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Bioresource Technology 243 (2017) 17–29

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

A model biorefinery for avocado (Persea americana mill.) processing


Javier A. Dávila a,⇑, Moshe Rosenberg b, Eulogio Castro c, Carlos A. Cardona d
a
Chemical Engineering Program, Department of Engineering. Universidad Jorge Tadeo Lozano, 110311 Bogotá, Colombia
b
Department of Food Science and Technology, University of California, Davis, Davis, CA 95616, USA
c
Departamento de Ingeniería Química, Ambiental y de los Materiales, Universidad de Jaén, Campus las Lagunillas, Spain
d
Instituto de Biotecnología y Agroindustria, Departamento de Ingeniería Química, Universidad Nacional de Colombia sede Manizales, km.7 via al Magdalena Campus la
Nubia, Manizales, Colombia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Avocado fruit has significant potential


for providing an array of products.
 Biorefinery based on avocado is
attractive for Colombian context.
 Economic analysis of biorefinery
based on avocado reveal reasonable
process costs.

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

Article history: This research investigated and evaluated a biorefinery for processing avocado Hass variety into microen-
Received 20 April 2017 capsulated phenolic compounds extract, ethanol, oil and xylitol. Avocado was first characterized for its
Received in revised form 9 June 2017 potential valuable compounds; then, the techno-economic and environmental aspects of the biorefinery
Accepted 10 June 2017
were developed and finally the total production costs and potential environmental impact of the pro-
Available online 15 June 2017
posed biorefinery were investigated. Four scenarios of the biorefinery were evaluated with different
extent of mass and energy integration as well as the incorporation of a cogeneration system. Results indi-
Keywords:
cated that the main fatty acid in the pulp of the investigated avocado variety was oleic acid (50.96%) and
Biorefinery
Avocado
that this fruit contained significant amount of holocellulose (52.88% and 54.36% in the peel and seed,
Ethanol respectively). Techno-economic and environmental assessment suggested an attractive opportunity for
Xylitol a biorefinery for complete utilization of the avocado fruit as well the importance of the level of
Phenolic compounds extracts integration.
Oil Ó 2017 Elsevier Ltd. All rights reserved.
Techno-economic analysis
Environmental analysis

1. Introduction the second largest number of plant species in the world, 51,220,
some of which are exotic fruits containing important and valuable
Colombia enjoys 433 species of native fruits that represent one compounds (Restrepo et al., 2014). Avocado (Persea Americana
of the most diverse varieties of fruits in the world (Restrepo et al., mill.) is one of the most important fruits that is cultivated in
2014). Colombia leads in biodiversity per square kilometer and has Colombia and in 2013 Colombia produced 303,340 tons of avocado,
accounting for 6.43% of the global avocado production (FAOSTAT,
2017). Colombia is the third largest avocado producer in the world
⇑ Corresponding author at: Carrera 4 # 22-61, Módulo 6, Oficina 303, Bogotá, D.C,
after Mexico (1,467,837 tons) and Dominican Republic
Colombia.
E-mail address: davila2344@yahoo.com (J.A. Dávila).
(387,546 tons). Avocado varieties that are cultivated in Colombia

http://dx.doi.org/10.1016/j.biortech.2017.06.063
0960-8524/Ó 2017 Elsevier Ltd. All rights reserved.
18 J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29

include: Choquette, Santana, Lorena, Semil, Booth-8, Fuerte and ficients of all the compounds were estimated from the compounds’
Hass. The Hass variety has the highest among-varieties oil content mole fractions in the liquid phase. The Hayden O’Conell (HOC)
and accounts for 38% of the total Colombian avocado production equation was used to calculate the properties of the relevant com-
(ASOHOFRUCOL, 2013). Typically, the avocado fruit is either con- pounds in vapor phases (Jaramillo et al., 2012). Thus, these meth-
sumed fresh or its pulp is processed into fresh, frozen and shelf- ods allow successful calculation of phase equilibria in mixtures
stable spreads, such as guacamole, fresh chilled halves and frozen with non-conventional compounds (Jaramillo et al., 2012). The sec-
cubes (Barbosa-Martin et al., 2016). In addition to oil, the avocado ond step of the simulation consisted of economic analysis and was
pulp contains different bioactive phytochemicals such as: carote- carried out using Aspen Process Economic Analyzer (AspenTech:
noids, vitamins B, C and E, D-mannoheptulose, b-sitosterol, perse- Cambridge, MA, USA). The third step consisted of environmental
none A and B, minerals (potassium, phosphorous, calcium, iron, analysis, which was carried out using WAste Reduction Algorithm
sodium) and essential amino acids such as valine, lysine, pheny- (WAR) developed by the US Environmental Protection Agency
lalanine, isoleucine, threonine and methionine (Barbosa-Martin (Young and Cabezas, 1999).
et al., 2016; López-Cobo et al., 2016).
The avocado oil can be extracted industrially at a yield of 21– 2.1. Experimental part
30% of the fruit weight. The avocado oil contains, high levels of
mono-unsaturated fatty acids (around 70% of oleic acid) and other 2.1.1. Raw material
valuable compounds with health benefits such as tocopherols, phy- Fully ripened Hass avocado was purchased at a local market in
tosterols, lutein and vitamins (López-Cobo et al., 2016). Manizales Colombia. The fruit was thoroughly washed with dis-
The seed and peel of avocado are obtained as residues after its tilled water then, the pulp, peel and seed of avocado were manu-
processing. The avocado seed (15–16% of the fruit weight) is one ally separated. The pulp was immediately used for oil extraction
of the best sources of dietary fiber and it contains valuable com- and analysis of fatty acid profile while the peel and seed were each
pounds such as fatty acids, polyphenols, steroids, antioxidants milled to obtain particles that pass mesh 20 (850 lm) sieve and be
and potassium (Barbosa-Martin et al., 2016). Avocado seed also retained on mesh 80 (180 lm) sieve (Hames et al., 2014). Avocado
contains saponin, flavonoids, phenols and cyanogenic glycosides fractions (peel, seed and pulp) that had been obtained and treated
(Arukwe et al., 2012) phytosterols, triterpenes, furanoic acids, fla- in this way were then stored at 20 °C pending analysis.
vonol dimers and proanthocyanidins. Avocado peel has been
reported to contain flavonoids, saponins, tannins, phenols and ster-
2.1.2. Composition analyses
oids and thus exhibits antioxidative activity (Arukwe et al., 2012;
Moisture content was determined, in triplicates, according to
Saavedra et al., 2017). The avocado processing industry generates
the Technical Report NREL/TP 510-42620 (Hames et al., 2014). In
significant amounts of waste (peel and seed) that can thus poten-
short, weighed samples were placed in aluminum weighing dishes
tially be processed to yield value added products for which promis-
and were then dried at 105 °C to a constant weight. The moisture
ing and significant applications in the food and related industries
content was calculated according to Eq. (1).
exists. The latter, along with the valuable oil that can be extracted
 
