors, The Halcon SD Group proposed a process based on the
but it is normally conducted by reactive distillation.135 acetic acid esterification route for the production of etha-
The reactive distillation of acetic acid and methyl acetate nol using methanol and natural gas as feedstock.101 In
is currently the best available technology (BAT) for the this process, methanol is carbonylated to produce acetic
production of methyl acetate.136 The reaction system was acid using a proprietary technology similar to Monsantos
developed by the Eastman Kodak Company and it uses an process. Esterification of acetic acid is carried out with
acid catalyst, for example, sulfuric acid or a sulfonic acid methanol recycled from the hydrogenation section using
ion exchange resin, for the esterification.137,138 proprietary technology (Eastman Kodak). Produced
Esterification of ethanol and acetic acid is also an methyl acetate is hydrogenated to yield an equimolar mix-
equilibrium-limited reaction, but in this case, a ternary ture of methanol and ethanol. CO and H2 for the process
azeotrope is present.101,139 Industrial production of ethyl are produced by reforming natural gas.101 BASF AG pro-
acetate can be conducted in batch or CSTR reactors along posed another alternative based on this route which used
with several distillation columns.140 The same considera- acid carbonylation (Table 5).122 In this process, methanol
tions as in the esterification with methanol are applicable is carbonylated to yield a mixture of methyl acetate, acetic

Table 5. Reaction conditions and product distribution for methanol acid carbonylation catalysts.
reaction conditiona product yield (%)
CO/methanol Methyl
Catalyst T (C) P (bar) GSHV (h1) molar ratio Conversion acetate Acetic acid
Rh-I-triphenylphosphine 175 40 1 N/A 64.0% Methanol 41.6 22.4
b 134
Rh-Ir 255 10 2500 2 99.8% Methanol 80.1 18.3
Rh-Ir-Ib 126,127 150200 1550 200010000 10.2 100% CO 5075 2550
Referred to all catalysts.
Supported catalyst (on activated carbon).
N/A= not available.

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 559
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

acid, DME, and to a lesser extent, ethanol and propionic

acid.122 Produced methyl acetate is then hydrogenated, as
commented before. In this process, acetic acid from the
acid carbonylation is recycled to the carbonylation reac-
tor for total conversion to methyl acetate. There are other
process alternatives such as that by the Korea Institute
of Science and Technology, which proposed a supported
catalyst for the acid carbonylation of methanol with no Figure 5. Chemical scheme for DME carbonylation.
recycling of acetic acid.134
Recently, Enerkem Inc., proposed the modification
(depending on the syngas composition and plant configu-
of previous BASF and Korea Institute of Science and
ration) normally leads to a net production of H2.
Technology processes by adding a stage for acetic acid
The carbonylation of DME occurs in the presence of
esterification in order to achieve complete conversion to
some kinds of zeolites, for example, mordenites, ferrierites
methyl acetate.126 In this process, methanol is carbon-
and ZSM-35, at reaction conditions of up to 100 bar and
ylated to a mixture of methyl acetate and acetic acid in
150200C.131,156,157 The carbonylation reaction is said to
the vapor phase using a fi xed-bed reactor packed with a
be conducted with a stable rate and without significant
rhodium-based catalyst.127 Acetic acid is further esteri-
catalyst deactivation.131,156 Presence of water in the reac-
fied with methanol by reactive distillation yielding methyl
tion mixture decreases methyl acetate formation and
acetate. Methanol from the hydrogenation of methyl
slightly increases that of methanol. This is because of the
acetated is recycled to esterification section. If ethanol is
competition of water for the active sites of the zeolite.131,152
used instead of methanol for the esterification, only etha-
However, this effect is reversible and does not deactivate
nol would be produced (hydrogenation of ethyl acetate,
the catalyst.131 Methyl acetate synthesis rates are propor-
Eqn (13)) and no distillation of the methanol/ethanol
tional to CO pressure and independent of DME.131 DME
mixture would be required. However, the use of ethanol
carbonylation is primarily conducted in 8-MR channels,
does not result in the reduction of costs, due to the greater
in the case of mordenites, or in 10-MR channels, in the
complexity of the acetic acid esterification.101 Enerkem has
case of ZSM-35.156,157 There is a possible deactivation
announced that it expects to produce competitive bioetha-
due to coke formation on the catalyst.132,157 Details for
nol in the short term with its process.120
the kinetics of the DME carbonylation are given else-
where.133,152,156,158 The DME carbonylation route has
Methanol/DME to methyl acetate via DME been technoeconomically assessed along with the DME
carbonylation hydrocarbonylation route.44 Results showed that methyl
acetate can be produced economically from lignocellulosic
The DME carbonylation route relates the production of
methyl acetate through DME by using only heterogene-
ous catalysts. This route is based on the capability of
Methanol/DME to ethanol via DME
some catalysts, for example, zeolites, to synthetize methyl
acetate from CO and DME. The carbonylation of DME to
yield methyl acetate is a new and active field of research.152 The DME hydrocarbonylation route is the most recent
Although this route can be integrated with acetic anhy- attempt to find a feasible technoeconomic route to pro-
dride production, it is preferable to discuss each one duce ethanol from lignocellulosic biomass.44,52,149151,159
separately, since they are focused on a different product. The DME hydrocarbonylation route is an extension of the
Methyl acetate is currently available as a subproduct in the DME carbonylation route, where a hydrogenation step is
commercial production of acetic acid or produced by reac- added leading to ethanol production. In this route, pro-
tive distillation from acetic acid and methanol.153 The uses duced methyl acetate is hydrogenated to yield methanol,
of methyl acetate are as a solvent (substitute for acetone), which is recycled to complete conversion, and ethanol. For
and for the production of acetic anhydride.154,155 ethanol production, the DME hydrocarbonylation route
The DME carbonylation route comprises the combina- outweighs the above described processes focused on etha-
tion of DME synthesis and DME carbonylation (Eqn nol production (with acetic acid as intermediate), since the
(15)), as shown in Fig. 5. Syngas is used for DME synthesis number of process steps is lower and only heterogeneous
and to provide CO for the carbonylation of DME, which catalysts are employed.

560 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

The DME hydrocarbonylation route (Fig. 6) comprises

the following steps (some alternatives are possible): DME
synthesis, DME hydrocarbonylation (Eqn (16)) and
methanol dehydration (Eqn (4)). The hydrocarbonylation
of DME has been studied in a dual catalytic-bed reactor,
where catalysts for carbonylation of DME and hydro-
genation of methyl acetate were placed in series.149151,159
Results of these studies show that the hydrocarbonylation
can be effectively conducted at 220C and 15 bar using the
combination of a first catalytic bed of H-Mordenite and a
second catalytic bed of Cu-ZnO. 149151
The DME hydrocarbonylation route has been technoeco-
nomically assessed.44,52 The results showed that the DME
hydrocarbonylation route is cost-competitive for ethanol
production from lignocellulosic biomass, due to the mild
reaction conditions and high global selectivity to ethanol.
Figure 6. Chemical scheme for the DME hydrocarbonylation
route. Adapted from Haro et al.44 The dashed line means
Methanol/DME to acetic anhydride via recycling.
methyl acetate carbonylation
The methyl acetate carbonylation route was developed in
the 1980s in an attempt to overcome the ketene process in
the synthesis of acetic anhydride.136,160 Acetic anhydride
is one of the most important organic intermediates in
the industry and it is used for the production of cellulose
acetate and as a precursor of vinyl acetate monomer.161 In
the methyl acetate carbonylation route, acetic anhydride is
produced through acetic acid (Eqns (8,10)) or DME (Eqns
(4,15)), which leads to the two alternatives shown in Fig.7. Figure 7. Chemical scheme for methyl acetate carbonylation
Acetic anhydride production through acetic acid repre- through DME.
sents, along with the ketene process, the main commercial
means of acetic anhydride production.136,161
Methanol to ethanol via acetic anhydride
The carbonylation of methyl acetate is a process derived
from methanol carbonylation, using Rh-based homogene-
ous catalysts. In methyl acetate carbonylation, H2 has to The acetic anhydride esterification route was proposed
be present as a reduction agent for the catalyst, and also by the Halcon SD Group in the 1980s.101,160,163 This route
to avoid acetic anhydride hydrolysis. Other differences relates to the capability of acetic anhydride to yield
between methyl acetate and methanol carbonylation relate acetates via esterification with alcohols. Several process
to the choice of promoters (LiI) and the reaction mecha- configurations are applicable to this route, but only two
nism, as described by Zoeller.136,162 are appealing. In both configurations the main product is
The Eastman Kodak Company, in collaboration with the ethanol. However, neither one has been commercialized or
Halcon SD Group, proposed the first commercial process further investigated.
using methyl acetate carbonylation. The process aimed to In the first alternative, methanol reacts with acetic acid
use coal as feedstock and the final product would be cel- to form methyl acetate, which is then converted into acetic
lulose acetate.136,160 In this process, methyl acetate reacts anhydride by carbonylation with CO (Eqn (17)).163 The
with CO to yield acetic anhydride which is converted in acetic anhydride is esterified with ethanol (Eqn (18)) to
the plant into cellulose acetate. Reaction of acetic anhy- yield ethyl acetate and acetic acid. Acetic acid is recycled
dride and cellulose leads to the production of acetic acid to the first esterification (Eqn (10)), whereas ethyl acetate
as a by-product, which is used for the esterification with is hydrogenated to ethanol (Eqn (13)). A fraction of gen-
methanol.136 erated ethanol is used for the esterification with acetic

