Bioenerg. Res.
(2016) 9:1070–1086
DOI 10.1007/s12155-016-9786-3
An Olive Tree Pruning Biorefinery for Co-Producing High
Value-Added Bioproducts and Biofuels: Economic and Energy
Efficiency Analysis
J. M. Romero-García 1 & A. Sanchez 2 & G. Rendón-Acosta 2 & J. C. Martínez-Patiño 1 &
E. Ruiz 1 & G. Magaña 2 & E. Castro 1
Published online: 18 August 2016
# Springer Science+Business Media New York 2016
Abstract This work presents a conceptual design of an inte-
grated biorefinery using olive tree pruning as feedstock. The
biorefinery combines a state-of-the-art thermochemical tech-
nology for producing high value-added antioxidants with an
energy self-sufficient biochemical platform for lignocellulosic
ethanol production. These plants are integrated by exchanging
energy and feedstock. The process and design parameters
employed in the plant designs are based on the authors’ own
lab and pilot-scale data. The paper discusses the economic
dilemma of using this feedstock for producing high value-
added products in small amounts versus producing large
amounts of low-profit biofuels. The feasibility of this produc-
tion strategy at medium scale is demonstrated via a techno-
economic analysis based on total production cost for each co-
product. Each plant is energy integrated, and the energy per-
formance of the bioethanol plant is assessed by calculating the
end-use-energy ratio. Both analyses are parameterized with
respect to plant capacity (100–1500 t dry weight (dw)/day)
and raw material price (20–100 €/ton dry weight).
Keywords Olive tree pruning . Integrated biorefinery .
Natural antioxidants . Bioethanol . Techno-economic
analysis . Conceptual design
* A. Sanchez
arturo@gdl.cinvestav.mx
1
Department of Chemical, Environmental and Materials Engineering,
Agrifood Campus of International Excellence (ceiA3), Universidad
de Jaén, 23071 Jaén, Spain
2
Centro de Investigación y de Estudios Avanzados (CINVESTAV),
Unidad Guadalajara de Ingeniería Avanzada,
45019 Zapopan, Jalisco, Mexico
Introduction
Olive tree pruning is a common operation that takes place
every 2 years during cultivation. Old branches are cut back
to rejuvenate trees and increase production, resulting in the
production of large amounts of lignocellulosic biomass. The
olive tree pruning biomass (OTP) produced is estimated at 3 t/
(ha year) [1], equivalent to approximately 30 Mt/year from the
10 million hectares of olive trees cultivated worldwide [2].
Olive is one of the main crops in Mediterranean countries,
with Spain as the largest olive oil producer in the world.
OTP is usually burned or ground and left on-site as a soil
enricher. However, the threat of disease propagation and the
production of greenhouse gases are currently a matter of en-
vironmental and economic concern. Alternatively, OTP could
be considered a source of both bioproducts and bioethanol [3],
due to its relatively large quantity of extractives (14.1–31.4 %
w/w dry weight (dw)) and polysaccharides (26.1–36.6 % cel-
lulose, 20.0–25.0 % w/w dw) [4]. The province of Jaén, in
Andalusia, Spain, with more than 20 % of global olive oil
production, exhibits conditions for establishing biorefineries
using OTP as feedstock. Of olive groves, 585,000 ha produce
over one million tons of OTP per year [5, 6]. Moreover, a
suitable road network with a radius no larger than 24 to
35 km from the center of the province (Fig. 1, [7]) guarantees
acceptable logistics costs [8].
Thus far, research conducted with OTP has focused mainly
on producing bioethanol [9–11] to meet the European Union
(EU) targets for biofuel production and use [12] under strin-
gent sustainability criteria [13]. Nevertheless, OTP could also
be used to produce a variety of high value-added products of
great interest to the food and pharmaceutical industries
[14–16], such as natural antioxidants (e.g., hydroxytyrosol)
[3] or oligosaccharides [17]. OTP lignin has also been inves-
tigated [18] for its potential use in producing other
Bioenerg. Res. (2016) 9:1070–1086
80 km 50 km 35 km 24 km 12 km
Fig. 1 Olive grove distribution (green), a hypothetical biorefinery
location (red point), and OTP supply distance ratios (blue) in Jaén
province
compounds, such as phenols [19], polymers, or carbon fibers
[20, 21].
Transformation of OTP into biofuels, high added-value
bioproducts (antioxidants, food, materials or chemicals), and
energy (electricity or heat) can be carried out in biorefineries
[22–24]. Various OTP biorefinery schemes have been pro-
posed, with their designs depending on the desired products
[4, 10, 25]. However, these biorefineries typically use thermo-
chemical platforms for energy production (electricity or heat)
[26–28]. Olive leaves have been studied as feedstock in the
pharmaceutical and cosmetic industries or for compost or pel-
let production [29]. The olive stone has also been considered
as feedstock for both chemicals (xylitol, furfural, ethanol, and
poly-3-hydroxybutyrate (PHB)) and electricity production,
with and without a solid waste cogeneration stage [30].
This work presents an integrated biorefinery design [31]
using OTP for producing high-value antioxidants and
bioethanol (as a biofuel for the transportation sector) based
on the authors’ experience in the design of biochemical plat-
form biorefineries for lignocellulosic biofuel production and
from their own lab and pilot-scale experimental data of biofuel
and antioxidant production using this feedstock. The antioxi-
dants are produced in a state-of-the art module based on ther-
mochemical technology, termed antioxidant plant, while the
bioethanol is produced in a high-yield biochemical platform,
termed bioethanol plant, streamlined to achieve energy self-
sufficiency [32], including wastewater treatment (WWT) and
steam-electricity cogeneration (CHP) stages. The integration
between plants is achieved by exchanging feedstock and elec-
tricity, thus improving the economics of both plants. The
1071
discarded OTP from the antioxidant plant is sold to the
bioethanol plant at discounted prices, while the bioethanol
plant sells surplus electricity to the antioxidant plant. The fea-
sibility of using this production strategy at medium scales is
demonstrated with a techno-economic analysis based on total
production cost (TPC) for each of the co-products. Energy
performance is also evaluated using heat integration by
Pinch analysis for maximum energy recovery (MER) [33].
The energy efficiency of the ethanol plant is evaluated by
calculating the end-use-energy ratio (EER). Both analyses
are parameterized with respect to plant capacity and feedstock
[34] to explore the sensitivity of the biorefinery with respect to
feedstock availability in Jaén (Andalusia, Spain). This paper
discusses in detail the economic and operational conditions
required for the biorefinery to be as profitable and energetical-
ly self-sufficient as possible, emphasizing the impact of the
economic and energy integration aspects of the design. This
analysis highlights the economic tradeoffs involved in produc-
ing high value-added products in small amounts (i.e., antiox-
idants) versus large amounts of low-profit products (i.e.,
bioethanol) and advances a feasible solution for revalorizing
an agricultural waste in the bioeconomy sector.
Materials and Methods
Feedstock
The feedstock considered in the calculations in this work is the
OTP described by Martínez-Patiño et al. [11], collected in
Jaén after olive harvesting and air-dried to an equilibrium
moisture content of approximately 7 % w. The OTP was char-
acterized using the National Renewable Energy Laboratory
standard biomass analytical procedures [35]. The OTP com-
position (% dw) was 26.0 cellulose (as glucose); 17.4 xylan
(including xylose, galactose, arabinose, and mannose); 20.1
lignin; 25.6 extractives (5.9 glucose; 3.7 mannitol; 1.3 xylan);
2.5 acetyl group; 2.8 ash; and 5.6 dirt.
Process Description of the Biorefinery Design
The proposed conceptual design of the integrated biorefinery
is composed of two processing plants, as shown in the block
diagram of Fig. 2, namely the antioxidant plant and the
bioethanol plant. A detailed process diagram of the antioxi-
dant plant is depicted in Fig. 8 of the Appendix. These include
conditioning (size reduction, dirt removal, and sieving), ex-
traction (aqueous extraction and separation of solid and liquid
phases), and separation–purification (extraction with ethyl ac-
etate and ethyl acetate recovery and purification via non-ionic
adsorption chromatography). The corresponding stages of the
bioethanol plant are shown in Figs. 9, 10, and 11 of the
Appendix. These are pretreatment (dilute acid pretreatment
1072
of extracted material and detoxification), enzymatic co-
saccharification and co-fermentation, separation (standard
rectifying-stripping distillation and molecular sieves), WWT,
and CHP.
In the first stage of the antioxidant plant, OTP dirt (soil,
small stones, etc.) was removed. Clean OTP was milled and
sieved to homogenize the particle size between 4 mm and
1 cm. In the second stage, the OTP was subjected to a contin-
uous water extraction with 1 h residence time at 120 °C with a
20 % (w/v) solid/liquid ratio, solubilizing approximately
20 %(w/w) of the material [11]. The remaining OTP solids
were filtered off in a rotatory filter and sent to the bioethanol
plant as feedstock fed into the pretreatment step. The filtered
liquid contained phenolic compounds (3.1 g gallic acid equiv-
alent (GAE)/100 g OTP, [11]), which can be used as high
value-added products [36], and all initial mannitol present in
the OTP [11]. In the separation–purification step, this liquid
was extracted with ethyl acetate (EA) at 3:1 (v/v) liquid-
solvent ratio at room temperature (35 °C) for 15 min [3].
Under these conditions, 55 % of the phenolic compounds in
the liquid was recovered, with an extract purity of 36.95 % (g
GAE/g EA extract). In the OTP EA extracts, Conde et al. [3]
identified hydrolysate compounds such as hydroxytyrosol
(the most abundant), oleuropein, tyrosol, and 3,4-
dihydroxybenzaldehyde, which are all known as natural anti-
oxidants with great potential use in the pharmaceutical, food,
and cosmetic sectors [37–39]. The ethyl acetate was recovered
by a combination of pervaporation and distillation steps,
reaching a purity of 99 % and then recirculated into the
separation-purification stage. A non-ionic adsorption chroma-
tography system was used for purification of the natural anti-
oxidants [40]. A mixture of natural antioxidants, with a purity
greater than 60 % (w/w), was recovered (antioxidant recovery
Fig. 2 Block diagram of the olive Air
tree pruning (OTP) biorefinery.
H 2SO4
Black arrows represent process
inputs or outputs. Red arrows Resin
represent streams between Ethyl acetate
different process steps H 2O
OTP
H 2O
H 3PO 4
H 2SO4
Ca(OH) 2
E. coli MS04
KOH
Enzymes
Nutrients
Bacteria
Air
Bioenerg. Res. (2016) 9:1070–1086
greater than 80 % of that present in the liquid). In this antiox-
idant mixture, the majority was hydroxytyrosol. The chroma-
tography column was loaded with a stream of 125 g EA ex-
tract/l, using a load ratio of 45.5 % (v/v) load stream/resin. For
elution, slightly acidic water (0.01 % H2SO4) and an elution
ratio of 8 (v/v) eluent/load stream were used.
The remaining OTP solids (extracted OTP) were subjected
to a 30 % (w/v) solid loading continuous pretreatment using a
diluted solution (0.5 % (w/v)) of H3PO4 at 170 °C for 10 min
[11]. The prehydrolysate was separated and detoxified at
50 °C, adjusting its pH to 10 with Ca(OH) 2 (batch
overliming). After that, it was further subjected to a batch
enzymatic co-saccharification at 50 °C for 72 h using the
commercial enzyme complex Cellic CTec3 (Novozymes