from the fruit’s pulp present tangible attractive opportunities to WeightInitial  Weightdried
Moisture ð%Þ ¼  100 ð1Þ
enhance the agro-industry of the avocado fruit. Weightinitial
It has to be noted that the functional and commercial value of
some of the compounds that can be separated and extracted from Water and ethanol extractive contents were determined, in
all parts of the avocado fruit can be enhanced by application of triplicates, according to the procedure described for lignocellulosic
advanced technological approaches such as microencapsulation, biomass (Han and Rowell, 1997). It has been established that water
nanofiltration, cryogenic distillation, etc. This approach can be extractives contained organic material, sugars and nitrogenous
carry out using the biorefinery processing concept and configura- materials, minerals, etc., while the ethanol extractives consisted
tion that integrates biomass conversion processes in a given of chlorophyll, natural pigments, etc. (Han and Rowell, 1997).
scheme for the production of an array of different products. Among Briefly, extraction with 250 ml of either solvent (water or etha-
such products are: biomolecules, biomaterials, bioenergy and bio- nol) was carried out using a Soxhlet extraction unit for 24 h at the
fuels, etc. (Davila et al., 2017; Moncada et al., 2014a, 2013). corresponding boiling temperature of the solvent. The difference in
The objective of the presented research was to design and mass prior and following extraction was used to calculate the
assess a biorefinery for processing avocado into phenolic com- extractive content according to Eq. (2).
pounds extract, ethanol, xylitol and oil. Four scenarios of the biore-
!
Weightsample after extraction
finery, with different extent of mass and energy integration as well Extractives ð%Þ ¼ 100   100 ð2Þ
Weightinitial sample
as the incorporation of a cogeneration system, were investigated
for their techno-economic and environmental aspects. Holocellulose was determined, in triplicates, according to ASTM
Standard D-1104 (Han and Rowell, 1997). Briefly, the method is
based on treating the plant-derived material with a mixture of
2. Materials and methods water and acetic acid at 70 °C for 60 min. The latter allows com-
plete separation of the fiber from the lignin components. The mass
The methodology employed in this work consists of two parts; difference prior and following the acid treatment was used to cal-
the first one describes the determination of holocellulose content culate the holocellulose content according to Eq. (3).
in avocado peel and seed as well as the fatty acid profile of avo- !
cado’s pulp. The second part describes the process simulation that Weightfinal sample
was used in order to obtain the mass and energy balances of the Holocellulose ð%Þ ¼  100 ð3Þ
Weightinitial sample
biorefinery, utilizing Aspen Plus V8.0 (AspenTech: Cambridge,
MA). In the first step of simulation, the physicochemical properties The cellulose is defined as the insoluble residual part obtained
of all the compounds involved in the simulation were obtained after treating the biomass with NaOH (Han and Rowell, 1997).
from the National Institute of Standards of Technology (NIST, Briefly, an amount of 1 g of extractives-free holocellulose sample
2013). In order, the Non Random Two Liquids (NRTL) and Unifac was treated with 10 ml of NaOH solution at 17.5% (each 5 min until
models were used in the liquid phase. In all cases, the activity coef- complete 45 min) at 20 °C. Then, the mixture was filtered at
J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29 19