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 561
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

Figure 8. Chemical scheme for the acetic anhydride esterification route (with ethanol).
Dashed lines mean recycling.

anhydride. Figure 8 shows the chemical scheme in the case found in Olsbye et al.166 The conversion of methanol/DME
of acetic acid esterification with ethanol. into gasoline results in light gases, hydrocarbons in the
In the second alternative, an equimolar mixture of light and heavy gasoline range, and water. The most prob-
methanol and ethanol react with acetic anhydride to yield lematic compound of the heavy gasoline fraction is durene
a mixture of methyl and ethyl acetate, (Eqns (19) and (1,2,4,5-tetramethyl-benzene) which needs to be further
(18)).101 Methyl acetate is recycled for acetic anhydride processed in order to meet current gasoline specifica-
production (Eqn (17)) and ethyl acetate hydrogenated (Eqn tions.170 The upgraded heavy gasoline is blended with the
(13)) to yield ethanol as a product. light gasoline fraction to give commercial grade gasoline.
Both fi xed-bed and fluidized-bed technologies have
Methanol/DME to gasoline been proven for the MTG route in commercial plants.
Details of process design and plant economics are given
The methanol-to-gasoline (MTG) route was developed in
elsewhere.164,165,171 Technoeconomic assessments on gaso-
the 1980s in response to the crude oil crisis. The consid-
line production from lignocellulosic biomass have been
ered feedstock was natural gas, as a substitute to crude oil,
recently published.21,170,172,173
which made the process especially attractive for isolated
locations with access to natural gas.164,165 The first com-
mercial plant based on the MTG route was constructed in
Methanol/DME to olefins
New Zealand (1985) using fi xed-bed technology.166 Other The methanol/DME to olefins (ethylene and propylene)
facilities were constructed, but most of them were shut route was developed simultaneously with the methanol/
down when crude oil prices made the process unprofit- DME to gasoline route and both routes have important
able.164 DME can also be used (and is sometimes preferred similarities.164,172 Regarding conversion section, UOP has
for the thermal integration of the reactor) as the chemi- developed the so-called methanol-to-olefins (MTO) proc-
cal intermediate for conversion to gasoline.167 At present, ess using a fluidized catalytic reactor.164,166,168 This design
there is new interest on this route, not focused only on is the best available technology for methanol conversion to
natural gas as the feedstock but also on coal and biomass. olefins.164
Exxon Mobile and Haldor Topsoe are the most important Details for the kinetics and reaction conditions for the
licensors of this technology. methanol/DME conversion into olefins are presented else-
Kinetics for methanol/DME to gasoline conversion where.164,166169 In general, catalysts (zeolites) for the produc-
is described elsewhere (focused on methanol conver- tion of olefins are characterized by smaller pore sizes com-
sion).164,168,169 Methanol/DME to gasoline conversion is a pared to the production of gasoline.169 Lower partial pres-
complex reaction pattern of methylation, oligomerization, sures of DME and higher reaction temperatures lead to a shift
hydrocarbon formation and cracking using zeolites as in the product distribution to lighter hydrocarbons.167 The
catalysts.168,169 Further discussion on process technolo- main products are ethylene and propylene, making up about
gies and other aspects such as catalyst deactivation can be 84% on mass basis of total hydrocarbons produced.164,174

562 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

This route has been recently assessed.172 Results showed is commercially available.176,178 Some industrial projects are
that olefins could be produced efficiently from lignocellu- currently being carried out.179
losic biomass but at higher costs than current production, The dehydration of ethanol (Eqn (20), Fig. 9) is con-
mainly due to the feedstock price. ducted at 180400C and atmospheric pressure achieving
selectivities of over 95% to ethylene.176,179183 As in the case
Methanol/DME to fuels (gasoline, diesel of methanol dehydration, zeolites are the preferred catalyst
and jet fuel) for ethanol dehydration, but a carbon-based catalyst has
also been studied.180,184 Main by-products depend on the
In this route, olefins are converted into hydrocarbons in
employed catalyst, but the most cited are ethane, propyl-
the range of gasoline, diesel and jet fuel. The conversion of
ene, butylenes, and diethyl-ether.178,180,181 The presence of
olefins can be conducted in a fi xed-bed reactor at variable
water in the reaction mixture has an important effect on
reaction conditions which leads to different productions
selectivity to by-products and on ethanol conversion.180,181
of each fraction. A description of such a process is given
Water prevents catalyst deactivation due to coke forma-
by Avidan and was developed by Mobil.164,175 Despite the
tion.180 Details on the kinetic and process conditions can
greater complexity of this route, the gasoline fraction is
be found elsewhere.180183,185
usually better quality, as the durene content is lower com-
The BETE (bioethanol-to-ethylene) process was studied
pared to gasoline produced via the MTG route.164,169,175
in the 1980s as an attempt to use raw ethanol from first-
However, there is a lack of public information on specific
generation processes as feedstock.185 However, there is no
reaction conditions and process configuration.
new information about this process. Currently, there are
several projects in Brazil, due to the availability of low-cost
Ethanol as a platform chemical ethanol.176,186 A technoeconomic assessment for ethylene
production using bioethanol as feedstock has been recently
The following routes relate to the use of ethanol as a plat-
carried out.187
form chemical. Obviously, these routes are independent of
the origin of ethanol, which could come from lignocellu-
losic biomass (second-generation processes), for example,
Ethanol to propylene
from sugarcane, corn or sugarbeet (first-generation proc- Propylene can be produced from ethanol.188 In this route,
esses), or even from a fossil feedstock. Hence, the discus- the ethanol feedstock is dehydrated to ethylene and then a
sion will include the processing of all kinds of ethanol portion of ethylene is dimerized to produce normal butene.
regardless of their provenance. The butenes are then reacted with the remaining ethylene
via the metathesis reaction to produce propylene.188 The
Ethanol dehydration to ethylene chemistry of olefins metathesis is described elsewhere.189,190
The ethanol dehydration route relates to the production of
ethylene using ethanol. There is growing interest in this route,
Ethanol to butanol
since the apparent relatively low-cost of bioethanol makes it Recently, some companies have focused their efforts on the
attractive for chemical synthesis.176 Ethylene production from production of renewable butanol from ethanol, because of
ethanol represents one of the most feasible options at present the enhanced properties of butanol as a gasoline substitute
from both a technical and economic point of view.177 The and as a chemical precursor.191 The conversion of etha-
dehydration of ethanol is an established technology which nol to butanol (Eqn (21)) is called catalytic condensation,

Figure 9. Conceptual diagram for the ethanol dehydration route.

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 563
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