A/S, Denmark) with an enzyme/cellulose ratio of 4.9 %
(w/w). The solid loading was 20 % (w/v), the highest value
that has been reported with no significant enzymatic hydroly-
sis performance loss [41]. After pretreatment and saccharifi-
cation, nearly 70 % of the sugars from the initial extracted
OTP were recovered [11]. For co-fermentation, the modified
microorganism Escherichia coli MS04 was used. The pH was
adjusted to 7 with KOH, and nutrients were added. The batch
fermentation was carried out for 72 h, and all the glucose and
more than 93 % of the xylose were consumed, with a yield of
0.46 g ethanol/g sugar consumed (90.2 % of theoretical) [11],
greater than that obtained with E. coli MM160 with olive
stone [42]. The previous extraction stage in the antioxidant
plant has been demonstrated to improve the solid phase total
sugar recovery in the saccharification stage and hydrolysate
fermentability [43, 44].
Finally, in the separation step, ethanol was obtained by
using a standard two-column sequential rectifying-stripping
distillation system, achieving a 91 % ethanol concentration,
“AntioxidantsPlant”
Wastes
Ethyl acetate
Separation
Conditioning Extraction
Purification Antioxidants
CO2
Saccharification
Pretreatment
Fermentation
Separation Bioethanol
Gypsum +
(Ca)3(PO 4)2
Electricity
Vapor
Gases
Waste water H 2O
Cogeneration
treatment
Ash
“Bioethanol Plant”
H 2O
Bioenerg. Res. (2016) 9:1070–1086
followed by molecular sieves to achieve 99.7 % purity. As
regards WWT, biomass and biogas are produced from the
remnants resulting from the separation stage. At the cogene-
ration stage, biomass and biogas produced in the WWT stage
as well as solids removed in the separation step are burned to
produce steam (high and low pressure) and electricity. The
WWT stage includes a sequential continuous anaerobic–aero-
bic reactor train. In the first reactor, 41 % v/v methane and
59 % v/v carbon dioxide are produced. A clarifier separates
solids from liquids. Solids are sent to a vacuum filter and from
there to the cogeneration stage, while liquid is reused as pro-
cess water. A detailed description of the distillation WWT and
cogeneration models can be found in [34].
Process Model and Simulation
Available OTP amounts and costs were established according
to conditions in Jaén province. As noted in Section 1, OTP
availability is on the order of 1 million ton dw per year.
Assuming an availability of 50 % of biomass for biorefining,
1500 t dw/day can be considered as a technically and econom-
ic feasible upper bound. Feedstock costs were estimated based
on literature references [7, 45] and on first-hand information
of prices in the last years in some local plants for electricity
production from biomass, resulting in a wide range of costs
between 20 €/t dw (minimum transportation costs with no
profit) and 100 €/t dw (expected prices once the OTP is
revalorized due to its use as feedstock). This cost interval
employed can be corroborated with the CIEMAT
BIORAISE application, available at http://bioraise.ciemat.
es/bioraise/. Therefore, the values chosen for plant capacities
and raw material prices were 100, 250, 500, 1000, and 1500 t
dw/day and 20, 40, 60, 80, and 100 €/t dw, respectively. A
capacity of 100 t dw/day may be typical of small-scale facil-
ities, whereas 1500 t dw/day corresponds to a medium-scale
alternative [34].
Steady-state mass and energy balances were solved with
SuperPro Designer v8.5 (SPD). The model comprises 55 unit
operations, 7 reactor stages, and 22 heat exchanger stages built
using SPD standard models. Most design, operational and
kinetic parameters, and property values were taken from the
authors’ own experiments in pilot facilities or investigations
[3, 4, 11, 17, 40], previous preliminary configurations [9], or
conceptual designs of biochemical platform biorefineries pro-
posed by the authors [32, 34] and the SPD database. Table A1
in the Appendix shows the main reactions and conversion
values considered. The results of the mass and energy bal-
ances for the 1500-ton/day biorefinery are included in the
Appendix (Tables 6 and 7) as an illustration of the order-of-
magnitude values and for the interested reader to verify calcu-
lations and results provided in this paper. More detailed infor-
mation, as well as the process model itself, is available from
the authors upon request.
1073
Energy Analysis
A Pinch Point analysis was carried out to determine the MER
[33] in both plants. The EER [46] was introduced to evaluate
the energy efficiency of the bioethanol plant. The EER is
defined as the ratio of energy produced (steam, electricity,
and chemical energy of ethanol) to the total energy consumed
in the process (heating/cooling requirements and electricity)
and was calculated using data from the energy balances. SPD
calculated the mass flow rates, heating/cooling (high (HP) and
low pressure (LP) steam and cooling water) as well as elec-
tricity demands for each piece of process equipment. As an
example of the calculations performed for energy integration,
Figs. 12 and 13 in the Appendix show the composite curves of
the Pinch Point analysis for the 1500-t dw/day plants. Tables 8
and 9 introduce the corresponding temperature deltas and en-
ergy duties for the streams considered. The stream numbering
corresponds to the detailed process diagrams included in the
Appendix.
Economic Analysis
The TPC was calculated for the two products separately, using
discounted cash flow analysis (DCFA) for net present value
(NPV) = 0. The NPV formula is solved as described in
Sanchez et al. [34] as a function of plant capacity and feed-
stock prices for fixed financial conditions. Chemical and prod-
uct storage is not included as part of the model. Thus, their
associated costs are not considered in the TPC.
Equipment size and cost were calculated using SPD
based on plant capacity. All costs and financial parameters
correspond to current conditions (c. 2015) of the Spanish
economy. The enzyme price was established as 3 €/kg
based on a wholesale quote from a European producer,
including transportation costs to Spain. The construction
and plant life period were fixed at 3 and 15 years, respec-
tively, with 330 operation days per year. The interest rate
was set at 6 % [47] and equity at 70 %. The back-payment
was planned from year 3 onwards for the following
3 years. Full production was assumed to begin by the
end of the biorefinery’s commissioning. Equipment prices
were considered to be similar to the US average [48].
Salaries were taken from the Spanish National Institute
of Statistics [49] and local income tax (28 %) from the
Spanish Ministry of Finance and Public Administration
[50]. The antioxidant plant sells the OTP solid phase after
hot water extraction to the bioethanol plant at 30 % its
initial value, matching feedstock values for agro-residues
previously used in similar calculations [34]. This amount
is credited to the TPC of the antioxidant plant. Surplus
energy from the bioethanol plant was sold at market price
to the antioxidant plant.
1074
Results and Discussion
Process Performance
Table 1 shows the daily and annualized feedstock inputs
of OTP, as well as the production of co-products, etha-
nol, and natural antioxidants, as a function of plant
capacity.
The maximum annual production of bioethanol (i.e., 1500 t
dw/day capacity) is 89.16 Ml, representing 24.1 % of total
biofuel requirement in Spain [51]. Therefore, a biorefinery
of this capacity would help to meet the current Spanish obli-
gations in biofuel production and usage before the EU [52]
using local resources.
The natural antioxidant market is large because they can be
used in the food, pharmaceutical, and cosmetic industries. The
maximum annual production in the proposed biorefinery is
10.91 kt dw. In 2012, the market for natural antioxidants
(mainly vitamin C, vitamin E, polyphenols, and carotenoids)
was approximately 150.5 kt and is expected to double by 2022
[53]. In 2007, the market value of vitamins (E, C, B group, and
others) was USD2,272 M [54]. By 2009, the market value was
over USD3,400 M for vitamin C and USD1,390 M for vita-
min E, with selling prices from USD70 to USD300, depend-
ing on purity [55]. Hydroxytyrosol (a major component of the
natural antioxidant mixture obtained in the proposed
biorefinery design) has an antioxidant capacity very similar
to that of vitamin E (α-tocopherol, E307) and vitamin C (L-
ascorbic acid, E300) [56] and is widely used in the food in-
dustry as an antioxidant additive [57]. Therefore, these fig-
ures, together with the results of the economic analysis shown
in Section 3 of this paper, provide a solid basis for proceeding
with the business plan of this biorefinery. Other food additives
commonly used as antioxidants are the synthetic compounds
tertiarybutylhydroquinone (TBHQ, E319),
butylhydroxyanisole (BHA, E320), and butylhydroxytoluene
(BHT, E321) derived from petroleum and ethylenediaminetet-
raacetate calcium and disodium (EDTA calcium and
disodium, E385). However, these can have adverse health
effects [58] and could be replaced by natural antioxidants
obtained from the proposed biorefinery [59].
Table 1 Consumption of
feedstock (OTP) and co-product Plant OTP
production (bioethanol and capacity (kt dw/year)
natural antioxidants) in the (t dw/day)
biorefinery
100 33.00
250 82.50
500 165.00
1000 330.00
1500 495.00
Bioenerg. Res. (2016) 9:1070–1086
Energy Analysis Results
The biorefinery’s annual consumption and production of LP
and HP steam, as well as electricity, without energy integra-
tion, are shown in Table 2. Cooling demands for both plants
are also included, together with the energy savings in heating/
cooling resulting from integration. This integration savings
make the bioethanol plant self-sufficient in cooling/heating
with an average of 6 % surplus steam.
The most energy-intensive operation in the antioxidant
plant is the flash effect (P29/03-V-104 after the chromato-
graphic extraction in Fig. 8), with 8.6 and 129.4 MW for the
100- and 1500-t dw/day capacities, respectively, representing
33 % of the plant’s energy duty. The design challenge of this
plant to move closer to energy self-sufficiency is, therefore, to
improve this operation by reducing its energy demand.
Regarding electricity, the bioethanol plant is also self-
sufficient with a 33.4 % surplus for the smallest plant to
58.1 % for the 1500 t dw/day plant. This surplus electricity
from the bioethanol plant is sold to the antioxidant plant, con-
tributing to meeting the electricity demand from 6.9 % for the
smallest antioxidant plant to 5.6 % for the 1500 t dw/day
capacity antioxidant plant. An important reduction in electric-
ity consumption in the bioethanol plant took place because the
milling process was allocated to the antioxidant plant. For
instance, for the 1500-t dw/day bioethanol plant, the reduction
was from 8.5 MW in the base-case design [32] to 0.45 MW.
The sensitivity of EER values for the bioethanol plant for
plant capacities is shown in Fig. 3. All capacities produce
more than 2.5 the energy employed by the process. The
EER reduction from 1000 to 1500 t dw/day is because SPD
included as part of the 1500 design two rotatory filter units in
the purification stage (115 kWh/h each) against one filter unit
with 300 kW power in the 1000-t dw/day plant.
Economic Analysis Results
Relevant economic parameters are shown in Table 3. The
total equipment cost is between 32 and 342 M€, the in-
vestment between 100 and 1100 M€, and the operation
costs between 13 and 121 M€/year, with most of these
Bioethanol Natural
(Ml/year) antioxidants
(kt dw/year)
5.94 0.73
14.86 1.82
29.72 3.64
59.44 7.28
89.16 10.91
Bioenerg. Res. (2016) 9:1070–1086 1075