350 mmbar and the separated solid phase was washed, first with determination of the fatty acid composition, 1 ll of the sample
100 ml of a NaOH solution at 8.3% and then with 100 ml of distilled was injected a Gas Chromatography (Hewlet Packard 5890 A, Min-
water. Then, the samples were dried at 40 °C. Finally, the samples nesota USA) with a flame-ionization detector. A total retention
were weighted and the cellulose content was calculated according time of 40 min on a fused silica column (50 m of length  0.25 mm
to Eq. (4) and the hemicellulose content was determined from dif- ID, Sugerlabor) was used. Helium, at a flow rate of 1 ml/min served
ference between holocellulose and cellulose content measured. as carrier gas. The temperature of the injector, and oven were set at
! 250 °C and 210 °C, respectively. The fatty acids composition of the
Weightfinal sample avocado oil was determined according to Regl2568/91.
Cellulose ð%Þ ¼  100 ð4Þ
Weightinitial sample
2.2. Process simulation
Lignin content of the samples was determined according to
TAPPI T-222 (Han and Rowell, 1997). Briefly, 200 mg of sample
Fig. 1 depicts the proposed scheme of a biorefinery for avocado
were placed into a 100 ml glass centrifuge tube. Then, 1 ml of
processing into ethanol, xylitol, microencapsulated extract of phe-
H2SO4 (72% w/w) was added to each 100 mg of sample. Then, the
nolic compounds and oil. Additionally, a cogeneration plant was
tubes were incubated in a water bath at 30 °C for 60 min. After,
evaluated for supplying part of the energy requirements of the
the sample was treated in an autoclave at 121 °C, 15 psi, for
biorefinery. The inlet flow of raw material was set at 10,000 kg/h
60 min. Then, samples were removed from the autoclave and the
and the biorefinery was planned to operate 8000 h, annually. The
lignin was filtered off, through glass fiber filters under reduced
constituent plants of the biorefinery have been designed to pro-
pressure (350 mmbar), keeping the solution at 70 °C. Residues
duce microencapsulated extract of phenolic compounds (extrac-
were washed with hot water (70 °C) and dried at 105 °C overnight
tion and microencapsulation plant), xylitol (xylitol plant), ethanol
in an oven. Finally, lignin content was calculated according to Eq.
(ethanol plant) and oil (oil extraction plant). A plant for sugars
(5).
(xylose and glucose) production was required for generating the
!
Weightfinal sample feedstock for the xylitol and ethanol plants. The process descrip-
Lignin ð%Þ ¼  100 ð5Þ tion and considerations that have been made in designing each
Weightinitial sample
one of the constituent plants of the biorefinery are discussed
Ash content was determined according to the Technical Report below.
NREL/TP 510-42622 (Sluiter et al., 2008). Triplicate samples were
incinerated at 575 °C for 3 h and the ash content was calculated 2.2.1. Extraction, microencapsulation and sugar plants
according to Eq. (6). The extraction of phenolic compounds is carried out using an
! enhanced-fluidity liquid extraction process (EFLE) with CO2 and
Weightincinerated sample ethanol (Ceron et al., 2012). Peel and seed of avocado are milled
Ash ð%Þ ¼  100 ð6Þ
Weightinitial sample to a particle sizes smaller than 0.45 mm. This size reduction results
in a large surface area of the treated material that enhances the
extraction yield while improving the ease of handling the solid
2.1.3. Oil extraction material (Dávila et al., 2014). Then, the raw material is dried to
A thermo-mechanical extraction procedure (Wong et al., 2010) 7% moisture, while limiting deterioration of antioxidative com-
was used. The pulp was macerated to a paste, using a porcelain pounds, at 40 °C (Ceron et al., 2012). The resulted mass of dried
maceration unit; then the paste was placed in a beaker and mixed particles is then placed in the extraction vessel where it is mixed
at 250 rpm for 60 min at 50 °C (Schott Duran, Germany), using a with CO2 (solvent) and ethanol (co-solvent). The extraction has
mechanical stirrer (Model AX686/1 AUXILAB S.L.). It has been been designed to operate at supercritical conditions of 300 bars
reported that elevated temperature promotes the extraction of and 40 °C. To reach these supercritical conditions, the CO2 is lique-
the oil from the oil-containing cells without affecting the quality fied, using a heat exchanger, and then pressurized to 300 bar, by a
of the oil (Wong et al., 2010). The oil phase was separated from pump. The treated CO2 is transferred to the extraction chamber
the pulp in two steps of centrifugations. First, the mixture was into which ethanol (co-solvent) was pumped at 300 bar.
spun in a high-speed decanting centrifuge (Hermle Z 206 A, Ger- After extracting of the antioxidant compounds from the solid
many) at 6000 rpm for 10 min at 20 °C and the separated oil was matrix for 120 min, the extract is transferred to a collecting vessel
collected with a syringe. This oil was then spun at 12,000 rpm for operated at 50 bar and 25 °C where the CO2 is separated from the
10 min at 20 °C using a high-speed decanting centrifuge (Hermle solid phase and the liquid extract. The process has been designed
Z 32 HK, Germany). Following centrifugation, the oil phase (super- to allow recovering about 90% of CO2 that is recycled back to the
natant) was collected using a syringe. Finally, oil was stored at process, thus only about 10% of new solvent has to be added to
20 °C pending for fatty acid profile analysis. the process. The extract is then separated from the solid material
and then it is concentrated by evaporation. This allows separating
2.1.4. Fatty acid profile part of the co-solvent (ethanol) and recycling it back to the process.
The fatty acids profile of the extracted oil was determined using However, because part of the ethanol is lost in the depressuriza-
the procedures for determination of fatty acid and isomers compo- tion, there is a need to add new ethanol to the process.
sition based on the regulations ‘‘Regl2568/91” and ‘‘Regl1429/92‘‘, Finally, the extract is microencapsulated by spray drying, using
respectively. Methyl esters were prepared by derivatization of oil maltodextrin as wall material or carrier agent (Warner, 2014).
(AOAC, 2000), 1 ml of boron trifluoride-methanol solution (14%, After being filtered to remove particulate solid material that can
Sigma Aldrich, St Louis, USA) was added to 50 ll of oil, and the clog the nozzle of the spray dryer the extract is mixed with a mal-
mixture was mixed for 15 s and was then placed in a water bath todrextrine DE10 solution 54% (w/w) at a carrier-to-extract ratio of
(Thermo Fisher Scientific model 2870, MA USA) at 80 °C for 2:1 (Pang et al., 2014). The mixture is spray dried using air at
40 min. Then, 2 ml of hexane (98%, Sigma Aldrich, St Louis, USA) 0.06 MPa and 125 °C and the microcapsules are recovered in a
were added and the mixture was mixed for 30 s. The treated mix- cyclone and collected. Fig. 2(a) depicts the process flow diagram
ture was allowed to separate into 2 phases over a period of 2 h at for the extraction and microencapsulation plant.
room temperature then, the supernatant (containing methyl For sugar plant, the solid material (Spent biomass rich in holo-
esters), was collected for fatty acid profile determination. For cellulose) that is obtained from extraction plant is used for sugar
20 J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29

Fig. 1. Scheme of the biorefinery based on avocado.