dimerization or reductive dehydration. Some catalysts methods leading to these routes (they were first studied
are active for the reaction: MgO,192 hydroxyapatites,193,194 some time ago) because they could be used in a multi-
Cu-Mg-Al mixed oxides and hydrotalcites.195,196,197 production plant. For this propose, an example of design
Depending on the selected catalyst, the reaction is con- is given, based on the use of DME as a platform chemical.
ducted at temperatures ranging from 250 to 450C and Since the reviewed routes were developed for the use of fos-
atmospheric pressures.192195,197 Details of ethanol conver- sil feedstock instead of biomass and waste, the impact of
sion to butanol are given elsewhere.192198 Technological the change in syngas composition needs to be clarified, for
development of this route is still limited and public techn- example, in the case of natural gas as original feedstock. This
oeconomic assessments on the routes are scarce.199 and other preliminary questions for the further design of
Butanol can be further processed for the production of thermochemical biorefineries are introduced.
renewable jet fuel and chemicals but further research is
still needed to optimize process conditions and quality of Example of thermochemical biorefinery
the fuel.200202
An example of thermochemical biorefinery based on
routes via platform chemicals has been recently proposed
Ethanol dehydrogenation to ethyl acetate by Haro et al.44 In this assessment, the DME carbonylation
Ethanol can be dehydrogenated to yield ethyl acetate, i.e. and hydrocarbonylation routes were selected to bring up to
the reverse reaction to Eqn (13). The chemistry basis of two sets of thermochemical biorefinery concepts. Potential
ethanol dehydrogenation is analogous to reverse hydro- products considered in that study were: methyl acetate, H2,
genation; details are given elsewhere.203205 The produc- DME and electric power (DME carbonylation), and etha-
tion of ethyl acetate from renewable ethanol using the nol, H2, DME and electric power (DME hydrocarbonyla-
technology licensed by Kvaerner Process Technology Ltd tion). The study proved that concepts based on routes via
has been recently reported indicating that the route could platform chemicals have better or at least similar econom-
be cost competitive.206,207 ics to BTL/G processes, despite their greater complexity.44
In addition, a previous study confirmed that the DME
Other routes to chemicals hydrocarbonylation route can overcome the limitation of
the direct synthesis of ethanol from without a negative
Important efforts are being made for the conversion of
effect on economics.4,5,20,52,55,217
ethanol into a wide range of hydrocarbons, for example,
gasoline and aromatics, following similar processing to
the methanol case. Information of this processing can be
Impact of feedstock and selection of the
found elsewhere.208213 mix of products
The impact of using lignocellulosic biomass or carbon-
Other platform chemicals based waste instead of other fossil fuels raises two
As shown earlier, there is limited development of ther- important considerations regarding the design of thermo-
mochemical routes via platform chemicals. To date, chemical biorefineries.
only methanol, DME, and ethanol have been considered First, each feedstock (coal, natural gas, biomass, or carbon-
platform chemicals, but there are other potential com- based waste) processing (gasification) leads to a different
pounds of interest, for example, butanol and methane. syngas composition, i.e. different H2/CO molar ratios, which
The conversion of light hydrocarbons to high-value com- must be compared with the optimum H2/CO ratio required
pounds could be one example, although these efforts are in each route. For the single production of ethanol the opti-
focused on the use of natural gas as feedstock. Currently mum H2/CO ratio would be 2, except for the Dry Ethanol
research is being conducted into the efficient conversion of Process (with a ratio of 0.5). For the single production of
methane into methanol.214216 gasoline and olefins from methanol/DME, the ratio is also
2. However, in the case of single methyl acetate production
the ratio would be 1.33, and 1 in the case of acetic anhydride.
Discussion Finally, in the case of ethanol as a platform chemical, only
in the case of ethanol dehydrogenation to ethyl acetate the
The review provides a variety of routes via platform chemi- ratio would be 1.5 instead of 2. If single production is sought,
cals to be taken into account for the design of thermochemi- then natural gas (which presents a H2/CO ratio of 3) would
cal biorefineries. However, it is still necessary to define the be more appealing than coal, biomass or carbon-based waste

564 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

as feedstock, which leads to much lower ratios in the syngas Conclusions

(0.51.0); and therefore, some routes via platform chemi-
cals were intended to use natural gas according to the given The use of recent and old-fashioned routes via a platform
description. Furthermore, the H2 excess in the processing chemical facilitates the design of new concepts of thermo-
leads to a net production of H2. In the case of lower H2/CO chemical biorefineries. The reviewed routes demonstrate
ratios using other feedstock, the water gas shift (WGS) reac- to be capable for the (simultaneous) multi-production of
tion is usually the best option to achieve enhanced conver- chemicals and fuels and therefore they serve as a keystone
sion to products, but with an important reduction of carbon for the future designs of thermochemical biorefineries.
and energetic efficiency. However, as thermochemical biore- Despite the lack of technoeconomic assessments based
fineries are focused on multi-production, a lack of H2 could on these routes the results from a recent publication show
be overcome by a balanced design of the mix of co-products, that they could be profitable if the mix of co-products is
i.e. what and in which amount will be produced from syngas well selected.44 The presented routes bring a wider range of
within the thermochemical biorefinery. An example was potential bio-products, both chemicals and commodities,
given earlier where ethanol production (which requires a different to those considered up to date and therefore allow
ratio of 2) was compensated with DME production (which more possibilities for the selection of the mix. The fact that
requires a ratio of 1). the reviewed routes could be applied to a fossil feedstock,
Second, it seems clear that beside syngas generation for example, coal and natural gas, is a natural consequence
and conditioning, the most important differences within of the concept of a thermochemical biorefinery and an
the feedstock relate to availability, price and sustainable advantage, since both the technology and the know-how
nature. These factors should be balanced by simultane- from the processing of fossil feedstocks can be adapted and
ously assessing the economics and sustainability of the integrated in a thermochemical biorefinery. Finally, some
process. In the case of carbon-based waste, for example, guides for the further work on thermochemical biorefineries
plastics, they are usually derived from crude oil so should are given like the need of a minimum basis of agreement on
not be classified as a neutral carbon feedstock. However, LCA methodology and sustainability criterion.
their growing volume represents a problem in landfi lls and
recycling suffers from a technical and economic mismatch.
The use of MSW in thermochemical processing may be
an interesting option to be assessed. Another opportunity This review has been funded by the Spanish Ministry
would be the study of co-feeding, i.e. combination of car- of the Economy and Competitiveness and carried out
bon neutral and other feedstock, such as plastics, natural in the framework of the project BIOTER (Proyecto de
gas or coal. Some authors have studied the subject, but Investigacin Fundamental No-Orientada; ENE2012-
further research is still necessary.218-223 31598). The grant given by the Spanish Ministry of the
Education (FPU Program; AP2010-0119) to P. Haro is
Further research on thermochemical acknowledged.
In the opinion of the authors, studies on thermochemical References
biorefineries need common criteria for sustainability and 1. European Commission, New Commission proposal to mini-
mise the climate impacts of biofuel production. [Online]. Press
comprehensive life cycle assessment (LCA) methodology,
release (2012). Available at: http://europa.eu/rapid/press-
which include the specificity of the multi-production, fos- release_IP-12-1112_en.htm [19, October 2012].
sil and waste feedstock co-feeding, and the integration of 2. Sims REH, Mabee W, Saddler JN and Taylor M, An overview of
carbon capture and sequestration (CCS) technologies. The second generation biofuel technologies. Bioresource Technol
101(6):15701580 (2010).
removal of CO2 in a plant using carbon neutral feedstock
3. Menon V and Rao M, Trends in bioconversion of lignocellu-
would lead to negative GHG emissions, ready to be sold lose: Biofuels, platform chemicals & biorefinery concept. Prog
as CO2 certificates. Hence, there is an opportunity in ther- Energ Combust 38(4):522550 (2012).
mochemical biorefineries and common BTL/G processes 4. Subramani V and Gangwal SK, A review of recent literature to
to improve economics and/or fulfill sustainability if co- search for an efficient catalytic process for the conversion of
syngas to ethanol. Energ Fuel 22(2):814839 (2008).
feeding is considered. These proposals should be performed
5. Spivey JJ and Egbebi A, Heterogeneous catalytic synthesis
in current and upcoming assessments of thermochemical of ethanol from biomass-derived syngas. Chem Soc Rev
biorefineries. 36(9):15141528 (2007).

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 565
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

6. Zinoviev S, Mller-Langer F, Das P, Bertero N, Fornasiero (2011). Available at: http://www.nrel.gov/docs/fy11osti/47594.