Table 2 Annual energy demand (without integration), production (LP and HP steam and electricity) and savings in heating with energy integration

Plant capacity (t dw/day)

100 250 500 1000 1500

Antioxidant plant
Annual demand
LP (MWh) 313,781 784,745 1,569,066 3,137,711 4,706,349
HP (MWh)
Electricity (MWh) 13,714 19,455 29,025 58,034 84,256
Total (103 MWh) 328 804 1598 3196 4791
Integration savings (heating) (%) 27 27 27 27 27
Integration savings (cooling) (%) 29 29 30 29 30

Bioethanol plant
Annual demand
LP (MWh) 78,011 195,231 390,592 781,330 1,153,749
HP (MWh) 29,506 74,861 149,719 299,443 449,158
Electricity (MWh) 2784 6383 12,383 24,382 34,161
Total (103 MWh) 110 276 553 1105 1637
Integration savings (heating) (%) 64 63 63 63 63
Integration savings (cooling) (%) 66 61 61 57 57
Annual production
LP (MWh) 41,819 104,632 209,316 418,693 628,059
HP (MWh) 22,093 55,582 111,395 223,025 334,648
Electricity (MWh) 3729 11,066 24,418 52,561 81,475
Total (103 MWh) 68 172 345 694 1044

values pertaining to the antioxidant plant, which accounts
for between 54 and 75 % of total costs. The utility cost is
between 2 and 36 M€/year, related, again, almost entirely
to the antioxidant plant (>95 %) due to the energy inte-
gration strategy discussed in the previous subsection.
The costs of the three most important inputs (resin, enzymes,
and ethyl acetate, although the latter is recovered in the process
itself and reused), besides OTP, are also shown in Table 3.
The influence of feedstock cost on the TPC of the bioethanol
and antioxidant plants is summarized in Table 4. As mentioned