production according to the scheme depicted in Fig. 2(b). In order is depicted in Fig. 3(b). The glucose is fermented to ethanol using
to improve the cellulose accessibility, hydrolysis, using diluted sul- Saccharomyces cerevisiae, at 37 °C, according to the kinetic model
furic acid (2% v/v) at 121 °C for 90 min is carrying out (Jin et al., that has been proposed by Rivera et al. (2006). Following the fer-
2011). Following the acid hydrolysis, the liquid stream is separated mentation, the ethanol concentration is increased to 96%, using
from remaining solids and is neutralized to a pH of 6.5, using 2% distillation and rectification towers. The ethanol is then dehy-
(w/v) NaOH solution. The precipitate (Na2SO4) is separated by cen- drated by molecular sieves according to process conditions and
trifugation (Mussatto et al., 2013) and the pH-adjusted hydrolysate yield that have been reported by Quintero et al. (2007).
(rich in xylose) is then directed to the xylose plant. The solid frac-
tion (rich in cellulose and lignin) is hydrolyzed enzymatically at
50 °C using endo-b-1,4 gluconases, according to a kinetic model 2.2.3. Oil extraction and cogeneration plants
that describes the decomposition of cellulose to cellobiose and glu- A thermo-mechanical method for extracting oil from avocado
cose as well as hydrolysis of cellobiose to yield glucose (Morales- pulp was used. This method consists of a moderate temperature
Rodriguez et al., 2011). Upon completion of the enzymatic hydrol- (50 °C) at atmospheric pressure grounding the pulp to a paste by
ysis, the liquid phase (rich in glucose) is separated from the means of mechanical agitation (60 rpm) from 40 to 60 min
remaining solids (rich in lignin) by filtration. (Wong et al., 2010). This procedure has been shown to promote
the extraction of the oil from the oil-containing cells without
adversely affecting the quality of the oil (Wong et al., 2010). The
2.2.2. Xylitol and ethanol plants oil (supernatant phase) is then separated and centrifuged at
The hydrolysate (rich in xylose) from sugar plant is used to pro- 6000 rpm and the recovered oil is cooled to 25 °C. Fig. 4(a) depicts
duce xylitol. The hydrolysate is concentrated to 70 g/l by a flash the oil extraction plant.
evaporator at 121 °C and 1 bar and is then cooled to 30 °C. The con- An electricity generation scheme was proposed to take advan-
centrated hydrolysate is fermented, using Candida guilliermondii at tage of the remaining solid stream (rich in lignin) from sugar plant.
30 °C and stirring rate of 200 rpm, according to the optimized con- For this purpose, a biomass-integrated gasifier/gas turbine (BIG/
ditions that have been reported by Mussatto and Roberto (2008). GT) scheme is used for achieving an electricity production at low
The fermentation generates CO2 that is separated from the liquid capital cost. No post-combustion was considered because the rela-
stream that is then filtered to separate the cell biomass. Finally, tively high cost associated to capital investments when it is applied
the xylitol stream is concentrated in a flash evaporator at 40 °C to simple-cycle gas turbines (Metz et al., 2005). Thus, an isother-
and the xylitol is crystallized out using ethanol (95.3% w/w) mal gasifier is used as well a simple gas turbine to generate elec-
(Vyglazov, 2004). Fig. 3(a) depicts de process flow diagram for tricity. The heat demand was calculated from the energy balance
the xylitol plant. from simulation. To conditioning the solid stream, the feedstock
Ethanol is produced from the glucose fraction that has been is dried to 10% moisture content at 87 °C and 1 bar; the dry feed-
generated by the sugar plant according to the process diagram that stock is then gasified at 850 °C at an air-to-fuel ratio of 0.4 (Ruiz
J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29 21

Fig. 2. Schemes for extraction and microencapsulation plant (a) and sugar plant (b).

et al., 2013). Depending on the composition of the biomass, a mix- an approximation on the performance of these units at industrial
ture of gases consisting of CO, CO2, H2O, H2, and CH4, among other scale. Similarly, for simulation purposes, the feedstock for the
constituents, can be obtained. After gasification, the hot gases are biorefinery was assumed as peel, seed and pulp separately thus,
utilized by a gas turbine to produce electricity while the exhausted not special machines or manual processes were taken into account
gases can be used for steam generation (at low pressure) for ther- for separating avocado parts. Finally, the microorganisms for xyli-
mal energy purposes at small industrial scale. Fig. 4(b) depicts the tol and ethanol plants are assumed to have not cost taken into
process flow diagram for the cogeneration plant. account that low concentrations of them are required and that also,
The objectives, assumptions, conditions and methods used for are recycled to fermentations processes.
the principal constituent units in the simulation are summarized
in Table 1. Some of the relevant assumptions associated to process
2.3. Economic analysis
simulation, are related to yields at laboratory level taken from lit-
erature (It includes yields for units of supercritical extraction, fer-
The economic analysis calculated the production cost per kg of
mentations as well as acid and enzymatic hydrolysis) for obtaining
products. The total production cost considered the total raw mate-
22 J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29

Fig. 3. Schemes for xylitol plant (a) and ethanol plant (b).

 
rial (fresh avocado fruit), inputs (reagents, solvents, etc.), utilities, Capital cost  Salvage value
Depreciation expense ¼ ð7Þ
depreciation expense calculated according to Eq. (7) and operating Useful life of the project
cost, this last is composed by labor and maintenance costs as well
The economic analysis was carried out considering four scenar-
as the operating charges, plant overhead and general and adminis-
ios that included several levels of heat and mass integrations,
trative costs. Additionally, tax and interest rates were taken
which are described in Table 3. Mass integration refers to CO2
according to the laws in Colombia as 25% and 17%, respectively.
and ethanol recovering from extraction plant (Fig. 2a) that allows
The useful life of the project was 10 years and the salvage value
calculating the savings of these inputs. Heat integration was car-
for depreciation expense was 20% of the initial capital cost using
ried out using the Pinch methodology supplied by Aspen Energy
the straight-line method. Fix capital cost was estimated based on
Analyzer software and, based on composite curves; the energy sav-
the purchased equipment costs and other direct (installation,
ing for all scenarios was calculated.
instrumentation and control, piping, electrical systems, buildings,
Because the total production cost was calculated for each pro-
yard improvements and service facilities) and indirect (engineering
duct (xylitol, ethanol and phenolic compounds), the cost associated
and supervision, construction expenses, legal expenses and contin-
to other plants was distributed among products plants. Thus, the
gency) costs. Table 2 shows the economic parameters taken for
costs associated with the sugar plant were distributed according
economic analysis. To obtain a best approach on the simulation
to holocellulose (hemicellulose and cellulose) content thereby,
and economic analysis, prices and economic data used in this
40% (based on hemicellulose content for producing xylitol) and
research corresponds to Colombian conditions, raw materials price
60% (based on cellulose content for producing ethanol) of the cost
were estimated according to the purchasing price of local compa-
associated to sugar plant were assigned for xylitol and ethanol
nies as well as transportations costs related to the collection of
plants, respectively. Similarly, the costs associated with cogenera-
these raw materials. The economic analysis also included products
tion plant were distributed according to the energy requirements
escalation (5% per year), raw material escalation (3.5% per year),
for each product plant thus, 39%, 58% and 3% for xylitol, ethanol
operating and maintenance labor escalation (3% per year) and util-
and phenolic compounds plants, respectively (Davila et al., 2017).
ities escalation (3% per year) as an uncertainty of prices through
The cost distribution of the depreciation expense was assigned
the time.
J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29 23