P, Kaltschmitt M et al., Next-generation biofuels: Survey pdf [1, October 2012]
of emerging technologies and sustainability issues. 22. He J and Zhang W, Techno-economic evaluation of thermo-
ChemSusChem 3(10):11061133 (2010). chemical biomass-to-ethanol. Appl Energ 88(4):12241232
7. Zhang W, Automotive fuels from biomass via gasification. Fuel (2011).
Process Technol 91(8):866876 (2010). 23. Dutta A, Talmadge M, Hensley J, Worley M, Dudgeon D
8. Floudas CA, Elia JA and Baliban RC, Hybrid and single feed- et al., Process Design and Economics for Conversion of
stock energy processes for liquid transportation fuels: A criti- Lignocellulosic Biomass to Ethanol: Thermochemical Pathway
cal review. Comput Chem Eng 41:2451 (2012). by Indirect Gasification and Mixed Alcohol Synthesis,
9. Tijmensen MJA, Faaij APC, Hamelinck CN and Van Hardeveld Report No. NREL/TP-5100-51400, Contract no. DE-AC36-
MRM, Exploration of the possibilities for production of fischer 08GO28308. National Renewable Energy Laboratory, Golden,
tropsch liquids and power via biomass gasification. Biomass CO (2011).
Bioenerg 23(2):129152 (2002). 24. Dutta A, Talmadge M, Hensley J, Worley M, Dudgeon D,
10. Hamelinck CN, Faaij APC, den Uil H and Boerrigter H, Barton D et al., Techno-economics for conversion of lignocel-
Production of FT transportation fuels from biomass; technical lulosic biomass to ethanol by indirect gasification and mixed
options, process analysis and optimisation, and development alcohol synthesis. Environ Prog Sustain Energ 31(2):182190
potential. Energy 29(11):17431771 (2004). (2012).
11. Zwart RWR and Boerrigter H, High efficiency co-production of 25. Katofsky RE, The Production of Fluid Fuels from Biomass,
synthetic natural gas (SNG) and fischer-tropsch (FT) transpor- Report no. 279. Princeton University, Center for Energy and
tation fuels from biomass. Energ Fuel 19(2):591597 (2005). Environmental Studies, Princeton, NJ (1993).
12. Kreutz TG, Larson ED, Liu G and Williams RH, Fischer-Tropsch 26. Hamelinck CN and Faaij APC, Future prospects for produc-
Fuels from Coal and Biomass. Proceedings of the 25th Annual tion of methanol and hydrogen from biomass. J Power Source
International Pittsburgh Coal Conference, PCC 29 September 111(1):122 (2002).
- 2 October (2008). 27. Yin X, Leung DYC, Chang J, Wang J, Fu Y and Wu C,
13. Larson ED, Jin H and Celik FE, Large-scale gasification-based Characteristics of the synthesis of methanol using biomass-
coproduction of fuels and electricity from switchgrass. Biofuel derived syngas. Energ Fuel 19(1):305310 (2005).
Bioprod Bioref 3(2):174194 (2009). 28. Clausen LR, Houbak N and Elmegaard B, Technoeconomic
14. Meerman JC, Ramrez A, Turkenburg WC and Faaij APC, analysis of a methanol plant based on gasification of bio-
Performance of simulated flexible integrated gasification mass and electrolysis of water. Energy 35(5):23382347
polygeneration facilities. Part A: A technical-energetic assess- (2010).
ment. Renew Sust Energ Rev 15(6):25632587 (2011). 29. Clausen LR, Elmegaard B, Ahrenfeldt J and Henriksen U,
15. Meerman JC, Ramrez A, Turkenburg WC and Faaij APC, Thermodynamic analysis of small-scale dimethyl ether (DME)
Performance of simulated flexible integrated gasification poly- and methanol plants based on the efficient two-stage gasifier.
generation facilities, part B: Economic evaluation. Renew Sust Energy 36(10):58055814 (2011).
Energ Rev 16(8):60836102 (2012). 30. van Rens GLMA, Huisman GH, de Lathouder H and
16. Trippe F, Frhling M, Schultmann F, Stahl R, Henrich E and Cornelissen RL, Performance and exergy analysis of biomass-
Dalai A, Comprehensive techno-economic assessment of to-fuel plants producing methanol, dimethylether or hydrogen.
dimethyl ether (DME) synthesis and FischerTropsch synthesis Biomass Bioenerg 35(1):S145S154 (2011).
as alternative process steps within biomass-to-liquid produc- 31. Holmgren KM, Berntsson T, Andersson E and Rydberg T,
tion. Fuel Process Technol 106:577586 (2012). System aspects of biomass gasification with methanol synthe-
17. Phillips SD, Technoeconomic analysis of a lignocellulosic bio- sis - process concepts and energy analysis. Energy 45(1):817
mass indirect gasification process to make ethanol via mixed 828 (2012).
alcohols synthesis. Ind Eng Chem Res 46(26):88878897 32. Hu J, Wang Y, Cao C, Elliott DC, Stevens DJ and White JF,
(2007). Conversion of biomass syngas to DME using a microchannel
18. Zhu Y, Gerber MA, Jones SB and Stevens DJ, Analysis of the reactor. Ind Eng Chem Res 44(6):17221727 (2005).
Effects of Compositional and Configurational Assumptions 33. Semelsberger TA, Borup RL and Greene HL, Dimethyl ether (DME)
on Product Costs for the Thermochemical Conversion as an alternative fuel. J Power Source 156(2):497511 (2006).
of Lignocellulosic Biomass to Mixed Alcohols FY 2007 34. Zhang X, Solli C, Hertwich EG, Tian X and Zhang S, Exergy
Progress Report, Pacific Northwest National Laboratory WA analysis of the process for dimethyl ether production through
(USA) (2008). biomass steam gasification. Ind Eng Chem Res 48(24):10976
19. Dutta A and Phillips S, Thermochemical Ethanol via Direct 10985 (2009).
Gasification and Mixed Alcohol Synthesis of Lignocellulosic 35. Clausen LR, Elmegaard B and Houbak N, Technoeconomic
Biomass. [Online]. NREL/TP-510-45913 (2009). Available at: analysis of a low CO2 emission dimethyl ether (DME)
http://www.nrel.gov/docs/fy07osti/41168.pdf [1, October 2012] plant based on gasification of torrefied biomass. Energy
20. Villanueva Perales AL, Reyes Valle C, Ollero P and Gmez- 35(12):48314842 (2010).
Barea A, Technoeconomic assessment of ethanol production 36. Tock L, Gassner M and Marchal F, Thermochemical produc-
via thermochemical conversion of biomass by entrained flow tion of liquid fuels from biomass: Thermo-economic modeling,
gasification. Energy 36(7):40974108 (2011). process design and process integration analysis. Biomass
21. Phillips SD, Tarud J, Biddy M and Dutta A, Gasoline from Bioenerg 34(12):18381854 (2010).
Wood via Integrated Gasification, Synthesis, and Methanol-to- 37. Simbeck D and Chang E, Hydrogen Supply: Cost Estimate for
Gasoline Technologies. [Online]. National Renewable Energy Hydrogen Pathways - Scoping Analysis, NREL/SR-540-32525.
Laboratory (NREL), Report no. NREL/TP-5100-47594. [Online] SFA Pacific Inc, Mountain View, CA (2002).