Fig. 3 Bioethanol plant EER

1076 Bioenerg. Res. (2016) 9:1070–1086

Table 3 Economic analysis

parameters Plant capacity (t dw/day)

100 250 500 1000 1500

Antioxidant plant
Equipment cost (M€) 17.34 41.57 85.62 168.76 252.64
Total investment (M€) 54.31 130.23 268.21 528.64 791.40
Resin cost (M€/year) 14.58 36.44 72.89 145.78 218.67
Ethyl acetate cost (M€/year) 6.21 15.44 30.83 61.60 92.37
Operation cost (M€/year) 7.17 15.73 31.22 60.57 90.16
Utilities (M€/year) 2.21 5.54 11.07 22.14 33.21
Annual income (M€/year) 27.43 60.25 119.98 237.25 354.70

Bioethanol plant
Equipment cost (M€) 14.79 21.51 35.92 62.63 89.11
Total investment (M€) 46.34 67.39 112.52 196.19 279.15
Enzymes cost (M€/year) 0.89 2.23 4.47 8.93 14.17
Operation cost (M€/year) 5.97 8.25 13.09 22.25 31.27
Utilities (M€/year) 0.12 0.29 0.57 1.13 2.55
Annual income (M€/year) 11.98 18.12 30.30 53.32 77.46

in Subsection 2.5, the antioxidant plant sells the discarded OTP
after extraction to the bioethanol plant at 30 % its original cost.
The biorefinery’s annual TPC is between 49 and 654 M€, with
the antioxidant plant representing between 74.5 % (100 t dw/
day, 100 €/t) and 87.3 % (1500 t dw/day, 20 €/t). The feedstock
costs as a percentage of TPC for the antioxidant plant are in the
range of 1.8 and 8.9 %. This small percentage is due to the high
equipment, investment, and resin costs (Table 3 and Fig. 4).
Note that this value shows a small dependence on plant capacity.
Therefore, as expected, economies of scale will not play such a
relevant role as with commodity products such as the
bioethanol. In the case of the bioethanol plant, the feedstock cost
contribution to TPC is more important, ranging between 2.7 and
24.4 %. The costs of raw material as a percentage of TPC for the
biorefinery (ratio between total costs of raw material and total
production costs, considering both the antioxidant and the
bioethanol plants) account from 2.0 % (for a smallest plant with
lowest price feedstock) to 11.2 % (for the largest plant with the
most expensive feedstock).
The sensitivity of TPC values for the antioxidant plant for
the defined intervals of plant capacities and feedstock prices is
shown in Fig. 4. The highest natural antioxidant TPC is
53.85 €/kg for the smaller plant and the most expensive
OTP (100 t dw/day, 100 €/t dw), and the lowest is 48.89 €/
kg (1500 t dw/day, 20 €/t dw), almost 10 % lower. The TPC
values exhibit the typical exponential decrease as a function of

Table 4 Influence of feedstock cost in bioethanol and antioxidants TPC

Plant capacity (t dw/day)

100 250 500 1000 1500

Antioxidant plant
Feedstock price (OTP) (€/t) 20 100 20 100 20 100 20 100 20 100
Feedstock cost (M€/year) 0.66 3.30 1.65 8.25 3.30 16.50 6.60 33.00 9.90 49.50
Total cost (M€/year) 37.75 39.18 90.07 93.64 179.63 186.77 356.55 370.82 533.66 555.07
Feedstock cost/total cost (%) 1.75 8.42 1.83 8.81 1.84 8.83 1.85 8.90 1.86 8.92

Bioethanol plant
Feedstock price (extracted OTP) (€/t) 6 30 6 30 6 30 6 30 6 30
Feedstock cost (M€/year) 0.32 1.60 0.80 4.00 1.60 8.01 3.20 16.01 4.80 24.02
Total cost (M€/year) 11.98 13.44 18.12 21.77 30.30 37.60 53.32 67.92 77.46 98.58
Feedstock cost/total cost (%) 2.67 11.91 4.42 18.39 5.29 21.29 6.01 23.58 6.20 24.37
Bioenerg. Res. (2016) 9:1070–1086 1077

55 53.85 2.27
2.5 2.22
53.36 2.16
54 52.87 2.09
2.03
Antioxidants TPC

53 52.37 2.0

Bioethanol TPC
51.88 51.47
51.33 1.46
52 50.98 1.41
(€/kg)

50.84 50.96

(€/l )
51 50.49 50.85 1.30 1.26
50.35 50.47 1.5 1.28 1.21
50.00 50.36 1.14
50 49.86 49.98 1.22 1.14 1.09 1.11
49.51 49.87 1.08 1.02 1.05
49 49.37 49.49 1.0 1.02 0.99
0.96
49.38 0.92
48 49.00 0.90
48.89 0.86
100 0.5
250
500 100
250
1000 500
Plant capacity 1000
1500 OTP price Plant capacity 1500 Extracted OTP price
(t dw/day) (€/t) (t dw/day) (€/t)
Fig. 4 Total production cost (TPC) of natural antioxidants versus plant Fig. 6 Bioethanol total production cost (TPC) versus plant capacity and
capacity and olive tree pruning (OTP) price extracted olive tree pruning (OTP) price

plant capacity. Interestingly, TPC decreases only 1.3 % almost identified in the OTP) may be between 75 and 300 €/kg for
linearly from 250 to 1500 t dw/day capacity. A linear tendency concentrations between 12 and 65 % w [60]. Using this max-
can also be observed with respect to OTP price changes. In imum selling price, a DCFA calculation was carried out for the
this case, the TPC increases as a function of OTP price, 1000-t dw/day (100 €/t dw) facility, achieving an IRR of 23 %
exhibiting a 3.9 % increase from 20 to 100 €/kg. Therefore, with a payback time of 4.2 years and an ROI of 23.6 %.
considering small-capacity biorefineries for natural antioxi- Therefore, this high profitability based on this preliminary
dants, production could be an interesting alternative from an design may well support to go forward in the construction of
economic point of view. The most important contributors to a business case.
the natural antioxidant TPC, as shown in Fig. 5, are raw ma- With respect to the high-volume production of low-price
terials, principally resin, with values from 37.3 to 41.1 %, bioethanol, Fig. 6 shows that TPC, in all cases, is greater than
followed by the operation costs, with values around 17.3– 0.86 €/l, with the highest value being 2.27 €/l for the smallest
19.8 %, and ethyl acetate, with contributions around 15.9– plant and the most expensive OTP (100 t dw/day, 100 €/t dw).
17.3 %. Service contribution is depicted separately from op- The lowest value is 0.86 €/l, as expected, for the largest plant
eration costs to highlight its contribution and its impact if heat (1500 t dw/day) and cheapest feedstock (6 €/t dw). TPC tenden-
integration is considered. cies are similar to the antioxidant TPC. Quasi-linear increments
The market price of natural antioxidant mixtures whose can be observed as function of plant capacity from 250 to 1500 t
main compound is hydroxytyrosol (one of the antioxidants dw/day and the complete interval of extracted OTP price.