Fig. 4. Schemes for oil extraction plant (a) and cogeneration plant (b).

according to the units associated to each product plant thus, 40%, (PCOP) and Acidification Potential (AP). The Potential Environmen-
40% and 20% for xylitol, ethanol and phenolic compounds plants tal Impact (PEI) of the process was calculated per kilogram of prod-
were used, respectively. The cost associated to raw materials and ucts (Dávila et al., 2014).
inputs were distributed according to the consumption of each The PEI was calculated according to Eq. (8). Where the sum over
plant therefore, 30% of raw material costs was assigned to xylitol j is taken over the streams of outputs (out), the sum over k is taken
plant (Approximately 25% of hemicellulose of the raw material, over all chemicals k, M_ ðoutÞ is the mass flow rate of the outlet stream
j
H2SO4 for acid hydrolysis, NaOH for neutralization of xylose, C. j, Xk,j is the mass fraction of chemical k in the outlet stream j and Wj
guilliermondii for fermentation and ethanol for washing xylitol), corresponds to the PEI of the chemical associated to an impact cat-
65% of raw material costs was assigned to ethanol plant (Approxi- egory, which are supplied by the software (Young and Cabezas,
mately 27% of cellulose, enzyme for enzymatic hydrolysis and S. 1999).
cerevisiae for fermentation) and 5% of the raw material costs was
P _ Out P
assigned to phenolic compounds plant (CO2, ethanol and mal-
~IOut ¼ j Mj K X K;jWj
todextrine). Finally, utilities cost was distributed according to the P _ ð8Þ
P
p P
energy consumption of each product plant thus, 39%, 58% and 3%
for xylitol, ethanol and phenolic compounds plants, respectively
(Davila et al., 2017).
3. Results and discussion

2.4. Environmental analysis 3.1. Chemical characterization

The environmental analysis evaluated eight environmental The results of the compositional characterization of avocado
impact categories which are: Human Toxicity Potential by Inges- peel and seed are presented in Table 4. The moisture content of
tion (HTPI), Human Toxicity Potential by Dermal and Inhalation both, peel and seed was similar to what has been previously
Exposure (HTPE), Terrestrial Toxicity Potential (TTP), Aquatic Tox- reported. For instance, a moisture content of 7.66% has been
icity Potential (ATP), Global Warming Potential (GWP), Ozone reported for seed of Hass avocado variety (Barbosa-Martin et al.,
Depletion Potential (ODP), Photochemical Oxidation Potential 2016). Moisture content of 5.33% and 9.22% for peel and seed of
Table 1

24
Purpose, conditions and methods used for the principal units in the simulation of the biorefinery.

Unit Purpose Conditions and unit specifications Method Assumptions


Pretreatment plant
Dryer Drying to 5.12% moisture 40 °C, 1 bar NRTL* No
Atmospheric dryer
(Model in Aspen Plus: Shortcut Dryer)
Mill Size reduction to 0.45 mm 1 bar (Model in Aspen Plus: Jaw Mill) N.A. N.A.
Plant for extraction and microencapsulation of phenolic compounds
Extractor Extract phenolic compounds 40 °C and 300 bar and 54% (w/w) maltodrextrine DE10 solution (Model in User model (Yield of 59.3%) Ceron et al. (2012)
Aspen Plus: Sep)
Evaporator Recovering part of the ethanol (Concentration of the 40 °C, 0.3 bar NRTL-HOC N.A.
extract) Standard tube vertical evaporator, one effect
(Model in Aspen Plus: Flash2)
Filter Removing particles from the extract 55 °C, 1 bar NRTL-HOC N.A.
(Model in Aspen Plus: Rotary Vacuum filter)
Spray drying Microcapsules formation 125 °C, carrier-to-extract ratio of 2:1. User model (Yields of 82.08%) Pang et al. (2014)
(Model in Aspen Plus: Shortcut Dryer)
Sugar plant

J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29


Acid hydrolysis Enhancing the efficiency of recovering cellulose and 121 °C, 1 bar, (2% v/v of H2SO4) User model (Yield of 0.6 g/g) Jin et al. (2011)
xylose
Neutralization Neutralization of acid 25 °C, 1 bar, pH of 6.5 with 2% w/v of NaOH User model Mussatto et al. (2013)
(Model in Aspen Plus: RYield) NRTL-HOC
Enzymatic Glucose production 50 °C, 1 bar, 7% (wt) using endo-b-1,4,glucanases User model (Concentration of Morales-Rodriguez et al.
hydrolysis Agitated tank 6.14 g/l) (2011)
(Model in Aspen Plus: RYield)
Heat Exchanger Reaction temperature 121 °C, 1 bar NRTL-HOC N.A.
Xylitol plant
Evaporation Removing part of the water (Concentration of 121 °C, 1 bar (until 70 gr/l) NRTL-HOC N.A.
xylose) Standard tube vertical evaporator, one effect
(Model in Aspen Plus: Flash2)
Fermentation Production of Xylitol 30 °C. Candida guilliermondii, 200 rpm**(Model in Aspen Plus: RYield) User model (Yield of 0.78 g/g) Mussatto and Roberto
(2008)
Crystallizer Xylitol crystallization 40 °C, Ethanol at 95.3% NRTL N.A.
(Model in Aspen Plus: Crystallizer)
Heat Exchanger Reaction temperature 121 °C, 1 bar NRTL-HOC N.A.
Ethanol plant
Fermentation Ethanol production 37 °C, using Saccharomyces cerevisiae User model (Concentration of Rivera et al. (2006)
(Model in Aspen Plus: RYield) 78 kg/m3)
Distillation Ethanol separation Distillation: 18 trays, 2.5 reflux ratio, total condenser NRTL-HOC N.A.
columns Rectification: 12 trays, 1.8 reflux ratio, total condenser
(Model in Aspen Plus: RadFrac)
Heat Exchanger Reaction temperature 121 °C, 1 bar NRTL-HOC N.A.
Oil extraction plant
Extractor Oil extraction 50 °C, 1 bar NRTL-HOC N.A.
(Model in Aspen Plus: Decanter) Assuming 70% of yield
Centrifuge Oil separation 50 °C, 1 bar, 6000 rpm NRTL-HOC N.A.
(Model in Aspen Plus: CFuge)
Heat Exchanger Reaction temperature 121 °C, 1 bar NRTL-HOC N.A.
Cogeneration plant
Gasifier Syngas generation 859 °C, 60 bar and a ratio of 0.4 air-to-fuel NRTL-HOC N.A.
(Model in Aspen Plus: RYield and RGibbs)
Turbine Electricity generation 1 bar, 70% efficiency NRTL-HOC N.A.
(Model in Aspen Plus: Turbine with isentropic efficiency)
*
NRTL corresponds to Non-Random Two Liquids model for activity coefficients calculation.
J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29 25