566 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

38. Tock L and Marchal F, Co-production of hydrogen and 56. Tijm PJA, Walker FJ and Brown DM, Methanol technology
electricity from lignocellulosic biomass: Process design and developments for the new millennium. Appl Catal A-Gen
thermo-economic optimization. Energy 45(1):339349 (2012). 221:275282 (2001).
39. Gassner M and Marchal F, Thermo-economic process model 57. Aasberg-Petersen K, Nielsen CS, Dybkjr I and Perregaard J,
for thermochemical production of synthetic natural gas (SNG) Large Scale Methanol Production from Natural Gas. [Online].
from lignocellulosic biomass. Biomass Bioenerg 33(11):1587 Available at: http://www.topsoe.com/business_areas/metha-
1604 (2009). nol/~/media/PDF%20files/Methanol/Topsoe_large_scale_
40. Jurak M, Sues A and Ptasinski KJ, Exergetic evaluation and methanol_prod_paper.ashx [1, October 2012].
improvement of biomass-to-synthetic natural gas conversion. 58. Lurgi Megamethanol, Lurgis brochure. [Online]. Available
Energ Environ Sci 2(7):791801 (2009). at: http://lurgi.com/website/fileadmin/user_upload/1_
41. Heyne S and Harvey S, Methane from biomass: Process- PDF/1_Broshures_Flyer/englisch/0312e_MegaMethanol.pdf
integration aspects. Proceedings of Institution of Civil [1, September 2012].
Engineers. Energy 162(1):1322 (2009). 59. Matsumoto H, Nagai H, Watanabe H, Morita K and Makihara
42. van der Meijden CM, Veringa HJ and Rabou LPLM, The pro- H, Advanced technology for large scale methanol plant.
duction of synthetic natural gas (SNG): A comparison of three Mitsubishi Heavy Industries Technical Review 34(2):5862
wood gasification systems for energy balance and overall effi- (1997).
ciency. Biomass Bioenerg 34(3):302311 (2010). 60. Advanced Casale Technologies, Casales brochure. [Online].
43. Gassner M and Marchal F, Thermo-economic optimisation of Available at: http://www.casale.ch/group/images/stories/
the polygeneration of synthetic natural gas (SNG), power and Casale_Group/Downloads/Documents/advanced_casale_
heat from lignocellulosic biomass by gasification and metha- technologies_june_2010.pdf [1, September 2012].
nation. Energ Environ Sci 5(2):57685789 (2012). 61. Olofsson I, Nordin A and Sderlind U, Initial Review and
44. Haro P, Ollero P, Villanueva Perales AL and Gmez-Barea Evaluation of Process Technologies and Systems Suitable
A, Thermochemical biorefinery based on dimethyl ether as for Cost-Efficient Medium-Scale Gasification for Biomass
intermediate: Technoeconomic assessment. Appl Energ to Liquid Fuels. Energy Technology & Thermal Process
102:950961 (2013). Chemistry, University of Ume, Sweden (2005).
45. Cherubini F, Jungmeier G, Wellisch M, Willke T, Skiadas I, 62. Heydorn EC, Diamond BW and Lilly RD, Commercial-scale
van Ree R et al., Toward a common classification approach demonstration of the liquid phase methanol (LPMEOHTM)
for biorefinery systems. Biofuel Bioprod Bioref 3(5):534546 process, Final report,Volume 2: Project performance and
(2009). economics, for the period 16 October 199230 June 2003.
46. van Ree R and Annevelink B, Status Report Biorefinery Department of Energy USA (2003).
2007, report 847. [Online]. SenterNovem, Wageningen, 63. Xu M, Lunsford JH, Goodman DW and Bhattacharyya A,
The Netherlands (2007). Available at: http://www. Synthesis of dimethyl ether (DME) from methanol over solid-
biorefinery.nl/fileadmin/biorefinery/docs/publications/ acid catalysts. Appl Catal A-Gen 149(2):289301 (1997).
StatusDocumentBiorefinery2007final211107.pdf [1, October 64. Jun K, Lee H, Roh H and Park S, Catalytic dehydration of
2012] methanol to dimethyl ether (DME) over solid-acid catalysts.
47. Bridgwater AV, Renewable fuels and chemicals by thermal Bull Korean Chem Soc 23(6):803806 (2002).
processing of biomass. Chem Eng J 91(2/3):87102 (2003). 65. Yaripour F, Baghaei F, Schmidt I and Perregaard J, Catalytic
48. Prins MJ, Ptasinski KJ and Janssen FJJG, More efficient bio- dehydration of methanol to dimethyl ether (DME) over solid-
mass gasification via torrefaction. Energy 31(15):34583470 acid catalysts. Catal Commun 6(2):147152 (2005).
(2006). 66. Mii T and Uchida M, Fuel DME plant in East Asia, in
49. Demirba A, Biomass resource facilities and biomass con- Proceedings of 15th Saudi-Japan joint symposium Dhahran,
version processing for fuels and chemicals. Energ Convers Saudi Arabia, November 2728. Toyo Engineering Corporation
Manage 42(11):13571378 (2001). (TEC) (2005).
50. Goyal HB, Seal D and Saxena RC, Bio-fuels from thermo- 67. Brown DM, Bhatt BL, Hsiung TH, Lewnard JJ and Waller FJ,
chemical conversion of renewable resources: A review. Renew Novel technology for the synthesis of dimethyl ether from syn-
Sust Energ Rev 12(2):504517 (2008). gas. Catal Today 8(3):279304 (1991).
51. Higman C and van der Burgt M, Gasification. Elsevier Science, 68. Stiefel M, Ahmad R, Arnold U and Dring M, Direct synthesis
USA (2003). of dimethyl ether from carbon-monoxide-rich synthesis gas:
52. Haro P, Ollero P, Villanueva Perales AL and Reyes Valle C, Influence of dehydration catalysts and operating conditions.
Technoeconomic assessment of lignocellulosic ethanol pro- Fuel Process Technol 92(8):14661474 (2011).
duction via DME (dimethyl ether) hydrocarbonylation. Energy 69. Garca-Trenco A and Martnez A, Direct synthesis of DME from
44(1):891901 (2012). syngas on hybrid CuZnAl/ZSM-5 catalysts: New insights into
53. Wender I, Reactions of synthesis gas. Fuel Process Technol the role of zeolite acidity. Appl Catal A-Gen 411/412:170179
48(3):189297 (1996). (2012).
54. Bartholomew CH and Farrauto RJ, Fundamentals of Industrial 70. Shikada T, Ohno Y, Ogawa T, Mizuguchi M, Ono M and
Catalytic Processes, 2nd Edn. John Wiley & Sons, Chichester Fujimoto K, Method for Producing Dimethyl Ether. US Patent
UK (2005). 2006/0052647 A1 (2006).
55. Spath PL and Dayton DC, Preliminary Screening 71. Wender I, Friedel RA and Orchin M, Ethanol from methanol.
Technical and Economic Assessment of Synthesis Gas to Science 113:206207 (1951).
Fuels and Chemicals with Emphasis on the Potential for 72. Chen MJ, Feder HM and Rathke JW, A general homogeneous
Biomass-Derived Syngas, Report NREL/TP-510-34929. NREL, catalytic method for the homologation of methanol to ethanol.
Golden, CO (2003). J Am Chem Soc 104(25):73467347 (1982).

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 567
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

73. Koermer GS and Slinkard WE, Methanol homologation and Chemical Transformations Program, May 2124.
reaction catalyzed by cobalt carbonyl. Ind Eng Chem Res Cambridge, Maryland (2006).
17(3):231236 (1978). 94. Ono H, Fujiwara K, Hashimoto M, Sugiyama E and Yoshida K,
74. Watabane K, Kudo K and Sugita N, Kinetics and mechanistic Promotion effect of mixed halides on homogeneous ruthenium
study of the methanol homologation with cobalt-ruthenium catalysis in direct synthesis of ethanol from hydrogen and car-
mixed catalyst. N Bull Chem Soc Jpn 58:20292037 (1985). bon monoxide. J Mol Catal A-Chem 57(1):113123 (1989).
75. Franoisse PB and Thyrion FC, Methanol to ethanol by 95. Jenner G and Andrianary P, One and two-stage synthesis of
homologation: Kinetic approach. Ind Eng Chem Res ethanol by hydrocarbonylation of methanol in chelating sol-
22(4):542548 (1983). vents. J Catal 88(2):535537 (1984).
76. Santacesaria E, Di Serio M, Gelosa D and Carr S, Kinetics 96. Braca G, Paladini L, Sbrana G, Valentini G, Andrich G and
of methanol homologation. Part I. Behaviour of cobalt- Gregorio G, Carbonylation and homologation of dimethyl
phosphine-iodine catalysts. J Mol Catal A-Chem 58(1):2742 ether in the presence of ruthenium catalysts. Ind Eng Chem
(1990). Res 20(1):115122 (1981).
77. Nowicki L, Ledakowicz S and Zarzycki R, Kinetics of rho- 97. Rathke J, Chen M, Klingler B, Gerald R, Marshall C and
dium-catalyzed methanol carbonylation. Ind Eng Chem Res Rodgers J, Selective Catalytic Ethanol Synthesis. Argonne
31(11):24722475 (1992). National Research Laboratory, USA September (2009).
78. Catalyst deactivation and regeneration, Kirk-Othmer 98. Carbon monoxide, Kirk-Othmer Encyclopedia of Chemical
Encyclopedia of Chemical Technology. DOI: 10.1002/047123 Technology. DOI: 10.1002/0471238961.0301180216090518.
8961.1415021218150209.a01.pub2 (2003) a02.pub2 (2001)
79. Maitlis PM, Haynes A, James BR, Catellani M and Chiusoli 99. Jenner G, The selectivity problem in the homogeneous car-
GP, Iodide effects in transition metal catalyzed reactions. bonylation and hydrocarbonylation of alcohols and esters.
Dalton Trans 21:34093419 (2004). Appl Catal 50(1):99118 (1989).
80. Klingler RJ, Chen MJ, Rathke JW and Kramarz KW, Effect of 100. Moloy KG and Wegman RW, Rhodium-catalyzed reductive
phosphines on the thermodynamics of the cobalt-catalyzed carbonylation of methanol. Organometallics 8(12):28832892
hydroformylation system. Organometallics 26(2):352357 (1989).
(2007). 101. Juran B and Porcelli RV, Convert methanol to ethanol.
81. Gane RB, Process for the hydrocarbonylation of methanol to Hydrocarb Process Int Ed 64(10):8587 (1985).
ethanol in the presence of added oxygen-containing com- 102. Ethanol, Ullmanns Encyclopedia of Industrial Chemistry.
pounds. US Patent 4,205,190 (1980). DOI: 10.1002/14356007.a09 587 (2002)
82. Gane RB, Process for the production of ethanol and/or 103. Rachmady W and Vannice MA, Acetic acid hydrogenation
acetaldehyde by reacting methanol with synthesis gas. US over supported platinum catalysts. J Catal 192(2):322334
Patent 4,262,154 (1981). (2000).
83. Gane RB, Process for the hydrocarbonylation of metha- 104. Howard MJ, Jones MD, Roberts MS and Taylor SA, C1 to ace-
nol to ethanol in the presence of an inert liquid. US Patent tyls: Catalysis and process. Catal Today 18(4):325354 (1993).
4,319,056 (1982).
105. Howard MJ, Sunley GJ, Poole AD, Watt RJ and Sharma BK,
84. Barclay JL, Hydrocarbonylation of methanol to ethanol in the New acetyls technologies from BP chemicals, in Studies in
presence of added compounds. US Patent 4,380,681 (1983). Surface Science and Catalysis, Volume 121, ed by Hattori H.
85. Ishogai N, Process for producing ethanol. US Patent and Otsuka K. Elsevier, USA, pp. 6168 (1999).
4,423,258 (1983). 106. BP documentation, Passing the Acid Test. [Online]. Frontiers.
86. Halttunen ME, Niemel MK, Krause AOI and Vuori AI, Liquid (2008). Available at: http://www.bp.com/liveassets/bp_inter-
phase methanol hydrocarbonylation with homogeneous and net/globalbp/STAGING/global_assets/downloads/B/
heterogeneous Rh and Ru catalysts. J Mol Catal A-Chem bpf23_30-33_cativa.pdf [1, June 2010].
109(3):209217 (1996). 107. Winter CL, Make ethanol via syngas. Hydrocarb Process
87. Halttunen ME, Niemel MK, Krause AOI and Vuori AI, Some 65(4):7173 (1986).
aspects on the losses of metal from the support in the hydro- 108. Schuster L, Continuous preparation of ethanol. US Patent
carbonylation of methanol. J Mol Catal A-Chem 144(2):307 4,517,391 (1985).
314 (1999).
109. Rachmady W and Vannice MA, Acetic acid reduction by H2
88. Walker E, Process for the selective homologation of methanol on bimetallic Pt-Fe catalysts. J Catal 209(1):8798 (2002).
to ethanol. US Patent 4,227,634 (1981).
110. Rachmady W and Vannice MA, Acetic acid reduction by H2
89. Wegman RW, Alcohol homologation. US Patent 4,720,200 over supported pt catalysts: A DRIFTS and TPD/TPR study.
(1988). J Catal 207(2):317330 (2002).
90. Chen MJ and Rathke JW, Homologation of methanol cata- 111. Pallassana V and Neurock M, Reaction paths in the hydrog-
lyzed by manganese carbonyl in tertiary amine-methanol enolysis of acetic acid to ethanol over pd(111), re(0001), and
solutions. Organometallics 8(2):515520 (1989). PdRe alloys. J Catal 209(2):289305 (2002).
91. Hargis D, Catalyst for converting methanol and synthesis gas 112. Cressely J, Farkhani D, Deluzarche A and Kiennemann A,
to ethanol. US Patent 4,361,499 (1982). Evolution des especes carboxylates dans le cadre des syn-
92. Hargis D, Ethanol from methanol and synthesis gas. US theses CO-H2. reduction de lacide acetique sur systeme Co,
Patent 4,370,507 (1983). Cu, Fe. Mater Chem Phys 11(5):413431 (1984).
93. Rathke JW, Chen MJ, Klingler RJ, Gerald RE, Marshall 113. Kitson M and Williams PS, Catalyzed hydrogenation of car-
CL and Rodgers JL, Selective catalytic ethanol synthesis. boxylic acids and their anhydrides to alcohols and/or ester.
Proceedings of the 2006 Meeting of the DOE/BES Catalysis US Patent 4,985,572 (1991).