Fig. 5 Contributions to the total Antioxidants TPC €( /kg)

production cost (TPC) of 51.88 48.89 52.37 49.38 52.87 49.87
100%
antioxidants 5.89% 6.07% 5.8% 6.0% 5.67% 5.8%
6.0% 6.2% 4.3% 4.3%
90% 7.9% 8.07% 1.5%
3.6% 1.5% 3.5%
3.6% 1.58% 5.6% 6.0%
5.8% 6.1%
80% 5.9% 6.22%
17.3%
70% 17.5% 19.3%
Contributions to TPC (%)

17.77% 19.5%
19.8%
60%

50%
39.5%
40.3% 37.3%
40% 41.11% 38.0%
38.7%
30%

20%
15.9% 16.6%
16.1% 17.0%
10% 16.4% 17.31%

5.1% 5.5% 8.4% 8.9%

0% 1.7% 1.86%
100-20 1500-20 100-60 1500-60 100-100 1500-100
Plant capacity (t dw/day)-OTP price (€/t)
Feedstock Ethyl Acetate Inputs Operation Costs-Services
Services Electricity Total Investment Financial Expenses
1078 Bioenerg. Res. (2016) 9:1070–1086

Fig. 7 Contributions to the total Bioethanol TPC (€/l)

production cost (TPC) of 2.03 0.86 2.16 0.99 2.27 1.11
100%
bioethanol. BInputs^ refer to other 14.75% 11.6%
raw materials different from 15.83% 14.9% 14.5% 14.1%
90%
feedstock and enzymes 17.1%
80% 21.81%
22.0% 21.4% 20.9% 2.6%
23.4%
70%
3.30%
0.9%

Contributions to TPC ( %)
0.9% 0.9%
60% 1.0%
32.3%
50%
40.37%
45.8% 44.7% 1.1%
40% 47.1%
49.9%
15.8%
30%
1.38%
20% 0.5%
0.5%
18.29% 0.6% 7.7%
7.9% 24.4%
10% 0.6% 7.7%
7.5% 9.8% 11.9%
6.20% 7.5%
0% 2.7%
-0.8% -6.11% -0.7% -0.7% -0.7% -4.8%
-10%
100-6 1500-6 100-18 1500-18 100-30 1500-30
Plant capacity (t dw/day)-Extracted OTP price€/t)
(
Feedstock Enzymes Inputs Operation Costs-Services
Services Electricity Total Investment Financial Expenses

However, TPC differences between boundary plant capacities
are 42 %, while for boundary, extracted OTP prices are 29 %.
Therefore, economies of scale become important for bioethanol
production facilities. The TPC contributions are shown in Fig. 7.
The largest contributor is operation costs with a range between
32.3 and 49.9 %, depending on the combination of plant capac-
ity and extracted OTP price. Total investment follows, with
values of approximately 17.1–23.4 %. Financial expenses also
play an important role. Feedstock contribution increases up to
24.4 % for the largest extracted OTP price.
The bioethanol TPC obtained in this study was compared with
previous values [34, 61] published between 1982 and 2013 for
different lignocellulosic feedstocks (softwood, hardwood, corn
stover, wheat straw, etc.) with plant capacities ranging between
100 and 8521 t dw/day and the price of raw material ranging
between 22 and 91.5 €/t dw and using biochemical platforms
forlignocellulosicethanolproduction.Accordingtothesestudies,
the updated bioethanol TPC for plant capacities from 600 to
2100 t dw/day is between 0.95 and 0.70 €/l. In the current study,
TPC is within this range if the extracted OTP price is 6–12 €/t dw
and plant capacity is between 1000 and 1500 t dw/day.
The market price of bioethanol in Europe (Ethanol T2 FOB
Rotterdam) in September 2015 was 824.15 €/t (0.64 €/l) [51]. The
bestTPC resultobtained was0.86€/l,34 % higherthan the current
market price. This provides an indicator of the deficit amount
(from TPC to selling price) that should be considered as a subsidy
in the business case of the bioethanol plant for the current crude oil
market conditions. This deficit could also be used for
benchmarking other factors beyond the techno-economics of
bioethanol production that may contribute to diminishing the def-
icit, for instance, monetizing the contribution of this plant to
meeting the Spanish targets of biofuel production or the improve-
ment of the environmental conditions by reducing the GHG
emissions.
Conclusions
This biorefinery design highlights the importance of including
aspects not usually considered in techno-economic analyses be-
yond basic economics in order to provide a suitable answer to the
bioeconomy conundrum of low-cost large-volume commodity
versus high value-added low-quantity specialty production.
Monetizing other aspects usually arising from sustainability anal-
yses or life cycle (LCA) analyses may become a key factor for
improving the profitability ofthiskind ofschemesin the emerging
bioeconomy.
As regards this particular agroindustrial residue, locating an
OTP biorefinery in the province of Jaén may be worth exploring
further in a more detailed business case thanks to the abundance of
this raw material that would meet the demand for bioethanol in
Andalusia and nearby regions of southern Spain, thus contribut-
ing to the energy matrix in this particular geographical area while
simultaneously helping to solve a severe regional environmental
problem. This same approach could be envisaged in other olive
production regions in Italy, Greece, Turkey, and Morocco or the
northwest region of Mexico, where there is an incipient but highly
dynamic and fast-growing olive oil industry.
Acknowledgments The authors wish to express their gratitude for
partial financial support from Consejería de Economía, Innovación
y Ciencia (Junta de Andalucía), Proyecto de Investigación de
Bioenerg. Res. (2016) 9:1070–1086 1079

Excelencia AGR-6103, including JMRG scholarship, Campus de
Excelencia Internacional Agroalimentario (ceiA3), and Banco
Santander S.A. (BBecas Iberoamérica. Jóvenes Profesores e
Investigadores, 2014. Santander Universidades^). Partial financial
support is also acknowledged from the Mexican Council of
Science and Technology (CONACYT), Bioenergy Thematic
Network (BRed Temática de Bioenergía^), grant 260457, and the
Energy Sustainability Fund 2014-05 (CONACYT-SENER),
Mexican Bioenergy Innovation Centre, Bioalcohols Cluster
(249564). Special thanks are due to Antonio Lama-Muñoz and
Subproductos Vegetales del Mediterráneo, S.L. (Ctra. Isla Menor,
s/n CP 41014 Bellavista, Seville, Spain) for their collaboration
and advice. The feedback from the reviewers is also deeply
appreciated.

Appendix

Table 5 Main reaction and conversion values of the bioethanol plant

(mole basis)

Reaction Conversion (%) Ref.

Pretreatment + enzymatic co-saccharification Table 6 Antioxidant plant mass and energy balance for plant capacity
Cellulose + water → glucose 63.8 11 1500 t dw/day
Hemicellulose + water → xylose 65.6 11
Conditioning
Hemicellulose + water → arabinose 12.9 11
Electricity (MWh/day) 178.8
Overliming (prehydrolysate) Flow in (t/day) Flow out (t/day)
2 H3PO4 + 3 Ca(OH)2 → 6 H2O + Ca3(PO4)2 100 OTP 1500.0 1413.8
Wastes 86.2
pH adjusted to 5 for co-saccharification Extraction
Ca(OH)2 + H2SO4 → 2 H2O + CaSO4 100 Electricity (MWh/day) 18.0
Heat (MWh/day) 1899.4
pH adjusted to 7 for co-fermentation Flow in (t/day) Flow out (t/day)
H2SO4 + 2 KOH → 2 H2O + K2SO4 100 OTP 1413.8
H3PO4 + 3 KOH → 3 H2O + K3PO4 100 Water 5135.6 5239.6
Extracted OTP 1011.7
Co-fermentation
Water extract 167.0
Glucose → 2 CO2 + 2 ethanol 98 11
Cellulose 44.3
0.07 nutrients + glucose → 2.4 water + 2 11
Glucose 21.9
6 E. coli MS04
3 xylose → 5 CO2 + 5 ethanol 93 11 Xylose 13.9
0.07 nutrients + xylose → 2 water + 2 11 Mannitol 51.1
5 E. coli MS04
3 arabinose → 5 CO2 + 5 ethanol 98 11 Separation-purification
0.07 nutrients + arabinose → 2 2 11 Electricity (MWh/day) 58.5
water + 5 E. coli MS04 Heat (MWh/day) 12,362.1
Anaerobic reactors Flow in (t/day) Flow out (t/day)
Acetic acid → CO2 + methane 95 34 Water 9950.8 9950.8
Ethanol → 0.5 CO2 + 1.5 methane 95 34 Water extract 167.0 134.2
Acetic acid → 2.44 biomass 3 34 Cellulose 44.3 44.3
Ethanol → 1.87 biomass 3 34 Glucose 20.8 20.8
Xylose 13.9 13.9
Aerobic reactors
Mannitol 50.6 50.6
Acetic acid + 2 O2 → 2 CO2 + 2 water 60 34
Ethyl acetate 1176.1 8.0
Ethanol + 3 O2 → 2 CO2 + 3 water 60 34
Sulfuric acid 0.4 0.4
Acetic acid → 2.44 biomass 30 34
Air 16.1
Ethanol → 1.87 biomass 30 34
Resin (l/day) 30,535.8 30,535.8
Cogeneration Wet air 19.3
S-product + O2 (air) → SO2 + water 100 34 Ethyl acetate recovered (99 % w) 1164.6
C-product + O2 (air) → CO2 + water 100 34 Antioxidants (99 % w) 33.1
1080 Bioenerg. Res. (2016) 9:1070–1086