Table 2 ables products such as biofuels, organic acids, bioenergy and bio-
Costs of raw materials and services to the Biorefinery. materials. Results of this research along with those reported
Item Price Unit earlier thus clearly suggest that avocado waste streams (peel and
Feedstock a
21 (USD/Ton) seed) can be transformed into valuable products for different food
Waterb 1.25 (USD/m3) applications (Saavedra et al., 2017).
Sulfuric acidc 0.094 (USD/kg)
Sodium hydroxidec 0.098 (USD/kg)
Enzymed 3 (USD/kg) 3.2. Fatty acids profile
Operator labor costb 2.14 (USD/h)
Supervisor labor costb 4.19 (USD/h) Results of fatty acid constituents indicated that the presence of
Electricity costb 0.1 (USD/KWh)
Fuele 7.28 (USD/MMBTU)
fatty acids ranging from C14 to C18. The major fatty acids of the
Ethanol at 99.5%f 0.94 (USD/l) avocado oil were oleic acid (C18:1, 50.96%), palmitic acid (C16:0,
CO2g 0.01 (USD/kg) 24.74%,), linoleic acid (C18:2, 15.07%), palmitoleic acid (C16:1,
Maltodextrineh 0.2 (USD/kg) 5.97%) and linolenic acid (C16:3, 1.66%). Other fatty acids such as
Phenolicsi 167.48 (USD/kg)
myristic (C14:0, 0.05%), margaric (C17:0, 0.03%), margaroleic
Xylitolj 2.95 (USD/kg)
Avocado fruitk 0.47 (USD/kg) (C17:1, 0.08%), estearic (C18:0, 0.84%), arachidic (C20:0, 0.14%),
Avocado oill 0.61 (USD/kg) gadoleic (C20:1, 0.27%), behenic (C22:0, 0.27%), lignoceric (C24:0,
a
0.06%) and other isomers trans of C18 were present only at low
Calculated for transportation of SBP over a distance of 140 km with a truck of
three axles.
concentration.
b
Typical price in Colombia. In agreement with what has been previously reported for avo-
c
Taken from ICIS Prices (ICIS, 2013). cado oil, oleic acid was the main fatty acid in the Hass avocado
d
Prices based on Alibaba International Prices (Alibaba, 2013). oil and constituted more than 50% of the total fatty acids content
e
Estimated cost of Gas for the years 2015–2035 (NME, 2013).
f (Pedreschi et al., 2016). Although a few variations of fatty acid
National price in Colombia (Fedebiocombustibles, 2013).
g
Taken from international prices. composition of avocado oil have been reported by several authors,
h
Taken from (Alibaba, 2013). it is important to note that postharvest ripening strategies did not
i
Taken from (Warner, 2014). have any detrimental effect on the fatty acid profile while other
j
Taken from (Mussatto et al., 2013). variables such as ripening stage, region, seasonal variations and
k
Taken from typical prices in Colombia.
l
Taken from (Peña et al., 2012).
processing methods had a significant effect on the fatty acid com-
position of avocado oil (Pedreschi et al., 2016). The selection and
application of an appropriate extraction method, as an integral part
avocado, respectively, has been previously reported (Arukwe et al., of the processing of avocado in a biorefinery is of great importance.
2012). The mass of total extractives was 34.38% and 35.95% (on dry The latter has to be considered based on the combined influence of
basis) of the extracted peel and seed, respectively. Other studies technological aspects, compositional and oxidative stability
have reported that water and ethanol extractives content of avo- aspects as well as economic considerations.
cado ranged from 15.33% to 23.11% (Indumathi and Krishna,
2014). It has been reported that extracts from avocado seed and 3.3. Techno-economic analysis
peel (obtained by soxhlet method) contain flavonoids, steroids, ter-
penoids, saponins and tanins as well as phenolic compounds, alka- The mass balance for the avocado biorefinery reveals that the
loids and steroids (Arukwe et al., 2012; Warner, 2014). Other ethanol production corresponds to 47.4 kg (60.08 l) per ton of solid
valuable compounds found in peel and seed of avocado are per- material (seed and peel) that leaves the extraction and microen-
seitol, quinic acid, chlorogenic acid, quercetin derivates, rutin citric capsulation plant. It has been reported that 31.8 kg of ethanol
acid, tyrosol glucoside, penstemide and vanillic acid glucoside could be produced per ton of avocado seeds (Woldu and Tsigie,
(López-Cobo et al., 2016). 2015). Other type of biomass, olive tree pruning has been pro-
Ash content of avocado peel (1.04%) and seed (0.87%) was sim- cessed according to the biorefinery concept to yield 63.37 l of etha-
ilar to what has been previously reported: 1.50% and 1.29% for peel nol per ton of feedstock (Hernández et al., 2014).
and seed, respectively (Vinha et al., 2013). Holocellulose content Results indicated that xylitol was obtained at a yield level of
for peel (52.88%) and seed (54.37%) was similar to what has been 25.51 kg per ton of solid material (peel and seed). This value is
reported for avocado peel (45.74%) and seed (51.21%), respectively lower than what has been reported by others for lignocellulosic
(Arukwe et al., 2012). Other researchers have reported that holo- biomass. For instance, 103 kg of xylitol per ton of lignocellulosic
cellulose content of avocado seed was 27.45% while cellulose con- feedstock consisting of brewer’s spent grains has been reported
tent of avocado peel ranged from 18.7% to 28%, depending on the (Mussatto et al., 2013).
repining stage (Barbosa-Martin et al., 2016). Both, peel and seed Results indicated that oil extraction yielded 142 kg of oil per ton
of avocado contain significant amounts of holocellulose and thus of avocado. Other authors reported an extraction yield of 100 kg of
can be used as feedstock for obtaining C5 and C6 sugars (Dávila oil per ton of avocado at a pilot plant scale level (Martínez Nieto
et al., 2014) that, in turn, can then be processed to yield other valu- et al., 1992). Techniques such as cold-press oil extraction and

Table 3
Description of scenarios.