568 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

114. Stites RC, Methods and apparatus for selectively producing in side pockets and large channels of mordenite. Phys Chem
ethanol from synthesis gas. International Patent WO/2010 Chem Phys 13(7):26032612 (2011).
068318 A1 (2010). 134. Uhm SJ, Process for the preparation of ethanol from metha-
115. Johnston VJ, Process for making ethanol from acetic acid. nol. US Patent 5,414,161 (1995).
US Patent 2010/0197985 A1 (2010). 135. Bessling B, Lning J, Ohligschlger A, Schembecker G and
116. BASF, Make the right move with NanoSelect Catalysts. Sundmacher K, Investigations on the synthesis of methyl
[Online]. Available at: http://www.basf.de/basf2/img/ acetate in a heterogeneous reactive distillation process.
pharma/2009-01/BASF_NanoSelect.pdf [1, June 2010]. Chem Eng Technol 21(5):393400 (1998).
117. Zhu Y and Jones SB, Techno-economic Analysis for the 136. Zoeller JR, Eastman chemical companys chemicals
Thermochemical Conversion of Lignocellulosic Biomass from coal program: The first quarter century. Catal Today
to Ethanol via Acetic Acid Synthesis, Report PNNL-18483. 140(3/4):118126 (2009).
Pacific Northwest National Laboratory, WA (USA) (2009). 137. Agreda VH, Reactive distillation process for the production of
118. Jetvic R, Zhou Z, Franjkic I, Johnsoton VJ, Lee D and Weiner methyl acetate. US Patent 4,435,595 (1984).
H, Process to make ethanol from acetic acid using acidic 138. Huss RS, Chen F, Malone MF and Doherty MF, Reactive
catalyst. US Patent 2011/0082322 A1 (2011). distillation for methyl acetate production. Comput Chem Eng
119. Bradley MW. Process for the production of ethanol. 27(12):18551866 (2003).
International Patent WO/1983 03409 (1983). 139. Esterification, Kirk-Othmer Encyclopedia of Chemical
120. Labrie M-, Enerkem technology to convert waste into biofuels Technology. DOI: 10.1002/0471238961.0519200501191201.
and green chemicals at new research facility June 23, 2011. a01 (2000).
Enerkem. [Online]. Available at: www.enerkem.com [May 140. Ethanol. Kirk-Othmer Encyclopedia of Chemical Technology.
2012]. DOI: 10.1002/0471238961.0520080112150719.a01.pub2 (2004).
121. Kapoor MP and Matsumura Y, Liquid-phase methanol carbo- 141. Blanchard LA and Brennecke JF, Esterification of acetic
nylation catalyzed over tin promoted nickel-aluminium lay- acid with ethanol in carbon dioxide. Green Chem 3(1):1719
ered double hydroxide. Catal Today 9395:287291 (2004). (2001).
122. Kummer R, Taglieber V and Schneider H-W, Continuous pro- 142. Wyczesany A, Modeling of simultaneous chemical and phase
duction of ethanol and plural stage distillation of the same. equilibria in esterification of acetic acid with ethanol in high-
US Patent 4,454,358 (1984). pressure carbon dioxide. Ind Eng Chem Res 46(16):5437
123. Merenov AS and Abraham MA, Catalyzing the carbonylation 5445 (2007).
of methanol using a heterogeneous vapor phase catalyst. 143. Zhang B, Lin L, Zhuang J, Liu Y, Peng L and Jiang L,
Catal Today 40(4):397404 (1998). Hydrogenation of ethyl acetate to ethanol over ni-based
124. Nefedov BK, Shutkina EM and Eidus YT, Rh-NaX as a hetero- catalysts obtained from Ni/Al hydrotalcite-like compounds.
geneous catalyst for the synthesis of methyl acetate by the Molecules 15(8):51395152 (2010).
carbonylation of methanol with carbon monoxide at atmos- 144. van Beijnum J, van Dillen AJ and Geus JW, Hydrogenolysis
pheric pressure. B Acad Sci USSR CH+ 24(3):657658 (1975). reaction and catalyst suitable therefor. US Patent 5,198,592
125. Nefedov BK, Sergeeva NS, Zueva TV, Shutkina EM and Eidus (1993).
YT, Carbonylation reactions - communication 22. Synthesis 145. Ryashentseva MA and Avaev VI, Hydrogenation of ethyl
of methyl acetate by carbonylation of methanol with carbon acetate over supported rhenium catalysts. Russian Chem B+
monoxide in presence of Rh-zeolite NaX catalyst at atmos- 48(5):9981000 (1999).
pheric pressure. B Acad Sci USSR CH+ 25(3):565569
146. Wehner PS and Gustafson BL, Catalytic hydrogenation of
esters over Pd/ZnO. J Catal 135(2):420426 (1992).
126. Chornet E, Production of ethanol from methanol. US Patent
147. Bournonville J-, Candy J- and Mabilon G, Process for pro-
2009/0221725 A1 (2009).
ducing alcohols by hydrogenolysis of carboxylic acid esters
127. Marie-Rose SC, Chornet E, Lynch D and Lavoie J, From in the presence of a catalyst containing nickel and tin, ger-
biomass-rich residues into fuels and green chemicals via manium or lead. US Patent 4,628,130 (1986).
gasification and catalytic synthesis. WIT TransEcol Environ
148. Travers C, Trinh Snappe, Snappe R and Bournonville J-,
143:123132 (2011).
Catalytic process for manufacturing alcohols by hydrogenol-
128. Cheung P, Iglesia E, Sunley JG, Bhan A and Law DJ, Process ysis of carboxylic acid esters. US Patent 4,456,775 (1984).
for carbonylation of alkyl ethers. US Patent 7,465,822 B2 (2008).
149. San X, Zhang Y, Shen W and Tsubaki N, New synthesis
129. Smith WJ, Process for preparing carboxylic acids and deriva- method of ethanol from dimethyl ether with a synergic effect
tives thereof. US Patent 7,642,372 B2 (2010). between the zeolite catalyst and metallic catalyst. Energ Fuel
130. Smith WJ, Process for preparing carboxylic acids. US Patent 23(5):28432844 (2009).
5,420,345 (1995). 150. Zhang Y, San X, Tsubaki N, Tan Y and Chen J, Novel ethanol
131. Cheung P, Bhan A, Sunley GJ, Law DJ and Iglesia E, Site synthesis method via C1 chemicals without any agriculture
requirements and elementary steps in dimethyl ether carbonyla- feedstocks. Ind Eng Chem Res 49(11):54855488 (2010).
tion catalyzed by acidic zeolites. J Catal 245(1):110123 (2007). 151. Li X, San X, Zhang Y, Ichii T, Meng M, Tan Y et al., Direct syn-
132. Liu J, Xue H, Huang X, Wu P, Huang S, Liu S et al., Stability thesis of ethanol from dimethyl ether and syngas over com-
enhancement of H-mordenite in dimethyl ether carbonyla- bined H-mordenite and Cu/ZnO catalysts. ChemSusChem
tion to methyl acetate by pre-adsorption of pyridine. Cuihua 3(10):11921199 (2010).
Xuebao/Chinese J Catal 31(7):729738 (2010). 152. Cheung P, Bhan A, Sunley GJ and Iglesia E, Selective carbon-
133. Boronat M, Martnez C and Corma A, Mechanistic differ- ylation of dimethyl ether to methyl acetate catalyzed by acidic
ences between methanol and dimethyl ether carbonylation zeolites. Angewandte Chemie Int Ed 45(10):16171620 (2006).