Table 7 Bioethanol plant energy and mass balance for plant capacity Table 7 (continued)
1500 t dw/day
WWT system
Pretreatment, enzymatic co-saccharification, and co-fermentation Electricity (MWh/day) 6.5
Flow in (t/day) Flow out (t/day)
Electricity (MWh/day) 78.2 Water 414.0
Heat (MWh/day) 1876.3 Nutrients 0.9 0.8
Flow in (t/day) Flow out (t/day) Acetic acid 1.7 0
(pretreatment) (co-fermentation) Ethanol 2.2 0
Air 216.2 216.2
Water 4375.3 4288.2
Methane 1.5
Cellulose 375.7 144.2 Carbon dioxide 2.2
Hemicellulose 244.3 54.5 Biomass (55 % w) 0.1
Lignin 280.4 280.4 Treated water (99.8 % w) 414.1
Ash 39.0 39.0
Cogeneration (electricity and steam) (CHP)
Extractives 35.8 35.8 Electricity (MWh/day) −235.1
Phosphoric acid 5.0 0 Heat (MWh/day) −2917.3
Calcium hydroxide 5.4 0 Flow in (t/day) Flow out (t/day)
Water 2956.2 159.0
Sulfuric acid 0.2 0 Cellulose 144.2
Enzymes 17.4 17.4 Hemicellulose 54.5
Potassium hydroxide 0.8 0 Lignin 280.4
Ash 39.0
Nutrients 10.5 8.7
Extractives 35.8
Xylose 13.1 Enzymes 17.4
Acetic acid 35.0 Potassium hydroxide 0.0
Gypsum and calcium 9.1 Nutrients 7.1
phosphate (82.5 % w) Xylose 13.1
Potassium sulfate 0.3 Acetic acid 21.3
Potassium sulfate 0.3
Tri-potassium phosphate 0.7
Tri-potassium phosphate 0.7
E. coli MS04 37.1 E. coli MS04 37.1
Ethanol 217.8 Ethanol 0.1
Carbon dioxide 208.5 Methane 1.5
Carbon dioxide 2.2
Biomass (55 %) 0.1
Bioethanol separation
Air 2707.6
Electricity (MWh/day) 7.0 Gases (CO2, SO2, air, water) 4499.1
Heat (MWh/day) 2981.5 Ash 52.7
Flow in (t/day) Flow out (t/day) LP steam 1113.1
HP steam 494.7
Water 4332.6 4332.6
Cellulose 144.2 144.2
Hemicellulose 54.5 54.5
Lignin 280.4 280.4
Ash 39.0 39.0
Extractives 35.8 35.8
Enzymes 17.4 17.4
Potassium hydroxide 0.0 0.0
Nutrients 8.7 8.7
Xylose 13.1 13.1
Acetic acid 35.0 35.0
Potassium sulfate 0.3 0.3
Tri-potassium phosphate 0.7 0.7
E. coli MS04 37.1 37.1
Ethanol 217.8 3.9
Bioethanol (99.7 % w) 213.9
(270.2 m3/day)
Bioenerg. Res. (2016) 9:1070–1086 1081

Table 8 Temperature deltas and energy duties of energy integration composite curves for antioxidant plant

No. Stream Input temp. (°C) Output temp. (°C) ΔT (°C) Duty (kW) Accumulated
total duty (kW)

Hot composite curve

1 S-119 26 28 2 2 2
2 S-119 + S-120 28 30 2 205 206
3 S-119 + S-120 + S145 30 35 5 1440 1646
4 S-119 + S-120 + S145 + S108 35 50 16 7958 9604
5 S-119 + S-120 + S145 + S108 + ultrafiltration 50 70 20 15,401 25,006
6 S-120 + S108 + ultrafiltration 70 77 7 5508 30,514
7 S-120 77 90 13 1280 31,794
8 S-107′ + S-120ʹ 90 90 0 14,534 46,329
9 A101 90 100 10 2875 49,204
10 S130ʹ 100 100 0 133,585 182,788
11 S101 100 120 20 5750 188,538

Cold composite curve

12 S130 + S129 25 35 10 4972 4972
13 Extract liq-liq 35 35 0 327 5299
14 S134 + S129 + S115 + S-112 35 70 35 28,656 33,955
15 Rotatory drying 70 70 0 156 34,112
16 S134 + S129 + S115 + S-112 70 80 10 8187 42,299
17 S134 + S115 + S129 80 90 10 5916 48,215
18 S-116ʹ 90 90 0 1156 49,371
19 S134 + S129 90 100 10 4972 54,343
20 S-132′ + S141ʹ 100 100 0 143,539 197,882
21 S134 100 120 20 5705 203,588

Table 9 Temperature deltas and energy duties of energy integration composite curves for bioethanol plant

No. Stream Input temp. (°C) Output temp. (°C) ΔT (°C) Duty (kW) Accumulated total duty (kW)

Hot composite curve

1 513A + 521A 26 35 9 2230.32 2230.32
2 513A + 521A + 611A 35 37 2 536.36 2766.68
3 513A + 521A + 611A + 911A 37 50 13 6516.43 9283.12
4 513A + 521A + 311A + 611A + 411B 50 64 14 7042.90 16,326.01
5 513A+521A + 311A + 611A 64 78 14 5034.59 21,360.61
6 512´ 78 78 0 22,335.82 43,696.42
7 513A + 521A + 311C + 611A 78 80 2 715.14 44,411.56
8 513A´ 80 80 0 2968.56 47,380.13
9 521A + 311A + 611A 80 90 10 3118.36 50,498.48
10 521A + 611A + 224B 90 100 10 4596.00 55,094.48
11 224B 100 170 70 16,600.67 71,695.15

Cold composite curve

12 211C + 223B + 402 25 37 12 2433.85 2433.85
13 211C + 223B + 511A + 402 37 50 13 6146.31 8580.16
14 223B + 511A + 212B 50 90 40 16,458.28 25,038.44
15 223B + 212B 90 95 5 707.42 25,745.87
16 223B + 212B + 511A 95 100 5 2057.29 27,803.15
17 521´ + 541A´ 100 100 0 25,719.80 53,522.96
18 223B + 212B 100 170 70 9903.95 63,426.91
1082 Bioenerg. Res. (2016) 9:1070–1086

Fig. 8 Process diagram of antioxidant plant

Fig. 9 Process diagram of bioethanol plant. Pretreatment stage

Bioenerg. Res. (2016) 9:1070–1086 1083

Fig. 10 Process diagram of bioethanol plant. Saccharification, fermentation, and separation stages

Fig. 11 Process diagram of bioethanol plant. Cogeneration and WWT stages

1084 Bioenerg. Res. (2016) 9:1070–1086

Fig. 12 Composite diagram of

heat integration for antioxidant
plant (1500 t dw/day)