Scenario Energy integration level Mass integration level


No Integration Full Integration No Integration Full Integration
Scenario 1 X X
Scenario 2 X X
Scenario 3 X X
*
Scenario 4 X X
*
Scenario 4 includes heat and mass integrations such scenario 3 but it includes a cogeneration system.
26 J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29

Table 4 ties consumption, heat integration can lower the impact of the
Chemical characterization for peel and seed of avocado. biorefinery on the environment, due to the lower consumption of
Component Avocado (mass%) external fuel that affects the green house gases (GHG) emissions
Peel Seed (Moncada et al., 2013).
Results indicated that the cost of raw material (fresh avocado
Moisture 7.33 ± 1.15 7.02 ± 0.18
Extractives 34.38 ± 0.34 35.95 ± 1.95
fruit) gained importance as a major economic factor when the level
Cellulose 27.58 ± 1.18 6.48 ± 0.38 of integration increased, reflecting the lower cost share of utilities
Hemicellulose 25.30 ± 1.24 47.88 ± 2.14 and thus, higher cost share for raw material. Additionally, the rel-
Lignin 4.37 ± 0.13 1.79 ± 0.04 atively high price of avocado fruit (0.47 USD/kg, Table 2) renders
Ash 1.04 ± 0.05 0.87 ± 0.06
this raw material an important economic factor in the biorefinery
Total 100 100 design. The latter is in contrast to cost of raw materials in biore-
fineries that are aimed at processing second generation raw mate-
rials that are cheaper; for example, 0.042 and 0.021 USD/kg of
supercritical CO2 extraction allowed obtaining 15.8% (v/w) and brewer’s spent grains and blackberry residues, respectively have
39.8% (w/w) of avocado oil, respectively (Costagli and Betti, been reported (Davila et al., 2017; Mussatto et al., 2013). The high
2015). These techniques are more expensive than traditional meth- costs associated with cost of feedstock and inputs as well as the
ods for oil extraction and therefore a thermo-mechanical extrac- high energy consumption have been noted by others as the most
tion process followed by centrifugation seems to be the method important economic factors that affect significantly the design of
of choice for extraction of avocado oil in developing countries integrated biorefineries (Moncada et al., 2014b). Thus, the highest
(Bizimana et al., 1993), such as the country in which this research levels of energy and mass integrations should be practiced in order
was conducted. to ensure the most profitable scenario of a biorefinery, in particular
Table 5 presents the cost and cost share of each of the evaluated when biorefineries that use first generations feedstocks such as
scenarios of the avocado biorefinery. For scenario 1, results indi- avocado are considered.
cated that the most important economic factor of the total produc- Table 6 depicts the cost and cost share of each input over the
tion cost was utilities, reflecting the high-energy consumption of a total input costs for scenarios without (scenarios 1 and 2) and with
process configuration that does not include heat integration. How- (scenarios 3 and 4) mass integration. Studying the influence of
ever, results indicated that when mass and energy integration (sce- inputs on the total production cost indicated that, enzyme is the
narios 2 and 3) as well as a co-generation system (scenario 4) have most expensive input that contributes to more than 50% of the
been introduced, the raw material became the most important eco- total cost of inputs in all scenarios (see Table 6). This fact has also
nomic factor in affecting the total production cost, reflecting the been highlighted by other authors, who suggested that despite the
relatively high cost of avocado (fresh fruit). In agreement with pre- significant progress in developing robust enzymes, enzymatic pro-
vious reports, results of the study highlighted the merits of integra- cesses included in the biorefinery concept are still not economi-
tion strategies as useful approaches for designing multi-product cally competitive (Long et al., 2016). Therefore, research directed
biorefineries (Davila et al., 2017; Moncada et al., 2013). Results at the selection of appropriate enzyme preparations should be
indicated that the level of mass and energy integration in the avo- addressed in the biorefineries design to enhance the use of inputs
cado based biorefinery is a major factor that should be considered that can lower mass consumption and thus, lower cost of inputs in
when reducing the total production cost of all the products that are the biorefinery.
associated with a given biorefinery concept is considered. Ethanol is the second input with high contribution to total cost
When utilities consumption is considered, results indicated that of inputs, however, after mass integration there is a possibility for
heat integration is of importance and, as demonstrated in scenario saving 57.65% ethanol. Similarly, a saving of 23.70% water was
2, the cost of energy consumption of the entire biorefinery could be achieved after mass integration. This extent of savings for ethanol
reduced by 69.48%, relative to scenario 1 (without heat integra- and water indicates that mass integration is a very useful and nec-
tion). This result is in agreement with earlier reports about heat essary approach for reducing inputs consumption, environmental
integration in a biorefiney. For example, a reduction of 63.23% impact as well as total production cost. It has been reported that,
and 54.91% of the total energy requirements of biorefineries for residual water from a biorefinery should be recovered at the high-
processing fruits and brewer’s spent grains, respectively has been est level possible (as in this research) in order to address the large
reported (Davila et al., 2017; Mussatto et al., 2013). Including a volume of water that is needed in biotechnological processes and
cogeneration system in the avocado biorefinery (scenario 4) is presents a major concern in the processes design (Mussatto
unattractive because the reduction of energy consumption is only et al., 2013). When process streams are integrated, such as when
marginal (0.63%) in comparison to what can be accomplished with lignocellulosic biomass (peel and seed of avocado) is used for pro-
heat integration (scenarios 2 and 3), however, it should be carried ducing ethanol and xylitol, production cost can decrease signifi-
out in order to attain the highest possible reduction in energy cantly. In fact, one of the greatest challenges in the production of
requirements. It has to be noted that in addition to reducing utili- second-generation biofuels is the cost associated with transporta-

Table 5
Cost and share of avocado biorefinery.