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 569
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

153. Acetic Acid, Ullmanns Encyclopedia of Industrial Chemistry. 172. Haro P, Trippe F, Stahl R and Henrich E, Bio-syngas to
DOI: 10.1002/14356007.a01_045 gasoline and olefins via DME A comprehensive techno-
154. Solvents. Ullmanns Encyclopedia of Industrial Chemistry. economic assessment. Applied Energy (2013). doi: 10.1016/j.
DOI: 10.1002/14356007.a24_437 apenergy.2013.03.015
155. Cellulose Esters, Organic Esters. Kirk-Othmer Encyclopedia 173. Zhu Y, Jones SB, Biddy MJ, Dagle RA and Palo DR, Single-
of Chemical Technology (2000). DOI: 10.1002/0471238961.15 step syngas-to-distillates (S2D) process based on biomass-
18070107050415.a01 derived syngas - A techno-economic analysis. Bioresource
Technol 117:341351 (2012).
156. Bhan A, Allian AD, Sunley GJ, Law DJ and Iglesia E,
Specificity of sites within eight-membered ring zeolite chan- 174. Haro P, Reyes Valle C, Villanueva Perales AL, Ollero P,
nels for carbonylation of methyls to acetyls. J Am Chem Soc Caraballo J. Garca Redondo JA et al., Techno-Economic
129(16):49194924 (2007). Assessment of Production of Olefins via Thermochemical
157. Liu J, Xue H, Huang X, Li Y and Shen W, Dimethyl ether Conversion of Biomass (BioMTO process). Proceedings of
carbonylation to methyl acetate over HZSM-35. Catal Lett the 19th European Biomass Conference, 610 June 2011.
139(1/2):3337 (2010). Berlin, pp. 11131116 (2011).

158. Boronat M, Martnez-Snchez C, Law D and Corma A, 175. Avidan AA, Gasoline and distillate fuels from methanol,
Enzyme-like specificity in zeolites: A unique site position in in Studies in Surface Science and Catalysis. Methane
mordenite for selective carbonylation of methanol and dime- Conversion, Proceedings of a Symposium on the Production
thyl ether with CO. J Am Chem Soc 130(48):1631616323 of Fuels and Chemicals from Natural Gas, volume 36, ed by
(2008). Bibby DM. Elsevier, pp. 307323 (1988).
159. Yang G, San X, Jiang N, Tanaka Y, Li X, Jin Q et al., A new 176. Ethylene. Ullmanns Encyclopedia of Industrial Chemistry
method of ethanol synthesis from dimethyl ether and syngas (2009). DOI: 10.1002/14356007.a10_045.pub3
in a sequential dual bed reactor with the modified zeolite and 177. Thinnes B, Bio-based polymers could be next big thing.
Cu/ZnO catalysts. Catal Today 164(1):425428 (2011). Hydrocarbon Process 91(2): 19-20 (2012).
160. Ehrler JL and Juran B, VAM and Ac2O by carbonylation. 178. Ethylene from Ethanol. Chematur Brochure. [Online].
Hydrocarb Process Int Ed 61(12):109113 (1982). Available at: http://www.chematur.se/sok/download/
161. Acetic Anhydride and Mixed Fatty Acid Anhydrides. Ethylene_rev_0904.pdf [1, February 2012].
Ullmanns Encyclopedia of Industrial Chemistry (2000). 179. Tretyakov VF, Makarfi YI, Tretyakov KV, Frantsuzova NA and
DOI: 10.1002/14356007.a01_065 Talyshinskii RM, The catalytic conversion of bioethanol to
162. Zoeller JR, Agreda VH, Cook SL, Lafferty NL, Polichnowski hydrocarbon fuel: A review and study. Catal Ind 2(4):402420
SW and Pond DM, Eastman chemical company acetic anhy- (2010).
dride process. Catal Today 13(1):7391 (1992). 180. Chen Y, Wu Y, Tao L, Dai B, Yang M, Chen Z et al.,
163. Wan C-G, Process for the preparation of ethanol from metha- Dehydration reaction of bio-ethanol to ethylene over modified
nol, carbon monoxide and hydrogen. US Patent 4,497,967 SAPO catalysts. J Ind Eng Chem 16(5):717722 (2010).
(1984). 181. Phillips CB and Datta R, Production of ethylene from hydrous
164. Keil FJ, Methanol-to-hydrocarbons: Process technology. ethanol on H-ZSM-5 under mild conditions. Ind Eng Chem
Micropor Mesopor Mat 29(1/2):4966 (1999). Res 36(11):44664475 (1997).
165. Fuels, Synthetic, Liquid Fuels. Kirk-Othmer Encyclopedia of 182. Takahara I, Saito M, Inaba M and Murata K, Dehydration of
Chemical Technology (2000). DOI: 10.1002/0471238961.1209 ethanol into ethylene over solid acid catalysts. Catal Lett
1721080114.a01 105(3/4):249252 (2005).
166. Olsbye U, Svelle S, Bjrgen M, Beato P, Janssens TVW, 183. Hu Y, Zhan N, Dou C, Huang H, Han Y, Yu D et al., Selective
Joensen F et al., Conversion of methanol to hydrocarbons: dehydration of bio-ethanol to ethylene catalyzed by lantha-
How zeolite cavity and pore size controls product selectivity. num-phosphorous-modified HZSM-5: Influence of the fusel.
Angewandte Chemie Int Ed 51(24):58105831 (2012). Biotechnol J 5(11):11861191 (2010).
167. Chang CD and Silvestri AJ, The conversion of methanol and 184. Bedia J, Barrionuevo R, Rodrguez-Mirasol J and Cordero
other O-compounds to hydrocarbons over zeolite catalysts. J T, Ethanol dehydration to ethylene on acid carbon catalysts.
Catal 47(2):249259 (1977). Appl Catal B-Environ 103(3/4):302310 (2011).
168. Mokrani T and Scurrell M, Gas conversion to liquid fuels and 185. Le Van Mao R, Nguyen TM and McLaughlin GP, The bioetha-
chemicals: The methanol route-catalysis and processes nol-to-ethylene (B.E.T.E.) process. Appl Catal 48(2):265277
development. Catal Rev Sci Eng 51(1):1145 (2009). (1989).
169. Kvisle S, Fuglerud T, Kolboe S, Olsbye U, Lillerud KP 186. Morschbacker A, Bio-ethanol based ethylene. Polym Rev
and Vora BV, Methanol-to-Hydrocarbons. Handbook of 49(2):7984 (2009).
Heterogeneous Catalysis. Wiley-VCH Verlag GmbH & Co 187. Haro P, Trippe F, Ollero P and Stahl R, Ethylene from bio-
KGaA, Germany (2008). mass: A comparison between bioethanol dehydration
170. Jones SB and Zhu Y, Techno-economic Analysis for the and other thermochemical processes. Fuel Processing
Conversion of Lignocellulosic Biomass to Gasoline via the Technology (2013). doi: 10.1016/j.fuproc.2013.03.024
Methanol-to-Gasoline (MTG) Process, Report no.: PNNL- 188. NEXANT, Green Propylene, Chem System PERP Program,
18481. Pacific Northwest National Laboratory (PNNL); report Abstract, PERP07/08S11. [Online] (2009). Available
Richland, WA, USA (2009). at: http://www.chemsystems.com/reports/search/docs/
171. Tabak SA and Yurchak S, Conversion of methanol over abstracts/0708S11_abs.pdf [1, October 2012]
ZSM-5 to fuels and chemicals. Catal Today 6(3):307327 189. Huang S, Liu S, Xin W, Bai J, Xie S, Wang Q et al., Metathesis
(1990). of ethene and 2-butene to propene on W/Al 2O 3-HY

570 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb
Review: Potential Routes for Thermochemical Biorefineries P Haro et al.