Fig. 13 Composite diagram of

heat integration for bioethanol
plant (1500 t dw/day)
Bioenerg. Res. (2016) 9:1070–1086
References
1. Cara C, Ruiz E, Ballesteros M, Manzanares P, Negro MJ, Castro E
(2008) Production of fuel ethanol from steam-explosion pretreated
olive tree pruning. Fuel 87:692–700. doi:10.1016/j.
fuel.2007.05.008
2. FAOSTAT (2015) Food and Agriculture Organization of the United
N a t i o n s ( FA O ) . R o m e , I t a l y. h t t p : / / f a o s t a t 3 . f a o .
org/browse/Q/QC/S. Accessed 29 Oct 2015
3. Conde E, Cara C, Moure A, Ruiz E, Castro E, Domínguez H (2009)
Antioxidant activity of the phenolic compounds released by hydro-
thermal treatments of olive tree pruning. Food Chem 114:806–812.
doi:10.1016/j.foodchem.2008.10.017
4. Romero-García JM, Niño L, Martínez-Patiño C, Álvarez C, Castro
E, Negro MJ (2014) Biorefinery based on olive biomass. State of
the art and future trends. Bioresour Technol 159:421–432.
doi:10.1016/j.biortech.2014.03.062
5. SODEAN (2004) Andalucia Energy Development Society
(SODEAN S.A.). Use and potentials of olive grove biomass in
A n d a l u s i a ( i n S p a n i s h ) . h t t p : / / w w w. i n f a o l i v a .
com/documentos/documentos/Potencial%20y%20
Aprovechamiento%20del%20Olivar.pdf. Accessed 15 Nov 2015
6. García-Maraver A, Zamorano M, Ramos-Ridao A, Díaz LF (2012)
Analysis of olive grove residual biomass potential for electric and
thermal energy generation in Andalusia (Spain). Renew Sust Energ
Rev 16:745–751. doi:10.1016/j.rser.2011.08.040
7. Castro-Galiano E, Torres-Velasco E, Gallego-Álvarez FJ (2010)
Logistics of olive grove biomass as a source of renewable energy
(in Spanish). Proc. National Congress on Environment
(CONAMA10), Madrid 2010
8. Aden A, Ruth M, Ibsen K, Jechura J, Neeves K, Sheehan J (2002)
Lignocellulosic biomass to ethanol process design and economics
utilising co current dilute acid prehydrolysis and enzymatic hydro-
lysis for corn stover. Technical Report. National Renewable Energy
Laboratory (NREL) NREL/TP-510-32438
9. Manzanares P, Negro MJ, Oliva JM, Saéz F, Ballesteros I,
Ballesteros M, Cara C, Castro E, Ruiz E (2011) Different process
configurations for bioethanol production from pretreated olive
pruning biomass. J Chem Technol Biotechnol 86:881–887.
doi:10.1002/jctb.2604
10. Toledano A, Alegría I, Labidi J (2013) Biorefining of olive tree
(Olea europea) pruning. Biomass Bioenergy 59:503–511.
doi:10.1016/j.biombioe.2013.10.019
11. Martínez-Patiño JC, Romero-García JM, Ruiz E, Oliva JM, Álvarez
C, Romero I, Negro MJ, Castro E (2015) High solids loading pre-
treatment of olive tree pruning with dilute phosphoric acid for
bioethanol production by Escherichia coli. Energy Fuel 29:1735–
1742. doi:10.1021/ef502541r
12. Sanna A (2014) Advanced biofuels from thermochemical process-
ing of sustainable biomass in Europe. Bioenerg Res 7:36–47.
doi:10.1007/s12155-013-9378-4
13. Directive 2009/28/EC (2009) European Parliament and Council, 23
April 2009, relative to promoting the use of energy from renewable
sources
14. Spizzirri UG, Restuccia D, Chiricosta S, Ol P, Cirillo G,
Curcio M, Iemma F, Puoci F, Picci N (2011) Olive stones as
a source of antioxidants for food industry. J Food Nutr Res 50:
57–67
15. Vegas R, Alonso JL, Domínguez H, Parajó JC (2005) Manufacture
and refining of oligosaccharides from industrial solid wastes. Ind
Eng Chem Res 44:614–620
16. Aranda-Barradas JS, Garibay-Orijel C, Badillo-Corona JA,
Salgado-Manjarrez E (2010) A stoichiometric analysis of biologi-
cal xylitol production. Biochem Eng J 50:1–9. doi:10.1016/j.
bej.2009.10.023
1085
17. Cara C, Ruiz E, Carvalheiro F, Moura P, Ballesteros I, Castro E,
Gírio F (2012) Production, purification and characterisation of oli-
gosaccharides from olive tree pruning autohydrolysis. Ind Crop
Prod 40:225–231. doi:10.1016/j.indcrop.2012.03.017
18. Toledano A, Serrano L, Labidi J (2011) Enhancement of lignin
production from olive tree pruning integrated in a green biorefinery.
Ind Eng Chem Res 50:6573–6579. doi:10.1021/ie102142f
19. Yoshikawa T, Shinohara S, Yagi T, Ryumon N, Nakasaka Y, Tago
T, Masuda T (2014) Production of phenols from lignin-derived
slurry liquid using iron oxide catalyst. Appl Catal B Environ 146:
289–297. doi:10.1016/j.apcatb.2013.03.010
20. Baker DA, Rials TG (2013) Recent advances in low-cost carbon
fibre manufacture from lignin. J Appl Polym Sci 130:713–728.
doi:10.1002/app.39273
21. Pohjanlehto H, Setälä HM, Kiely DE, McDonald AG (2014)
Lignin-xylaric acid-polyurethane-based polymer network systems:
Preparation and characterization. J Appl Polym Sci 131. doi:
10.1002/app.39714
22. Kamm B, Kamm M (2004) Principles of biorefineries. Appl
Microbiol Biotechnol 64:137–145. doi:10.1007/s00253-003-
1537-7
23. IEA (2009) International Energy Agency. Task 42 biorefineries.
h t t p : / / w w w. i e a - b i o e n e r g y . t a s k 4 2 - b i o r e f i n e r i e s .
com/en/ieabiorefinery.htm. Accessed 15 Nov 2015
24. National Renewable Energy Laboratory (2009). What is a
biorefinery? http://www.nrel.gov/biomass/biorefinery.html.
Accessed 15 Nov 2015
25. Requejo A, Peleteiro S, Garrote G, Rodríguez A, Jiménez L (2012)
Biorefinery of olive pruning using various processes. Bioresour
Technol 111:301–307. doi:10.1016/j.biortech.2012.01.156
26. Dávila JA, Hernández V, Romero-García JM, Castro-Galiano E,
Cardona CA (2014) Techno-economic assessment of gasification
schemes for electricity generation from olive tree pruning. Paper
presented at the 13th European Workshop on Lignocellulosics and
Pulp Proceedings. ISBN: 978–84–616-9842-4 2014
27. Sagani A, Hagidimitriou M, Dedoussis V (2014) Techno-economic
evaluation of tree pruning biomass fired power plants for electricity
generation: the case of three prefectures in Greece. Proc. 22nd
European Biomass Conference and Exhibition. ISSN 2282–5819
2014
28. Vera D, Jurado F, Margaritis NK, Grammelis P (2014)
Experimental and economic study of a gasification plant fuelled
with olive industry wastes. Energ Sustain Dev 23:247–257.
doi:10.1016/j.esd.2014.09.011
29. Charisiou ND, Paraskeva CA, Goula MA, Papadakis VG (2014)
Techno-economical & sustainability analyses for multilateral ex-
ploitation of olive tree cultivation residues. J Environ Sci Technol
Res 1:1–6
30. Hernández V, Romero-García JM, Dávila JA, Castro E, Cardona
CA (2014) Techno-economic and environmental assessment of an
olive stone based biorefinery. Resour Conserv Recycl 92:145–150.
doi:10.1016/j.resconrec.2014.09.008
31. Bozell JJ, Astner A, Baker D, Biannic B, Cedeno D, Elder T,
Hosseinaei O, Delbeck L, Kim JW, O’Lenick CJ, Young T (2014)
Integrating separation and conversion-conversion of biorefinery
