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Review

Potential routes for thermochemical


biorefineries
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
syngas.
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
biomass.
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
Catalyst
component Acetate Carbonate Carbonyl Formate Oxide Carboxylate Elemental Chloride Organic Ref.
4,71,88,89
Co-Rh
active 72,90
Mn
component
9193
Fe-Rh-Mn
94
promoter I
85
P
9496
Ru

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
additivesb

n-propanol
n-butanol
homologation of methanol should be carried out, for

acetone
81,84
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-

90.8
N/A
N/A
N/A
N/A
nol homologation following Eqn (6). Although general
references claim that methanol homologation needs pres-

N/A
N/A
6.1

~6
0
sure of about 300 bar, that was only true in the first stage
of development of the homologation catalyst.98 The use

N/A
N/A
N/A
8.5
of promoters allowed a reduction of operating pressure,

0
which is limited by the condition of retaining methanol

N/A
N/A
N/A
N/A
N/A
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

2.03e
Table 2. Reaction conditions, product distribution and main additives for homologation catalysts.

NA
NA
12.0
the use of additives, ethanol selectivity is improved up to

~8
9193%.89

Methanol to ethanol via acetic acid

Ethyl

NA
NA
NA
3.71
6.3
hydrogenation
The acetic hydrogenation route consists of a set of com-

11.55d
mon steps: methanol synthesis (Eqn (1)), acetic acid syn-

NA
NA
NA
4.7
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
38.8

25.5
32.8
Produced methanol is carbonylated using a homogene- 89f
ous catalyst. Acetic acid is then directly hydrogenated to
76.4%

35.1%
47.0%
ethanol and water. Regarding the conditions of the acetic
NA
70%

acid hydrogenation, i.e. considered catalyst and reaction


conditions, more steps could be needed for subproduct
N/A
N/A
N/A
N/A
N/A

conversion by recycling or chemical conversion in addi-


tional reactors.101
H2/CO
reaction conditionsa

The acetic acid hydrogenation route was developed in


1
2
3
2
1

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


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

acetates using heterogeneous catalysts. The employment


480
300
180
120
120

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.


205
100
83
200
200

crude oil crisis was the main reason for its withdrawal,
but in the case of the acetic acid hydrogenation route, the
180185

corrosiveness of the reaction mixture (with a detrimen-


T (C)

190
140
185
205

tal effect on the life of hydrogenation catalyst) was also


determinant.101103
Refers to all catalysts.
Co(OAc)24H2O-I-P83

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


Other oxygenates.

N/A = not available.


81

tant examples of industrial processes using homogene-


Co(OAc)24H2O
Co-I catalyst88
Rh/(Ru-I-P)100

Acetic acid.

ous catalysts. When the hydrogenation of the acetic acid


[Co(CO)4]271
Catalyst

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
b

d
a

e
f

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.

Water
N/A
Others
N/A
CH4
N/A
Figure 2. Chemical scheme for the acetic acid
hydrogenation to ethanol.
Oxygenatesb CO2
N/A
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
N/A

has emerged as the best available technology for acetic acid


production.105 The Cativa process is similar to Monsantos
acetate
Ethyl

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


N/A

catalyst is used, featuring a higher catalyst lifetime and


better stability and recovery.105,106
Propanol

The hydrogenation of acetic acid is carried out at liquid


N/A

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-
N/A

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
N/A

dispersed on silica support,112 supported Pt-based and


Pd-based catalyst.103,109,110,111,113 These studies differ from
XCO
N/A
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


ratio

achieve very low per pass conversion of acetic acid (around


1/3

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


tion mechanism, acetaldehyde is the main intermediate of
Residence
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.
360

(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-


300

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


in the aqueous phase, and with low gas formation (CO and
180220
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,
93,97

which leads to rapid catalyst degradation, and becomes


Fe-Rh-Mn
Catalyst

the main limitation for the reaction. Although reaction in


the vapor phase could avoid catalyst degradation by reduc-
b

ing the corrosiveness of the reaction mixture, extremely


a

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
115
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
a
Referred to all catalysts.
b
Other oxygenates.
c
Defined as L/(kgcath).
d
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
122
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
a
Referred to all catalysts.
b
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
biomass.
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
hydrocarbonylation
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-
esterification
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.
Acknowledgements
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.
biorefineries
In the opinion of the authors, studies on thermochemical References
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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