catalysts with different HY contents. J Mol Catal A-Chem 209. Barthos R, Szchenyi A and Solymosi F, Decomposition and
226(1):6168 (2005). aromatization of ethanol on ZSM-based catalysts. J Phys
190. Mol JC, Industrial applications of olefin metathesis. J Mol Chem B 110(43):2181621825 (2006).
Catal A-Chem 213(1):3945 (2004). 210. Inaba M, Murata K, Saito M and Takahara I, Production of
191. NEXANT, Biobutanol: The Next Big Biofuel. Chem Systems, olefins from ethanol by fe-supported zeolite catalysts. Green
topical report, Chem Systems [1, October 2012] (2008). Chem 9(6):638646 (2007).
192. Ndou AS, Plint N and Coville NJ, Dimerisation of ethanol 211. Gayubo AG, Alonso A, Valle B, Aguayo AT, Olazar M and
to butanol over solid-base catalysts. Appl Catal A-Gen Bilbao J, Hydrothermal stability of HZSM-5 catalysts modi-
251(2):337345 (2003). fied with Ni for the transformation of bioethanol into hydro-
carbons. Fuel 89(11):33653372 (2010).
193. Tsuchida T, Sakuma S, Takeguchi T and Ueda W, Direct
synthesis of n-butanol from ethanol over nonstoichiomet- 212. Sun J, Zhu K, Gao F, Wang C, Liu J, Peden CHF et al.,
ric hydroxyapatite. Ind Eng Chem Res 45(25):86348642 Direct conversion of bio-ethanol to isobutene on nanosized
(2006). Znx Zr yOz mixed oxides with balanced acid - base sites. J Am
Chem Soc 133(29):1109611099 (2011).
194. Ogo S, Onda A and Yanagisawa K, Selective synthesis of
1-butanol from ethanol over strontium phosphate hydroxya- 213. Viswanadham N, Saxena SK, Kumar J, Sreenivasulu P
patite catalysts. Appl Catal A-Gen 402(1/2):188195 (2011). and Nandan D, Catalytic performance of nano crystalline
H-ZSM-5 in ethanol to gasoline (ETG) reaction. Fuel 95:298
195. Marcu I-, Tichit D, Fajula F and Tanchoux N, Catalytic valori-
304 (2012).
zation of bioethanol over Cu-Mg-Al mixed oxide catalysts.
Catal Today 147(3/4):231238 (2009). 214. Okazaki K, Kishida T, Ogawa K and Nozaki T, Direct conver-
sion from methane to methanol for high efficiency energy
196. Len M, Daz E and Ordez S, Ethanol catalytic condensa-
system with exergy regeneration. Energ Convers Manage
tion over mg-al mixed oxides derived from hydrotalcites.
43(9/12):14591468 (2002).
Catal Today 164(1):436442 (2011).
215. Indarto A, A review of direct methane conversion to metha-
197. Carvalho DL, De Avillez RR, Rodrigues MT, Borges LEP and
nol by dielectric barrier discharge. IEEE Trans Dielectr Electr
Appel LG, Mg and Al mixed oxides and the synthesis of n-buta-
Insul 15(4):10381043 (2008).
nol from ethanol. Appl Catal A-Gen 415/416:96100 (2012).
216. Chen L, Zhang X, Huang L and Lei L, Partial oxidation of
198. Tsodikov MV, Yandieva FA, Kugel VY, Chistyakov AV,
methane with air for methanol production in a post-plasma
Gekhman AE and Moiseev II, Reductive dehydration of etha-
catalytic system. Chem Eng Process: Process Intensification
nol: A new route towards alkanes. Catal Lett 121(3/4):199
48(8):13331340 (2009).
208 (2008).
217. Reyes Valle C, Villanueva Perales AL, Ollero P and
199. Dahlbom S, Landgren H and Fransson P, Alternatives for Bio-
Gmez-Barea A, Techno-economic assessment of
Butanol Production. [Online]. Lund University. Available at:
biomass-to-ethanol by indirect fluidized bed gasification:
Impact of reforming technologies and comparison with
pdf [1, September 2012].
entrained flow gasification. Appl Energy. In Press (2013).
200. Mascal M, Chemicals from biobutanol: Technologies and
218. Baliban RC, Elia JA, Weekman V and Floudas CA, Process
markets. Biofuel Bioprod Bioref 6(4):483493 (2012).
synthesis of hybrid coal, biomass, and natural gas to liquids via
201. Wright ME, Harvey BG and Quintana RL, Highly efficient fischer-tropsch synthesis, ZSM-5 catalytic conversion, metha-
zirconium-catalyzed batch conversion on 1-butene: A new nol synthesis, methanol-to-gasoline, and methanol-to-olefins/
route to jet fuels. Energ Fuel 22(5):32993302 (2008). distillate technologies. Comput Chem Eng 47:2956 (2012).
202. Wass DF and Dowson GRM, Conversion of Alcohols. 219. Baliban RC, Elia JA, Misener R and Floudas CA, Global
International Patent WO 2012/004572 A1 (2012). optimization of a MINLP process synthesis model for ther-
203. Inui K, Kurabayashi T and Sato S, Direct synthesis of ethyl mochemical based conversion of hybrid coal, biomass, and
acetate from ethanol over Cu-Zn-Zr-Al-O catalyst. Appl Catal natural gas to liquid fuels. Comput Chem Eng 42:6486
A-Gen 237(1/2):5361 (2002). (2012).
204. Carotenuto G, Tesser R, Di Serio M and Santacesaria E, 220. Baliban RC, Elia JA and Floudas CA, Optimization framework
Kinetic study of ethanol dehydrogenation to ethyl acetate for the simultaneous process synthesis, heat and power inte-
promoted by a copper/copper-chromite based catalyst. gration of a thermochemical hybrid biomass, coal, and natu-
Catal Today 203:202210 (2012) ral gas facility. Comput Chem Eng 35(9):16471690 (2011).
205. Santacesaria E, Carotenuto G, Tesser R and Di Serio M, 221. Elia JA, Baliban RC, Xiao X and Floudas CA, Optimal energy
Ethanol dehydrogenation to ethyl acetate by using copper supply network determination and life cycle analysis for
and copper chromite catalysts. Chem Eng J 179:209220 hybrid coal, biomass, and natural gas to liquid (CBGTL)
(2012). plants using carbon-based hydrogen production. Comput
206. Colley SW, Fawcett CR, Rathmell C and Tuck MWM, Chem Eng 35(8):13991430 (2011).
Process. kvaerner process technology Ltd. European Patent 222. Baliban RC, Elia JA and Floudas CA, Toward novel hybrid
0,990,638 (2000). biomass, coal, and natural gas processes for satisfying cur-
207. Hong Thuy NT, Kikuchi Y, Sugiyama H, Noda M and Hirao M, rent transportation fuel demands, 1: Process alternatives,
Techno-economic and environmental assessment of bioeth- gasification modeling, process simulation, and economic
anol-based chemical process: A case study on ethyl acetate. analysis. Ind Eng Chem Res 49(16):73437370 (2010).
Environ Prog Sustain Energ 30(4):675684 (2011). 223. Elia JA, Baliban RC and Floudas CA, Toward novel hybrid bio-
208. Inaba M, Murata K, Saito M and Takahara I, Ethanol conver- mass, coal, and natural gas processes for satisfying current
sion to aromatic hydrocarbons over several zeolite catalysts. transportation fuel demands, 2: Simultaneous heat and power
Reaction Kinetics and Catal Lett 88(1):135141 (2006). integration. Ind Eng Chem Res 49(16):73717388 (2010).

2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb 571
P Haro et al. Review: Potential Routes for Thermochemical Biorefineries

Pedro Haro ngel Luis Villanueva Perales

Pedro Haro is a PhD student (FPU Dr. ngel Luis Villanueva Perales is an
grant) at the Bioenergy Group associate professor at the University of
since 2010. His work deals with the Seville and member of the Bioenergy
conceptual design, technoeconomic Group. His research interests are
assessment and sustainability of biorefineries and process design,
thermochemical biorefineries based integration and control of chemical
on DME as a platform chemical. He processes. He leads the research
studied Chemical Engineering at the line Design and optimization of
University of Seville. thermochemical biorefineries.

Pedro Ollero
Fernando Vidal Barrero
Prof. Pedro Ollero is a full professor of
Chemical Engineering at the University Dr. Fernando Vidal Barrero is an asso-
of Seville. In 1999 Prof. Ollero founded ciate professor of Chemical Engineer-
the Bioenergy Group, which has par- ing and member of Bioenergy Group.
ticipated in several European Projects. Prof. Vidal Barrero has participated in
In addition, the Bioenergy Group several public and privately financed
collaborates with private companies research projects. Since 2004, he
as a consultant in the field of biomass leads the Biofuels Laboratory at the
conversion technology. University of Seville.

572 2013 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:551572 (2013); DOI: 10.1002/bbb