process streams to biobased chemicals and fuels. Bioenerg Res 7:
856–866. doi:10.1007/s12155-014-9424-x
32. Sanchez A, Magaña G, Partida MI, Sanchez S (2016) Bi-
dimensional sustainability analysis of a multi-feed biorefinery de-
sign for biofuels co-production from lignocellulosic residues and
agro-industrial wastes. Chem Eng Res Des Vol 107C(2016):195–
217
33. Kemp IC (2007) Pinch analysis and process integration. 2nd ed.
Butterworth-Heinemann
34. Sanchez A, Sevilla-Güitrón V, Magaña G, Gutierrez L (2013)
Parametric analysis of total costs and energy efficiency of 2G
1086
enzymatic ethanol production. Fuel 113:165–179. doi:10.1016/j.
fuel.2013.05.034
35. National Renewable Energy Laboratory (2013) (NREL) Chemical
analysis and testing laboratory analytical procedures. Washington
D.C., EE.UU. http://www.eere.energy.gov/biomass/analytical_
procedures.html. Accessed 15 Oct 2015
36. Fernández-Bolaños J, Rodríguez G, Gómez E, Guillén R, Jiménez A,
Heredia A, Rodríguez R (2004) Total recovery of the waste of two-
phase olive oil processing: isolation of added-value compounds. J
Agric Food Chem 52:5849–5855. doi:10.1021/jf030821y
37. El SN, Karakaya S (2009) Olive tree (Olea europaea) leaves: po-
tential beneficial effects on human health. Nutr Rev 67:632–638.
doi:10.1111/j.1753-4887.2009.00248.x
38. Erbay Z, Icier F (2010) The importance and potential uses of olive
leaves. Food Rev Int 26:319–334. doi:10.1080/87559129.2010.496021
39. Rodrigues F, Pimentel FB, Oliveira MPP (2015) Olive by-products:
challenge application in cosmetic industry. Ind Crop Prod 70:116–
124. doi:10.1016/j.indcrop.2015.03.027
40. Fernández-Bolaños J, Rodríguez Gutiérrez G, Lama Muñoz A,
Rubio-Senent F, Fernandez-Bolaños Guzmán JM, Maya I, López
López Ó, Marset Castro A (2013) Procedure to obtain
hydroxytyrosol extract, hydroxytyrosol extract mixture and 3, 4-
dihydroxifenilglicol, and hydroxytyrosile acetate extract, a from
olive subproducts and their purification (in Spanish). Spanish patent
ES 2 395 317 B1. Patent WO 2013007850 A1
41. Cara C, Moya M, Ballesteros I, Negro MJ, González A, Ruiz E
(2007) Influence of solid loading on enzymatic hydrolysis of steam
exploded or liquid hot water pretreated olive tree biomass. Process
Biochem 42:1003–1009. doi:10.1016/j.procbio.2007.03.012
42. Romero-García JM, Martínez-Patiño C, Ruiz E, Romero I, Castro E
(2016) Ethanol production from olive stone hydrolysates by xylose
fermenting microorganisms. Bioethanol 2(1):51–65. doi:10.1515
/bioeth-2016-0002
43. Ballesteros I, Ballesteros M, Cara C, Sáez F, Castro E, Manzanares
P, Negro MJ, Oliva JM (2011) Effect of water extraction on sugars
recovery from steam exploded olive tree pruning. Bioresour
Technol 102:6611–6616. doi:10.1016/j.biortech.2011.03.077
44. Negro MJ, Alvarez C, Ballesteros I, Romero I, Ballesteros M,
Castro E, Manzanares P, Moya M, Oliva JM (2014) Ethanol pro-
duction from glucose and xylose obtained from steam exploded
water-extracted olive tree pruning using phosphoric acid as catalyst.
B i o r e s o u r Te c h n o l 1 5 3 : 1 0 1 – 1 0 7 . d o i : 1 0 . 1 0 1 6 / j .
biortech.2013.11.079
45. Lopez FJ, Pinzi S, Ruiz JJ, Lopez A, Dorado MP (2010) Economic
viability of the use of olive tree pruning as fuel for heating systems
in public institutions in South Spain. Fuel 89:1386–1391
46. Patterson MG (1996) What is energy efficiency? Concepts, indica-
tors and methodological issues. Energ Policy 24:377–390.
doi:10.1016/0301-4215(96)00017-1
47. Bank of Spain (2015). Interest rates by entity (in Spanish).
h t t p : / / w w w. b d e . e s / c l i e n t e b a n c a / e s / a r e a s / Ti p o s _ d e _
Interes/entidades/. Accessed 15 Nov 2015
48. Perry RH, Green DW (1999) Perry’s chemical engineers’ hand-
book. McGraw-Hill, New York
Bioenerg. Res. (2016) 9:1070–1086
49. National Institute of Statistics (2015) I ETCL. Trimestral survey of
laboral economics 2/2015 (in Spanish). http://www.ine.
es/daco/daco42/etcl/etcl0215.pdf. Accessed 15 Nov 2015
50. Ministry of Finance and Public Administration (2015). Government
approves fiscal reform to reduce taxes to 20 million tax payers (in
Spanish). http://www.minhap.gob.
es/Documentacion/Publico/GabineteMinistro/Notas%20
Prensa/2014/S.E.%20HACIENDA/01-08-14%20Nota%20
aprobaci%C3%B3n%20reforma%20fiscal.pdf. Accessed 15
Nov 2015
51. CNMC (2015) Spanish Commission of Trade and Competitiveness.
Biofuels statistics (2015) (in Spanish). http://www.cnmc.es/es-
es/energ%C3%ADa/hidrocarburosl%C3%ADquidos/estad%C3
%ADsticasdelmercado.aspx?p=p7&ti=Biocarburantes. Accessed
15 Nov 2015
52. ePure (2014) European renewable ethanol. Renewable ethanol:
driving jobs, growth and innovation throughout Europe State of
t h e I n d u s t r y R e p o r t 2 0 1 4 . h t t p : / / w w w. e p u r e .
org/sites/default/files/publication/140612-222-State-of-the-
Industry-Report-2014.pdf. Accessed 15 Nov 15 2015
53. Grand View Research (2015) Natural antioxidants market analysis
by product (vitamin C, vitamin E, polyphenols, carotenoids) and
segment forecasts to 2022. http://www.grandviewresearch.
com/industry-analysis/natural-antioxidants-market. Accessed 24
Nov 2015
54. BCC Research (2003) The global market for vitamins in food, feed,
pharma and cosmetics. http://www.bccresearch.com/market-
research/food-and-beverage/FOD014C.html. Accessed 24
Nov 2015
55. Euromonitor (2012) Antioxidants use in industry (in Spanish).
http://www.alimentacion.enfasis.com/articulos/64237-el-consumo-
antioxidantes-la-industria%C2%A0. Accessed 24 Nov 2015
56. Rodríguez G, Rodríguez R, Fernández-Bolaños J, Guillén R,
Jiménez A (2007) Antioxidant activity of effluents during the
purification of hydroxytyrosol and 3,4-dihydroxyphenyl gly-
col from olive oil waste. Eur Food Res Technol 224:733–741.
doi:10.1007/s00217-006-0366-1
57. Regulation (EC) (2008) No 1333/2008 of the European Parliament
and of the Council of 16 December 2008 on food additives
58. World Health Organization (2015). Food additives series (FAS).
http://www.who.int/foodsafety/publications/monographs/en/.
Accessed 15 Nov 2015
59. Fki I, Allouche N, Sayadi S (2005) The use of polyphenolic extract,
purified hydroxytyrosol and 3,4-dihydroxyphenyl acetic acid from
olive mill wastewater for the stabilization of refined oils: a potential
alternative to synthetic antioxidants. Food Chem 93:197–204.
doi:10.1016/j.foodchem.2004.09.014
60. Personal communication. Olivefen®, Subproductos Vegetales del
Mediterraneo, S.L. Seville, Spain
61. Sanchez A, Gomez D (2014) Analysis of historical total production
costs of cellulosic ethanol and forecasting for the 2020-decade. Fuel
130:100–104. doi:10.1016/j.fuel.2014.04.0372