Item Scenario 1 Scenario 2 Scenario 3 Scenario 4


Fix capital investment 24,612,125 15,391,750 15,391,750 18,145,512
Cost (USD/Year) Share (%) Cost (USD/Year) Share (%) Cost (USD/Year) Share (%) Cost (USD/Year) Share (%)
Depreciation expense 1,968,970 1.41 1,231,340 1.35 1,231,340 1.42 1,451,641 1.88
Raw material 41,315,739 29.56 41,315,739 45.26 41,313,010 47.69 41,313,010 53.52
Inputs 16,924,661 12.11 16,924,661 18.54 12,277,612 14.17 12,277,612 15.90
Utilities 68,712,100 49.17 20,970,933 22.97 20,970,933 24.21 20,838,659 26.99
Operating cost 10,836,500 7.75 10,836,500 11.88 10,836,500 12.51 10,836,500 1.71
Total 139,757,970 100 91,279,173 100 86,629,395 100 77,197,615 100
J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29 27

Table 6
Cost and cost share of inputs for avocado biorefinery.

Item Scenarios 1 and 2 Scenarios 3 and 4


Cost (USD/Year) Share (%) Cost (USD/Year) Share (%)
Enzyme 8,528,337 50.39 8,158,473 66.45
H2SO4 873,313 5.16 836,105 6.81
NaOH 191,249 1.13 182,936 1.49
Maltodextrin 1693 0.01 1228 0.01
CO2 3385 0.02 3683 0.03
Ethanol 6,932,341 40.96 2,807,892 22.87
Water 394,343 2.33 287,295 2.34
Total 16,924,661 100 12,277,612 100

found that the production of anthocyanins under biorefinery con-


cept has the highest contributions on sales (Moncada et al.,
2013) thus, the extractions and production of bioactive compounds
(such as microencapsulated phenolic compounds in this research)
in these kinds of processes should be considered because the
importance and relevance to the food, pharmaceutical and chemi-
cal industries.
In light of the results obtained above, a biorefinery based on
avocado could be attractive in the Colombian context for several
reasons. For instance, taken into account that avocado as feedstock
in this biorefinery corresponds to 26.37% of the entire Colombian
production then, a potential impact on food competition can be
minimal. Besides, potential improvements on agro-industrial chain
of avocado in Colombia could be obtained if valuable products
from this fruit are processed such in this research. This point of
Fig. 5. Sale price to total production cost ratio for avocado biorefinery. view allows enhancing the actual added value of avocado, obtain-
ing valuable products that can open regional and foreign markets.

tion and availability of raw materials (Moncada et al., 2013). There- 3.4. Environmental analysis
fore, integrating processes into one biorefinery (such as in this
research) is necessary for reaching the most profitable biorefinery Fig. 6 depicts the leaving PEI where, the most affected environ-
configuration. Results of this research also suggest that integration mental categories correspond to HTPI, TTP, PCOP and AP. The latter
of first and second generation biorefineries should be considered as reflects the impact of the organic matter that is included in the liq-
an integrated way for processing a given raw material (such as avo- uid streams, such as stillage, leaving the biorefinery. Similar obser-
cado) into value added products in a feasible way, in agreement vation was reported by Moncada et al. (2014a)) for a biorefinery for
with suggestions of others (Moncada et al., 2015). sugarcane processing where HTPI and TTP were affected by organic
Fig. 5 depicts the sale-price-to-total production cost ratio matter content of the effluents. PCOP is associated with CO2 pro-
(Mussatto et al., 2013) which was calculated using the prices duction (Montoya et al., 2006) and thus, the CO2 leaving the xylitol
reported in Table 2. For the best scenario (scenario 4), ethanol, xyl- and ethanol plants as well as the CO2 losses from phenolic com-
itol and oil exhibited the highest production cost (3.71, 32.77 and pounds plant contribute to PCOP. Similar results have been
212 USD/kg respectively) in comparison to their sale prices (see reported by Hernández et al. (2014) where PCOP was the most
Table 2). Microencapsulated phenolic compounds had the lowest important environmental category that contributed to the PEI of
production cost (1.8 USD/kg) and, in light of the high sale price a biorefinery for olive stone processing. Acidification potential
for microencapsulated phenolic compounds (167.48 USD/kg from (AP) exhibited high values that corresponds to the consumption
Table 2), it presents the most promising value added product to of external energy to cover the energy requirements (Moncada
be obtained from a biorefinery based on avocado. This fact suggests et al., 2014a).
that, under biorefinery concept, a given product, such as the Both, heat and mass integrations lowered the PEI but mass inte-
microencapsulated one in this research (or a few products) can gration had the most significant effect due to the savings of ethanol
provide a ‘‘subsidy” for the production of other products (ethanol, (57.65%) and water (23.70%). Mass integration (scenarios 3 and 4)
xylitol and oil in this research), similar to what has been reported reduces PEI by 2.65 and 3.37 folds in comparison to biorefineries
for a biorefinery based on sugarcane (Moncada et al., 2013). Thus, with heat integration (scenario 2) and without heat integration
scenario 4 has the highest sale-price-to-total-production cost ratio (scenario 1), respectively. Other authors found reduction of PEI
indicating that mass and energy integrations can reduce signifi- by a factor of 2.9 and 4 for biorefineries considering heat and mass
cantly the total production cost while scenario 1 (without mass integrations, respectively, relative to a biorefinery without any
and energy integrations) is not attractive because it increases the level of integration (Moncada et al., 2015). Results indicated that
total production cost which, in turn, reduces the sale-price-to- scenarios 3 and 4 were the most environmentally friendly, reflect-
total-production cost ratio. ing the lower leaving PEI due to not only to the savings in mass
Despite of the low production volumes of microencapsulated (ethanol and water) but also lower heating and cooling fluids for
phenolic compounds (6.27 kg/h), the high sale prices can compen- energy requirements (69.48% with heat integration).
sate the high productions costs associated to all products in the Because mass integration had a positive impact from both the
biorefinery therefore, the sale-price-to-total production cost ratio environmental and economic points of view, recovering and recy-
is higher than unity for all scenarios (see Fig. 5). Other authors cling process streams, at highest possible level, allows a better
28 J.A. Dávila et al. / Bioresource Technology 243 (2017) 17–29

Fig. 6. Leaving PEI for avocado biorefinery.

waste management as well as an efficient use of energy that con- Bizimana, V., Breene, W.M., Csallany, A.S., 1993. Avocado oil extraction with
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